Spatial study on a multibubble system for sonochemistry by laser-light scattering

Volumetric oscillation of multiple cavitation bubbles in an ultrasonic standing-wave field is investigated spatially through the intensity measurements of scattered light from bubbles changing the measuring position in the direction of sound propagation. When a thin light sheet finer than half of wavelength of sound is introduced into the cavitation bubbles, at an antinode of sound pressure the scattered light intensity oscillates. The peak-to-peak light intensity corresponds to the number of the bubbles which contribute to the sonochemical reaction because the radius for oscillating bubbles at pressure antinodes is restrictive in a certain range due to the shape instability and the action of Bjerknes force that expels from the antinode bubbles that are larger than the resonant size. The experimental results show that the intensity waveform of oscillating scattered light measured at the side near the sound source is similar to the waveform as seen in a single-bubble experiment. The peak-to-peak light intensity for the scattered light waveform is low at the side near the sound source where the progressive wave is dominant, while at the side near the water surface far from the sound source the intensity is relatively high and has periodic structure corresponding to the periodicity of half wavelength from the standing wave. These tendencies of high intensity near the water surface and the periodicity correspond to the periodic luminescent stripes seen in images of luminescence in an ultrasonic standing wave as reported by Hatanaka et al. [Jpn. J. Appl. Phys. 39 (2000) 2962]. The present method of light scattering is promising for evaluating spatial distribution of violently oscillating cavitation bubbles which effect sonochemical reactions.     

Measurement of acoustic power in studying cavitation processes

A comparative calorimetric method for measuring the acoustic power generated by a sound source under cavitation conditions and the power absorbed by a liquid with bubbles is developed. The conditions under which the whole of the generated power is absorbed by the liquid with bubbles are determined experimentally. An instrument for power calibration of sound sources operating under cavitation conditions is designed. The instrument is found to provide a high measurement accuracy (3% or better). The requirements on the dimensions of the vessel and on the volume of the liquid in which the sound source operates are formulated to make the power generated under cavitation conditions independent of these parameters. For the first time, it is shown experimentally (by the example of the reaction of nitric oxide formation under the action of sound) that, if these conditions are satisfied and the sound intensity exceeds the threshold intensity, the rate of a number of sonochemical reactions is proportional to the sound intensity in the range from 1.7 to at least 47 W/cm². It is shown that the dependence of the rate of cavitation processes on the sound intensity with a maximum at 8.6 W/cm² and a sharp decrease in the rate with a further intensity increase is determined by the fact that the measured quantity was the electric power at the transducer rather than the acoustic one.     

Quantitative calculation of reaction performance in sonochemical reactor by bubble dynamics

In order to design a sonochemical reactor with high reaction efficiency, it is important to clarify the size and intensity of the sonochemical reaction field. In this study, the reaction field in a sonochemical reactor is estimated from the distribution of pressure above the threshold for cavitation. The quantitation of hydroxide radical in a sonochemical reactor is obtained from the calculation of bubble dynamics and reaction equations. The distribution of the reaction field of the numerical simulation is consistent with that of the sonochemical luminescence. The sound absorption coefficient of liquid in the sonochemical reactor is much larger than that attributed to classical contributions which are heat conduction and shear viscosity. Under the dual irradiation, the reaction field becomes extensive and intensive because the acoustic pressure amplitude is intensified by the interference of two ultrasonic waves.     

Dissolved gas and ultrasonic cavitation – A review

The physics and chemistry of nonlinearly oscillating acoustic cavitation bubbles are strongly influenced by the dissolved gas in the surrounding liquid. Changing the gas alters among others the luminescence spectrum, and the radical production of the collapsing bubbles. An overview of experiments with various gas types and concentration described in literature is given and is compared to mechanisms that lead to the observed changes in luminescence spectra and radical production. The dissolved gas type changes the bubble adiabatic ratio, thermal conductivity, and the liquid surface tension, and consequently the hot spot temperature. The gas can also participate in chemical reactions, which can enhance radical production or luminescence of a cavitation bubble. With this knowledge, the gas content in cavitation can be tailored to obtain the desired output.     

Sonoluminescence

Sonoluminescence (SL) is the name given to the light emitted when a liquid is cavitated in a particular (rather violent) manner. The appropriate cavitation conditions can be realized by using high intensity ultrasound, a spark discharge, a laser pulse, or by flowing the liquid through a Venturi tube. SL occurs in a wide variety of liquids, its intensity and spectrum depending on the nature of the solvent and the solute (including dissolved gas). The intensity, but apparently not the spectrum, also depends on the frequency of the sound and on the temperature and hydrostatic pressure of the liquid. In a standing wave sound field the SL originates from bubbles attracted to the pressure antinodes and has its maximum intensity when the bubble volume is a minimum. The phase of the sound cycle at which this occurs depends on the amplitude and frequency of the sound field. Spectral measurements show that SL originates mainly from the recombination of free radicals created within the high temperature and high pressure environment of a bubble undergoing an adiabatic compression, as may happen either during transient cavitation or during highly non-linear, but stable, cavitation. In discussing these, and other, attributes of SL this review emphasizes developments over the past 20 years. Because of the importance of the dynamical theory of bubbles to a full understanding of SL, it includes an account of bubble dynamics. In addition, it describes the various experimental techniques employed in the creation and analysis of SL. Although the review lays particular stress on the SL produced via acoustic cavitation, it also examines the characteristics of the SL produced using other methods of cavitation.     

The effect of dissolve gas concentration in the initial growth stage of multi cavitation bubbles. Differences between vacuum degassing and ultrasound degassing

The sonochemical luminescence intensity from luminol was measured at a sampling rate of several kilohertz. This was noted at three different periods: first, the latent period in which no light emission occurs at all; second, the increased emission period from the start of light emission to the time when a steady state is reached; and third, the steady state period in which light emission occurs at the steady state value. When irradiated with ultrasound of different intensities, the times of the latent period and increased emission period are shorter for higher ultrasound intensities. To know how the dissolved oxygen content is involved in early-stage cavitation growth, an experiment was conducted using solutions with varying dissolved oxygen contents from 100% to 37%. For dissolved air content of 50% or less, it was found that the latent period was 30 times longer in a saturated condition. It was also found that the increased emission period was 10 times longer. However, the emission intensity in the steady state did not change at all even when the initial dissolved gas concentration of the sample was changed. From this, it was found that the reuse of collapsed bubbles takes place efficiently in the steady state. Dissolved oxygen was reduced by the use of a vacuum pump and by the degassing action of ultrasound, and it was discovered that the behavior of transient emission differed for the two ways of degassing.     

A study on effect of sonochemistry in a reverberation field

In this paper,an ultrasound with frequency of 815 kHz was used to re-search the sonochemical yield in a small-size reverberation field by the methodof fluorescent spectrum analysis.There are two characteristics on the effect ofsonochemistry in the reverberation field:First,the cavitation threshold wasabout 0.3W/cm~2(it was 0.7W/cm~2 in travelling field);Second,when thesound intensity was larger than the threshold,the sonochemical yield increasedas the intensity increased and increased rapidly after the intensity was at1.69-2.13W/cm~2,so that there was a upturned point in the curve of the result(which would tend to saturation in the travelling field).The theoretical analysisshows that the reason of the threshold decrease is that the sound energy densitybecomes high in the reverberation field,and the upturned point results from thedisturbance of the radiation pressure on the liquid surface.Therefore,by exper-iment and theory this paper shows that a reverberation field has to be built forthe higher sonoche     

Effect of dissolved gases in water on acoustic cavitation and bubble growth rate in 0.83 MHz megasonic of interest to wafer cleaning

Changes in the cavitation intensity of gases dissolved in water, including H₂, N₂, and Ar, have been established in studies of acoustic bubble growth rates under ultrasonic fields. Variations in the acoustic properties of dissolved gases in water affect the cavitation intensity at a high frequency (0.83 MHz) due to changes in the rectified diffusion and bubble coalescence rate. It has been proposed that acoustic bubble growth rates rapidly increase when water contains a gas, such as hydrogen faster single bubble growth due to rectified diffusion, and a higher rate of coalescence under Bjerknes forces. The change of acoustic bubble growth rate in rectified diffusion has an effect on the damping constant and diffusivity of gas at the acoustic bubble and liquid interface. It has been suggested that the coalescence reaction of bubbles under Bjerknes forces is a reaction determined by the compressibility and density of dissolved gas in water associated with sound velocity and density in acoustic bubbles. High acoustic bubble growth rates also contribute to enhanced cavitation effects in terms of dissolved gas in water. On the other hand, when Ar gas dissolves into water under ultrasound field, cavitation behavior was reduced remarkably due to its lower acoustic bubble growth rate. It is shown that change of cavitation intensity in various dissolved gases were verified through cleaning experiments in the single type of cleaning tool such as particle removal and pattern damage based on numerically calculated acoustic bubble growth rates.     

Advancement of high power ultrasound technology for the destruction of surface active waterborne contaminants

The current paper explores recent advances in sonochemical techniques to improve the ultrasound-mediated degradation efficiency of surface active, waterborne contaminants. Sonochemical degradation efficiency of surface active contaminants generally has a strong dependence on the concentration of contaminant at the gas/solution surface of cavitation bubbles. This in turn depends on the thermodynamic and diffusion/kinetic-controlled adsorption properties of the surfactant at the rapidly pulsating gas/solution surface of acoustic cavitation bubbles. The adsorption properties of surfactants can be exploited to enhance their sonochemical decomposition by varying ultrasound exposure parameters such that changes in the nature of the bubble population (especially the bubble life-time and rate of pulsations) cause changes in the amount of surfactant that adsorbs to the gas/solution interface of cavitation bubbles. Herein we describe recent results on the effect of ultrasound frequency and pulsing mode on sonochemical degradation of surfactants in aqueous solutions and show how the exposure parameters can be adjusted in ways to produce more efficient decomposition of contaminants, even under exposure conditions where seemingly poor sonochemical activity is detected in the bulk solution. The relevance of these results to scale-up of ultrasound decontamination processes is discussed.     

Method for comparing the efficiency of ultrasound irradiation independent of the shape and the volume of the reaction vessel in sonochemical experiments

The method described herein this review compares the efficiency of ultrasound irradiation in sonochemical experiments in organic solvents. This method was shown to be independent of the shape and volume of the reaction vessel.

The principle of this method is based on the fact that the concentration of dissolved oxygen in the entire reaction volume during acoustic cavitation depends on the ultrasound power or intensity of ultrasound field respectively. The concentration of dissolved oxygen is determined by the measurement of the fluorescence intensity with fluorescence probes.     

A comparative study on the modeling of sound pressure field distributions in a sonoreactor with experimental investigation

In sonochemical reactors the effect of emerging cavitation bubbles has significant influence on the amplitude and structure of the developing sound field. Calculations show that the damping parameter and the phase velocity may, depending on the pressure amplitude, change by several orders of magnitude. For example, the sound velocity in water comes to 1500 ms⁻¹, whereas in a bubbly liquid it may decrease to 20 ms⁻¹, which is much below the velocity of sound in air (about 340 ms⁻¹). In this paper, a method of calculating the time dependent three-dimensional pressure field in sonochemical reactors of various shapes is presented. It takes into account inhomogeneous distributed wave parameters which are a function of the spatial depending pressure amplitude. The modeled results are then compared with experimentally measured values of a certain kind of reaction vessel. The agreement is found to be satisfactory.     

Sonochemical method for producing titanium metal powder

We demonstrate a sonochemical method for producing titanium metal powder. The method uses low intensity ultrasound in a hydrocarbon solvent at near-ambient temperatures to first create a colloidal suspension of liquid sodium–potassium alloy in the solvent and then to reduce liquid titanium tetrachloride to titanium metal under cavitation conditions. XRD data collected for the reaction products after the solvent removal show only NaCl and KCl, with no diffraction peaks attributable to titanium metal or other titanium compounds, indicating either the formation of amorphous metal or extremely small crystallite size. TEM micrographs show that hollow spheres formed of halide salts and titanium metal, with diameters with diameters ranging from 100 to 500 nm and a shell thickness of 20 to 40 nm form during the synthesis, suggesting that the sonochemical reaction occurs inside the liquid shell surrounding the cavitation bubbles. Metal particle sizes are estimated to be significantly smaller than 40 nm from TEM data. XRD data of the powder after annealing and prior to removal of the alkali chloride salts provides direct evidence that titanium metal was formed during the sonochemical synthesis.     

Sonochemical and sonocatalytic degradation of monolinuron in water

The degradation of the phenylurea monolinuron (MLN) by ultrasound irradiation alone and in the presence of TiO(2) was investigated in aqueous solution. The experiments were carried out at low and high frequency (20 and 800 kHz) in complete darkness. The degradation of MLN by ultrasounds occurred mainly by a radical pathway, as shown the inhibitory effect of adding tert-butanol and bicarbonate ions to scavenge hydroxyl radicals. However, CO(3)(-) radicals were formed with bicarbonate and reacted in turn with MLN. In this study, the degradation rate of MLN and the rate constant of H(2)O(2) formation were used to evaluate the oxidative sonochemical efficiency. It was shown that ultrasound efficiency was improved in the presence of nanoparticles of TiO(2) and SiO(2) only at 20 kHz. These particles provide nucleation sites for cavitation bubbles at their surface, leading to an increase in the number of bubbles when the liquid is irradiated by ultrasound, thereby enhancing sonochemical reaction yield. In the case of TiO(2), sonochemical efficiency was found to be greater than with SiO(2) for the same mass introduced. In addition to the increase in the number of cavitation bubbles, activated species may be formed at the TiO(2) surface that promote the formation of H(2)O(2) and the decomposition of MLN.     

Sonochemical and high-speed optical characterization of cavitation generated by an ultrasonically oscillating dental file in root canal models

Ultrasonically Activated Irrigation makes use of an ultrasonically oscillating file in order to improve the cleaning of the root canal during a root canal treatment. Cavitation has been associated with these oscillating files, but the nature and characteristics of the cavitating bubbles were not yet fully elucidated. Using sensitive equipment, the sonoluminescence (SL) and sonochemiluminescence (SCL) around these files have been measured in this study, showing that cavitation occurs even at very low power settings. Luminol photography and high-speed visualizations provided information on the spatial and temporal distribution of the cavitation bubbles. A large bubble cloud was observed at the tip of the files, but this was found not to contribute to SCL. Rather, smaller, individual bubbles observed at antinodes of the oscillating file with a smaller amplitude were leading to SCL. Confinements of the size of bovine and human root canals increased the amount of SL and SCL. The root canal models also showed the occurrence of air entrainment, resulting in the generation of stable bubbles, and of droplets, near the air–liquid interface and leading eventually to a loss of the liquid.     

Optical cavitation probe using light scattering from bubble clouds

To understand the behaviour of systems containing clouds of bubbles (multibubble system) in real sonochemical reactors, a new diagnosis method, i.e., optical cavitation probe (OCP), has been proposed. When a laser beam is introduced into the cavitation bubble cloud, the scattered light intensity changes by the collective oscillation of cavitation bubbles. The frequency domain spectrum of the scattered light contains rich information on the cavitation bubble clouds, comparable with the acoustic emission spectra detected by a hydrophone. The significant merits of OCP, such as capability for spatially resolved, non-invasive measurement of the cavitation bubble clouds, robustness even in a violent cavitation field have been experimentally demonstrated.     

空化水中HO2自由基的测定

采用频率为1．8MHz,声强为1－5W／cm2的超声波引发水中的空化效应,通过采用吡啶溶液作为HO2自由基捕获剂,测出了实验条件下空化水中HO2自由基的浓度水平为10－5M。     

Kinetics of nitrous acid formation in nitric acid solutions under the effect of power ultrasound

Sonochemical nitrous acid formation was investigated in 0.1-4.0 mol dm(-3) aqueous nitric acid solutions under the effect of power ultrasound with 20 kHz frequency. HNO2 steady-state concentration was obtained under long-time sonication; the excess HNO2 formed is decomposed and evoluted from the solution as NO and NO2 gases. The HNO2 steady-state concentration and the HNO2 initial formation rate depend linearly on the HNO3 concentration and acoustic intensity (1.8-3.5 W cm(-2)) and decrease with rising temperature in the range 21-50 degrees C. The HNO2 formation rate depends on the type of saturating gas as follows: Ar > N2 > He > air. NO and O2 are the major gaseous products of HNO3 sonication. The NO2 accumulation of in the gas phase is observed only when the decomposition of HNO2 formed becomes noticeable. The gaseous products formation rates depend on the HNO3 concentration, acoustic intensity and the type of saturating gas. The mechanism of HNO2 sonochemical formation is assumed to be the thermal decomposition of HNO3 in the gaseous vicinity of collapsing bubbles or in the overheated liquid reaction zone surrounding the cavitational bubbles.     

Oscillating bubble concentration and its size distribution using acoustic emission spectra

New method has been proposed for the estimation of size and number density distribution of oscillating bubbles in a sonochemical reactor using acoustic emission spectra measurements. Bubble size distribution has been determined using Minnaert's equation [M. Minnaert, On musical air bubbles and sound of running water, Philanthr. Mag. 16 (1933) 235], i.e., size of oscillating bubble is inversely related to the frequency of its volume oscillations. Decomposition of the pressure signal measured by the hydrophone in frequency domain of FFT spectrum and then inverse FFT reconstruction of the signal at each frequency level has been carried out to get the information about each of the bubble/cavity oscillation event. The number mean radius of the bubble size is calculated to be in the range of 50-80mum and it was not found to vary much with the spatial distribution of acoustic field strength of the ultrasound processor used in the work. However, the number density of the oscillating bubbles and the nature of the distribution were found to vary in different horizontal planes away from the driving transducer surface in the ultrasonic bath. A separate set of experiments on erosion assessment studies were carried out using a thin aluminium foil, revealing a phenomena of active region of oscillating bubbles at antinodal points of the stationary waves, identical to the information provided by the acoustic emission spectra at the same location in the ultrasonic bath.     

How do dissolved gases affect the sonochemical process of hydrogen production? An overview of thermodynamic and mechanistic effects – On the “hot spot theory”

Although most of researchers agree on the elementary reactions behind the sonolytic formation of molecular hydrogen (H₂) from water, namely the radical attack of H₂O and H₂O₂ and the free radicals recombination, several recent papers ignore the intervention of the dissolved gas molecules in the kinetic pathways of free radicals, and hence may wrongly assess the effect of dissolved gases on the sonochemical production of hydrogen. One may fairly ask to which extent is it acceptable to ignore the role of the dissolved gas and its eventual decomposition inside the acoustic cavitation bubble? The present opinion paper discusses numerically the ways in which the nature of dissolved gas, i.e., N₂, O₂, Ar and air, may influence the kinetics of sonochemical hydrogen formation. The model evaluates the extent of direct physical effects, i.e., dynamics of bubble oscillation and collapse events if any, against indirect chemical effects, i.e., the chemical reactions of free radicals formation and consequently hydrogen emergence, it demonstrates the improvement in the sonochemical hydrogen production under argon and sheds light on several misinterpretations reported in earlier works, due to wrong assumptions mainly related to initial conditions. The paper also highlights the role of dissolved gases in the nature of created cavitation and hence the eventual bubble population phenomena that may prevent the achievement of the sonochemical activity. This is particularly demonstrated experimentally using a 20 kHz Sinaptec transducer and a Photron SA 5 high speed camera, in the case of CO₂-saturated water where degassing bubbles are formed instead of transient cavitation.     

Sonochemical reaction of selected cyclic C6Hx hydrocarbons in organic solvents

The rates and products of the sonochemical reactions of benzene, 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene, and cyclohexane in selected organic solvents have been investigated. The sonochemical reactions of these educts in the investigated organic solvents follow first-order kinetics. Generally, they are sonicated more rapidly in polar than in non-polar solvent; higher volatility of the solute results in faster sonolysis in the organic solvents. However, the sonication of cyclohexane in n-decane and the sonication of benzene in n-propanol are exceptional cases. Since cyclohexane exhibits a much higher lipophilicity and benzene a much higher hydrophilicity than other educts, it might be more difficult to transfer either educt from the bulk liquid into the cavitation bubbles. In tetrachloroethylene, the reactivity of the tested educts with in situ generated chlorine as well as chlorine-containing radical intermediates can accelerate the rate of sonochemical reactions under the employed conditions. In n-propanol and n-decane, the pyrolysis during the collapse of the cavitation bubbles is the only reaction pathway of sonolysis. In tetrachloroethylene, the pyrolysis during the collapse of the cavitation bubbles and the free radical reaction in the bulk liquid may occur simultaneously. Except for the products generated from sonolysis, products formed from chlorine transformations (substitution or addition reactions) are detected. Benzene is hardly decomposed in tetrachloroethylene. However, when FeCl3 is added into the reaction system, benzene is sonoconverted rapidly, and the product chlorobenzene was detected. In organic solvents, the sonoreaction rates and the sonoproducts are dependent on the physicochemical properties of the solvents used, as well as the volatility, the polarity and the reactivity of educts.