Small droplets on superhydrophobic substrates.

We investigate the wetting behavior of liquid droplets on rough hydrophobic substrates for the case of droplets that are of comparable size to the surface asperities. Using a simple three-dimensional analytical free-energy model, we have shown in a recent letter [M. Gross, F. Varnik, and D. Raabe, EPL 88, 26002 (2009)] that, in addition to the well-known Cassie-Baxter and Wenzel states, there exists a further metastable wetting state where the droplet is immersed into the texture to a finite depth, yet not touching the bottom of the substrate. Due to this new state, a quasistatically evaporating droplet can be saved from going over to the Wenzel state and instead remains close to the top of the surface. In the present paper, we give an in-depth account of the droplet behavior based on the results of extensive computer simulations and an improved theoretical model. In particular, we show that releasing the assumption that the droplet is pinned at the outer edges of the pillars improves the analytical results for larger droplets. Interestingly, all qualitative aspects, such as the existence of an intermediate minimum and the "reentrant transition," remain unchanged. We also give a detailed description of the evaporation process for droplets of varying sizes. Our results point out the role of droplet size for superhydrophobicity and give hints for achieving the desired wetting properties of technically produced materials.