ABSTRACT
Interfaces between aqueous solutions and hydrophobic solid surfaces are important in various areas of science and technology. Many researchers have found that forces between hydrophobic surfaces in aqueous solution are significantly different from the classical DLVO theory. Long-range attractive forces (non-DLVO forces) are thought to be affected by nanoscopic gaseous domains at the interfaces. This is a review of the latest research on nanobubbles at hydrophobic surfaces from experimental and simulation studies. The review focusses on non-intrusive optical view of surface nanobubbles and gas enrichment on solid surfaces by imaging and force mapping. By use of these recent experimental data in conjunction with molecular simulation work, all major theories on surface nanobubble formation and stability are critically reviewed. Even though the current body of research cannot comprehensively explain all properties of surface nanobubbles observed, the fundamental understanding has been significantly improved. Line tension has been shown to be incapable of explaining the contact angle of nanobubbles. Dense gas layer theory provides a new explanation on both large contact angle and long-time stability. The high density of gas in these domains may significantly affect the gas-water interface which is in line with some observation made on bulk nanobubbles. Along this line of inquiry, experimental and simulation effort should be focussed on measuring the density within surface nanobubbles and the properties of the gas water interface which may be the key to explaining the stability of these nanobubbles.
ABSTRACT
Interfacial gas enrichment (IGE) covering the entire area of hydrophobic solid-water interface has recently been detected by atomic force microscopy (AFM) and hypothesized to be responsible for the unexpected stability and anomalous contact angle of gaseous nanobubbles and the significant change from DLVO to non-DLVO forces. In this paper, we provide further proof of the existence of IGE in the form of a dense gas layer (DGL) by molecular dynamic simulation. Nitrogen gas adsorption at the water-graphite interface is investigated using molecular dynamic simulation at 300 K and 1 atm normal pressure. The results show that a DGL with a density equivalent to a gas at pressure of 500 atm is formed and equilibrated with a normal pressure of 1 atm. By varying the number of gas molecules in the system, we observe several types of dense gas domains: aggregates, cylindrical caps, and DGLs. Spherical cap gas domains form during the simulation but are unstable and always revert to another type of gas domain. Furthermore, the calculated surface potential of the DGL-water interface, -17.5 mV, is significantly closer to 0 than the surface potential, -65 mV, of normal gas bubble-water interface. This result supports our previously stated hypothesis that the change in surface potential causes the switch from repulsion to attraction for an AFM tip when the graphite surface is covered by an IGE layer. The change in surface potential comes from the structure change of water molecules at the DGL-water interface as compared with the normal gas-water interface. In addition, the contact angle of the cylindrical cap high density nitrogen gas domains is 141°. This contact angle is far greater than 85° observed for water on graphite at ambient conditions and much closer to the 150° contact angle observed for nanobubbles in experiments.
