The role of entropy in wetting of polymer brushes.

The wetting of polymer brushes exhibits a much richer phenomenology than wetting of normal solid substrates. These brushes allow for three wetting states, which are partial wetting, complete wetting and mixing. Here, we study the transitions between these wetting states for brushes in contact with polymer melts and compare them to predictions using enthalpic arguments based on brush and melt interactions. We show that the transitions are shifted compared to the enthalpic predictions and that the shifts can be positive or negative depending on the length of the melt polymer and the brush grafting density. The reason for this is that these brush and melt parameters can have a positive or negative effect on the entropic contribution to the free energy of the system. Our results highlight the relevance of entropy in predicting the exact wetting transitions, which is important for the design of brush-based coating applications.

Wetting of Polymer Brushes by Polymeric Nanodroplets.

End-anchoring polymers to a solid surface to form so-called polymer brushes is a versatile method to prepare robust functional coatings. We show, using molecular dynamics simulations, that these coatings display rich wetting behavior. Depending on the interaction between the brushes and the polymeric droplets as well as on the self-affinity of the brush, we can distinguish between three wetting states: mixing, complete wetting, and partial wetting. We find that transitions between these states are largely captured by enthalpic arguments, while deviations to these can be attributed to the negative excess interfacial entropy for the brush droplet system. Interestingly, we observe that the contact angle strongly increases when the softness of the brush is increased, which is opposite to the case of drops on soft elastomers. Hence, the Young to Neumann transition owing to softness is not universal but depends on the nature of the substrate.