Entropic stress of grafted polymer chains in shear flow

Abstract

We analyze the shear response of grafted polymer chains in shear flow via coarse-grained molecular dynamics simulations. Our simulations confirm that the shear response is dominated by the brush's outermost correlation volume, which depends on shear rate at high Weissenberg number. The system's shear stress can be approximated by the brush's entropic stress. The simulations further reveal that at low Weissenberg number, the entropic shear stress of grafted chains is independent of the Weissenberg number. Increasing the Weissenberg number leads to Wi-dependent behavior: chains first reorient along the shear direction and elongate at higher Wi. The entropic shear stress increases linearly with Weissenberg number in this regime. We relate these calculations to experimental observations on the velocity dependence of brush and hydrogel friction.