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

Sachar, Harnoor Singh; Sivasankar, Vishal Sankar; Das, Siddhartha

doi:10.1039/c8sm02163e

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

Journal Article · Mon Nov 26 00:00:00 EST 2018 · Soft Matter

DOI:https://doi.org/10.1039/c8sm02163e· OSTI ID:1595322

Sachar, Harnoor Singh ^[1]; Sivasankar, Vishal Sankar ^[1];

^[1]

Univ. of Maryland, College Park, MD (United States)

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.

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Research Organization:: Univ. of Maryland, College Park, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017741

OSTI ID:: 1595322

Alternate ID(s):: OSTI ID: 1484835

Journal Information:: Soft Matter, Vol. 15, Issue 4; ISSN 1744-683X

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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