Handbook of Polymer Crystallization

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.

“I believe that this book will stimulate further much deeper investigation and effective collaboration in this field.”  (Materials Views, 3 February 2014)

• Preface xiiiContributors xv1 Experimental Techniques 1Benjamin S. Hsiao, Feng Zuo, and Yimin Mao, Christoph Schick1.1 Introduction, 11.2 Optical Microscopy, 21.2.1 Reflection and Transmission Microscopy, 21.2.2 Contrast Modes, 21.2.3 Selected Applications, 31.3 Electron Microscopy, 51.3.1 Imaging Principle, 51.3.2 Sample Preparation, 61.3.3 Relevant Experimental Techniques, 71.3.4 Selected Applications, 81.4 Atomic Force Microscopy, 91.4.1 Imaging Principle, 91.4.2 Scanning Modes, 91.4.3 Comparison between AFM and EM, 101.4.4 Recent Development: Video AFM, 101.4.5 Selected Applications, 101.5 Nuclear Magnetic Resonance, 121.5.1 Chemical Shift, 131.5.2 Relevant Techniques, 131.5.3 Recent Development: Multidimensional NMR, 141.5.4 Selected Applications, 141.6 Scattering Techniques: X-Ray, Light, and Neutron, 151.6.1 Wide-Angle X-Ray Diffraction, 151.6.2 Small-Angle X-Ray Scattering, 171.6.3 Small-Angle Light Scattering, 191.6.4 Small-Angle Neutron Scattering, 211.7 Differential Scanning Calorimetry, 221.7.1 Modes of Operation, 221.7.2 Determination of Degree of Crystallinity, 251.8 Summary, 25Acknowledgments, 26References, 262 Crystal Structures of Polymers 31Claudio De Rosa and Finizia Auriemma2.1 Constitution and Confi guration of Polymer Chains, 312.2 Conformation of Polymer Chains in Crystals and Conformational Polymorphism, 332.3 Packing of Macromolecules in Polymer Crystals, 432.4 Symmetry Breaking, 492.5 Packing Effects on the Conformation of Polymer Chains in the Crystals: The Case of Aliphatic Polyamides, 502.6 Defects and Disorder in Polymer Crystals, 552.6.1 Substitutional Isomorphism of Different Chains, 562.6.2 Substitutional Isomorphism of Different Monomeric Units, 572.6.3 Conformational Isomorphism, 582.6.4 Disorder in the Stacking of Ordered Layers (Stacking Fault Disorder), 582.7 Crystal Habits, 602.7.1 Rounded Lateral Habits, 66Acknowledgments, 67References, 673 Structure of Polycrystalline Aggregates 73Buckley Crist3.1 Introduction, 733.2 Crystals Grown from Solution, 753.2.1 Facetted Monolayer Crystals from Dilute Solution, 753.2.2 Dendritic Crystals from Dilute Solution, 813.2.3 Growth Spirals in Dilute Solution, 853.2.4 Concentrated Solutions, 923.3 Crystals and Aggregates Grown from Molten Films, 943.3.1 Structures in Thin Films, 943.3.2 Structures in Ultrathin Films, 983.3.3 Edge-On Lamellae in Molten Films, 1023.4 Spherulitic Aggregates, 1043.4.1 Optical Properties of Spherulites, 1053.4.2 Occurrence of Spherulites, 1083.4.3 Development of Spherulites, 1103.4.4 Banded Spherulites and Lamellar Twist, 116Acknowledgments, 121References, 1214 Polymer Nucleation 125Kiyoka N. Okada and Masamichi Hikosaka4.1 Introduction, 1264.2 Classical Nucleation Theory, 1264.2.1 Nucleation Rate (I), 1264.2.2 Free Energy for Formation of a Nucleus ΔG(N), 1274.2.3 Free Energy for Formation of a Critical Nucleus (ΔG*), 1274.2.4 Shape of a Nucleus Is Related to Kinetic Parameters, 1284.2.5 Diffusion, 1284.3 Direct Observation of Nano-Nucleation by Synchrotron Radiation, 1284.3.1 Introduction and Experimental Procedure, 1284.3.2 Observation of Nano-Nucleation by SAXS, 1284.3.3 Extended Guinier Plot Method and Iteration Method, 1294.3.4 Kinetic Parameters and Size Distribution of the Nano-Nucleus, 1304.3.5 Real Image of Nano-Nucleation, 1314.3.6 Supercooling Dependence of Nano-nucleation, 1334.3.7 Relationship between Nano-Nucleation and Macro-Crystallization, 1334.4 Improvement of Nucleation Theory, 1354.4.1 Introduction, 1354.4.2 Nucleation Theory Based on Direct Observation of Nucleation, 1354.4.3 Confirmation of the Theory by Overall Crystallinity, 1374.5 Homogeneous Nucleation from the Bulk Melt under Elongational Flow, 1394.5.1 Introduction and Case Study, 1394.5.2 Formulation of Elongational Strain Rate e, 1394.5.3 Nano-Oriented Crystals, 1404.5.4 Evidence of Homogeneous Nucleation, 1444.5.5 Nano-Nucleation Results in Ultrahigh Performance, 1474.6 Heterogeneous Nucleation, 1484.6.1 Introduction, 1484.6.2 Experimental, 1494.6.3 Role of Epitaxy in Heterogeneous Nucleation, 1504.6.4 Acceleration Mechanism of Nucleation of Polymers by Nano-Sizing of Nucleating Agent, 1534.7 Effect of Entanglement Density on the Nucleation Rate, 1564.7.1 Introduction and Experimental, 1564.7.2 Increase of νe Leads to a Decrease of I, 1574.7.3 Change of νe with Δt, 1584.7.4 Two-Step Entangling Model, 1594.8 Conclusion, 160Acknowledgments, 161References, 1615 Growth of Polymer Crystals 165Kohji Tashiro5.1 Introduction, 1655.1.1 Complex Behavior of Polymers, 1655.2 Growth of Polymer Crystals from Solutions, 1675.2.1 Single Crystals, 1675.2.2 Crystallization from Solution under Shear, 1685.2.3 Solution Casting Method, 1685.3 Growth of Polymer Crystals from Melt, 1695.3.1 Positive and Negative Spherulites, 1695.3.2 Spherulite Morphology and Crystalline Modification, 1705.3.3 Spherulite Patterns of Blend Samples, 1725.4 Crystallization Mechanism of Polymer, 1735.4.1 Basic Theory of Crystallization of Polymer, 1735.4.2 Growth Rate of Spherulites, 1775.5 Microscopically Viewed Structural Evolution in the Growing Polymer Crystals, 1785.5.1 Experimental Techniques, 1785.5.2 Structural Evolution in Isothermal Crystallization, 1795.5.3 Shear-Induced Crystallization of the Melt, 1865.6 Crystallization upon Heating from the Glassy State, 1895.6.1 Cold Crystallization, 1895.6.2 Solvent-Induced Crystallization of Polymer Glass, 1895.7 Crystallization Phenomenon Induced by Tensile Force, 1915.8 Photoinduced Formation and Growth of Polymer Crystals, 1915.9 Conclusion, 192References, 1936 Computer Modeling of Polymer Crystallization 197Gregory C. Rutledge6.1 Introduction, 1976.2 Methods, 1986.2.1 Molecular Dynamics, 1996.2.2 Langevin Dynamics, 2006.2.3 Monte Carlo, 2006.2.4 Kinetic Monte Carlo, 2016.3 Single-Chain Behavior in Crystallization, 2026.3.1 Solid-on-Solid Models, 2026.3.2 Molecular and Langevin Dynamics, 2036.4 Crystallization from the Melt, 2046.4.1 Lattice Monte Carlo Simulations, 2056.4.2 Molecular Dynamics Using Coarse-Grained Models, 2066.4.3 Molecular Dynamics Using Atomistic Models, 2076.5 Crystallization under Deformation or Flow, 2086.6 Concluding Remarks, 210References, 2117 Overall Crystallization Kinetics 215Ewa Piorkowska and Andrzej Galeski7.1 Introduction, 2157.2 Measurements, 2167.3 Simulation, 2177.4 Theories: Isothermal and Nonisothermal Crystallization, 2187.4.1 Introductory Remarks, 2187.4.2 Extended Volume Approach, 2187.4.3 Probabilistic Approaches, 2207.4.4 Isokinetic Model, 2237.4.5 Rate Equations, 2237.5 Complex Crystallization Conditions: General Models, 2247.6 Factors Influencing the Overall Crystallization Kinetics, 2247.6.1 Crystallization in a Uniform Temperature Field, 2247.6.2 Crystallization in a Temperature Gradient, 2257.6.3 Crystallization in a Confi ned Space, 2267.6.4 Flow-Induced Crystallization, 2287.7 Analysis of Crystallization Data, 2307.7.1 Isothermal Crystallization, 2307.7.2 Nonisothermal Crystallization, 2317.8 Conclusions, 233References, 2348 Epitaxial Crystallization of Polymers: Means and Issues 237Annette Thierry and Bernard A. Lotz8.1 Introduction and History, 2378.2 Means of Investigation of Epitaxial Crystallization, 2398.2.1 Global Techniques, 2398.2.2 Thin Film Techniques, 2398.2.3 Sample Preparation Techniques, 2408.2.4 Other Samples and Investigation Procedures, 2418.3 Epitaxial Crystallization of Polymers, 2418.3.1 General Principles, 2418.3.2 Epitaxial Crystallization of “Linear” Polymers, 2438.3.3 Epitaxy of Helical Polymers, 2458.3.4 Polymer/Polymer Epitaxy, 2508.4 Epitaxial Crystallization: Further Issues and Examples, 2528.4.1 Topographic versus Lattice Matching, 2528.4.2 Epitaxy of Isotactic Polypropylene on Isotactic Polyvinylcyclohexane, 2548.4.3 Epitaxy Involving Fold Surfaces of Polymer Crystals, 2548.5 Epitaxial Crystallization: Some Issues and Applications, 2568.5.1 Epitaxial Crystallization and the Design of New Nucleating Agents, 2568.5.2 Epitaxial Crystallization and the Design of Composite Materials, 2578.5.3 Conformational and Packing Energy Analysis of Polymer Epitaxy, 2588.5.4 Epitaxy as a Means to Generate Oriented Opto- or Electroactive Materials, 2598.6 Conclusions, 260References, 2629 Melting 265Marek Pyda9.1 Introduction to the Melting of Polymer Crystals, 2659.2 Parameters of the Melting Process, 2679.3 Change of Conformation, 2689.4 Heat of Fusion and Degree of Crystallinity, 2709.4.1 Heat of Fusion, 2709.4.2 Degree of Crystallinity, 2729.5 Equilibrium Melting, 2749.5.1 The Equilibrium Melting Temperature, 2749.5.2 The Equilibrium Thermodynamic Functions, 2759.6 Other Factors Affecting the Melting Process of Polymer Crystals, 2779.6.1 The Influence of the Polymer’s Chemical Structure on the Melting Process, 2779.6.2 The Effect of Polymer Molar Mass on the Melting Behavior, 2779.6.3 Influence of Heating Rate on the Melting, 2789.6.4 Multiple Melting Peaks of Polymers, 2799.6.5 Influence of Pressure on the Melting Process, 2819.6.6 The Melting Process by Other Methods, 2819.6.7 Diluents Effect: The Influence of Small Diluents on the Melting Process, 2829.7 Irreversible and Reversible Melting, 2829.8 Conclusions, 284References, 28510 Crystallization of Polymer Blends 287Mariano Pracella10.1 General Introduction, 28710.2 Thermodynamics of Polymer Blends, 28810.2.1 General Principles, 28810.3 Miscible Polymer Blends, 29010.3.1 Introduction, 29010.3.2 Phase Morphology, 29110.3.3 Crystal Growth Rate, 29210.3.4 Overall Crystallization Kinetics, 29410.3.5 Melting Behavior, 29510.3.6 Blends with Partial Miscibility, 29610.3.7 Crystallization Behavior of Amorphous/Crystalline Blends, 29710.3.8 Crystallization Behavior of Crystalline/Crystalline Blends, 29810.4 Immiscible Polymer Blends, 30310.4.1 Introduction, 30310.4.2 Morphology and Crystal Nucleation, 30310.4.3 Crystal Growth Rate, 30410.4.4 Crystallization Behavior of Immiscible Blends, 30510.5 Compatibilized Polymer Blends, 30710.5.1 Compatibilization Methods, 30710.5.2 Morphology and Phase Interactions, 30810.5.3 Crystallization Behavior of Compatibilized Blends, 31110.6 Polymer Blends with Liquid-Crystalline Components, 31410.6.1 Introduction, 31410.6.2 Mesomorphism and Phase Transition Behavior of Liquid Crystals and Liquid Crystal Polymers, 31410.6.3 Crystallization Behavior of Polymer/LC Blends, 31610.6.4 Crystallization Behavior of Polymer/LCP Blends, 31710.7 Concluding Remarks, 320Abbreviations, 321References, 32211 Crystallization in Copolymers 327Sheng Li and Richard A. Register11.1 Introduction, 32711.2 Crystallization in Statistical Copolymers, 32811.2.1 Flory’s Model, 32811.2.2 Solid-State Morphology, 33011.2.3 Mechanical Properties, 33411.2.4 Crystallization Kinetics, 33511.2.5 Statistical Copolymers with Two Crystallizable Units, 33711.2.6 Crystallization Thermodynamics, 33711.3 Crystallization of Block Copolymers from Homogeneous or Weakly Segregated Melts, 34011.3.1 Solid-State Morphology, 34011.3.2 Crystallization-Driven Structure Formation, 34211.4 Summary, 343References, 34412 Crystallization in Nano-Confi ned Polymeric Systems 347Alejandro J. Müller, Maria Luisa Arnal, and Arnaldo T. Lorenzo12.1 Introduction, 34712.2 Confined Crystallization in Block Copolymers, 34812.2.1 Crystallization within Diblock Copolymers that are Strongly Segregated or Miscible and Contain only One Crystallizable Component, 35112.2.2 Crystallization within Strongly Segregated Double-Crystalline Diblock Copolymers and Triblock Copolymers, 35512.3 Crystallization of Droplet Dispersions and Polymer Layers, 36112.4 Polymer Blends, 36812.4.1 Immiscible Polymer Blends, 36812.4.2 Melt Miscible Blends, 37112.5 Modeling of Confi ned Crystallization of Macromolecules, 37112.6 Conclusions, 372References, 37213 Crystallization in Polymer Composites and Nanocomposites 379Ewa Piorkowska13.1 Introduction, 37913.2 Microcomposites with Particulate Fillers, 38013.3 Fiber-Reinforced Composites, 38213.4 Modeling of Crystallization in Fiber-Reinforced Composites, 38513.5 Nanocomposites, 38813.6 Conclusions, 393Appendix, 393References, 39414 Flow-Induced Crystallization 399Gerrit W.M. Peters, Luigi Balzano, and Rudi J.A. Steenbakkers14.1 Introduction, 39914.2 Shear-Induced Crystallization, 40114.2.1 Nature of Crystallization Precursors, 40514.3 Crystallization during Drawing, 40714.3.1 Spinning, 40814.3.2 Elongation-Induced Crystallization; Lab Conditions, 40914.4 Models of Flow-Induced Crystallization, 41014.4.1 Flow-Enhanced Nucleation, 41114.4.2 Flow-Induced Shish Formation, 41914.4.3 Application to Injection Molding, 42114.5 Concluding Remarks, 426References, 42715 Crystallization in Processing Conditions 433Jean-Marc Haudin15.1 Introduction, 43315.2 General Effects of Processing Conditions on Crystallization, 43315.2.1 Effects of Flow, 43315.2.2 Effects of Pressure, 43515.2.3 Effects of Cooling Rate, 43615.2.4 Effects of a Temperature Gradient, 43715.2.5 Effects of Surfaces, 43915.3 Modeling, 44015.3.1 General Framework, 44015.3.2 Simplifi ed Expressions, 44115.3.3 General Systems of Differential Equations, 44115.4 Crystallization in Some Selected Processes, 44215.4.1 Cast Film Extrusion, 44215.4.2 Fiber Spinning, 44515.4.3 Film Blowing, 44815.4.4 Injection Molding, 45415.5 Conclusion, 458References, 459Index 463