Ultrasound-assisted selective hydrogenation of C-5 acetylene alcohols with Lindlar catalysts

The selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) was performed in the presence of Lindlar catalyst, comparing conventional stirring with sonication at different frequencies of 40, 380 and 850 kHz. Under conventional stirring, the reaction rates were limited by intrinsic kinetics, while in the case of sonication, the reaction rates were 50–90% slower. However, the apparent reaction rates were found to be significantly frequency dependent with the highest rate observed at 40 kHz. The original and the recovered catalysts after the hydrogenation reaction were compared using bulk elemental analysis, powder X-ray diffraction and scanning and transmission electron microscopy coupled with energy-dispersive X-ray analysis. The studies showed that sonication led to the frequency-dependent fracturing of polycrystalline support particles with the highest impact caused by 40 kHz sonication, while monocrystals were undamaged. In contrast, the leaching of Pd/Pb particles did not depend on the frequency, which suggests that sonication removed only loosely-bound catalyst particles.     

Effect of amplitude and frequency of ultrasonic irradiation on morphological characteristics control of calcium carbonate

We have previously reported on the morphological control of calcium carbonate by changing synthetic conditions such as temperature, pH and degree of supersaturation in liquid reaction. The present study reports the effect of amplitude and frequency of ultrasonic irradiation on the particle size of calcium carbonate using a horn type ultrasonic apparatus at two different frequencies. The calcium carbonate precipitated by mechanical stirring had a particle size of about 20 μm. By contrast, the particle size of vaterite formed under ultrasonic irradiation was about 2 μm, with a specific surface area of 25–30 m²/g. The major polymorph of calcium carbonate formed by ultrasonic irradiation was vaterite with some calcite present. For 40 kHz ultrasonic irradiation, the specific surface area of the calcium carbonate increased with increasing amplitude. The particle size of vaterite formed at this frequency was about 2 μm, and its distribution was sharper than that obtained at 20 kHz. The mode diameter of the synthesized vaterite was found to decrease with increasing amplitude at 40 kHz.     

Ultrasound assisted enzymatic pre-treatment of high fat content dairy wastewater

This paper illustrates the application of ultrasound in a dairy waste water treatment for the removal of fat using enzyme as a catalyst. Lipase Z was used to perform the enzymatic pre-hydrolysis of a synthetic dairy wastewater containing around 2000 mg/L of fat content coupled with ultrasound irradiation. Different process parameters like effect of enzyme loading, temperature, ultrasound power, frequency, duty cycle and speed of agitation are optimized. The maximum hydrolysis of 78% is achieved at 0.2% enzyme loading (w/v), 30 °C temperature, 165 W of ultrasonication power at 25 kHz and 66% duty cycle. It was observed that the enzymatic pre-hydrolysis under the influence of ultrasound drastically reduces the reaction time from 24 h to 40 min as compared to conventional stirring with improved yield.     

Numerical simulation of ultrasonic enhancement on mass transfer in liquid–solid reaction by a new computational model

Mass transfer coefficient is an important parameter in the process of mass transfer. It can reflect the degree of enhancement of mass transfer process in liquid–solid reaction and in non-reactive systems like dissolution and leaching, and further verify the issues by experiments in the reaction process. In the present paper, a new computational model quantitatively solving ultrasonic enhancement on mass transfer coefficient in liquid–solid reaction is established, and the mass transfer coefficient on silicon surface with a transducer at frequencies of 40 kHz, 60 kHz, 80 kHz and 100 kHz has been numerically simulated. The simulation results indicate that mass transfer coefficient increases with the increasing of ultrasound power, and the maximum value of mass transfer coefficient is 1.467 × 10⁻⁴ m/s at 60 kHz and the minimum is 1.310 × 10⁻⁴ m/s at 80 kHz in the condition when ultrasound power is 50 W (the mass transfer coefficient is 2.384 × 10⁻⁵ m/s without ultrasound). The extrinsic factors such as temperature and transducer diameter and distance between reactor and ultrasound source also influence the mass transfer coefficient on silicon surface. Mass transfer coefficient increases with the increasing temperature, with the decreasing distance between silicon and central position, with the decreasing of transducer diameter, and with the decreasing of distance between reactor and ultrasound source at the same ultrasonic power and frequency. The simulation results indicate that the computational model can quantitatively solve the ultrasonic enhancement on mass transfer coefficient.     

Pretreatment of defatted wheat germ proteins (by-products of flour mill industry) using ultrasonic horn and bath reactors: Effect on structure and preparation of ACE-inhibitory peptides

The ultrasonic horn and bath reactors were compared based on production of angiotensin-converting-enzyme (ACE) inhibitory peptides from defatted wheat germ proteins (DWGP). The DWGP was sonicated before hydrolysis by Alcalase. Degree of hydrolysis, ACE-inhibitory activity, surface hydrophobicity, fluorescence intensity, free sulfhydryl (SH), and disulfide bond (SS) were determined. The highest ACE-inhibitory activity of DWGP hydrolysate was obtained at power intensity of 191.1 W/cm² for 10 min in the ultrasonic horn reactor. The fixed frequency of 33 kHz and the sweep frequency of 40 ± 2 kHz resulted in the maximum ACE-inhibitory activity. The combined irradiation of dual fixed frequency (24/68 kHz) produced significant increase in ACE-inhibitory activity compared with single frequency (33 kHz). The ultrasonic probe resulted in significant higher ACE-inhibitory activity compared with ultrasonic bath operating at single or dual fixed and sweep frequencies. The changes in conformation of the DWGP due to sonication were confirmed by the changes in fluorescence intensity, surface hydrophobicity, SH_f and SS contents and they were found in conformity with the ACE-inhibitory activity in case of the ultrasonic horn reactor but not in bath reactor.     

Coumarin fluorometry to quantitatively detectable OH radicals in ultrasound aqueous medium

When ultrasound (US) was exposed to aqueous coumarin solution in air atmosphere, the UV–visible and fluorescence spectra of the probe were measured at different US exposure times. The US exposure was carried out at 43 kHz and 500 kHz with different out-put power. It was found that the 500 kHz US produced umbelliferone fluorescence, while the 43 kHz US had no fluorescence. In addition, the coumarin absorbance at 270 nm maximum was decreased with in cases of the US exposure time. In contrary, the fluorescent intensity of umbelliferone at 460 nm increased with increasing of US exposure time. This exhibited that the coumarin probe was converted to umbelliferone by the US exposure, when the 500 kHz US was operated. This was facted that the coumarin framework was caused with addition of OH groups which was generated by the 500 kHz US. Therefore, the umbelliferone fluorescent became a probe to estimate OH radical in US medium. Furthermore, the chemo-fluorometry showed that the emission maximum of the formed umbelliferone could probe the bulk pHs in the US aqueous medium.     

Esterification of sodium 4-hydroxybenzoate by ultrasound-assisted solid–liquid phase-transfer catalysis using dual-site phase-transfer catalyst

The catalytic esterification of sodium 4-hydroxybenzoate with benzyl bromide by ultrasound-assisted solid–liquid phase-transfer catalysis (U-SLPTC) was investigated using the novel dual-site phase-transfer catalyst 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl dichloride (BTBAMBC), which was synthesized from the reaction of 4,4′-bis(chloromethyl)-1,1′-biphenyl and tributylamine. Without catalyst and in the absence of water, the product yield at 60 °C was only 0.36% in 30 min of reaction even under ultrasound irradiation (28 kHz/300 W) and 250 rpm of stirring speed. When 1 cm³ of water and 0.5 mmol of BTBAMBC were added, the yield increased to 84.3%. The catalytic intermediate 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl di-4-hydroxybenzoate was also synthesized to verify the intrinsic reaction which was mainly conducted in the quasi-aqueous phase locating between solid and organic phases. Pseudo-first-order kinetic equation was used to correlate the overall reaction, and the apparent rate coefficient with ultrasound (28 kHz/300 W) was 0.1057 min⁻¹, with 88% higher than that (0.0563 min⁻¹) without ultrasound. The esterification under ultrasonic irradiation using BTBAMBC by solid–liquid phase-transfer catalysis was developed.     

Single,simultaneous and sequential applications of ultrasonic frequencies for the elimination of ibuprofen in water

The study is about the assessment of single and multi-frequency operations for the overall degradation of a widely consumed analgesic pharmaceutical-ibuprofen (IBP). The selected frequencies were in the range of 20–1130 kHz emissions coming from probes, baths and piezo-electric transducers attached to plate-type devices. Multi-frequency operations were applied either simultaneously as “duals”, or sequentially at fixed time intervals; and the total reaction time in all operations was 30-min. The work also covers evaluation of the effect of zero-valent iron (ZVI) on the efficiency of the degradation process and the performance of the reaction systems. It was found that low-frequency probe type devices especially at 20 kHz were ineffective when applied singly and without ZVI, and relatively more effective in combined-frequency operations in the presence of ZVI. The power efficiencies of the reactors and/or reaction systems showed that 20-kHz probe was considerably more energy intensive than all others, and was therefore not used in multi-frequency operations. The most efficient reactor in terms of power consumption was the bath (200 kHz), which however provided insufficient mineralization of the test chemical. The highest percentage of TOC decay (37%) was obtained in a dual-frequency operation (40/572 kHz) with ZVI, in which the energy consumption was neither low nor exceptionally too high. A sequential operation (40 + 200 kHz) in that respect was more efficient, because it required much less energy for a similar TOC decay performance (30%). In general, the degradation of IBP increased with increased power consumption, which in turn reduced the sonochemical yield. The study also showed that advanced Fenton reactions with ZVI were faster in the presence of ultrasound, and the metal was very effective in improving the performance of low-frequency operations.     

Effects of multi-frequency ultrasound pretreatment under low power density on the enzymolysis and the structure characterization of defatted wheat germ protein

The effects of ultrasonic frequency mode, power density, pretreatment time and other parameters under low power density on the degree of hydrolysis (DH) of defatted wheat germ protein (DWGP) and angiotensin-I-converting enzyme (ACE) inhibitory activity of DWGP hydrolysate were studied in this research. Ultraviolet–visible (UV–Vis) spectra, free sulfhydryl (SH), disulfide bond (SS), surface hydrophobicity and hydrophobic protein content of ultrasound-pretreated protein and hydrophobic amino acid (HAA) content of alcalase-hydrolysate of DWGP were measured under optimized ultrasonic condition. The ultrasonic frequency mode with dual-fixed frequency combination of 28/40 kHz showed higher ACE inhibitory activity of DWGP hydrolysate compared with that of other ultrasound frequency modes and all the ultrasonic frequency combinations involving in 28 kHz showed higher ACE inhibitory activity. Under the dual-fixed frequency ultrasound mode of 28/40 kHz, ultrasonic power density of 60 W/L, pretreatment time of 70 min, temperature of 60°C and substrate concentration of 60 g/L, the ACE inhibitory activity of DWGP hydrolysate was the highest with its value of 74.75% (increased by 62.30% compared to control). However, all the ultrasonic pretreatment did not increase the DH of DWGP significantly (p > 0.05). The changes in UV–Vis spectra, SH and SS groups, surface hydrophobicity and hydrophobic protein content indicated that the structure of DWGP unfolded after ultrasound pretreatment. The HAA content of hydrolysate from the pretreated DWGP increased significantly (p < 0.05). The results proved that ultrasound pretreatment loosed the protein structure and exposed more HAA residues of protein to be attacked easily by alcalase. This resulted in the increase in the HAA content which related to the ACE inhibitory activity.     

Investigation of acoustic cavitation energy in a large-scale sonoreactor

Acoustic cavitation energy distributions were investigated for various frequencies such as 35, 72, 110 and 170 kHz in a large-scale sonoreactor. The energy analyses were conducted in three-dimensions and the highest and most stable cavitation energy distribution was obtained not in 35 kHz but in 72 kHz. However, the half-cavitation-energy distance was larger in the case of 35 kHz ultrasound than in the case of 72 kHz, demonstrating that cavitation energy for one cycle was higher for a lower frequency. This discrepancy was due to the large surface area of the cavitation-energy-meter probe. In addition, 110 and 170 kHz ultrasound showed a very low and poor cavitation energy distribution. Therefore larger input power was required to optimize the use of higher frequency ultrasound in the sonoreactor with long-irradiation distance. The relationship between cavitation energy and sonochemical efficiency using potassium iodide (KI) dosimetry was best fitted quadratically. From 7.77 × 10^?10 to 4.42 × 10^?9 mol/J of sonochemical efficiency was evaluated for the cavitation energy from 31.76 to 103. 67 W. In addition, the cavitation energy attenuation was estimated under the assumption that cavitation energy measured in this study would be equivalent to sound intensity, resulting in 0.10, 0.18 and 2.44 m^?1 of the attenuation coefficient (α) for 35, 72 and 110 kHz, respectively. Furthermore, α/(frequency)² was not constant, as some previous studies have suggested.     

Ultrasound-assisted transesterification of soybean oil using low power and high frequency and no external heating source

In this work, high frequency and low power ultrasound without external heating source and mechanical stirring in biodiesel production were studied. Transesterification of soybean oil with methanol and catalyzed by KOH was investigated using ultrasound equipment and ultrasonic transducer. The effect of ultrasonic output power (3 W–9 W), ultrasonic frequency (1 MHz and 3 MHz), and alcohol to oil molar ratio (6:1 and 8:1) have been investigated. The increase in ultrasonic power provided higher conversion rates. In addition, higher conversion rates were obtained by increasing the ultrasonic frequency from 1 MHz to 3 MHz (48.7% to 79.5%) for the same reaction time. Results also indicate that the speed of sound can be used to evaluate the produced biodiesel qualitatively. Further, the ultrasound system presented electric consumption (46.2 W∙h) four times lower than achieved using the conventional method (211.7 W∙h and 212.3 W∙h). Thus, biodiesel production using low power ultrasound in the MHz frequency range is a promising technology that could contribute to biodiesel production processes.     

Ultrasound assisted dispersal of a copper nanopowder for electroless copper activation

This paper describes the ultrasound assisted dispersal of a low wt./vol.% copper nanopowder mixture and determines the optimum conditions for de-agglomeration. A commercially available powder was added to propan-2-ol and dispersed using a magnetic stirrer, a high frequency 850 kHz ultrasonic cell, a standard 40 kHz bath and a 20 kHz ultrasonic probe. The particle size of the powder was characterized using dynamic light scattering (DLS). Z-Average diameters (mean cluster size based on the intensity of scattered light) and intensity, volume and number size distributions were monitored as a function of time and energy input. Low frequency ultrasound was found to be more effective than high frequency ultrasound at de-agglomerating the powder and dispersion with a 20 kHz ultrasonic probe was found to be very effective at breaking apart large agglomerates containing weakly bound clusters of nanoparticles. In general, the breakage of nanoclusters was found to be a factor of ultrasonic intensity, the higher the intensity the greater the de-agglomeration and typically micron sized clusters were reduced to sub 100 nm particles in less than 30 min using optimum conditions. However, there came a point at which the forces generated by ultrasonic cavitation were either insufficient to overcome the cohesive bonds between smaller aggregates or at very high intensities decoupling between the tip and solution occurred. Absorption spectroscopy indicated a copper core structure with a thin oxide shell and the catalytic performance of this dispersion was demonstrated by drop coating onto substrates and subsequent electroless copper metallization. This relatively inexpensive catalytic suspension has the potential to replace precious metal based colloids used in electronics manufacturing.     

Synthesis of biodiesel from waste cooking oil using sonochemical reactors

Investigation into newer routes of biodiesel synthesis is a key research area especially due to the fluctuations in the conventional fuel prices and the environmental advantages of biodiesel. The present work illustrates the use of sonochemical reactors for the synthesis of biodiesel from waste cooking oil. Transesterification of used frying oil with methanol, in the presence of potassium hydroxide as a catalyst has been investigated using low frequency ultrasonic reactor (20 kHz). Effect of different operating parameters such as alcohol–oil molar ratio, catalyst concentration, temperature, power, pulse and horn position on the extent of conversion of oil have been investigated. The optimum conditions for the transesterification process have been obtained as molar ratio of alcohol to oil as 6:1, catalyst concentration of 1 wt.%, temperature as 45 °C and ultrasound power as 200 W with an irradiation time of 40 min. The efficacy of using ultrasound has been compared with the conventional stirring approach based on the use of a six blade turbine with diameter of 1.5 cm operating at 1000 rpm. Also the purification aspects of the final product have been investigated.     

Enhancing the adhesion strength of micro electroforming layer by ultrasonic agitation method and the application

Micro electroforming is widely used for fabricating micro metal devices in Micro Electro Mechanism System (MEMS). However, there is the problem of poor adhesion strength between micro electroforming layer and substrate. This dramatically influences the dimensional accuracy of the device. To solve this problem, ultrasonic agitation method is applied during the micro electroforming process. To explore the effect of the ultrasonic agitation on the adhesion strength, micro electroforming experiments were carried out under different ultrasonic power (0 W, 100 W, 150 W, 200 W, 250 W) and different ultrasonic frequencies (0 kHz, 40 kHz, 80 kHz, 120 kHz, 200 kHz). The effects of the ultrasonic power and the ultrasonic frequency on the micro electroforming process were investigated by polarization method and alternating current (a.c.) impedance method. The adhesion strength between the electroforming layer and the substrate was measured by scratch test. The compressive stress of the electroforming layer was measured by X-ray Diffraction (XRD) method. The crystallite size of the electroforming layer was measured by Transmission Electron Microscopy (TEM) method. The internal contact surface area of the electroforming layer was measured by cyclic voltammetry (CV) method. The experimental results indicate that the ultrasonic agitation can decrease the polarization overpotential and increase the charge transfer process. Generally, the internal contact surface area is increased and the compressive stress is reduced. And then the adhesion strength is enhanced. Due to the different depolarization effects of the ultrasonic power and the ultrasonic frequency, the effects on strengthening the adhesion strength are different. When the ultrasonic agitation is 200 W and 40 kHz, the effect on strengthening the adhesion strength is the best. In order to prove the effect which the ultrasonic agitation can improve the adhesion strength of the micro devices, micro pillar arrays were fabricated under ultrasonic agitation (200 W, 40 kHz). The experimental results show that the residual rate of the micro pillar arrays is increased about 17% by ultrasonic agitation method. This work contributes to fabricating the electroforming layer with large adhesion strength.     

Measurements and analysis of the acoustic signals produced by partial discharges in insulation oil

This paper focuses on the frequency analysis of acoustic signals produced by partial discharges (PDs) in insulation oil and the positioning of the PD occurrence for application in the diagnosis of oil-insulated transformers. Three types of electrode systems; the needle–plane, the plane–plane, and the wire–wire structures were assembled to simulate the partial discharge in insulation oil. A low-noise amplifier and a de-coupler were designed to detect the acoustic signal with high-sensitivity. The frequency ranges of the acoustic signal were 60–270 kHz in the needle–plane electrode system, 45–250 kHz in the plane–plane electrode system, and 50–180 kHz in the wire–wire electrode system. Their peak frequencies were 145 kHz, 118 kHz and 121 kHz, respectively.The position of the PD occurrence was calculated from the time difference of arrival (TOA) using three acoustic emission (AE) sensors. The position was found within a 1% error in the experimental set-up.     

Comparison of hydroxyl radical formation in aqueous solutions at different ultrasound frequencies and powers using the salicylic acid dosimeter

Ultrasonic frequencies of 20 kHz, 382 kHz, 584 kHz, 862 kHz (and 998 kHz) have been compared with regard to energy output and hydroxyl radical formation utilising the salicylic acid dosimeter. The 862 kHz frequency inputs 6 times the number of Watts into water, as measured by calorimetry, with the other frequencies having roughly the same value under very similar conditions. A plausible explanation involving acoustic fountain formation is proposed although enhanced coupling between this frequency and water cannot be discounted. Using the salicylic acid dosimeter and inputting virtually the same Wattages it is established that 862 kHz is around 10% more efficient at generating hydroxyl radicals than the 382 kHz but both of these are far more effective than the other frequencies. Also, it is found that as temperature increases to 42 °C then the total dihydroxybenzoic acid (Total DHBA) produced is virtually identical for 382 kHz and 862 kHz, though 582 kHz is substantially lower, when the power levels are set at approximately 9 W for all systems. An equivalent power level of 9 W could not be obtained for the 998 kHz transducer so a direct comparison could not be made in this instance. These results have implications for the optimum frequencies chosen for both Advanced Oxidation Processes (AOPs) and organic synthesis augmented by ultrasound.     

Fabrication of bacterial cellulose thin films self-assembled from sonochemically prepared nanofibrils and its characterization

Bacterial cellulose (BC) film formation could be a critical issue in nanotechnology applications such as biomedical or smart materials products. In this research, purified pretreated BC was subjected to high intensity ultrasound (HIUS) and was investigated for the development of BC films. The morphological, structural and thermal properties of the obtained films were studied by using FE-SEM, AFM, FT-IR, XRD, TGA and DSC characterizations. Results showed that the most favorable purification treatment was the 0.01 M NaOH at 70 °C for 2 h under continuous stirring. The most suitable ultrasound operating conditions were found to be, 1 cm distance of ultrasonic probe from the bottom of the beaker, submerged in cold water bath cooling around 12 ± 2 °C. The power (25 W/cm²), time (30 min), BC concentration (0.1% w/w), amplitude (20 μm) and frequency (20 kHz) were maintained constant.     

Ultrasound assisted intensified recovery of lactose from whey based on antisolvent crystallization

The current work deals with understanding the fundamental aspects of intensified recovery of lactose from paneer (cottage cheese) whey using the anti-solvent induced sonocrystallization. Ultrasonic horn (22 kHz) with varying power levels over the range of 40–120 W has been used for initial experiments at 100% duty cycle and two different levels of ultrasonic exposure time as 10 min and 20 min. Similar experiments were also performed using ultrasonic bath for the same time of exposure but with at two ultrasonic frequencies (22 kHz and 33 kHz). It was observed that the lactose recovery as well as purity increased with an increase in ultrasonic power at 100% duty cycle for the case of treatment time as 10 min whereas the lactose recovery and purity increased only till an optimum power for the 20 min treatment. In the case of ultrasonic bath, lactose purity increased with an increase in the ultrasonic frequency from 22 kHz to 33 kHz though the lactose recovery marginally decreased. Overall, it was observed that the maximum lactose recovery was ∼98% obtained using ultrasonic horn while the maximum lactose purity was ∼97%. It was also observed that maximum lactose recovery was ∼94% for the case of ultrasonic bath while the maximum lactose purity was ∼92%. The work has enabled to understand the optimized application of ultrasound so as to maximize both the lactose yield and purity during the recovery from whey.     

Kinetics of microplasma atmospheric ion generation correlated with discharge current

The conditions necessary for achieving a stable bipolar ion generation (in the order of 10⁶ ion/cm³) and lower ozone concentration (less than 50 ppb) using a surface discharge microplasma device (SMD) by adjusting the applied voltage and frequency were experimentally determined and investigated. Measurements of the discharge current characteristics of the SMD revealed saturation against the frequency (1.5–2.5 kHz, depending on the applied voltage). The ion and ozone concentrations both increased in step with the discharge current in the lower frequency region. The ion concentration reached equilibrium in the frequency range of 200–500 Hz, and the point of equilibrium within that range depended on the applied voltage. The ozone concentration did not reach equilibrium under our experimental conditions (ozone concentration < 100 ppb). The kinetics of the ion/ozone generation rate with a focus on the plasma reaction and recombination of bipolar ions is discussed.     

High pulse repetition frequency RF excited waveguide CO2 laser with mechanical Q-switching

In this paper, a mechanical Q-switching is used in radio frequency (RF) excited waveguide CO₂ laser to obtain high pulse repetition frequency (PRF) laser. The Q-switching system includes two confocal ZnSe lenses and a high speed mechanical chopper, which is inserted into the cavity. The peak power is up to 730 W and the pulse width 200 ns at the highest PRF 20 kHz. The laser also has the advantages of compact, small-volume, and low-cost.