Effect of Dispersity on Dynamic Properties of Polymer Melts: Insights from Coarse-Grained Molecular Dynamics Simulations

TL;DR

This study uses coarse-grained molecular dynamics simulations to explore how dispersity affects the static and dynamic properties of polymer melts, revealing increased chain stiffness and faster dynamics with higher dispersity.

Contribution

It provides new insights into how dispersity influences chain conformation, entanglement, and mobility in polymer melts through detailed simulation analysis.

Findings

Higher dispersity increases chain stiffness at small scales.

Entanglement time decreases with dispersity at high molecular weight.

Mobility and reptation of chains are significantly enhanced in disperse melts.

Abstract

Synthetic polymers have a distribution of chain lengths which can be characterized by dispersity, D. Macroscopic properties of polymers are influenced by chain mobility in the melt and manipulating D can significantly impact these properties. n this work, we present a detailed study of the static and dynamic behavior of fully flexible polymer chains that follow Schulz Zimm molecular weight distribution of up to dispersity two using molecular dynamics simulation. Static analysis shows that global conformation of test chains that are equal to the average molecular weight remain ideal. At small length scales, we observe systematic deviation from Gaussian statistics as D increases, given by the structure factor plots, indicating an increased stiffness of chains in disperse melts due to contributions from longer chains. We find that the average entanglement time of chains decreases with dispersity, however, this is only seen in systems with high D and MW, for systems with low MW and D, there is no change in the entanglement time. The mobility of entangled chains is considerably enhanced due to the interplay of different dynamic mechanisms, resulting in accelerated reptation as dispersity increases. Short chains offer constraint release to the longer chains, contributing to faster dynamics and early onset of disentanglement. We capture this relaxation mechanism by the coherent dynamic structure factor for entangled probe chains in the melt, which corresponds to the weakening of tube confinement. These findings provide insights into the rich dynamic heterogeneities of highly disperse polymer melts.