Ultrasonic cavitation in CO2-expanded N,N-dimethylformamide (DMF)

Due to the tunability in mass transfer, solvation and solubility, gas-expanded liquids show advantages over traditional organic solvents in many characteristics. Ultrasonication is a commonly used method to promote heat and mass transfer. The introduction of ultrasonic technology into the gas-expanded liquid system can promote the polymerization of polymer monomers, enhance extraction efficiency, and control the growth size of nanocrystals, etc. Although acoustic cavitation has been extensively explored in aqueous solutions, there are still few studies on cavitation in organic liquids, especially in gas-expanded liquid systems. In this article, the development of cavitation bubble cloud structure in CO₂-expanded N, N-dimethylformamide (DMF) was observed by a high-speed camera, and the cavitation intensity was recorded using a spherical hydrophone. It was found that the magnitude of the transient cavitation energy was not only related to input power, but also closely related to CO₂ content. The combination of ultrasound (causing a rapid alternation of gas solubility) and gas-expanded liquid system (causing a decrease in viscosity and surface tension of liquids) is expected to provide a perfect platform for high-speed mass transfer.     

Cavitation under spherical focusing of acoustic pulses

The early stage of the dynamics of interacting cavitation bubbles in a transmitted spherically focused pulsed wave consisting of compression and rarefaction phases is studied. The cavitation is investigated away from the liquid boundaries for negative pressures up to −42 MPa with a decrease rate of −40 MPa/μs by high-speed microscopic filming (100 million frames per second and a spatial resolution of 5–50μm/pixel) and pressure measurements. It is demonstrated that, according to the kinematics of size variation, the bubbles are separated into two fractions: expanding and collapsing ones. Experimental data provide grounds to assume that the formation of a two-fraction bubble cluster occurs on account of different threshold values of pressure in the rarefaction wave for two characteristic sizes of nuclei, namely, micronuclei (d _I < 10μm) and nanonuclei (“bubstons,” d _II ∼ 1 nm), which become detectable only when the rarefaction wave amplitude exceeds the critical one. Pulsed compression of small bubbles in the process of transformation of a rarefaction wave into a compression wave occurs under the effect of a cluster’s internal pressure up to 20 MPa and proceeds with the conservation of the spherical shape of the second-fraction bubbles. It is demonstrated that the velocity of the center of mass of a bubble reaches its peak value close to the moment of bubble collapse. The translational and radial dynamics of a bubble are studied in a numerical experiment using the Rayleigh-Plesset equation and taking into account the viscous force and the pressure gradient. The results of measuring the translational shift may be useful for estimating the minimum bubble radius by comparing the numerical results with the experiment.     

Ultrasound coupled with supercritical carbon dioxide for exfoliation of graphene: Simulation and experiment

Ultrasound coupled with supercritical CO₂ has become an important method for exfoliation of graphene, but behind which a peeling mechanism is unclear. In this work, CFD simulation and experiment were both investigated to elucidate the mechanism and the effects of the process parameters on the exfoliation yield. The experiments and the CFD simulation were conducted under pressure ranging from 8 MPa to 16 MPa, the ultrasonic power ranging from 12 W to 240 W and the frequency of 20 kHz. The numerical analysis of fluid flow patterns and pressure distributions revealed that the fluid shear stress and the periodical pressure fluctuation generated by ultrasound were primary factors in exfoliating graphene. The distribution of the fluid shear stress decided the effective exfoliation area, which, in turn, affected the yield. The effective area increased from 5.339 cm³ to 8.074 cm³ with increasing ultrasonic power from 12 W to 240 W, corresponding to the yield increasing from 5.2% to 21.5%. The pressure fluctuation would cause the expansion of the interlayers of graphite. The degree of the expansion increased with the increase of the operating pressure but decreased beyond 12 MPa. Thus, the maximum yield was obtained at 12 MPa. The cavitation might be generated by ultrasound in supercritical CO₂. But it is too weak to exfoliate graphite into graphene. These results provide a strategy in optimizing and scaling up the ultrasound-assisted supercritical CO₂ technique for producing graphene.     

MnO2/CeO2 for catalytic ultrasonic degradation of methyl orange

Catalytic ultrasonic degradation of aqueous methyl orange was studied in this paper. Heterogeneous catalyst MnO₂/CeO₂ was prepared by impregnation of manganese oxide on cerium oxide. Morphology and specific surface area of MnO₂/CeO₂ catalyst were characterized and its composition was determined. Results showed big differences between fresh and used catalyst. The removal efficiency of methyl orange by MnO₂/CeO₂ catalytic ultrasonic process was investigated. Results showed that ultrasonic process could remove 3.5% of methyl orange while catalytic ultrasonic process could remove 85% of methyl orange in 10 min. The effects of free radical scavengers were studied to determine the role of hydroxyl free radical in catalytic ultrasonic process. Results showed that methyl orange degradation efficiency declined after adding free radical scavengers, illustrating that hydroxyl free radical played an important role in degrading methyl orange. Theoretic analysis showed that the resonance size of cavitation bubbles was comparable with the size of catalyst particles. Thus, catalyst particles might act as cavitation nucleus and enhance ultrasonic cavitation effects. Measurement of H₂O₂ concentration in catalytic ultrasonic process confirmed this hypothesis. Effects of pre-adsorption on catalytic ultrasonic process were examined. Pre-adsorption significantly improved methyl orange removal. The potential explanation was that methyl orange molecules adsorbed on catalysts could enter cavitation bubbles and undergo stronger cavitation.     

Numerical study of the synergistic effect of cavitation and micro-abrasive particles

In ultrasonic-assisted machining, the synergistic effect of the cavitation effect and micro-abrasive particles plays a crucial role. Studies have focused on the investigation of the micro-abrasive particles, cavitation micro-jets, and cavitation shock waves either individually or in pairs. To investigate the synergy of shock waves and micro-jets generated by cavitation with micro-abrasive particles in ultrasonic-assisted machining, the continuous control equations of a cavitation bubble, shock wave, micro-jet, and micro-abrasive particle influenced by the dimensionless amount (R/R₀), a particle size-velocity–pressure model of the micro-abrasive particle was established. The effects of ultrasonic frequency, sound pressure amplitude, and changes in particle size on micro-abrasive particle velocity and pressure were numerically simulated. At an ultrasonic frequency of 20 kHz and ultrasonic sound pressure of 0.1125 MPa, a smooth spherical SiO₂ micro-abrasive particle (size = 5 µm) was obtained, with a maximum velocity of 190.3–209.4 m/s and pressure of 79.69–89.41 MPa. The results show that in the range of 5–50 μm, smaller particle sizes of the micro-abrasive particles led to greater velocity and pressure. The shock waves, micro-jets, and micro-abrasive particles were all positively affected by the dimensionless amount (R/R₀) of cavitation bubble collapse, the larger the dimensionless quantity, the faster their velocity and the higher their pressure.     

Study of ultrasonic cavitation during extraction of the peanut oil at varying frequencies

The ultrasonic extraction of oils is a typical physical processing technology. The extraction process was monitored from the standpoint of the oil quality and efficiency of oil extraction. In this study, the ultrasonic cavitation fields were measured by polyvinylidene fluoride (PVDF) sensor. Waveform of ultrasonic cavitation fields was gained and analyzed. The extraction yield and oxidation properties were compared. The relationship between the fields and cavitation oxidation was established. Numerical calculation of oscillation cycle was done for the cavitation bubbles. Results showed that the resonance frequency, f_r, of the oil extraction was 40 kHz. At f_r, the voltage amplitude was the highest; the time was the shortest as reaching the amplitude of the waveform. Accordingly, the cavitation effect worked most rapidly, resulting in the strongest cavitation intensity. The extraction yield and oxidation properties were closely related to the cavitation effect. It controlled the cavitation oxidation effectively from the viewpoint of chemical and physical aspects.     

Realization of cavitation fields based on the acoustic resonance modes in an immersion-type sonochemical reactor

Different modes of cavitation zones in an immersion-type sonochemical reactor have been realized based on the concept of acoustic resonance fields. The reactor contains three main components, namely a Langevin-type piezoelectric transducer (20 kHz), a metal horn, and a circular cylindrical sonicated cell filled with tap water. In order to diminish the generation of cavitation bubbles near the horn-tip, an enlarged cone-shaped horn is designed to reduce the ultrasonic intensity at the irradiating surface and to get better distribution of energy in the sonicated cell. It is demonstrated both numerically and experimentally that the cell geometry and the horn position have prominent effects on the pressure distribution of the ultrasound in the cell. With appropriate choices of these parameters, the whole reactor works at a resonant state. Several acoustic resonance modes observed in the simulation are realized experimentally to generate a large volume of cavitation zones using a very low ultrasonic power.     

Influence of bubble clustering on multibubble sonoluminescence

Influence of clustering of cavitation bubbles on multibubble sonoluminescence (MBSL) in standing wave fields is studied through measurement of MBSL intensity with a photomultiplier tube and observation of corresponding bubble behavior with a high-speed video camera and an intensified charge-coupled device one. It is clarified that, when the SL is quenched suddenly at excessive ultrasonic power, the behavior of bubbles clearly changes; the bubbles which form dendritic branches of filaments change into clusters due to the secondary Bjerknes force. The cluster is composed of several bubbles surrounded by many tiny bubbles, in which bubbles repeatedly coalesce and fragment, and run away from pressure antinodes. When the clusters are broken up by forced fluid motion, the quenching of MBSL is suppressed.     

Ultrasonic cavitation at liquid/solid interface in a thin Ga–In liquid layer with free surface

Cavitation in thin layer of liquid metal has potential applications in chemical reaction, soldering, extraction, and therapeutic equipment. In this work, the cavitation characteristics and acoustic pressure of a thin liquid Ga–In alloy were studied by high speed photography, numerical simulation, and bubble dynamics calculation. A self-made ultrasonic system with a TC4 sonotrode, was operated at a frequency of 20 kHz and a max output power of 1000 W during the cavitation recording experiment. The pressure field characteristic inside the thin liquid layer and its influence on the intensity, types, dimensions, and life cycles of cavitation bubbles and on the cavitation evolution process against experimental parameters were systematically studied. The results showed that acoustic pressure inside the thin liquid layer presented alternating positive and negative characteristics within 1 acoustic period (T). Cavitation bubbles nucleated and grew during the negative-pressure stage and shrank and collapsed during the positive-pressure stage. A high bubble growth speed of 16.8 m/s was obtained and evidenced by bubble dynamics calculation. The maximum absolute pressure was obtained at the bottom of the thin liquid layer and resulted in the strongest cavitation. Cavitation was divided into violent and weak stages. The violent cavitation stage lasted several hundreds of acoustic periods and had higher bubble intensity than the weak cavitation stage. Cavitation cloud preferentially appeared during the violent cavitation stage and had a life of several acoustic periods. Tiny cavitation bubbles with life cycles shorter than 1 T dominated the cavitation field. High cavitation intensities were observed at high ultrasonication power and when Q235B alloy was used because such conditions lead to high amplitudes on the substrate and further high acoustic pressure inside the liquid.     

The size of active bubbles for the production of hydrogen in sonochemical reaction field

The sonication of aqueous solution generates microscopic cavitation bubbles that may growth and violently collapse to produce highly reactive species (i.e. OH, HO₂ and H₂O₂), hydrogen and emit light, sonoluminescence. The bubble size is a key parameter that influences the chemical activity of the system. This wok aims to study theoretically the size of active bubbles for the production of hydrogen in ultrasonic cavitation field in water using a single bubble sonochemistry model. The effect of several parameters such as frequency of ultrasound, acoustic intensity and liquid temperature on the range of sonochemically active bubbles for the production of hydrogen was clarified. The numerical simulation results showed that the size of active bubbles is an interval which includes an optimum value at which the production rate of H₂ is maximal. It was shown that the range of ambient radius for an active bubble as well as the optimum bubble radius for the production of hydrogen increased with increasing acoustic intensity and decreased with increasing ultrasound frequency and bulk liquid temperature. It was found that the range of ambient bubble radius dependence of the operational conditions followed the same trend as those reported experimentally for sonoluminescing bubbles. Comparison with literature data showed a good agreement between the theoretical determined optimum bubble sizes for the production of hydrogen and the experimental reported sizes for sonoluminescing bubbles.     

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

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

功率超声珩磨磨削区空化声场的建模与仿真研究

通过建立Φ47功率超声珩磨磨削区流体-结构耦合声场的理论模型,采用ANSYS有限元分析软件对磨削区的空化声场进行了仿真分析,得出磨削区二维、三维空化声场的分布情况和声压幅值,并利用超声波功率测量仪对磨削区的空化声场进行模拟实验测量。结果表明:在谐振频率18.6 kHz下,声场主要集中在油石的中部,二维和三维声场的声压最大值分别为1.39 MPa和1.47 MPa,与实验测得声压最大值1.3 MPa在同一个数量级,为进一步研究功率超声珩磨空化效应提供理论和实验的基础。      

Study on fracture of tungsten wire induced by acoustic cavitation at different hydrostatic pressures and driving electric powers

The near-solid wall multi-bubble cavitation is an extremely complex phenomenon, and cavitation has strong erosiveness. The melting point (about 3410 °C) of tungsten is highest among all pure metals, and its hardness is also very high (its yield strength is greater than 1 GPa). What would happen to pure tungsten wire under extreme conditions caused by collapsing cavitation bubbles at high hydrostatic pressure? In this paper, we have studied the fracture process of pure tungsten wire with diameter of 0.2 mm mounted at the focus of a standing acoustic wave produced by a spherical cavity transducer with two open ends placed in a near spherical pressure container, and also studied the macro and micro morphological characteristics of the fracture and the surface damage at different fracture stages of tungsten wire under various hydrostatic pressures and driving electric powers. The results have shown that the fracture time of tungsten wire is inversely proportional to avitation intensity with hydrostatic pressure and driving electric power, the higher the acoustic pressure caused by higher electric power, the shorter the fracture time. The possible fracture mechanisms of tungsten wire in this situation we found mainly contributed to asymmetrically bubbles collapse near the surface of tungsten wire, leading to tearing the surface apart; consequently cracks along the radial and axial directions of a tungsten wire extend simultaneously, classified as trans-granular fracture and inter-granular fracture, respectively. With the increase of cavitation intensity, the cracks tend to extend more radially and the axial crack propagation path becomes shorter, that is, mainly for trans-granular fracture; with the decrease of cavitation intensity, intergranular fracture becomes more obvious. When the hydrostatic pressure was 10 MPa and the driving electric power was 2 kW, the fibers became softener due to the fracture of the tungsten wire. The fracture caused by acoustic cavitation was different from conventional mechanical fracture, such as tensile, shear, fatigue fracture, on macro and micro morphology.     

Monte Carlo simulations of CO2-expanded acetonitrile

The structure and phase-equilibrium properties of CO₂-expanded acetonitrile (MeCN) were examined using Gibbs Ensemble Monte Carlo simulations. The results showed that the mole fraction of the CO₂ in the binary system increased linearly with pressure and the predicted volume expansion of the liquid phase with pressure is nonlinear and in agreement with experiment. The site–site radial distribution functions (RDFs) were determined for this binary mixture, which show that the homomolecular CO₂–CO₂ and heteromolecular CO₂–MeCN do not exhibit a significant dependence on CO₂ mole fraction. The only major structural change that is seen to occur as the CO₂ mole fraction is increased in the mixture is a decrease in the fraction of nearest neighbour MeCN molecules with parallel dipole orientations.     

High frequency ultrasonic-assisted CO2 absorption in a high pressure water batch system

Physical absorption process is always nullified by the presence of cavitation under low frequency ultrasonic irradiation. In the present study, high frequency ultrasonic of 1.7 MHz was used for the physical absorption of CO₂ in a water batch system under elevated pressure. The parameters including ultrasonic power and initial feed pressure for the system have been varied from 0 to 18 W and 6 to 41 bar, respectively. The mass transfer coefficient has been determined via the dynamic pressure-step method. Besides, the actual ultrasonic power that transmitted to the liquid was measured based on calorimetric method prior to the absorption study. Subsequently, desorption study was conducted as a comparison with the absorption process. The mechanism for the ultrasonic assisted absorption has also been discussed. Based on the results, the mass transfer coefficient has increased with the increasing of ultrasonic power. It means that, the presence of streaming effect and the formation of liquid fountain is more favorable under high frequency ultrasonic irradiation for the absorption process. Therefore, high frequency ultrasonic irradiation is suggested to be one of the potential alternatives for the gas separation process with its promising absorption enhancement and compact design.     

Measurement of acoustic power in studying cavitation processes

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

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

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

A fundamental study on the degradation of paracetamol under single- and dual-frequency ultrasound

The degradation of paracetamol, a widely found emerging pharmaceutical contaminant, was investigated under a wide range of single-frequency and dual-frequency ultrasonic irradiations. For single-frequency ultrasonic irradiation, plate transducers of 22, 98, 200, 300, 400, 500, 760, 850, 1000, and 2000 kHz were employed and for dual-frequency ultrasonic irradiation, the plate transducers were coupled with a 20 kHz ultrasonic horn in opposing configuration. The sonochemical activity was quantified using two dosimetry methods to measure the yield of HO• and H₂O₂ separately, as well as sonochemiluminescence measurement. Moreover, the severity of the bubble collapses as well as the spatial and size distribution of the cavitation bubbles were evaluated via sonoluminescence measurement. The paracetamol degradation rate was maximised at 850 kHz, in both single and dual-frequency ultrasonic irradiation. A synergistic index higher than 1 was observed for all degrading frequencies (200 – 1000 kHz) under dual-frequency ultrasound irradiation, showing the capability of dual-frequency system for enhancing pollutant degradation. A comparison of the results of degradation, dosimetry, and sonoluminescence intensity measurement revealed the stronger dependency of the degradation on the yield of HO• for both single and dual-frequency systems, which confirms degradation by HO• as the main removal mechanism. However, an enhanced degradation for frequencies higher than 500 kHz was observed despite a lower HO• yield, which could be attributed to the improved mass transfer of hydrophilic compounds at higher frequencies. The sonoluminescence intensity measurements showed that applying dual-frequency ultrasonic irradiation for 200 and 400 kHz made the bubbles larger and less uniform in size, with a portion of which not contributing to the yield of reactive oxidant species, whereas for the rest of the frequencies, dual-frequency ultrasound irradiation made the cavitation bubbles smaller and more uniform, resulting in a linear correlation between the overall sonoluminescence intensity and the yield of reactive oxidant species.     

CO_2膨胀液体的分子动力学模拟

采用分子动力学方法,模拟了CO2膨胀甲醇体系、CO2膨胀乙醇体系的热力学性质和输运性质,以及对氯硝基苯在CO2膨胀甲醇体系、苯甲腈在CO2膨胀乙醇体系中的扩散性质。CO2膨胀甲醇体系的密度模拟值略高于实验值,而CO2膨胀乙醇体系的密度模拟值与实验值非常接近。模拟结果表明:CO2使甲醇和乙醇溶液的膨胀非常明显,当CO2的摩尔分数达到0.5时,溶液膨胀约100%;得到了CO2、甲醇、乙醇、对氯硝基苯以及苯甲腈的扩散系数,其中对氯硝基苯和苯甲腈在两种膨胀液体中的扩散系数与实验结果接近;通过扩散系数关联了两种膨胀液体的粘度,计算结果与修正的Wilke-Chang方程得到的体系粘度规律一致。     

弱酸试纸法测量功率超声珩磨空化声场的研究*

为了简便、直观地测量功率超声珩磨磨削区的空化声场强度及分布情况,提出了利用弱酸PH试纸测量磨削区空化声场的方法。利用超声空化效应产生的弱酸空化泡在PH试纸表面溃灭后,形成深浅和分布不同的变色区域,间接地表征油石表面空化声场的强弱和分布规律。通过对比不同超声频率、测试距离和时间,得出了最佳测试距离和时间。结果表明,当超声频率为18.6 kHz,距离为10 mm时,测得油石表面的空化声场强度和分布最佳。该方法可形象地评价功率超声珩磨磨削区空化声场的强度和分布情况,具有一定的实际应用价值。