Molecular Dynamics of Glass-Forming Systems - Effects of Pressure

Preface

Contents

Chapter 1: The Glass ``Transition´´

1.1 Introduction

1.2 Pressure Dependence of the Structural (a-) Relaxation Time

1.3 The Glass Transition Temperature

1.4 The Concept of Fragility

1.5 Relative Importance of Thermal Energy and Density

Appendix1

Appendix2

References

Chapter 2: Origin of Glass Formation

2.1 Thermodynamic Scaling of Molecular Dynamics in Viscous Systems

2.1.1 A General Idea of Thermodynamic Scaling

2.1.2 A New Measure of the Relative Temperature-Volume Influence on Molecular Dynamics

2.1.3 The Relaxation Time Description in Accordance with Thermodynamic Scaling

2.1.4 Thermodynamic Scaling on Isothermal Conditions and Its Consequences

2.1.5 Doubts About the Thermodynamic Scaling Universality

2.2 The Role of Monomer Volume and Local Packing on the Glass-Transition Dynamics

References

Chapter 3: Models of Temperature-Pressure Dependence of Structural Relaxation Time

3.1 The Generalized Vogel-Fulcher-Tammann Equation

3.2 The Adam-Gibbs Model

3.3 The Avramov Model

3.4 Cluster Kinetics Model

3.5 Defect Diffusion Model

3.6 Dynamic Lattice Liquid Model

References

Chapter 4: New Physics Gained by the Application of Pressure in the Study of Dynamics of Glass Formers

4.1 Dynamics Under Pressure

4.2 General Dynamic Properties of Glass Formers Discovered by Applying Pressure

4.2.1 Coinvariance of taua and Width of Dispersion to Changes in P and T

4.2.2 Crossover of T or P Dependence of ta (or h ) at the Sameta (or h ) Independent on T, P, and V at the Crossover

4.2.2.1 Experimental Facts

4.2.2.2 Coupling Model Explanation

4.2.3 An Important Class of Secondary Relaxations Bearing Strong Connection to the a-Relaxation

4.2.3.1 Spin-Lattice Relaxation Weighted Stimulated-Echo Spectroscopy

4.2.3.2 Invariance of the Ratio tauJG /taua for Different T and P When taua Is Kept Constant

4.2.3.3 TVgamma-Dependence of tauJG

Evidence Indicating T-1V-gamma: Dependence Originating from the Primitive Relaxation

4.2.3.4 Dependences of the Global and Segmental Dynamics in Polymers on TVgamma: Same gamma but Different Functional Forms

4.2.3.5 Change of T-Dependence of JG beta-Relaxation Time and Relaxation Strength on Crossing Tg

4.2.3.6 Relation Between the Activation Energies of tauJG and taua in the Glassy State

4.2.3.7 Pressure-Temperature History Dependence of tauJG in the Glassy State

4.2.3.8 JG beta-Relaxation Causes Cage Decay and Terminates the Nearly Constant Loss

4.2.3.9 JG beta-Relaxation Is Responsible for the Anomalous T-Dependence of gamma-Relaxation Time

4.3 Conclusions

References

Chapter 5: Pressure Effects on Polymer Blends

5.1 Theoretical Background

5.2 Effect of Pressure on the Dynamics of Miscible Polymer Blends: Dynamic Heterogeneity

5.2.1 Athermal Polymer Blends/Copolymers (PI-PVE, PMMA/PEO)

5.2.1.1 PI-b-PVE

5.2.1.2 PMMA/PEO

5.2.2 Miscible But Not Athermal Polymer Blends (PS/PMPS, PS/PVME, and PCHMA/PaMS)

5.2.2.1 PS/PMPS

5.2.2.2 PS/PVME

5.2.2.3 PCHMA/PaMS

5.2.3 Polymer Blends with Strong Specific Interactions

5.3 Effect of Pressure on Nanophase Separated Copolymers

5.3.1 PMVE-b-PiBVE

5.3.2 pODMA-b-ptBA-b-pODMA

References

Chapter 6: Polypeptide Dynamics

6.1 Introduction

6.2 Polypeptide Liquid-to-Glass ``Transition´´ and its Origin

6.3 Correlation Length of a-Helices

6.4 Effects of Nanoconfinement on the Peptide Secondary Structure and Dynamics

6.4.1 ``Soft´´ Confinement: Confinement Within the Nanodomains of Block Copolypeptides

6.4.2 ``Hard´´ Confinement: Confinement Inside Nanoporous Anodic Aluminum Oxide

6.5 Conclusion

References

Index