Preface ..................................................... IX
Abbreviations ............................................... XI
1 Polymers as Binders and Plasticizers-Historical
Perspective .................................................. 1
1.1 Nitrocellulose .......................................... 1
1.2 Polysulfides ............................................ 2
1.3 Polybutadienes (PBAA, PBAN, and CTPB) ................... 3
1.4 Polyurethanes ........................................... 4
1.5 Hydroxy Terminated Polybutadiene ........................ 5
1.6 Explosive Binders ....................................... 5
1.7 Thermoplastic Elastomers ................................ 6
1.8 Energetic Polymers (Other Than NC) as Binders ........... 8
1.8.1 Polyglycidyl Nitrate ............................. 8
1.8.2 GAP .............................................. 9
1.8.3 Energetic Polyoxetanes .......................... 10
1.8.4 Polyphosphazenes ................................ 11
1.8.5 Energetic Thermoplastic Elastomers .............. 11
1.9 Energetic Polymer Plasticizers ......................... 12
References .................................................. 15
2 High Nitrogen Content Polymers .............................. 19
2.1 Introduction ........................................... 19
2.2 Preparation of Energetic Azido Polymers ................ 19
2.2.1 Glycidyl Azide Polymer .......................... 19
2.2.2 Azido Polymers from Oxetanes .................... 22
2.2.2.1 Poly(BAMO) ............................. 23
2.2.2.2 Poly(AMMO) ............................. 24
2.3 Physical Properties of Azido Polymers .................. 25
2.4 Curing of Azido Polymers ............................... 25
2.4.1 Curing by Polyisocyanates ....................... 25
2.4.1.1 Preparation ............................ 26
2.4.1.2 Structure of Cured Polyurethane
Elastomer .............................. 28
2.4.1.3 Kinetics of Curing of Azido Polymers ... 29
2.4.1.4 Gel-Time Characteristics ............... 31
2.4.1.5 Post-Cure Properties ................... 33
2.5 Curing of Azido Polymers by Dipolarophiles ............. 38
2.6 Thermal Decomposition Characteristics of Azido
Polymers ............................................... 41
2.6.1 Mechanism of Thermal Decomposition .............. 41
2.6.2 Kinetics of Thermal Decomposition of Azido
Polymers ........................................ 43
2.7 Combustion of Azido Polymers ........................... 47
2.8 Thermal Decomposition and Combustion of Energetic
Formulations with Azido Polymers ....................... 49
2.8.1 Thermal Decomposition of Azido Polymer/
Nitramine Mixtures .............................. 50
2.8.2 Combustion of Azido Polymer/Nitramine
Propellant Mixtures ............................. 54
2.8.3 Combustion of Azido Polymer/Ammonium Nitrate
Composite Propellants ........................... 57
2.8.4 Combustion of Azido Polymer Propellants with
HNF ............................................. 58
2.9 Performance of Azido Polymer-Based Propellants ......... 61
2.10 Azido Polymers as Explosive Binders .................... 63
2.10.1 Azido Polymer Based PBX Formulations for
Underwater Explosives ........................... 65
2.11 Tetrazole Polymers and Their Salts ..................... 66
2.12 N-N-Bonded Epoxy Binders ............................... 69
References .................................................. 70
3 Nitropolymers as Energetic Binders .......................... 81
3.1 Introduction ........................................... 81
3.2 Preparation of Nitropolymers ........................... 82
3.2.1 Nitrocellulose .................................. 82
3.2.2 Poly(Glycidyl Nitrate) (PGN) .................... 83
3.2.2.1 Curing of PGN .......................... 85
3.2.3 Poly(Nitratomethyl-methyl Oxetane)
(Poly(NIMMO)) ................................... 88
3.2.4 Nitrated HTPB (NHTPB) ........................... 90
3.2.5 Nitrated Cyclodextrin Polymers (Poly(CDN)) ...... 90
3.3 Thermal Decomposition Behavior of Nitropolymers ........ 91
3.3.1 Nitrocellulose .................................. 91
3.3.2 Poly(Nitratomethyl-Methyl Oxetane)
(Poly(NIMMO)) ................................... 94
3.3.3 Poly(Glycidyl Nitrate) (PGN) .................... 98
3.4 Combustion of Nitrate Ester Polymers and
Propellants ........................................... 100
3.4.1 NC Based Double-Base Propellants ............... 100
3.4.2 Composite Modified Double-Base (CMDB)
Propellants .................................... 101
3.4.3 Poly(NIMMO)-Based Composite Propellants ........ 106
3.4.4 PGN-Based Composite Propellants ................ 109
3.5 Nitropolymer-Based Explosive Compositions ............. 111
References ................................................. 115
4 Energetic Thermoplastic Elastomers ......................... 121
4.1 Introduction .......................................... 121
4.2 Preparation of Energetic Thermoplastic Elastomers ..... 122
4.3 Thermal Decomposition and Combustion of ETPEs ......... 132
4.4 Combustion of ETPE Propellant Formulations ............ 137
4.5 Performance of ETPE Based Propellant Formulations ..... 139
4.6 Melt-Cast Explosives Based on ETPEs ................... 141
4.7 ETPE Based Polymer Nanocomposites ..................... 142
References ............................................ 144
5 Fluoropolymers as Binders .................................. 147
5.1 Introduction .......................................... 147
5.2 Poly(tetrafluoroethylene) (PTFE) ...................... 148
5.2.1 Phase Transitions of PTFE ...................... 148
5.2.2 Energetic Composites of PTFE ................... 149
5.3 Copolymers of Tetrafluoroethylene ..................... 152
5.3.1 Kel-F800 ....................................... 153
5.3.1.1 Dynamic Behavior of Kel-F800 under
Shock ................................. 153
5.3.1.2 Thermal Decomposition ................. 155
5.3.2 Viton A ........................................ 156
5.3.2.1 Thermal Decomposition of Viton ........ 158
5.4 Energetic Polymers Containing Fluorine ................ 159
5.5 Miscellaneous Energetic Fluoropolymers ................ 161
5.6 PBX Formulations with Fluoropolymers .................. 162
References ................................................. 165
6 Energetic Plasticizers for High Performance ................ 171
6.1 Introduction .......................................... 171
6.2 Energetic Plasticizers Based on Azido Compounds ....... 172
6.2.1 Azido Acetate Ester Based Plasticizers ......... 172
6.2.2 Azido Based Oligomeric Plasticizers ............ 174
6.3 Performance of Propellant Formulations Containing
Azido Plasticizers .................................... 178
6.4 Nitrate Ester Plasticizers ............................ 180
6.4.1 General Characteristics ........................ 180
6.4.2 Performance .................................... 183
6.5 Nitrate Ester Oligomers as Energetic Plasticizers ..... 184
6.6 Miscellaneous Plasticizers Based on Nitro-Groups ...... 186
6.6.1 Polynitro-Aliphatic Plasticizers ............... 186
6.6.2 Nitratoethylnitramine (NENA) Plasticizers ...... 188
References ................................................. 189
7 Application of Computational Techniques to Energetic
Polymers and Formulations .................................. 193
7.1 Introduction .......................................... 193
7.2 Overview of Computational Techniques .................. 193
7.3 Application of Computational Modeling Techniques to
Energetic Polymer Formulations ........................ 197
7.3.1 Quantum Mechanical Methods ..................... 197
7.3.2 Molecular Dynamics (MD) Simulations ............ 201
7.3.3 Mesoscale Simulations .......................... 205
7.3.4 Macroscale Simulations ......................... 206
7.4 Future Outlook ........................................ 207
References ................................................. 208
Index ...................................................... 211
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