A polymer brush theory for quantitative prediction of maximum height change between dry and wet states

TL;DR

This paper develops a thermodynamic model combining elasticity and mixing theories to quantitatively predict polymer brush heights in dry and wet states, aiding the design of brushes with maximal height change for various applications.

Contribution

It introduces a novel quantitative theory for predicting maximum height change of polymer brushes, integrating elasticity and mixing models for practical design guidance.

Findings

Model accurately predicts brush heights consistent with experimental data.

Conditions for maximizing height change are identified.

Theory can be coupled with other models for complex behaviors.

Abstract

Polymer brushes can grow on almost any solid surface, and by design, exhibit diverse properties and functionalities, thus they have been widely used in many emerging applications in engineering, energy, and medicine. In particular, some applications such as actuation, molecule release, and friction switch require the polymer brushes to change their heights between dry and wet states, and maximizing such height change is critical for the optimal performance of these applications. While scaling laws have long been proposed to qualitatively determine brush heights, a theory that can quantitatively predict brush heights and conditions for maximizing brush height change is still lacking yet is valuable for the practical design of polymer brushes. Here, we take a thermodynamic approach to formulate a polymer brush theory to calculate brush heights at various conditions of graft area, degree of polymerization (DP), and solvent qualities. Our model consists of two parts-the freely-jointed chain model to describe the elasticity of brushes and the Flory-Rehner model to describe the mixing of brushes and solvents. The calculated brush heights at both dry and wet states fairly agree with the experimental data from the literature. The calculated brush heights are further used to determine the conditions for the maximum brush height change. Our theory can guide the design of polymer brushes for optimal functional performance in various applications and also can couple with other models to describe more complex behaviors of polymer brushes.