Adhesion forces between glass and silicon surfaces in air studied by AFM: Effects of relative humidity, particle size, roughness, and surface treatment

Using the atomic force microscope (AFM), the pull-off forces between flat glass or silicon surfaces and silicon AFM tips or glass microspheres of different sizes have been extensively studied as a function of relative humidity (RH) in the range 5-90%, as model systems for the behavior of cohesive powders. The glass and silicon substrates were treated to render them either hydrophobic or hydrophilic. All the hydrophilic surfaces gave simple force curves and pull-off forces increasing uniformly with RH. Small contacts (R 20 nm) gave pull-off forces close to values predicted by simple Laplace-Kelvin theory (similar to20 nN), but the values with microspheres (R similar to 20 mum) fell well below predictions for sphere-flat or sphere-sphere geometry, due to roughness and asperity contacts. The hydrophobic silicon surfaces also exhibited simple behavior, with no significant RH dependence. The pull-off force again fell well below predicted values (Johnson-Kendall-Roberts contact mechanics theory) for the larger contacts. Hydrophobic glass gave similar adhesion to silicon over most of the RH range, but against both silicon tips and glass microspheres, there was an anomalously large adhesion in the RH range 20-40%, accompanied by a long-range noncontact force. The adhesion on fully hydrophilic surfaces and its RH dependence can be mostly explained by current theories of capillary bridges, but the interpretation is complicated by the sensitivity of theoretical predictions to contact geometry (and hence to roughness effects) and by uncertainties in the thickness of adsorbed water layers. The anomalous behavior on hydrophobic glass surfaces at intermediate values of RH is not fully understood, but possible causes are (1) dipole layers in the partially formed water film, giving rise to patch charges and long-range forces, or (2) fixed charges at a reactive glass surface, involving specific bonding reactions. The results may be useful in explaining the behavior of cohesive powders with different coatings or those which show a large humidity dependence (e.g., zeolites) or show electrostatic charging effects (e.g., silica aerogels).