Cluster prevalence in concentrated ring-chain mixtures under shear

Abstract

Semiflexible ring polymers are known to exhibit clustering behavior and form stacks in concentrated solutions. Recently, weak shear was suggested to re-orient these stacks with flow, a phenomenon more easily visible in more concentrated solutions [Liebetreu et al., ACS Appl. Polym. Mater., 2020, 2(8), 3505–3517, DOI: 10.1021/acsapm.0c00522]. In this work, we investigate the impact of mixing linear chains and rings in a similar system under shear, studying clustering in the presence of semiflexible, rod-like chains. We present a correlation between chain monomer fraction and clustering behavior as linear chains take up less space, thus decreasing the system's effective density and, subsequently, clustering. However, we suggest mixtures with a low chain concentration to maintain or potentially enhance clustering at equilibrium while this effect is destroyed under shear. The mixing of chains and rings may therefore be used to create more strongly organized structures susceptible to reorientation via weak shear.