Validation and Refinement of Unified Analytic Model for Flexible and Semiflexible Polymer Melt Entanglement.

Abstract

We combine molecular dynamics simulations and topological analyses (TA) to validate and refine a recently proposed unified analytic model [Hoy, R. S.; Kröger, M. Phys. Rev. Lett. 2020, 124, 147801] for the reduced entanglement length, tube diameter, and plateau modulus of polymer melts. While the functional forms of the previously published expressions are insensitive to the choice of the TA method and N e -estimator, obtaining better statistics and eliminating all known sources of systematic error in the N e -estimation alters their numerical coefficients. Our revised expressions quantitatively match bead-spring simulation data over the entire range of chain stiffnesses for which systems remain isotropic, semiquantitatively match all available experimental data for flexible, semiflexible, and stiff polymer melts (including new data for conjugated polymers that lie in a previously unpopulated stiffness regime), and outperform previously developed unified scaling theories.