Entanglements via Slip Springs with Soft, Coarse-Grained Models for Systems Having Explicit Liquid–Vapor Interfaces

Abstract

Recent advances in nano-rheology require that new techniques and models be developed to precisely describe the equilibrium and non-equilibrium characteristics of entangled polymeric materials and their interfaces at a molecular level. In this study, a slip-spring (SLSP) model is proposed to capture the dynamics of entangled polymers at interfaces, including those between liquids, liquids and vapors, and liquids and solids. The SLSP model employs a highly coarse-grained approach, which allows for comprehensive simulations of entire nano-rheological characterization systems using a particle-level description. The model relies on many-body dissipative particle dynamics (MDPD) non-bonded interactions, which permit explicit description of liquid−vapor interfaces; a compensating potential is introduced to ensure an unbiased representation of the shape of the liquid−vapor interface within the SLSP model. The usefulness of the proposed MDPD + SLSP approach is illustrated by simulating a capillary breakup rheometer (CaBR) experiment, in which a liquid droplet splits into two segments under the influence of capillary forces. We find that the predictions of the MDPD + SLSP model are consistent with experimental measurements and theoretical predictions. The proposed model is also verified by comparison to the results of explicit molecular dynamics simulations of an entangled polymer melt using a Kremer−Grest chain representation, both at equilibrium and far from equilibrium. Taken together, the model and methods presented in this study provide a reliable framework for molecular-level interpretation of high-polymer dynamics in the presence of interfaces.