内容

目次

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 1.2.1 Reflection and Transmission Microscopy, 2 1.2.2 Contrast Modes, 2 1.2.3 Selected Applications, 3 1.3 Electron Microscopy, 5 1.3.1 Imaging Principle, 5 1.3.2 Sample Preparation, 6 1.3.3 Relevant Experimental Techniques, 7 1.3.4 Selected Applications, 8 1.4 Atomic Force Microscopy, 9 1.4.1 Imaging Principle, 9 1.4.2 Scanning Modes, 9 1.4.3 Comparison between AFM and EM, 10 1.4.4 Recent Development: Video AFM, 10 1.4.5 Selected Applications, 10 1.5 Nuclear Magnetic Resonance, 12 1.5.1 Chemical Shift, 13 1.5.2 Relevant Techniques, 13 1.5.3 Recent Development: Multidimensional NMR, 14 1.5.4 Selected Applications, 14 1.6 Scattering Techniques: X–Ray, Light, and Neutron, 15 1.6.1 Wide–Angle X–Ray Diffraction, 15 1.6.2 Small–Angle X–Ray Scattering, 17 1.6.3 Small–Angle Light Scattering, 19 1.6.4 Small–Angle Neutron Scattering, 21 1.7 Differential Scanning Calorimetry, 22 1.7.1 Modes of Operation, 22 1.7.2 Determination of Degree of Crystallinity, 25 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 2.6.1 Substitutional Isomorphism of Different Chains, 56 2.6.2 Substitutional Isomorphism of Different Monomeric Units, 57 2.6.3 Conformational Isomorphism, 58 2.6.4 Disorder in the Stacking of Ordered Layers (Stacking Fault Disorder), 58 2.7 Crystal Habits, 60 2.7.1 Rounded Lateral Habits, 66 Acknowledgments, 67 References, 67 3 Structure of Polycrystalline Aggregates 73 Buckley Crist 3.1 Introduction, 73 3.2 Crystals Grown from Solution, 75 3.2.1 Facetted Monolayer Crystals from Dilute Solution, 75 3.2.2 Dendritic Crystals from Dilute Solution, 81 3.2.3 Growth Spirals in Dilute Solution, 85 3.2.4 Concentrated Solutions, 92 3.3 Crystals and Aggregates Grown from Molten Films, 94 3.3.1 Structures in Thin Films, 94 3.3.2 Structures in Ultrathin Films, 98 3.3.3 Edge–On Lamellae in Molten Films, 102 3.4 Spherulitic Aggregates, 104 3.4.1 Optical Properties of Spherulites, 105 3.4.2 Occurrence of Spherulites, 108 3.4.3 Development of Spherulites, 110 3.4.4 Banded Spherulites and Lamellar Twist, 116 Acknowledgments, 121 References, 121 4 Polymer Nucleation 125 Kiyoka N. Okada and Masamichi Hikosaka 4.1 Introduction, 126 4.2 Classical Nucleation Theory, 126 4.2.1 Nucleation Rate (I), 126 4.2.2 Free Energy for Formation of a Nucleus ΔG(N), 127 4.2.3 Free Energy for Formation of a Critical Nucleus (ΔG∗), 127 4.2.4 Shape of a Nucleus Is Related to Kinetic Parameters, 128 4.2.5 Diffusion, 128 4.3 Direct Observation of Nano–Nucleation by Synchrotron Radiation, 128 4.3.1 Introduction and Experimental Procedure, 128 4.3.2 Observation of Nano–Nucleation by SAXS, 128 4.3.3 Extended Guinier Plot Method and Iteration Method, 129 4.3.4 Kinetic Parameters and Size Distribution of the Nano–Nucleus, 130 4.3.5 Real Image of Nano–Nucleation, 131 4.3.6 Supercooling Dependence of Nano–nucleation, 133 4.3.7 Relationship between Nano–Nucleation and Macro–Crystallization, 133 4.4 Improvement of Nucleation Theory, 135 4.4.1 Introduction, 135 4.4.2 Nucleation Theory Based on Direct Observation of Nucleation, 135 4.4.3 Confirmation of the Theory by Overall Crystallinity, 137 4.5 Homogeneous Nucleation from the Bulk Melt under Elongational Flow, 139 4.5.1 Introduction and Case Study, 139 4.5.2 Formulation of Elongational Strain Rate e, 139 4.5.3 Nano–Oriented Crystals, 140 4.5.4 Evidence of Homogeneous Nucleation, 144 4.5.5 Nano–Nucleation Results in Ultrahigh Performance, 147 4.6 Heterogeneous Nucleation, 148 4.6.1 Introduction, 148 4.6.2 Experimental, 149 4.6.3 Role of Epitaxy in Heterogeneous Nucleation, 150 4.6.4 Acceleration Mechanism of Nucleation of Polymers by Nano–Sizing of Nucleating Agent, 153 4.7 Effect of Entanglement Density on the Nucleation Rate, 156 4.7.1 Introduction and Experimental, 156 4.7.2 Increase of νe Leads to a Decrease of I, 157 4.7.3 Change of νe with Δt, 158 4.7.4 Two–Step Entangling Model, 159 4.8 Conclusion, 160 Acknowledgments, 161 References, 161 5 Growth of Polymer Crystals 165 Kohji Tashiro 5.1 Introduction, 165 5.1.1 Complex Behavior of Polymers, 165 5.2 Growth of Polymer Crystals from Solutions, 167 5.2.1 Single Crystals, 167 5.2.2 Crystallization from Solution under Shear, 168 5.2.3 Solution Casting Method, 168 5.3 Growth of Polymer Crystals from Melt, 169 5.3.1 Positive and Negative Spherulites, 169 5.3.2 Spherulite Morphology and Crystalline Modification, 170 5.3.3 Spherulite Patterns of Blend Samples, 172 5.4 Crystallization Mechanism of Polymer, 173 5.4.1 Basic Theory of Crystallization of Polymer, 173 5.4.2 Growth Rate of Spherulites, 177 5.5 Microscopically Viewed Structural Evolution in the Growing Polymer Crystals, 178 5.5.1 Experimental Techniques, 178 5.5.2 Structural Evolution in Isothermal Crystallization, 179 5.5.3 Shear–Induced Crystallization of the Melt, 186 5.6 Crystallization upon Heating from the Glassy State, 189 5.6.1 Cold Crystallization, 189 5.6.2 Solvent–Induced Crystallization of Polymer Glass, 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 6.2.1 Molecular Dynamics, 199 6.2.2 Langevin Dynamics, 200 6.2.3 Monte Carlo, 200 6.2.4 Kinetic Monte Carlo, 201 6.3 Single–Chain Behavior in Crystallization, 202 6.3.1 Solid–on–Solid Models, 202 6.3.2 Molecular and Langevin Dynamics, 203 6.4 Crystallization from the Melt, 204 6.4.1 Lattice Monte Carlo Simulations, 205 6.4.2 Molecular Dynamics Using Coarse–Grained Models, 206 6.4.3 Molecular Dynamics Using Atomistic Models, 207 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 7.4.1 Introductory Remarks, 218 7.4.2 Extended Volume Approach, 218 7.4.3 Probabilistic Approaches, 220 7.4.4 Isokinetic Model, 223 7.4.5 Rate Equations, 223 7.5 Complex Crystallization Conditions: General Models, 224 7.6 Factors Influencing the Overall Crystallization Kinetics, 224 7.6.1 Crystallization in a Uniform Temperature Field, 224 7.6.2 Crystallization in a Temperature Gradient, 225 7.6.3 Crystallization in a Confi ned Space, 226 7.6.4 Flow–Induced Crystallization, 228 7.7 Analysis of Crystallization Data, 230 7.7.1 Isothermal Crystallization, 230 7.7.2 Nonisothermal Crystallization, 231 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 8.2.1 Global Techniques, 239 8.2.2 Thin Film Techniques, 239 8.2.3 Sample Preparation Techniques, 240 8.2.4 Other Samples and Investigation Procedures, 241 8.3 Epitaxial Crystallization of Polymers, 241 8.3.1 General Principles, 241 8.3.2 Epitaxial Crystallization of “Linear” Polymers, 243 8.3.3 Epitaxy of Helical Polymers, 245 8.3.4 Polymer/Polymer Epitaxy, 250 8.4 Epitaxial Crystallization: Further Issues and Examples, 252 8.4.1 Topographic versus Lattice Matching, 252 8.4.2 Epitaxy of Isotactic Polypropylene on Isotactic Polyvinylcyclohexane, 254 8.4.3 Epitaxy Involving Fold Surfaces of Polymer Crystals, 254 8.5 Epitaxial Crystallization: Some Issues and Applications, 256 8.5.1 Epitaxial Crystallization and the Design of New Nucleating Agents, 256 8.5.2 Epitaxial Crystallization and the Design of Composite Materials, 257 8.5.3 Conformational and Packing Energy Analysis of Polymer Epitaxy, 258 8.5.4 Epitaxy as a Means to Generate Oriented Opto– or Electroactive Materials, 259 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 9.4.1 Heat of Fusion, 270 9.4.2 Degree of Crystallinity, 272 9.5 Equilibrium Melting, 274 9.5.1 The Equilibrium Melting Temperature, 274 9.5.2 The Equilibrium Thermodynamic Functions, 275 9.6 Other Factors Affecting the Melting Process of Polymer Crystals, 277 9.6.1 The Influence of the Polymer’s Chemical Structure on the Melting Process, 277 9.6.2 The Effect of Polymer Molar Mass on the Melting Behavior, 277 9.6.3 Influence of Heating Rate on the Melting, 278 9.6.4 Multiple Melting Peaks of Polymers, 279 9.6.5 Influence of Pressure on the Melting Process, 281 9.6.6 The Melting Process by Other Methods, 281 9.6.7 Diluents Effect: The Influence of Small Diluents on the Melting Process, 282 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 10.2.1 General Principles, 288 10.3 Miscible Polymer Blends, 290 10.3.1 Introduction, 290 10.3.2 Phase Morphology, 291 10.3.3 Crystal Growth Rate, 292 10.3.4 Overall Crystallization Kinetics, 294 10.3.5 Melting Behavior, 295 10.3.6 Blends with Partial Miscibility, 296 10.3.7 Crystallization Behavior of Amorphous/Crystalline Blends, 297 10.3.8 Crystallization Behavior of Crystalline/Crystalline Blends, 298 10.4 Immiscible Polymer Blends, 303 10.4.1 Introduction, 303 10.4.2 Morphology and Crystal Nucleation, 303 10.4.3 Crystal Growth Rate, 304 10.4.4 Crystallization Behavior of Immiscible Blends, 305 10.5 Compatibilized Polymer Blends, 307 10.5.1 Compatibilization Methods, 307 10.5.2 Morphology and Phase Interactions, 308 10.5.3 Crystallization Behavior of Compatibilized Blends, 311 10.6 Polymer Blends with Liquid–Crystalline Components, 314 10.6.1 Introduction, 314 10.6.2 Mesomorphism and Phase Transition Behavior of Liquid Crystals and Liquid Crystal Polymers, 314 10.6.3 Crystallization Behavior of Polymer/LC Blends, 316 10.6.4 Crystallization Behavior of Polymer/LCP Blends, 317 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 11.2.1 Flory’s Model, 328 11.2.2 Solid–State Morphology, 330 11.2.3 Mechanical Properties, 334 11.2.4 Crystallization Kinetics, 335 11.2.5 Statistical Copolymers with Two Crystallizable Units, 337 11.2.6 Crystallization Thermodynamics, 337 11.3 Crystallization of Block Copolymers from Homogeneous or Weakly Segregated Melts, 340 11.3.1 Solid–State Morphology, 340 11.3.2 Crystallization–Driven Structure Formation, 342 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 12.2.1 Crystallization within Diblock Copolymers that are Strongly Segregated or Miscible and Contain only One Crystallizable Component, 351 12.2.2 Crystallization within Strongly Segregated Double–Crystalline Diblock Copolymers and Triblock Copolymers, 355 12.3 Crystallization of Droplet Dispersions and Polymer Layers, 361 12.4 Polymer Blends, 368 12.4.1 Immiscible Polymer Blends, 368 12.4.2 Melt Miscible Blends, 371 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 14.2.1 Nature of Crystallization Precursors, 405 14.3 Crystallization during Drawing, 407 14.3.1 Spinning, 408 14.3.2 Elongation–Induced Crystallization; Lab Conditions, 409 14.4 Models of Flow–Induced Crystallization, 410 14.4.1 Flow–Enhanced Nucleation, 411 14.4.2 Flow–Induced Shish Formation, 419 14.4.3 Application to Injection Molding, 421 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 15.2.1 Effects of Flow, 433 15.2.2 Effects of Pressure, 435 15.2.3 Effects of Cooling Rate, 436 15.2.4 Effects of a Temperature Gradient, 437 15.2.5 Effects of Surfaces, 439 15.3 Modeling, 440 15.3.1 General Framework, 440 15.3.2 Simplifi ed Expressions, 441 15.3.3 General Systems of Differential Equations, 441 15.4 Crystallization in Some Selected Processes, 442 15.4.1 Cast Film Extrusion, 442 15.4.2 Fiber Spinning, 445 15.4.3 Film Blowing, 448 15.4.4 Injection Molding, 454 15.5 Conclusion, 458 References, 459 Index 463