Rouse mode analysis of chain relaxation in homopolymer melts

Kalathi, Jagannathan T.; Kumar, Sanat K.; Rubinstein, Michael; Grest, Gary S.

doi:10.1021/ma500900b

Rouse mode analysis of chain relaxation in homopolymer melts

Journal Article · Mon Sep 15 00:00:00 EDT 2014 · Macromolecules

DOI:https://doi.org/10.1021/ma500900b· OSTI ID:1145768

Kalathi, Jagannathan T. ^[1]; Kumar, Sanat K. ^[1]; Rubinstein, Michael ^[2]; Grest, Gary S. ^[3]

Columbia Univ., New York, NY (United States)
Univ. of North Carolina, Chapel Hill, NC (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

We use molecular dynamics simulations of the Kremer–Grest (KG) bead–spring model of polymer chains of length between 10 and 500, and a closely related analogue that allows for chain crossing, to clearly delineate the effects of entanglements on the length-scale-dependent chain relaxation in polymer melts. We analyze the resulting trajectories using the Rouse modes of the chains and find that entanglements strongly affect these modes. The relaxation rates of the chains show two limiting effective monomeric frictions, with the local modes experiencing much lower effective friction than the longer modes. The monomeric relaxation rates of longer modes vary approximately inversely with chain length due to kinetic confinement effects. The time-dependent relaxation of Rouse modes has a stretched exponential character with a minimum of stretching exponent in the vicinity of the entanglement chain length. None of these trends are found in models that allow for chain crossing. As a result, these facts, in combination, argue for the confined motion of chains for time scales between the entanglement time and their ultimate free diffusion.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1145768

Report Number(s):: SAND--2014-4138J; 518305

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 19 Vol. 47; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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