Determining Tube Theory Parameters by Slip-Spring Model Simulations of Entangled Star Polymers in Fixed Networks

Polymers (Basel). 2019 Mar 14;11(3):496. doi: 10.3390/polym11030496.

Abstract

Dynamical properties of branched polymer melts are determined by the polymer molecular weights and architectures containing junction points. Relaxation of entangled symmetric star polymers proceeds via arm-retraction and constraint release (CR). In this work, we investigate arm-retraction dynamics in the framework of a single-chain slip-spring model without CR effect where entanglements are treated as binary contacts, conveniently modeled as virtual "slip-links", each involving two neighboring strands. The model systems are analogous to isolated star polymers confined in a permanent network or a melt of very long linear polymers. We find that the distributions of the effective primitive path lengths are Gaussian, from which the entanglement molecular weight N e , a key tube theory parameter, can be extracted. The procured N e value is in good agreement with that obtained from mapping the middle monomer mean-square displacements of entangled linear chains in slip-spring model to the tube model prediction. Furthermore, the mean first-passage (FP) times of destruction of original tube segments by the retracting arm end are collected in simulations and examined quantitatively using a theory recently developed in our group for describing FP problems of one-dimensional Rouse chains with improbable extensions. The asymptotic values of N e as obtained from the static (primitive path length) and dynamical (FP time) analysis are consistent with each other. Additionally, we manage to determine the tube survival function of star arms μ ( t ) , or equivalently arm end-to-end vector relaxation function ϕ ( t ) , through the mean FP time spectrum τ ( s ) of the tube segments after careful consideration of the inner-most entanglements, which shows reasonably good agreement with experimental data on dielectric relaxation.

Keywords: arm retraction dynamics; entangled polymers; first passage time; primitive path; relaxation correlation function; slip-link; slip-spring model; tube theory.