Effect of particle addition on sonochemical reaction

Enhancement of chemical reaction with a photocatalyst of titanium dioxide (TiO(2)) by ultrasonic irradiation is studied through the absorbance measurements for liberation of iodine from a KI aqueous solution as an index of oxidation reaction. It is well known as a synergetic effect that the addition of TiO(2) fine particles under UV has an ability to enhance the yield in chemical reaction with OH-radical from hot spot at violent collapse of cavitation bubbles with intense ultrasound. In this study, the absorbance is measured after simultaneous irradiation of ultrasound and UV with the addition of TiO(2) much less than the usual concentration by two orders of content. It is shown that, even in case of quite a little TiO(2) addition where the photocatalytic effect is less, the yield is enhanced obviously in comparison with the summation in yield of independent procedure of ultrasound without TiO(2) and UV with TiO(2). The absorbance-peak deviation to the shorter wavelength implies the generation of titanium peroxide (TiO(3)). The effect of particle addition is due to the chemically activated particle surface on the TiO(2) and probably to the increase in the cavitation bubbles that results in promoting a transfer of OH-radical and other oxidants to bulk liquid region at the collapse.     

Physical insights into the sonochemical degradation of recalcitrant organic pollutants with cavitation bubble dynamics

This paper tries to discern the mechanistic features of sonochemical degradation of recalcitrant organic pollutants using five model compounds, viz. phenol (Ph), chlorobenzene (CB), nitrobenzene (NB), p-nitrophenol (PNP) and 2,4-dichlorophenol (2,4-DCP). The sonochemical degradation of the pollutant can occur in three distinct pathways: hydroxylation by OH radicals produced from cavitation bubbles (either in the bubble–bulk interfacial region or in the bulk liquid medium), thermal decomposition in cavitation bubble and thermal decomposition at the bubble–liquid interfacial region. With the methodology of coupling experiments under different conditions (which alter the nature of the cavitation phenomena in the bulk liquid medium) with the simulations of radial motion of cavitation bubbles, we have tried to discern the relative contribution of each of the above pathway to overall degradation of the pollutant. Moreover, we have also tried to correlate the predominant degradation mechanism to the physico-chemical properties of the pollutant. The contribution of secondary factors such as probability of radical–pollutant interaction and extent of radical scavenging (or conservation) in the medium has also been identified. Simultaneous analysis of the trends in degradation with different experimental techniques and simulation results reveals interesting mechanistic features of sonochemical degradation of the model pollutants. The physical properties that determine the predominant degradation pathway are vapor pressure, solubility and hydrophobicity. Degradation of Ph occurs mainly by hydroxylation in bulk medium; degradation of CB occurs via thermal decomposition inside the bubble, degradation of PNP occurs via pyrolytic decomposition at bubble interface, while hydroxylation at bubble interface contributes to degradation of NB and 2,4-DCP.     

Method for comparing the efficiency of ultrasound irradiation independent of the shape and the volume of the reaction vessel in sonochemical experiments

The method described herein this review compares the efficiency of ultrasound irradiation in sonochemical experiments in organic solvents. This method was shown to be independent of the shape and volume of the reaction vessel.

The principle of this method is based on the fact that the concentration of dissolved oxygen in the entire reaction volume during acoustic cavitation depends on the ultrasound power or intensity of ultrasound field respectively. The concentration of dissolved oxygen is determined by the measurement of the fluorescence intensity with fluorescence probes.     

Effect of nuclei concentration on cavitation cluster dynamics

Cavitation cluster dynamics after the passage of a single pressure wave is studied for different concentrations of artificial cavitation nuclei (30 to 3x10(5) nuclei/ml). With increasing concentration of cavitation nuclei the lifetime of the cavitation cluster is prolonged. Additionally, it is found that the spatial extent of the cluster decreases with higher nuclei concentration. The experimental data for concentrations less than 400 nuclei/ml are compared to simulations with a Rayleigh-Plesset-type equation, taking into account bubble-bubble interaction. For higher concentrations (more than 1000 nuclei/ml) the observed radial cluster dynamics is compared with calculations from an axisymmetric cavity-collapse model.     

Quantitative calculation of reaction performance in sonochemical reactor by bubble dynamics

In order to design a sonochemical reactor with high reaction efficiency, it is important to clarify the size and intensity of the sonochemical reaction field. In this study, the reaction field in a sonochemical reactor is estimated from the distribution of pressure above the threshold for cavitation. The quantitation of hydroxide radical in a sonochemical reactor is obtained from the calculation of bubble dynamics and reaction equations. The distribution of the reaction field of the numerical simulation is consistent with that of the sonochemical luminescence. The sound absorption coefficient of liquid in the sonochemical reactor is much larger than that attributed to classical contributions which are heat conduction and shear viscosity. Under the dual irradiation, the reaction field becomes extensive and intensive because the acoustic pressure amplitude is intensified by the interference of two ultrasonic waves.     

Effects of ultrasonic frequency and liquid height on sonochemical efficiency of large-scale sonochemical reactors

The sonochemical efficiency of a cylindrical sonochemical reactor has been investigated as a function of frequency and liquid height. The irradiation frequencies were 45, 129, 231 and 490 kHz. The liquid height was varied from 10 to 700 mm. The sonochemical efficiency of the cylindrical reactor was evaluated by potassium iodide (KI) dosimetry and calorimetry. In our study, the sonochemical efficiency depended on the frequency and liquid height; further, the plots of sonochemical efficiency against liquid height exhibit one or two peaks for each frequency. The sonochemical efficiency up to the first peak increased monotonically with the logarithm of the frequency, and the liquid height for the first peak was inversely proportional to the frequency. From these results, the optimum frequency for a sonochemical reactor can be determined if the liquid height is specified for scale-up of the sonochemical reactor.     

A standard method to calibrate sonochemical efficiency of an individual reaction system

Fricke reaction, KI oxidation and decomposition of porphyrin derivatives by use of seven types of sonochemical apparatus in four different laboratories were examined in the range of frequency of 19.5 kHz to 1.2 MHz. The ultrasonic energy dissipated into an apparatus was determined also by calorimetry. Sonochemical efficiency of Fricke reaction and KI oxidation was defined as the number of reacted molecule per unit ultrasonic energy. The sonochemical efficiency is independent of experimental conditions such as the shape of sample cell and irradiation instruments, but depends on the ultrasonic frequency. We propose the KI oxidation dosimetry using 0.1 moldm(-3) KI solution as a standard method to calibrate the sonochemical efficiency of an individual reaction system.     

Effect of supercritical water shell on cavitation bubble dynamics

Based on reported experimental data, a new model for single cavitation bubble dynamics is proposed considering a supercritical water(SCW) shell surrounding the bubble. Theoretical investigations show that the SCW shell apparently slows down the oscillation of the bubble and cools the gas temperature inside the collapsing bubble. Furthermore, the model is simplified to a Rayleigh–Plesset-like equation for a thin SCW shell. The dependence of the bubble dynamics on the thickness and density of the SCW shell is studied. The results show the bubble dynamics depends on the thickness but is insensitive to the density of the SCW shell. The thicker the SCW shell is, the smaller are the wall velocity and the gas temperature in the bubble. In the authors' opinion, the SCW shell works as a buffering agent. In collapsing, it is compressed to absorb a good deal of the work transformed into the bubble internal energy during bubble collapse so that it weakens the bubble oscillations.     

Sonoluminescence and sonochemical reactions in cavitation fields. A review

Contemporary ideas on the nature of cavitation are reviewed in this paper. The general theories of sonoluminescence and sonochemical reactions, the origin, stability and splitting of cavitation bubbles, the dynamics of cavitation field evolution, the peculiarities of cavitation effects at low intensity and low-frequency acoustic oscillations, the sonoluminescence quenching effect and some questions on the energetics of cavitation fields are discussed. The electrical theory of the splitting of cavitation bubbles may, as shown in the paper, become an alternative to the thermal theories of cavitation in the future.     

The effects of acoustic flow and mechanical flow on the sonochemical efficiency in a rectangular sonochemical reactor

Visualization of cavitation behavior in a rectangular sonochemical reactor at 490 kHz was carried out by a laser sheet technique and the distribution of liquid flow was measured by a laser Doppler velocimeter. The pattern of liquid flow and distribution of acoustic pressure of the rectangular sonochemical reactor were investigated as a function of the input power from 10 to 50 W. The liquid moved upward above the transducer at every power. As increasing the input power, the random flow out side the cylindrical part above the transducer changed into the convective one and the region of the visualized standing wave which was formed in the cylindrical part changed with the input power. The position showing the sonochemical luminescence exists inside or near the region where the standing wave was visualized. Introduction of a stirrer resulted in disturbance of liquid flow and expanded the position showing the sonochemical luminescence, but the luminescence intensity was weakened. The sonochemical efficiency was enhanced by about twice by introduction of the stirrer. From these results, we discussed the effects of liquid flow on sonochemical efficiency with and without a stirrer.     

Limitations of the Weissler reaction as a model reaction for measuring the efficiency of hydrodynamic cavitation

The Weissler reaction in which iodide is oxidised to a tri-iodide complex (I(3)(-)) has been widely used for measurement of the intensity of ultrasonic and hydrodynamic cavitation. It was used in this work to compare ultrasonic cavitation at 24kHz with hydrodynamic cavitation using two different devices, one a venturi and the other a sudden expansion, operated up to 8.7bar. Hydrodynamic cavitation had a maximum efficiency of about 5x10(-11) moles of I(3)(-) per joule of energy compared with the maximum of almost 8x10(-11)molJ(-1) for ultrasonic cavitation. Hydrodynamic cavitation was found to be most effective at 10 degrees C compared with 20 degrees C and 30 degrees C and at higher upstream pressures. However, it was found that in hydrodynamic conditions, even without cavitation, I(3)(-) was consumed at a rapid rate leading to an equilibrium concentration. It was concluded that the Weissler reaction was not a good model reaction for the assessment of the effectiveness of hydrodynamic cavitation.     

Effect of ultrasonic cavitation on dynamics and characteristics of electric discharge in liquid

Characteristics of electric discharges in liquid media under intense ultrasonic vibrations are studied. The difference in current dynamics and discharge voltages in the presence and in the absence of cavitation is shown.     

Ultrasonic cavitation applied to the treatment of bisphenol A. Effect of sonochemical parameters and analysis of BPA by-products

Bisphenol A (BPA), a chemical compound largely used in the plastics industry, can end up in aquatic systems, which it disturbs by its endocrine disrupting effect (EDE). This study investigated the BPA degradation upon ultrasonic action under different experimental conditions. The effect of saturating gas (oxygen, argon and air), BPA concentration (0.15-460 micromol L(-1)), ultrasonic frequency (300-800 kHz) and power (20-80 W) were evaluated. For a 118 micromol L(-1)-BPA solution, with the best performance obtained at 300 kHz, 80 W, with oxygen as saturating gas. In these conditions, BPA can be readily eliminated by the ultrasound process (approximately 90 min). However, even after long ultrasound irradiation times (9 h), more than 50% of chemical oxygen demand (COD) and 80% of total organic carbon (TOC) remained in the solution. Analyses of intermediates using HPLC-MS investigation identified several products: monohydroxylated bisphenol A, 4-isopropenylphenol, quinone of monohydroxylated bisphenol A, dihydroxylated bisphenol A, quinone of dihydroxylated bisphenol A, monohydroxylated-4-isopropenylphenol and 4-hydroxyacetophenone. The presence of these hydroxylated aromatic structures showed that the main ultrasonic BPA degradation pathway is related to the reaction of BPA with the *OH radical. After 2h, these early products were converted into biodegradable aliphatic acids.     

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.     

Blood vessel deformations on microsecond time scales by ultrasonic cavitation

Transient interactions among ultrasound, microbubbles, and microvessels were studied using high-speed photomicrography. We observed liquid jets, vessel distention (motion outward against the surrounding tissue), and vessel invagination (motion inward toward the lumen). Contrary to current paradigms, liquid jets were directed away from the nearest vessel wall and invagination exceeded distention. These observations provide insight into the mechanics of bubble-vessel interactions, which appear to depend qualitatively upon the mechanical properties of biological tissues.     

基于聚类算法的血管直径测量研究

血管形态的变化与疾病密切相关,血管直径是血管形态的主要参数之一,测量血管直径有助于疾病的筛查与预防。提出一种基于聚类算法的血管直径测量方法,对微血管进行测量。大多数显微血管图像(如光学显微成像或光声显微成像)中存在噪声,通过非线性变换函数对显微图像进行增强;使用训练后的U-Net网络模型进行图像分割;利用结合聚类算法以及射线算法的测量方法对分割得到的血管进行测量,得到血管直径。实验表明,算法与传统测量结果一致(P0.05),与传统算法相比,本算法的测量精度得到提升,将测量误差由4.21%降低至2.27%,满足血管测量的准确度需求。     

Acoustic cavitation, bubble dynamics and sonoluminescence

Basic facts on the dynamics of bubbles in water are presented. Measurements on the free and forced radial oscillations of single spherical bubbles and their acoustic (shock waves) and optic (luminescence) emissions are given in photographic series and diagrams. Bubble cloud patterns and their dynamics and light emission in standing acoustic fields are discussed.     

Ultrafast dynamics and temperature effects on the quantum efficiency of the ring-opening reaction of a photochromic indolylfulgide

The ultrafast ring-opening reaction of the molecular switch 1,2-Dimethyl-3-indolylfulgide dissolved in acetonitrile is investigated by temperature dependent quantum efficiency measurements and time-resolved transient absorption spectroscopy in the ultraviolet and visible spectral range. The photoreaction is found to be thermally activated with an activation energy of about 1640 cm^− 1. The transient absorption signal is bi-exponential with the time constants τ₁ = 0.7 ps and τ₂ = 12 ps. The fast time constant is due to solvation dynamics, while the main component τ₂ is attributed to the excited state lifetime and product formation. A long-lived intermediate state in the photoreaction can be excluded.