Dynamics and Rheology of Polymer Melts via Hierarchical Atomistic, Coarse-Grained, and Slip-Spring Simulations

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 underlying atomistic system and the interchain topological constraints (entanglements) are preserved. The mCG interaction 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, restricting the lateral motion of polymer chains. 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 a test case, the hierarchical methodology is applied to cis-1,4-polybutadiene (cPB) at 413 K. Dynamical single-chain and linear viscoelastic properties of cPB melts are calculated for a broad range of molecular weights, ranging from unentangled to well-entangled chains. The calculations are compared, and found in good agreement, with experimental data from the literature.

Coupling between Polymer Conformations and Dynamics Near Amorphous Silica Surfaces: A Direct Insight from Atomistic Simulations

“…These chains exhibit Rouse-like dynamics with a characteristic MSD ∼ t 0.5 behavior up to t ≈ 10 4 ps, where a slightly negative slope can be observed for segments in the middle of the film (labels fifth and higher). A negative slope in this representation indicates the presence of entanglements [68], as also shown in our recent study of bulk PB [69].…”

Analysis of Elongational Viscosity of Entangled Poly (Propylene Carbonate) Melts by Primitive Chain Network Simulations

“…We note that these parameters could be determined from atomistic and coarse-grained molecular simulations, as attempted earlier [43][44][45][46][47][48]. However, we did not employ such a bottom-up approach due to practical difficulties for atomistic simulations of PPC.…”

Dynamics of Long Entangled Polyisoprene MeltsviaMultiscale Modeling

“…Recently, we introduced a hierarchical triple-scale scheme to model the dynamic properties of cis-1,4 polybutadiene melts over a broad spatiotemporal scale. 68 The systematic bottom-up parameterization of the SLSP representation based on the dynamics of the end-to-end vector in a moderate CG model (employed as a bridging resolution between the SLSP simulations and atomistic detail) allowed us to explore viscoelastic properties of PB up to ≈108,000 g/mol. In the present work, we combine the three different levels of modeling, namely, a united-atom (UA) model, a CG model, and an even more highly CG SLSP model, to explore the conformational properties and dynamics of PI over a broad range of M extending to ≈204,000 g/mol.…”