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Title: Viscoelastic Response of Dispersed Entangled Polymer Melts

Abstract

Any polymer synthesis routes result in molecular weight dispersity DAI, depending on the polymerization mechanism. The lowest dispersity polymers are those made by anionic and atom-transfer radical polymerization, which exhibit relatively narrow distributions DM=g,„1A172 — 1.02-1.04. This small divergence from monodispersity results in significant number of molecules that differ in their molecular weight from the average and their impact on the viscoelastic response remains an open question. Here the effects of low dispersity on stress relaxation and shear viscosity of entangled melts are studied using a coarse-grained model for polyethylene. Polymer melts with chain length dispersity set to follow a Schulz-Zimm distribution of Dm = 1.0 — 1.16 for an entangled polyethylene melt using molecular dynamic simulations. The systems were studied to times up to 800 ,us which is beyond the terminal time. These systems are compared to those with binary and ternary distributions. The stress relaxation functions were extracted from the Green-Kubo relation and from stress-strain relaxation following a uniaxial extension. We find on the entanglement time scale, both the mean squared displacement and the stress relaxation are independent of Dm. The tube diameter and the rubbery plateau for entangled dynamics do not depend on Dm. At longer times,more » the terminal relaxation time decreases as the faster motion of the shorter chains results in constraint release for the longer chains. Probing this low dispersity regime opens the way to evaluate the degree of dispersity that affects mechanical properties.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. U. S. Army Research Lab., Aberdeen, MD (United States)
  3. Univ. of South Carolina, Columbia, SC (United States)
  4. Clemson Univ., SC (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1671805
Report Number(s):
SAND2020-8593J
Journal ID: ISSN 0024-9297; 690045
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 53; Journal Issue: 19; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Peters, Brandon L., Salerno, K. Michael, Ge, Ting, Perahia, Dvora, and Grest, Gary S. Viscoelastic Response of Dispersed Entangled Polymer Melts. United States: N. p., 2020. Web. doi:10.1021/acs.macromol.0c01403.
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Peters, Brandon L., Salerno, K. Michael, Ge, Ting, Perahia, Dvora, & Grest, Gary S. Viscoelastic Response of Dispersed Entangled Polymer Melts. United States. https://doi.org/10.1021/acs.macromol.0c01403
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Peters, Brandon L., Salerno, K. Michael, Ge, Ting, Perahia, Dvora, and Grest, Gary S. Thu . "Viscoelastic Response of Dispersed Entangled Polymer Melts". United States. https://doi.org/10.1021/acs.macromol.0c01403. https://www.osti.gov/servlets/purl/1671805.
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@article{osti_1671805,
title = {Viscoelastic Response of Dispersed Entangled Polymer Melts},
author = {Peters, Brandon L. and Salerno, K. Michael and Ge, Ting and Perahia, Dvora and Grest, Gary S.},
abstractNote = {Any polymer synthesis routes result in molecular weight dispersity DAI, depending on the polymerization mechanism. The lowest dispersity polymers are those made by anionic and atom-transfer radical polymerization, which exhibit relatively narrow distributions DM=g,„1A172 — 1.02-1.04. This small divergence from monodispersity results in significant number of molecules that differ in their molecular weight from the average and their impact on the viscoelastic response remains an open question. Here the effects of low dispersity on stress relaxation and shear viscosity of entangled melts are studied using a coarse-grained model for polyethylene. Polymer melts with chain length dispersity set to follow a Schulz-Zimm distribution of Dm = 1.0 — 1.16 for an entangled polyethylene melt using molecular dynamic simulations. The systems were studied to times up to 800 ,us which is beyond the terminal time. These systems are compared to those with binary and ternary distributions. The stress relaxation functions were extracted from the Green-Kubo relation and from stress-strain relaxation following a uniaxial extension. We find on the entanglement time scale, both the mean squared displacement and the stress relaxation are independent of Dm. The tube diameter and the rubbery plateau for entangled dynamics do not depend on Dm. At longer times, the terminal relaxation time decreases as the faster motion of the shorter chains results in constraint release for the longer chains. Probing this low dispersity regime opens the way to evaluate the degree of dispersity that affects mechanical properties.},
doi = {10.1021/acs.macromol.0c01403},
journal = {Macromolecules},
number = 19,
volume = 53,
place = {United States},
year = {Thu Oct 01 00:00:00 EDT 2020},
month = {Thu Oct 01 00:00:00 EDT 2020}
}
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