Dissolved Gas. Very Small Bubbles, and Interparticle Interactions

The colloidal stability of synthetic silica spheres with clean, methylated and dehydroxylated sur¬faces was studied at different concentrations of dissolved gas and KCl electrolyte at a fixed pH of 4.2. A classic stability ratio/electrolyte concentration analysis shows that hydrophobic, methy¬lated particles undergo faster rates of aggregation with increasing concentrations of dissolved carbon dioxide. Similar data for hydrophilic particles and dehydroxylated particles show no change as a function of dissolved carbon dioxide concentration. Zeta potential data behave simi¬larly, showing a strong influence of dissolved gas only for methylated particles. The results are interpreted in terms of DLVO theory, with the surface-to-surface interaction dominated by the presence of very small protruding bubbles. Direct evidence for the existence of these very small gas bubbles (or "nanobubbles") was obtained using tapping mode atomic force microscopy. Small bubbles do not form on smooth, hydrophilic, or dehydroxylated silicon oxide water sur¬faces immersed in aqueous solutions under known levels of gas supersaturation. Randomly dis¬tributed small bubbles were observed over the whole surface of observation on methylated surfaces of controlled roughness. Bubbles formed on rough, methylated surfaces were larger and less-densely distributed than those on a smooth surface of similar hydrophobicity. The process of bubble coalescence was observed as a function of time. The macroscopic contact angle, measured with respect to the aqueous or gas phase, is very different from the microscopic contact angle detected by TMAFM and appears to be due to the influence of line tension at the pinned three¬phase contact line. The latter has a value of -3 x 10-10 N and acts to stabilize the small bubbles, flattening them and thereby reducing the Laplace pressure.