Dynamics and Rheology of Polymer Melts via Hierarchical Atomistic, Coarse-grained, and Slip-spring Simulations

TL;DR

This paper introduces a hierarchical simulation approach combining atomistic, coarse-grained, and slip-spring models to accurately predict the dynamics and rheology of high molecular weight entangled polymer melts, validated on polybutadiene.

Contribution

The novel multi-scale methodology preserves chemical and topological details across models, enabling accurate rheological predictions of polymer melts.

Findings

Good agreement with experimental rheological data

Effective matching of static and dynamic properties across scales

Validated on high molecular weight polybutadiene

Abstract

A hierarchical (triple scale) simulation methodology is presented for the prediction of the dynamical and rheological properties of high molecular weight entangled polymer melts. The methodology consists of atomistic, moderately coarse-grained (mCG), and highly coarse-grained slip-spring (SLSP) simulations. At the mCG level, a few chemically bonded atoms are lumped into one coarse-grained bead. At this level, the chemical identity of the atomistic system, and the interchain topological constraints (entanglements) are preserved. The mCG potentials are derived by matching local structural distributions of the mCG model to those of the atomistic model through iterative Boltzmann inversion. For matching mCG and atomistic dynamics, the mCG time is scaled by a time scaling factor, which compensates for the lower monomeric friction coefficient of the mCG model than that of the atomistic one. At the SLSP level, multiple Kuhn segments of a polymer chain are represented by one coarse-grained bead. The very soft nonbonded interactions between beads do not prevent chain crossing and, hence, can not capture entanglements. The topological constraints are represented by slip-springs. A compensating pair potential is used in the SLSP model, to keep the static macromolecular properties unaltered upon the introduction of slip-springs. The static and kinetic parameters of the SLSP model are determined based on the lower level simulation models. Particularly, matching the orientational autocorrelation of the end-to-end vector, we determine the number of slip-springs and calibrate the timescale of the SLSP model. As the test case, the hierarchical methodology is applied to $cis$-1,4-polybutadiene (cPB) at 413 K. Dynamical properties of cPB melts are calculated for a broad range of molecular weights. The calculations are compared, and found in good agreement, with experimental data from the literature.