Brownian dynamics simulations of bottlebrush polymers in dilute solution under simple shear and uniaxial extensional flows.

Abstract

We study the dynamics of bottlebrush polymer molecules in dilute solutions subjected to shear and uniaxial extensional flows using Brownian dynamics simulations with hydrodynamic interaction (HI). Bottlebrush polymers are modeled using a coarse-grained representation, consisting of a set of beads interacting pairwise via a purely repulsive potential and connected by finitely extensible nonlinear springs. We present the results for molecular stretching, stress, and solution viscosity during the startup of flow as well as under steady state as a function of side chain length while keeping the backbone length fixed. In extensional flow, the backbone fractional extension and the first normal stress difference decrease with an increase in side chain length at a fixed Weissenberg number (Wi). Using simulation results both in the presence of and in the absence of HI, we show that this is primarily a consequence of steric interaction resulting from the dense grafting of side chains. In shear flow, we observe a shear-thinning behavior in all cases, although it becomes less pronounced with increasing side chain length. Furthermore, nonmonotonicity in the backbone fractional extension is observed under shear, particularly at high Wi. We contextualize our simulation results for bottlebrush polymers with respect to existing studies in the literature for linear polymers and show that the unique dynamical features characterizing bottlebrush polymers arise on account of their additional molecular thickness due to the presence of densely grafted side chains.