Effects of gas sparging and mechanical mixing on sonochemical oxidation activity

The effects of air sparging (0–16 L min⁻¹) and mechanical mixing (0–400 rpm) on enhancing the sonochemical degradation of rhodamine B (RhB) was investigated using a 28 kHz sonoreactor. The degradation of RhB followed pseudo first-order kinetics, where sparging or mixing induced a large sonochemical enhancement. The kinetic constant varied in three stages (gradually increased → increased exponentially → decreased slightly) as the rate of sparging or mixing increased, where the stages were similar for both processes. The highest sonochemical activity was obtained with sparging at 8 L min⁻¹ or mixing at 200 rpm, where the standing wave field was significantly deformed by sparging and mixing, respectively. The cavitational oxidation activity was concentrated at the bottom of the sonicator when higher sparging or mixing rates were employed. Therefore, the large enhancement in the sonochemical oxidation was attributed mainly to the direct disturbance of the ultrasound transmission and the resulting change in the cavitation-active zone in this study. The effect of the position of air sparging and mixing was investigated. The indirect inhibition of the ultrasound transmission resulted in less enhancement of the sonochemical activity. Moreover, the effect of various sparging gases including air, N₂, O₂, Ar, CO₂, and an Ar/O₂ (8:2) mixture was compared, where all gases except CO₂ induced an enhancement in the sonochemical activity, irrespective of the concentration of dissolved oxygen. The highest activity was obtained with the Ar/O₂ (8:2) mixture. Therefore, it was revealed that the sonochemical oxidation activity could be further enhanced by applying gas sparging using the optimal gas.     

Quantification of sonochemical and sonophysical effects in a 20 kHz probe-type sonoreactor: Enhancing sonophysical effects in heterogeneous systems with milli-sized particles

Even though acoustic cavitation has been widely investigated, only few researchers focused on the relationship between sonochemical and sonophysical activities and on the enhancement of sonophysical activity. In this study, sonochemical and sonophysical activities were investigated in a heterogeneous system to understand the relationship between these two activities and to suggest optimal conditions for ultrasonic desorption/extraction processes comprising milli-sized glass beads. The sonochemical activity was quantitatively analyzed using potassium iodide dosimetry in homogeneous and heterogeneous systems. Sonophysical activity was quantitatively and qualitatively analyzed using paint-coated bead desorption tests and aluminum foil erosion tests under three probe positions of “T” (1 cm below the liquid surface), “B” (1 cm above the vessel bottom), and “M” (midpoint between “T” and “B”). Three different sizes of glass beads (diameter: 0.2, 1.0, and 4.0 mm) were used in this study. The highest sonochemical activity was obtained at “B” in both homogeneous and heterogeneous systems. However, three times lower sonochemical activity was observed in the heterogeneous system than in the homogeneous system because significant attenuation and unstable reflection of ultrasound occurred in the bead layer and suspension. Higher sonophysical activity was observed, when the bead size decreased and the probe approached the bottom. However, no significant sonophysical activity was detected when the beads were attached to the bottom. Therefore, the sonophysically active region was the zone around the probe body, opposite to the ultrasound irradiation tip, and only suspended beads could undergo severe cavitational actions. This was confirmed via aluminum foil tests. Several erosion marks on the foil were observed in the area around the probe body, whereas no severe damage was observed at the bottom. Moreover, the degree of sonophysical activity did not change for various saturating gases. This might be due to the different thresholds of sonochemical and sonophysical activities.     

Investigation of sonochemical activities at a frequency of 334 kHz: The effect of geometric parameters of sonoreactor

In this study, the effect of the dimensions of the bottom plate and liquid height was investigated for high-frequency sonoreactors under a vertically irradiated system. The dimensions of the bottom plate did not significantly influence sonochemical activity considering power density. However, as the bottom plate was increased in size, the hydroxyl radical generation rate decreased because of a decrease in power density. It is therefore recommended that sonoreactors with bottom-plate dimensions close to those of the ultrasonic transducer module be used. Liquid height had a significant effect on sonochemical activity, but the trend of the activity considering power density changed as the initial pollutant concentration changed. In the case of low initial concentration of As(III) (1 mg/L), the maximum cavitation yield for As(III) oxidation was observed at liquid heights of 150 mm.     

Geometric and operational optimization of 20-kHz probe-type sonoreactor for enhancing sonochemical activity

The use of a 20-kHz probe-type sonicator irradiating downward in a 500 mL vessel was optimized for the enhancement of the sonochemical activity in terms of the geometric and operational factors. These factors included the probe immersion depth (the vertical position of the probe), input power, height of the liquid from the bottom, horizontal position of the probe, and thickness of bottom plate The sonochemical oxidation reactions were investigated both quantitatively and qualitatively using calorimetry, KI dosimetry, and luminol (Sonochemiluminescence, SCL) techniques. The sonochemical activity was very positively affected by the vertical boundaries. The highest sonochemical activity was obtained when the probe was placed close to the bottom of the vessel (immersion depth of 60 mm), with a high input power (input power of 75%), and optimal liquid height condition (liquid height of 70 mm). The SCL image analysis showed that the cavitational activity zone gradually expanded around the probe body and changed into a circular shape as the experimental conditions were optimized, and consequently the sonochemical activity increased. The formation of a large bright circular-shaped activity zone could be attributed to the strong reflections of the ultrasound firstly, at the vessel bottom and secondly, at the liquid surface. On the other hand, the cavitational activity zone and the sonochemical activity were negatively affected by the horizontal boundaries when the probe was placed close to the side wall of the vessel. In addition, it was found that the sonochemical activity was also significantly affected by the thickness of the support plate owing to the reflection and transmission of the ultrasound at the boundary between the liquid and the solid media.     

Simulation of the spatial distribution of the acoustic pressure in sonochemical reactors with numerical methods: A review

Numerical methods for the calculation of the acoustic field inside sonoreactors have rapidly emerged in the last 15 years. This paper summarizes some of the most important works on this topic presented in the past, along with the diverse numerical works that have been published since then, reviewing the state of the art from a qualitative point of view. In this sense, we illustrate and discuss some of the models recently developed by the scientific community to deal with some of the complex events that take place in a sonochemical reactor such as the vibration of the reactor walls and the nonlinear phenomena inherent to the presence of ultrasonic cavitation. In addition, we point out some of the upcoming challenges that must be addressed in order to develop a reliable tool for the proper designing of efficient sonoreactors and the scale-up of sonochemical processes.     

Effects of gas saturation and sparging on sonochemical oxidation activity in open and closed systems,Part I: H2O2 generation

Cavitational/sonochemical activity can be significantly enhanced or reduced depending on the gases dissolved in the liquid. Although many researchers have suggested the order of importance of dissolved gas conditions that affect the degree of sonoluminescence (SL), sonochemiluminescence (SCL), and compound degradation, the most suitable gas condition for sonochemical oxidation reactions is currently unknown. In this study (Part I), the effects of gas saturation and sparging on the generation of H₂O₂ were investigated in a 28-kHz sonoreactor system. Four gas modes, saturation/closed, saturation/open, sparging/closed, and sparging/open, were applied to Ar, O₂, N₂, and binary gas mixtures. The change in dissolved oxygen (DO) concentration during ultrasonic irradiation was measured and was used as an indicator of whether the gaseous exchange between liquid and air altered the gas content of the liquid. Considerable difference in the DO concentration was observed for the gas saturation/open mode, ranging from –11.5 mg/L (O₂ 100 %) to +4.3 mg/L (N₂ 100 %), while no significant difference was observed in the other gas modes. The change in the gas content significantly reduced the linearity for H₂O₂ generation, which followed pseudo-zero-order kinetics, and either positively or negatively affected H₂O₂ generation. Ar:O₂ (75:25) and Ar:O₂ (50:50) resulted in the highest and second-highest H₂O₂ generation for both gas saturation and sparging, respectively. In addition, gas sparging resulted in much higher H₂O₂ generation for all gas conditions compared to gas saturation; this was because of the significant change in the cavitational active zone and concentrated ultrasonic energy, which formed a bulb-shaped active zone, especially for the Ar/O₂ mixtures adjacent to the transducer at the bottom. The sparging flow rate and position also significantly affected H₂O₂ generation; the highest H₂O₂ generation was obtained when the sparger was placed at the bottom adjacent to the transducer, with a flow rate of 3 L/min.In Part II, the generation of nitrogen oxides, including nitrite (NO₂^–) and nitrate (NO₃^–), was investigated using the same ultrasonic system with three gas modes: saturation/open, saturation/closed, and sparging/closed.     

Acoustic cavitation at low gas pressures in PZT-based ultrasonic systems

The generation of cavitation-free radicals through evanescent electric field and bulk-streaming was reported when micro-volumes of a liquid were subjected to 10 MHz surface acoustic waves (SAW) on a piezoelectric substrate [Rezk et al., J. Phys. Chem. Lett. 2020, 11, 4655–4661; Rezk et al., Adv. Sci. 2021, 8, 2001983]. In the current study, we have tested a similar hypothesis with PZT-based ultrasonic units (760 kHz and 2 MHz) with varying dissolved gas concentrations, by sonochemiluminescence measurement and iodide dosimetry, to correlate radical generation with dissolved gas concentrations. The dissolved gas concentration was adjusted by controlling the over-head gas pressure. Our study reveals that there is a strong correlation between sonochemical activity and dissolved gas concentration, with negligible sonochemical activity at near-vacuum conditions. We therefore conclude that radical generation is dominated by acoustic cavitation in conventional PZT-based ultrasonic reactors, regardless of the excitation frequency.     

A comparative study on the modeling of sound pressure field distributions in a sonoreactor with experimental investigation

In sonochemical reactors the effect of emerging cavitation bubbles has significant influence on the amplitude and structure of the developing sound field. Calculations show that the damping parameter and the phase velocity may, depending on the pressure amplitude, change by several orders of magnitude. For example, the sound velocity in water comes to 1500 ms⁻¹, whereas in a bubbly liquid it may decrease to 20 ms⁻¹, which is much below the velocity of sound in air (about 340 ms⁻¹). In this paper, a method of calculating the time dependent three-dimensional pressure field in sonochemical reactors of various shapes is presented. It takes into account inhomogeneous distributed wave parameters which are a function of the spatial depending pressure amplitude. The modeled results are then compared with experimentally measured values of a certain kind of reaction vessel. The agreement is found to be satisfactory.     

A phenomenological investigation into the opposing effects of fluid flow on sonochemical activity at different frequency and power settings. 1. Overhead stirring

The effect of flow in an ultrasonic reactor is an important consideration for practical applications and for the scale-up of ultrasonic processing. Previous literature on the influence of flow on sonochemical activity has reported conflicting results. Therefore, this work examined the effect of overhead stirring at four different frequencies, 40, 376, 995 and 1179 kHz, in two different reactor configurations. Comparable power settings were utilised to elucidate the underlying mechanisms of interactions between the flow and sonochemical activity. The sonochemical activity was determined by the yield of hydrogen peroxide, measured by iodide dosimetry, and the active region was visualised with sonochemiluminescence imaging. The overhead stirring in the low frequency reactor altered the yield of hydrogen peroxide so it produced the maximum yield out of the four frequencies. The increase in hydrogen peroxide yield was attributed to a reduction in coalescence at 40 kHz. However at the higher frequencies, coalescence was not found to be the main reason behind the observed reductions in sonochemical yield. Rather the prevention of wave propagation and the reduction of the standing wave portion of the field were considered.     

Electromechanical,acoustical and thermodynamical characterization of a low-frequency sonotrode-type transducer in a small sonoreactor at different excitation levels and loading conditions

The paper reports and compares the results of the electromechanical, acoustical and thermodynamical characterization of a low-frequency sonotrode-type ultrasonic device inside a small sonoreactor, immersed in three different loading media, namely, water, juice and milk, excited at different excitation levels, both below and above the cavitation threshold. The electroacoustic efficiency factor determined at system resonance through electromechanical characterization in degassed water as the reference medium is 88.7% for the device in question. This efficiency can be reduced up to three times due to the existence of a complex sound field in the reactor in linear driving conditions below the cavitation threshold. The behaviour of the system is more stable at higher excitation levels than in linear operating conditions.During acoustical characterization, acoustic pressure is spatially averaged, both below and above the cavitation threshold. The standing wave patterns inside the sonoreactor have a stronger influence on the variation of the spatially distributed RMS pressure in linear operating conditions. For these conditions, the variation of ±1.7 dB was obtained, compared to ±1.4 dB obtained in highly nonlinear regime. The acoustic power in the sonoreactor was estimated from the magnitude of the averaged RMS pressure, and from the reverberation time of the sonoreactor as the representation of the losses. The electroacoustic efficiency factors obtained through acoustical and electromechanical characterization are in a very good agreement at low excitation levels. The irradiated acoustic power estimated in nonlinear conditions differs from the dissipated acoustic power determined with the calorimetric method by several orders of magnitude.The number of negative pressure peaks that represent transient cavitation decreases over time during longer treatments of a medium with high-power ultrasound. The number of negative peaks decreases faster when the medium and the vessel are allowed to heat up.     

Visualization and optimization of cavitation activity at a solid surface in high frequency ultrasound fields

Despite the increasing use of high frequency ultrasound in heterogeneous reactions, knowledge about the spatial distribution of cavitation bubbles at the irradiated solid surface is still lacking. This gap hinders controllable surface sonoreactions. Here we present an optimization study of the cavitation bubble distribution at a solid sample using sonoluminescence and sonochemiluminescence imaging. The experiments were performed at three ultrasound frequencies, namely 580, 860 and 1142 kHz. We found that position and orientation of the sample to the transducer, as well as its material properties influence the distribution of active cavitation bubbles at the sample surface in the reactor. The reason is a significant modification of the acoustic field due to reflections and absorption of the ultrasonic wave by the solid. This is retraced by numerical simulations employing the Finite Element Method, yielding reasonable agreement of luminescent zones and high acoustic pressure amplitudes in 2D simulations. A homogeneous coverage of the test sample surface with cavitation is finally reached at nearly vertical inclination with respect to the incident wave.     

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.     

Effect of dissolved gases on sonochemical oxidation in a 20 kHz probe system: Continuous monitoring of dissolved oxygen concentration and sonochemical oxidation activity

Dissolved gases have a substantial influence on acoustic cavitation and sonochemical oxidation reactions. Little research on the changes in dissolved gases and the resultant changes in sonochemical oxidation has been reported, and most studies have focused only on the initial dissolved gas conditions. In this study, the dissolved oxygen (DO) concentration was measured continuously during ultrasonic irradiation using an optical sensor in different gas modes (saturation/open, saturation/closed, and sparging/closed modes). Simultaneously, the resulting changes in sonochemical oxidation were quantified using KI dosimetry. In the saturation/open mode using five gas conditions of Ar and O₂, the DO concentration decreased rapidly when O₂ was present because of active gas exchange with the atmosphere, and the DO concentration increased when 100% Ar was used. As a result, the order of the zero-order reaction constant for the first 10 min (k_0-10) decreased in the order Ar:O₂ (75:25) > 100% Ar ≈ Ar:O₂ (50:50) > Ar:O₂ (25:75) > 100% O₂, whereas that during the last 10 min (k_20-30) when the DO concentration was relatively stable, decreased in the order 100% Ar > Ar:O₂ (75:25) > Ar:O₂ (50:50) ≈ Ar:O₂ (20:75) > 100% O₂. In the saturation/closed mode, the DO concentration decreased to approximately 70–80% of the initial level because of ultrasonic degassing, and there was no influence of gases other than Ar and O₂. Consequently, k_0-10 and k_20-30 decreased in the order Ar:O₂ (75:25) > Ar:O₂ (50:50) > Ar:O₂ (25:75) > 100% Ar > 100% O₂. In the sparging/closed mode, the DO concentration was maintained at approximately 90% of the initial level because of the more active gas adsorption induced by gas sparging, and the values of k_0-10 and k_20-30 were almost the same as those in the saturation/closed mode. In the saturation/open and sparging/closed modes, the Ar:O₂ (75:25) condition was most favorable for enhancing sonochemical oxidation. However, a comparison of k_0-10 and k_20-30 indicated that there would be an optimal dissolved gas condition that was different from the initial gas condition. In addition, the mass-transfer and ultrasonic-degassing coefficients were calculated using changes in the DO concentration in the three modes.     

Observations of changes in acoustic emission waveform for varying seeded defect sizes in a rolling element bearing

The investigation reported in this paper was centered on the application of the acoustic emissions (AE) technology for characterising the defect sizes on a radially loaded bearing. An experimental test-rig was designed such that defects of varying sizes could be seeded onto the outer and inner races of a test bearing. The aim of this investigation was to correlate defect size with specific AE parameters and to ascertain the relationship between the duration of AE transient bursts associated with seeded defects to the actual geometric size of the defect. In addition, the use of AE to detect inner race defects was explored particularly as this known to be fraught with difficulty. It is concluded that the geometric defect size of outer race defects can be determined from the AE waveform.     

Improving sono-activated persulfate oxidation using mechanical mixing in a 35-kHz ultrasonic reactor: Persulfate activation mechanism and its application

This study investigated the degradation of ibuprofen (IBP), an activated persulfate (PS), when subjected to ultrasonic (US) irradiation and mechanical mixing (M). The effects of several critical factors were evaluated, including the effect of rpm on M, PS concentration, and initial pH, and that of temperature on IBP degradation kinetics and the PS activation mechanism. The resulting IBP oxidation rate constant was significantly higher at 400 rpm. As the PS load increased, the IBP oxidation rate constant increased. The value of the IBP reaction rate increased with decreasing pH; below pH 4.9, there was no significant difference in the IBP oxidation rate constant. The IBP oxidation activation energy when using the US/M-PS system was 18.84 kJ mol⁻¹. In the US/M-PS system, PS activation was the primary effect of temperature at the interface during the explosion of cavitation bubbles. These encouraging results suggest that the US-PS/M process is a promising strategy for the treatment of IBP-based water pollutants.     

Acoustic emission source location in plates using wavelet analysis and cross time frequency spectrum

In this study, the theories of wavelet transform and cross-time frequency spectrum (CTFS) are used to locate AE source with frequency-varying wave velocity in plate-type structures. A rectangular array of four sensors is installed on the plate. When an impact is generated by an artificial AE source such as Hsu–Nielsen method of pencil lead breaking (PLB) at any position of the plate, the AE signals will be detected by four sensors at different times. By wavelet packet decomposition, a packet of signals with frequency range of 0.125–0.25 MHz is selected. The CTFS is calculated by the short-time Fourier transform of the cross-correlation between considered packets captured by AE sensors. The time delay is calculated when the CTFS reaches the maximum value and the corresponding frequency is extracted per this maximum value. The resulting frequency is used to calculate the group velocity of wave velocity in combination with dispersive curve. The resulted locating error shows the high precision of proposed algorithm.     

High pressure and emission spectra of Eu3+ in L-EuBO3

Effects of the high pressure on the emission spectra of Eu³⁺-activated L-EuBO₃ were considered at room temperature up to 100 kbar. The position of five 0–2 lines in the ⁵D₀→⁷F₂ transition region was determined. The pressure does not have the same effect on all these lines. In four of them, high pressure induced a red shift with different shift rates:+0.0022,+0.0035,+0.0034 and+0.0027 nm kbar^?1, respectively, whereas in the last one, high pressure induced a blue shift with shift rate?0.0034 nm kbar^?1. Possible reasons for the mentioned pressure effects on the line positions were considered.     

Acoustic noise simulation and measurement of a gradient insert in a 4 T MRI

High speed switching of current in gradient coils within high magnetic field strength magnetic resonance imaging (MRI) scanners results in high acoustic sound pressure levels (SPL) in and around these machines. Many studies have already been conducted to characterize the sound field in and around MRIs and various methods have been investigated to attenuate the noise generated. In the work presented here a computational vibro-acoustic model was developed based on an iteratively modified and validated finite element (FE) model to characterize the acoustic noise properties of the gradient coil. The simulation results from the computational model were verified through experimental noise measurement for the gradient coil insert in a 4 T MRI scanner by using swept sinusoidal time waveform inputs. Comparisons show that the computational model predicts the noise characteristic properties extremely accurately. There are three dominant frequency bands where the SPL is much higher than those at other frequencies. The SPL in the horizontal direction is much higher than that in the vertical direction due to the excitation to the horizontally placed X coil. The SPL to the inner surface of the coil is higher than far from the inner surface, which proves that the acoustic noise is radiated from the inner surface and primarily caused by the normal vibration of the inner surface. Further verification was conducted by using two types of trapezoidal sequence inputs usually used, which is to simulate real scanning sequences for small animals. Again the accuracy of the developed model is verified. The validated acoustic computational model could be used as an effective method to predict the noise that would be produced by a coil in the design stage. Modification of the structural design or the excitation pulse could be performed to reduce the acoustic noise when the gradient coil is in scanning.