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Title: A force-level theory of the rheology of entangled rod and chain polymer liquids. I. Tube deformation, microscopic yielding, and the nonlinear elastic limit

Abstract

In this paper, we employ a first-principles-based, force-level approach to construct the anharmonic tube confinement field for entangled fluids of rigid needles, and also for chains described at the primitive-path (PP) level in two limiting situations where chain stretch is assumed to either be completely equilibrated or unrelaxed. The influence of shear and extensional deformation and polymer orientation is determined in a nonlinear elastic limit where dissipative relaxation processes are intentionally neglected. For needles and PP-level chains, a self-consistent analysis of transverse polymer harmonic dynamical fluctuations predicts that deformation-induced orientation leads to tube weakening or widening. In contrast, for deformed polymers in which chain stretch does not relax, we find tube strengthening or compression. For all three systems, a finite maximum transverse entanglement force localizing the polymers in effective tubes is predicted. The conditions when this entanglement force can be overcome by an externally applied force associated with macroscopic deformation can be crisply defined in the nonlinear elastic limit, and the possibility of a “microscopic absolute yielding” event destroying the tube confinement can be analyzed. For needles and contour-relaxed PP chains, this force imbalance occurs at a stress of order the equilibrium shear modulus and a strain of order unity,more » corresponding to a mechanically fragile entanglement tube field. However, for unrelaxed stretched chains, tube compression stabilizes transverse polymer confinement, and there appears to be no force imbalance. These results collectively suggest that the crossover from elastic to irreversible viscous response requires chain retraction to initiate disentanglement. Finally, we qualitatively discuss comparisons with existing phenomenological models for nonlinear startup shear, step strain, and creep rheology experiments.« less

Authors:
 [1];  [2]
+ Show Author Affiliations
  1. Univ. of Illinois, Urbana, IL (United States). Dept. of Materials Science. Dept. of Chemistry
  2. Syracuse Univ., NY (United States). Dept. of Physics
Publication Date:
Research Org.:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1465673
Alternate Identifier(s):
OSTI ID: 1334367
Grant/Contract Number:  
FG02-07ER46471
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 21; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; diffusion; polymers; retraction; reptation; tube theories; elasticity; shear deformation; mean field theory; free energy; nonlinear dynamics

Citation Formats

Schweizer, Kenneth S., and Sussman, Daniel M. A force-level theory of the rheology of entangled rod and chain polymer liquids. I. Tube deformation, microscopic yielding, and the nonlinear elastic limit. United States: N. p., 2016. Web. doi:10.1063/1.4968516.
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Schweizer, Kenneth S., & Sussman, Daniel M. A force-level theory of the rheology of entangled rod and chain polymer liquids. I. Tube deformation, microscopic yielding, and the nonlinear elastic limit. United States. https://doi.org/10.1063/1.4968516
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Schweizer, Kenneth S., and Sussman, Daniel M. Mon . "A force-level theory of the rheology of entangled rod and chain polymer liquids. I. Tube deformation, microscopic yielding, and the nonlinear elastic limit". United States. https://doi.org/10.1063/1.4968516. https://www.osti.gov/servlets/purl/1465673.
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@article{osti_1465673,
title = {A force-level theory of the rheology of entangled rod and chain polymer liquids. I. Tube deformation, microscopic yielding, and the nonlinear elastic limit},
author = {Schweizer, Kenneth S. and Sussman, Daniel M.},
abstractNote = {In this paper, we employ a first-principles-based, force-level approach to construct the anharmonic tube confinement field for entangled fluids of rigid needles, and also for chains described at the primitive-path (PP) level in two limiting situations where chain stretch is assumed to either be completely equilibrated or unrelaxed. The influence of shear and extensional deformation and polymer orientation is determined in a nonlinear elastic limit where dissipative relaxation processes are intentionally neglected. For needles and PP-level chains, a self-consistent analysis of transverse polymer harmonic dynamical fluctuations predicts that deformation-induced orientation leads to tube weakening or widening. In contrast, for deformed polymers in which chain stretch does not relax, we find tube strengthening or compression. For all three systems, a finite maximum transverse entanglement force localizing the polymers in effective tubes is predicted. The conditions when this entanglement force can be overcome by an externally applied force associated with macroscopic deformation can be crisply defined in the nonlinear elastic limit, and the possibility of a “microscopic absolute yielding” event destroying the tube confinement can be analyzed. For needles and contour-relaxed PP chains, this force imbalance occurs at a stress of order the equilibrium shear modulus and a strain of order unity, corresponding to a mechanically fragile entanglement tube field. However, for unrelaxed stretched chains, tube compression stabilizes transverse polymer confinement, and there appears to be no force imbalance. These results collectively suggest that the crossover from elastic to irreversible viscous response requires chain retraction to initiate disentanglement. Finally, we qualitatively discuss comparisons with existing phenomenological models for nonlinear startup shear, step strain, and creep rheology experiments.},
doi = {10.1063/1.4968516},
journal = {Journal of Chemical Physics},
number = 21,
volume = 145,
place = {United States},
year = {Mon Dec 05 00:00:00 EST 2016},
month = {Mon Dec 05 00:00:00 EST 2016}
}
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