Stress Relaxation in Highly Oriented Melts of Entangled Polymers

O’Connor, Thomas C.; Hopkins, Austin; Robbins, Mark O.

doi:10.1021/acs.macromol.9b01161

Stress Relaxation in Highly Oriented Melts of Entangled Polymers

Journal Article · Mon Oct 21 00:00:00 EDT 2019 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.9b01161· OSTI ID:1574479

^[1]; Hopkins, Austin ^[2]; ^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Johns Hopkins Univ., Baltimore, MD (United States)

Here, molecular dynamics simulations are used to study relaxation of entangled polymer melts deformed far from equilibrium by uniaxial extensional flow. Melts are elongated to a Hencky strain of 6 at Rouse–Weissenberg numbers from 0.16 to 25, producing states with a wide range of chain alignment. Then flow is ceased and the systems are allowed to relax until twice the equilibrium disentanglement time. The relaxation of the stress is correlated with changes in the conformation of chains and the geometry of the tube confining them. Independent of initial alignment, chains relax to conformations consistent with the equilibrium tube length and diameter on the equilibrium Rouse time. Subsequent relaxation is the same for all systems and controlled by the equilibrium distentanglement time. These results are counter to prior work that indicates orientation causes a large, stretch-dependent reduction in the entanglement density that can only be recovered slowly by reptation on the equilibrium disentanglement time, raising fundamental questions about the nature of entanglement in aligned polymer melts.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1574479

Report Number(s):: SAND--2019-13792J; 681376

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 22 Vol. 52; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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