The fate of bulk nanobubbles under gas dissolution

Artificially added or undesired organic and inorganic contaminants in solution that are interfacially active always tend to be adsorbed at the gas-liquid interface of micro- and nano-bubbles, affecting the stability of the tiny bubbles. In this work, by using molecular dynamics simulations we study how the adsorbed surfactant-like molecules, with their amphiphilic character, affect the dissolution of the existing bulk nanobubbles under low gas supersaturation environments. We find that, depending on the concentration of the dissolved gas and the molecular structure of surfactants, two fates of bulk nanobubbles whose interfaces are saturated by surfactants are found: either remaining stable or being completely dissolved. With gas dissolution, the bubble shrinks and the insoluble surfactants form a monolayer with an increasing areal density until an extremely low (close to 0) surface tension is reached. In the limit of vanishing surface tension, the chemical structure of surfactants crucially affects the bubble stability by changing the monolayer elastic energy. Two basic conditions for stable nanobubbles at low gas saturation are identified: vanishing surface tension due to bubble dissolution and positive spontaneous curvature of the surfactant monolayer. Based on this observation, we discuss the similarity in the stability mechanism of bulk nanobubbles and that of microemulsions.