Quantifying interfacial tensions of surface nanobubbles: How far can Young's equation explain?†
Nanobubbles at solid–liquid interfaces play a key role in various physicochemical phenomena and it is crucial to understand their unique properties. However, little is known about their interfacial tensions due to the lack of reliable calculation methods. Based on mechanical and thermodynamic insights, we quantified for the first time the liquid–gas, solid–liquid, and solid–gas interfacial tensions of submicron-sized nitrogen bubbles at graphite–water interfaces using molecular dynamics (MD) analysis. It was revealed that Young's equation holds even for nanobubbles with different radii. We found that the liquid–gas and solid–liquid interfacial tensions were not largely affected by the gas density inside the nanobubbles. In contrast, the size effect on the solid–gas interfacial tension was observed, namely, the value dramatically decreased upon an increase in the gas density due to gas adsorption on the solid surface. However, our quantitative evaluation also revealed that the gas density effect on the contact angles is negligible when the footprint radius is larger than 50 nm, which is a typical range observed in experiments, and thus the flat shape and stabilization of submicron-sized surface bubbles observed in experiments cannot be explained only by the changes in interfacial tensions due to the van der Waals interaction-induced gas adsorption, namely by Young's equation without introducing the pinning effect. Based on our analysis, it was clarified that additional factors such as the differences in the studied systems are needed to explain the unresolved open issues – a satisfactory explanation for the nanobubbles in MD simulations being ultradense, non-flat, and stable without pinning.