Relaxation and Thermodynamics in Polymers Glass Transition Book

Introduction

I Fundamentals

1. The 10-nm scale: structure elements of 2 … 20 nm size

1.1 The 1-nm scale: ρ level

1.2 Classification of length scales in polymers

1.3 Macromolecular coils

1.4 Polymer concentration

1.5 Entanglement

1.6 Polymer networks

1.7 Chain folded crystallites

1.8 Structure and dynamics - an outline

2. Linear response

2.1 Mechanical models for viscoelasticity

2.2 Discussion of the mechanical models

2.3 General linear response

2.4 Relaxation and retardation spectra

2.5 Correlation function and spectral density

2.6 Fluctuation dissipation theorem (FDT)

2.7 Different activities

2.8 General scaling principle (GSP). Mode lengths

3. Thermodynamics

3.1 Network thermodynamics

3.2 Discussion

3.3 Flory Huggins formula

3.4 Discussion

3.5 Thermodynamic systems: spatial and temporal aspects

3.6 Subsystems

3.7 FDT again: What is a thermodynamic experiment?

3.8 Small systems

3.9 Functional subsystems. Thermokinetic structure

4. Theoretical Physics code

4.1 Analytical methods

1. Order parameter and mean field

2. Effective Hamiltonian

3. Field theory methods

4. Renormalization

5. Direct correlation function

6. General Langevin equation (GLE)

7. Random phase approximation (RPA)

8. Directory

4.2 Scaling and Crossover

1. General scaling principle (GSP) again

2. Absence of typical length

3. Reduction of variables

4. Reduction and dimensional analysis

5. Critical scaling (Widom scaling)

6. Crossover

7. Confined scaling

4.3 Computer simulation

II Relaxation

5. Three simple models

5.1 Barrier model. Arrhenius mechanism

5.2 Discussion

5.3 Rouse modes

5.4 Discussion

5.5 Reptation: tube model

5.6 Discussion

6. Glass transition. Multiplicity in amorphous polymers

6.1 Glass transition in simple glass formers

6.2 Comparison: phase transition and dynamic glass transition

6.3 WLF scaling

6.4 Ideal dynamic glass transition

6.5 Glass transition multiplicity

6.6 Dispersion zones in amorphous polymers

1. Secondary relaxations

2. General remarks to main and flow transition and their sequential predecessors

3. Main transition

4. Flow transition (or terminal zone)

6.7 Deviations from WLF scaling

6.8 Minimal cooperativity, cage effects, and excess cluster scattering

1. Minimal cooperativity and splitting point

2. Nonactivated process

3. Excess cluster scattering

6.9 Activity arrangement across dispersion zones

6.10 η activity and D activity

1. Dispersion zone and transport (or flow) zone

2. η and D activity

3. Model for flow transition

7. Thermal glass transition

7.1 Fictive temperature. Material time

1. The conceptions

2. Narayanaswamy scheme

3. Discussion

7.2 Freezing-in at thermal glass transition

7.3 Nonlinearity, overshoots, and Kovacs’ expansion gap

7.4 Physical aging

7.5 Conventional thermodynamics of thermal glass transition

7.6 Low temperature behavior

8. Examples

8.1 Relaxation cards for amorphous polymers

8.2 Control of T_g

8.3 Relaxation in polymer solutions

8.4 Mixtures and statistical copolymers

8.5 Relaxation in semicrystalline polymers

8.6 Free volume and configurational entropy

8.7 Ionic conductivity

8.8 Glass structure

8.9 Thermostimulation

III Thermodynamics

9. Thermodynamics of mixtures

9.1 Mixing and excess variables

9.2 Small-molecule mixtures

9.3 Flory Huggins again

9.4 Polymer-polymer mixtures and polymer solutions

9.5 Swelling equilibrium of polymer networks

10. Compatibility of polymers

10.1 Terminology

10.2 Ornstein Zernicke (OZ) approach to critical phenomena

1. Classical treatment for small-molecule systems

2. Adaptation for polymers

3. Discussion

10.3 Spinodal phase decomposition

1. Cahn Hilliard approach

2. Further ingredients

3. General discussion

10.4 Homogeneous nucleation

10.5 Diffusion

10.6 Interface

10.7 Microphase decomposition of block copolymers

10.8 Gradient term and natural subsystem

10.9 Granulated phase decomposition

11. Semicrystalline polymers

11.1 Terminology and salient facts

11.2 Primary and secondary nucleation

11.3 Nucleation-controlled crystal growth

11.4 Crystallization and melting

11.5 Why lamellas?

Appendices

A1. Fourier and Fourier Laplace transforms as used in this book

A2. Molecular mass and chemical configuration of the monomeric unit for several polymers

List of tables

Frequently used symbols, acronyms, and synonyms

References

Subject index