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Title: Cluster Morphology-Polymer Dynamics Correlations in Sulfonated Polystyrene Melts: Computational Study

Abstract

Reaching exceptionally long times up to 500 ns in equilibrium and nonequilibrium molecular dynamics simulations studies, we have attained a fundamental molecular understanding of the correlation of ionomer clusters structure and multiscale dynamics, providing new insight into one critical, long-standing challenge in ionic polymer physics. The cluster structure in melts of sulfonated polystyrene with Na+ and Mg2+ counterions are resolved and correlated with the dynamics on multiple length and time scales extracted from measurements of the dynamic structure factor and shear rheology. We find that as the morphology of the ionic clusters changes from ladderlike for Na+ to disordered structures for Mg2+, the dynamic structure factor is affected on the length scale corresponding to the ionic clusters. Lastly, rheology studies show that the viscosity for Mg2+ melts is higher than for Na+ ones for all shear rates, which is well correlated with the larger ionic clusters’ size for the Mg2+ melts.

Authors:
 [1];  [2];  [3]
+ Show Author Affiliations
  1. Clemson Univ., SC (United States); Washington Univ., St. Louis, MO (United States)
  2. Clemson Univ., SC (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (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:
1249074
Alternate Identifier(s):
OSTI ID: 1246765
Report Number(s):
SAND-2016-3002J
Journal ID: ISSN 0031-9007; PRLTAO; 637607
Grant/Contract Number:  
AC04-94AL85000; SC007908; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 116; Journal Issue: 15; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Agrawal, Anupriya, Perahia, Dvora, and Grest, Gary S. Cluster Morphology-Polymer Dynamics Correlations in Sulfonated Polystyrene Melts: Computational Study. United States: N. p., 2016. Web. doi:10.1103/PhysRevLett.116.158001.
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Agrawal, Anupriya, Perahia, Dvora, & Grest, Gary S. Cluster Morphology-Polymer Dynamics Correlations in Sulfonated Polystyrene Melts: Computational Study. United States. https://doi.org/10.1103/PhysRevLett.116.158001
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Agrawal, Anupriya, Perahia, Dvora, and Grest, Gary S. Mon . "Cluster Morphology-Polymer Dynamics Correlations in Sulfonated Polystyrene Melts: Computational Study". United States. https://doi.org/10.1103/PhysRevLett.116.158001. https://www.osti.gov/servlets/purl/1249074.
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@article{osti_1249074,
title = {Cluster Morphology-Polymer Dynamics Correlations in Sulfonated Polystyrene Melts: Computational Study},
author = {Agrawal, Anupriya and Perahia, Dvora and Grest, Gary S.},
abstractNote = {Reaching exceptionally long times up to 500 ns in equilibrium and nonequilibrium molecular dynamics simulations studies, we have attained a fundamental molecular understanding of the correlation of ionomer clusters structure and multiscale dynamics, providing new insight into one critical, long-standing challenge in ionic polymer physics. The cluster structure in melts of sulfonated polystyrene with Na+ and Mg2+ counterions are resolved and correlated with the dynamics on multiple length and time scales extracted from measurements of the dynamic structure factor and shear rheology. We find that as the morphology of the ionic clusters changes from ladderlike for Na+ to disordered structures for Mg2+, the dynamic structure factor is affected on the length scale corresponding to the ionic clusters. Lastly, rheology studies show that the viscosity for Mg2+ melts is higher than for Na+ ones for all shear rates, which is well correlated with the larger ionic clusters’ size for the Mg2+ melts.},
doi = {10.1103/PhysRevLett.116.158001},
journal = {Physical Review Letters},
number = 15,
volume = 116,
place = {United States},
year = {Mon Apr 11 00:00:00 EDT 2016},
month = {Mon Apr 11 00:00:00 EDT 2016}
}
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https://doi.org/10.1103/PhysRevLett.116.158001
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