Interaction forces between oil-water particle interfaces--non-DLVO forces

The interaction force between a rigid silica sphere and a butyl or octyl acetate droplet was measured in an aqueous environment using atomic force microscopy (AFM). The force measurements were performed without added stabilizers and the observed force behavior was found to be dependent on the type of inorganic electrolyte present, where the interfacial tension was constant over the electrolyte concentration range used. Force measurements in the presence of sodium nitrate showed repulsion at all concentrations. Force measurements in the presence of calcium nitrate or sodium perchlorate exhibited an initial repulsion followed by an attraction resulting in a mechanical instability in the AFM cantilever, termed jump-in. The force behavior observed was independent of the water solubility of the organic liquid, in that the same force-distance characteristics were obtained for slightly water soluble butyl acetate and the water sparingly soluble octyl acetate droplets. Modeling of the drop profile during particle-droplet interactions for this type of AFM measurement showed that the force-distance data for the sodium nitrate system obeys typical DLVO interactions. The disagreement between the DLVO predictions for the sodium perchlorate and calcium nitrate systems is attributed to a specific ion effect at the liquid-liquid interface, which gives rise to an attraction force that is greater than the electrostatic double layer repulsion over the length scale of 5 to 10 nm.