The silicon wafer hydrophobized with OTS was immersed into water to observe the surface in-situ by tapping-mode AFM. A large number of nano-size domain images were found on the surface. Their shapes were characterized by the height image procedure of AFM, and the differences of the properties compared to those of the bare surface were analyzed using the phase image procedure and the interaction force curves. All the results consistently implied that the domains represent the nanoscopic bubbles attached on the surface. This was confirmed by the fact that no domain was observed in the case of the surfaces hydrophobized in the AFM fluid cell without exposure to air. The apparent contact angle of the bubbles was much smaller than that expected macroscopically, which was postulated to be the reason bubbles were able to sit stably on the surface.
To clarify the origin of the long-range attraction between hydrophobic surfaces in water, the interaction between the surfaces silanated by the popular method (type I) and that between the surfaces silanated without exposing to air (type II) were examined using an atomic force microscope (AFM) and their characteristics were compared. The interaction between type I surfaces was long-ranged, and a discontinuous step appeared in the approaching and separating force curves, respectively, whereas the interaction between type II surfaces was short-ranged and no step was found. Once type II surfaces were exposed to air, however, the similar interaction to that for type I surfaces appeared. As for type I surfaces, the force curves depended on the local property of the surface, and the interaction in the first cycle of force measurements differed from those in the later cycles. These findings enabled us to estimate the following mechanism for the long-range attraction. When surfaces are hydrophobized, they are usually exposed to air during the hydrophobizing reaction or in the drying process. Then they are immersed in water to measure the interaction without removing microscopic bubbles on the surfaces completely. These bubbles coalesce before the surfaces contact and generate a strong long-range interaction. Hence, this interaction is not the genuine hydrophobic attraction.
Adsorption of hydrated cations on hydrophilic surfaces has been related to a variety of phenomena associated with the short-range interaction forces and mechanisms of the adhesive contact between the surfaces. Here we have investigated the effect of the adsorption of cations on the lateral interaction. Using lateral force microscopy (LFM), we have measured the friction force between a silica particle and silica wafer in pure water and in electrolyte solutions of LiCl, NaCl, and CsCl salts. A significant lubrication effect was demonstrated for solutions of high electrolyte concentrations. It was found that the adsorbed layers of smaller and more hydrated cations have a higher lubrication capacity than the layers of larger and less hydrated cations. Additionally, we have demonstrated a characteristic dependence of the friction force on the sliding velocity of surfaces. A mechanism for the observed phenomena based on the microstructures of the adsorbed layers is proposed.
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