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.