DR. EWA PIORKOWSKA, is Professor and the Head of the Department of Polymer Structure at the Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Poland. Her research interests include crystallization, structure and properties of polymers, polymer blends, composites and nanocomposites.

DR. GREGORY C. RUTLEDGE, is the Lammot du Pont Professor in the Department of Chemical Engineering at the Massachusetts Institute of Technology. His research interests include polymer science and engineering, statistical thermodynamics, molecular simulation, and nanotechnology.

Preface xiii

Contributors xv

1 Experimental Techniques 1
Benjamin S. Hsiao, Feng Zuo, and Yimin Mao, Christoph Schick

1.1 Introduction, 1

1.2 Optical Microscopy, 2

1.3 Electron Microscopy, 5

1.4 Atomic Force Microscopy, 9

1.5 Nuclear Magnetic Resonance, 12

1.6 Scattering Techniques: X-Ray, Light, and Neutron, 15

1.7 Differential Scanning Calorimetry, 22

1.8 Summary, 25

Acknowledgments, 26

References, 26

2 Crystal Structures of Polymers 31
Claudio De Rosa and Finizia Auriemma

2.1 Constitution and Confi guration of Polymer Chains, 31

2.2 Conformation of Polymer Chains in Crystals and Conformational Polymorphism, 33

2.3 Packing of Macromolecules in Polymer Crystals, 43

2.4 Symmetry Breaking, 49

2.5 Packing Effects on the Conformation of Polymer Chains in the Crystals: The Case of Aliphatic Polyamides, 50

2.6 Defects and Disorder in Polymer Crystals, 55

2.7 Crystal Habits, 60

Acknowledgments, 67

References, 67

3 Structure of Polycrystalline Aggregates 73
Buckley Crist

3.1 Introduction, 73

3.2 Crystals Grown from Solution, 75

3.3 Crystals and Aggregates Grown from Molten Films, 94

3.4 Spherulitic Aggregates, 104

Acknowledgments, 121

References, 121

4 Polymer Nucleation 125
Kiyoka N. Okada and Masamichi Hikosaka

4.1 Introduction, 126

4.2 Classical Nucleation Theory, 126

4.3 Direct Observation of Nano-Nucleation by Synchrotron Radiation, 128

4.4 Improvement of Nucleation Theory, 135

4.5 Homogeneous Nucleation from the Bulk Melt under Elongational Flow, 139

4.6 Heterogeneous Nucleation, 148

4.7 Effect of Entanglement Density on the Nucleation Rate, 156

4.8 Conclusion, 160

Acknowledgments, 161

References, 161

5 Growth of Polymer Crystals 165
Kohji Tashiro

5.1 Introduction, 165

5.2 Growth of Polymer Crystals from Solutions, 167

5.3 Growth of Polymer Crystals from Melt, 169

5.4 Crystallization Mechanism of Polymer, 173

5.5 Microscopically Viewed Structural Evolution in the Growing Polymer Crystals, 178

5.6 Crystallization upon Heating from the Glassy State, 189

5.7 Crystallization Phenomenon Induced by Tensile Force, 191

5.8 Photoinduced Formation and Growth of Polymer Crystals, 191

5.9 Conclusion, 192

References, 193

6 Computer Modeling of Polymer Crystallization 197
Gregory C. Rutledge

6.1 Introduction, 197

6.2 Methods, 198

6.3 Single-Chain Behavior in Crystallization, 202

6.4 Crystallization from the Melt, 204

6.5 Crystallization under Deformation or Flow, 208

6.6 Concluding Remarks, 210

References, 211

7 Overall Crystallization Kinetics 215
Ewa Piorkowska and Andrzej Galeski

7.1 Introduction, 215

7.2 Measurements, 216

7.3 Simulation, 217

7.4 Theories: Isothermal and Nonisothermal Crystallization, 218

7.5 Complex Crystallization Conditions: General Models, 224

7.6 Factors Influencing the Overall Crystallization Kinetics, 224

7.7 Analysis of Crystallization Data, 230

7.8 Conclusions, 233

References, 234

8 Epitaxial Crystallization of Polymers: Means and Issues 237
Annette Thierry and Bernard A. Lotz

8.1 Introduction and History, 237

8.2 Means of Investigation of Epitaxial Crystallization, 239

8.3 Epitaxial Crystallization of Polymers, 241

8.4 Epitaxial Crystallization: Further Issues and Examples, 252

8.5 Epitaxial Crystallization: Some Issues and Applications, 256

8.6 Conclusions, 260

References, 262

9 Melting 265
Marek Pyda

9.1 Introduction to the Melting of Polymer Crystals, 265

9.2 Parameters of the Melting Process, 267

9.3 Change of Conformation, 268

9.4 Heat of Fusion and Degree of Crystallinity, 270

9.5 Equilibrium Melting, 274

9.6 Other Factors Affecting the Melting Process of Polymer Crystals, 277

9.7 Irreversible and Reversible Melting, 282

9.8 Conclusions, 284

References, 285

10 Crystallization of Polymer Blends 287
Mariano Pracella

10.1 General Introduction, 287

10.2 Thermodynamics of Polymer Blends, 288

10.3 Miscible Polymer Blends, 290

10.4 Immiscible Polymer Blends, 303

10.5 Compatibilized Polymer Blends, 307

10.6 Polymer Blends with Liquid-Crystalline Components, 314

10.7 Concluding Remarks, 320

Abbreviations, 321

References, 322

11 Crystallization in Copolymers 327
Sheng Li and Richard A. Register

11.1 Introduction, 327

11.2 Crystallization in Statistical Copolymers, 328

11.3 Crystallization of Block Copolymers from Homogeneous or Weakly Segregated Melts, 340

11.4 Summary, 343

References, 344

12 Crystallization in Nano-Confi ned Polymeric Systems 347
Alejandro J. Müller, Maria Luisa Arnal, and Arnaldo T. Lorenzo

12.1 Introduction, 347

12.2 Confined Crystallization in Block Copolymers, 348

12.3 Crystallization of Droplet Dispersions and Polymer Layers, 361

12.4 Polymer Blends, 368

12.5 Modeling of Confi ned Crystallization of Macromolecules, 371

12.6 Conclusions, 372

References, 372

13 Crystallization in Polymer Composites and Nanocomposites 379
Ewa Piorkowska

13.1 Introduction, 379

13.2 Microcomposites with Particulate Fillers, 380

13.3 Fiber-Reinforced Composites, 382

13.4 Modeling of Crystallization in Fiber-Reinforced Composites, 385

13.5 Nanocomposites, 388

13.6 Conclusions, 393

Appendix, 393

References, 394

14 Flow-Induced Crystallization 399
Gerrit W.M. Peters, Luigi Balzano, and Rudi J.A. Steenbakkers

14.1 Introduction, 399

14.2 Shear-Induced Crystallization, 401

14.3 Crystallization during Drawing, 407

14.4 Models of Flow-Induced Crystallization, 410

14.5 Concluding Remarks, 426

References, 427

15 Crystallization in Processing Conditions 433
Jean-Marc Haudin

15.1 Introduction, 433

15.2 General Effects of Processing Conditions on Crystallization, 433

15.3 Modeling, 440

15.4 Crystallization in Some Selected Processes, 442

15.5 Conclusion, 458

References, 459

Index 463