Preface ...................................................... xiii
1 Introduction ................................................. 1
1.1 Thermosetting Polymers .................................. 1
1.2 Thermosetting Polymer Composites in Structure
Applications ............................................ 3
1.3 Damage in Fiber Reinforced Thermosetting Polymer
Composite Structures .................................... 3
1.3.1 Damage in Laminated Composites ................... 4
1.3.2 Damage in Sandwich Composites .................... 4
1.3.3 Damage in 3-D Woven Fabric Reinforced
Composites ....................................... 7
1.3.4 Damage in Grid Stiffened Composites .............. 8
1.4 Repair of Damage in Thermosetting Polymer Composite
Structures ............................................. 11
1.5 Classification of Self-Healing Schemes ................. 13
1.6 Organization of This Book .............................. 14
References .................................................. 15
2 Self-Healing in Biological Systems .......................... 21
2.1 Self-Healing in Plants ................................. 21
2.2 Seal-Healing in Animals ................................ 21
2.2.7 Self-Healing by Self-Medicine ................... 22
2.2.2 Self-Healing Lizard ............................. 22
2.2.3 Self-Healing Starfish ........................... 23
2.2.4 Self-Healing of Sea Cucumbers ................... 24
2.2.5 Self-Healing of Earthworms ...................... 25
2.2.6 Self-Healing of Salamanders ..................... 25
2.3 Self-Healing in Human Beings ........................... 26
2.3.1 Psychological Self-Healing ...................... 26
2.3.2 Physiological Self-Healing ...................... 26
2.4 Summary ................................................ 29
2.5 Implications from Nature ............................... 30
References .................................................. 30
3 Thermoset Shape Memory Polymer and Its Syntactic Foam ....... 35
3.1 Characterization of Thermosetting SMP and SMP Based
Syntactic Foam ......................................... 38
3.1.1 SMP Based Syntactic Foam ........................ 38
3.1.2 Raw Materials and Syntactic Foam Preparation .... 38
3.1.3 DMA Testing ..................................... 39
3.1.4 Fourier Transform Infrared (FTIR) Spectroscopy
Analysis ........................................ 42
3.1.5 X-Ray Photoelectron Spectroscopy ................ 43
3.1.6 Coefficient of Thermal Expansion Measurement .... 44
3.1.7 Isothermal Stress-Strain Behavior ............... 44
3.1.8 Summary ......................................... 41
3.2 Programming of Thermosetting SMPs ...................... 48
3.2.1 Classical Programming Methods ................... 49
3.2.2 Programming at Temperatures Below TR - Cold
Programming ..................................... 51
3.3 Thermomechanical Behavior of Thermosetting SMP and
SMP Based Syntactic Foam Programmed Using the
Classical Method ....................................... 54
3.3.1 One-Dimensional Stress-Controlled Compression
Programming and Shape Recovery .................. 54
3.3.2 Programming Using the 2-D Stress Condition and
Free Shape Recovery ............................. 62
3.3.3 Programming Using the 3-D Stress Condition and
Constrained Shape Recovery ...................... 68
3.4 Thermomechanical Behavior of Thermosetting SMP and
SMP Based Syntactic Foam Programmed by Cold
Compression ............................................ 77
3.4.1 Cold-Compression Programming of Thermosetting
SMP ............................................. 11
3.4.2 Cold-Compression Programming of Thermosetting
SMP Based Syntactic Foam ........................ 82
3.5 Behavior of Thermoset Shape Memory Polymer Based
Syntactic Foam Trained by Hybrid Two-Stage
Programming ............................................ 86
3.5.1 Hybrid Two-Stage Programming .................... 86
3.5.2 Free Shape Recovery Test ........................ 90
3.5.3 Thermomechanical Behavior ....................... 91
3.5.4 Recovery Sequence and Weak Triple Shape ......... 97
3.5.5 Summary ........................................ 101
3.6 Functional Durability of SMP Based Syntactic Foam ..... 102
3.6.1 Programming the SMP Based Syntactic Foam ....... 103
3.6.2 Environmental Conditioning ..................... 103
3.6.3 Stress Recovery Test ........................... 103
3.6.4 Summary ........................................ 105
References ................................................. 105
4 Constitutive Modeling of Amorphous Thermosetting Shape
Memory Polymer and Shape Memory Polymer Based Syntactic
Foam ....................................................... 109
4.1 Some Fundamental Relations in the Kinematics of
Continuum Mechanics ................................... 111
4.1.1 Deformation Gradient ........................... 111
4.1.2 Relation Between Deformation Gradient and
Displacement Gradient .......................... 113
4.1.3 Polar Decomposition of Deformation Gradient .... 113
4.1.4 Definition of Strain ........................... 115
4.1.5 Velocity Gradient .............................. 118
4.2 Stress Definition in Solid Mechanics .................. 119
4.3 Multiplicative Decomposition of Deformation Gradient .. 121
4.4 Constitutive Modeling of Cold-Compression Programmed
Thermosetting SMP ..................................... 123
4.4.1 General Considerations ......................... 123
4.4.2 Deformation Response ........................... 124
4.4.3 Structural Relaxation Response ................. 125
4.4.4 Stress Response ................................ 126
4.4.5 Viscous Flow ................................... 128
4.4.6 Determination of Materials Constants ........... 129
4.4.7 Model Validation ............................... 131
4.4.8 Prediction and Discussion ...................... 134
4.4.9 Summary ........................................ 138
4.5 Thermoviscoplastic Modeling of Cold-Compression
Programmed Thermosetting Shape Memory Polymer
Syntactic Foam ........................................ 139
4.5.7 General Considerations ......................... 139
4.5.2 Kinematics ..................................... 139
4.5.3 Constitutive Behavior of Glass Microsphere
Inclusions ..................................... 141
4.5.4 Model Summary .................................. 142
4.5.5 Determination of Materials Constants ........... 142
4.5.6 Model Validation ............................... 142
4.5.7 Prediction by the Model ........................ 146
4.5.8 Summary ........................................ 149
References ................................................. 150
5 Shape Memory Polyurethane Fiber ............................ 155
5.1 Strengthening of SMPFs Through Strain Hardening by
Cold-Drawing Programming .............................. 155
5.7.1 SMPFs with a Phase Segregated Micro structure .. 155
5.7.2 Raw Materials and Fiber Fabrication ............ 162
5.1.2 Cold-Drawing Programming ....................... 163
5.1.3 Microstructure Change by Cold-Drawing
Programming .................................... 164
5.7.5 Summary ........................................ 169
5.2 Characterization of Thermoplastic SMPFs ............... 169
5.2.7 Thermomechanical Characterization .............. 169
5.2.2 Damping Properties of SMPFs .................... 174
5.2.3 Summary ........................................ 179
5.3 Constitutive Modeling of Semicrystalline SMPFs ........ 179
5.5.7 Micromechanics Based Approaches ................ 180
5.3.2 Constitutive Law of Semicrystalline SMPFs ...... 184
5.3.3 Kinematics ..................................... 192
5.3.4 Computational Aspects .......................... 193
5.3.5 Results and Discussion ......................... 197
5.3.6 Summary ........................................ 200
5.4 Stress Memory versus Strain Memory .................... 200
5.4.1 Stress-Strain Decomposition during
Thermomechanical Cycle ......................... 200
5.4.2 Summary ........................................ 206
References ................................................. 208
6 Self-Healing with Shape Memory Polymer as Matrix ........... 213
6.1 SMP Matrix Based Biomimetic Self-Healing Scheme ....... 219
6.1.1 Raw Materials, Specimen Preparation, and
Testing ........................................ 225
6.1.2 Characterizations of the Composite Materials ... 227
6.1.3 Results and Discussion ......................... 228
6.1.4 Summary ........................................ 244
6.2 Self-Healing of a Sandwich Structure with PSMP Based
Syntactic Foam core ................................... 245
6.2.1 Raw Materials and Syntactic Foam Fabrication ... 245
6.2.2 Smart Foam Cored Sandwich Fabrication .......... 246
6.2.3 Compression Programming ........................ 247
6.2.4 Low Velocity Impact Tests ...................... 249
6.2.5 Characterization of Low Velocity Impact
Response ....................................... 250
6.2.6 Crack Closing Efficiency in Terms of Impact
Responses ...................................... 253
6.2.7 Crack Closing Efficiency in Terms of
Compression after Impact Test .................. 254
6.2.8 Ultrasonic and SEM Inspection .................. 257
6.2.9 Summary ........................................ 259
6.3 Grid Stiffened PSMP Based Syntactic Foam Cored
Sandwich for Mitigating and Healing Impact Damage ..... 260
6.3.1 Raw Materials .................................. 263
6.3.2 Grid Stiffened Smart Syntactic Foam Cored
Sandwich Fabrication ........................... 264
6.3.3 Thermomechanical Programming ................... 265
6.3.4 Low Velocity Impact Testing and Healing ........ 266
6.3.5 Impact Response in Terms of Wave Propagation ... 267
6.3.6 Compression after Impact Test .................. 268
6.3.7 Summary ........................................ 270
6.4 Three-Dimensional Woven Fabric Reinforced PSMP Based
Syntactic Foam Panel for Impact Tolerance and Damage
Healing ............................................... 270
6.4.1 Experimentation ................................ 271
6.4.2 Results and Discussion ......................... 275
6.4.3 Summary ........................................ 280
References ................................................. 281
7 Self-Healing with Embedded Shape Memory Polymer Fibers ..... 287
7.1 Bio-inspired Self-Healing Scheme Based on SMP Fibers .. 287
7.2 SMP Fiber versus SMA (Shape Memory Alloy) Fiber ....... 289
7.3 Healing of Thermosetting Polymer by Embedded
Unidirectional (1-D) Shape Memory Polyurethane Fiber
(SMPF) ................................................ 293
7.3.1 Experimentation ................................ 294
7.3.2 Results and Discussion ......................... 298
7.3.3 Summary ........................................ 307
7.4 Healing of Thermosetting Polymer by Embedded 2-D
Shape Memory Polyurethane Fiber (SMPF) ................ 307
7.4.1 Specimen Preparation ........................... 309
7.4.2 Self-Healing of the Grid Stiffened Composite ... 310
7.4.3 Summary ........................................ 314
7.5 Healing of Thermosetting Polymer by Embedded 3-D
Shape Memory Polyurethane Fiber (SMPF) ................ 314
7.5.1 Experiment ..................................... 315
7.5.2 Results and Discussion ......................... 318
7.5.3 Summary ........................................ 325
References ................................................. 325
8 Modeling of Healing Process and Evaluation of Healing
Efficiency ................................................. 329
8.1 Modeling of Healing Process ........................... 330
8.1.1 Modeling of Healing Process Using
Thermoplastic Healing Agent .................... 330
8.1.2 Summary ........................................ 333
8.2 Evaluation of Healing Efficiency ...................... 334
8.2.1 Healing Efficiency for a Double Cantilever
Beam (DCB) Specimen ............................ 335
8.2.2 Healing Efficiency for an End-Notched Flexure
(ENF) Specimen ................................. 343
8.2.3 Healing Efficiency for a Single-Lag Bending
(SLB) Specimen ................................. 346
8.2.4 Summary ........................................ 349
References ................................................. 351
9 Summary and Future Perspective of Biomimetic Self-Healing
Composites ................................................. 355
9.1 Summary of SMP Based Biomimetic Self-Healing .......... 355
9.2 Future Perspective of SMP Based Self-Healing
Composites ............................................ 356
9.2.1 In-Service Self-Healing ........................ 357
9.2.2 Healing on Demand .............................. 357
9.2.3 Self-Healing by a Combination of Shape Memory
and Intrinsic Self-Healing Polymers ............ 358
9.2.4 Manufacturing of SMP Fibers with Higher
Strength and Higher Recovery Stress ............ 358
9.2.5 Determination of Critical Fiber Length ......... 359
9.2.6 Damage-Healing Modeling ........................ 360
9.2.7 Development of Physics Based Constitutive
Modeling of Shape Memory Polymers .............. 361
9.2.8 A New Evaluation System ........................ 361
9.2.9 Potential Applications in Civil Engineering .... 362
References ................................................. 365
Index ......................................................... 367
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