Dynamics and Stress Relaxation of Bidisperse Polymer Melts with Unentangled and Moderately Entangled Chains

TL;DR

This study investigates how bidispersity in polymer chains influences their dynamics and stress relaxation, revealing that short chains accelerate long-chain dynamics and unentangled short chains retain classical behavior.

Contribution

It provides new insights into the dynamics of bidisperse polymer melts, especially how different chain lengths interact and affect overall rheological properties.

Findings

Short chains significantly accelerate long-chain dynamics.

Unentangled short chains follow classical Rouse dynamics even with entangled chains present.

Semi-empirical mixing rules can predict linear viscoelasticity of polydisperse polymers.

Abstract

Polydispersity is inevitable in industrially produced polymers. Established theories of polymer dynamics and rheology, however, were mostly built on monodisperse linear polymers. Dynamics of polydisperse polymers is yet to be fully explored -- especially how chains of different lengths affect the dynamics of one another in a mixture. This study explored the dynamics of bidisperse polymer melts using molecular dynamics and a bead-spring chain model. Binary mixtures between a moderately entangled long-chain species and an unentangled or marginally entangled short-chain species were investigated. We found that adding short chains can significantly accelerate the dynamics of the long chains by substantially lessening their extent of entanglement. Meanwhile, although introducing long chains also hinders the motion of the short chains, it does not qualitatively alter the nature of their dynamics -- unentangled short chains still follow classical Rouse dynamics even in a matrix containing entangled chains. Detailed Rouse mode analysis was used to reveal the effects of entanglement at chain segments of different scales. Stress relaxation following a step shear strain was also studied and semi-empirical mixing rules that predict the linear viscoelasticity of polydisperse polymers based on that of monodisperse systems were evaluated with simulation results.