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Title: Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight

Abstract

Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene- r-propylene) blocks (B), and end-capped by a poly( t-butylstyrene) block (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. In conclusion, the water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.

Authors:
 [1];  [2];  [3]; ORCiD logo [4]
  1. Clemson Univ., Clemson, SC (United States); Univ. of Texas at Austin, Austin, TX (United States)
  2. Clemson Univ., Clemson, SC (United States); Washington Univ. in St. Louis, St. Louis, MO (United States)
  3. Clemson Univ., Clemson, SC (United States)
  4. 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 Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1389594
Report Number(s):
SAND-2017-9435J
Journal ID: ISSN 0743-7463; 656707
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 41; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Aryal, Dipak, Agrawal, Anupriya, Perahia, Dvora, and Grest, Gary S. Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight. United States: N. p., 2017. Web. doi:10.1021/acs.langmuir.7b02485.
Aryal, Dipak, Agrawal, Anupriya, Perahia, Dvora, & Grest, Gary S. Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight. United States. doi:10.1021/acs.langmuir.7b02485.
Aryal, Dipak, Agrawal, Anupriya, Perahia, Dvora, and Grest, Gary S. Wed . "Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight". United States. doi:10.1021/acs.langmuir.7b02485. https://www.osti.gov/servlets/purl/1389594.
@article{osti_1389594,
title = {Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight},
author = {Aryal, Dipak and Agrawal, Anupriya and Perahia, Dvora and Grest, Gary S.},
abstractNote = {Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene-r-propylene) blocks (B), and end-capped by a poly(t-butylstyrene) block (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. In conclusion, the water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.},
doi = {10.1021/acs.langmuir.7b02485},
journal = {Langmuir},
number = 41,
volume = 33,
place = {United States},
year = {Wed Aug 23 00:00:00 EDT 2017},
month = {Wed Aug 23 00:00:00 EDT 2017}
}

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