Correlation between Electrostatic and Hydration Forces on Silica and Gibbsite Surfaces: An Atomic Force Microscopy Study

[Image: see text] The balance between hydration and Derjaguin–Landau–Verwey–Overbeek (DLVO) forces at solid–liquid interfaces controls many processes, such as colloidal stability, wetting, electrochemistry, biomolecular self-assembly, and ion adsorption. Yet, the origin of molecular scale hydration forces and their relation to the surface charge density that controls the continuum scale electrostatic forces is poorly understood. We argue that these two types of forces are largely independent of each other. To support this hypothesis, we performed atomic force microscopy experiments using intermediate-sized tips that enable the simultaneous detection of DLVO and molecular scale oscillatory hydration forces at the interface between composite gibbsite:silica–aqueous electrolyte interfaces. We extract surface charge densities from forces measured at tip–sample separations of 1.5 nm and beyond using DLVO theory in combination with charge regulation boundary conditions for various pH values and salt concentrations. We simultaneously observe both colloidal scale DLVO forces and oscillatory hydration forces for an individual crystalline gibbsite particle and the underlying amorphous silica substrate for all fluid compositions investigated. While the diffuse layer charge varies with pH as expected, the oscillatory hydration forces are found to be largely independent of pH and salt concentration, supporting our hypothesis that both forces indeed have a very different origin. Oscillatory hydration forces are found to be distinctly more pronounced on gibbsite than on silica. We rationalize this observation based on the distribution of hydroxyl groups available for H bonding on the two distinct surfaces.