Preface	6
	Contents	8
	1 High Performance, Low Sensitivity: The Impossible (or Possible) Dream?	10
	Abstract	10
	1 The Problem	10
	2 Detonation Performance	11
	2.1 Measurement	11
	2.2 Some Governing Factors	12
	3 Sensitivity	14
	3.1 Measurement	14
	3.2 Some Governing Factors	15
	4 An Apparent Dilemma	23
	5 In Quest of the Impossible Dream	26
	5.1 Molecular Dimensions	26
	5.2 Molecular Framework	27
	5.3 Molecular Stoichiometry	27
	5.4 Amino Substituents	27
	5.5 Molecular Structural Modifications	28
	6 Final Remarks	29
	References	29
	2 Recent Advances in Gun Propellant Development: From Molecules to Materials	32
	Abstract	32
	1 Gun Propellant Ballistics in a Nutshell	32
	2 Ignition of Propellants	35
	3 Combustion of Propellants	37
	4 Propellant Ingredients	42
	4.1 Energetic Molecules	42
	4.2 Energetic Binders	43
	4.3 Energetic Plasticizers	46
	4.4 Energetic Fillers	52
	4.4.1 High Nitrogen Content (HNC) Energetic Materials and Polynitrogen	53
	4.4.2 Nanomaterials	57
	4.4.3 Co-crystalization	59
	5 Low Weight Percentage Additives	61
	6 Propellant Formulation Modeling and Design	63
	7 Processing Effects	66
	8 Summary	69
	References	69
	3 How to Use QSPR Models to Help the Design and the Safety of Energetic Materials	75
	Abstract	75
	1 Introduction	75
	2 Quantitative Structure-Property Relationships	76
	2.1 Principle	76
	2.2 Validation of QSPR Models	78
	2.3 Robust Use of QSPR Models	80
	3 Short Overview of QSPR Models for Energetic Materials	80
	3.1 Detonation Properties	81
	3.2 Brisance	82
	3.3 Density	83
	3.4 Heat of Formation	83
	3.5 Melting Point	84
	3.6 Sensitivity	85
	3.7 Thermal Stability	87
	4 Case Study: QSPR Models to Predict the Impact Sensitivity of Nitro Compounds	88
	5 How to Use of QSPR Models for Energetic Materials	90
	5.1 Use of QSPR Models in Regulatory Context	90
	5.2 Use of QSPR Models for the Design of New Energetic Materials	92
	6 Conclusions and Challenges	95
	References	96
	4 Energetic Polymers: Synthesis and Applications	99
	Abstract	99
	1 Introduction	99
	2 Non-crosslinkable Energetic Binders	100
	2.1 Nitrocellulose	100
	2.2 Poly(vinyl nitrate)	102
	2.3 Energetic Polyesters, Polyamides and Polyurethanes	102
	2.4 Energetic Polyacrylates	104
	2.5 Polynitrophenylene (PNP)	104
	2.6 Nitramine Polymers	104
	2.7 Poly(phosphazene)s	106
	3 Crosslinkable Non-energetic Binder Systems for Propellant Formulations	109
	3.1 Polysulfides	109
	3.2 Polybutadienes with Carboxyl Functional Groups	110
	3.3 Polyurethanes and Hydroxy-Terminated Polybutadiene (HTPB)	111
	3.4 Nitrated HTPB	112
	3.5 Cyclodextrin Nitrate (CDN)	112
	4 Development of Binder Systems in Explosive Formulations	114
	5 Oxirane-Based Crosslinkable Energetic Polymers	115
	5.1 Poly(glycidyl nitrate) (PGN)	116
	5.2 End-Group Modification of Poly(glycidyl nitrate)	119
	5.3 Glycidyl Azide Polymer (GAP)	121
	5.4 Variants of Glycidyl Azide Polymer (GAP)	123
	5.5 Other Oxirane-Based Energetic Polymers	124
	6 Oxetane-Based Energetic Polymers	126
	6.1 Ring-Substituted Oxetanes	126
	6.2 Methyl-Substituted Oxetanes	128
	6.3 Energetic Thermoplastic Elastomers (ETPE’s)	130
	References	137
	5 Pyrophoric Nanomaterials	143
	Abstract	143
	1 Introduction	143
	2 Nanoscale Powders	144
	2.1 Introduction	144
	2.2 Aluminum Nanopowder	146
	2.3 Iron Nanopowder	148
	3 Milled Powders	149
	3.1 Introduction	149
	3.2 Mechanism	150
	3.3 Process Control	152
	3.3.1 Types of Mills	152
	3.3.2 Selection of Raw Materials	153
	3.3.3 Time and Intensity	154
	3.3.4 Process Control Agents	154
	3.3.5 Media	154
	3.3.6 Atmosphere	155
	3.3.7 Contamination	155
	3.4 Tunability	156
	4 Coating/Substrates	158
	4.1 Introduction	158
	4.2 Substrate/Structure Production Techniques	159
	4.2.1 Chemical Leaching	159
	4.2.2 Sol-Gel Techniques	160
	4.2.3 Filtration	162
	4.2.4 Tape Casting	163
	4.2.5 Cold Isostatic Pressing	164
	4.3 Dynamic Combustion Characteristics	164
	4.3.1 Carbon-Based Substrates	164
	4.3.2 Iron/Ceramic Composite Substrates	165
	4.3.3 Iron/Ceramic Composite Structures	165
	4.4 Tunability Through Addition of Tertiary Reactives	167
	5 Pyrophoric Foams	167
	5.1 Introduction	167
	5.2 Metallic Foams	168
	5.3 Metallic Composite Foams	171
	6 Safety Considerations	173
	6.1 Safety, Handling, and Characterization	173
	7 Conclusions	176
	References	176
	6 The Relationship Between Flame Structure and Burning Rate for Ammonium Perchlorate Composite Propellants	179
	Abstract	179
	1 Introduction and Background	180
	2 Flame Structure Models	183
	3 Research Methods	185
	3.1 Linear Burning Rate Measurements	185
	3.2 Optical Emission and Transmission	186
	3.3 Laser Induced Fluorescence	187
	4 Formulation Effect on Flame Structure	188
	4.1 Counterflow Diffusion Flames	189
	4.2 Ported Pellets	190
	4.3 Sandwich/Lamina	191
	4.4 Monomodal	195
	4.5 Bimodal	200
	4.5.1 Coarse-to-Fine Ratio	200
	Global Burning Rate	200
	Flame Structure	202
	Coarse Crystal Burning Characteristics	205
	4.5.2 Catalysts	206
	4.5.3 Binder	209
	4.5.4 Aluminum	210
	5 Predicted Flame Structures	211
	6 Conclusions	213
	References	216
	7 PAFRAG Modeling and Experimentation Methodology for Assessing Lethality and Safe Separation Distances of Explosive Fragmentation Ammunitions	220
	Abstract	220
	1 Introduction: Fragmentation of Explosively Driven Shells	220
	2 The Fragmentation Arena Test Methodology	224
	3 The PAFRAG Fragmentation Model	225
	4 The PAFRAG-Mott Fragmentation Model	227
	5 PAFRAG-Mott Model Validation: Charge a Analyses	231
	6 Charge B Modeling and Experimentation	236
	7 Charge C Modeling and Experimentation	240
	8 Charge C PAFRAG Model Analyses: Assessment of Lethality and Safety Separation Distance	245
	9 Summary	246
	Acknowledgements	246
	References	246
	8 Grain-Scale Simulation of Shock Initiation in Composite High Explosives	249
	Abstract	249
	1 Introduction	249
	2 Multi-crystal Simulations	251
	2.1 Microstructure Characterization and Reconstruction	252
	2.2 Survey of HE Shock Initiation Work	253
	3 Single-Crystal Simulations	257
	3.1 Continuum Model of HMX	258
	3.1.1 Solid Phase	258
	3.1.2 Fluid Phases	260
	3.1.3 Thermal Properties	260
	3.1.4 Chemistry	260
	3.2 Simulations of Intragranular Pore Collapse	262
	3.2.1 Basic Results for a Reference Case	263
	3.2.2 Heat Conduction Considerations	266
	3.2.3 Model Sensitivity to Solid Flow Strength	267
	3.2.4 Model Sensitivity to Liquid Viscosity	269
	4 Concluding Remarks	271
	Acknowledgements	273
	References	273
	9 Computational Modeling for Fate, Transport and Evolution of Energetic Metal Nanoparticles Grown via Aerosol Route	277
	Abstract	277
	1 Introduction	278
	1.1 Energetic Nanomaterials: A Broad Overview	278
	1.2 Modeling Work to Study Fate, Transport and Growth of Metal Nanoparticles	280
	2 Homogeneous Gas-Phase Nucleation of Metal Nanoparticles	282
	2.1 Classical Nucleation Theory (CNT)	285
	2.2 Modeling Nucleation: KMC Based Model and Deviations from CNT	289
	3 Non-isothermal Coagulation and Coalescence	295
	3.1 Mathematical Model and Theory	298
	3.1.1 Smoluchowski Equation and Collision Kernel Formulation	298
	3.1.2 Energy Equations for Coalescence Process	299
	3.1.3 Effect of Lowered Melting Point of Nanoparticles on Coalescence	303
	3.1.4 Radiation Heat Loss Term for Nanoparticles: A Discussion	305
	3.2 Modeling Non-isothermal Coagulation and Coalescence: Coagulation Driven KMC Model	305
	3.2.1 Implementation of MC Algorithm: Determination of Characteristic Time Scales for Coagulation	307
	3.2.2 Model Metrics and Validation for the KMC Algorithm	309
	3.3 Results and Discussions: Effects of Process Parameters on Nanoparticle Growth via Coagulations and Non-isothermal Coalescence	311
	3.3.1 Effect of Background Gas Temperature	311
	3.3.2 Effect of Background Gas Pressure	313
	3.3.3 Effect of Volume Loading	317
	4 Surface Oxidation	317
	4.1 Mathematical Model and Theory	320
	4.1.1 Morphology: Surface Fractal Dimension	320
	4.1.2 Collision Kernel and Characteristic Collision Time	320
	4.1.3 Coalescence	324
	4.1.4 Surface Oxidation: Transport Model and Species Balance	324
	4.1.5 Energy Balance	330
	4.2 Modeling Surface Oxidation: Coagulation Driven KMC Model	331
	4.3 Effect of Morphology and Non-isothermal Coalescence on Surface Oxidation of Metal Nanoparticles: Results from the Study	332
	4.3.1 Estimation of Primary Particle Size	332
	4.3.2 Estimation of Particle Morphology	333
	4.3.3 Surface Oxidation and Evolution of Fractal-like Al/Al2O3 Nanoparticles	335
	4.3.4 Implications of Coalescence-Driven Fractal like Morphology on the Surface Oxidation of Al/Al2O3 Nanoparticles	339
	5 Conclusion	340
	Acknowledgements	341
	References	341
	10 Physical Properties of Select Explosive Components for Assessing Their Fate and Transport in the Environment	348
	Abstract	348
	1 Introduction	349
	2 Model Predictions	352
	2.1 Physical Properties Prediction Using Estimation Programs Interface (EPI) Suite	352
	2.2 Physical Properties Prediction Using SPARC Performed Automated Reasoning in Chemistry (SPARC) Package	355
	2.3 Theoretical Background for SPARC Approach for Calculating Physical Properties	356
	2.4 SPARC approach for estimation of Water Solubility (Sw) and Activity Coefficient (?)	357
	2.5 SPARC Approach for Estimation of Vapor Pressure (VP)	357
	2.6 SPARC Approach for Estimation of Boiling Point (BP)	358
	2.7 SPARC Approach for Estimation of Octanol-Water Partition Coefficient (Kow)	358
	2.8 SPARC Approach for Estimation of Henry’s Law Constant (KH)	359
	2.9 SPARC Approach for Estimation of Enthalpy of Vaporization (?Hvap)	359
	3 Group Contribution and COSMOtherm Approach	359
	4 Experimental Approaches	361
	4.1 Experimental Approach For Measuring Octanol-Water Partition Coefficient (Kow)	361
	4.2 Vapor Pressure (VP)	362
	5 Conclusion	365
	Acknowledgements	373
	References	374
	11 High Explosives and Propellants Energetics: Their Dissolution and Fate in Soils	377
	Abstract	377
	1 Introduction	379
	2 Field Deposition	380
	2.1 Propellants	381
	2.2 High Explosives	382
	3 Dissolution of Energetic Compounds	386
	3.1 Propellants	386
	3.2 High Explosives	390
	4 Physicochemical Properties of Explosive and Propellant Constituents	393
	5 Soil Interactions	394
	5.1 TNT, DNT and Their Transformation Products	394
	5.2 RDX and HMX	399
	5.3 Nitroglycerine	399
	5.4 Nitroguanidine	400
	5.5 Reactive Transport	400
	5.6 Conclusions	405
	Acknowledgements	405
	References	406
	12 Insensitive Munitions Formulations: Their Dissolution and Fate in Soils	411
	Abstract	411
	1 Introduction	411
	2 Field Deposition	413
	3 Dissolution of IM Detonation Residues	417
	3.1 Indoor Drip Tests	417
	3.2 Outdoor Dissolution Tests	418
	3.3 Mass Balance for Outdoor Tests	422
	3.4 Photo-Transformation of IM	424
	3.5 PH of the IM Solutions	426
	4 Physiochemical Properties of Insensitive Munitions Formulations	427
	5 Soil Interactions	428
	5.1 Batch Soil Adsorption Studies	430
	5.1.1 NTO	430
	5.1.2 DNAN	434
	5.2 Solution Transport for NTO and DNAN and HYDRUS-1D Modeling Results	437
	5.3 Dissolution and Transport of IM Formulations	440
	6 Summary	443
	References	444
	13 Toxicity and Bioaccumulation of Munitions Constituents in Aquatic and Terrestrial Organisms	448
	Abstract	448
	1 Introduction	449
	2 Toxicity to Soil Microorganisms and Invertebrates	450
	3 Toxicity to Terrestrial Plants	456
	4 Toxicity to Aquatic Autotrophs	460
	5 Toxicity to Tadpoles and Fish	460
	6 Toxicity to Aquatic Invertebrates in Aqueous Exposures	461
	7 Toxicity of Photo-Transformation Products	469
	8 Toxicity to Aquatic Invertebrates and Fish in Exposures to Spiked Sediment	469
	9 Bioaccumulation in Soil Invertebrates and Terrestrial Plants	471
	9.1 Bioaccumulation in Fish and Aquatic Invertebrates	472
	10 Summary and Conclusions	472
	References	474
	Index	483