- ISBN: 9780470380239 | 0470380233
- Cover: Hardcover
- Copyright: 7/1/2013
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.
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
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
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