The formation of very small gas bubbles (so-called "nanobubbles") at structured solid-water interfaces has been studied using the tapping mode atomic force microscopy (TMAFM) imaging technique. Silicon oxide wafer surfaces were prepared with different degrees of nanometer scale surface roughness and hydrophobicity. Small bubbles do not form on smooth, hydrophilic, or dehydroxylated silicon oxide wafer surfaces immersed in aqueous solutions under known levels of gas supersaturation. Randomly distributed 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 × 10 -10 N and acts to stabilize the small bubbles, flattening them and thereby reducing the Laplace pressure.

The kinetics of adsorption of CO(2) molecules dissolved in aqueous solution onto a hydrophobised silica surface were investigated using a quartz crystal microbalance (QCM). The results of this investigation were compared with those obtained earlier from tapping mode atomic force microscopy (TMAFM) under the same experimental conditions (J. Yang, J. Duan, D. Fornasiero, J. Ralston, J. Phys. Chem. B., 2003, 107(25), 6139-6147; ref. 1). The QCM results represent the early stage of CO(2) gas adsorption (<20 min), before CO(2) gas bubbles adsorbed on the surface can be directly observed by TMAFM. The QCM results confirmed our observation from TMAFM imaging: that CO(2) gas molecules present in solution only adsorb on silica when its surface is hydrophobic. More importantly, the results showed that gas adsorption/bubble growth undergoes two consecutive kinetic processes: a slow and a fast adsorption process.

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