In this work, we study the wetting of a surface decorated with one nanogroove by a bulk Lennard-Jones liquid at various temperatures and densities. We used atomistic simulations aimed at computing the free energy of the stable and metastable states of the system, as well as the intermediate states separating them. We found that the usual description in terms of Cassie-Baxter and Wenzel states is insufficient, as the system presents two states of the Cassie-Baxter type. These states are characterized by different curvatures of the meniscus. The measured free energy barrier separating the Cassie-Baxter from the Wenzel state (and vice versa) largely exceeds the thermal energy, attesting the existence of Cassie-Baxter/Wenzel metastabilities. Finally, we found that the Cassie-Baxter/Wenzel transition follows an asymmetric path, with the formation of a liquid finger on one side of the groove and a vapor bubble on the opposite side.

In this Letter, we develop a continuum theory for the Cassie-Baxter-Wenzel (CB-W) transition. The proposed model accounts for the metastabilities in the wetting of rough hydrophobic surfaces, allows us to reconstruct the transition mechanism, and identifies the free energy barriers separating the CB and W states as a function of the liquid pressure. This information is crucial in the context of superhydrophobic surfaces, where there is interest in extending the duration of the metastable superhydrophobic CB state. The model is validated against free energy atomistic simulations.

Superhydrophobic coatings repel liquids by trapping air inside microscopic surface textures. However, the resulting composite interface is prone to collapse under external pressure. Nanometer-size textures should facilitate more resilient coatings owing to geometry and confinement effects at the nanoscale. Here, we use in situ x-ray diffraction to study the collapse of the superhydrophobic state in arrays of approximate to 20 nm-wide silicon textures with cylindrical, conical, and linear features defined by block-copolymer self-assembly and plasma etching. We reveal that the superhydrophobic state vanishes above critical pressures which depend on texture shape and size. This phenomenon is irreversible for all but the conical surface textures which exhibit a spontaneous, partial reappearance of the trapped gas phase upon liquid depressurization. This process is influenced by the kinetics of gas-liquid exchange