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.     

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.     

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.     

Laser diagnostics of the Bubston phase in the bulk of aqueous salt solutions

Stable gas nanobubbles in the bulk of NaCl aqueous solutions and clusters of these nanobubbles have been investigated at different ion concentrations by four independent laser techniques (phase microscopy, dynamic light scattering, optical breakdown, and measurement of angular dependences of the light scattering matrix). The results obtained by these radically different techniques are in good agreement. It is found that the nanobubble size is practically constant and amounts to approximately 100nm in the range of ion concentrations 10^?6<C <1M. It is shown that a necessary condition for nanobubble nucleation is the saturation of solution with dissolved air. It is revealed that nanobubble clusters form a thermodynamically nonequilibrium phase with a lifetime of several months.     

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.     

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 role of precursor gases on the surface restructuring of catalyst films during carbon nanotube growth

Catalyst films undergo considerable surface morphology restructuring prior to carbon nanotube nucleation, deeply influencing the nanostructures obtained. Here we study the influence of different gaseous atmospheres on the structure of thin Fe films. The morphology is influenced by process temperature and substrate interactions and varying the gas type and pressure can control the average catalyst island height.     

不同衬底条件下石墨烯结构形核过程的晶体相场法研究

利用可描述气-固转变的三模晶体相场模型,在原子尺度上研究了不同衬底条件下石墨烯结构的形核过程.结果表明:无论衬底存在与否,气态原子均是先聚集为无定形过渡态团簇,随着气态原子的不断堆积和固相团簇中原子位置的不断调整,过渡态团簇逐渐转变为有序的石墨烯晶核,在此过程中,五元环结构具有重要的过渡作用;石墨烯在结构匹配较好的衬底(如面心立方(face-centered cubic,FCC)结构(111)和(110))上生长时,可形成几乎没有结构缺陷单晶石墨烯岛;在无衬底或结构匹配性较差的衬底(如FCC结构(100)面)上生长时,形成的石墨烯岛结构缺陷和晶界较多,不利于高质量石墨烯的制备.     

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.     

Superstability of surface nanobubbles

Shock wave induced cavitation experiments and atomic force microscopy measurements of flat polyamide and hydrophobized silicon surfaces immersed in water are performed. It is shown that surface nanobubbles, present on these surfaces, do not act as nucleation sites for cavitation bubbles, in contrast to the expectation. This implies that surface nanobubbles are not just stable under ambient conditions but also under enormous reduction of the liquid pressure down to -6 MPa. We denote this feature as superstability.     

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.     

Local structure of liquid carbon controls diamond nucleation

Diamonds melt at temperatures above 4000 K. There are no measurements of the steady-state rate of the reverse process, i.e., diamond nucleation from the melt, because experiments are difficult at these extreme temperatures and pressures. Using numerical simulations, we estimate the diamond nucleation rate and find that it increases by many orders of magnitude when the pressure is increased at constant supersaturation. The reason is that by increasing the pressure the local coordination of the liquid changes from threefold to fourfold, and we show that the free-energy cost to create a diamond-liquid interface is lower in the fourfold than in the threefold liquid. We speculate that this mechanism for nucleation control is relevant for crystallization in many network-forming liquids. We conclude that homogeneous diamond nucleation is likely in carbon-rich stars and unlikely in gaseous planets.     

High density gas state at water/graphite interface studied by molecular dynamics simulation

In this paper molecular dynamics simulations are performed to study the accumulation behaviour of N2 and H2 at water/graphite interface under ambient temperature and pressure. It finds that both N2 and H2 molecules can accumulate at the interface and form one of two states according to the ratio of gas molecules number to square of graphite surface from our simulation results： gas films （pancake-like） for a larger ratio and nanobubbles for a smaller ratio. In addition, we discuss the stabilities of nanobubbles at different environment temperatures. Surprisingly, it is found that the density of both kinds of gas states can be greatly increased, even comparable with that of the liquid N2 and liquid H2. The present results are expected to be helpful for the understanding of the stable existence of gas film （pancake-like） and nanobubbles.     

Electrokinetic potential reduction of fine particles induced by gas nucleation

Electrokinetic potential of particles has been extensively studied in colloidal systems over the past century, while up to date, the influence of gas on electrokinetic behaviors of particles has not been fully understood yet. In this study, the electrokinetic response of particles to gas nucleation was systematically investigated with coal as the object. The results showed that the nucleation of gas (both on particle surfaces and in water) significantly changed the particle’ electrokinetic behaviors. Higher gas content and particle’s surface hydrophobicity normally trigger more intensive gas nucleation, thus inducing more significant reduction of particle zeta potential. After gas nucleation, numerous nanobubbles (NBs) appear in the suspensions mainly in two forms: NBs adhering onto solid surfaces (ANBs) and NBs stagnating in bulk solutions (BNBs). ANBs not only enhance the surface heterogeneity, but also cause the “steric hindrance” effect, and electric double layer (EDL) overlapping and associated ions shielding towards charged particles, which significantly decrease their electrokinetic potentials. Although BNBs can also reduce the zeta potential of particles by EDL compressing, their functions are rather limited.     

The approach to diamond growth on levitating seed particles

We demonstrate the approach of diamond growth on levitating seed particles in a rf plasma. We introduce a hot filament chemical vapor deposition (CVD) technique into the rf plasma chamber in order to obtain improved crystal growth. Firstly, we confirmed diamond nucleation on seed particles placed on a Si substrate using the hot filament CVD. The deposition conditions, namely the total pressure and the rf power, were chosen so that they correspond to particles levitation conditions. We observe that a hydrogen pre-treatment on the seed particles improves the nucleation. Secondly, we confirm the levitation of particles at high temperatures. Fine particles levitated in a plasma are particularly sensitive to thermophoretic effects due to inhomogeneities in the gas heating. Therefore, proper heating procedures are required for successful particles levitation.     

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.     

Ice nucleation of water droplet containing solid particles under weak ultrasonic vibration

Water with small volume (a few microlitres or less) often maintains its liquid state even at temperatures much lower than 0 °C. In this study, we examine the onset of ice nucleation in micro-sized water droplets with immersed solid particles under weak ultrasonic vibrations. The experimental results show that ice nucleation inside the water droplets can be successfully induced at relatively high temperatures. The experimental observations indicate that the nucleation sites are commonly encountered in the region between the particle and the substrate. A numerical study is conducted to gain insight into the possible underlying phenomenon for ice nucleation in such systems. The simulation results show that the collapse of cavitation bubbles in the crevice at the particle surface is structure sensitive with the hemisphere-shape crevice generating pressures as high as 1.63 GPa, which is theoretically suitable for inducing ice nucleation.     

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.     

The effects of oxygen concentration and gas temperature on coal stream ignition and particle surface temperature in reducing-to-oxidizing environments

In the near-burner region of pulverized coal burners, two zones exist, with very different oxygen concentrations. The first zone is a locally reducing environment, caused by the fast release of volatiles from a region of dense coal particles, and the second zone, which is surrounding the first zone, is a hot oxidizing environment. The transition of coal particles from the reducing zone to the oxidizing zone affects early stage coal combustion characteristics, such as devolatilization, ignition and particle temperature history. In this work, we used a two-stage Hencken flat-flame burner to simulate the conditions that coal particles experience in practical combustors when they transition from a reducing environment to an oxidizing environments. The composition of the reducing environment was chosen to approximate that of a typical coal volatile. Three oxygen concentrations (5, 10 and 15 vol%) in the “ambient” oxidizing environment were tested, corresponding to those at different distances downstream from a commercial burner. The corresponding gas temperatures for the oxidizing environments were adjusted for the different oxygen concentrations such that the “volatile” flame temperatures were the same, as this is what would be expected in a commercial combustor. High speed videography was used to obtain the ignition characteristics, and RGB color pyrometry was used to measure particle surface temperatures. Two different sizes of coal particles were used. It is found that when particles undergo a reducing-to-oxidizing transition at high temperatures, the particles are preheated such that the critical factor for ignition delay is point at which the particle is in the presence of oxygen, not the concentration of oxygen. The ignition delay of large particles is found to be 53% longer than that of small particles due to their higher thermal mass and slower devolatilization. The oxygen concentration in the ambient have a negligible effect on early-stage particle temperatures.     

Coupled radiation and turbulent multiphase flow in an aluminised solid propellant rocket engine

We present in this paper numerical simulations of coupled radiative transfer and turbulent flows at high temperature and pressure, typical of multiphase flows encountered in aluminised solid propellant rocket engines. The radiating medium is constituted of gases and of liquid or solid particles of oxidised aluminum. The turbulent flow of the gaseous phase is treated by using a four equation, low Reynolds number, boundary-layer-type turbulence model. The distributions of concentrations, temperatures, and temperature fluctuation variances of particles are calculated from a Lagrangian approach and a turbulence dispersion model. Thermal and mechanical non-equilibrium between the gas and different classes of particles is allowed. A locally one dimensional, iteratively based, radiative transfer solver is developed to compute wall fluxes and radiative source terms. It is shown that the thermal boundary layer attenuates significantly the radiative fluxes coming from the outer regions. Particle radiation is found to be much more important than gas radiation. Turbulent dispersion of particles in the boundary layer induces a decrease of particle concentration in the region of maximum turbulent kinetic energy, and then, decreases the attenuation effect of wall fluxes due to the boundary layer. The effects of turbulent temperature fluctuations are found to be small in the problem under consideration.