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Title: The effect of multivalent counterions to the structure of highly dense polystyrene sulfonate brushes

Abstract

Surface tethered polyelectrolyte brushes are scientifically interesting and technologically relevant to many applications, ranging from colloidal stabilization to responsive and tunable materials to lubrication. Many applications operate in environments containing multi-valent ions, media in which our scientific understanding is not yet well-developed. In this paper, we synthesized high-density polystyrene sulfonate (PSS) brushes via surface initiated atom-transfer radical polymerization, and performed neutron reflectivity (NR) measurements to investigate and compare the effects of mono-valent Rb+ and tri-valent Y3+ counterions to the structure of the densely tethered PSS brushes. Our NR results show that in mono-valent RbNO3 solution, the dense PSS brush retained its full thickness up to a salt concentration of 1 M, whereas it immediately collapsed upon adding 1.67 mM of tri-valent Y3+. Increasing the concentration of Y3+ beyond this level did not lead to any significant further structure change of the PSS brush. Finally, our findings demonstrate that the presence of multi-valent counterions can significantly alter the structure of polyelectrolyte brushes, in a manner different from mono-valent ions, which has implications for the functionality of the brushes.

Authors:
 [1];  [1];  [2];  [3];  [1];  [1]
  1. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). NIST Center for Neutron Research; Univ. of Akron, OH (United States). Dept. of Polymer Engineering
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). NIST Center for Neutron Research
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Contributing Org.:
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Akron, OH (United States)
OSTI Identifier:
1352673
Alternate Identifier(s):
OSTI ID: 1359786
Grant/Contract Number:  
AC02-06CH11357; DMR-1420709
Resource Type:
Accepted Manuscript
Journal Name:
Polymer
Additional Journal Information:
Journal Volume: 98; Journal ID: ISSN 0032-3861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Polyelectrolyte; Brush; Multivalentions; ATRP; Neutron; reflectivity

Citation Formats

Yu, Jing, Mao, Jun, Yuan, Guangcui, Satija, Sushil, Chen, Wei, and Tirrell, Matthew. The effect of multivalent counterions to the structure of highly dense polystyrene sulfonate brushes. United States: N. p., 2016. Web. doi:10.1016/j.polymer.2016.02.053.
Yu, Jing, Mao, Jun, Yuan, Guangcui, Satija, Sushil, Chen, Wei, & Tirrell, Matthew. The effect of multivalent counterions to the structure of highly dense polystyrene sulfonate brushes. United States. doi:10.1016/j.polymer.2016.02.053.
Yu, Jing, Mao, Jun, Yuan, Guangcui, Satija, Sushil, Chen, Wei, and Tirrell, Matthew. Tue . "The effect of multivalent counterions to the structure of highly dense polystyrene sulfonate brushes". United States. doi:10.1016/j.polymer.2016.02.053. https://www.osti.gov/servlets/purl/1352673.
@article{osti_1352673,
title = {The effect of multivalent counterions to the structure of highly dense polystyrene sulfonate brushes},
author = {Yu, Jing and Mao, Jun and Yuan, Guangcui and Satija, Sushil and Chen, Wei and Tirrell, Matthew},
abstractNote = {Surface tethered polyelectrolyte brushes are scientifically interesting and technologically relevant to many applications, ranging from colloidal stabilization to responsive and tunable materials to lubrication. Many applications operate in environments containing multi-valent ions, media in which our scientific understanding is not yet well-developed. In this paper, we synthesized high-density polystyrene sulfonate (PSS) brushes via surface initiated atom-transfer radical polymerization, and performed neutron reflectivity (NR) measurements to investigate and compare the effects of mono-valent Rb+ and tri-valent Y3+ counterions to the structure of the densely tethered PSS brushes. Our NR results show that in mono-valent RbNO3 solution, the dense PSS brush retained its full thickness up to a salt concentration of 1 M, whereas it immediately collapsed upon adding 1.67 mM of tri-valent Y3+. Increasing the concentration of Y3+ beyond this level did not lead to any significant further structure change of the PSS brush. Finally, our findings demonstrate that the presence of multi-valent counterions can significantly alter the structure of polyelectrolyte brushes, in a manner different from mono-valent ions, which has implications for the functionality of the brushes.},
doi = {10.1016/j.polymer.2016.02.053},
journal = {Polymer},
number = ,
volume = 98,
place = {United States},
year = {2016},
month = {2}
}

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