Preface ........................................................ XV
List of Contributors ......................................... XVII
1 General Concepts about Epoxy Polymers ...................... 7
Jean-Pierre Pascault and Roberto J.J. Williams
1.1 Polymerization Chemistry of Epoxy Monomers ................. 1
1.1.1 Typical Epoxy Monomers and Polymer Growth
Mechanisms ..........................................
1.1.2 Step Growth Polymerization .......................... 3
1.1.3 Chain Homopolymerization ............................ 3
1.1.4 Chain Copolymerization .............................. 4
1.1.5 Dual Polymerization Systems ......................... 5
1.2 Transformations During the Formation of an Epoxy Network
1.2.1 General Considerations .............................. 6
1.2.2 Gelation ............................................ 6
1.2.3 Vitrification ....................................... 8
1.2.4 Reaction-Induced Phase Separation ................... 8
1.2.5 Transformation Diagrams ............................. 9
1.3 General Properties of Epoxy Networks ...................... 11
References ................................................ 12
Part One New Polymers/Materials ................................ 73
2 Thermoplastic Epoxy Polymers .............................. 75
Jerry E. White
2.1 Introduction .............................................. 15
2.2 Synthesis and Characterization of Epoxy Thermoplastics .... 17
2.2.1 Poly(hydroxy ethers) and Poly(hydroxy ether
sulfides) .......................................... 17
2.2.2 Poly(hydroxy ether sulfonamides) ................... 22
2.2.3 Poly(hydroxy ester ethers) ......................... 23
2.2.4 Poly(hydroxy amino ethers) ......................... 26
2.3 Fundamental Properties of Epoxy Thermoplastics ............ 27
2.3.1 Mechanical Behavior ................................ 27
2.3.2 Adhesive Characteristics ........................... 31
2.3.3 Optical Properties of Poly(hydroxy amino ether)
19b ................................................ 32
2.3.4 Gas Barrier Properties of Epoxy Thermoplastics ..... 33
2.4 Conclusions ............................................... 36
Acknowledgments ........................................... 36
References ................................................ 37
3 Epoxy Functional Acrylic Polymers for High Performance
Coating Applications ...................................... 39
Carmen Flosbach and Roger Fugier
3.1 Introduction .............................................. 39
3.2 Epoxy Functional Acrylic Polymers (Epoxy Acrylates) ....... 39
3.3 Synthesis of Epoxy Acrylates .............................. 40
3.3.1 Semi-Batch Process ................................. 40
3.3.2 Mass Polymerization ................................ 41
3.3.3 Suspension Polymerization .......................... 41
3.3.4 Polymerization in Supercritical Carbon Dioxide ..... 42
3.4 Design of Epoxy Acrylates as Film-forming Components in
Coatings .................................................. 42
3.4.1 Glass Transition Temperature ....................... 42
3.4.2 Molar Mass ......................................... 43
3.4.3 Choice of Co-monomers .............................. 43
3.4.4 Epoxy Acrylates with a Dual-Cure ................... 45
3.4.5 Structure of the Polymer: Block Copolymers ......... 45
3.4.6 Structure of the Polymer: Branched Epoxy
Acrylates .......................................... 46
3.5 Cross-linking Reactions in Coating Systems ................ 48
3.5.1 Epoxy Acrylates in Etch-resistant One-Component
Liquid Coatings .................................... 49
3.5.2 Epoxy Acrylates in Powder Coatings ................. 51
3.5.3 Epoxy Acrylates in Water-Borne Coatings ............ 53
3.6 Conclusions ............................................... 53
References ................................................ 53
4 Epoxy Polymers Based on Renewable Resources ............... 55
Alessandro Candini
4.1 Introduction .............................................. 55
4.2 Synthesis and Polymerization of Monomers and
Macromonomers Bearing Multiple Epoxy Functions ............ 56
4.2.1 Vegetable Oils ..................................... 56
4.2.2 Natural Rubber ..................................... 62
4.2.3 Lignin ............................................. 65
4.2.4 Cellulosics and Wood ............................... 69
4.2.5 Sugars ............................................. 70
4.2.6 Terpenes ........................................... 72
4.3 Synthesis and Polymerization of Monomers Bearing a
Single Epoxy Group ........................................ 72
4.3.1 2-Furyloxirane ..................................... 72
4.3.2 Other Monomers 75
4.4 Conclusions ............................................... 76
References ................................................ 76
Part Two (Nano)Structured Epoxy Networks ....................... 79
5 Nanostructured Epoxies by the Use of Block Copolymers ..... 81
Sixun Zheng
5.1 Introduction .............................................. 81
5.2 Formation Mechanisms of Nanostructures in Thermosets ...... 83
5.2.1 Self-Assembly Approach ............................. 84
5.2.2 Reaction-Induced Microphase Separation ............. 84
5.3 Morphologies of Epoxy Thermosets Modified With Block
Copolymers ................................................ 87
5.3.1 Selection of Block Copolymers ...................... 87
5.3.2 Nanophase Behavior of Epoxies Containing Block
Copolymers ......................................... 89
5.3.3 Demixing Behavior of Epoxy-Miscible Blocks
Induced by Curing Reaction ........................ 100
5.4 Thermomechanical Properties of Nanostructured
Thermosets ............................................... 102
5.4.1 Glass Transition Temperatures ..................... 102
5.4.2 Fracture Toughness of Nanostructured Thermosets ... 103
5.5 Conclusions .............................................. 104
References ............................................... 105
6 Self-Assembly of Epoxy-Based Polymers .................... 709
Cristina E. Hoppe and Roberto J.J. Williams
6.1 Introduction ............................................. 109
6.2 Linear Nanostructured Epoxies ............................ 111
6.3 Crosslinked Nanostructured Epoxies ....................... 115
6.3.1 Modification of an Epoxy Network with a Linear
Amphiphilic Epoxy Polymer ......................... 115
6.3.2 Amphiphilic Epoxy Networks Based on the Epoxy-
Fatty Acid Chemistry .............................. 116
6.3.3 Precursors Based on Monofunctional Epoxies ........ 116
6.4 Possible Applications of Nanostructured Epoxies .......... 119
References ............................................... 120
7 Polymer Dispersed Liquid Crystal, Thermotropic and
Other Responsive Epoxy Polymers .......................... 127
Agnieszka Tercjak and Iñaki Mondragon
7.1 Epoxy-Based Polymer Dispersed Liquid Crystal ............. 121
7.2 Polymer Dispersed Liquid Crystal Prepared by PIPS ........ 123
7.3 Block Copolymers Used as a Polymer Dispersing Agent for
Liquid Crystal ........................................... 129
7.4 Epoxy Polymers Based on Azo-Benzene Organic Molecules .... 133
7.5 Conclusions and Perspectives ............................. 135
References ............................................... 136
8 POSS and Other Hybrid Epoxy Polymers ..................... 737
Libor Matĕjka
8.1 Introduction ............................................. 137
8.2 Epoxy-Silica Hybrids ..................................... 139
8.2.1 Structure and Morphology of the Hybrids ........... 139
8.2.2 Thermomechanical Properties of the Hybrids ........ 140
8.2.3 Rubbery Hybrid Formation, Structure and
Thermomechanical Properties ....................... 141
8.2.4 Application of the Hybrids ........................ 143
8.3 Epoxy-POSS Hybrids ....................................... 144
8.3.1 Types of POSS Hybrids ............................. 144
8.3.2 Structure and Morphology of the POSS Hybrid
Network ........................................... 145
8.3.3 Reactivity of the Epoxy-Functional POSS ........... 145
8.3.4 Hybrids with Pendant POSS ......................... 146
8.3.5 Hybrids with POSS as Network Junctions ............ 147
8.3.6 Hybrids with Unbound POSS ......................... 149
8.3.7 Properties of POSS Hybrids ........................ 149
8.3.8 Properties of Hybrids with Pendant POSS ........... 150
8.3.9 Properties of Hybrids with POSS in Junctions ...... 151
8.3.10 Self-Assembled Epoxy-POSS Hybrids ................ 154
8.3.11 Application of POSS Hybrids ...................... 154
8.4 Conclusions .............................................. 155
Acknowledgment ........................................... 156
References ............................................... 156
9 Lamellar Silicate-Modified Epoxies ....................... 759
Jannick Duchet-Rumeau and Henry Sautereau
9.1 Introduction ............................................. 159
9.2 Structure and Properties of Lamellar (Phyllo) Silicates .. 160
9.3 Morphologies of Lamellar Silicates-Polymer
Nanocomposites ........................................... 161
9.4 Chemical Modification of Lamellar Silicates for Epoxy
Networks ................................................. 163
9.4.1 Different Chemistries for Modification of
Lamellar Silicates ................................ 163
9.5 Dispersion and Structuration of Lamellar Silicates in
the Initial Formulation .................................. 165
9.5.1 Dispersion Methods ................................ 166
9.5.2 Evolution of the OLS Structuration in the
Initial Formulation ............................... 166
9.5.2.1 Swelling ................................. 166
9.5.2.2 Physical Gelation ........................ 167
9.5.2.3 Viscosity of Suspensions ................. 169
9.5.2.4 Thixotropy ............................... 169
9.6 Structuration of Lamellar Silicates in a Reactive
Medium ................................................... 169
9.6.1 Structuration During Reaction ..................... 169
9.6.2 Catalytic Effect of OLS on Epoxy Reactions and
Gel Time .......................................... 171
9.6.3 Structuration at the End of Reaction .............. 172
9.7 Mechanical Properties of Lamellar Silicates-Modified
Epoxies .................................................. 173
9.7.1 Modeling the Modulus of Nanocomposites ............ 174
9.7.2 Stiffness and Toughness of Glassy Epoxy
Nanocomposites .................................... 174
9.7.3 Stiffness and Toughness of Rubbery Epoxy
Nanocomposites .................................... 177
9.8 Ternary Blends Based on Epoxy/Layered Silicates .......... 178
9.9 Barrier Properties of Nanoclay-Modified Epoxies .......... 179
9.10 Conclusions .............................................. 180
References ............................................... 181
10 Epoxy/Carbon Nanotube Nanocomposites ..................... 185
Luyi Sun and Hung-Jue Sue
10.1 Introduction ............................................. 185
10.2 Preparation of Epoxy/CNT Nanocomposites .................. 187
10.2.1 Processing Techniques ............................. 187
10.2.2 Non-Covalent Functionalization .................... 188
10.2.3 Covalent Functionalization ........................ 390
10.2.4 Effect of CNT on the Curing of Epoxy .............. 194
10.2.5 Alignment of CNTs in Nanocomposites ............... 195
10.2.5.1 Magnetic Field ........................... 196
10.2.5.2 Electric Field ........................... 196
10.2.5.3 Mechanical Deformation ................... 198
10.2.5.4 Epoxy Infusion into Pre-aligned CNTs ..... 198
10.3 Properties of Epoxy/CNT Nanocomposites ................... 201
10.3.1 Mechanical Properties ............................. 201
10.3.2 Electrical Properties ............................. 203
10.3.3 Thermal Properties ................................ 204
10.4 Summary and Outlook ...................................... 205
References ............................................... 206
Part Three Innovative Formulations and Processing ............ 213
11 Epoxy Adhesives: A View of the Present and the Future .... 275
Senén Paz Abuin
11.1 Introduction ............................................. 215
11.2 Requirements and Conditions for the Design of an Epoxy
Formulation .............................................. 216
11.2.1 Surfaces (Adherents) ............................. 216
11.2.2 Temperature ....................................... 217
11.2.3 Mechanical Requirements ........................... 219
11.2.4 Environmental Aging ............................... 220
11.2.5 Toxicology ........................................ 221
11.3 Criteria for Selecting Adhesive Formulations ............. 222
11.3.1 Selection of Components ........................... 222
11.3.1.1 Epoxy Prepolymers ........................ 222
11.3.1.2 Curing Agents ............................ 222
11.3.1.3 Additives ................................ 223
11.3.2 Ambient-Cure Formulation (Steel/Concrete
Adhesive) ......................................... 223
11.3.3 Medium to High-Temperature Cure Formulation
(Steel/Steel Adhesive) ............................ 224
11.3.3.1 Mechanical and Thermal Properties of
Different Formulations ................... 227
11.3.3.2 Aging in Water at 60 °C .................. 231
11.4 Conclusions and Perspectives ............................. 232
Acknowledgments .......................................... 233
References ............................................... 233
12 UV-Cured Nanostructured Epoxy Coatings ................... 235
Marco Sangermano
12.1 Introduction ............................................. 235
12.2 Organic-Organic Nanocomposite Epoxy Coatings ............. 236
12.2.1 Block Copolymers as Organic Nanobuilding Blocks ... 237
12.2.2 Hyperbranched Polymers ............................ 239
12.3 Organic-Inorganic Nanocomposite Epoxy Coatings ........... 243
12.3.1 Dispersion of Inorganic Nanobuilding Blocks ....... 244
12.3.2 In situ Generation of Inorganic Domains ........... 246
12.4 Conclusions .............................................. 248
Acknowledgments .......................................... 249
References ............................................... 249
13 Electron Beam Curing of Epoxy Composites ................. 253
Felipe Wolff-Fabris and Volker Altstädt
13.1 Introduction to Electron Beam Curing ..................... 253
13.1.1 Historical Aspects ................................ 253
13.1.2 Curing Reaction ................................... 254
13.1.3 Parameters Influencing the Curing ................. 255
13.1.3.1 Irradiation Energy ....................... 255
13.1.3.2 Irradiation Dose ......................... 256
13.1.3.3 Impurities ............................... 256
13.1.3.4 Initiator Content ........................ 256
13.1.3.5 Thermal History .......................... 257
13.1.4 Curing Facilities and Safety Issues ............... 257
13.2 Material's Features ...................................... 259
13.2.1 Initiators ........................................ 259
13.2.2 Epoxy Monomers .................................... 261
13.2.3 Toughness Modification ............................ 262
13.2.4 Interfacial Properties Between Fibers and Matrix .. 263
13.3 Manufacturing Process .................................... 264
13.4 Perspectives ............................................. 265
13.4.1 Cost Analysis ..................................... 265
13.4.2 Thermal Curing Versus Electron Beam Curing ........ 266
13.4.3 Potential Applications ............................ 266
References ............................................... 267
14 Composite Processing: State of the Art and Future
Trends ................................................... 277
Stephan Costantino and Urs Waldvogel
14.1 Introduction ............................................. 271
14.2 Infusion ................................................. 271
14.2.1 Process ........................................... 271
14.2.2 SCRIMP Process .................................... 272
14.2.3 Vacuum Assisted Process ........................... 273
14.2.4 Controlled Atmospheric Pressure Resin Infusion .... 274
14.3 Resin Transfer Molding ................................... 275
14.4 Prepreg .................................................. 276
14.4.1 Process and Applications .......................... 276
14.4.2 Out of Autoclave Prepregs ......................... 277
14.5 Alternative Mold Heating Methods ......................... 278
14.5.1 Roctool: The Cage System to make fast RTM ......... 278
14.5.2 Quickstep: Another Way to Cure .................... 278
14.6 Sheet Molding Compound (SMC)/Bulk Molding Compound
(BMC) .................................................... 281
14.6.1 SMC ............................................... 281
14.6.2 BMC ............................................... 281
14.6.3 Features of SMC/BMC Technologies .................. 282
14.7 Filament Winding ......................................... 283
14.7.1 Process and Applications .......................... 283
14.7.2 Automated Tape Laying ............................. 284
14.7.3 Automated Fiber Placement ......................... 284
14.8 Pultrusion ............................................... 285
14.8.1 Process and Applications .......................... 285
14.8.2 Pullwinding ....................................... 286
14.9 Expandable Epoxy Systems ............................ 286
14.9.1 Process and Applications .......................... 286
14.9.2 Conti Duo Technology .............................. 286
14.10 Conclusions and Trends for the Future ................... 287
References ............................................... 287
15 Thermoplastic Curable Formulations ....................... 289
Thomas Fine, Raber Inoubli, Pierre Gerard, and Jean-
Pierre Pascault
15.1 Introduction ............................................. 289
15.1.1 Engineering Thermosetting Epoxies ................. 289
15.1.2 BCPs as Additives for Controlling Properties ...... 290
15.1.3 BCPs as Additives for Controlling Processing ...... 291
15.1.4 Our Aim ........................................... 291
15.2 Typical Preparation of Thermoplastic Curable
Formulations ............................................. 291
15.2.1 Materials ......................................... 291
15.2.2 Sample Preparation ................................ 292
15.3 Rheological Behavior of Blends of Block Copolymer and
Thermoset Precursors ..................................... 293
15.4 Choice of the Hardener ................................... 296
15.5 Processing and Properties ................................ 298
15.5.1 Thermoplastic Processing .......................... 298
15.5.2 Properties ........................................ 298
15.6 Conclusions .............................................. 301
Acknowledgments .......................................... 301
References ............................................... 301
16 Structural Epoxy Foams ................................... 303
Lisa A. Mondy, Rekha R. Rao, Harry Moffat, Doug Adolf,
and Mathew Celina
16.1 Background ............................................... 303
16.2 Continuum-Level Model for Foaming Materials .............. 305
16.3 Material Models and Experiments to Populate Numerical
Model .................................................... 306
16.3.1 Variable Density and Gas Production Models ........ 306
16.3.2 Epoxy Polymerization Model ........................ 307
16.3.3 Viscosity and Slip Models ......................... 307
16.3.4 Thermal Properties Models ......................... 311
16.4 Numerical Method ......................................... 311
16.5 Model Validation ......................................... 313
16.5.1 Experiment and Model Set-Up ....................... 313
16.5.2 Results ........................................... 314
16.6 Discussion and Suggested Improvements to the Model ....... 316
16.7 New Foaming Strategies to Minimize Gravity-Induced
Density Gradients ........................................ 317
16.7.1 Chemical Blowing .................................. 317
16.7.2 Maleic Anhydride Polymerization and C02
Generation ........................................ 318
16.7.3 Epoxy Systems Foamed Via Maleic Anhydride
Polymerization .................................... 319
16.7.4 BOC Based Foaming and Enhanced Foam Stability ..... 320
16.8 Summary .................................................. 321
Acknowledgments .......................................... 322
References ............................................... 323
17 Self-Healing Epoxy Composites ............................ 325
Michael W. Keller
17.1 Introduction ............................................. 325
17.2 Sequestered Healing-Agent Systems ........................ 326
17.2.1 Microcapsule-Based Self-Healing ................... 326
17.2.2 Alternative Healing Chemistries ................... 337
17.2.3 Hollow-Fiber-Based Healing ........................ 338
17.2.4 Microvascular Healing Systems ..................... 339
17.3 Intrinsically Healing Materials .......................... 340
17.3.1 Remendable Polymers ............................... 340
17.3.2 Supramolecular Assembly ........................... 341
17.4 Potential Applications of Self-Healing Materials in
a Bio-Engineering Setting ................................ 341
17.5 Outlook for Self-Healing Materials ....................... 343
References ............................................... 343
Part Four Conclusions and Perspectives ........................ 345
18 Conclusions and Perspectives ............................. 347
Jean-Pierre Pascault and Roberto J.J. Williams
18.1 Definitions of Epoxy Polymers ............................ 347
18.2 New Monomers and Formulations ............................ 348
18.3 Nanostructured Epoxies ................................... 349
18.4 Engineering Properties ................................... 351
18.5 Functional Properties .................................... 353
18.6 Health-Related Issues .................................... 354
18.7 Life-Cycle Assessment .................................... 354
References ............................................... 355
Index .................................................... 357
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