What Can Probing Liquid-Air Menisci Inside Nanopores Teach Us About Macroscopic Wetting Phenomena?

Solid surfaces with excellent nonwetting ability have drawn significant interest from interfacial scientists and engineers. While much effort was devoted to investigating macroscopic wetting phenomena on nonwetting surfaces, the otherwise microscopic wetting has received less attention, and the surface/interface properties at the microscopic scale are not well resolved and correlated with the macroscopic wetting behavior. Herein, we first characterize the nanoscopic morphology and effective stiffness of liquid-air interfaces inside nanopores (nanomenisci) on diverse nonwetting nanoporous surfaces underneath water droplets using atomic force microscopy. Detailed three-dimensional imaging of the droplet-surface contact region reveals that water only slightly penetrates into the nanopores, allowing for quantitative prediction of the macroscopic contact angle using the Cassie-Baxter model. By gradually increasing the scanning force, we observe incrementally wetting of nanopores by water, and dewetting occurs when the force is lowered again, exhibiting reversible wetting-dewetting transitions. Further, nanoindentation measurements demonstrate that the nanomenisci show apparent elastic deformation and size-dependent effective stiffness at small indenting forces. Finally, we correlate the effective stiffness of the nanomenisci with the transition from complete rebound to partial rebound for impinging droplets on nanoporous surfaces. Our study suggests that probing the physical properties of the liquid-air menisci at the nanoscale is essential to rationalize macroscopic static and dynamic wetting phenomena on structured surfaces.