Effect of pre-shear and dispersity on crystallization of a model polymer with soft pair interactions using molecular dynamics simulations

Abstract

Polymer crystallization is a process of great interest in both fundamental theory and industrial settings, particularly in polymer processing and applications involving semi-crystalline materials. The effect of processing on the initial stages of crystallization is not fully understood. Our study investigates the influence of pre-shear on monodisperse melts and bidisperse blends of a generic, segmentally coarse-grained polymer model. Through molecular dynamics simulations, we explore how polydispersity affects crystallization, where we found that the addition of short chains to a melt of longer chains increased the end-of-simulation crystallinity by about 10% and increased the initial growth rate by roughly a factor of two. In contrast, however, pre-shearing the hot melt before quenching only showed a minor increase in both growth rates and final crystallinity, except in monodisperse melts of short chains. Crystal grain shapes were most influenced by pre-shearing monodisperse melts, where both asphericity and prolateness decreased. In addition, we determined topological connectivity of crystal grains through tie- and loop-chain analysis. Again, only monodisperse melts showed a significant increase of tie chain fractions with pre-shear, while all other systems showed only modest increases. Our findings provide insight into the changes of crystallinity and cluster morphologies that emerge when pre-sheared, offering a deeper understanding of the initial crystallization processes in polymer melts when subjected to pre-shear.