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.     

The influence of acoustic power on multibubble sonoluminescence in aqueous solution containing organic solutes

The effect of varying the applied acoustic power on the extent to which the addition of water-soluble solutes affect the intensity of aqueous multibubble sonoluminescence (MBSL) has been investigated. Under most of the experimental conditions used, the addition of aliphatic alcohols to aqueous solutions was found to suppress the MBSL intensity, although an enhancement of the MBSL intensity was also observed under certain conditions. In contrast, the presence of an anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solutions generally enhanced the observed MBSL intensity. For a series of aliphatic alcohols and SDS, a strong dependence of the MBSL intensity on the applied acoustic power (in the range of 0.78-1.61 W/cm(2)) at 358 kHz was observed. The relative SL quenching was significantly higher at higher acoustic powers for the alcohol solutions, whereas the relative SL enhancement was lower at higher acoustic powers in SDS solutions. These observations have been interpreted in terms of a combination of material evaporation into the bubble, rectified diffusion, bubble clustering and bubble-bubble coalescence.     

Acoustic emission spectra from 515 kHz cavitation in aqueous solutions containing surface-active solutes

The effect of adding surface-active solutes to water being insonated at 515 kHz has been investigated by monitoring the acoustic emission from the solutions. At low concentrations (<3 mM), sodium dodecyl sulfate causes marked changes to the acoustic emission spectrum which can be interpreted in terms of preventing bubble coalescence and declustering of bubbles within a cavitating bubble cloud. By conducting experiments in the presence of background electrolytes and also using non-ionic surfactants, the importance of electrostatic effects has been revealed. The results provide further mechanistic evidence for the interpretation of the effect of surface-active solutes on acoustic cavitation and hence on the mechanism of sonochemistry. The work will be valuable to many researchers in allowing them to optimize reaction and process conditions in sonochemical systems.     

Study of the coalescence of acoustic bubbles as a function of frequency, power, and water-soluble additives

The effect that surface-active solutes, such as aliphatic alcohols and sodium dodecyl sulfate (SDS), have on the extent of bubble coalescence in liquids under different sonication conditions has been investigated by measuring the volume change of the solution following a period of sonication. In general, the adsorption of surface-active solutes onto the bubble surface retards bubble coalescence. Within the limitations of the measurement method and the systems studied, bubble coalescence does not appear to be dependent on the applied acoustic power. Also, varying the applied acoustic frequency has a minimal effect on the extent of bubble coalescence in systems where long-range electrostatic repulsion between bubbles, imparted by the adsorbed surface-active solutes, dominates. However, when short-range steric repulsion (or other short-range repulsive forces) is the primary factor in inhibiting bubble coalescence, the dependence on the applied acoustic frequency becomes apparent, with less coalescence inhibition at higher frequencies. It is also concluded that SDS does not reach an equilibrium adsorption level at the bubble/solution interface under the sonication conditions used. On the basis of this conclusion, a method is proposed for estimating nonequilibrium surface excess values for solutes that do not fully equilibrate with the bubble/solution interface during sonication. For the case of SDS in the presence of excess NaCl, the method was further employed to estimate the maximum lifetime of bubbles in a multibubble field. It was concluded that an acoustic bubble in a multibubble field has a finite lifetime, and that this lifetime decreases with increasing applied frequency, ranging from up to 0.35 +/- 0.05 ms for 213 kHz to 0.10 +/- 0.05 ms for 1062 kHz. These estimated lifetimes equate to a bubble in a multibubble field undergoing an upper limit of 50-200 oscillations over its lifetime for applied ultrasound frequencies between 200 kHz and 1 MHz.     

The effect of surface active solutes on bubbles exposed to ultrasound

A review of the effects of a range of surface active solutes, aliphatic alcohols, alkyl amines, carboxylic acids and surfactants on bubbles exposed to ultrasound is presented. The solutes are shown to affect the phenomenon of sonoluminescence (SL) in quite a number of different ways. Ionic surfactants have a strong influence on interbubble interactions which at low concentrations (1 mM) results in an enhancement in SL. Alcohols and the neutral forms of the organic acids and amines induce SL quenching. The SL quenching is attributed to the formation and accumulation of decomposition products in the hot core of an oscillating bubble resulting from the evaporation of volatile solute adsorbed at the bubble interface. Some results are presented on the influence of low concentrations of alcohol on the SL generated from a single bubble and on the bubble dynamics, when exposed to ultrasound. These results add support to the interpretation given for solute-induced effects observed in multibubble systems. It is also shown that SL can be used as an internal light source to excite aromatic solutes that subsequently fluoresce, a process referred to as sonophotoluminescence.     

Acoustic emission from cavitating solutions: implications for the mechanisms of sonochemical reactions

The acoustic emission from collapsing cavitation bubbles generated using ultrasound of 20 kHz and 515 kHz frequencies in water has been measured and correlated with sonoluminescence and hydroxyl radical production to yield further information on the frequency dependence of sonochemical reactions. A reasonable correlation was found, and the results suggest differences in the predominant types of cavitation observed under laboratory conditions.     

Nonequilibrium vibrational excitation of OH radicals generated during multibubble cavitation in water

The sonoluminescence (SL) spectra of OH(A(2)Σ(+)) excited state produced during the sonolysis of water sparged with argon were measured and analyzed at various ultrasonic frequencies (20, 204, 362, 609, and 1057 kHz) in order to determine the intrabubble conditions created by multibubble cavitation. The relative populations of the OH(A(2)Σ(+)) v' = 1-4 vibrational states as well as the vibronic temperatures (T(v), T(e)) have been calculated after deconvolution of the SL spectra. The results of this study provide evidence for nonequilibrium plasma formation during sonolysis of water in the presence of argon. At low ultrasonic frequency (20 kHz), a weakly excited plasma with Brau vibrational distribution is formed (T(e) ~ 0.7 eV and T(v) ~ 5000 K). By contrast, at high-frequency ultrasound, the plasma inside the collapsing bubbles exhibits Treanor behavior typical for strong vibrational excitation. The T(e) and T(v) values increase with ultrasonic frequency, reaching T(e) ~ 1 eV and T(v) ~ 9800 K at 1057 kHz.     

Effects of pulsed ultrasound on the adsorption of n-alkyl anionic surfactants at the gas/solution interface of cavitation bubbles

Sonolysis of argon-saturated aqueous solutions of the nonvolatile surfactants sodium dodecyl sulfate (SDS) and sodium 1-pentanesulfonate (SPSo) was investigated at three ultrasonic frequencies under both continuous wave (CW) and pulsed ultrasound. Secondary carbon-centered radicals were detected by spin trapping using 3,5-dibromo-4-nitrosobenzenesulfonic acid (DBNBS) and electron paramagnetic resonance (EPR) spectroscopy. Following sonolysis, -*CH- radicals were observed for both surfactants under both sonication modes. Under CW at 354 kHz, the maximum plateau -*CH- radical yield was higher for SPSo than for SDS, indicating that SDS, which is more surface active under equilibrium conditions, accumulates at the gas/solution interface of cavitation bubbles to a lesser degree, compared with the less surface active surfactant, SPSo. However, after sonolysis (354 kHz) under pulsed ultrasound with a pulse length of 100 ms and an interval of 500 ms, the -*CH- radical yield at the plateau concentrations was higher for SDS than for SPSo due to increased amounts of SDS accumulation on the bubble surfaces. In contrast to the findings following sonolysis at 354 kHz, sonolysis of aqueous surfactant solutions at 620 kHz and 803 kHz showed a higher -*CH- radical yield for SDS compared with SPSo under CW but lower -*CH- radical yield with increasing pulsing interval, indicating a frequency dependence on accumulation. Results indicate that pulsing the ultrasonic wave has a significant effect on the relative adsorption ability of n-alkyl surfactants at the gas/solution surface of cavitation bubbles.     

Bubble coalescence during acoustic cavitation in aqueous electrolyte solutions

Bubble coalescence behavior in aqueous electrolyte (MgSO(4), NaCl, KCl, HCl, H(2)SO(4)) solutions exposed to an ultrasound field (213 kHz) has been examined. The extent of coalescence was found to be dependent on electrolyte type and concentration, and could be directly linked to the amount of solubilized gas (He, Ar, air) in solution for the conditions used. No evidence of specific ion effects in acoustic bubble coalescence was found. The results have been compared with several previous coalescence studies on bubbles in aqueous electrolyte and aliphatic alcohol solutions in the absence of an ultrasound field. It is concluded that the impedance of bubble coalescence by electrolytes observed in a number of studies is the result of dynamic processes involving several key steps. First, ions (or more likely, ion-pairs) are required to adsorb at the gas/solution interface, a process that takes longer than 0.5 ms and probably fractions of a second. At a sufficient interfacial loading (estimated to be less than 1-2% monolayer coverage) of the adsorbed species, the hydrodynamic boundary condition at the bubble/solution interface switches from tangentially mobile (with zero shear stress) to tangentially immobile, commensurate with that of a solid-liquid interface. This condition is the result of spatially nonuniform coverage of the surface by solute molecules and the ensuing generation of surface tension gradients. This change reduces the film drainage rate between interacting bubbles, thereby reducing the relative rate of bubble coalescence. We have identified this point of immobilization of tangential interfacial fluid flow with the "critical transition concentration" that has been widely observed for electrolytes and nonelectrolytes. We also present arguments to support the speculation that in aqueous electrolyte solutions the adsorbed surface species responsible for the immobilization of the interface is an ion-pair complex.     

Influence of degree of gas saturation on multibubble sonoluminescence intensity

The influence of the degree of saturation (DOS) of a gas in a solution on the intensity of multibubble sonoluminescence (MBSL) excited by ultrasound with a frequency of 261 kHz is investigated at various ultrasonic powers and with different concentrations of ethanol, which is added as a volatile solute. At relatively low powers and a high DOS, low ethanol concentrations give higher sonoluminescence (SL) intensities than those obtained with pure water. This intensity enhancement decreases as sonication proceeds because the SL intensity for pure water increases with time, whereas it remains almost constant or decreases slightly in solutions containing ethanol. At relatively low powers, a partially degassed solution has a higher SL intensity than a solution with a high DOS for both pure water and solutions containing ethanol. The reason why the DOS decreases more when ethanol is added is considered mainly to be the accumulation of hydrocarbon products and the promotion of rectified diffusion. Adding an alcohol to a solution enhances ultrasonic degassing.     

Mixing enhancement for high viscous fluids in a microfluidic chamber

Due to small channel dimensions and laminar flows, mixing in microfluidic systems is always a challenging task, especially for high viscous fluids. Here we report a method of enhancing microfluidic mixing for high viscous fluids using acoustically induced bubbles. The bubbles can be generated in an acoustically profiled microfluidic structure by using a piezoelectric disk activated at a working frequency range between 1.5 kHz and 2 kHz. The mixing enhancement is achieved through interactions between the oscillating bubbles and fluids. Both experimental studies and numerical simulations are conducted. In the experiments, DI water-glycerol mixture solutions with various viscosities were used. The results, based on the mixing efficiency calculated from experimentally acquired fluorescent images, showed that good mixing can occur in the DI water-glycerol solutions with their maximum viscosity up to 44.75 mPa s, which to our best knowledge is the highest viscosity of fluids in microfluidic mixing experiments. To explain the mechanisms of bubble generation, the numerical simulation results show that, corresponding to the actuations at the working frequency range used in the experiment, there exists a low pressure region where the pressure is lower than the water vapor pressure in the DI water-glycerol solutions, resulting in the generation of bubbles.     

Determination of temperatures within acoustically generated bubbles in aqueous solutions at different ultrasound frequencies

Mean acoustic bubble temperatures have been measured using a methyl radical recombination (MRR) method, at three ultrasound frequencies (20, 355, and 1056 kHz) in aqueous tert-butyl alcohol solutions (0-0.5 M). The method is based on yield measurements of some of the hydrocarbon products formed from the recombination of methyl radicals that are thermally generated within collapsing bubbles containing tert-butyl alcohol vapor. The mean bubble temperatures were found to decrease substantially with increasing tert-butyl alcohol concentration at 355 and 1056 kHz but only to a small extent at 20 kHz. Extrapolating the mean temperatures measured to zero concentration of tert-butyl alcohol, at a bulk solution temperature of 20 degrees C, gave the order 355 kHz (4300 +/- 200 K) > 1056 kHz (3700 +/- 200 K) > 20 kHz (3400 +/- 200 K). It is also concluded that the temperature derived from the MRR method is a useful diagnostic parameter for sensing the thermal conditions within an active acoustic bubble. However, attention must be given to the fact that the temperature derived from the MRR method is not theoretically well defined.     

Effect of alcohols on the initial growth of multibubble sonoluminescence

The effect of alcohols on the initial growth of the multibubble sonoluminescence (MBSL) intensity in aqueous solutions has been investigated. With increasing concentrations of the alcohols, the number of pulses required to grow the MBSL intensity to a steady state (N(crit)) increases (relative to that of water) initially to a maximum for all the alcohols used in this study, followed by a decrease for methanol and ethanol. The cause of the initial increase in N(crit) is attributed to the inhibition of bubble coalescence in the system. This inhibition in bubble coalescence results in a population of bubbles with a smaller size range and thus a larger number of pulses is required to grow the bubbles to their sonoluminescing size range. It is suggested that the decrease in the N(crit) at higher alcohol concentrations may be caused by an increase in the bubble growth by rectified diffusion.     

Novel Applications of Non Hofmeister Ion Specificity in Bubble Interactions

The ion specificity of bubble-bubble interactions in water remains unexplained. Whatever their valence all ion pairs either completely inhibit bubble coalescence or have no effect whatever. The phenomenon appears unrelated to Hofmeister specificity. Salts which inhibit coalescence enable the formation of a high density bubble column evaporator (BCE). If hot gas bubbles are injected into the bubble column evaporator at a significantly higher temperature than the water, the hot bubble surfaces can be used to produce thermal effects in dissolved and dispersed solutes. These two properties can be exploited for a wide range of applications. Among these, high temperature aqueous reactions catalyzed at low solution temperatures, measurement of enthalpies of vaporization of concentrated salt solutions, wastewater treatments by sterilization and de-watering and desalination are a few.     

Bubble-size dependence of the critical electrolyte concentration for inhibition of coalescence

The interaction of pairs of bubbles with equal diameters grown on adjacent capillaries in aqueous magnesium sulfate solutions is observed for varying electrolyte concentrations and bubble diameters. As in previous investigations, a sharp transition from coalescence to bubble detachment without coalescence is observed with increasing electrolyte concentration. The critical electrolyte concentration for this transition is found to increase with decreasing bubble diameter for bubble diameters of 1.4 to 4.2 mm.     

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.     

Sonoluminescence of aqueous solutions of sulfuric acid and sulfur dioxide

Sonoluminescence (SL) of aqueous solutions of sulfuric acid and sulfur dioxide enhances with an increase in their concentration and reaches a maximum at 16 and 0.05 mol L^–1, respectively. The further increase in the concentration of these substances decreases the SL intensity. The SL spectra of the solutions have a broad maximum at 450 nm. Excited SO₂ molecules formed in sulfuric acid due to sonolysis are luminescence emitters. The proposed mechanism of bright SL in these systems is based on the energy transfer from the electron-excited sonolysis products to the SO₂ molecules in cavitation bubbles.     

Fluorescence Quenching of 1-Pyrenemethanol by Methylviologen in Polystyrene Latex Dispersions

Fluorescence quenching of 1-pyrenemethanol by methylviologen through photoinduced electron transfer is investigated in polystyrene (PS) latex dispersions as well as in aqueous homogeneous solutions. In aqueous homogeneous solutions, the Stern-Volmer plot for the intensity is linear and close to that for the lifetime, indicating a dynamic quenching mechanism. In PS latex dispersions, however, the Stern-Volmer plots for the intensity are downward curving and the decay curves are not so much affected by the quencher as those for aqueous solutions, implying a significant contribution of static quenching. The downward-curving Stern-Volmer plots are well described by a two-site model that assumes accessible and inaccessible sites to the acceptor on latex particles. The Stern-Volmer constants obtained indicate that in the latex dispersions the fluorescence quenching occurs several hundreds times more efficiently than that in an aqueous homogeneous solution. This drastic enhancement of the quenching in latex dispersions is attributed to the increase in the local concentrations of the reactants on the latex surface. We have demonstrated the usefulness of latex surfaces as a new type of reaction field for photoinduced electron transfer.     

Coalescence map for bubbles in surfactant-free aqueous electrolyte solutions

Factors influencing bubble coalescence in surfactant-free aqueous electrolyte solutions are considered in this compilation of literature results. These factors include viscous and inertial thin film drainage, surface deformation, surface elasticity, mobility or otherwise of the air-water interface, and disjoining pressure. Several models from the literature are discussed, with particular attention paid to predictions of transitions between regions where behaviour is qualitatively different. The transitions are collated onto a single chart with salt concentration and bubble approach speed as the axes. This creates a map of the regions in which different mechanisms operate, giving an overall picture of bubble coalescence behaviour over a wide range of concentration and speed. Only mm-size bubbles in water and NaCl solutions are discussed in this initial effort at creating such a map. Data on bubble coalescence or non-coalescence are collected from the literature and plotted on the same map, generally aligning well with the predicted transitions and thus providing support for the theoretical reasoning that went into creating the coalescence map.     

Inhibition of bubble coalescence: effects of salt concentration and speed of approach

Bubble coalescence experiments have been performed using a sliding bubble apparatus, in which mm-sized bubbles in an aqueous electrolyte solution without added surfactant rose toward an air meniscus at different speeds obtained by varying the inclination of a closed glass cylinder containing the liquid. The coalescence times of single bubbles contacting the meniscus were monitored using a high speed camera. Results clearly show that stability against coalescence of colliding air bubbles is influenced by both the salt concentration and the approach speed of the bubbles. Contrary to the widespread belief that bubbles in pure water are unstable, we demonstrate that bubbles formed in highly purified water and colliding with the meniscus at very slow approach speeds can survive for minutes or even hours. At higher speeds, bubbles in water only survive for a few seconds, and at still higher speeds they coalesce instantly. Addition of a simple electrolyte (KCl) removes the low-speed stability and shifts the transition between transient stability and instant coalescence to higher approach speeds. At high electrolyte concentration no bubbles were observed to coalesce instantly. These observations are consistent with recent results of Yaminsky et al. (Langmuir 26 (2010) 8061) and the transitions between different regions of behavior are in semi-quantitative agreement with Yaminsky's model.