Current state of the theory of local electrification of cavitation bubbles

The fundamental propositions of the theory of local electrification of cavitation bubbles, which explains the phenomena of sonoluminescence (SL) and sonochemical reactions, are outlined. Key debatable questions are answered. It is shown that, unlike thermal theories, the local electrification theory agrees with a vast body of experimental data for cavitation clouds. The following experimental results that support this theory are considered: the decisive role of electrokinetic phenomena in initiation of SL, the presence of lines and bands in SL spectra of ultrasonically and laser-induced bubbles in their deformation and splitting, results of experiments with SL quenchers, the asymmetric-in-time profile of SL bursts, the SL at small pulsations of bubbles, etc.     

The dynamics of a bubble ensemble in a cavitation field

A system of equations was obtained to describe the dynamics of bubbles in a cavitation cloud taking into account the interaction of pulsating bubbles involved in translational motion. The kinetics of cavitation bubble concentration changes, changes in the compressibility of the liquid, and phase transitions within a cavitation bubble and in the neighboring volume of the liquid were taken into account. The role played by bubble deformation in a cavitation cloud was considered. The Bernoulli pressure effect was shown to be negligible. The interaction of cavitation bubbles was a substantial factor that strongly influenced the dynamics of bubbles. It was suggested that there was at least one more mechanism that reduced sonoluminescence intensity from the multiple-bubble cavitation field, namely, a fairly high efficiency of sonoluminescence quenching could additionally be related to the arrival of a cumulative liquid stream at the central cavitation bubble region, where the concentration of active species was high. The dynamics of bubbles in the cavitation field is not only related to the expansion and compression of cavitation bubbles in the acoustic field, but also governed to a great extent by their interaction, translational motion, deformation, and the influence of cumulative streams penetrating the bubbles.     

Bubble dynamics for broadband microrheology of complex fluids

Bubbles in complex fluids are often desirable, and sometimes simply inevitable, in the processing of formulated products. Bubbles can rise by buoyancy, grow or dissolve by mass transfer, and readily respond to changes in pressure, thereby applying a deformation to the surrounding complex fluid. The deformation field around a stationary, spherical bubble undergoing a change in radius is simple and localized, thus making it suitable for rheological measurements. This article reviews emerging approaches to extract information on the rheology of complex fluids by analysing bubble dynamics. The focus is on three phenomena: changes in radius by mass transfer, harmonic oscillations driven by an acoustic wave, and bubble collapse. These phenomena cover a broad range of deformation frequencies, from 10⁻⁴–10⁶ Hz, thus paving the way to broadband microrheology using bubbles as active probes. The outstanding challenges that need to be overcome to achieve a robust technique are also discussed.     

An electron diffusion model of the space-time distribution of radicals in a multibubble cavitation field

Conditions under which electric discharges can arise in cavitation bubbles pulsating in a multibubble cavitation field are considered. Possible electric discharge types are discussed. It is shown that, in an electric breakdown in a cavitation bubble, the probability of the formation of a streamer (all the more, a leader) or corona discharge is negligibly small. It was found that, in a cavitation bubble, the development of an electron avalanche is most probable. The basic parameters of an elementary electron avalanche are estimated.     

Dynamic adsorption properties of n-alkyl glucopyranosides determine their ability to inhibit cytolysis mediated by acoustic cavitation

Suspensions of human leukemia (HL-60) cells readily undergo cytolysis when exposed to ultrasound above the acoustic cavitation threshold. However, n-alkyl glucopyranosides (hexyl, heptyl, and octyl) completely inhibit ultrasound-induced (1057 kHz) cytolysis (Sostaric, et al. Free Radical Biol. Med. 2005, 39, 1539-1548). The efficacy of protection from ultrasound-induced cytolysis was determined by the n-alkyl chain length of the glucopyranosides, indicating that protection efficacy depended on adsorption of n-alkyl glucopyranosides to the gas/solution interface of cavitation bubbles and/or the lipid membrane of cells. The current study tests the hypothesis that "sonoprotection" (i.e., protection of cells from ultrasound-induced cytolysis) in vitro depends on the adsorption of glucopyranosides at the gas/solution interface of cavitation bubbles. To test this hypothesis, the effect of ultrasound frequency (from 42 kHz to 1 MHz) on the ability of a homologous series of n-alkyl glucopyranosides to protect cells from ultrasound-induced cytolysis was investigated. It is expected that ultrasound frequency will affect sonoprotection ability since the nature of the cavitation bubble field will change. This will affect the relative importance of the possible mechanisms for ultrasound-induced cytolysis. Additionally, ultrasound frequency will affect the lifetime and rate of change of the surface area of cavitation bubbles, hence the dynamically controlled adsorption of glucopyranosides to their surface. The data support the hypothesis that sonoprotection efficiency depends on the ability of glucopyranosides to adsorb at the gas/solution interface of cavitation bubbles.     

The effect of surface-active solutes on bubble coalescence in the presence of ultrasound

The sonication of an aqueous solution generates cavitation bubbles, which may coalesce and produce larger bubbles. This paper examines the effect of surface-active solutes on such bubble coalescence in an ultrasonic field. A novel capillary system has been designed to measure the change in the total volume resulting from the sonication of aqueous solutions with 515 kHz ultrasound pulses. This volume change reflects the total volume of larger gas bubbles generated by the coalescence of cavitation bubbles during the sonication process. The total volume of bubbles generated is reduced when surface-active solutes are present. We have proposed that this decrease in the total bubble volume results from the inhibition of bubble coalescence brought about by the surface-active solutes. The observed results revealed similarities with bubble coalescence data reported in the literature in the absence of ultrasound. It was found that for uncharged and zwitterionic surface-active solutes, the extent of bubble coalescence is affected by the surface activity of the solutes. The addition of 0.1 M NaCl to such solutes had no effect on the extent of bubble coalescence. Conversely, for charged surface-active solutes, the extent of bubble coalescence appears to be dominated by electrostatic effects. The addition of 0.1 M NaCl to charged surfactant solutions was observed to increase the total bubble volume close to that of the zwitterionic surfactant. This suggests the involvement of electrostatic interactions between cavitation bubbles in the presence of charged surfactants in the solution.     

Effect of ultrasound frequency on pulsed sonolytic degradation of octylbenzene sulfonic acid

It has been shown that pulsed ultrasound can influence the amount of surfactant that can adsorb to and decompose at the surface of cavitation bubbles. However, the effect of ultrasound frequency on this process has not been considered. The current study investigates the effect of ultrasound frequency on the pulsed sonolytic degradation of octyl benzenesulfonate (OBS). Furthermore, the effect of pulsing and ultrasound frequency on the rate of *OH radical formation was determined. OBS degradation rates were compared to the rates of *OH radical formation. In this way, conclusions were made regarding the relative importance of accumulation of OBS at cavitation bubble surfaces versus sonochemical activity to the sonochemical decomposition of OBS under different conditions of sonolysis. Comparisons of the data in this way indicate that sonolytic degradation of OBS depends on both the sonochemical activity (i.e., *OH yield) and the accumulation of OBS on cavitation bubble surfaces. However, under a certain set of pulsing and ultrasound frequency exposure conditions, enhanced accumulation of OBS at the gas/solution interface of cavitation bubbles is the sole mechanism of enhanced degradation due to pulsing. On the basis of this finding, conclusions on how pulsing at various ultrasound frequencies affects cavitation bubbles were made.     

Nonequilibrium bubbles in a flowing langmuir monolayer

We investigate the nonequilibrium behavior of two-dimensional gas bubbles in Langmuir monolayers. A cavitation bubble is induced in liquid expanded phase by locally heating a Langmuir monolayer with an IR-laser. At low IR-laser power the cavitation bubble is immersed in quiescent liquid expanded monolayer. At higher IR-laser power thermo capillary flow around the laser-induced cavitation bubble sets in. The thermo capillary flow is caused by a temperature dependence of the gas/liquid line tension. The slope of the line tension with temperature is determined by measuring the thermo capillary flow velocity. Thermodynamically stable satellite bubbles are generated by increasing the surface area of the monolayer. Those satellite bubbles collide with the cavitation bubble. Upon collision the satellite bubbles either coalesce with the cavitation bubble or slide past the cavitation bubble. Moreover we show that the satellite bubbles can also be produced by the emission from the laser-induced cavitation bubbles.     

Sonochemistry and its dosimetry

The effects of ultrasound originate primarily in acoustic cavitation. The cavitation bubbles collapse violently enough to lead to interesting chemical effects, known as sonochemistry. There is a great need to relate the efficiency of sonochemical reaction to the energy of ultrasonic irradiation used to produce them. In this paper, three OH radical dosimeters, Fricke dosimeter, terephthalate dosimeter, and iodide dosimeter, are compared from the analytical point of view. The dosimeters based on photometry, i.e., Fricke and iodide, produced reliable and reproducible results, but the sensitivity is not enough for special applications, such as chemical monitoring of single bubble cavitation. The dosimeter based on fluorometry, terephthalate dosimeter, offered high sensitivity, 1.2×10¹¹ molecules ml⁻¹. The effects of some experimental parameters in sonochemistry, i.e., solution temperature and the dissolved gas species, were evaluated with the dosimeters.     

In situ bubble‐stretching dispersion mechanism for additives in polymers

An in situ bubble‐stretching (ISBS) model has been proposed on the basis of an analysis of the dispersion process of inorganic additives in polymers. The ISBS model is applicable to a dispersion of solid granular aggregates in polymer melts because the dispersed phase itself serves as a nucleation agent, giving rise to bubbles that expand at the surface of the microgranules and their aggregates. In terms of bidirectional stretching, the ISBS process can increase the degrees of freedom of granule dispersion, which favors more homogeneous dispersion. According to theoretical predictions and indirect experimental estimations of the dispersion of nanoscale CaCO₃ and nanoscale hydrotalcite in high‐density polyethylene (HDPE), when the bubble expands, the stretching rate of the polymer melt on the bubble wall can reach 10⁵–10⁶ s^?1. The field emission scanning electron microscopic images indicated that the granular size of dispersed CaCO₃ and hydrotalcite in HDPE with the ISBS method is about 60–80 nm, two orders of magnitude smaller than that attained with a shearing rate of 10³ s^?1 in a capillary rheometer. It is also predicted that elastic bubble oscillations may be generated through suitable control of process parameters and that their oscillatory frequency can be in the ultrasound range. This type of bubble oscillation can also promote dispersion. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1051–1058, 2003     

Effects of vapour pressure on the motion of cavitation bubble

Two models of bubble dynamics with constant vapour pressure and vapour content were newly developed. The mass flux of water vapour at bubble wall was simplified to facilitate the analysis. Based on these two models and the approximation of the mass flux, more simplified equations corresponding to the models were deduced from dynamic equation of bubble corrected by Sochard et al. MATLAB and the Runge–Kutta algorithm were applied to calculate and analyse the dynamical behaviour of cavitation bubbles under an ultrasonic field. Numerical results reveal that bubbles under the constant vapour pressure model exhibit larger amplitudes and move more violently to generate acoustic cavitation effect than the constant vapour content model. Nevertheless, the kinetic characteristics of bubbles under the constant vapour content model are similar to those of bubbles without water vapour. Moreover, vapour content exerts certain influence on the maximum radius, minimum radius and collapse intensity of bubbles.     

Dynamic Visualization of Free Radicals at Single Oxygen Bubbles using Chemiluminescence

The generation of free radicals is a key process in the formation and the collapse of the bubbles in water, however, the direct and dynamic observation of the radicals in this process at single bubbles has never been achieved. Here, the hydroxyl (OH^.) and oxygen (O₂^.−) radicals at single oxygen bubbles are continuously traced using chemiluminescence (CL), in which these radicals at the bubble react with the surrounding luminol in the solution emitting the light. Varied increase trends of luminescence are observed in the generation of a bubble, floating, short parking at the water/air interface and the final explosion, revealing the complexity in the distribution of radicals at the bubble unprecedentedly. Despite more radicals are observed at the bubble generated at a deep position under the water for the stabilization, almost the same amount of radicals are included in the bubbles that is independent on the water pressure during the production of the bubble. This rich information collected from the dynamic study of bubbles illustrates the complicated generation and distribution process of radicals at the bubbles, and will facilitate the understanding of the function about the bubbles.     

On the mechanism of multi-bubble sonoluminescence

The thermal chemiluminescent model of multibubble sonoluminescence (MBSL) is considered, and the contradictions that follow from its basic propositions are analyzed. It is shown that, if the thermal mechanism of sonoluminescence (SL) is operative, the continuous spectrum should be emitted before the band spectrum. It is established that, if the thermal recombination mechanism of a solid is operative, the duration of SL should be at least two orders of magnitude longer than that observed experimentally (<5 ns); according to the chemiluminescent model of SL, the SL burst time must be several orders of magnitude longer. Consideration is given to the previously proposed mechanism of emission of spectral lines of metals from solutions of alkali and alkaline-earth metal salts, which correlates with results of sonolysis of salt solutions under the action of ultrasound (US) pulses. A mechanism based on the theory of local electrification of cavitation bubbles in the US field is put forward to treat MBSL. It is shown that this mechanism agrees with experimental results: the SL burst time corresponds to the characteristic time of fluorescence.     

Effect of surfactants on inertial cavitation activity in a pulsed acoustic field

It has previously been reported that the addition of low concentrations of ionic surfactants enhances the steady-state sonoluminescence (SL) intensity relative to water (Ashokkumar; et al. J. Phys. Chem. B 1997, 101, 10845). In the current study, both sonoluminescence and passive cavitation detection (PCD) were used to examine the acoustic cavitation field generated at different acoustic pulse lengths in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS). A decrease in the SL intensity was observed in the presence of low concentrations of SDS and short acoustic pulse lengths. Under these conditions, the inhibition of bubble coalescence by SDS leads to a population of smaller bubbles, which dissolve during the pulse "off time". As the concentration of surfactant was increased at this pulse length, an increase in the acoustic cavitation activity was observed. This increase is partly attributed to enhanced growth rate of the bubbles by rectified diffusion. Conversely, at long pulse lengths acoustic cavitation activity was enhanced at low SDS concentrations as a larger number of the smaller bubbles could survive the pulse "off time". The effect of reduced acoustic shielding and an increase in the "active" bubble population due to electrostatic repulsion between bubbles are also significant in this case. Finally, as the surfactant concentration was increased further, the effect of electrostatic induced impedance shielding or reclustering dominates, resulting in a decrease in the SL intensity.     

Micro air bubble manipulation by electrowetting on dielectric (EWOD): transporting, splitting, merging and eliminating of bubbles

This paper describes various manipulations of micro air bubbles using electrowetting on dielectric (EWOD): transporting, splitting, merging and eliminating. First, in order to understand the response of bubbles to EWOD, the contact angle modulation is measured in a capped air bubble and confirmed to be in good agreement with the Lippmann-Young equation until saturation. Based on the contact angle measurement, testing devices for the bubble manipulations are designed and fabricated. Sequential activations of patterned electrodes generate continuous bubble transportations. Bubble splitting is successfully realized by activating a single electrode positioned in the middle of bubble base. However, it is found that there are criteria that make splitting possible only in certain conditions. For successful splitting, smaller channel gap, larger bubble size, wider splitting electrode and/or larger contact angle changes by EWOD are preferred. These criteria are verified by a series of experiments as well as a static analysis. Bubble merging is achieved by moving bubbles towards each other in two different channel configurations: (1) channel I, where bubbles are in contact with the bottom channel plate only, and (2) channel II, where bubbles in contact with the top as well as bottom channel plates. Furthermore, eliminating a bubble to the ambient air is accomplished. All the bubble manipulation techniques may provide a versatile integrated platform not only to manipulate micro objects by utilizing micro bubbles as micro carriers, but also to enable a discrete bubble-based gas analysis system.     

Ultrasound-induced polymerization of methyl methacrylate in liquid carbon dioxide: a clean and safe route to produce polymers with controlled molecular weight

Ultrasound-induced cavitation is known to enhance chemical reactions as well as mass transfer at ambient pressures. Ultrasound is rarely studied at higher pressures, since a high static pressure hampers the growth of cavities. Recently, we have shown that pressurized carbon dioxide can be used as a medium for ultrasound-induced reactions, because the static pressure is counteracted by the higher vapor pressure, which enables cavitation. With the use of a dynamic bubble model, the possibility of cavitation and the resulting hot-spot formation upon bubble collapse have been predicted. These simulations show that the implosions of cavities in high-pressure fluids generate temperatures at which radicals can be formed. To validate this, radical formation and polymerization experiments have been performed in CO₂-expanded methyl methacrylate. The radical formation rate is approximately 1.5*10¹⁴ s⁻¹ in this system. Moreover, cavitation-induced polymerizations result in high-molecular weight polymers. This work emphasizes the application potential of sonochemistry for polymerization processes, as cavitation in CO₂-expanded monomers has shown to be a clean and safe route to produce polymers with a controlled molecular weight.     

Characteristic analysis of cavitation bubbles in carbon dioxide fluid

After analysing the characteristics of bubble cavitation in high-pressure carbon dioxide (CO₂) fluid, cavitation conditions and some correlative physical characteristics are investigated. The results show that the ultrasonic intensity of liquid carbon dioxide to make cavitation occur is affected by the initial radius of the bubbles, hydrostatic pressure, temperature and vapour pressure within the bubbles in liquid CO₂. At the low frequency of ultrasound, the phase-speed of the liquid CO₂ gradually approaches the sound speed of the pure liquid when void fraction increases. At high frequency, the phase-speed is nearly equal to the sound speed in the liquid under different void fractions. The attenuation of ultrasound in liquid carbon dioxide reaches a maximum near the resonance frequency and then decreases when frequency either increases or decreases. At the resonance frequency, the phase-speed and the attenuation increase when the void fraction increases.     

Flow field in a downward diverging channel and its application

The flow in a downward divergent channel turns out to be an interesting experimental setup for the observation of upward floating bubbles that appear to be levitating in view of the observer. A more detailed analysis of this flow and its characteristic parameters is necessary for better understanding of this phenomenon. The boundary layer theory was used to derive the velocity field for the experimental setup. The actual flow of a liquid in the presence of a bubble was studied experimentally by measuring the position of the bubble; the data were then statistically processed by an image analysis. Observation of the bubble positions distribution showed that it is reasonable to assume a flat velocity profile of the liquid in the channel and that the bubbles do not tend to move into the boundary layer. In our experiments, volume of the air bubbles floating in water was 200 mm and of that of bubbles floating in aqueous glycerin was 300 mm³. Thus, the experiment used in this work is suitable for reliable determination of instantaneous and average bubble rising velocities as well as of those of horizontal and vertical oscillations.     

Physico-chemical approach to ultrasonic cavitation dynamics on ultrasonic cavitation from the viewpoint of sonochemical reactions

Summary The present theory treats ultrasonic cavitation as a train of expansion and contraction of a bubble, while most theories (e. g.Rayleigh's andGüth's) treated only contraction step.As a measure for the cavitation effect on sonochemical reaction, we used the reaction rateB mole l^–1 sec^–1. Especially in the case of ultrasonic depolymerisation of linear polymers we can use the final valueg of the degree of polymerisation besides initial rateB of depolymerisation.The theory can explain many experimental results of sonochemistry, e. g., effects of ultrasonic intensity and frequency, static pressure, size of bubble, gas in bubble, the kind of solvent, concentration of solution and temperature. The fact that the mono-disperse solution is easily obtained by ultrasonic depolymerisation can be explained, too.The use of two characteritic constantsB andg contributes also to the research on mechanism of cavitation, e. g., the existence of a prephenomenon, the significance of imperfect cavitation and the diagraming of conditions for cavitation.With 13 figures and 3 tables