Primitive chain network simulations for H-polymers under fast shear

Abstract

Branchpoint Withdrawal (BPW) has been recognized as one of the important molecular mechanisms for the description of the dynamics of entangled branched polymers under fast flows. However, the relation to the other known molecular mechanisms has not been fully elucidated yet. In this study we performed primitive chain network (i.e., multi-chain slip-link) Brownian simulations for a melt of a well-characterized monodisperse polystyrene H-polymer, for which the linear viscoelasticity and shear viscosity growth curves at several shear rates are available in the literature. After confirming the consistency of the simulations with the rheological data, we used the simulations to analyze the molecular motion in detail. The results reveal that molecular tumbling occurs in branched polymers just as in linear ones, and that it is accelerated by BPW. Furthermore, BPW not only mitigates backbone stretch, as expected, but also arm stretch. However, because the transient startup viscosity is anyhow dominated by chain stretch dynamics rather than by molecular tumbling, our results rationalize the fact that pom–pom theories successfully ignore tumbling in shear flows.