Polymer Nucleation under High-Driving Force, Long-Chain Conditions: Heat Release and the Separation of Timescales

Abstract

This study reveals important features of polymer crystal formation at high-driving forces in entangled polymer melts based on simulations of polyethylene. First and in contrast to small-molecule crystallization, the heat released during polymer crystallization does not appreciably influence structural details of early-stage, crystalline clusters (crystal nuclei). Second, early-stage polymer crystallization (crystal nucleation) can occur without substantial chain-level relaxation and conformational changes. This study's results indicate that local structures and environments guide crystal nucleation in entangled polymer melts under high-driving force conditions. Given that such conditions are often used to process polyethylene, local structures and the separation of timescales associated with crystallization and chain-level processes are anticipated to be of substantial importance to processing strategies. This study highlights new research directions for understanding polymer crystallization.