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.     

Physical features of ultrasound-enhanced heterogeneous permanganate oxidation

This paper addresses the matter of mechanistic features of ultrasound-assisted permanganate oxidation of organic compounds in aqueous phase. This reaction system is essentially a liquid–liquid heterogeneous one, which is limited by the mass transfer characteristics. Previous research has established that ultrasound irradiation of reaction mixture enhances the kinetics and yield of permanganate oxidation. The principal physical effect of ultrasonic cavitation is formation of fine emulsion between immiscible phases that eliminates the mass transfer resistance, while principal chemical effect is production of radicals through transient collapse of cavitation bubbles, which accelerate the reaction. In this paper, we have tried to discriminate between these physical and chemical effects by coupling experiments with different conditions (which alter the nature of cavitation phenomena in the medium) to simulations of cavitation bubble dynamics. It is revealed that in absence of radical conserving agent, the enhancement effect is merely physical. Diffusion of radicals towards interface between phases, where the oxidation reaction occurs is the limiting factor in contribution of chemical effect of ultrasonic cavitation towards enhancement of oxidation. Enhancement of total radical production in the aqueous phase (by degassing of the medium) increases the overall oxidation yield, but only marginally. On the other hand, addition of a radical conserver such as FeSO₄·7H₂O results in marked enhancement in oxidation yield, as the conserver assists deeper penetration of radicals in the aqueous medium and diffusion towards interface.     

Numerical simulation of cavitation bubble dynamics induced by ultrasound waves in a high frequency reactor

The use of high frequency ultrasound in chemical systems is of major interest to optimize chemical procedures. Characterization of an open air 477 kHz ultrasound reactor shows that, because of the collapse of transient cavitation bubbles and pulsation of stable cavitation bubbles, chemical reactions are enhanced. Numerical modelling is undertaken to determine the spatio-temporal evolution of cavitation bubbles. The calculus of the emergence of cavitation bubbles due to the acoustic driving (by taking into account interactions between the sound field and bubbles' distribution) gives a cartography of bubbles' emergence within the reactor. Computation of their motion induced by the pressure gradients occurring in the reactor show that they migrate to the pressure nodes. Computed bubbles levitation sites gives a cartography of the chemical activity of ultrasound. Modelling of stable cavitation bubbles' motion induced by the motion of the liquid gives some insight on degassing phenomena.     

Mechanistic investigation of the sonochemical synthesis of zinc ferrite

In this investigation, an attempt has been made to establish the physical mechanism of sonochemical synthesis of zinc ferrite with concurrent analysis of experimental results and simulations of cavitation bubble dynamics. Experiments have been conducted with mechanical stirring as well as under ultrasound irradiation with variation of pH and the static pressure of the reaction medium. Results of this study reveal that physical effects produced by transient cavitation bubbles play a crucial role in the chemical synthesis. Generation of high amplitude shock waves by transient cavitation bubbles manifest their effect through in situ micro-calcination of metal oxide particles (which are generated through thermal hydrolysis of metal acetates) due to energetic collisions between them. Micro-calcination of oxide particles can also occur in the thin liquid shell surrounding bubble interface, which gets heated up during transient collapse of bubbles. The sonochemical effect of production of OH radicals and H₂O₂, in itself, is not able to yield ferrite. Moreover, as the in situ micro-calcination involves very small number of particles or even individual particles (as in intra-particle collisions), the agglomeration between resulting ferrite particles is negligible (as compared to external calcination in convention route), leading to ferrite particles of smaller size (6 nm).     

Reactive mixing performance for a nanoparticle precipitation in a swirling vortex flow reactor

Mixing performance for a consecutive competing reaction system has been investigated in a swirling vortex flow reactor (SVFR). The direct quadrature method of moments combined with the interaction by exchange with the mean (DQMOM-IEM) method was employed to model such reacting flows. This type of reactors is able to generate a strong swirling flow with a great shear gradient in the radial direction. Firstly, mixing at both macroscale and microscale was assessed by mean mixture fraction and its variance, respectively. It is found that macromixing can be rapidly achieved throughout the whole reactor chamber due to its swirling feature. However, micromixing estimated by Bachelor length scale is sensitive to turbulence. Moreover, the additional introduction of ultrasound irradiation can significantly improve the mixing uniformity, namely, free of any stagnant zone presented in the reactor chamber on a macroscale, and little variance deviating from the mean environment value can be observed on a microscale. Secondly, reaction progress variable and the reactant conversion serve as indicators for the occurrence of side reaction. It is found that strong turbulence and a relatively fast micromixing process compared to chemical reaction can greatly reduce the presence of by-product, which will then provide homogenous environment for particle precipitation. Moreover, due to the generation of cavitation bubbles and their subsequent collapse, ultrasound irradiation can further intensify turbulence, creating rather even environment for chemical reactions. Low conversion rate was observed and little by-products were generated consequently. Therefore, it is suggested that the SVFR especially intensified by ultrasound irradiation has the ability to provide efficient mixing performance for the fine-particle synthesis process.     

High-speed imaging of ultrasonic emulsification using a water-gallium system

Aiming at elucidating ultrasonic emulsification mechanisms, the interaction between a single or multiple acoustic cavitation bubbles and gallium droplet interface was investigated using an high-speed imaging technique. To our best knowledge, the moment of emulsification and formation of fine droplets during ultrasound irradiation were observed for the first time. It was found that the detachment of fine gallium droplets occurs from the water-gallium interface during collapse of big cavitation bubbles. The results suggest that the maximum size of cavitation bubble before collapsing is of prime importance for emulsification phenomena. Previous numerical simulation revealed that the collapse of big cavitation bubble is followed by generation of high-velocity liquid jet directed toward the water-gallium interface. Such a jet is assumed to be the prime cause of liquid emulsification. The distance between cavitation bubbles and water-gallium interface was found to slightly affect the emulsification onset. The droplet fragmentation conditions are also discussed in terms of the balance between (1) interfacial and kinetic energies and (2) dynamic and Laplace pressure during droplet formation.     

TiO2 nanosized powders controlling by ultrasound sol-gel reaction

We studied that anatase-TiO2 powders prepared from sol-gel process of titanium tetra-isopropoxide (TTIP) were developed under ultrasonic irradiation with different frequency of 28, 45 and 100 kHz. The irradiated ultrasound (US) was controlled by using semi-cylindrical reflection plate that was placed onto the vicinity of reaction vessel. The focused US influenced the reduction of particles size and increased the surface area of resultant nanosized TiO2 powders. We also examined photodegradation of rhodamine 640 dye (Rh-640) solution by the resultant TiO2 under UV light exposure. It was observed that low frequency for TiO2 photocatalyst preparation and low calcination temperature were more affected onto the photodegradation of the dye.     

Ultrasonic depolymerization of aqueous polyvinyl alcohol.

Ultrasonication has proved to be a highly advantageous method for depolymerizing macromolecules because it reduces their molecular weight simply by splitting the most susceptible chemical bond without causing any changes in the chemical nature of the polymer. Most of the effects involved in controlling molecular weight can be attributed to the large shear gradients and shock waves generated around collapsing cavitation bubbles. In general, for any polymer degradation process to become acceptable to industry, it is necessary to be able to specify the sonication conditions which lead to a particular relative molar mass distribution. This necessitates the identification of the appropriate irradiation power, temperature, concentration and irradiation time. According to the results of this study the reactors constructed worked well in depolymerization and it was possible to degrade aqueous polyvinyl alcohol (PVA) polymer with ultrasound. The most extensive degradation took place at the lowest frequency used in this study, i.e. 23 kHz, when the input power was above the cavitation threshold and at the lowest test concentration of PVA, i.e. 1% (w/w). Thus this study confirms the general assumption that the shear forces generated by the rapid motion of the solvent following cavitational collapse are responsible for the breakage of the chemical bonds within the polymer. The effect of polymer concentration can be interpreted in terms of the increase in viscosity with concentration, causing the molecules to become less mobile in solution and the velocity gradients around the collapsing bubbles to therefore become smaller.     

Effect of ultrasound pre-treatment on carbonaceous copper-bearing shale flotation

Although numerous studies have been implemented on identifying the impact of acoustic waves on mineral beneficiation, its fundamental aspects remain unclear in the literature. The present work, for the first time, systematically investigates the role of ultrasound pre-treatment (UPT) in the carbonaceous copper-bearing shale flotation. To this end, conditioning was carried out at different powers of applied ultrasound. Non-treated and UPT shale flotation tests were performed in the presence of frother (MIBC) and collector (KEX). To analyse particle surface charge variation and collector adsorption properties after application of UPT, zeta potential and ultraviolet–visible spectroscopy measurements were implemented, respectively. The generation of sub-micron bubbles due to the acoustic cavitation was characterised by laser-based particle size measurements. Shale hydrophobicity was determined using the sessile drop and captive bubble techniques.The micro-flotation results showed that the mass recovery increased by 40% at 20 W of applied ultrasonic power. The positive effect of UPT on the copper-bearing shale flotation was related to: i) generation of ultrafine bubbles due to the acoustic cavitation phenomenon and ii) the cleaning effect through transient bubble collapse. However, rigorous ultra-sonication diminished the recoverability of the sample owing to the less intensified number of ultrafine bubbles on the particle surfaces and formation of free H and OH radicals, which led to the oxidation of particle surfaces. These statements were correlated well with the observations of the zeta potential, particle size analysis and quantified ultrafine bubbles. Finally, we briefly highlighted fundamental knowledge gaps in flotation and ultrasound-related issues for future work.     

Sonocatalytic facilitation of hydroxyl radical generation in the presence of TiO2

The generation of hydroxyl (OH) radicals was investigated during ultrasonic irradiation and in the presence of TiO(2). The effect of TiO(2) on an ultrasonic system's oxidation power was evaluated by examining the oxidation of salicylic acid. The generation of the salicylic acid derivatives, 2,3-dihydroxybenzoic acid (DHBA) and 2,5-DHBA, was measured by high-performance liquid chromatography coupled with electrochemical detection under different experimental conditions. The presence of TiO(2) enhanced the generation of DHBA during ultrasonic irradiation, thus indicating a higher oxidation power in the ultrasonic system. Al(2)O(3) also increased the generation of DHBA during irradiation; however, the effect of TiO(2) was found to be higher than that of Al(2)O(3). The addition of OH radical scavengers such as dimethylsulfoxide (DMSO), methanol and mannitol significantly suppressed the production of DHBA, and DMSO was found to have the highest suppressive effect among all scavengers. The effects of dissolved gases on the generation of OH radicals were further studied, and their power was found to be in the order Xe > Ar > O(2) > N(2). The degassing of the irradiation solution completely suppressed the generation of OH radicals. These results indicate that the presence of TiO(2) accelerates the generation of OH radicals during ultrasonic irradiation, and that the process may be mediated through the induction of cavitation bubbles in irradiating solutions.     

Removal of organic matter and ammonia nitrogen from landfill leachate by ultrasound

Experiments on the removal of organic matters and ammonia nitrogen from landfill leachate by ultrasound irradiation were carried out. The effects of COD reduction and ammonia removal of power input, initial concentration, initial pH and aeration were studied. It was found that the sonolysis of organic matters proceeds via reaction with ()OH radicals; a thermal reaction also occurs with a small contribution. The rise of COD at some intervals could be explained by the complexity of organic pollutant sonolysis in landfill leachate. Ultrasonic irradiation was shown to be an effective method for the removal of ammonia nitrogen from landfill leachate. After 180 min ultrasound irradiation, up to 96% ammonia nitrogen removal efficiency can be obtained. It was found that the mechanism of ammonia nitrogen removal by ultrasound irradiation is largely that the free ammonia molecules in leachate enter into the cavitation bubbles and transform into nitrogen molecules and hydrogen molecules via pyrolysis under instant high temperature and high pressure in the cavitation bubbles.     

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.     

Effects of medium viscoelasticity on bubble collapse strength of interacting polydisperse bubbles

Due to its physical and/or chemical effects, acoustic cavitation plays a crucial role in various emerging applications ranging from advanced materials to biomedicine. The cavitation bubbles usually undergo oscillatory dynamics and violent collapse within a viscoelastic medium, which are closely related to the cavitation-associated effects. However, the role of medium viscoelasticity on the cavitation dynamics has received little attention, especially for the bubble collapse strength during multi-bubble cavitation with the complex interactions between size polydisperse bubbles. In this study, modified Gilmore equations accounting for inter-bubble interactions were coupled with the Zener viscoelastic model to simulate the dynamics of multi-bubble cavitation in viscoelastic media. Results showed that the cavitation dynamics (e.g., acoustic resonant response, nonlinear oscillation behavior and bubble collapse strength) of differently-sized bubbles depend differently on the medium viscoelasticity and each bubble is affected by its neighboring bubbles to a different degree. More specifically, increasing medium viscosity drastically dampens the bubble dynamics and weakens the bubble collapse strength, while medium elasticity mainly affects the bubble resonance at which the bubble collapse strength is maximum. Differently-sized bubbles can achieve resonances and even subharmonic resonances at high driving acoustic pressures as the elasticity changes to certain values, and the resonance frequency of each bubble increases with the elasticity increasing. For the interactions between the size polydisperse bubbles, it indicated that the largest bubble generally has a dominant effect on the dynamics of smaller ones while in turn it is almost unaffected, exhibiting a pattern of destructive and constructive interactions. This study provides a valuable insight into the acoustic cavitation dynamics of multiple interacting polydisperse bubbles in viscoelastic media, which may offer a potential of controlling the medium viscoelasticity to appropriately manipulate the dynamics of multi-bubble cavitation for achieving proper cavitation effects according to the desired application.     

Enhancement of ultrasonic cavitation yield by multi-frequency sonication

The paper reports the enhanced effect of multi-frequency ultrasonic irradiation on cavitation yield. The cavitation yield is characterized by electrical conductivity determination, fluorescence intensity determination and iodine release method. Two-frequency (28 kHz/0.87 MHz) orthogonal continuous ultrasound, two-frequency (28 kHz/0.87 MHz) orthogonal pulse ultrasound and three-frequency (28 kHz/1.0 MHz/1.87 MHz) orthogonal continuous ultrasound have been used. It has been found that the combined irradiation of two or more frequencies of ultrasound can produce a significant increase in cavitation yield compared with single frequency irradiation. The possible mechanisms of the enhanced effect are briefly discussed.     

Sono-synthesis of core-shell nanocrystal (CdS/TiO2) without surfactant

A core-shell nanocomposite (CdS/TiO(2)) was synthesized at relatively low temperature (70°C) with small particle sizes (~11 nm). First, CdS nanoparticles were prepared by a combination of ultrasound and new micro-emulsion (O/W) without surfactant. Then the synthesized CdS was easily combined with TiO(2) under sonication. The formation of uniform surface layer of TiO(2) with depths of 0.75-1.1 nm on the CdS led to an increase of particle size. Ultrasonic irradiation can control the hydrolysis and condensation of titanium tetra-isopropoxide (TTIP) and the formation of TiO(2) shell around the CdS core. This technique avoids some of the problems that exist in conventional microemulsion synthesis such as the presence of different additives and calcinations. It was found that nanocomposite particles extend the optical absorption spectrum into the visible region in comparison with pure TiO(2) and pure CdS. In addition, a larger depth of TiO(2) led to a red-shift of the absorption band in nanocomposite. The characterization of nanocomposites has been studied by HRTEM, TEM, XRD, EDAX, BET and, UV-vis.     

Spatio-temporal dynamics of cavitation bubble clouds in a low frequency reactor: comparison between theoretical and experimental results.

The propagation of ultrasound through a liquid induces the growth of inceptions and germs into bubbles. In a low frequency reactor, fragmentary transient bubbles emerge due to the acoustic driving. They violently collapse in one cycle and fragment into many smaller bubbles than in turn cavitate. This violent collapse is responsible for the mechanical effects of ultrasounds effects. The latter bubbles gather in a ball-shaped cloud and migrate to pressure antinodes. During their migration, their nonexplosive collapses mainly contribute to activate chemical reactions by producing OH. radicals. Mathematical modelling is performed as a new approach to predict the bubbles field. Through numerical simulation, we determinate emergence sites of mechanically active cavitation bubbles. Calculus are compared with aluminium foil degradation. The modelling of bubble migration allow us to have an insight on the privileged sites of the chemical reactions. Validation of the modelling is made through direct comparison with chemiluminescence photo. All experiments and computations are made in a 28.2 kHz sonoreactor.     

The inception of cavitation bubble clouds induced by high-intensity focused ultrasound

In many therapeutic applications of high-intensity focused ultrasound (HIFU) the appearance of cavitation bubbles is unavoidable, whereas the dynamics of the bubbles induced by HIFU have not been clarified. The objective of the present work is to observe the inception process of cavitation bubble clouds generated by HIFU transducer in water using high-speed photography. Sequential images captured within 600 micros after the onset of ultrasound transmission show the dynamics of cavitation bubbles' generation, growth, deformation, expansion and collapse in the focal region. However, when the observation time is narrowed to the initial 145 micros, both the still and streak images reveal that the cavitation bubbles astonishingly stay stable in the focal region for at least 60 micros. The results imply that through adjusting the HIFU exposure time while other physical parameters are appropriately chosen, it might be possible to control the generation of stable cavitation bubbles locally in the focal region.     

Dynamical process of cavitation bubble adsorbed in gold nanoparticle under combined irradiations of laser and ultrasound

Under combined irradiation of laser and ultrasound,cavitary bubbles are generated on the surface of gold nanoparticle.The laser-induced thermal effect,ultrasonic cavitation effect and the synergistic effect of laser and ultrasound are studied by means of the investigation of the dynamical process for the vibration of the cavitation bubble,with different external conditions such as laser power,ultrasound intensity,etc.It is found that dynamical process of the cavitation bubble can be modified by the irradiation of laser or ultrasound.The enhancement of laser power can increase the critical radius of the cavitation bubble,while that of ultrasound may intensify the vibration.Cavitation bubble may become more stable due to the synergistic effect of laser and ultrasound.It is also found that variation of the coupling between laser and ultrasound can affect synergistic effect.     

Sonodynamic therapy using water-dispersed TiO2-polyethylene glycol compound on glioma cells: comparison of cytotoxic mechanism with photodynamic therapy

Sonodynamic therapy is expected to be a novel therapeutic strategy for malignant gliomas. The titanium dioxide (TiO(2)) nanoparticle, a photosensitizer, can be activated by ultrasound. In this study, by using water-dispersed TiO(2) nanoparticles, an in vitro comparison was made between the photodynamic and sonodynamic damages on U251 human glioblastoma cell lines. Water-dispersed TiO(2) nanoparticles were constructed by the adsorption of chemically modified polyethylene glycole (PEG) on the TiO(2) surface (TiO(2)/PEG). To evaluate cytotoxicity, U251 monolayer cells were incubated in culture medium including 100 μg/ml of TiO(2)/PEG for 3h and subsequently irradiated by ultraviolet light (5.0 mW/cm(2)) or 1.0MHz ultrasound (1.0 W/cm(2)). Cell survival was estimated by MTT assay 24h after irradiation. In the presence of TiO(2)/PEG, the photodynamic cytotoxic effect was not observed after 20 min of an ultraviolet light exposure, while the sonodynamic cytotoxicity effect was almost proportional to the time of sonication. In addition, photodynamic cytotoxicity of TiO(2)/PEG was almost completely inhibited by radical scavenger, while suppression of the sonodynamic cytotoxic effect was not significant. Results of various fluorescent stains showed that ultrasound-treated cells lost their viability immediately after irradiation, and cell membranes were especially damaged in comparison with ultraviolet-treated cells. These findings showed a potential application of TiO(2)/PEG to sonodynamic therapy as a new treatment of malignant gliomas and suggested that the mechanism of TiO(2)/PEG mediated sonodynamic cytotoxicity differs from that of photodynamic cytotoxicity.