The structure of two model room temperature ionic liquids, [BMIM](+)[PF(6)](-) and [BMIM](+)[BF(4)](-), near the solid/liquid interface with charged Al(2)O(3)(0001) (sapphire) was determined with subnanometer resolution by high energy (72.5 keV) x-ray reflectivity. [BMIM](+)[PF(6)](-) exhibits alternately charged, exponentially decaying, near-surface layering. By contrast, the smaller-anion compound, [BMIM](+)[BF(4)](-), shows only a single layer of enhanced electron density at the interface. The different layering behaviors, and their characteristic length scales, correspond well to the different bulk diffraction patterns, also measured in this study. Complementary measurements of the surface and interface energies showed no significant different between the two RTILs. The combined bulk-interface results support the conclusion that the interfacial ordering is dominated by the same electrostatic ion-ion interactions dominating the bulk correlations, with hydrogen bonding and dispersion interactions playing only a minor role.
Capillary forces can significantly contribute to the adhesion of biological and artificial micro- and nanoscale objects. In this paper, we study numerically the effect of meniscus size on the force between two homogeneous flat plates for different contact angles. The force distance curves show excellent quantitative agreement with previous investigations. The results for n menisci of equal total liquid volume reveal interesting scaling properties and an unexpected maximum force for moderately hydrophilic surfaces (i.e., contact angles around 70 degrees ). Further, we calculate the minimum solid-liquid area for multiple bridges, the cohesive stress (i.e., force per area) between the plates, and the work required to separate them. The results are presented in two-dimensional maps, which may be useful in the understanding of biological attachment structures and in the design of artificial contact systems.
Motivated by experimental results, we present numerical and analytical calculations of the capillary force exerted by a capillary bridge spanning the gap between two parallel flat plates of asymmetric wettability. Depending on whether the sum of the two contact angles is smaller or larger than 180 degrees, the capillary force is either attractive or repulsive at small separations D between the plates. In either cases the magnitude of the force diverges as D approaches zero. The leading order of this divergence is captured by an analytical expression deduced from the geometry of the meniscus of a flat capillary bridge. The results for substrates with different wettability reveal an interesting behavior: with the sum of the contact angles fixed, the magnitude of the capillary force and the rupture separation decreases as the asymmetry in contact angles is increased. In addition, we present the rupture separation, i.e., the maximal extension of a capillary bridge, as a function of the contact angles. Our results provide an extensive picture of surface wettability effects on capillary adhesion.
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