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