Handbook of Polymer Crystallization

Polymeric crystals are more complex in nature than other materials' crystal structures due to significant structural disorder present. The only comprehensive reference on polymer crystallization, Handbook of Polymer Crystallization provides readers with a broad, in-depth guide on the subject, covering the numerous problems encountered during crystallization as well as solutions to resolve those problems to achieve the desired result. Edited by leading authorities in the field, topics explored include neat polymers, heterogeneous systems, polymer blends, polymer composites orientation induced crystallization, crystallization in nanocomposites, and crystallization in complex thermal processing conditions.

Table of Contents:
Preface E. Piorkowska, G.C. Rutledge Contributors 1. Experimental techniques B. Hsiao, Feng Zuo, Yimin Mao, C. Schick 2 Introduction 2.1 Optical Microscopy 2.1.1 Reflection and Transmission Microscopy 2.1.2 Contrast Modes 2.1.2.1 Polarized Optical Microscopy 2.1.2.2 Phase Contrast Optical Microscopy 2.1.2.3 Near-Field Scanning Optical Microscopy 2.1.3 Selected Applications 2.2 Electron Microscopy 2.2.1 Imaging Principle 2.2.1.1 Transmission Electron Microscopy 2.2.1.2 Scanning Electron Microscopy 2.2.2 Sample Preparation 2.2.2.1 Thin-Film Preparation 2.2.2.2 Conducting Problem 2.2.2.3 Contrast Problem 2.2.3 Relevant Experimental Techniques 2.2.3.1 Environmental SEM 2.2.3.2 High Resolution EM 2.2.3.3 Electron Diffraction 2.2.4 Selected Applications 2.3 Atomic Force Microscopy 2.3.1 Imaging Principle 2.3.2 Scanning Modes 2.3.3 Comparison between AFM and EM 2.3.4 Recent Development: Video AFM 2.3.5 Selected Applications 2.4 Nuclear Magnetic Resonance 2.4.1 Chemical Shift 2.4.2 Relevant Techniques 2.4.2.1 Pulsed Fourier Transform NMR 2.4.2.2 Dipolar Decoupling 2.4.2.3 Magic Angle Spinning 2.4.2.4 Cross Polarization 2.4.3 Recent Development: Multi-Dimensional NMR 2.4.4 Selected Applications 2.5 Scattering Techniques: X-ray, Light and Neutron 2.5.1 Wide-Angle X-ray Diffraction 2.5.1.1 Determination of Crystallinity 2.5.1.2 Degree of Orientation 2.5.1.3 Determination of Crystal Dimension 2.5.2 Small-Angle X-ray Scattering 2.5.2.1 Correlation Function 2.5.2.2 Interface Distribution 2.5.2.3 Interpretation of Anisotropic 2D Scattering Pattern 2.5.3 Small-Angle Light Scattering 2.5.3.1 Spherulite Radius 2.5.3.2 Optical Sign of Spherulite 2.5.3.3 Ring-Banded Spherulite 2.5.3.4 Deformed Spherulite 2.5.3.5 Anisotropic Fluctuation Approach 2.5.4 Small-Angle Neutron Scattering 2.6 Differential Scanning Calorimetry 2.6.1 Modes of Operation 2.6.1.1 Thermal Scan 2.6.1.2 Isothermal Heat Flow Rate Measurements 2.6.1.3 Temperature Modulation 2.6.1.4 Fast Scanning Calorimetry 2.6.2 Determination of Degree of Crystallinity 2. Crystal structures of polymers C. De Rosa, F. Auriemma 3.1. Constitution and configuration of polymer chains 3.2. Conformation of polymer chains in crystals and conformational polymorphism 3.3. Packing of macromolecules in polymer crystals 3.4. Symmetry breaking 3.5. Packing effects on the conformation of polymer chains in the crystals: the case of aliphatic polyamides 3.6. Defects and disorder in polymer crystals 3.6.1 Substitutional isomorphism of different chains 3.6.2 Substitutional isomorphism of different monomeric units 3.6.3 Conformational isomorphism 3.6.4 Disorder in the stacking of ordered layers (stacking fault disorder) 3.7. Crystal habits 3.7.1 Rounded lateral habits 3.8. References 3. Structure of polycrystalline aggregates B. Crist 4.1 Introduction 4.2 Crystals Grown from Solution 4.2.1 Facetted Monolayer Crystals from Dilute Solution 4.2.2 Dendritic Crystals from Dilute Solution 4.2.3 Spiral Growths in Dilute Solution 4.2.4 Concentrated Solutions 4.3 Crystals Grown in Molten Films 4.3.1 Structures in Thin Films 4.3.2 Structures in Ultra-thin Films 4.3.3 Edge-on Lamellae from Molten Films 4.4 Spherulites 4.4.1 Optical Properties of Spherulites 4.4.2 Occurrence of Spherulites 4.4.3 Development of Spherulites 4.4.4 Banded Spherulites and Lamellar Twist 4.5. Acknowledgements 4.6 References 4. Polymer nucleation M. Hikosaka, K.N. Okada 5.1 Introduction 5.2 Classical nucleation theory (CNT) 5.2.1 Nucleation rate (I) 5.2.2 Free energy for formation of a nucleus, ?'G(N) 5.2.3 Free energy necessary for formation of a critical nucleus (?'G*) 5.2.4 Shape of a nucleus is related to kinetic parameters 5.2.5 Diffusion 5.3 Direct observation of nano-nucleation by synchrotron radiation 5.3.1 Introduction and experimental 5.3.2 Direct observation of nano-nucleation by SAXS 5.3.3 Extended Guinier plot method and iteration method 5.3.4 Kinetic parameters and size distribution of nano-nucleus 5.3.5 Real image of nano-nucleation 5.3.6 Supercooling dependence of nano-nucleation 5.3.7 Relationship between nano-nucleation and macro-crystallization 5.4 Improvement of nucleation theory 5.4.1 Introduction 5.4.2 Nucleation theory based on direct observation of nucleation 5.4.3 Confirmation of the new theory by overall crystallinity 5.5 Homogeneous nucleation from the bulk melt under elongational flow 5.5.1 Introduction and experimental 5.5.2 Formulation of elongational strain rate, 5.5.3 "Nano-oriented crystals (NOCs)" 5.5.4 Evidence of homogeneous nucleation 5.5.5 Nano-nucleation results in ultra high performance 5.6 Heterogeneous nucleation 5.6.1 Introduction 5.6.2 Experimental 5.6.3 Role of epitaxy in heterogeneous nucleation 5.6.4 Acceleration mechanism of nucleation of polymers by nano-sizing of nucleating agent 5.7 Effect of entanglement density on the nucleation rate 5.7.1 Introduction and experimental 5.7.2 Increase of ??e leads to decrease of I 5.7.3 Change of ??e against ?'t 5.7.4 Two-step entangling model 5.8 Conclusion 5.9 Acknowledgement 5.10 References 5. Growth of polymer crystals K. Tashiro 6.1. Introduction 6.1.1. Complicated Crystallization Behavior of Polymers 6.1.1.1. Morphologies 6.1.1.2. Crystallization of Blend Samples 6.1.1.3. Epitaxial Crystallization 6.1.1.4. Additional Phase Transitions during Crystallization 6.2. Growth of Polymer Crystals from Solutions 6.2.1. Single Crystals 6.2.2. Crystallization from the Solution under Shear 6.2.3. Solution Casting Method 6..3. Growth Polymer Crystals from Melt 6.3.1. Positive and Negative Spherulites 6.3.2. Spherulite Morpholgy and Crystalline Modification 6.3.3. Spherulite of Blend Samples 6.4. Crystallization Mechanism of Polymer 6.4.1. Basic Theory of Crystallization of Polymer 6.4.1.1. Primary Nucleation 6.4.1.2. Growth of Secondary Nuclei 6.4.1.3. Crystal Growth Rate 6.4.1.4. Regimes 6.4.1.5. Thickening Phenomena of Lamellae 6.4.1.6. Molecular Simulation of Crystallization 6.4.2. Growth Rate of Spherulites 6.4.2.1. Isothermal Crystallization 6.4.2.2. Non-isothermal Crystallization 6..5. Microscopically-viewed Structural Evolution in the Growing Polymer Crystals 6.5.1. Experimental Techniques 6.5.1.1. Time-resolved Measurements 6.5.2. Structural Evolution in Isothermal Crystallization 6.5.2.1. Helical Regularization and Domain Formation of isotactic Polypropylene (iPP) 6.5.2.2. Generation of Disordered Phase in Isothermal Crystallization of Polyethylene 6.5.2.3. Generation of Tie Chains in Isothermal Crystallization of Polyoxymethylene 6.5.2.4. Role of Hydrogen Bonds in Isothermal Crystallization of Aliphatic Nylons 6.5.2.5. Crystallization and Chain Folding Mode 6.5.3. Shear-induced Crystallization of the Melt 6.6. Crystallization upon Heating from the Glassy State 6.6.1. Cold Crystallization 6.6.2. Solvent-induced Crystallization of Polymer Glass 6.7. Crystallization Phenomenon induced by Tensile Force 6.8. Photo-induced Formation and Growth of Polymer Crystals 6.9. Conclusion 6. Computer modeling of polymer crystallization G.C. Rutledge 7.1 Introduction 7.2 Methods 7.2.1 Molecular Dynamics 7.2.2 Langevin Dynamics 7.2.3 Monte Carlo 7.2.4 Kinetic Monte Carlo 7.3 Single Chain Behavior in Crystallization 7.3.1 Solid-on-Solid Models 7.3.2 Molecular and Langevin Dynamics 7.4 Crystallization from the Melt 7.4.1 Lattice Monte Carlo Simulations 7.4.2 Molecular Dynamics using Coarse-Grained Models 7.4.3 Molecular Dynamics using Atomistic Models 7.5 Crystallization under Deformation or Flow 7.6 Concluding Remarks 7. Overall crystallization kinetics E. Piorkowska, A. Galeski 8.1 Introduction 8.2 Measurements 8.3 Simulation 8.4 Theories: isothermal and nonisothermal crystallization 8.4.1. Introductory remarks 8.4.2. Extended volume approach 8.4.3. Probabilistic approach 8.4.4. Isokinetic model 8.4.5. Rate equations 8.5. Complex crystallization conditions -- general models 8.6. Factors influencing the overall crystallization kinetics. 8.6.1. Crystallization in a uniform temperature field 8.6.2. Crystallization in a temperature gradient 8.6.3. Crystallization in a confined space 8.6.4. Flow induced crystallization 8.7. Analysis of crystallization data 8.7.1. Isothermal crystallization 8.7.2. Nonisothermal crystallization 8.8. Conclusions 8. Epitaxial crystallization of polymers: means and issues A.Thierry, B.Lotz, 9.1 Introduction and History 9.2. Means of investigation of epitaxial crystallization 9.2.1. Global techniques 9.2.2. Thin film techniques 9.2.3. Sample preparation techniques 9.2.4 Other samples and investigation procedures 9.3. Epitaxial crystallization of polymers 9.3.1 General principles 9.3.2 Epitaxial crystallization of "linear" polymers 9.3.3. Epitaxy of helical polymers 9.3.3.1. Isotactic polypropylene 9.3.3.2. A case of self-epitaxy in polymers: epitaxy of isotactic polypropylene 9.3.3.3 Epitaxy of isotactic poly(1-butene) 9.3.4. Polymer/polymer epitaxy 9.3.4.1 Epitaxy between linear polymers 9.3.4.2 Epitaxy between linear and helical polymers 9.4. Epitaxial crystallization: Further issues and examples 9.4.1 Topographic versus lattice matching 9.4.1.1 The ac face of isotactic polypropylene 9.4.1.2. Forms I and II of syndiotactic polypropylene 9.4.2 Epitaxy of isotactic polypropylene on isotactic polyvinylcyclohexane 9.4.3 Epitaxy involving fold surfaces of polymer crystals 9.5 Epitaxial crystallization: some issues and applications 9.5.1 Epitaxial crystallization and the design of new nucleating agents 9.5.2 Epitaxial crystallization and the design of composite materials 9.5.3 Conformational and packing energy analysis of polymer epitaxy 9.5.4. Epitaxy as a means to generate oriented opto- or electro-active materials 9.6. Conclusion 9. Melting M. Pyda 10.1 Introduction to melting crystal polymers 10.2 Parameters of melting process 10.3 Change of conformation 10.4 Heat of fusion, Degree of Crystallinity 10.5 Equilibrium melting. 10.6 Other Factors affecting the melting temperature of polymer crystals. 10.7 Irreversible and Reversible melting, 10.8 Conclusions 10.9 References 10. Crystallization in polymer blends M. Pracella 11.1 General Introduction 11.2 Thermodynamics of Polymer Blends 11.2.1 General principles 11.3 Miscible Polymer Blends 11.3.1 Introduction 11.3.2 Phase morphology 11.3.3 Crystal growth rate 11.3.4 Overall crystallization kinetics 11.3.5 Melting behaviour 11.3.6 Blends with partial miscibility 11.3.7 Crystallization behaviour of crystalline/amorphous blends 11.3.7.1 PEO/PMMA blends 11.3.8 Crystallization behaviour of crystalline/crystalline blends 11.3.8.1 Isotactic polypropylene/poly(1-butene) blends 11.3.8.2 Blends of polypropylene copolymers 11.4 Immiscible Polymer Blends 11.4.1 Introduction 11.4.2 Morphology and crystal nucleation 11.4.3 Crystal growth rate 11.4.4 Crystallization behaviour of immiscible blends 11.4.4.1 Polyethylene/polypropylene blends 11.5 Compatibilized Polymer Blends 11.5.1 Compatibilization methods 11.5.2 Morphology and phase interactions 11.5.3 Crystallization behaviour of compatibilized blends 11.5.3.1 Fractionated crystallization in compatibilized blends 11.6 Polymer Blends with Liquid Crystalline Components 11.6.1 Introduction 11.6.2 Mesomorphism and phase transition behaviour of liquid crystals (LCs) and liquid crystal polymers (LCPs) 11.6.3 Crystallization behaviour of Polymer/LC blends 11.6.4 Crystallization behaviour of Polymer/LCP blends 11.7 Concluding Remarks 11.8 Nomenclature 11.9 References 11. Crystallization in copolymers R. Register, Sheng Li 12.1. Introduction. 12.2. Crystallization in Statistical Copolymers 12.2.1 Flory's Model 12.2.2 Solid-State Morphology 12.2.2.1 Supermolecular Structure 12.2.2.2 Lamellar Structure and Crystallite Size 12.2.2.3 Crystal Unit Cell Structure 12.2.3 Mechanical Properties 12.2.4 Crystallization Kinetics 12.2.5 Statistical Copolymers with Two Crystallizable Units 12.2.6 Crystallization Thermodynamics 12.3 Crystallization of Block Copolymers from Homogeneous or Weakly Segregated Melts 12.3.1 Solid-State Morphology 12.3.2 Crystallization-Driven Structure Formation 12.4 Summary 12.5 References 12. Crystallization in nano-confined systems A. Muller, M.L. Arnal, A.T. Lorenzo 13.1. Introduction 13.2. Confined crystallization in block copolymers. 13.2.1 Crystallization within diblock copolymers that are strongly segregated or miscible and contain only one crystallizable component. 13.2.2 Crystallization within strongly segregated double crystalline diblock copolymers and triblock copolymers. 13.3. Crystallization of droplet dispersions and polymer layers. 13.4. Polymer blends. 13.4.1 Immiscible polymer blends. 13.4.2 Melt miscible blends. 13.5. Modeling of confined crystallization of macromolecules 13.6. Conclusions 13.7. References 13. Crystallization in polymer composites and nanocomposites E.Piorkowska 14.1 Introduction 14.2 Microcomposites with particulate fillers 14.3 Fiber-reinforced composites 14.4 Modeling of crystallization in fiber-reinforced composites 14,5 Nanocomposites 14.6 Conclusions 14. Flow-induced crystallization G.W.M. Peters, L. Balzano, R.J.A Steenbakkers 15.0 Introduction 15.1 Shear induced crystallization: 15.1.1 Nature of crystallization precursors 15.2. Crystallization during drawing. 15.2.1 Spinning 15.2.2 Elongation-induced crystallization; lab conditions 15.3. Models of flow-induced crystallization. 15.3.1 Flow-enhanced crystallization 15.3.2 Flow-induced shish formation 15.3.3 Application to injection modeling 15. Crystallization in processing conditions J. M. Haudin 16.1 Introduction 16.2 General effects of processing conditions on crystallization 16.2.1. Effects of flow 16.2.1.1 Thermodynamics and kinetics 16.2.1.2. Morphologies 16.2.2 Effects of pressure 16.2.3. Effects of cooling rate 16.2.4. Effects of a temperature gradient 16.2.4.1. General features 16.2.4.2. Physical models 16.2.4.3. Mathematical modelling 16.2.5. Effects of surfaces 16.3 Modeling 16.3.1. General framework 16.3.2 Simplified expressions 16.3.3. General systems of differential equations 16.4. Crystallization in some selected processes 16.4.1. Cast film extrusion 16.4.1.1. Presentation of the process 16.4.1.2. Thermomechanical model 16.4.1.3. Results of the calculations 16.4.1.4. Influence of processing on structure development 16.4.2. Fiber spinning 16.4.2.1. Presentation of the process 16.4.2.2. Characterization of crystalline orientation by X-ray diffraction 16.4.2.3. Typical experimental results and morphological models 16.4.2.4. Modeling 16.4.3. Film blowing 16.4.3.1. Presentation of the process 16.4.3.2. Orientation studies 16.4.3.3. Morphological models 16.4.3.4. Modeling 16.4.4. Injection molding 16.4.4.1. Presentation of the process 16.4.4.2. Typical experimental results 16.4.4.3. Morphological models 16.4.4.4. Modeling 16.5. Conclusion Index

About the Author :
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.