Pressure anisotropy in polymer brushes and its effects on wetting

TL;DR

This study investigates how lateral pressure in polymer brushes affects their interfacial tension and wettability, finding that grafting density does not influence contact angle but impacts interfacial tension differences.

Contribution

It introduces a molecular dynamics simulation approach to analyze the impact of grafting-induced pressure on brush wettability and proposes a method to separate grafting effects from interfacial tension.

Findings

Grafting density does not affect the contact angle.

Difference in interfacial tension accurately describes wettability.

A method to isolate grafting effects from interfacial tension is proposed.

Abstract

Polymer brushes, coatings consisting of densely grafted macromolecules, experience an intrinsic lateral compressive pressure, originating from chain elasticity and excluded volume interactions. This lateral pressure complicates a proper definition of the interface and, thereby, the determination and interpretation of the interfacial tension and its relation to the wetting behavior of brushes. Here, we study the link between grafting-induced compressive lateral pressure in polymer brushes, interfacial tension, and brush wettability using coarse-grained molecular dynamics simulations. We focus on grafting densities and polymer-liquid affinities such that the polymer and liquid do not tend to mix. For these systems, a central result is that the liquid contact angle is independent of the grafting density, which implies that the grafting-induced lateral compressive pressure in the brush does not influence its wettability. Although the definition of brush interfacial tensions is complicated by the grafting-induced pressure, the difference in interfacial tension between wet and dry brushes is perfectly well-defined. We confirm explicitly from Young's law that this difference offers an accurate description of the brush wettability. We then explore a method to isolate the grafting-induced contribution to the lateral pressure, assuming the interfacial tension to be independent of grafting density. This scenario indeed allows to disentangle interfacial and grafting effects for a broad range of parameters, except close to the mixing point. We separately discuss the latter case in the light of autophobic dewetting.