Shear Thinning from Bond Orientation in Model Unentangled Bottlebrush Polymer Melts

TL;DR

This study uses molecular dynamics simulations to explore how molecular architecture influences shear thinning in unentangled bottlebrush polymers, revealing the critical role of bond orientation and molecular shape in flow behavior.

Contribution

It provides new molecular-level insights into shear thinning mechanisms in bottlebrush polymers, linking architecture, bond orientation, and rheological properties.

Findings

Bond orientation correlates strongly with shear-thinning behavior.

Densely grafted bottlebrushes show reduced alignment and shear thinning.

Molecular shape parameters indicate flow-induced alignment across architectures.

Abstract

The rheology of molecular brushes remains challenging to control due to the multiple length scales and relaxation processes involved and the lack of direct observation of molecular conformation during flow. We use molecular dynamics simulations to determine the shear thinning of unentangled bottlebrush polymers with varying architecture, from linear chains to combs, to densely grafted bottlebrushes, to star-like and star polymers. We find shear thinning exponents in line with theoretical and experimental results and characterize the shape and orientation of bottlebrushes in steady-state flow. Many shape parameters derived from the gyration tensor show molecular alignment with the flow for all systems. Yet, the orientation of individual bonds is what most strongly correlates with the architecture-dependent shear-thinning exponents. In densely grafted bottlebrushes, the packing of side chains prevents alignment with the flow, causing a reduction in shear thinning. The molecular insight from our simulations is useful to tune the architecture of bottlebrushes to control their rheology.