Preface ...................................................... xiii
Part 1. Nanocomposite Interfaces/Interphases
1 Polymer Nanocomposite Interfaces: The Hidden Lever for
Optimizing Performance in Spherical NanofiUed Polymers ..... 3
Ying Li, Yanhui Huang, Timothy Krentz, Bharath Natarajan,
Tony Neely and Linda S. Schadler
1.1 Introduction ............................................... 4
1.1.1 Dispersion Control .................................. 5
1.1.2 Interface Structure ................................. 6
1.1.3 Interface Properties ................................ 6
1.1.4 Measuring and Modeling the Interface ................ 7
1.2 Dispersion Control through Interfacial Modification ........ 8
1.2.1 Introduction ........................................ 8
1.2.2 Short Ligands ....................................... 8
1.2.3 Polymer Brush ...................................... 11
1.2.3.1 Polymer Brush Synthesis Methods ................ 12
1.2.3.2 Enthalpie and Entropie Contributions of
Polymer Brushes ................................ 12
Dispersion Control ........................................ 13
1.3 Interface Structure ....................................... 16
1.3.1 Introduction ....................................... 16
1.3.2 Effects of Particle Size ........................... 17
1.3.3 Effects of Crystallinity and Cross-linking ......... 18
1.3.4 Effectsof Polymer Brush Penetration ................ 19
1.3.4.1 The Athermal Case .............................. 19
1.3.4.2 The Enthalpie Case ............................. 21
1.3.5 Characterizing the Interface Structure ............. 22
1.4 Interface Properties and Characterization Techniques ...... 24
1.4.1 Introduction ....................................... 24
1.4.2 Molecular Mobility in Nanocomposite Interfaces ..... 25
1.4.3 Thermomechanical Properties and Measurements ....... 28
1.4.3.1 Direct Measurement ............................. 30
1.4.3.2 Indirect Methods ............................... 32
1.4.4 Dielectric Properties and Measurements ............. 40
1.4.4.1 Effects of Nanofillers ......................... 42
1.4.4.2 Measurement Techniques ......................... 43
1.4.4.3 Indirect Measurement ........................... 44
1.4.4.4 Finite Element ModeHng ......................... 50
1.4.5 Remarks on Characterization Methods ................ 52
1.5 Summary ................................................... 53
Acknowledgements .......................................... 54
References ................................................ 55
2 Interphase Engineering with Nanofillers in Fiber-
Reinforced Polymer Composites ............................. 71
József Karger-Kocsis, Sándor Кéкі, Haroon Mahmood
and Alessandro Pegoretti
2.1 Introduction .............................................. 72
2.2 Interphase Tailoring for Stress Transfer .................. 74
2.2.1 Coating with Nanofillers ........................... 74
2.2.2 Creation of Hierarchical Fibers .................... 80
2.2.2.1 Chemical Grafting of Nanofillers ............... 80
2.2.2.2 Chemical Vapor Deposition (CVD) ................ 81
2.2.2.3 Other "Grafting" Techniques .................... 83
2.2.3 Effects of Matrix Modification with Nanofillers .... 85
2.3 Interphase Tailoring for Functionality .................... 87
2.3.1 Sensing/Damage Detection ........................... 87
2.3.2 Self-healing/Repair ................................ 89
2.3.3 Damping ............................................ 91
2.4 Outlook and Future Trends ................................. 91
2.5 Summary ................................................... 93
Acknowledgements .......................................... 93
Nomenclature .............................................. 94
References ................................................ 94
3 Formation and Functionality of Interphase in Polymer
Nanocomposites ........................................... 103
Peng-Cheng Ma, Bin Hao and Jang-Kyo Kim
3.1 Introduction ............................................. 103
3.2 Formation of Interphase in Polymer Nanocomposites ........ 105
3.3 Functionality of Interphase in Polymer Nanocomposites .... 111
3.3.1 Load Transfer in Nanocomposites ................... 111
3.3.2 Reduction in Growth Rate of Fatigue Cracks in
Nanocomposites .................................... 116
3.3.3 Controlling the Fracture Behavior of
Nanocomposites .................................... 119
3.3.4 Enhancing the Damping Properties
of Nanocomposites ........................................ 121
3.3.5 Channels for the Transport of Ions and Moisture
in Nanocomposites ................................. 123
3.3.6 Phonon Scattering in Nanocomposites ............... 125
3.3.7 Electron Transfer in Nanocomposites ............... 128
3.4 Summary and Prospects .................................... 130
Acknowledgements ......................................... 133
References ............................................... 133
4 Impact of Crystallization on the Interface in Polymer
Nanocomposites ........................................... 139
Nandika D'Souza, Siddhi Pendse, Laxmi Sahu, Ajit Ranade
and Shailesh Vidhate
4.1 Introduction ............................................. 140
4.2 Thermodynamics of Crystallization ........................ 142
4.3 Nylon Nanocomposites ..................................... 144
4.3.1 Dispersion of MLS in Nylon Nanocomposites ......... 145
4.3.2 Effect of MLS on Thermal Transitions in Nylon ..... 146
4.3.3 Permeability ...................................... 149
4.4 PET Nanocomposites ....................................... 151
4.4.1 Dispersion of MLS in PET Nanocomposites ........... 151
4.4.2 Effect of MLS on Thermal Transitions in PET ....... 151
4.5 PEN Nanocomposites ....................................... 156
4.5.1 Dispersion of MLS in PEN Nanocomposites ........... 156
4.5.2 Effect of MLS on Thermal Transitions in PEN ....... 157
4.5.3 Permeability ...................................... 162
4.5.4 The Role of the Interface in Permeability: PET
versus PEN ........................................ 162
4.6 Summary .................................................. 167
Acknowledgements ......................................... 167
References ............................................... 168
5 Improved Nanofiller-Matrix Bonding and Distribution in
GnP-reinforced Polymer Nanocomposites by Surface Plasma
Treatments of GnP ........................................ 171
Rafael J. Zaldivar and Hyun I. Kim
5.1 Introduction ............................................. 172
5.2 Experimental ............................................. 173
5.2.1 Composite Fabrication ............................. 173
5.2.2 Image Analysis .................................... 174
5.2.3 Raman Spectroscopy ................................ 174
5.2.4 X-ray Photoelectron Spectroscopy (XPS) ............ 174
5.2.5 Scanning Electron Microscopy (SEM) ................ 175
5.2.6 Mechanical Testing ................................ 175
5.3 Results .................................................. 175
5.4 Conclusions .............................................. 187
Acknowledgement .......................................... 187
References ............................................... 187
6 Interfacial Effects in Polymer Nanocomposites Studied
by Thermal and Dielectric Techniques ..................... 191
Panagiotis Klonos, Apostolus Kyritsis and Polycarpos
Pissis
6.1 Introduction ............................................. 192
6.2 Experimental Techniques .................................. 197
6.2.1 Differential Scanning Calorimetry (DSC) ........... 197
6.2.2 Dielectric Techniques ............................. 202
6.2.2.1 Broadband Dielectric Spectroscopy (BDS) ....... 203
6.2.2.2 Thermally Stimulated Depolarization Current
(TSDC) Techniques ............................. 207
6.3 Evaluation in Terms of Interfacial Characteristics ....... 209
6.3.1 Analysis of DSC Measurements ...................... 209
6.3.2 Analysis of Dielectric Measurements ............... 211
6.3.3 Thickness of the Interfacial Layer ................ 213
6.4 Examples ................................................. 214
6.4.1 DSC Measurements .................................. 214
6.4.2 Dielectric Measurements ........................... 221
6.5 Prospects ................................................ 235
6.6 Summary .................................................. 236
Abbreviations ............................................ 237
Symbols .................................................. 238
Greek Symbols ............................................ 239
Acknowledgements ......................................... 240
References ............................................... 241
Part 2 Techniques to Characterize/Control Nanoadhesion
7 Investigation of Interfacial Interactions between
Nanofillers and Polymer Matrices Using a Variety of
Techniques ............................................... 255
Luqi Liu
7.1 Introduction ............................................. 255
7.2 Observation of Interfacial Layer in Nanostructured
Carbon Materials-based Nanocomposites .................... 257
7.2.1 Characterization of Interfacial Layer Around
CNTs .............................................. 257
7.2.2 Characterization of Interfacial Layer Around
Graphene Sheets ................................... 259
7.3 Interfacial Properties between Nanofiller and Polymer
Matrix ................................................... 260
7.3.1 Theoretical Simulations of CNT and/or
Graphene-based Nanocomposites ..................... 260
7.3.1.1 Theoretical Simulation of CNT-based
Nanocomposites ................................ 260
7.3.1.2 Theoretical Simulation of Graphene-based
Nanocomposites ................................ 262
7.3.2 Experimental Studies to Characterize Interfacial
Behavior in CNT and/or Graphene-based
Nanocomposites .................................... 264
7.3.2.1 Indirect Measurement .......................... 265
7.3.2.2 Direct Measurement ............................ 265
7.4 Summary .................................................. 274
Acknowledgements ......................................... 275
References ............................................... 275
8 Chemical and Physical Techniques for Surface
Modification of Nanocellulose Reinforcements ............. 283
Viktoriya Pakharenko, Muhammad Pervaiz, Hitesh Pande
and Mohini Sain
8.1 Introduction ............................................. 283
8.2 Chemical Surface Modification ............................ 285
8.2.1 Acetylation ....................................... 285
8.2.2 Silylation ........................................ 288
8.2.3 Bacterial Treatment ............................... 289
8.2.4 Grafting .......................................... 291
8.2.5 Surfactant Adsorption ............................. 293
8.2.6 TEMPO-mediated Oxidation .......................... 294
8.2.7 Click Chemistry ................................... 296
8.3 Physical Surface Modification ............................ 296
8.3.1 Plasma ............................................ 296
8.3.2 Corona ............................................ 301
8.3.3 Laser ............................................. 303
8.3.4 Flame ............................................. 303
8.3.5 Use of Ions ....................................... 304
8.4 Summary .................................................. 304
Acknowledgments .......................................... 305
References ............................................... 305
9 Nondestructive Sensing of Interface/Interphase Damage
in Fiber/Matrix Nanocomposites ........................... 311
Zuo-Jia Wang, Dong-Jun Kwon, Jong-Hyun Kim, Pyeong-Su
Shin, K. Lawrence DeVries and Joung-Man Park
9.1 Introduction ............................................. 312
9.2 Experimental Specimens and Methods ....................... 315
9.2.1 Gradient Specimen Test ............................ 315
9.2.2 Dual Matrix Fragmentation Test .................... 318
9.3 Damage Sensing Using Electrical Resistance Measurements .. 321
9.3.1 Electrical Resistance Measurement for Strain
Sensing Application ............................... 321
9.3.2 Electrical Resistance Measurement for Interface/
Interphase Evaluation ............................. 325
9.4 Summary .................................................. 331
References ............................................... 331
10 Development of Polymeric Biocomposites: Particulate
Incorporation, Interphase Generation and Evaluation by
Nanoindentation .......................................... 337
Oisik Das and Debes Bhattacharyya
10.1 Introduction ............................................. 338
10.2 The Definitions of Composite and its Constituents ........ 341
10.2.1 Composite ......................................... 341
10.2.2 Biocomposite ...................................... 341
10.2.3 The Reinforcement ................................. 341
10.2.4 The Matrix ........................................ 342
10.3 Physical and Chemical Structures of Bio-based
Reinforcements ........................................... 343
10.3.1 Plant/Vegetable-based Reinforcements/Fibres ....... 343
10.3.1.1 Physical Structure .............................. 343
10.3.1.2 Chemical Structure .............................. 343
10.3.2 Animal-based Reinforcements/Fibres ................ 346
10.3.2.1 Physical Structure ............................ 346
10.3.2.2 Chemical Structure ............................ 347
10.4 Particulate and Short Fibre Composites ................... 348
10.4.1 Biochar as Potential New Bio-based Particulate
Reinforcement ..................................... 349
10.4.2 Properties of Particulate-based Composites:
Governing Factors ................................. 355
10.4.2.1 Particulate Properties ........................ 355
10.4.2.2 Particulate Structure ......................... 359
10.5 Nanoindentation Technique to Determine Interphase and
Composite Properties ..................................... 362
10.5.1 The Technique and Theory of Nanoindentation ....... 362
10.5.1.1 Different Types of Indenter Tips .............. 364
10.5.1.2 Nanoindentation Theory ........................ 366
10.5.1.3 Nanoindentation Instrument .................... 368
10.5.2 Nanoindentation on Polymeric Composites and
their Interphase .................................. 368
10.6 Concluding Remarks ....................................... 373
References ............................................... 374
11 Perspectives on the Use of Molecular Dynamics
Simulations to Characterize Filler-Matrix Adhesion
and Nanocomposite Mechanical Properties .................. 379
Sanket A. Deshmukh, Benjamin J. Hanson,
Qian Jiang and Melissa A. Pasquinelli
11.1 Introduction ............................................. 380
11.2 Overview of Molecular Dynamics (MD) Simulations .......... 381
11.3 Characterization of Interfacial Adhesion with
MD Simulations ........................................... 385
11.3.1 Quantifying Adhesion Strength ..................... 385
11.3.2 Effect of the Strength of Matrix-filler
Interactions ...................................... 387
11.3.3 Effect of Filler Geometry ......................... 390
11.3.4 Effect of Ordering and Cross-linking within
the Polymer Matrix ................................ 392
11.4 Characterization of Mechanical Properties with MD
Simulations .............................................. 395
11.4.1 Predicting Static Mechanical Properties ........... 396
11.4.2 Predicting Dynamic Mechanical Properties .......... 399
11.5 Prospects ................................................ 403
11.6 Summary .................................................. 404
Acknowledgements ......................................... 404
References ............................................... 404
Index ......................................................... 413
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