Entanglement dynamics at flat surfaces: Investigations using multi-chain molecular dynamics and a single-chain slip-spring model.

Abstract

The dynamics of an entangled polymer melt confined in a channel by parallel plates is investigated by Molecular Dynamics (MD) simulations of a detailed, multi-chain model. A primitive path analysis predicts that the density of entanglements remains approximately constant throughout the gap and drops to lower values only in the immediate vicinity of the surface. Based on these observations, we propose a coarse-grained, single-chain slip-spring model with a uniform density of slip-spring anchors and slip-links. The slip-spring model is compared to the Kremer-Grest MD bead-spring model via equilibrium correlation functions of chain orientations. Reasonably good agreement between the single-chain model and the detailed multi-chain model is obtained for chain relaxation dynamics, both away from the surface and for chains whose center of mass positions are at a distance from the surface that is less than the bulk chain radius of gyration, without introducing any additional model parameters. Our results suggest that there is no considerable drop in topological interactions for chains in the vicinity of a single flat surface. We infer from the slip-spring model that the experimental plateau modulus of a confined polymer melt may be different to a corresponding unconfined system even if there is no drop in topological interactions for the confined case.