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Title: Consequences of Delayed Chain Retraction on the Rheology and Stretch Dynamics of Entangled Polymer Liquids under Continuous Nonlinear Shear Deformation

Abstract

Here, we generalize our recent new ideas for the continuous startup shear rheology of entangled polymer liquids in the transient stress overshoot regime to formulate a theory for the full constitutive response and nonequilibrium dynamics over all time scales, deformation rates, and degrees of entanglement. The convective constraint release (CCR) idea that chain retraction locally triggers disentanglement in a shear-rate-dependent manner is significantly modified to be physically consistent with our nonclassical treatment of delayed retraction due to an entanglement grip force. A detailed numerical study of the predictions of the theory is presented for the full stress–strain response, scaling behavior of the stress overshoot and undershoot features, orientational stress, primitive path contour length dynamics, and nonequilibrium steady-state properties spanning the slow and fast nonlinear deformation regimes. For deformations slow enough there is little or no chain stretch, our results are qualitatively the same as in prior tube-based models. However, under fast deformation conditions, we make qualitatively new predictions for all rheological and dynamic properties that are not contained in any existing models. No-fit-parameter quantitative comparisons are made with experimental and simulation studies, and very good agreement is found; testable predictions are made. Finally, strong connections between properties (stress and degreemore » of chain stretch) at the overshoot and in the steady state are found, which suggests common physics exists at the elastic–viscous crossover (stress overshoot) and for long time flow associated with a delayed onset of primitive path retraction and emergence of CCR.« less

Authors:
ORCiD logo [1];  [1]
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  1. Univ. of Illinois, Urbana, IL (United States). Dept. of Materials Science. Dept. of Chemistry. Dept. of Chemical & Biomolecular Engineering
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:
1479752
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 11; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Xie, Shi-Jie, and Schweizer, Kenneth S. Consequences of Delayed Chain Retraction on the Rheology and Stretch Dynamics of Entangled Polymer Liquids under Continuous Nonlinear Shear Deformation. United States: N. p., 2018. Web. doi:10.1021/acs.macromol.8b00671.
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Xie, Shi-Jie, & Schweizer, Kenneth S. Consequences of Delayed Chain Retraction on the Rheology and Stretch Dynamics of Entangled Polymer Liquids under Continuous Nonlinear Shear Deformation. United States. https://doi.org/10.1021/acs.macromol.8b00671
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Xie, Shi-Jie, and Schweizer, Kenneth S. Wed . "Consequences of Delayed Chain Retraction on the Rheology and Stretch Dynamics of Entangled Polymer Liquids under Continuous Nonlinear Shear Deformation". United States. https://doi.org/10.1021/acs.macromol.8b00671. https://www.osti.gov/servlets/purl/1479752.
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@article{osti_1479752,
title = {Consequences of Delayed Chain Retraction on the Rheology and Stretch Dynamics of Entangled Polymer Liquids under Continuous Nonlinear Shear Deformation},
author = {Xie, Shi-Jie and Schweizer, Kenneth S.},
abstractNote = {Here, we generalize our recent new ideas for the continuous startup shear rheology of entangled polymer liquids in the transient stress overshoot regime to formulate a theory for the full constitutive response and nonequilibrium dynamics over all time scales, deformation rates, and degrees of entanglement. The convective constraint release (CCR) idea that chain retraction locally triggers disentanglement in a shear-rate-dependent manner is significantly modified to be physically consistent with our nonclassical treatment of delayed retraction due to an entanglement grip force. A detailed numerical study of the predictions of the theory is presented for the full stress–strain response, scaling behavior of the stress overshoot and undershoot features, orientational stress, primitive path contour length dynamics, and nonequilibrium steady-state properties spanning the slow and fast nonlinear deformation regimes. For deformations slow enough there is little or no chain stretch, our results are qualitatively the same as in prior tube-based models. However, under fast deformation conditions, we make qualitatively new predictions for all rheological and dynamic properties that are not contained in any existing models. No-fit-parameter quantitative comparisons are made with experimental and simulation studies, and very good agreement is found; testable predictions are made. Finally, strong connections between properties (stress and degree of chain stretch) at the overshoot and in the steady state are found, which suggests common physics exists at the elastic–viscous crossover (stress overshoot) and for long time flow associated with a delayed onset of primitive path retraction and emergence of CCR.},
doi = {10.1021/acs.macromol.8b00671},
journal = {Macromolecules},
number = 11,
volume = 51,
place = {United States},
year = {Wed May 23 00:00:00 EDT 2018},
month = {Wed May 23 00:00:00 EDT 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.macromol.8b00671
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Citation Metrics:
Cited by: 20 works
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Figures / Tables:

Figure 1 Figure 1: (a) Depiction of the interchain grip and intrachain retraction forces per ref 14. (b) Schematic of unentangled polymers under shear that stretch in one-spatial direction beyond the Pincus tension blob size per ref 24.
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    Works referencing / citing this record:

    Nonlinear shear of entangled polymers from nonequilibrium molecular dynamics
    journal, November 2019

    • Anwar, Muhammad; Graham, Richard S.
    • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 24
    • DOI: 10.1002/polb.24904

    Production of Hollow Ceramic Rods by SHS Extrusion
    journal, February 2019

    From Wall Slip to Bulk Shear Banding in Entangled Polymer Solutions
    journal, October 2018

    Production of hollow ceramic rods by SHS extrusion
    journal, May 2019

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      Figures / Tables found in this record:

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