Generalized entropy theory investigation of the relatively high segmental fragility of many glass-forming polymers
Xiaolei Xu, Jack F. Douglas, Wen‐Sheng Xu
Abstract
with molecular mass, chain stiffness, and intermolecular interaction strength can be traced to the variation of , which is shown to provide a measure of packing frustration defined in terms of the dimensionless thermal expansion coefficient and isothermal compressibility. The often relatively high fragility and large extent of cooperative motion are found in the GET to derive from the often relatively large packing frustration in this class of polymer glass-forming liquids. Finally, we also develop a tentative model of the "dynamical segmental relaxation time" based on the GET, in which the polymers on a coarse-grained scale are modeled as strings of structureless "beads", as assumed in the Rouse and reptation models of polymer dynamics.