Effect of chain stiffness on the dynamics and microstructure of crystallizable bead-spring polymer melts

TL;DR

This study investigates how chain stiffness influences the dynamics and microstructure of crystallizable bead-spring polymer melts, revealing that intermediate stiffness leads to glassy behavior due to unique cooperative motion patterns.

Contribution

It demonstrates that chain stiffness nonmonotonically affects polymer melt dynamics, linking intermediate stiffness to glass formation through distinct dynamical heterogeneity and cooperative motion.

Findings

Flexible and rodlike chains crystallize with simple Arrhenius dynamics.

Intermediate-stiffness chains exhibit Vogel-Fulcher dynamical arrest.

Unique chain-backbone correlated motion causes glassy behavior in intermediate stiffness polymers.

Abstract

We constrast the dynamics in model unentangled polymer melts of chains of three different stiffnesses: flexible, intermediate, and rodlike. Flexible and rodlike chains, which readily solidify into close-packed crystals (respectively with randomly oriented and nematically aligned chains), display simple melt dynamics with Arrhenius temperature dependence and a discontinuous change upon solidification. Intermediate-stiffness chains, however, are fragile glass-formers displaying Vogel-Fulcher dynamical arrest, despite the fact that they also possess a nematic-close-packed crystalline ground state. To connect this difference in dynamics to the differing microstructure of the melts, we examine how various measures of structure, including cluster-level metrics recently introduced in studies of colloidal systems, vary with chain stiffness and temperature. No clear static-structural cause of the dynamical arrest is found. However, we find that the intermediate-stiffness chains display qualitatively different dynamical heterogeneity. Specifically, their stringlike correlated motion (cooperative rearrangement) is correlated along chain backbones in a way not found for either flexible or rodlike chains. This activated "crawling" motion seems to be the cause of the dynamical arrest observed for these systems, and shows that the factors controlling the crystallization vs.\ glass formation competition in polymers likely depend nonmonotonically on chain stiffness.