A History of Nanobubbles.

The effect of ultrasound on bulk and surface nanobubbles: A review of the current status

Surface nanobubbles are experimentally known to survive for days at hydrophobic surfaces immersed in gas-oversaturated water. This is different from bulk nanobubbles, which are pressed out by the Laplace pressure against any gas oversaturation and dissolve in submilliseconds, as derived by Epstein and Plesset [J. Chem. Phys. 18, 1505 (1950)]. Pinning of the contact line has been speculated to be the reason for the stability of the surface nanobubbles. Building on an exact result by Popov [Phys. Rev. E 71, 036313 (2005)] on coffee stain evaporation, here we confirm this speculation by an exact calculation for single surface nanobubbles. It is based only on (i) the diffusion equation, (ii) Laplace pressure, and (iii) Henry's equation, i.e., fluid dynamical equations which are all known to be valid down to the nanometer scale. The crucial parameter is the gas oversaturation ζ of the liquid. At the stable equilibrium, the gas overpressures due to this oversaturation and the Laplace pressure balance. The theory predicts how the contact angle of the pinned bubble depends on ζ and the surface nanobubble's footprint lateral extension L. It also predicts an upper lateral extension threshold for stable surface nanobubbles to exist.

Using molecular dynamics simulations, the effects of gas concentration and species on the coalescence and growth of nanobubbles were systematically investigated. With increasing gas concentration, not only surface nanobubbles but also bulk nanobubbles are formed. The bulk nanobubble in water is less explored so far. Here, its coalescence, stability, movement trajectory and velocity are discussed. A comparison of the motion and coalescence of the bulk nanobubble to the surface nanobubble, directly demonstrates that the three-phase contact line plays a crucial role for surface nanobubble stability. Compared with the bubble size, the distance between surface nanobubbles is a more important factor to decide the merging order among three nanobubbles. The study also shows that three factors including the oversaturated gas concentration, the distance between surface nanobubbles, and the stronger solid-gas interactions influence the formation of the gas-enrichment layer at the solid-liquid interface. The result has an important significance to enhancing the boundary slip due to the presence of nanobubbles.

Progress on the Surface Nanobubble Story: What is in the bubble? Why does it exist?

Stability of surface and bulk nanobubbles

Nanobubble technology has found extensive use in enhancing the flotation efficiency of various minerals. The utilization of nanobubbles in flotation encompasses bulk nanobubbles, surface nanobubbles, and microbubbles; however, a comprehensive comparison of their respective roles is lacking. Furthermore, there is a dearth of studies on employing nanobubble systems in the flotation of coal fly ash. The coal fly ash characters were initially studied to reveal its ultrafine size (d50: 24.80 μm) and porous structure that includes a multitude of hydrophilic functional groups. These attributes contribute to the inadequate hydrophobicity of unburned carbon within the ash. Subsequently, the effects of different collector types, frother types, and air flow rates on the efficiency of carbon removal using conventional flotation methods were examined. Comparative analysis showed that conventional flotation using diesel oil outperformed that which employed kerosene as the collector. Additionally, higher carbon removal efficiency was achieved using MIBC, with a longer carbon chain length, as the frother, as opposed to sec-Octyl alcohol. Furthermore, a direct relationship between air flow rate and coal fly ash flotation performance was observed – higher air flow rates corresponded to improved flotation outcomes. Finally, a comparison between conventional flotation and nanobubble-assisted flotation (utilizing bulk nanobubbles, surface nanobubbles, and micro-nanobubbles) was conducted. Remarkably, micro-nanobubble flotation yielded the most promising results, with the lowest loss-on-ignition in flotation tailings (3.15%) and the highest removal efficiency of unburned carbon (85.01%). These findings satisfied the loss-on-ignition requirements of Grade I fly ash standards.

The nucleation of nanobubbles was studied through molecular dynamics (MD) simulations. The wettability and surface atomic-level structural features of the substrate were found to play a role in a ternary (solid, liquid, and gas) system that was composed of only simple Lennard-Jones fluids. The simulation first revealed that surface nanobubbles form only on a hydrophobic substrate, while for a hydrophilic substrate, bulk nanobubbles are formed in the liquid. Second, the existence form of nanobubbles and some behavioral characteristics strongly depend on the surface structural features. Specifically, we deduced the phase diagram of the nanobubbles with respect to the critical structural parameters and then defined a critical region for the formation of surface nanobubbles: cap-shaped surface nanobubbles can stably form above the upper critical line but not below the lower critical line; the contact angle decreases as the parameter value increases. Finally, the existence of nanobubbles was found to affect the dynamic properties of the system.

Gas micronuclei are gas-filled voids in liquids from which bubbles can form at low gas supersaturation. If water is depleted of gas micronuclei, high gas supersaturation is required for bubble formation. This high gas supersaturation is required in part to overcome the Laplace pressure at the point of transition from dissolved gas to a bubble of perhaps nanometer-scale radius. The sum of gas and vapour partial pressures inside a spherical bubble (Pbub) of radius r exceeds the ambient barometric pressure (Pamb) and is given by the Young-LaPlace equation: Pbub = Pamb + 2γ/r for a bubble not in contact with a solid surface. The second term on the right-hand side is the Laplace pressure across the gas-liquid interface due to surface tension (γ). For instance, for a surface tension characteristic of blood of 0.056 N·m⁻¹, de novo formation of a bubble of r = 10 nm requires gas supersaturation exceeding 2γ/r = 11.2 MPa. However, in humans, detectable venous gas bubbles follow decompression to sea level from as shallow as 138 kPa air saturation, implying gas supersaturation of only a few kPa are required for decompression bubble formation. It is widely accepted that bubbles that form at such low gas supersaturation grow from pre-existing, micron-scale gas micronuclei. For such gas micronuclei to already exist prior to gas supersaturation they cannot simply be small bubbles because positive feedback of Laplace pressure causes a micron radius bubble to dissolve in a fraction of a second. Theoretical candidates for gas micronuclei are bubbles coated in surfactants that counteract the Laplace pressure or crevices where gas voids assume shapes that negate the Laplace pressure. However, to date, the nature of gas micronuclei that underly decompression-induced bubbles and decompression sickness have yet to be identified. Consequently, I was intrigued that in two previous issues of Diving and Hyperbaric Medicine (2018 Volume 48, Issue 2, page 114 and Issue 3, page 197), letters from Ran Arieli to the Editor hypothesized a mechanism for decompression bubble formation in blood vessels and in the skin. Both letters stated "It is known that nanobubbles form spontaneously when a smooth hydrophobic surface is submerged in water containing dissolved gas. We have shown that nanobubbles are the gas micronuclei underlying decompression bubbles and decompression sickness". Surface nanobubbles have been extensively described in the physical chemistry literature, but the second sentence is supported by citation of an hypothesis article. The latter is based on experimental work (referenced therein) in which sections of large blood vessels from sheep were incubated in saline and compressed to 1.013 MPa for 18 hours then rapidly decompressed to the surface, whereupon macroscopic bubbles were photographed forming on the luminal surface of the vessels. The authors speculate that the bubbles were forming from surface nanobubbles on the vessel lumen, but no experimental or analytical evidence was presented that surface nanobubbles were present on the vessel lumen or were the precursors of the observed macroscopic bubbles. Surface nanobubbles form on atomically smooth, hard surfaces in gas supersaturated liquids and, imaged with atomic force microscopy, appear as spherical caps of gas. As far as I can determine, surface nanobubbles have not been reported on biological tissue surfaces. Surface nanobubbles typically have diameters less than 100 nanometers but have lifetimes that are orders of magnitude longer than would a bubble of similar dimensions. Surface nanobubbles do not grow into macroscopic bubbles when exposed to pressure waves sufficient to cause bubble formation from adventitious gas micronuclei elsewhere in the apparatus. This is surely not the last word in this new and active field of research into nanoscopic gas species; however, based on current evidence one must treat with skepticism speculation that unobserved surface nanobubbles are the gas micronuclei from which bubbles form in humans with low gas supersaturation and which underlie decompression sickness.

Surface and bulk nanobubbles are two types of nanoscopic gaseous domain that have recently been discovered in interfacial physics. Both are expected to be unstable to dissolution because of the high internal pressure driving diffusion and the surface tension which squeezes the gas out, but there is a rapidly growing body of experimental evidence that demonstrates both bubble types to be stable. However, the two types of bubbles also differ in many respects: surface nanobubble stability is most probably assisted by the nearby wall, which can repel the water (in the case of hydrophobicity), accept physisorbed gas molecules, and reduce the surface area through which outfluxing can occur; bulk nanobubbles, on the other hand, must stabilise themselves. This is perhaps through ionic shielding, perhaps through diffusive shielding, or perhaps through both. Herein, the features of both bubble types are described individually, their common and disparate features are discussed, and emerging applications are examined.

Surface nanobubbles are nanoscopic gaseous domains on immersed substrates which can survive for days. They were first speculated to exist about 20 years ago, based on stepwise features in force curves between two hydrophobic surfaces, eventually leading to the first atomic force microscopy (AFM) image in 2000. While in the early years it was suspected that they may be an artifact caused by AFM, meanwhile their existence has been confirmed with various other methods, including through direct optical observation. Their existence seems to be paradoxical, as a simple classical estimate suggests that they should dissolve in microseconds, due to the large Laplace pressure inside these nanoscopic spherical-cap-shaped objects. Moreover, their contact angle (on the gas side) is much smaller than one would expect from macroscopic counterparts. This review will not only give an overview on surface nanobubbles, but also on surface nanodroplets, which are nanoscopic droplets (e.g., of oil) on (hydrophobic) substrates immersed in water, as they show similar properties and can easily be confused with surface nanobubbles and as they are produced in a similar way, namely, by a solvent exchange process, leading to local oversaturation of the water with gas or oil, respectively, and thus to nucleation. The review starts with how surface nanobubbles and nanodroplets can be made, how they can be observed (both individually and collectively), and what their properties are. Molecular dynamic simulations and theories to account for the long lifetime of the surface nanobubbles are then reported on. The crucial element contributing to the long lifetime of surface nanobubbles and nanodroplets is pinning of the three-phase contact line at chemical or geometric surface heterogeneities. The dynamical evolution of the surface nanobubbles then follows from the diffusion equation, Laplace's equation, and Henry's law. In particular,

The development of the interfacial gas enrichment layer at the solid-liquid interface is coupled with the stability of surface nanobubbles. Depending upon the concentration of gas molecules, solid-liquid-gas interaction strengths, and other thermodynamic parameters, gas molecules can take several different forms such as dense gas layer, bulk and surface nanobubble, and other gaseous domains. Using molecular dynamics simulations we study the characteristics of gas accumulation into a dense gas layer, surface nanobubble and local gas aggregation at the graphene-water interface with no pinning sites. We find that gas molecules can migrate over the solid surface and can collect together to take the morphological form of a surface nanobubble. The developed nanobubble is mobile and can move over the homogeneous hydrophobic solid surface without losing its shape. We find that the gas adsorption on surfaces in the presence of a solvent is strongly affected by the wetting characteristics of the solid. In the absence of a solvent, gas adsorption is found to be universal for all surface types. Individual gas adsorption is found to be prominent and occurs in a short period, and is essential for the stability of the formed gaseous domains. Simulation results show gas adsorption density on surfaces to have a strong dependence on the solid-liquid interaction parameter than on solid-gas interaction strength.

Surface nanobubbles should not be stable for more than a few milliseconds; however they have been shown to persist for days. Pinning of the three-phase contact line of surface nanobubbles has been proposed to explain the discrepancy between the theoretical and experimental results. According to this model, two factors stabilize surface nanobubbles, namely solution oversaturation and surface pinning. Hereby, we investigate experimentally the impact of the solution saturation on the stability of nanobubbles. For this purpose, surface nanobubbles have been nucleated on hydrophobic surfaces by two methods, and then characterized by Atomic Force Microscopy (AFM). Thereafter, the surrounding liquid has been exchanged multiple times with partially degassed water. Two degassing techniques are presented. Both sets of experiments lead to the conclusion that surface nanobubbles are stable in undersaturated conditions for hours. We compare the measured lifetime of nanobubbles to calculations for pinned nanobubbles in undersaturated conditions. The stability of surface nanobubbles in undersaturated solutions observed here is incommensurate with the pinning mechanism as the origin of the long-term stability of surface nanobubbles.

Computational investigation of the stability and dissolution of nanobubbles

Nanobubbles are expected to dissolve in milliseconds. Experimental evidence of nanobubbles that were stable for days had thus been first received with circumspection. If the large number of experimental confirmations has now made clear that surface nanobubbles could exist, bulk nanobubbles are still subject to debate. When observations are reported, the main problem is to make sure the observed particles are really made of gas. We show that ultrasound is an ideal tool for investigating the existence of bulk nanobubbles: 1) it is sensitive to minute quantities of gas, 2) it allows one to determine the bubble size distribution, 3) it discriminates unambiguously between gaseous and solid/liquid inclusions. To illustrate the efficiency of ultrasonic detection, we performed size measurements of bubbles produced by a commercial nano-/microbubble generator. No nanobubble was detected with this device. It would be insightful to use ultrasonic detection in experimental situations for which stable nanobubbles were reported.

Nanobubble Dynamics in Aqueous Surfactant Solutions Studied by Liquid-Phase Transmission Electron Microscopy