Influence of mixing and ultrasound frequency on antisolvent crystallisation of sodium chloride

Ultrasound is known to promote nucleation of crystals and produce a narrower size distribution in a controlled and reproducible manner for the crystallisation process. Although there are various theories that suggest cavitation bubbles are responsible for sonocrystallisation, most studies use power ultrasonic horns that generate both intense shear and cavitation and this can mask the role that cavitation bubbles play. High frequency ultrasound from a plate transducer can be used to examine the effect of cavitation bubbles without the intense shear effect. This study reports the crystal size and morphology with various mixing speeds and ultrasound frequencies. The results show high frequency ultrasound produced sodium chloride crystals of similar size distribution as an ultrasonic horn. In addition, ultrasound generated sodium chloride crystals having a more symmetrical cubic structure compared to crystals produced by a high shear mixer.     

Bubble size distribution in acoustic droplet vaporization via dissolution using an ultrasound wide-beam method

Performance and efficiency of numerous cavitation enhanced applications in a wide range of areas depend on the cavitation bubble size distribution. Therefore, cavitation bubble size estimation would be beneficial for biological and industrial applications that rely on cavitation. In this study, an acoustic method using a wide beam with low pressure is proposed to acquire the time intensity curve of the dissolution process for the cavitation bubble population and then determine the bubble size distribution. Dissolution of the cavitation bubbles in saline and in phase-shift nanodroplet emulsion diluted with undegassed or degassed saline was obtained to quantify the effects of pulse duration (PD) and acoustic power (AP) or peak negative pressure (PNP) of focused ultrasound on the size distribution of induced cavitation bubbles. It was found that an increase of PD will induce large bubbles while AP had only a little effect on the mean bubble size in saline. It was also recognized that longer PD and higher PNP increases the proportions of large and small bubbles, respectively, in suspensions of phase-shift nanodroplet emulsions. Moreover, degassing of the suspension tended to bring about smaller mean bubble size than the undegassed suspension. In addition, condensation of cavitation bubble produced in diluted suspension of phase-shift nanodroplet emulsion was involved in the calculation to discuss the effect of bubble condensation in the bubble size estimation in acoustic droplet vaporization. It was shown that calculation without considering the condensation might underestimate the mean bubble size and the calculation with considering the condensation might have more influence over the size distribution of small bubbles, but less effect on that of large bubbles. Without or with considering bubble condensation, the accessible minimum bubble radius was 0.4 or 1.7 μm and the step size was 0.3 μm. This acoustic technique provides an approach to estimate the size distribution of cavitation bubble population in opaque media and might be a promising tool for applications where it is desirable to tune the ultrasound parameters to control the size distribution of cavitation bubbles.     

Spatio-temporal dynamics of an encapsulated gas bubble in an ultrasound field

Coupled equations describing the radial and translational dynamics of an encapsulated gas bubble in an ultrasound field are derived by using the Lagrangian formalism. The equations generalize Church's theory by allowing for the translation motion of the bubble and radiation losses due to the compressibility of the surrounding liquid. The expression given by Church for the inner bubble radius corresponding to the unstrained state of the bubble shell is also refined, assuming that the shell can be of arbitrary thickness and impermeable to gas. Comparative linear analysis of the radial equation is carried out relative to Church's theory. It is shown that there are substantial departures from predictions of Church's theory. The proposed model is applied to evaluate radiation forces exerted on encapsulated bubbles and their translational displacements. It is shown that in the range of relatively high frequencies encapsulated bubbles are able to translate more efficiently than free bubbles of the equivalent size.     

A study on the primary and secondary nucleation of ice by power ultrasound

Several different investigations have been carried out to study the primary and secondary nucleation of ice by sonocrystallisation. Firstly, the primary nucleation of discrete ice crystals in a supercooled sucrose solution has been observed. For increasing concentrations of sucrose solutions from 0 to 45 wt%, the nucleation temperature consistently occurs at a higher nucleation temperature in the presence of ultrasound. The nucleation temperature also increases as the power output and duty cycle of a commercial ultrasonic horn are increased. Snap shot images of the bubble clouds obtained from the ultrasonic horn also show that the number of bubbles appears to increase as the ultrasonic output is increased. This suggests that the nucleation of ice is related to the power output and number of cavitation bubbles. The effect of a single bubble on the sonocrystallisation of ice is discussed. High-speed movies (1120 fps) have shown that the crystallisation appears to occur in the immediate vicinity of the single bubble. In most cases, many crystals are observed and it is not known whether a single ice crystal is being fragmented by the bubble or whether many crystals are being initiated. The bubble appears to undergo a dancing regime, frequently splitting and rejoining and also emitting some small microbubbles. A study on the secondary nucleation of ice in sucrose solutions has been carried out using a unique ultrasonic cold stage device. Images taken using a microscope system show that the pre-existing ice dendrite crystals can be broken up into smaller fragments by an ultrasonic field. Cavitation bubbles appear to be important during the fragmentation process, possibly melting any ice crystals in their path. Flow patterns around cavitation bubbles have also been observed, and these may be responsible for the fragmentation of ice crystals.     

球状泡群内气泡的耦合振动

振动气泡形成辐射场影响其他气泡的运动, 故多气泡体系中气泡处于耦合振动状态. 本文在气泡群振动模型的基础上, 考虑气泡间耦合振动的影响, 得到了均匀球状泡群内振动气泡的动力学方程, 以此为基础分析了气泡的非线性声响应特征. 气泡间的耦合振动增加了系统对每个气泡的约束, 降低了气泡的自然共振频率, 增强了气泡的非线性声响应. 随着气泡数密度的增加, 振动气泡受到的抑制增强; 增加液体静压力同样可抑制泡群内气泡的振动, 且存在静压力敏感区(1–2 atm, 1 atm=1.01325×10⁵ Pa); 驱动声波对气泡振动影响很大, 随着声波频率的增加, 能够形成空化影响的气泡尺度范围变窄. 在同样的声条件、泡群尺寸以及气泡内外环境下, 初始半径小于5 μm 的气泡具有较强的声响应. 气泡耦合振动会削弱单个气泡的空化影响, 但可延长多气泡系统空化泡崩溃发生的时间间隔和增大作用范围, 整体空化效应增强.     

Effect of static pressure on acoustic energy radiated by cavitation bubbles in viscous liquids under ultrasound

The effect of static pressure on acoustic emissions including shock-wave emissions from cavitation bubbles in viscous liquids under ultrasound has been studied by numerical simulations in order to investigate the effect of static pressure on dispersion of nano-particles in liquids by ultrasound. The results of the numerical simulations for bubbles of 5 μm in equilibrium radius at 20 kHz have indicated that the optimal static pressure which maximizes the energy of acoustic waves radiated by a bubble per acoustic cycle increases as the acoustic pressure amplitude increases or the viscosity of the solution decreases. It qualitatively agrees with the experimental results by Sauter et al. [Ultrason. Sonochem. 15, 517 (2008)]. In liquids with relatively high viscosity (～200 mPa s), a bubble collapses more violently than in pure water when the acoustic pressure amplitude is relatively large (～20 bar). In a mixture of bubbles of different equilibrium radius (3 and 5 μm), the acoustic energy radiated by a 5 μm bubble is much larger than that by a 3 μm bubble due to the interaction with bubbles of different equilibrium radius. The acoustic energy radiated by a 5 μm bubble is substantially increased by the interaction with 3 μm bubbles.     

Difference frequency and its harmonic emitted by microbubbles under dual frequency excitation

Vibro-acoustography is an elasticity imaging method that uses two ultrasound beams of slightly different frequency to excite an object and detects the resulting acoustic emission (AE) at the difference frequency. This method is especially sensitive to bubbles due to their nonlinearity. This study explores the harmonic acoustic emission (HAE) at twice the difference frequency emitted from bubbles. A perturbation method based on the dynamic bubble equation is used to derive the AE and HAE from a single bubble excited by dual frequency waves. Simulation shows that HAE is generated only by microbubbles whose resonant frequencies match the incident ultrasound frequencies. In contrast, AE is more sensitive to resonance at the difference frequency, which is relevant to sub-millimeter bubbles. This finding was confirmed by experiments where HAE was produced from Optison microbubbles, but not from larger air bubbles which are off resonance at the incident ultrasound frequency. In conclusion, harmonic acoustic emission is present for microbubbles. It is very sensitive to the size of the bubble and may be used for selective detection of microbubbles.     

Dynamics of double bubbles under the driving of burst ultrasound

This paper investigates the pulsations and translation of bubbles in a double-bubble system driven by burst ultrasound. Results illustrate that for two identical bubbles, decreasing the frequency of burst or increasing its amplitude can enhance the pulsations and improve the translation velocities of bubbles. In a certain scope, large bubble brings about fast translation velocity, but the velocity will fall down for too large bubble, such as the bubble with ambient radius over about its resonance radius. When the ambient radii of two bubbles are different, translation of the large bubble is smaller than that of the small bubble. In addition, the effect of initial distance between bubbles is described as well. If burst serials are used, shortening the time interval between each burst and improving the acoustic amplitude of bursts are beneficial for the translations of bubbles.     

Evaluation of the properties of daughter bubbles generated by inertial cavitation of preformed microbubbles

Inertial cavitation (IC) of the preformed microbubbles is being investigated for ultrasound imaging and therapeutic applications. However, microbubbles rupture during IC, creating smaller daughter bubbles (DBs), which may cause undesired bioeffects in the target region. Thus, it is important to determine the properties of DBs to achieve controllable cavitation activity for applications. In this study, we theoretically calculated the dissolution dynamics of sulfur hexafluoride bubbles. Then, we applied a 1-MHz single tone burst with different peak negative pressures (PNPs) and pulse lengths (PLs), and multiple 5-MHz tone bursts with fixed acoustic conditions to elicit IC of the preformed SonoVue microbubbles and scattering of DBs, respectively. After the IC and scattering signals were received by a 7.5-MHz transducer, time- and frequency-domain analysis was performed to obtain the IC dose and scattering intensity curve. The theoretical dissolution curves and measured scattering intensity curves were combined to determine the effect of the incident pulse parameters on the lifetime, mean radius and distribution range of DBs. Increased PNP reduced the lifetime and mean size of the DBs population and narrowed the size distribution. The proportion of small DBs (less than resonance size) increased from 36.83% to 85.98% with an increase in the PNP from 0.6 to 1.6 MPa. Moreover, increased PL caused a shift of the DB population to the smaller bubbles with shorter lifetime and narrower distribution. The proportion of small bubbles increased from 25.74% to 95.08% as the PL was increased from 5 to 100 µs. Finally, increased IC dose caused a smaller mean size, shorter lifetime and narrower distribution in the DB population. These results provide new insight into the relationship between the incident acoustic parameters and the properties of DBs, and a feasible strategy for achieving controllable cavitation activity in applications.     

Comparison between maximum radial expansion of ultrasound contrast agents and experimental postexcitation signal results

Experimental postexcitation signal data of collapsing Definity microbubbles are compared with the Marmottant theoretical model for large amplitude oscillations of ultrasound contrast agents (UCAs). After taking into account the insonifying pulse characteristics and size distribution of the population of UCAs, a good comparison between simulated results and previously measured experimental data is obtained by determining a threshold maximum radial expansion (Rmax) to indicate the onset of postexcitation. This threshold Rmax is found to range from 3.4 to 8.0 times the initial bubble radius, R0, depending on insonification frequency. These values are well above the typical free bubble inertial cavitation threshold commonly chosen at 2R0. The close agreement between the experiment and models suggests that lipid-shelled UCAs behave as unshelled bubbles during most of a large amplitude cavitation cycle, as proposed in the Marmottant equation.     

含气泡液体中气泡振动的研究

研究了含气泡液体中单个气泡在驱动声场一定情况下的振动过程. 让每次驱动声场作用的时间特别短, 使气泡半径发生微小变化后再将其变化反馈到气泡群对驱动声场的散射作用中去, 从而可以得到某单个气泡周围受气泡散射影响后的声场, 接着再让气泡在该声场作用下做短时振动, 如此反复. 通过这样的方法, 研究了液体中单个气泡的振动情况并对其半径变化进行了数值模拟, 结果发现, 在液体中含有大量气泡的情况下, 某单个气泡的振动过程明显区别于液体中只有一个气泡的情况. 由于大量气泡和驱动声场的相互作用, 使气泡半径的变化存在多种不同的振动情况, 在不同的气泡大小和含量的情况下, 半径变化过程分别表现为: 在平衡位置附近振荡的过程; 周期性的空化过程; 一次空化过程后保持某一大小振荡的过程; 增长后维持某一大小振荡的过程等. 所以, 对于含气泡液体中气泡振动的研究, 在驱动声场一定的情况下, 必须考虑气泡含量的因素. 关键词： 含气泡液体 超声空化 散射 数值模拟     

Hydrodynamic behavior of bubbles at gas-evolving electrode in ultrasonic field during water electrolysis

In electrochemical processes, gas bubbles on the electrode can cause an increase in both overpotential and ohmic voltage drop which leads to higher energy consumption. Applying power ultrasound during water electrolysis can help to reduce the overpotential, enhance mass transfer, and save energy. In this study, we investigated the effect of ultrasound (20 kHz) on the hydrogen evolution reaction (HER) on a stainless steel plate with varying concentrations of NaOH solutions at 298 K, using linear sweep voltammetry (LSV). We especially focused on understanding the bubble behavior on the stainless steel plate during HER using high-speed imaging in ultrasonic field. When ultrasound was applied to solutions with NaOH concentrations of 0.1, 0.5, 1 M, the current density increased by about 9.0, 5.9, 2.8 %, respectively. As the ultrasound irradiation began, the bubbles tended to hover around on the electrode surface, coalescing with other bubbles, rather than rising. When the size of the coalesced bubbles became too large to stay on the surface of the electrode, they were expelled from the ultrasonic field. The repeated collapse and coalescence of these bubbles was observed while they were rising. The velocity increased about 2 times when ultrasound irradiation began, and increased by more than 6 times in the ultrasonic field. More nucleation of bubbles was observed on the electrode in the ultrasonic field. Using ultrasound reduced the critical diameter of bubbles which detached from the electrode, from 58.0 to 15.9 μm, and the residence time of the bubbles, from 533 to 118 ms. Further, when the ultrasound was applied, the mean diameter of bubbles decreased from 71.8 to 17 μm. Hence, bubble coverage on the electrode surface decreased from 8.3 to 1 % despite an increase in the total number of bubbles. As a result, ultrasound was found to be effective for hydrogen production during water electrolysis, increasing current by the faster removal of gas from the stainless steel plate.     

Numerical modeling of ultrasonic cavitation by dividing coated microbubbles into groups

Homogeneous cavitation models usually use an average radius to predict the dynamics of all bubbles. However, bubbles with different sizes may have quite different dynamic characteristics. In this study, the bubbles are divided into several groups by size, and the volume-weighted average radius is used to separately calculate the dynamics of each group using a modified bubble dynamics equation. In the validation part, the oscillations of bubbles with two sizes are simulated by dividing them into 2 groups. Comparing with the predictions by the Volume of Fluid (VOF) method, the bubble dynamics of each size are precisely predicted by the proposed model. Then coated microbubbles with numerous sizes are divided into several groups in equal quantity, and the influence of the group number is analyzed. For bubble oscillations at f = 0.1 MHz and 1 MHz without ruptures, the oscillation amplitude is obviously under-estimated by the 1-group model, while they are close to each other after the group number increases to 9. For bubble ruptures triggered by Gaussian pulses, the predictions are close to each other when more than 5 groups are used.     

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.     

Collapse pressure measurement of single hollow glass microsphere using single-beam acoustic tweezer

Microbubbles are widely used in medical ultrasound imaging and drug delivery. Many studies have attempted to quantify the collapse pressure of microbubbles using methods that vary depending on the type and population of bubbles and the frequency band of the ultrasound. However, accurate measurement of collapse pressure is difficult as a result of non-acoustic pressure factors generated by physical and chemical reactions such as dissolution, cavitation, and interaction between bubbles. In this study, we developed a method for accurately measuring collapse pressure using only ultrasound pulse acoustic pressure. Under the proposed method, the collapse pressure of a single hollow glass microsphere (HGM) is measured using a high-frequency (20–40 MHz) single-beam acoustic tweezer (SBAT), thereby eliminating the influence of additional factors. Based on these measurements, the collapse pressure is derived as a function of the HGM size using the microspheres’ true density. We also developed a method for estimating high-frequency acoustic pressure, whose measurement using current hydrophone equipment is complicated by limitations in the size of the active aperture. By recording the transmit voltage at the moment of collapse and referencing it against the corresponding pressure, it is possible to estimate the acoustic pressure at the given transmit condition. These results of this study suggest a method for quantifying high-frequency acoustic pressure, provide a potential reference for the characterization of bubble collapse pressure, and demonstrate the potential use of acoustic tweezers as a tool for measuring the elastic properties of particles/cells.     

Impact of bubble coalescence in the determination of bubble sizes using a pulsed US technique: Part 1 – Argon bubbles in water

A powerful experimental approach to measure the size distribution of bubbles active in sonoluminescence and/or sonochemistry is a technique based on pulsed ultrasound and sonoluminescence emission. While it is an accepted technique, it is still lacking an understanding of the effect of various experimental parameters, including the duration of the pulse on-time, the nature of the dissolved gas, the presence of a gas flow rate, etc. The present work, focusing on Ar-saturated water sonicated at 362 kHz, shows that increasing the pulse on-time leads to the measurement of coalesced bubbles. Reducing the on-time to a minimum and/or adding sodium dodecyl sulfate to water allows to reducing coalescence so that natural active cavitation bubble sizes can be measured. A radius of 2.9–3.0 µm is obtained in Ar-saturated water at 362 kHz. The effects of acoustic power and possible formation of a standing-wave on coalescence and measured bubble sizes are discussed.     

Preparation and growth mechanism of micro spherical ammonium dinitramide crystal based on ultrasound-assisted solvent-antisolvent method

Micro-sized spherical ammonium dinitramide (ADN) crystals are successfully prepared by a facile ultrasound-assisted solvent-antisolvent recrystallization method without introducing any additives. The influences of the volume ratio of solvent to antisolvent, the antisolvent temperature and the ultrasound power on the micro-morphologies and properties of ADN crystals are studied systematically. The changes of morphology, particle size, crystal structure and melting point of the ADN crystals are characterized through scanning electron microscopy (SEM), laser particle size analyzer (LPSA), X-ray diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The results show that the optimal experimental parameters for the ADN crystal of spherical morphology are as follows: the volume ratio of solvent to antisolvent is 1:50, the antisolvent temperature is 20 ℃, and the ultrasound power is 70 W. The predicted hexagonal-flake and spherical morphologies for the ADN are close to the experimental morphologies. The growth mechanism of the spherical ADN crystal changes with supersaturation of the ADN solution. As the degree of supersaturation increases, the growth models of the spherical ADN change from the spiral growth to the rough growth, and the morphologies of ADN change from the large-sized ADN ball to the small-sized ADN ball.     

Forced linear oscillations of microbubbles in blood capillaries

A theoretical investigation of the forced linear oscillations of a gas microbubble in a blood capillary, whose radius is comparable in size to the bubble radius is presented. The natural frequency of oscillation, the thermal and viscous damping coefficients, the amplitude resonance, the energy resonance, as well as the average energy absorbed by the system, bubble plus vessel, have been computed for different kinds of gas microbubbles, containing air, octafluropropane, and perflurobutane as a function of the bubble radius and applied frequency. It has been found that the bubble behavior is isothermal at low frequencies and for small bubbles and between isothermal and adiabatic for larger bubbles and higher frequencies, with the viscous damping dominating over the thermal damping. Furthermore, the width of the energy resonance is strongly dependent on the bubble size and the natural frequency of oscillation is affected by the presence of the vessel wall and position of the bubble in the vessel. Therefore, the presence of the blood vessel affects the way in which the bubble absorbs energy from the ultrasonic field. The motivation of this study lies in the possibility of using gas microbubbles as an aid to therapeutic focused ultrasound treatments.     

Theoretical prediction of the scattering of spherical bubble clusters under ultrasonic excitation

Due to the nonlinear vibration of ultrasound contrast agent bubbles, a nonlinear scattered sound field will be generated when bubbles are driven by ultrasound. A bubble cluster consists of numerous bubbles gathering in a spherical space. It has been noted that the forward scattering of a bubble cluster is larger than its backscattering, and some studies have experimentally found the angular dependence of a bubble cluster’s scattering signal. In this paper, a theory is proposed to explain the difference of acoustic scattering at different directions of a bubble cluster when it is driven by ultrasound, and predicts the angular distribution of scattered acoustic pressure under different parameters. The theory is proved to be correct under circumstances of small clusters and weak interactions by comparing theoretical results with numerical simulations. This theory not only sheds light on the physics of bubble cluster scattering, but also may contribute to the improvement of ultrasound imaging technology, including ultrasonic harmonic imaging and contrast-enhanced ultrasonography.     

Oscillating bubble concentration and its size distribution using acoustic emission spectra

New method has been proposed for the estimation of size and number density distribution of oscillating bubbles in a sonochemical reactor using acoustic emission spectra measurements. Bubble size distribution has been determined using Minnaert's equation [M. Minnaert, On musical air bubbles and sound of running water, Philanthr. Mag. 16 (1933) 235], i.e., size of oscillating bubble is inversely related to the frequency of its volume oscillations. Decomposition of the pressure signal measured by the hydrophone in frequency domain of FFT spectrum and then inverse FFT reconstruction of the signal at each frequency level has been carried out to get the information about each of the bubble/cavity oscillation event. The number mean radius of the bubble size is calculated to be in the range of 50-80mum and it was not found to vary much with the spatial distribution of acoustic field strength of the ultrasound processor used in the work. However, the number density of the oscillating bubbles and the nature of the distribution were found to vary in different horizontal planes away from the driving transducer surface in the ultrasonic bath. A separate set of experiments on erosion assessment studies were carried out using a thin aluminium foil, revealing a phenomena of active region of oscillating bubbles at antinodal points of the stationary waves, identical to the information provided by the acoustic emission spectra at the same location in the ultrasonic bath.