Entropy theory of polymer glass formation revisited. I. General formulation.
A generalized entropy theory of glass formation is developed by merging the lattice cluster theory for the thermodynamics of semiflexible polymer melts at constant pressure with the Adam-Gibbs relation between the structural relaxation time and the configurational entropy. Since experimental studies have suggested that the relative rigidity of the chain backbone and the side groups is an essential parameter governing the nature of glass formation in polymers, we incorporate this rigidity disparity parameter, along with monomer structure, into our new theoretical description of the polymer fluid thermodynamics. Our entropy theory is compared with alternative theories that describe the rate of structural relaxation in glass-forming liquids in terms of an activated rate process.
Dudowicz
Jacek
J
The James Franck Institute, The University of Chicago, Illinois 60637, USA. dudowicz@kffl.uchicago.edu
Freed
Karl F
KF
Douglas
Jack F
JF