Quantitative Model for Clusters of String-like Cooperative Motion in a Coarse-Grained Glass-Forming Polymer Melt

Abstract

ABSTRACTWe apply a living polymerization theory to describe cooperative string-like particle rearrangement clusters observed in simulations of a coarse-grained polymer melt. The theory quantitatively describes the interrelation between the average string length L, configurational entropy Sconf, and the order parameter for string assembly Φ without free parameters. Combining this theory with the Adam-Gibbs (AG) model allows us to predict the relaxation time τ in a lower temperature T range than accessible by current simulations. In particular, the combined theories suggest a return to Arrhenius behavior near Tg and a low T residual entropy, thus avoiding a Kauzmann ‘entropy crisis’.