Investigation on nanobubbles on graphite substrate produced by the water–NaCl solution replacement

How to produce nanobubbles repeatedly on a certain surface with sufficient amount is a key issue in nanobubbles research. It is well known that nanobubbles can be produced by exchanging water with organic solutions like alcohol which contains higher concentration of dissolved gas than that in water. However, it is not clear if this mechanism would work when exchanging water with the relatively low concentrations of dissolved gas such as salt solutions. In this paper, we employed NaCl solutions with different concentrations to replace water on graphite surface. We found that nanobubbles could indeed be generated and showed similar properties with those produced by other methods. Nanobubbles could be apparently observed when the NaCl concentration was as low as 0.15 M and their densities increased with the salt concentrations. When the concentration of NaCl was higher than 2.00 M, the number of nanobubbles increased slowly and nearly kept a constant. We also showed that the dissolved gas played an important role in the formation process of nanobubbles.     

The existence and stability of bulk nanobubbles:a long-standing dispute on the experimentally observed mesoscopic inhomogeneities in aqueous solutions

In theory,nanobubbles can stably exist with a lifetime of microseconds at most,but numerous experimental observations demonstrate that nanobubbles in bulk solution can be stable from hours to weeks.Although various conjectures on the stability mechanism of bulk nanobubbles,such as the contaminant mechanism,skin mechanism,surface zeta potential mechanism,are proposed,there has not yet been a unified conclusion.Since bulk nanobubbles show great potential in a wide spectrum of applications and are relevant to a number of unsolved questions on cavitation and nucleation,the debate over their stability mechanisms has been active.In the past,extensive studies have been carried out to understand the mechanism of nanobubble stability,and important insights have already been provided.This paper will provide a brief overview of our current understanding of the unexpected stability of bulk nanobubbles.     

NANOBUBBLES AT THE LIQUID/SOLID INTERFACE STUDIED BY ATOMIC FORCE MICROSCOPY

Bubbles on the nanometer scale were produced by a special method on solid surfaces. Atomic Force Microscopy (AFM) was used to detect these bubbles. It shows that nanobubbles can be seen clearly in the interfaces of liquid/graphite and liquid/mica. In AFM images, the nanobubbles appeared like bright spheres. Some of the bubbles kept stable for hours during the experiments. The bubbles were disturbed under high load during AFM imaging. The conformation of the bubbles is influenced by the atomic steps on the graphite substrate. In addition, a shadow was found around the bubbles, which was due to the interactions between a bubble adhered to the tip and a bubble on the substrate.     

Formation and stability of ultrasonic generated bulk nanobubbles

Although various and unique properties of bulk nanobubbles have drawn researchers' attention over the last few years,their formation and stabilization mechanism has remained unsolved. In this paper, we use ultrasonic methods to produce bulk nanobubbles in the pure water and give a comprehensive study on the bulk nanobubbles properties and generation. The ultrasonic wave gives rise to constant oscillation in water where positive and negative pressure appears alternately. With the induced cavitation and presence of dissolved air, the bulk nanobubbles formed. "Nanosight"(which is a special instrument that combines dynamic light scattering with nanoparticle tracking analysis) was used to analyze the track and concentration of nanobubbles. Our results show that in our experiment, sufficient bulk nanobubbles were generated and we have proven they are not contaminations. We also found nanobubbles in the ultrasonic water change in both size and concentration with ultrasonic time.     

Long lifetime of nanobubbles due to high inner density

As predicted by classical macroscopic theory, the lifetime for nanoscale gas bubbles is extremely short. However, stable gas nanobubbles have been experimentally observed in recent years. In this report, we theoretically show that, if the inner density of gas bubbles is sufficiently high, the lifetime of nanobubbles can increase by at least 4 orders of magnitude, and even approaches the timescale for experimental observations. Supported by the National Natural Science Foundation of China (Grant Nos. 10474109 and 10674146)     

Does salting-out effect nucleate nanobubbles in water: Spontaneous nucleation?

The solubility of gases in aqueous salt solution decreases with the salt concentration, often termed the “salting-out effect.” The dissolution of salt in water is followed by dissociation of salt and further solvation of ions with water molecules. The solvation weakens the affinity of gaseous molecules, and thus it releases the excess dissolved gas. Now it is interesting to know that what happens to the excess gas released during salting-out? Since it is imperative to note that the transfer of the dissolved gas in the bulk liquid may often occur in the form of nanobubbles. In this work, we have answered this question by investigating the nano-entities nucleation during the salting-out effect. The solubility of gases in aqueous salt solution decreases with the salt concentration, and it is often termed as the “salting-out effects.” The dissolution of salt in water undergoes dissociation of salt and further solvation of ions with water molecules. The solvation weakens the affinity of gaseous molecules, and thus it releases the excess dissolved gas. Now it is interesting to know that what happens to the excess gas released during salting-out? While it is also imperative to note that the gas transfer in the bulk liquid often occurs in the form of bubbles. With this hypothesis, we have experimentally investigated that whether the salting-out effect nucleates nanobubble or not. What is the strong scientific evidence to prove that they are nanobubbles? Does the salting-out parameter affect the number density? The answers to such questions are essential for the fundamental understanding of the origin and driving force for nanobubble generation. We have provided three distinct proofs for the nano-entities to be the nanobubbles, namely, (1) by freezing and thawing experiments, (2) by destroying the nanobubbles under ultrasound field, and (3) we also proposed a novel method for refractive index estimation of nanobubbles to differentiate them from nano drops and nanoparticles. The refractive index (RI) of nanobubbles was estimated to be 1.012 for mono- and di-valent salts and 1.305 for trivalent salt. The value of RI closer to 1 provides strong evidence of gas-filled nanobubbles. Both positive and negative charged nanobubbles nucleate during the salting-out effect depending upon the valency of salt. The nanobubbles during the salting-out effect are stable only for up to three days. This shorter stability could plausibly be due to reduced colloidal stability at a low surface charge.     

Interfacial nanobubbles produced by long-time preserved cold water

Interfacial gaseous nanobubbles which have remarkable properties such as unexpectedly long lifetime and significant potential applications, are drawing more and more attention. However, the recent dispute about the contamination or gas inside the nanobubbles causes a large confusion due to the lack of simple and clean method to produce gas nanobubbles.Here we report a convenient and clean method to effectively produce interfacial nanobubbles based on a pure water system.By adding the cold water cooled at 4℃ for more than 48 h onto highly oriented pyrolytic graphite(HOPG) surface, we find that the average density and total volume of nanobubbles are increased to a high level and mainly dominated by the concentrations of the dissolved gases in cold water. Our findings and methods are crucial and helpful for settling the newly arisen debates on gas nanobubbles.     

纳米通道内超疏水性表面气泡的运动

疏水表面纳米气泡的运动有重要的应用价值和研究意义。本文采用分子动力学方法,模拟了纳米通道壁面为超疏水性时壁面上气泡的运动状况。在质量力驱动下,随着外界驱动力的增大,两壁面上的气泡被逐渐拉长,同时逐渐变得扁平;前端"接触角"逐渐增大,而后端"接触角"逐渐减小。纳米通道内疏水性表面的纳米气泡随着外部驱动力的变化呈现出不同的形态,变化程度随着驱动力的增大而增大。在不同驱动力作用下,两个气泡总是保持相同的速度,气泡的速度与外力驱动的大小呈线性增长趋势。随着外力的增大,边界层及通道中心速度皆呈现增大趋势。     

Effect of temperature on the morphology of nanobubbles at mica/water interface

The great implication of nanobubbles at a solid/water interface has drawn wide attention of the scientific community and industries. However, the fundamental properties of nanobubbles remain unknown as yet. In this paper, the temperature effects on the morphology of nanobubbles at the mica/water interface are explored through the combination of AFM direct image with the temperature control. The results demonstrate that the apparent height of nanobubbles in AFM images is kept almost constant with the increase of temperature, whilst the lateral size of nanobubbles changes significantly. As the temperature increases from 28℃ to 42℃, the lateral size of nanobubbles increases, reaching a maximum at about 37℃, and then decreases at a higher temperature. The possible explanation for the size change of nanobubbles with temperature is suggested.     

Synthesis and Characterization of Ag@TiO2 Core-shell Nanoparticles and TiO2 Nanobubbles

Ag@TiO₂ core-shell structured particles of nano-size dimensions have been successfully prepared via a one-step way, which has proved quite effective in procuring stable colloids. Transmission electron microscopy (TEM) was employed to characterize the core size and the shell thickness, which typically were 20~40 nm and ~2 nm, respectively. X-ray diffraction (XRD) indicated the existence of silver. Optical absorption dependence on core size and synthetic temperature has been explored by UV–Vis absorption spectroscopy. Finally, the interesting titanium dioxide nanobubbles with silver core leached out by a unique means, were studied, which consequently proved the core-shell structure of the prepared nanoparticles, confirming the TEM observation.     

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

The generation, and stability of nanobubbles are of particular interest for fundamental research and have potential application in numerous fields. Several attempts were made in the literature to produce nanobubbles through acoustic cavitation. However, the generation and stability mechanisms of nanobubbles in the acoustic field are unclear. Here, we review the effect of ultrasound parameters on bulk nanobubbles and surface nanobubbles. On this basis, we discuss the proposed generation and stability mechanisms of nanobubbles from the perspective of transient and stable acoustic cavitation. Moreover, we propose some future research directions for a deeper understanding of the role of ultrasound in the generation and stability of nanobubbles.     

Influence of bulk nanobubble concentration on the intensity of sonoluminescence

The present study mainly examined the effects of the volumetric concentration of nanobubbles (ultrafine bubbles) on the intensity of sonoluminescence (SL). The addition of nanobubbles at high acoustic amplitude enhanced the SL intensity for various bubble concentrations in comparison with that in pure water. This probably means that the resulting high amplitude is over the Blake threshold, and accordingly nanobubbles expand to some extent, leading to higher SL intensity. Therefore, nanobubbles have the potential to provide nucleation sites for sonochemistry. The influence of bubble size on the intensity of SL was also evaluated.     

Identification of surface nanobubbles and resolving their size-dependent stiffness

We report a comparative investigation of the topographic features and nanomechanical responses of surface nanobubbles,polymeric nanodrops, and solid microparticles submerged in water and probed by atomic force microscopy in different operating modes. We show that these microscopic objects exhibit similar topographies, either hemispherical or hemiellipsoidal, in the standard tapping mode, and thus are difficult to distinguish. However, distinct differences, caused not only by their different mechanical properties but also by different cantilever tip-sample mechanical interactions that are affected by tip wettability, were observed in successive topographic imaging with controlled scanning forces and the nanoindentation tests, allowing for the identification of surface nanobubbles. Based on the indentation force-distance curves, we further extrapolated the stiffness of surface nanobubbles spanning a wide range of sizes and then developed a simple theoretical model to explain this size dependence. We also demonstrate how size-dependent stiffness can be used to determine the surface tension of nanobubbles,which was found to be much lower than the bulk value of water.     

The effect of preparation time and aeration rate on the properties of bulk micro-nanobubble water using hydrodynamic cavitation

Fundamental research on bulk micro-nanobubbles (BMNBs) has grown rapidly due to the demand for their industrial applications and potential role in interfacial sciences. This work focuses on examining properties of such bubbles, including the number, concentration, zeta potential, and surface tension in water. For this purpose, BMNBs were generated by the hydrodynamic cavitation (HC) mechanism. Distilled water and air in the experiments were the liquid and gas phases, respectively. The characterization of bulk microbubbles (BMBs) and bulk nanobubbles (BNBs) were performed through focused beam reflectance measurement (FBRM) and nanoparticle tracking analysis (NTA) techniques, respectively. Zeta potential and surface tension of aqueous solutions were measured at different time and aeration rates. The results showed that aeration rate and preparation time had an important role in the properties of BNBs (concentration, bubble size, and surface charge) and BMBs (number, and bubble size). The instability of BMBs led to the rapid changes in the dissolved oxygen (DO) content in the water. The number of BMBs decreased when preparation time and aeration rate increased, but their size remained constant. By enhancing the preparation time and aeration rate, the concentration of BNBs improved first and then reduced. Additionally, the surface tension of an aqueous solution containing BNBs was significantly lower than that of pure water.     

Effect of ultrasonication on the flotation of fine graphite particles: Nanobubbles or not?

It has been reported that nanobubbles can be produced by ultrasonication. However, it remains unclear whether part of the contribution of ultrasonication on flotation performance can be attributed to the generation of nanobubbles. In this work, we systematically studied this point of ultrasonication by combining a series of techniques including flotation testing, AFM (atomic force microscope) measurement, and settling testing. AFM imaging showed that no surface nanobubbles were found at the HOPG-water interface before and after subjection to ultrasonication. Further, surface nanobubbles were generated with solution exchange before ultrasonciation and then they were subjected to ultrasonication. It was found that ultrasonication did not destroy the pre-existing surface nanobubbles at the HOPG (highly oriented pyrolytic graphite) -water interface. Settling tests and flotation tests indicate that ultrasonication has a negligible influence on the interaction between graphite particles and thus flotation performance. Nanobubbles were not one of the outcomes for ultrasonication.     

Inertial cavitation initiated by polytetrafluoroethylene nanoparticles under pulsed ultrasound stimulation

Nanoscale gas bubbles residing on a macroscale hydrophobic surface have a surprising long lifetime (on the order of days) and can serve as cavitation nuclei for initiating inertial cavitation (IC). Whether interfacial nanobubbles (NBs) reside on the infinite surface of a hydrophobic nanoparticle (NP) and could serve as cavitation nuclei is unknown, but this would be very meaningful for the development of sonosensitive NPs. To address this problem, we investigated the IC activity of polytetrafluoroethylene (PTFE) NPs, which are regarded as benchmark superhydrophobic NPs due to their low surface energy caused by the presence of fluorocarbon. Both a passive cavitation detection system and terephthalic dosimetry was applied to quantify the intensity of IC. The IC intensities of the suspension with PTFE NPs were 10.30 and 48.41 times stronger than those of deionized water for peak negative pressures of 2 and 5 MPa, respectively. However, the IC activities were nearly completely inhibited when the suspension was degassed or ethanol was used to suspend PTFE NPs, and they were recovered when suspended in saturated water, which may indicates the presence of interfacial NBs on PTFE NPs surfaces. Importantly, these PTFE NPs could sustainably initiate IC for excitation by a sequence of at least 6000 pulses, whereas lipid microbubbles were completely depleted after the application of no more than 50 pulses under the same conditions. The terephthalic dosimetry has shown that much higher hydroxyl yields were achieved when PTFE NPs were present as cavitation nuclei when using ultrasound parameters that otherwise did not produce significant amounts of free radicals. These results show that superhydrophobic NPs may be an outstanding candidate for use in IC-related applications.     

A review of recent theoretical and computational studies on pinned surface nanobubbles

The observations of long-lived surface nanobubbles in various experiments have presented a theoretical challenge, as they were supposed to be dissolved in microseconds owing to the high Laplace pressure. However, an increasing number of studies suggest that contact line pinning, together with certain levels of oversaturation, is responsible for the anomalous stability of surface nanobubbles. This mechanism can interpret most characteristics of surface nanobubbles. Here, we summarize recent theoretical and computational work to explain how the surface nanobubbles become stable with contact line pinning. Other related work devoted to understanding the unusual behaviors of pinned surface nanobubbles is also reviewed here.     

Degradation of organic wastewater by hydrodynamic cavitation combined with acoustic cavitation

In this paper, the decomposition of Rhodamine B (RhB) by hydrodynamic cavitation (HC), acoustic cavitation (AC) and the combination of these individual methods (HAC) have been investigated. The degradation of 20 L RhB aqueous solution was carried out in a self-designed HAC reactor, where hydrodynamic cavitation and acoustic cavitation could take place in the same space simultaneously. The effects of initial concentration, inlet pressure, solution temperature and ultrasonic power were studied and discussed. Obvious synergies were found in the HAC process. The combined method achieved the best conversion, and the synergistic effect in HAC was even up to 119% with the ultrasonic power of 220 W in a treatment time of 30 min. The time-independent synergistic factor based on rate constant was introduced and the maximum value reached 40% in the HAC system. Besides, the hybrid HAC method showed great superiority in energy efficiency at lower ultrasonic power (88–176 W). Therefore, HAC technology can be visualized as a promising method for wastewater treatment with good scale-up possibilities.     

分子动力学模拟压水反应堆中联氨对水的影响

本文采用分子动力学方法模拟在常温常压下(1 atm,298 K)和在压水堆环境下(155 atm,626 K),水分子数为256,联氨(N₂H₄)分子数为0,25,50,75等不同数目时,水和联氨粒子系统的动力性质和微观结构.同时探讨了联氨分子的引入对水中溶解氧的影响.从模拟结果可知,在常温常压下,当联氨的分子数为0,25,50,75时,粒子系统的均方位移会随联氨分子数的增加而增加;联氨分子数为0与为25,50,75比较时会少一个数量级;压水堆环境下,联氨分子数 关键词： 分子动力学 压水堆 联氨     

Formation of surface nanobubbles and the universality of their contact angles: a molecular dynamics approach

We study surface nanobubbles using molecular dynamics simulation of ternary (gas, liquid, solid) systems of Lennard-Jones fluids. They form for a sufficiently low gas solubility in the liquid, i.e., for a large relative gas concentration. For a strong enough gas-solid attraction, the surface nanobubble is sitting on a gas layer, which forms in between the liquid and the solid. This gas layer is the reason for the universality of the contact angle, which we calculate from the microscopic parameters. Under the present equilibrium conditions the nanobubbles dissolve within less of a microsecond, consistent with the view that the experimentally found nanobubbles are stabilized by a nonequilibrium mechanism.