Stable bulk nanobubbles can be regarded as gaseous analogues of microemulsions

Abstract

In our previous work [2022 Phys. Chem. Chem. Phys. 24 9685], we used molecular dynamics simulations to show that bulk nanobubbles can be stabilized by forming a compressed amphiphile monolayer at bubble interfaces. This observation closely matches the origin of stability of microemulsions and inspired us to propose here that, in certain cases, stable bulk nanobubbles can be regarded as gaseous analogues of microemulsions: the nanobubble phase and the bubble-containing solution phase coexist with the external gas phase. This three-phase coexistence is then validated by molecular dynamics simulations. The stability mechanism for bulk nanobubbles is thus given: the formation of a compressed amphiphilic monolayer because of microbubble shrinking leads to a vanishing surface tension, and consequently the curvature energy of the monolayer dominates the thermodynamic stability of bulk nanobubbles. With the monolayer model, we further interpret several strange behaviors of bulk nanobubbles: gas supersaturation is not a prerequisite for nanobubble stability because of the vanishing surface tension, and the typical nanobubble size of 100 nm can be explained through the small bending constant of the monolayer. Finally, through analyzing the compressed amphiphile monolayer model we propose that bulk nanobubbles can exist ubiquitously in aqueous solutions.