Free-energy landscapes of intrusion and extrusion of liquid in truncated and inverted truncated conical pores: implications to the Cassie-Baxter to Wenzel transition

Abstract

As the simplest model of transition between the superhydrophobic Cassie-Baxter (CB) and Wenzel (W) states of a macroscopic droplet sitting on a microscopically rough or corrugated substrate, a substrate whose surface is covered by identical truncated or inverted truncated conical pores is considered. The free energy landscapes of the intrusion and extrusion processes of a liquid into single pore are analyzed when the liquid is compressed or stretched so that the liquid phase is either stable or metastable relative to the vapor phase. Therefore, this model is also relevant to the stability of the superhydrophobic submerged substrates. In this study, the macroscopic classical capillary theory is adopted. Even within this simplified model, two simple geometries of truncated and inverted truncated cones lead to completely different free-energy landscapes. A simple criterion for the stability of the CB state based on Laplace pressure is shown not to be sufficient to understand the destruction and recovery of the CB state. The free-energy landscapes indicate that a gradual and an abrupt destruction of CB state is possible, which depends on the orientation of the conical pore and whether the liquid is compressed or stretched. The extensions of these theoretical results to more complex geometries are briefly discussed.