Chain rotational dynamics in dilute polymer solutions and melts under shear flow

Abstract

We present detailed scaling characteristics of the chain rotation dynamics in shear flow for melt and dilute linear polymer systems using extensive atomistic and coarse-grained Brownian dynamics (BD) molecular dynamics simulations, respectively. We find that the dilute systems with hydrodynamic interaction (HI) and excluded volume (EV) effects generally exhibit two distinct scaling behavior of the chain rotation time τrot between the intermediate and strong flow regimes, whereas the free-draining dilute polymer systems display a relatively simple single-scaling behavior for τrot with respect to the shear rate throughout the intermediate-to-strong flow regimes. This dynamic feature correlates with the scaling characteristics of average chain deformation and orientation of the system with respect to the flow strength. Notably, the combined HI and EV effects generally weaken the structural change of polymer chains in response to the applied flow and enhance the overall chain rotation dynamics by disturbing the chain stretch and alignment to the flow direction. Accordingly, due to the variation in the HI and EV effects (in association with chain deformation) with the flow strength, the dilute systems with HI and EV turn out to reveal relatively lower and higher scaling behaviors of τrot in the intermediate and strong flow regimes, respectively, in comparison to the corresponding free-draining systems. Despite the absence of HI and EV effects, the melt systems also exhibit two distinct scaling behaviors of τrot between the intermediate and strong flow regimes. This feature arises from the intermolecular interactions between chains, resulting in a significant influence of interchain entanglement and interchain dynamic collision on the chain rotation dynamics. It is further observed that the overall τrot scaling behavior for each system is predominantly determined by the corresponding scaling behavior of the kinematically stable (diffusive) angular regions near the flow direction, where the flow force is relatively weak. Additionally, polymer chains in kinematically unstable (convective) angular regions exhibit nearly affine chain rotation dynamics conforming to the imposed flow field, independent of the polymer concentration and chain length. This is considered to be a universal feature for general polymeric liquids in shear flow.