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Title: Revisiting the strong stretching theory for pH-responsive polyelectrolyte brushes: effects of consideration of excluded volume interactions and an expanded form of the mass action law

Abstract

In this work, we develop a theory to account for the effect of excluded volume (EV) interactions in the strong stretching theory (SST) based description of pH-responsive polyelectrolyte (PE) brushes. The existing studies have considered the PE brushes to be present in a θ-solvent and hence have neglected the EV interactions; however, such a consideration cannot describe the situations where the pH-responsive brushes are in a “good” solvent. Secondly, we consider a more expanded form of the mass action law, governing the pH-dependent ionization of the PE molecules, in the SST description of the PE brushes. This expanded form of the mass action law considers different values of γa3 (γ is the density of chargeable sites on the PE molecule and a is the PE Kuhn length) and therefore is an improvement over the existing SST models of PE brushes as well as other theories involving pH-responsive PE molecules that always consider γa3 = 1. Our findings demonstrate that the EV effects enhance the brush height by inducing additional PE inter-segmental repulsion. Similarly, the consideration of the expanded form of the mass action law would lead to a reduced (enhanced) brush height for γa3 < 1 (γa3 > 1). Wemore » also quantify variables such as the monomer density distribution, the distribution of the ends of the PE brush, and the EDL electrostatic potential and explain their differences with respect to those obtained with no EV interactions or γa3 = 1.« less

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Univ. of Maryland, College Park, MD (United States)
Publication Date:
Research Org.:
Univ. of Maryland, College Park, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1595322
Alternate Identifier(s):
OSTI ID: 1484835
Grant/Contract Number:  
SC0017741
Resource Type:
Accepted Manuscript
Journal Name:
Soft Matter
Additional Journal Information:
Journal Volume: 15; Journal Issue: 4; Journal ID: ISSN 1744-683X
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING

Citation Formats

Sachar, Harnoor Singh, Sivasankar, Vishal Sankar, and Das, Siddhartha. Revisiting the strong stretching theory for pH-responsive polyelectrolyte brushes: effects of consideration of excluded volume interactions and an expanded form of the mass action law. United States: N. p., 2018. Web. doi:10.1039/c8sm02163e.
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Sachar, Harnoor Singh, Sivasankar, Vishal Sankar, & Das, Siddhartha. Revisiting the strong stretching theory for pH-responsive polyelectrolyte brushes: effects of consideration of excluded volume interactions and an expanded form of the mass action law. United States. https://doi.org/10.1039/c8sm02163e
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Sachar, Harnoor Singh, Sivasankar, Vishal Sankar, and Das, Siddhartha. Mon . "Revisiting the strong stretching theory for pH-responsive polyelectrolyte brushes: effects of consideration of excluded volume interactions and an expanded form of the mass action law". United States. https://doi.org/10.1039/c8sm02163e. https://www.osti.gov/servlets/purl/1595322.
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@article{osti_1595322,
title = {Revisiting the strong stretching theory for pH-responsive polyelectrolyte brushes: effects of consideration of excluded volume interactions and an expanded form of the mass action law},
author = {Sachar, Harnoor Singh and Sivasankar, Vishal Sankar and Das, Siddhartha},
abstractNote = {In this work, we develop a theory to account for the effect of excluded volume (EV) interactions in the strong stretching theory (SST) based description of pH-responsive polyelectrolyte (PE) brushes. The existing studies have considered the PE brushes to be present in a θ-solvent and hence have neglected the EV interactions; however, such a consideration cannot describe the situations where the pH-responsive brushes are in a “good” solvent. Secondly, we consider a more expanded form of the mass action law, governing the pH-dependent ionization of the PE molecules, in the SST description of the PE brushes. This expanded form of the mass action law considers different values of γa3 (γ is the density of chargeable sites on the PE molecule and a is the PE Kuhn length) and therefore is an improvement over the existing SST models of PE brushes as well as other theories involving pH-responsive PE molecules that always consider γa3 = 1. Our findings demonstrate that the EV effects enhance the brush height by inducing additional PE inter-segmental repulsion. Similarly, the consideration of the expanded form of the mass action law would lead to a reduced (enhanced) brush height for γa3 < 1 (γa3 > 1). We also quantify variables such as the monomer density distribution, the distribution of the ends of the PE brush, and the EDL electrostatic potential and explain their differences with respect to those obtained with no EV interactions or γa3 = 1.},
doi = {10.1039/c8sm02163e},
journal = {Soft Matter},
number = 4,
volume = 15,
place = {United States},
year = {Mon Nov 26 00:00:00 EST 2018},
month = {Mon Nov 26 00:00:00 EST 2018}
}
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