Polymorphism of syndiotactic polystyrene crystals from multiscale simulations

TL;DR

This study uses multiscale simulations to characterize the complex polymorphic behavior of syndiotactic polystyrene crystals, demonstrating the effectiveness of coarse-grained modeling in capturing key polymorphs and transition temperatures.

Contribution

The paper introduces a transferable coarse-grained model that accurately predicts polymorph stability and transition temperatures in syndiotactic polystyrene, bridging atomistic and large-scale simulations.

Findings

CG model stabilizes α and β polymorphs consistent with experiments

Transition temperatures from CG model agree with atomistic simulations

CG modeling efficiently characterizes polymer-crystal polymorphism at large scale

Abstract

Syndiotactic polystyrene (sPS) exhibits complex polymorphic behavior upon crystallization. Computational modeling of polymer crystallization has remained a challenging task because the relevant processes are slow on the molecular time scale. We report herein a detailed characterization of sPS-crystal polymorphism by means of coarse-grained (CG) and atomistic (AA) modeling. The CG model, parametrized in the melt, shows remarkable transferability properties in the crystalline phase. Not only is the transition temperature in good agreement with atomistic simulations, it stabilizes the main $\alpha$ and $\beta$ polymorphs, observed experimentally. We compare in detail the propensity of polymorphs at the CG and AA level and discuss finite-size as well as box-geometry effects. All in all, we demontrate the appeal of CG modeling to efficiently characterize polymer-crystal polymorphism at large scale.