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).     

Experimental investigation of conical bubble structure and acoustic flow structure in ultrasonic field

The objective of this paper is to investigate the transient conical bubble structure (CBS) and acoustic flow structure in ultrasonic field. In the experiment, the high-speed video and particle image velocimetry (PIV) techniques are used to measure the acoustic cavitation patterns, as well as the flow velocity and vorticity fields. Results are presented for a high power ultrasound with a frequency of 18 kHz, and the range of the input power is from 50 W to 250 W. The results of the experiment show the input power significantly affects the structures of CBS, with the increase of input power, the cavity region of CBS and the velocity of bubbles increase evidently. For the transient motion of bubbles on radiating surface, two different types could be classified, namely the formation, aggregation and coalescence of cavitation bubbles, and the aggregation, shrink, expansion and collapse of bubble cluster. Furthermore, the thickness of turbulent boundary layer near the sonotrode region is found to be much thicker, and the turbulent intensities are much higher for relatively higher input power. The vorticity distribution is prominently affected by the spatial position and input power.     

Effect of amplitude and frequency of ultrasonic irradiation on morphological characteristics control of calcium carbonate

We have previously reported on the morphological control of calcium carbonate by changing synthetic conditions such as temperature, pH and degree of supersaturation in liquid reaction. The present study reports the effect of amplitude and frequency of ultrasonic irradiation on the particle size of calcium carbonate using a horn type ultrasonic apparatus at two different frequencies. The calcium carbonate precipitated by mechanical stirring had a particle size of about 20 μm. By contrast, the particle size of vaterite formed under ultrasonic irradiation was about 2 μm, with a specific surface area of 25–30 m²/g. The major polymorph of calcium carbonate formed by ultrasonic irradiation was vaterite with some calcite present. For 40 kHz ultrasonic irradiation, the specific surface area of the calcium carbonate increased with increasing amplitude. The particle size of vaterite formed at this frequency was about 2 μm, and its distribution was sharper than that obtained at 20 kHz. The mode diameter of the synthesized vaterite was found to decrease with increasing amplitude at 40 kHz.     

Effect of gold nanoparticle size on acoustic cavitation using chemical dosimetry method

When a liquid is irradiated with high intensities of ultrasound irradiation, acoustic cavitation occurs. Acoustic cavitation generates free radicals from the breakdown of water and other molecules. Cavitation can be fatal to cells and is utilized to destroy cancer tumors. The existence of particles in liquid provides nucleation sites for cavitation bubbles and leads to decrease the ultrasonic intensity threshold needed for cavitation onset. In the present investigation, the effect of gold nanoparticles with appropriate amount and size on the acoustic cavitation activity has been shown by determining hydroxyl radicals in terephthalic acid solutions containing 15, 20, 28 and 35 nm gold nanoparticles sizes by using 1 MHz low level ultrasound. The effect of sonication intensity in hydroxyl radical production was considered.The recorded fluorescence signal in terephthalic acid solutions containing gold nanoparticles was considerably higher than the terephthalic acid solutions without gold nanoparticles at different intensities of ultrasound irradiation. Also, the results showed that the recorded fluorescence signal intensity in terephthalic acid solution containing finer size of gold nanoparticles was lower than the terephthalic acid solutions containing larger size of gold nanoparticles. Acoustic cavitation in the presence of gold nanoparticles can be used as a way for improving therapeutic effects on the tumors.     

Sonication effects on non-radical reactions. A sonochemistry beyond the cavitation?

The kinetics of pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated under ultrasonic irradiation with an application of 10% of the maximum power of the equipment and without sonication in acetonitrile–water binary mixtures with a content of acetonitrile ranging from 0.008 to 35 wt.%. Similar kinetic investigations were performed at intensities corresponding to 10%, 20%, 30%, 40%, and 50% of the input energy in solvent mixtures containing 10 wt.% and 25 wt.% acetonitrile. In parallel, the responses of KI and terephthalic acid dosimeters at applied irradiation levels were registered under the same experimental conditions. Significant kinetic sonication effects were found at sound intensities presumably not inducing cavitation in the solution. This result provides an experimental evidence of kinetic effects of ultrasound in the absence of cavitation. A disturbing impact of cavitation on the ultrasonic acceleration of the reaction was found. The implications of these findings were discussed.     

Effect of potassium monopersulfate (oxone) and operating parameters on sonochemical degradation of cationic dye in an aqueous solution

In this study, removal of Cresol Red (CR), a cationic triphenylmethane dye, by 300 kHz ultrasound was investigated. The effect of additive such as potassium monopersulfate (oxone) was studied. Additionally, sonolytic degradation of CR was investigated at varying power and initial pH. RC can be readily eliminated by the ultrasound process. The obtained results showed that. Sonochemical degradation of CR was strongly affected by ultrasonic power and pH. The degradation rate of the dye increased substantially with increasing ultrasonic power in the range of 20–80 W. This improvement could be explained by the increase in the number of active cavitation bubbles. The significant degradation was achieved in acidic conditions (pH = 2) where the color removal was 99% higher than those observed in higher pH aqueous solutions. The ultrasonic degradation of dye was enhanced by potassium monopersulfate (oxone) addition. It was found that the degradation of the dye was accelerated with increased concentrations of oxone for a reaction time of 75 min.     

Ultrasound assisted enzyme catalyzed transesterification of waste cooking oil with dimethyl carbonate

This work reports the production of biodiesel with waste cooking oil and dimethyl carbonate in solvent free system through transesterification by immobilized enzyme (Novozym 435) under the influence of ultrasound irradiation. The experiments were conducted in an ultrasonic water bath under three different conditions i.e. ultrasonic irradiation (UI) without stirring, UI coupled with stirring and only stirring to compare their overall effects on fatty acid methyl esters (FAME) conversion. As compared with the conventional stirring method, where FAME conversion was 38.69% at 4 h, the UI without stirring significantly enhanced the conversion of enzymatic transesterification to 57.68% for the same reaction time. However the reaction rate was further increased under the condition of ultrasonication coupled with stirring and resulted into higher conversion of 86.61% for the same reaction time. Effects of reaction parameters, such as temperature, ratio of DMC/oil, speed of agitation and enzyme loading on the conversion were investigated. Furthermore, repeated use of Novozym 435 showed gradual decline in both conversion as well as enzyme activity.     

Synthesis of NaP zeolite at room temperature and short crystallization time by sonochemical method

NaP zeolite nano crystals were synthesized by sonochemical method at room temperature with crystallization time of 3 h. For comparison, to insure the effect of sonochemical method, the hydrothermal method at conventional synthesis condition, with same initial sol composition was studied. NaP zeolites are directly formed by ultrasonic treatment without the application of autogenous pressure and also hydrothermal treatment. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, the crystallinity of the powders decreased but phase purity remain unchanged. The synthesized powders were characterized by XRD, IR, DTA TGA, FESEM, and TEM analysis. FESEM images revealed that 50 nm zeolite crystals were formed at room temperature by using sonochemical method. However, agglomerated particles having cactus/cabbage like structure was obtained by sonochemical method followed by hydrothermal treatment. In sonochemical process, formation of cavitation and the collapsing of bubbles produced huge energy which is sufficient for crystallization of zeolite compared to that supplied by hydrothermal process for conventional synthesis. With increasing irradiation energy and time, the crystallinity of the synthesized zeolite samples increased slightly.     

Mechanistic insight into sonochemical biodiesel synthesis using heterogeneous base catalyst

The beneficial effect of ultrasound on transesterification reaction is well known. Heterogeneous (or solid) catalysts for biodiesel synthesis have merit that they do not contaminate the byproduct of glycerol. In this paper, we have attempted to identify the mechanistic features of ultrasound–enhanced biodiesel synthesis with the base–catalyst of CaO. A statistical design of experiments (Box–Behnken) was used to identify the influence of temperature, alcohol to oil molar ratio and catalyst loading on transesterification yield. The optimum values of these parameters for the highest yield were identified through Response Surface Method (with a quadratic model) and ANOVA. These values are: temperature = 62 °C, molar ratio = 10:1 and catalyst loading = 6 wt.%. The activation energy was determined as 82.3 kJ/mol, which is higher than that for homogeneous catalyzed system (for both acidic and basic catalyst). The experimental results have been analyzed vis–à–vis simulations of cavitation bubble dynamics. Due to 3–phase heterogeneity of the system, the yield was dominated by intrinsic kinetics, and the optimum temperature for the highest yield was close to boiling point of methanol. At this temperature, the influence of cavitation bubbles (in terms of both sonochemical and sonophysical effect) is negligible, and ultrasonic micro–streaming provided necessary convection in the system. The influence of all parameters on the reaction system was found to be strongly inter–dependent.     

Transesterification of soybean oil by using the synergistic microwave-ultrasonic irradiation

Microwave and ultrasound have been demonstrated to be outstanding process intensification techniques for transesterification of oil. According to their mechanisms, simultaneous effects can surely bring about better enhancement than sole microwave or ultrasound. Therefore, this study aimed to investigate the important factors and their suitable levels in the KOH-catalyzed transesterification of soybean oil with methanol by using synergistic assistance of microwave-ultrasound (CAMU). The feasibility of application of CAMU in transesterification of oil was demonstrated. When the dosage of methanol, soybean oil and KOH were 15.4 g, 34.7 g (with methanol-to-oil molar ratio of 12:1) and 1 g, respectively, and the microwave power, ultrasonic power, ultrasonic mode, reaction temperature and reaction time were 700 W, 800 W, 1:0, 65 °C and 6 min, respectively, the transesterification reached 98.0% of yield, being the highest yield among all the results obtained; while by using 600 W of microwave plus stirring instead of CAMU, only 57.4% of yield could be obtained. Compared with other reaction techniques, the transesterification by applying novel CAMU was found to have remarkable advantages. Furthermore, by monitoring the variation of real-time temperature and microwave power during transesterification reactions with different microwave operation time and by taking comparison of the corresponding yield, it was demonstrated that the main reason for the acceleration of microwave-assisted transesterification was the polarization and further activation of reactants caused by microwave irradiation, but not the factor of fast heating.     

Towards an understanding and control of cavitation activity in 1 MHz ultrasound fields

Various industrial processes such as sonochemical processing and ultrasonic cleaning strongly rely on the phenomenon of acoustic cavitation. As the occurrence of acoustic cavitation is incorporating a multitude of interdependent effects, the amount of cavitation activity in a vessel is strongly depending on the ultrasonic process conditions. It is therefore crucial to quantify cavitation activity as a function of the process parameters. At 1 MHz, the active cavitation bubbles are so small that it is becoming difficult to observe them in a direct way. Hence, another metrology based on secondary effects of acoustic cavitation is more suitable to study cavitation activity. In this paper we present a detailed analysis of acoustic cavitation phenomena at 1 MHz ultrasound by means of time-resolved measurements of sonoluminescence, cavitation noise, and synchronized high-speed stroboscopic Schlieren imaging. It is shown that a correlation exists between sonoluminescence, and the ultraharmonic and broadband signals extracted from the cavitation noise spectra. The signals can be utilized to characterize different regimes of cavitation activity at different acoustic power densities. When cavitation activity sets on, the aforementioned signals correlate to fluctuations in the Schlieren contrast as well as the number of nucleated bubbles extracted from the Schlieren Images. This additionally proves that signals extracted from cavitation noise spectra truly represent a measure for cavitation activity. The cyclic behavior of cavitation activity is investigated and related to the evolution of the bubble populations in the ultrasonic tank. It is shown that cavitation activity is strongly linked to the occurrence of fast-moving bubbles. The origin of this “bubble streamers” is investigated and their role in the initialization and propagation of cavitation activity throughout the sonicated liquid is discussed. Finally, it is shown that bubble activity can be stabilized and enhanced by the use of pulsed ultrasound by conserving and recycling active bubbles between subsequent pulsing cycles.     

Application and mechanism of ultrasonic static mixer in heavy oil viscosity reduction

In the present study, heavy oil viscosity reduction in Daqing oil field was investigated by using an ultrasonic static mixer. The influence of the ultrasonic power on the viscosity reduction rate was investigated and the optimal technological conditions were determined for the ultrasonic treatment. The mechanism for ultrasonic viscosity reduction was analyzed. The flow characteristics of heavy oil in the mixer under the effect of cavitation were investigated using numerical modeling, and energy consumptions were calculated during the ultrasonic treatment and vis-breaking processes. The experimental results indicated that the ultrasonic power made the largest impact on the viscosity reduction rate, followed by the reaction time and temperature. The highest viscosity reduction rate was 57.34%. Vacuole was migrated from the axis to the wall along the fluid, accelerating the two-phase transmission and enhancing the radial flow of the fluid, which significantly improved the ultrasonic viscosity reduction. Compared to the vis-breaking process, the energy consumption of ultrasonic treatment process was 43.03% lower when dealing with the same quality heavy oil. The optimal process conditions were found to be as follows: ultrasonic power of 1.8 kW, reaction time of 45 min and reaction temperature of 360 °C. The dissociation of the molecules of heavy oil after ultrasonication has been checked. After being kept at room temperature 12 days, some light components were produced by the cavitation cracking, so the viscosity of the residual oil could not return to that of the original residual oil, which meant that the “cage effect” was not reformed.     

Synchrotron radiation X-ray imaging of cavitation bubbles in Al–Cu alloy melt

Cavitation bubbles in Al–10 wt.%Cu melt has been investigated by adopting synchrotron radiation X-ray imaging technology. In-situ observation reveals that most of bubbles concentrate within an intense cavitation zone nearby the radiation face. The measured near-maximum bubble radii obey a similar truncated Gaussian distribution as in water but increase by nearly the magnitude of one order due to higher ultrasonic intensity applied in aluminum melt.     

Enhanced sonochemical degradation of perfluorooctanoic acid by sulfate ions

This study investigated the effects of sulfate ions on the decomposition of perfluorooctanoic acid (PFOA) by ultrasonic (US) irradiation at various pHs, sulfate doses, powers and temperatures. The removal of PFOA was augmented with an increased sulfate ion concentration, with PFOA being almost completely decomposed in 90 min at 25 °C with a sulfate dose of 117 mM. The two major mechanisms in the sulfate-assisted sonochemical system are the direct destruction of PFOA by cavitation and the indirect destruction of PFOA by sulfate free radicals. The decomposition of PFOA followed pseudo-first-order kinetics and was not influenced by pH. The reaction rate constants decreased with increases in temperature due to decreases in the surface tension of the solution.     

Reductive dechlorination of 2,4-dichlorophenol by Pd/Fe nanoparticles prepared in the presence of ultrasonic irradiation

Palladium/Iron (Pd/Fe) nanoparticles were prepared by using ultrasound strengthened liquid phase reductive method to enhance dispersion and avoid agglomeration. The dechlorination of 2,4-dichlorophenol (2,4-DCP) by Pd/Fe nanoparticles was investigated to understand its feasibility for an in situ remediation of contaminated groundwater. Results showed that 2,4-DCP was first adsorbed by Pd/Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). The induction of ultrasound during the preparation of Pd/Fe nanoparticles further enhanced the removal efficiency of 2,4-DCP, as a result, the phenol production rates increased from 65% (in the absence of ultrasonic irradiation) to 91% (in the presence of ultrasonic irradiation) within 2 h. Our data suggested that the dechlorination rate was dependent on various factors including Pd loading percentage over Fe⁰, Pd/Fe nanoparticles availability, temperature, mechanical stirring speed, and initial pH values. Up to 99.2% of 2,4-DCP was removed after 300 min reaction with these conditions: Pd loading percentage over Fe⁰ 0.3 wt.%, initial 2,4-DCP concentration 20 mg L^?1, Pd/Fe dosage 3 g L^?1, initial pH value 3.0, and reaction temperature 25 °C. The degradation of 2,4-DCP followed pseudo-first-order kinetics reaction and the apparent pseudo-first-order kinetics constant was 0.0468 min^?1.     

The effects of ultrasound on micromixing

The Villermaux–Dushman reaction is a widely used technique to study micromixing efficiencies with and without sonication. This paper shows that ultrasound can interfere with this reaction by sonolysis of potassium iodide, which is excessively available in the Villermaux–Dushman solution, into triiodide ions. Some corrective actions, to minimize this interference, are proposed. Furthermore, the effect of ultrasonic frequency, power dissipation, probe tip surface area and stirring speed on micromixing were investigated. The power and frequency seem to have a significant impact on micromixing in contrast to the stirring speed and probe tip surface area. Best micromixing was observed with a 24 kHz probe and high power intensities. Experiments with different frequencies but a constant power intensity, emitter surface, stirring speed, cavitation bubble type and reactor design showed best micromixing for the highest frequency of 1135 kHz. Finally, these results were used to test the power law model of Rahimi et al. This model was not able to predict micromixing accurately and the addition of the frequency, as an additional parameter, was needed to improve the simulations.     

Influence of dissolved gases on sonochemistry and sonoluminescence in a flow reactor

In the present work, the influence of gas addition is investigated on both sonoluminescence (SL) and radical formation at 47 and 248 kHz. The frequencies chosen in this study generate two distinct bubble types, allowing to generalize the conclusions for other ultrasonic reactors. In this case, 47 kHz provides transient bubbles, while stable ones dominate at 248 kHz. For both bubble types, the hydroxyl radical and SL yield under gas addition followed the sequence: Ar > Air > N₂ >> CO₂. A comprehensive interpretation is given for these results, based on a combination of thermal gas properties, chemical reactions occurring within the cavitation bubble, and the amount of bubbles. Furthermore, in the cases where argon, air and nitrogen were bubbled, a reasonable correlation existed between the OH-radical yield and the SL signal, being most pronounced under stable cavitation at 248 kHz. Presuming that SL and OH originate from different bubble populations, the results indicate that both populations respond similarly to a change in acoustic power and dissolved gas. Consequently, in the presence of non-volatile pollutants that do not quench SL, sonoluminescence can be used as an online tool to qualitatively monitor radical formation.     

Catalytic dechlorination of 2,4-dichlorophenol by Ni/Fe nanoparticles prepared in the presence of ultrasonic irradiation

In this study, nickle/iron (Ni/Fe) nanoparticles were synthesized by liquid phase reductive method in the presence of 20 kHz ultrasonic irradiation to improve nanoparticles’ disparity and avoid agglomeration. The characterized results showed that this method has obviously modified most of the particles in term of sizes and specific surface areas. Meanwhile, the improved nanoscale Ni/Fe particles were employed for the reductive dechlorination of 2,4-dichlorophenol (2,4-DCP) as a function of some influential factors (Ni content, Ni/Fe nanoparticles dosage, reaction temperature and initial pH values) and degradation path. Experimental results showed that 2,4-DCP was first adsorbed by Ni/Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). The application of ultrasonic irradiation for Ni/Fe nanoparticles synthesis was found to significantly enhance the removal efficiency of 2,4-DCP. Consequently, the phenol production rates increased from 68% (in the absence of ultrasonic irradiation) to 87% (in the presence of ultrasonic irradiation) within 180 min. Nearly 96% of 2,4-DCP was removed after 300 min reaction with these optimized conditions: Ni content over Fe⁰ 3 wt%, initial 2,4-DCP concentration 20 mg L⁻¹, Ni/Fe dosage 3 g L⁻¹, initial pH value 3.0, and reaction temperature 25 °C. The degradation of 2,4-DCP followed pseudo-first-order kinetics reaction and the apparent pseudo-first-order kinetics constant was 0.0737 min⁻¹. This study suggested that the presence of ultrasonic irradiation in the synthesis of nanoscale Ni/Fe particles could be a promising technique to enhance nanoparticle’s disparity and avoid agglomeration.     

Ultrasound assisted enzyme catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate

The present work illustrates the transesterification of glycerol to glycerol carbonate (GlyC) from dimethyl carbonate (DMC) using commercial immobilized lipase (Novozym 435) under ultrasonic irradiation. The experiments were performed in a batch reactor placed in an ultrasonic water bath using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound power on the conversion of glycerol to GlyC. It has been found that ultrasound-assisted lipase-catalyzed transesterification of glycerol would be a potential alternative to conventional alkali-catalyzed method, as high conversion (99.75%) was obtained at mild operating conditions: molar ratio of DMC to glycerol 3:1, catalyst amount of 13% (w/w), lower power input (100 W), duty cycle 50% and temperature (60 °C) in a relatively short reaction time (4 h) using Novozym 435 as catalyst. Ultrasound reduces the reaction time up to 4 h as compared to conventional stirring method (14 h) catalyzed by Novozym 435. The repeated use of the catalyst under the optimum experimental condition resulted in decay in both enzyme activity and product conversion.     

Generation and control of acoustic cavitation structure

The generation and control of acoustic cavitation structure are a prerequisite for application of cavitation in the field of ultrasonic sonochemistry and ultrasonic cleaning. The generation and control of several typical acoustic cavitation structures (conical bubble structure, smoker, acoustic Lichtenberg figure, tailing bubble structure, jet-induced bubble structures) in a 20–50 kHz ultrasonic field are investigated. Cavitation bubbles tend to move along the direction of pressure drop in the region in front of radiating surface, which are the premise and the foundation of some strong acoustic cavitation structure formation. The nuclei source of above-mentioned acoustic cavitation structures is analyzed. The relationship and mutual transformation of these acoustic cavitation structures are discussed.