Multi-chain Slip-spring Model for Entangled Polymer Dynamics

TL;DR

This paper introduces a multi-chain slip-spring model for entangled polymer dynamics that bridges single chain models and multi-chain simulations, accurately capturing entanglement effects through slip-springs.

Contribution

The study develops a novel multi-chain slip-spring model with a well-defined free energy and detailed balance, offering a new approach to simulate entangled polymers.

Findings

Reproduces bead number dependence in Rouse and entangled regimes

Derives explicit linear relaxation modulus expression

Proposes a numerical scheme for simulations

Abstract

It has been established that the entangled polymer dynamics can be reasonably described by single chain models such as tube and slip-link models. Although the entanglement effect is a result of the hard-core interaction between chains, linkage between the single chain models and the real multi-chain system has not been established yet. In this study, we propose a multi-chain slip-spring model where bead-spring chains are dispersed in space and connected by slip-springs inspired by the single chain slip-spring model [A. E. Likhtman, Macromolecules 38, 6128 (2005)]. In this model the entanglement effect is replaced by the slip-springs, not by the hard-core interaction between beads so that this model is located in the niche between conventional multi-chain simulations and single chain models. The set of state variables are the position of beads and the connectivity (indices) of the slip-springs between beads. The dynamics of the system is described by the time evolution equation and stochastic transition dynamics for these variables. We propose a simple model which is based on the well-defined total free-energy and the detailed balance condition. The free energy in our model contains a repulsive interaction between beads, which compensate the attractive interaction artificially generated by the slip-springs. The explicit expression of linear relaxation modulus is also derived by the linear response theory. We also propose a possible numerical scheme to perform simulations. Simulations reproduced expected bead number dependence in transitional regime between Rouse and entangled dynamics for the chain structure, the central bead diffusion, and the linear relaxation modulus.