Stress anisotropy in polymer brushes and its effects on wetting

Abstract

Polymer brushes, coatings consisting of densely grafted macromolecules, have been known to experience an intrinsic lateral compressive stress, originating from chain elasticity and excluded volume interactions. This lateral stress complicates a proper definition of the interface and, thereby, of the interfacial tension. Moreover, its effect on wettability has remained unclear. Here, we study the link between grafting-induced compressive lateral stress in polymer brushes, interfacial tension, and brush wettability using coarse-grained molecular dynamics simulations. A central result is that the liquid contact angle is independent of grafting density, which implies that the strength of the compressive stress inside brush has no influence on the wettability. Interestingly, though the interfacial tensions lack a proper definition, 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. It is demonstrated how these results can be explained from the fact that the compressive stress appears "symmetrically" in wet and dry brushes. We discuss our findings in the light of autophobic dewetting and point out the connection to the Shuttleworth effect for wetting on elastomers