Dynamics of Polymer Chains in Disperse Melts: Insights from Coarse- Grained Molecular Dynamics Simulations

T Tejuosho and S Kollipara and S Patankar and J Sampath, JOURNAL OF PHYSICAL CHEMISTRY B, 128, 11846-11854 (2024).

DOI: 10.1021/acs.jpcb.4c05610

Synthetic polymers have a distribution of chain lengths which can be characterized by dispersity, & Dstrok;. Their macroscopic properties are influenced by chain mobility in the melt, and controlling & Dstrok; can significantly impact these properties. In this work, we present a detailed study of the static and dynamic behavior of fully flexible polymer chains that follow the Schulz-Zimm molecular weight distribution up to & Dstrok; = 2.0 using coarse-grained molecular dynamics simulations. We analyze the behavior of test chains with molecular weights that are equal to, above, or below the molecular weight (M-w) of the melt. Static analysis shows that the conformation of these test chains remains unaffected by the heterogeneity of the surrounding chains. To study the dynamics, we computed the mean-squared displacement of test chains in melts of the same M-w and different dispersities. The mobility of test chains with N > M-w steadily increases with dispersity, due to the shorter chains contributing to early onset of disentanglement of the long chains. However, the dynamics of test chains of length N < M-w is nonmonotonic with respect to dispersity; this behavior arises from a trade-off between the increased mobility of shorter chains and the corresponding slowdown caused by the presence of longer chains. We examine the dynamic structure factor and find a weakening of tube confinement, with the effects becoming less pronounced with increasing dispersity and M-w. These findings provide insights into the rich dynamic heterogeneity of disperse polymer melts.

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