Shukla / Boddu / Steevens Energetic Materials

From Cradle to Grave
1. Auflage 2017
ISBN: 978-3-319-59208-4
Verlag: Springer Nature Switzerland
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band 25, 484 Seiten

Reihe: Challenges and Advances in Computational Chemistry and Physics

This book offers a comprehensive account of energetic materials, including their synthesis, computational modeling, applications, associated degradation mechanisms, environmental consequences and fate and transport. This multi-author contributed volume describes how armed forces around the world are moving their attention from legacy explosive compounds, which are heat and shock sensitive (thus posing greater challenges in terms of handling and storage), to the insensitive munitions compounds/formulations such as insensitive munitions explosive (IMX) and the Picatinny Arsenal Explosive (PAX) series of compounds. The description of energetic materials focuses on explosives, pyrotechnic compositions, and propellants. The contributors go on to explain how modern generation energetic compounds must be insensitive to shock and heat but at the same time yield more energy upon explosion. Nanoinspired and/or co-crystallized energetic materials offer another route to generate next-generation energetic materials, and this authoritative book bridges a large gap in the literature by providing a comprehensive analysis of these compounds. Additionally, it includes a valuable overview of energetic materials, a detailed discussion of recent advances on future energetic compounds, nanotechnology in energetic materials, environmental contamination and toxicity, assessment of munitions lethality, the application quantitative structure-activity relationship (QSAR) in design of energetics and the fate and transport of munition compounds in the environment.

Manoj Shukla is Computational Chemistry Team Leader at the Environmental Laboratory, US Army Engineer Research and Development Center, Vicksburg, MS, USA. Veera M. Boddu is the Research Leader of the Plant Polymer Research Unit (PPL) at the National Center for Agriculture Utilization Research (NCAUR), Agriculture Research Service, US Department of Agriculture, ARS/USDA, 1815 N. University St., Peoria, IL  61604, USAJeffery Steevens is a Research Toxicologist at the U.S. Geological Survey, Columbia Environmental Research Center, Columbia, MO, USA.
Damavarapu Reddy is Research Chemist at the U.S. Army Armament Research, Development, and Engineering Center, Picatinny, NJ, USA.
Jerzy Leszczynski is a Professor of Chemistry and President's Distinguished Fellow at the Jackson State University, Jackson, MS, USA. 

Autoren/Hrsg.

Shukla, Manoj K.

Boddu, Veera M.

Steevens, Jeffery A.

Damavarapu, Reddy

Leszczynski, Jerzy

Inhaltsverzeichnis

1;Preface;6
2;Contents;8
3;1 High Performance, Low Sensitivity: The Impossible (or Possible) Dream?;10
3.1;Abstract;10
3.2;1 The Problem;10
3.3;2 Detonation Performance;11
3.3.1;2.1 Measurement;11
3.3.2;2.2 Some Governing Factors;12
3.4;3 Sensitivity;14
3.4.1;3.1 Measurement;14
3.4.2;3.2 Some Governing Factors;15
3.5;4 An Apparent Dilemma;23
3.6;5 In Quest of the Impossible Dream;26
3.6.1;5.1 Molecular Dimensions;26
3.6.2;5.2 Molecular Framework;27
3.6.3;5.3 Molecular Stoichiometry;27
3.6.4;5.4 Amino Substituents;27
3.6.5;5.5 Molecular Structural Modifications;28
3.7;6 Final Remarks;29
3.8;References;29
4;2 Recent Advances in Gun Propellant Development: From Molecules to Materials;32
4.1;Abstract;32
4.2;1 Gun Propellant Ballistics in a Nutshell;32
4.3;2 Ignition of Propellants;35
4.4;3 Combustion of Propellants;37
4.5;4 Propellant Ingredients;42
4.5.1;4.1 Energetic Molecules;42
4.5.2;4.2 Energetic Binders;43
4.5.3;4.3 Energetic Plasticizers;46
4.5.4;4.4 Energetic Fillers;52
4.5.4.1;4.4.1 High Nitrogen Content (HNC) Energetic Materials and Polynitrogen;53
4.5.4.2;4.4.2 Nanomaterials;57
4.5.4.3;4.4.3 Co-crystalization;59
4.6;5 Low Weight Percentage Additives;61
4.7;6 Propellant Formulation Modeling and Design;63
4.8;7 Processing Effects;66
4.9;8 Summary;69
4.10;References;69
5;3 How to Use QSPR Models to Help the Design and the Safety of Energetic Materials;75
5.1;Abstract;75
5.2;1 Introduction;75
5.3;2 Quantitative Structure-Property Relationships;76
5.3.1;2.1 Principle;76
5.3.2;2.2 Validation of QSPR Models;78
5.3.3;2.3 Robust Use of QSPR Models;80
5.4;3 Short Overview of QSPR Models for Energetic Materials;80
5.4.1;3.1 Detonation Properties;81
5.4.2;3.2 Brisance;82
5.4.3;3.3 Density;83
5.4.4;3.4 Heat of Formation;83
5.4.5;3.5 Melting Point;84
5.4.6;3.6 Sensitivity;85
5.4.7;3.7 Thermal Stability;87
5.5;4 Case Study: QSPR Models to Predict the Impact Sensitivity of Nitro Compounds;88
5.6;5 How to Use of QSPR Models for Energetic Materials;90
5.6.1;5.1 Use of QSPR Models in Regulatory Context;90
5.6.2;5.2 Use of QSPR Models for the Design of New Energetic Materials;92
5.7;6 Conclusions and Challenges;95
5.8;References;96
6;4 Energetic Polymers: Synthesis and Applications;99
6.1;Abstract;99
6.2;1 Introduction;99
6.3;2 Non-crosslinkable Energetic Binders;100
6.3.1;2.1 Nitrocellulose;100
6.3.2;2.2 Poly(vinyl nitrate);102
6.3.3;2.3 Energetic Polyesters, Polyamides and Polyurethanes;102
6.3.4;2.4 Energetic Polyacrylates;104
6.3.5;2.5 Polynitrophenylene (PNP);104
6.3.6;2.6 Nitramine Polymers;104
6.3.7;2.7 Poly(phosphazene)s;106
6.4;3 Crosslinkable Non-energetic Binder Systems for Propellant Formulations;109
6.4.1;3.1 Polysulfides;109
6.4.2;3.2 Polybutadienes with Carboxyl Functional Groups;110
6.4.3;3.3 Polyurethanes and Hydroxy-Terminated Polybutadiene (HTPB);111
6.4.4;3.4 Nitrated HTPB;112
6.4.5;3.5 Cyclodextrin Nitrate (CDN);112
6.5;4 Development of Binder Systems in Explosive Formulations;114
6.6;5 Oxirane-Based Crosslinkable Energetic Polymers;115
6.6.1;5.1 Poly(glycidyl nitrate) (PGN);116
6.6.2;5.2 End-Group Modification of Poly(glycidyl nitrate);119
6.6.3;5.3 Glycidyl Azide Polymer (GAP);121
6.6.4;5.4 Variants of Glycidyl Azide Polymer (GAP);123
6.6.5;5.5 Other Oxirane-Based Energetic Polymers;124
6.7;6 Oxetane-Based Energetic Polymers;126
6.7.1;6.1 Ring-Substituted Oxetanes;126
6.7.2;6.2 Methyl-Substituted Oxetanes;128
6.7.3;6.3 Energetic Thermoplastic Elastomers (ETPE’s);130
6.8;References;137
7;5 Pyrophoric Nanomaterials;143
7.1;Abstract;143
7.2;1 Introduction;143
7.3;2 Nanoscale Powders;144
7.3.1;2.1 Introduction;144
7.3.2;2.2 Aluminum Nanopowder;146
7.3.3;2.3 Iron Nanopowder;148
7.4;3 Milled Powders;149
7.4.1;3.1 Introduction;149
7.4.2;3.2 Mechanism;150
7.4.3;3.3 Process Control;152
7.4.3.1;3.3.1 Types of Mills;152
7.4.3.2;3.3.2 Selection of Raw Materials;153
7.4.3.3;3.3.3 Time and Intensity;154
7.4.3.4;3.3.4 Process Control Agents;154
7.4.3.5;3.3.5 Media;154
7.4.3.6;3.3.6 Atmosphere;155
7.4.3.7;3.3.7 Contamination;155
7.4.4;3.4 Tunability;156
7.5;4 Coating/Substrates;158
7.5.1;4.1 Introduction;158
7.5.2;4.2 Substrate/Structure Production Techniques;159
7.5.2.1;4.2.1 Chemical Leaching;159
7.5.2.2;4.2.2 Sol-Gel Techniques;160
7.5.2.3;4.2.3 Filtration;162
7.5.2.4;4.2.4 Tape Casting;163
7.5.2.5;4.2.5 Cold Isostatic Pressing;164
7.5.3;4.3 Dynamic Combustion Characteristics;164
7.5.3.1;4.3.1 Carbon-Based Substrates;164
7.5.3.2;4.3.2 Iron/Ceramic Composite Substrates;165
7.5.3.3;4.3.3 Iron/Ceramic Composite Structures;165
7.5.4;4.4 Tunability Through Addition of Tertiary Reactives;167
7.6;5 Pyrophoric Foams;167
7.6.1;5.1 Introduction;167
7.6.2;5.2 Metallic Foams;168
7.6.3;5.3 Metallic Composite Foams;171
7.7;6 Safety Considerations;173
7.7.1;6.1 Safety, Handling, and Characterization;173
7.8;7 Conclusions;176
7.9;References;176
8;6 The Relationship Between Flame Structure and Burning Rate for Ammonium Perchlorate Composite Propellants;179
8.1;Abstract;179
8.2;1 Introduction and Background;180
8.3;2 Flame Structure Models;183
8.4;3 Research Methods;185
8.4.1;3.1 Linear Burning Rate Measurements;185
8.4.2;3.2 Optical Emission and Transmission;186
8.4.3;3.3 Laser Induced Fluorescence;187
8.5;4 Formulation Effect on Flame Structure;188
8.5.1;4.1 Counterflow Diffusion Flames;189
8.5.2;4.2 Ported Pellets;190
8.5.3;4.3 Sandwich/Lamina;191
8.5.4;4.4 Monomodal;195
8.5.5;4.5 Bimodal;200
8.5.5.1;4.5.1 Coarse-to-Fine Ratio;200
8.5.5.1.1;Global Burning Rate;200
8.5.5.1.2;Flame Structure;202
8.5.5.1.3;Coarse Crystal Burning Characteristics;205
8.5.5.2;4.5.2 Catalysts;206
8.5.5.3;4.5.3 Binder;209
8.5.5.4;4.5.4 Aluminum;210
8.6;5 Predicted Flame Structures;211
8.7;6 Conclusions;213
8.8;References;216
9;7 PAFRAG Modeling and Experimentation Methodology for Assessing Lethality and Safe Separation Distances of Explosive Fragmentation Ammunitions;220
9.1;Abstract;220
9.2;1 Introduction: Fragmentation of Explosively Driven Shells;220
9.3;2 The Fragmentation Arena Test Methodology;224
9.4;3 The PAFRAG Fragmentation Model;225
9.5;4 The PAFRAG-Mott Fragmentation Model;227
9.6;5 PAFRAG-Mott Model Validation: Charge a Analyses;231
9.7;6 Charge B Modeling and Experimentation;236
9.8;7 Charge C Modeling and Experimentation;240
9.9;8 Charge C PAFRAG Model Analyses: Assessment of Lethality and Safety Separation Distance;245
9.10;9 Summary;246
9.11;Acknowledgements;246
9.12;References;246
10;8 Grain-Scale Simulation of Shock Initiation in Composite High Explosives;249
10.1;Abstract;249
10.2;1 Introduction;249
10.3;2 Multi-crystal Simulations;251
10.3.1;2.1 Microstructure Characterization and Reconstruction;252
10.3.2;2.2 Survey of HE Shock Initiation Work;253
10.4;3 Single-Crystal Simulations;257
10.4.1;3.1 Continuum Model of HMX;258
10.4.1.1;3.1.1 Solid Phase;258
10.4.1.2;3.1.2 Fluid Phases;260
10.4.1.3;3.1.3 Thermal Properties;260
10.4.1.4;3.1.4 Chemistry;260
10.4.2;3.2 Simulations of Intragranular Pore Collapse;262
10.4.2.1;3.2.1 Basic Results for a Reference Case;263
10.4.2.2;3.2.2 Heat Conduction Considerations;266
10.4.2.3;3.2.3 Model Sensitivity to Solid Flow Strength;267
10.4.2.4;3.2.4 Model Sensitivity to Liquid Viscosity;269
10.5;4 Concluding Remarks;271
10.6;Acknowledgements;273
10.7;References;273
11;9 Computational Modeling for Fate, Transport and Evolution of Energetic Metal Nanoparticles Grown via Aerosol Route;277
11.1;Abstract;277
11.2;1 Introduction;278
11.2.1;1.1 Energetic Nanomaterials: A Broad Overview;278
11.2.2;1.2 Modeling Work to Study Fate, Transport and Growth of Metal Nanoparticles;280
11.3;2 Homogeneous Gas-Phase Nucleation of Metal Nanoparticles;282
11.3.1;2.1 Classical Nucleation Theory (CNT);285
11.3.2;2.2 Modeling Nucleation: KMC Based Model and Deviations from CNT;289
11.4;3 Non-isothermal Coagulation and Coalescence;295
11.4.1;3.1 Mathematical Model and Theory;298
11.4.1.1;3.1.1 Smoluchowski Equation and Collision Kernel Formulation;298
11.4.1.2;3.1.2 Energy Equations for Coalescence Process;299
11.4.1.3;3.1.3 Effect of Lowered Melting Point of Nanoparticles on Coalescence;303
11.4.1.4;3.1.4 Radiation Heat Loss Term for Nanoparticles: A Discussion;305
11.4.2;3.2 Modeling Non-isothermal Coagulation and Coalescence: Coagulation Driven KMC Model;305
11.4.2.1;3.2.1 Implementation of MC Algorithm: Determination of Characteristic Time Scales for Coagulation;307
11.4.2.2;3.2.2 Model Metrics and Validation for the KMC Algorithm;309
11.4.3;3.3 Results and Discussions: Effects of Process Parameters on Nanoparticle Growth via Coagulations and Non-isothermal Coalescence;311
11.4.3.1;3.3.1 Effect of Background Gas Temperature;311
11.4.3.2;3.3.2 Effect of Background Gas Pressure;313
11.4.3.3;3.3.3 Effect of Volume Loading;317
11.5;4 Surface Oxidation;317
11.5.1;4.1 Mathematical Model and Theory;320
11.5.1.1;4.1.1 Morphology: Surface Fractal Dimension;320
11.5.1.2;4.1.2 Collision Kernel and Characteristic Collision Time;320
11.5.1.3;4.1.3 Coalescence;324
11.5.1.4;4.1.4 Surface Oxidation: Transport Model and Species Balance;324
11.5.1.5;4.1.5 Energy Balance;330
11.5.2;4.2 Modeling Surface Oxidation: Coagulation Driven KMC Model;331
11.5.3;4.3 Effect of Morphology and Non-isothermal Coalescence on Surface Oxidation of Metal Nanoparticles: Results from the Study;332
11.5.3.1;4.3.1 Estimation of Primary Particle Size;332
11.5.3.2;4.3.2 Estimation of Particle Morphology;333
11.5.3.3;4.3.3 Surface Oxidation and Evolution of Fractal-like Al/Al2O3 Nanoparticles;335
11.5.3.4;4.3.4 Implications of Coalescence-Driven Fractal like Morphology on the Surface Oxidation of Al/Al2O3 Nanoparticles;339
11.6;5 Conclusion;340
11.7;Acknowledgements;341
11.8;References;341
12;10 Physical Properties of Select Explosive Components for Assessing Their Fate and Transport in the Environment;348
12.1;Abstract;348
12.2;1 Introduction;349
12.3;2 Model Predictions;352
12.3.1;2.1 Physical Properties Prediction Using Estimation Programs Interface (EPI) Suite;352
12.3.2;2.2 Physical Properties Prediction Using SPARC Performed Automated Reasoning in Chemistry (SPARC) Package;355
12.3.3;2.3 Theoretical Background for SPARC Approach for Calculating Physical Properties;356
12.3.4;2.4 SPARC approach for estimation of Water Solubility (Sw) and Activity Coefficient (?);357
12.3.5;2.5 SPARC Approach for Estimation of Vapor Pressure (VP);357
12.3.6;2.6 SPARC Approach for Estimation of Boiling Point (BP);358
12.3.7;2.7 SPARC Approach for Estimation of Octanol-Water Partition Coefficient (Kow);358
12.3.8;2.8 SPARC Approach for Estimation of Henry’s Law Constant (KH);359
12.3.9;2.9 SPARC Approach for Estimation of Enthalpy of Vaporization (?Hvap);359
12.4;3 Group Contribution and COSMOtherm Approach;359
12.5;4 Experimental Approaches;361
12.5.1;4.1 Experimental Approach For Measuring Octanol-Water Partition Coefficient (Kow);361
12.5.2;4.2 Vapor Pressure (VP);362
12.6;5 Conclusion;365
12.7;Acknowledgements;373
12.8;References;374
13;11 High Explosives and Propellants Energetics: Their Dissolution and Fate in Soils;377
13.1;Abstract;377
13.2;1 Introduction;379
13.3;2 Field Deposition;380
13.3.1;2.1 Propellants;381
13.3.2;2.2 High Explosives;382
13.4;3 Dissolution of Energetic Compounds;386
13.4.1;3.1 Propellants;386
13.4.2;3.2 High Explosives;390
13.5;4 Physicochemical Properties of Explosive and Propellant Constituents;393
13.6;5 Soil Interactions;394
13.6.1;5.1 TNT, DNT and Their Transformation Products;394
13.6.2;5.2 RDX and HMX;399
13.6.3;5.3 Nitroglycerine;399
13.6.4;5.4 Nitroguanidine;400
13.6.5;5.5 Reactive Transport;400
13.6.6;5.6 Conclusions;405
13.7;Acknowledgements;405
13.8;References;406
14;12 Insensitive Munitions Formulations: Their Dissolution and Fate in Soils;411
14.1;Abstract;411
14.2;1 Introduction;411
14.3;2 Field Deposition;413
14.4;3 Dissolution of IM Detonation Residues;417
14.4.1;3.1 Indoor Drip Tests;417
14.4.2;3.2 Outdoor Dissolution Tests;418
14.4.3;3.3 Mass Balance for Outdoor Tests;422
14.4.4;3.4 Photo-Transformation of IM;424
14.4.5;3.5 PH of the IM Solutions;426
14.5;4 Physiochemical Properties of Insensitive Munitions Formulations;427
14.6;5 Soil Interactions;428
14.6.1;5.1 Batch Soil Adsorption Studies;430
14.6.1.1;5.1.1 NTO;430
14.6.1.2;5.1.2 DNAN;434
14.6.2;5.2 Solution Transport for NTO and DNAN and HYDRUS-1D Modeling Results;437
14.6.3;5.3 Dissolution and Transport of IM Formulations;440
14.7;6 Summary;443
14.8;References;444
15;13 Toxicity and Bioaccumulation of Munitions Constituents in Aquatic and Terrestrial Organisms;448
15.1;Abstract;448
15.2;1 Introduction;449
15.3;2 Toxicity to Soil Microorganisms and Invertebrates;450
15.4;3 Toxicity to Terrestrial Plants;456
15.5;4 Toxicity to Aquatic Autotrophs;460
15.6;5 Toxicity to Tadpoles and Fish;460
15.7;6 Toxicity to Aquatic Invertebrates in Aqueous Exposures;461
15.8;7 Toxicity of Photo-Transformation Products;469
15.9;8 Toxicity to Aquatic Invertebrates and Fish in Exposures to Spiked Sediment;469
15.10;9 Bioaccumulation in Soil Invertebrates and Terrestrial Plants;471
15.10.1;9.1 Bioaccumulation in Fish and Aquatic Invertebrates;472
15.11;10 Summary and Conclusions;472
15.12;References;474
16;Index;483