The cavitation induced Becquerel effect and the hot spot theory of sonoluminescence

Over 150 years ago, Becquerel discovered the ultraviolet illumination of one of a pair of identical electrodes in liquid water produced an electric current, the phenomenon called the Becquerel effect. Recently, a similar effect was observed if the water surrounding one electrode is made to cavitate by focused acoustic radiation, which by similarity is referred to as the cavitation induced Becquerel effect. The current in the cavitation induced Becquerel effect was found to be semi-logarithmic with the standard electrode potential that is consistent with the oxidation of the electrode surface by the photo-decomposition theory of photoelectrochemistry. But oxidation of the electrode surface usually requires high temperatures, say as in cavitation. Absent high bubble temperatures, cavitation may produce vacuum ultraviolet (VUV) light that excites water molecules in the electrode film to higher H(2)O(*) energy states, the excited states oxidizing the electrode surface by chemical reaction. Solutions of the Rayleigh-Plesset equation during bubble collapse that include the condensation of water vapor show any increase in temperature or pressure of the water vapor by compression heating is compensated by the condensation of vapor to the bubble wall, the bubbles collapsing almost isothermally. Hence, the cavitation induced Becquerel effect is likely caused by cavitation induced VUV light at ambient temperature.     

鲁米诺增强声致发光应用研究的进展与问题

本文结合自己的工作，介绍了化学发光剂鲁米诺增强声致发光应用研究中的几种典型情况，并相应地 一些得到探讨的问题。     

Direct observation of cavitation fields at 23 and 515 kHz

Direct observation of cavitation fields using photography, sonoluminescence and luminol “mapping” is reported for a 23 kHz horn sonicator and a 515 kHz plate transducer system. The effect of sound intensity and added surfactant on the cavitation fields is described. The observations support previously reported results suggesting significant differences in the cavitation fields between the two sonication systems.     

Sonoluminescence and acoustic emission spectra at different stages of cavitation zone development

The way in which a cavitation zone develops in a focused pulsed ultrasound field is studied in this work. Sonoluminescence (SL), total hydrophone output and cavitation noise spectra have been recorded across a gradual, smooth increase in applied voltage. It is shown that the cavitation zone passes through a number of stages of evolution, according to increasing ultrasound intensity, decreasing pulse period and increasing ultrasound pulse duration. Sonoluminescence is absent in the first phase and the hydrophone output spectra consists of a main line with two or three harmonics whose intensity is much lower than that of the main (fundamental) line. The second stage sees the onset of SL whose intensity increases smoothly and is accompanied by the appearance of higher harmonics and subharmonics in the cavitation noise spectra. In some cases, the wide-band (WBN) component can be seen in noise spectra during the final part of the second stage. In the third stage, SL intensity increases significantly and often quite sharply, while WBN intensity increases in the same manner. This is accompanied by a synchronous increase in the absorption of ultrasound by the cavitation zone, which is manifested in a sharp decrease in the hydrophone output. In the fourth stage, both SL and WBN intensities tend to decrease despite the increased voltage applied to the transducer. Furthermore, the fundamental line tends to decrease in strength as well, despite the increasing ultrasound intensity. The obtained results clearly identify the different stages of cavitation zone development using cavitation noise spectra analyses. We then hypothesize that three of the above stages may be responsible for three known types of ultrasound action on biological cells: damping viability, reversible cell damage (sonoporation) and irreversible damage/cytotoxicity.     

Two components of Na emission in sonoluminescence spectrum from surfactant aqueous solutions

Sonoluminescence from sodium dodecyl sulfate (SDS) aqueous solutions exhibits Na emission. The spectrum of Na emission was measured as a function of sonication time for a total of 30 min at an ultrasonic frequency of 148 kHz. The spectral line profiles changed with the sonication time, suggesting that the Na emission consists of two components: broadened lines, which are shifted from the original D lines, and unshifted narrow lines. The intensity of the unshifted narrow lines decreased at a greater rate than that of the broadened lines with increasing sonication time. This effect was enhanced at a higher acoustic power. The shifted broadened lines remained after sonication for 30 min. We propose that these quenching effects are caused by the accumulation of gases decomposed from SDS molecules inside bubbles. The CO₂ gas dependence of Na emission in NaCl aqueous solutions showed a similar change in the line profiles to that in SDS aqueous solutions, which supported this proposition. The unshifted narrow lines are easily affected by foreign gases. The results suggest that the two components originate from different environments around the emitting species, although both of them originate from the gas phase inside bubbles. The generation mechanisms of the two components are discussed.     

Spatial distribution of sonoluminescence and sonochemiluminescence generated by cavitation bubbles in 1.2 MHz focused ultrasound field

An intensified charge coupled device (ICCD) camera was used to observe the spatial distribution of sonoluminescence (SL) and sonochemiluminescence (SCL) generated by cavitation bubbles in a 1.2 MHz focused ultrasound (FU) field in order to investigate the mechanisms of acoustic cavitation under different sonication conditions for FU therapeutic applications.It was found that SL emissions were located in the post-focal region. When the intensity of SL and SCL increased as the power rose, the growth of SCL was much higher than that of SL. In the post-focal region, the SCL emissions moved along specific paths and formed branch-like streamers. At the beginning of the ultrasound irradiation, cavitation bubbles generated SCL in both the pre-focal and the post-focal region. When the electrical power or the sonication time increased, the SCL in the post-focal region increased and became higher than that in the pre-focal region. The intensity of SCL in the focal region is usually the weakest because of “oversaturation”.The spatial distribution of SCL near a tissue boundary differed from that obtained in free fields. It organized into special structures under different acoustic amplitudes. When the electrical power was relatively low, the SCL emission was conical shape which suggested a standing wave formation at the tissue-fluid boundary. When the electrical power exceeded a certain threshold, only a bright spot could be captured in the focus. The cavitation bubbles which centralized in the focus concentrated energy and hindered the formation of standing waves. With rising electrical power at high levels, besides a bright spot in the focus, there were some irregular light spots in pre-focal region, which indicated some cavitation bubbles or small bubble clusters achieved the threshold of SCL and induced the reaction with the luminol solution.     

Sonoluminescence emission spectra of a 3.6 MHz HIFU in sweeping mode

Use of sweeping mode with a 3.6 MHz High Intensity Focused Ultrasound (HIFU) allows cavitation activity to be controlled. This is especially true in the pre-focal zone where the high concentration of bubbles acts as an acoustic reflector and quenches cavitation above this area. Previous studies attributed the enhancement of cavitation activity under negative sweep to the activation of more bubble nuclei, requiring deeper investigations. After mapping this activity with SCL measurements, cavitation noise spectra were recorded. The behavior of the acoustic broadband noise follows the sonochemical one i.e., showing the same attenuation (positive scan) or intensification (negative scan) of cavitational activity. In 1 M NaCl 3.7 mM 2-propanol solution saturated by a mixture of Ar-15.5%O₂-2.2%N₂, intensities of SL spectra are high enough to allow detection of several molecular emissions (OH, NH, C₂, Na) under negative frequency sweeps. This is the first report of molecular emissions at such high frequency. Their intensities are low, and they are very broad, following the trend obtained at fixed frequency up to 1 MHz. Under optimized conditions, CN emission chosen as a spectroscopic probe is strong enough to be simulated, which is reported for the first time at such high frequency. The resulting characteristics of the plasma do not show any spectral difference, so bubble nature is the same in the pre-and post-focal zone under different sweeping parameters. Consequently, SL and SCL intensification was not related to a change in plasma nature inside the bubbles but to the number of cavitation bubbles.     

On the dynamics of moving single bubble sonoluminescence

It is well known that the primary Bjerknes force is the origin of the trapping of sonoluminescing bubble in the sound field in liquid. In the present Letter, the quantitative investigation of the behavior of hydrodynamic force on the moving sonoluminescing (SL) bubble introduces the new role of stabilizing the trajectory motion of the bubble for primary Bjerknes force. Using a complete force balanced radial-translational dynamics, it is analytically discussed that by increasing the bubble distance from the antinode of the sound field the increase of the magnitude of inward Bjerknes force, controls the size of the domain of the bubble trajectory. At this time the wake produced by the rapid variation of the bubble's relative translational velocity to the surrounding liquid, changes the bubble direction of motion through the effect of history force. The required momentum for accelerating the SL bubble around the central antinode is produced by the added mass force at the bubble collapse. It is revealed in a re-examination of the coupled radial-translational dynamics for a trapping bubble that because of the bubble lower translational acceleration caused due to the lower added mass force and the bubble attraction towards the acoustic antinodes in presence of inward Bjerknes force, the small bubble will be trapped at the antinode of the sound field.     

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.     

输入电功率在大范围内变动时声致发光与电功率之间的关系

采用频率为１．１ＭＨｚ，声辐射面积为３ｃｍ＾２换能器，在输入电功率０－１２０Ｗ范围内研究了被空气自然饱和纯水中声致发光强度和输入电功率在大范围内变化时的关系，结果表明，声致发光在输入电功率为７０－９０Ｗ之间，不再随输入电功率的增加而增加，呈现出饱和现象，在饱和值的出现前，发光强度随输入电功率的增加呈不规则的阶状增加，在饱和值结束后，随输入电功率的增加，发光强度迅速减小，本文对实验结果进行了些定性的     

Multibubble sonoluminescence as a tool to study the mechanism of formic acid sonolysis

Sonoluminescence spectra collected from 0.1 to 3.0 M aqueous solutions of formic acid sparged with argon show the OH(A²Σ⁺−X²Π_i) and C₂(d³Π_g → a³Π_u) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C₂ Swan band. It is concluded that C₂ emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C₂ band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.     

Calculation of light emission in sonoluminescence

We modify a uniform model of single bubble sonoluminescence, in which heat diffusion, water vapor diffusion and chemical reactions are included to describe the bubble dynamics, and the processes of electron-atom bremsstrahlung, electron-ion bremsstrahlung and recombination radiation, radiative attachment of electrons to atoms and molecules, line emissions of OH radicals and Na atoms are taken into account to calculate the light emission. With this model, we compute the light pulse width, the photon number per flash, the continuum and line spectra and the gas species as the products of chemical reactions, and try to compare with all the experimental data available. We obtain good agreement with the observations of Ar and Xe bubbles in many cases, but fail to match the experimental data of the photon number per flash. We also find that for He bubble the computed photon number is always too small to interpret the observations. Supported by the National Natural Science Foundation of China (Grant Nos. 10674081 and 10434070)     

The role of primary and secondary delays in the effective resonance frequency of acoustically interacting microbubbles

Acoustically excited microbubbles (MBs) are known to be nonlinear oscillators with complex dynamics. This has enabled their use in a wide range of applications from medicine to industry and underwater acoustics. To better utilize their potential in applications and possibly invent new ones a comprehensive understanding of their dynamics is required. In this work, we explore the effect of bubble-bubble interactions on the resonance frequency of MB suspensions. MBs oscillate in response to an external acoustic wave and since bubbles in a cluster are at different locations compared to the excitation source, they are excited at different times. In this work we refer to these delays as primary delays. Interactions between the scattered pressure fields from adjacent bubbles have also been shown to alter the dynamics of MBs that exist within clusters. These secondary waves generated by MBs reach MBs in their proximity at different times that depend on their spatial location in the cluster. Here we refer to these delays as secondary delays. Inclusion of the secondary delays modifies the class of the differential equations governing the oscillations of interacting MBs in a cluster from ordinary differential equations to neutral delay differential equations. Previous work has not considered the all the delays associated with the bubble distances when modeling the interactions between bubbles. In this work we investigate the effect of both the primary and secondary delays on the effective resonance frequency of MB clusters. It is shown that primary delays cause spreading the resonance frequency of identical MBs within a range where the closest MB to the acoustic source exhibits the lowest resonance frequency and the furthest MB resonates at the highest frequency. This range has been shown to be up to 0.12 MHz for the examples investigated in this work. The effect of secondary delays is shown to be very significant. In the absence of secondary delays, the ordinary differential equation model predicts a decrease of up to 26% in the resonance frequency of 4 identical interacting MBs as the inter-bubble distances are decreased. However, we show that inclusion of the secondary delays result in the increase of the resonance frequency of MBs if they are situated close to each other. This increase is shown to be significant and for the case of 4 identical interacting MBs we show an increase of 58% in the resonance frequency.     

Experimental investigation on the ultrasonic impregnation of wood through measurements of the intensity of sonoluminescence

Ultrasonic impregnation is thought to be an effective way of permeation of liquid into material through the material-surface reforming with the attack by an ultrasonic cavitation jet or by the shock wave emitted from a collapsing bubble, or through dynamic transformation of material like a sponge. The action of a cavitation bubble can also provide penetration of liquid into the interior of the material. This paper investigates whether there is a correlation between the intensity of sonoluminescence (SL) measured at different positions and the increment in the mass of the wood material (cedar) after sonication with immersion into water in order to clarify the role of cavitation bubbles for ultrasonic impregnation. It was found that a high mass change was obtained for the material located at the position for high (the maximum) SL intensity. The number density of ultrasonic cavitation bubbles that are able to collapse leading to the emission of SL is correlated with the degree of ultrasonic impregnation.     

Turning single bubble sonoluminescence from blue in pure water to green by adding trace amount of carbon nanodots

Sonoluminescence (SL) is an interesting physical effect which can convert acoustic energy into light pulses. Up to now, the microscopic mechanism of the SL has not yet been fully clear. It is known that hydroxyl radicals play the important role for SL from water. In this work, we take advantage of carbon nano-dots (CNDs) as free radical captors to modulate the hydroxyl radicals (OH) in SL effect. Through studying the single bubble SL (SBSL) from CND aqueous solution (CNDAS) with trace amount of CNDs, we find that the color of SBSL is tuned dramatically from blue in water to green in CNDAS. Two different SL mechanisms can be identified from emission spectrum. One comes from blackbody-like radiation and another is attributed from the characteristic emission with identified peaks. The decrease in the yield of H₂O₂ in the presence of CNDs suggests the modulation effect on SL via OH interacting with CNDs. By comparison of the CNDs before and after sonication, it is found that hydroxyl radicals generated during SL can take part in the chain-like oxidation of the chemical groups attached to the CNDs to form larger amount of carboxyl groups. The blackbody temperature of blackbody-like radiation decreases from 15,600 K in water to 11,300 K in CNDAS. Moreover, the emission from hydroxyl radicals and two new luminescent centers related to carboxyl groups are introduced in SL from CNDAS. These important and interesting findings indicate that by adding trace amount of CNDs in water, the effect of SBSL can be significantly modulated, which can provide a macroscopic phenomenon for gaining an insight into the microscopic mechanism of the SL effect.     

Sonochemical and high-speed optical characterization of cavitation generated by an ultrasonically oscillating dental file in root canal models

Ultrasonically Activated Irrigation makes use of an ultrasonically oscillating file in order to improve the cleaning of the root canal during a root canal treatment. Cavitation has been associated with these oscillating files, but the nature and characteristics of the cavitating bubbles were not yet fully elucidated. Using sensitive equipment, the sonoluminescence (SL) and sonochemiluminescence (SCL) around these files have been measured in this study, showing that cavitation occurs even at very low power settings. Luminol photography and high-speed visualizations provided information on the spatial and temporal distribution of the cavitation bubbles. A large bubble cloud was observed at the tip of the files, but this was found not to contribute to SCL. Rather, smaller, individual bubbles observed at antinodes of the oscillating file with a smaller amplitude were leading to SCL. Confinements of the size of bovine and human root canals increased the amount of SL and SCL. The root canal models also showed the occurrence of air entrainment, resulting in the generation of stable bubbles, and of droplets, near the air–liquid interface and leading eventually to a loss of the liquid.     

Nonlinear dynamics and acoustic emissions of interacting cavitation bubbles in viscoelastic tissues

The cavitation-mediated bioeffects are primarily associated with the dynamic behaviors of bubbles in viscoelastic tissues, which involves complex interactions of cavitation bubbles with surrounding bubbles and tissues. The radial and translational motions, as well as the resultant acoustic emissions of two interacting cavitation bubbles in viscoelastic tissues were numerically investigated. Due to the bubble–bubble interactions, a remarkable suppression effect on the small bubble, whereas a slight enhancement effect on the large one were observed within the acoustic exposure parameters and the initial radii of the bubbles examined in this paper. Moreover, as the initial distance between bubbles increases, the strong suppression effect is reduced gradually and it could effectively enhance the nonlinear dynamics of bubbles, exactly as the bifurcation diagrams exhibit a similar mode of successive period doubling to chaos. Correspondingly, the resultant acoustic emissions present a progressive evolution of harmonics, subharmonics, ultraharmonics and broadband components in the frequency spectra. In addition, with the elasticity and/or viscosity of the surrounding medium increasing, both the nonlinear dynamics and translational motions of bubbles were reduced prominently. This study provides a comprehensive insight into the nonlinear behaviors and acoustic emissions of two interacting cavitation bubbles in viscoelastic media, it may contribute to optimizing and monitoring the cavitation-mediated biomedical applications.     

光电倍增管在磷酸液声致发光实验中的应用

对不同厚度液体进行光强测量,深入探索空化气泡的运动,研究发光机理很有意义。用超声激励法在磷酸液体中实现多泡声致发光,研究不同共振频率下发光的特点。利用光电倍增管多次测量发光强度相互比较,结果是在液体厚度10 cm、驱动频率f=21.061kHz和f=20.316kHz时,周期性较好为50μs,液体通过漩涡集中气泡可以使更多气泡发光;在液体厚度3 mm、驱动频率f=17.91kHz和f=19kHz时,周期性很好为25μs;且光信号都较强。结论是磷酸中声致发光强度、周期与液体厚度、驱动频率密切相关。本文以磷酸液多泡声致发光实验研究为基础,从内部和外部原理来出发,详细介绍了光电倍增管在多泡声致发光光强测量中的实用,为今后研究者提供了一些经验。根据实验过程中遇到的一些实际问题提出了建议和改善意见。     

Study of x-ray emission enhancement via a high-contrast femtosecond laser interacting with a solid foil

We observed the increase of the conversion efficiency from laser energy to Kalpha x-ray energy (eta(K)) produced by a 60 fs frequency doubled high-contrast laser pulse focused on a Cu foil, compared to the case of the fundamental laser pulse. eta(K) shows a strong dependence on the nonlinearly modified rising edge of the laser pulse. It reaches a maximum for a 100 fs negatively modified pulse. The hot electron efficient heating leads to the enhancement of eta(K). This demonstrates that high-contrast lasers are an effective tool for optimizing eta(K), via increasing the hot electrons by vacuum heating.     

A phenomenological investigation into the opposing effects of fluid flow on sonochemical activity at different frequency and power settings. 2. Fluid circulation at high frequencies

Sonochemical activity is dependent on flow patterns within the reactor and either no affect or a decrease in activity was observed at 376, 995, and 1179 kHz from overhead stirring. The interaction of fluid flow with ultrasound was further investigated in this study with circulatory flow. The effect of fluid circulation on radical production was investigated at two circulation speeds, with and without surface stabilisation. The sonochemical activity was determined by the yield of hydrogen peroxide, measured by iodide dosimetry. The sonochemically active region was pictured using sonochemiluminescence imaging and the flow fields were visualised with dyed flow videos. At 376 and 995 kHz, an increase in sonochemical activity was observed with the slower flow rate; however at 1179 kHz, the sonochemical activity was either not affected or decreased. The observed changes in sonochemical activity were attributed to an increase in asymmetry of the bubble collapse brought about by fluid motion.