Stability Of Surface Nanobubbles Research Articles

Enrichment of surface charge contributes to the stability of surface nanobubbles

Surface nanobubbles are spontaneously formed at the interface between hydrophobic surfaces and aqueous solutions, which show extraordinarily longer lifetime than that was predicted by the classical thermodynamics model. In the present work, by using a surface plasmon resonance microscopy (SPRM) to quantitatively measure the dissolution kinetics of individual surface nanobubbles in real time, we explored the effects of ionic strength and pH value on the dissolution rates (lifetime) of nanobubbles. The results revealed that nanobubbles could exist stably for a long time in low-concentration electrolyte solutions or high-concentration non-electrolyte solutions, while they dissolved quickly in high-concentration electrolyte solutions. With the increase of ionic strength, the dissolution rates were accelerated by 2–3 orders of magnitude, and thus the lifespan of these surface nanobubbles was significantly shortened. In addition to ionic strength, it was further found that, with the increase of acidity or alkalinity of the solution, the dissolution rates of the surface nanobubbles were faster than that in neutral solution. These results demonstrated that the interfacial charge enrichment significantly contributed to the extraordinary stability of the surface nanobubbles.

Experimental investigation on nucleation of surface nanobubbles with polycarbonate hydrophobic surface tested under heterogeneous boiling

The quick evaporation of a liquid coupled with bubble formation on a solid surface, called the heterogeneous boiling is the research topic of many heat transfer researchers. The nanoboiling heat transfer with hydrophobic surfaces results in the formation of surface nanobubbles between the surface and liquid. Here, we investigated the stability of surface nanobubbles at various temperatures up to the saturation temperature of water. The collision of surface nanobubbles produces microdroplets which again forms nanobubbles in contrast to the present nanobubbles theories. Lastly, bursting of nanobubbles and evaporation of microdroplets happens.

The stability and morphology of nanobubbles on homogeneous surfaces with different wettability

Surface nanobubbles were observed to survive with apparent long-term stability and small contact angles in contrast to larger microbubbles. Although the contact line pinning and hydrophobic attraction model can well explain the stability of pinned surface nanobubbles, their experimental morphology features on different surfaces are yet to be presented. With a linearized attraction potential related to surface wettability, in this work, we developed a model that distinguished the stability of nanobubbles and the instability of larger microbubbles reaching diffusive and mechanical equilibrium on homogeneous surfaces. The dynamic evolutions, stability, and morphology of nanobubbles on surfaces with different wettability were investigated. Its results demonstrated that bubbles with different initial sizes and gas oversaturation would present four dynamic states: shrinkage to dissolution, shrinkage or growth to the stable equilibrium, and expansion to burst. The bubbles at stable equilibrium have typical footprint radius ranges, limited heights, and small contact angles, as measured in experiments. Furthermore, with the increase in hydrophobicity, the stable contact radius of nanobubbles becomes larger while the required degree of gas saturation is alleviated. At the same contact radius, the height and contact angle of the bubble on hydrophilic surface are larger than that on hydrophobic surface, both increasing with the growing contact radius. These theoretical predictions are consistent with experimental observations and would be meaningful to understand the stability of surface nanobubbles.

Nanoscale gas accumulation at solid-liquid interfaces: a molecular dynamics study.

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.

Effects of Surface Tension on the Stability of Surface Nanobubbles

The existence of surface nanobubbles has already been confirmed by variable detection methods, but the mechanism of their extraordinary stability remains unclear and has aroused widespread research interest in the past 2 decades. Experiments and theoretical analyses have tried to account for these stabilities such as the very long lifetime, very high pressure and very small contact angle. Attractive hydrophobic potential was applied to complement the pinning-oversaturation theory and successfully explain the survival of surface nanobubbles in undersaturation environment by some researchers. However, the survival of nanobubbles on hydrophilic surface still requires sizeable oversaturation. In this paper, we introduce the variable surface tensions, namely Tolman-dependence and state-dependence, and show that they effectively promote the stability of nanobubbles. The decrease in surface tension can lead to larger contact angle and even make the nanobubbles survivable on the highly hydrophilic surface. In Tolman-dependence, the changing rate in the contact angle evolution slows down, which is more obvious when the bubble size is close to the Tolman length. The contact angle is also getting larger in the state-dependence, and the increase of the gas saturation degree is beneficial to the stability of surface nanobubbles. With the gas saturation ratio of 3, the bubbles on the quite hydrophilic surface can also be stable, while grow up on the hydrophobic surface. The variable surface tensions weaken the need of saturation degree for the surface nanobubbles’ stability.

Stability of pinned surface nanobubbles against expansion: Insights from theory and simulation

While growth and dissolution of surface nanobubbles have been widely studied in recent years, their stability under pressure changes or a temperature increase has not received the same level of scrutiny. Here, we present theoretical predictions based on classical theory for pressure and temperature thresholds (pc and Tc) at which unstable growth occurs for the case of air nanobubbles on a solid surface in water. We show that bubbles subjected to pinning have much lower pc and higher Tc compared to both unpinned and bulk bubbles of similar size, indicating that pinned bubbles can withstand a larger tensile stress (negative pressure) and higher temperatures. The values of pc and Tc obtained from many-body dissipative particle dynamics simulations of quasi-two-dimensional (quasi-2D) surface nanobubbles are consistent with the theoretical predictions, provided that the lateral expansion during growth is taken into account. This suggests that the modified classical thermodynamic description is valid for pinned bubbles as small as several nanometers. While some discrepancies still exist between our theoretical results and previous experiments, further experimental data are needed before a comprehensive understanding of the stability of surface nanobubbles can be achieved.

Role of substrate softness in stabilizing surface nanobubbles

The contact line pinning and supersaturation theory for the nanobubble stability has attracted extensive concerns from experimental investigators, and some experimenters argue that the contact line pinning is unnecessary. To interpret the experimental observations, we have proposed previously through molecular dynamics simulations that the deformation of soft substrates caused by surface nanobubbles may play an important role in stabilizing surface nanobubbles, while yet no quantitative theory is available for explanation of this mechanism. Here, the detailed mechanism of self-pinning-induced stability of surface nanobubbles is investigated through theoretical analysis. By manipulating substrate softness, we find that the formation of surface nanobubbles may create a deformation ridge nearby their contact lines which leads to the self-pinning effect. Theoretical analysis shows that the formation of nanobubbles on sufficiently rigid substrates or on liquid–liquid interfaces corresponds to a local free energy maximum, while that on the substrates with intermediate softness corresponds to a local minimum. Thus, the substrate softness could regulate the surface nanobubble stability. The critical condition for the self-pinning effect is determined based on contact line depinning, and the effect of gas supersaturation is explored. Finally, the approximate stability range for the surface nanobubbles is also predicted.

Ultrahigh Density of Gas Molecules Confined in Surface Nanobubbles in Ambient Water

To understand the unexpected and puzzling long-term stability of nanoscale gas bubbles, it is crucial to probe their nature and intrinsic properties. We report herein synchrotron-based scanning transmission X-ray microscopy (STXM) evidence of highly condensed oxygen gas molecules trapped as surface nanobubbles. Remarkably, the analysis of absorption spectra of a single nanobubble revealed that the oxygen density inside was 1-2 orders of magnitude higher than that in atmospheric pressure, and these bubbles were found in a highly saturated liquid environment with the estimated oxygen concentration to be hundreds of times higher than the known oxygen solubility in equilibrium. Molecular dynamics simulations were performed to investigate the stability of surface nanobubbles on a heterogeneous substrate in gas-oversaturated water. These results indicated that gas molecules within confinement such as the nanobubbles could maintain a dense state instead of the ideal gas state, as long as their surrounding liquid is supersaturated. Our findings should help explain the surprisingly long lifetime of the nanobubbles and shed light on nanoscale gas aggregation behaviors.

The interplay among gas, liquid and solid interactions determines the stability of surface nanobubbles.

Surface nanobubbles are gaseous domains found at immersed substrates, whose remarkable persistence is still not fully understood. Recently, it has been observed that the formation of nanobubbles is often associated with a local high gas oversaturation at the liquid-solid interface. Tan, An and Ohl have postulated the existence of an effective potential attracting the dissolved gas to the substrate and producing a local oversaturation within 1 nm from it that can stabilize nanobubbles by preventing outgassing in the region where gas flow would be maximum. It is this effective solid-gas potential - which is not the intrinsic, mechanical interaction between solid and gas atoms - its dependence on chemical and physical characteristics of the substrate, gas and liquid, that controls the stability and the other characteristics of surface nanobubbles. Here, we perform free energy atomistic calculations to determine, for the first time, the effective solid-gas interaction that allows us to identify the molecular origin of the stability and other properties of surface nanobubbles. By combining the Tan-An-Ohl model and the present results, we provide a comprehensive theoretical framework allowing, among others, the interpretation of recent unexplained experimental results, such as the stability of surface nanobubbles in degassed liquids, the very high gas concentration in the liquid surrounding nanobubbles, and nanobubble instability in organic solvents with high gas solubility.

Stability of Surface Nanobubbles without Contact Line Pinning.

Although the stability of most surface nanobubbles observed can be well interpreted by contact line pinning and supersaturation theory, there is increasing evidence that at least for certain situations, contact line pinning is not required for nanobubble stability. This raises a significant question of what is the stability mechanism for those sessile nanobubbles. Through theoretical analysis and molecular dynamics simulations, in this work, we report two mechanisms for stabilizing surface nanobubbles on flat and homogeneous substrates. One is attributed to constant adsorption of trace impurities on the nanobubble gas?liquid interface, through which nanobubble growing or shrinking causes the increase and decrease of interfacial tension, acting as a restoring force to bring the nanobubble to its equilibrium size. The other is attributed to the deformation of a soft substrate induced by the formed nanobubble, which in turn stabilizes the nanobubble via impeding the contact line motion, similar to self-pinning of microdroplets on soft substrates. Both mechanisms can interpret, depending on the specified conditions, how surface nanobubbles can remain stable in the absence of contact line pinning.

Long-Term Stability of Surface Nanobubbles in Undersaturated Aqueous Solution.

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.

Mechanical Stability of Surface Nanobubbles.

Bubble cavitation is important in technologies such as noninvasive cancer treatment and diagnosis, surface cleaning, and waste-water treatment. The cavitation threshold is the critical external tensile pressure that induces unstable growth of the bubble. Surface nanobubbles have been previously shown experimentally to be stable down to -6 MPa, in disagreement with the Blake threshold, which is the classical cavitation model that predicts bulk bubbles with radii ∼100 nm should be unstable below -0.6 MPa. Here, we use molecular dynamics to simulate quasi-two-dimensional (2D) and three-dimensional (3D) nitrogen surface nanobubbles immersed in water, subject to a range of pressure drops until unstable growth is observed. We propose and assess new cavitation threshold models, derived from mechanical equilibrium analyses for both the quasi-2D and 3D cavitating bubbles. The discrepancies from the Blake threshold are attributed to the pinned contact line, within which the surface nanobubbles grow with constant lateral contact diameter, and consequently a reduced radius of curvature. We conclude with a critical discussion of previous experimental results on the cavitation of relatively large surface nanobubbles.

The properties of surface nanobubbles formed on different substrates**Project supported by the National Natural Science Foundation of China (Grant Nos. 11290165, 11305252, and U1532260), the Knowledge Innovation Program of the Chinese Academy of Sciences, China (Grant No. KJZD-EW-M03), and the Key Research Program of Frontier Sciences, Chinese Academy of Sciences, China (Grant No. QYZDJ-SSW-SLH019).

The properties and stability of the reported surface nanobubbles are related to the substrate used and the generation method. Here, we design a series of experiments to study the influence of the hydrophobicity of the substrate and the production method on the formation and properties of nanobubbles. We choose three different substrates, dodecyltrichlorosilane (DTS) modified silicon, octadecyltrichlorosilane (OTS) modified silicon, and highly oriented pyrolytic graphite (HOPG) as nanobubble substrates, and two methods of ethanol–water exchange and 4-°C cold water to produce nanobubbles. It is found that using ethanol-water exchange method could produce more and larger nanobubbles than the 4-°C cold water method. The contact angle of nanobubbles produced by ethanol–water exchange depends on the hydrophobicity of substrates, and decreases with the increase of the hydrophobicity of substrates. More interestingly, nanoscopic contact angle approaches the macroscopic contact angle as the hydrophobicity of substrates increases. It is believed that these results would be very useful to understand the stability of surface nanobubbles.

Nanobubbles in confined solution: Generation, contact angle, and stability.

The formation of gas bubbles presents a frequent challenge to microfluidic operations, for which fluids are geometrically confined to a microscale space. Here, to understand the mechanism of nucleating gas bubbles in microfluidic devices, we investigate the formation and stability of nanobubbles in confined solutions. Our molecular dynamics simulations show that while pinning of the contact line is a prerequisite for the stability of surface nanobubbles in open systems that can exchange gas with surrounding environment, in confined solutions, stable nanobubbles can exist even without pinning. In supersaturated condition, stable bubbles can be found in confined solutions with acute or obtuse contact angle, depending on the substrate hydrophobicity. We also demonstrate that when open to the bulk solution, the stable nanobubbles in closed systems would become unstable unless both supersaturation and pinning of the contact line are satisfied. Our results not only shed light on the design of novel heterogeneous surfaces for generating nanobubbles in confined space with controllable shape and stability but also address the crucial effect of gas exchange with the surroundings in determining the stability of nanobubbles.

Formation and coalescence of nanobubbles under controlled gas concentration and species

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.

Growth and Detachment of Oxygen Bubbles Induced by Gold-Catalyzed Decomposition of Hydrogen Peroxide.

Whereas bubble growth out of gas-oversatured solutions has been quite well understood, including the formation and stability of surface nanobubbles, this is not the case for bubbles forming on catalytic surfaces due to catalytic reactions, though it has important implications for gas evolution reactions and self-propulsion of micro/nanomotors fueled by bubble release. In this work we have filled this gap by experimentally and theoretically examining the growth and detachment dynamics of oxygen bubbles from hydrogen peroxide decomposition catalyzed by gold. We measured the bubble radius R(t) as a function of time by confocal microscopy and find R(t) ∝ t1/2. This diffusive growth behavior demonstrates that the bubbles grow from an oxygen-oversaturated environment. For several consecutive bubbles detaching from the same position in a short period of time, a well-repeated growing behavior is obtained from which we conclude the absence of noticeable depletion effect of oxygen from previous bubbles or increasing oversaturation from the gas production. In contrast, for two bubbles far apart either in space or in time, substantial discrepancies in their growth rates are observed, which we attribute to the variation in the local gas oversaturation. The current results show that the dynamical evolution of bubbles is influenced by comprehensive effects combining chemical catalysis and physical mass transfer. Finally, we find that the size of the bubbles at the moment of detachment is determined by the balance between buoyancy and surface tension and by the detailed geometry at the bubble’s contact line.

Thermodynamics of Surface Nanobubbles.

In this paper, we examine the thermodynamic stability of surface nanobubbles. The appropriate free energy is defined for the system of nanobubbles on a solid surface submerged in a supersaturated liquid solution at constant pressure and temperature, under conditions where an individual nanobubble is not in diffusive contact with a gas phase outside of the system or with other nanobubbles on the time scale of the experiment. The conditions under which plots of free energy versus the radius of curvature of the nanobubbles show a global minimum, which denotes the stable equilibrium state, are explored. Our investigation shows that supersaturation and an anomalously high contact angle (measured through the liquid) are required to have stable surface nanobubbles. In addition, the anomalously high contact angle of surface nanobubbles is discussed from the standpoint of a framework recently proposed by Koch, Amirfazli, and Elliott that relates advancing and receding contact angles to thermodynamic equilibrium contact angles, combined with the existence of a gas enrichment layer.

AFM Study of Surface Nanobubbles on Binary Self-Assembled Monolayers on Ultraflat Gold with Identical Macroscopic Static Water Contact Angles and Different Terminal Functional Groups.

All experimental findings related to surface nanobubbles, such as their pronounced stability and the striking differences of macroscopic and apparent nanoscopic contact angles, need to be addressed in any theory or model of surface nanobubbles. In this work we critically test a recent explanation of surface nanobubble stability and their consequences and contrast this with previously proposed models. In particular, we elucidated the effect of surface chemical composition of well-controlled solid-aqueous interfaces of identical roughness and defect density on the apparent nanoscopic contact angles. Expanding on a previous atomic force microscopy (AFM) study on the systematic variation of the macroscopic wettability using binary self-assembled monolayers (SAMs) on ultraflat template stripped gold (TSG), we assessed here the effect of different surface chemical composition for macroscopically identical static water contact angles. SAMs on TSG with a constant macroscopic water contact angle of 81 ± 2° were obtained by coadsorption of a methyl-terminated thiol and a second thiol with different terminal functional groups, including hydroxy, amino, and carboxylic acid groups. In addition, surface nanobubbles formed by entrainment of air on SAMs of a bromoisobutyrate-terminated thiol were analyzed by AFM. Despite the widely differing surface potentials and different functionality, such as hydrogen bond acceptor or donor, and different dipole moments and polarizability, the nanoscopic contact angles (measured through the condensed phase and corrected for AFM tip broadening effects) were found to be 145 ± 10° for all surfaces. Hence, different chemical functionalities at identical macroscopic static water contact angle do not noticeably influence the apparent nanoscopic contact angle of surface nanobubbles. This universal contact angle is in agreement with recent models that rely on contact line pinning and the equilibrium of gas outflux due to the Laplace pressure and gas influx due to gas oversaturation in the aqueous medium.

Stability of Surface Nanobubbles: A Molecular Dynamics Study.

The stability and growth or dissolution of a single surface nanobubble on a chemically patterned surface are studied by molecular dynamics simulations of binary mixtures consisting of Lennard-Jones (LJ) particles. Our simulations reveal how pinning of the three-phase contact line on the surface can lead to the stability of the surface nanobubble, provided that the concentration of the dissolved gas is oversaturated. We have performed equilibrium simulations of surface nanobubbles at different gas oversaturation levels ζ > 0. The equilibrium contact angle θe is found to follow the theoretical result of Lohse and Zhang (Phys. Rev. E 2015, 91, 031003(R)), namely, sin θe = ζL/Lc, where L is the pinned length of the footprint and Lc = 4γ/P0 is a capillary length scale, where γ is the surface tension and P0 is the ambient pressure. For undersaturation ζ < 0 the surface nanobubble dissolves and the dissolution dynamics shows a "stick-jump" behavior of the three-phase contact line.

A unified mechanism for the stability of surface nanobubbles: contact line pinning and supersaturation.

In this paper, we apply the molecular dynamics simulation method to study the stability of surface nanobubbles in both pure fluids and gas-liquid mixtures. First, we demonstrate with molecular simulations, for the first time, that surface nanobubbles can be stabilized in superheated or gas supersaturated liquid by the contact line pinning caused by the surface heterogeneity. Then, a unified mechanism for nanobubble stability is put forward here that stabilizing nanobubbles require both the contact line pinning and supersaturation. In the mechanism, the supersaturation refers to superheating for pure fluids and gas supersaturation or superheating for the gas-liquid mixtures, both of which exert the same effect on nanobubble stability. As the level of supersaturation increases, we found a Wenzel or Cassie wetting state for undersaturated and saturated fluids, stable nanobubbles at moderate supersaturation with decreasing curvature radius and contact angle, and finally the liquid-to-vapor phase transition at high supersaturation.