Electrochemical behaviour of zinc in 20 kHz sonicated NaOH electrolytes.

This paper describes the influence of 20 kHz ultrasound upon the corrosion behaviour of zinc in NaOH electrolytes. A systematic study of the effects exerted by ultrasound on the electrochemical interface was first carried out, so as to determine the transmitted power and to characterize mass transfer at the electrode. Then attention was focused on the corrosion passivation mechanism of zinc in sonicated NaOH solutions (0.1 and 1 M). Investigations were carried out using electrochemical techniques to determine corrosion and passivation kinetics parameters. SEM analysis of the sonicated zinc surfaces provides complementary information on the oxide layer composition and structure.     

A novel method for the modification of zinc powder by ultrasonic impregnation in cerium nitrate solution

This work is devoted to an extensive study of cerium deposits distributed directly on zinc particles by simple impregnation or ultrasonic impregnation for the modification of zinc powder. Meantime, the characterization of modified zinc powder and the influence of ultrasound parameters in the modification process upon the dendritic growth, the corrosion behavior and the cyclic performance of zinc are investigated using scanning electron microscopy, energy dispersion spectrometry, potentiostatic polarization, potentiodynamic polarization and cyclic voltammetry. Compared with simple impregnation, the assistance of ultrasonic irradiation is found to have a significant effect on the sedimentary state and favorable properties of cerium deposits in a protective way. Besides the cyclic voltammetry measurements display that the application of ultrasound also improves the cyclic performance of zinc electrode containing modified zinc powder mainly because the cerium deposits formed under ultrasonic irradiation can greatly hinder the dissolution and diffusion of the oxidation product of zinc in the electrolyte and effectively favor the capacity maintenance of zinc electrode.     

The effect of ultrasound upon the oxidation of thiosulphate on stainless steel and platinum electrodes

Ultrasound was found to increase the oxidation peak current and hence the decomposition rate of thiosulphate 50-fold compared to silent conditions. The effects of the ultrasonic frequency (20 and 38 kHz) and power upon the electrochemical oxidation of thiosulphate in aqueous KCl (1 mol dm-3) at stationary stainless steel and platinum electrodes were studied chronoamperometrically and potentiostatically (at various scan rates). No sigmoidal-shaped voltammograms were observed for the redox couple S4O6(2-)/S2O3(2-) in the presence of ultrasound. However, application of ultrasound to this redox couple provided an increase in the oxidation peak current at the frequencies employed, the magnitude of which varied with concentration, scan rate and ultrasonic power. Under sonication at 20 and 38 kHz, the oxidation peak potential shifted anodically with increasing ultrasonic power. This anodic shift in potential may be due to the formation of hydroxyl radicals, changes in electrode surface composition and complex adsorption phenomena. The large increase in oxidation peak currents and the rates of decomposition of thiosulphate, in the presence of ultrasound, are explained in terms of enhanced mass transfer at the electrode due to cavitation and acoustic streaming together with microstreaming coupled with adsorption phenomena. It is also shown that changes in macroscopic temperature throughout the experiment are insufficient to cause the observed enhanced diffusion.     

Ultrasonically enhanced corrosion of 304L stainless steel II: the effect of frequency, acoustic power and horn to specimen distance

The effects of frequency in the range 20 to 60 kHz, acoustic power and horn to specimen distance on the corrosion of 304L stainless steel in an ultrasonic field were investigated. At 40 and 60 kHz, the corrosion rate increased to a maximum and thereafter decreased with increasing transmitted power. At 20 kHz, the corrosion rate increased continuously with increasing power over the range investigated. At 18 W transmitted power, the corrosion rate increased continuously with frequency. However, at 40 W transmitted power a pronounced maximum in the corrosion rate occurred at 40 kHz. A significant effect of horn to specimen distance was found, the corrosion rate increasing with decreasing distance. High corrosion rates in excess of 800 mm yr(-1) were observed when the specimen was situated 0.1 mm from the radiating face of the ultrasonic probe. In addition, the area affected by sonication was found to increase with increasing distance.     

Effects of ultrasound on both electrolytic and electroless nickel depositions

The effects of ultrasound on both electrolytic and electroless nickel depositions were investigated by polarization and a.c. impedance methods. The ultrasound accelerated the charge transfer process at the metal-electrolyte interface in the electrodeposition and the mass transport process in the electroless deposition. In the electrodeposition with Watts bath, the crystal orientations of deposited film largely changed in the presence of ultrasound. The imposition of ultrasound gave rise to decreasing cathodic overpotential and increasing exchange current density, and these effects depended upon the ultrasonic frequency. The values of exchange current density estimated from a.c. impedance were dependent upon the measured electrode potentials. In the electroless deposition with citrate bath, the deposition rates increased in the presence of ultrasound. There were two kinds of Ni(2+)-citrate complex which were reduced at -0.7 V and -1.1 V. The electroless deposition process was controlled by the Ni(2+)-citrate complex that was reduced at -0.7 V. This reduction rate was diffusion controlled and largely increased in the presence of ultrasound. The effects of ultrasonic frequency on both electrodeposition and electroless deposition increased in order of no irradiation < 100 kHz < 28 kHz < or = 45 kHz.     

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

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

The effect of ultrasonic waves on the oxidation current of chlorpromazine in the 38 and 96 kHz-ultrasonic vibrating electrode voltammetry

In the case of 38 and 96 kHz ultrasonic vibrating electrode (USVE) voltammetry of chlorpromazine, the oxidation current increased considerably with ultrasonic power (amplitude). Movement of the first oxidation product, crimson coloured cation radical, and the streaming of liquid in the neighbourhood of the USVE, were visually observed in order to understand the mechanism of the promotive effects of ultrasound on the oxidation reaction. The reaction profile of the oxidation of chlorpromazine in 38 kHz seems to be somewhat different from that in 96 kHz. However, the mechanical agitation of solution in the area nearest the electrode surface, which is essentially the same fundamental mechanism, takes place in both the cases of 38 and 96 kHz. Both micro- and macro-streamings due to the vibration of a small bubble on the electrode surface with a frequency lower than that of the ultrasonic wave were formed in 38 kHz. These streamings seemed to contribute to the agitation and the exchange of the solution near the electrode surface. However, at the same ultrasonic amplitude, the oxidation current at 96 kHz was much greater than that at 38 kHz. Such a promoting effect of ultrasound on the electrode reaction was considered to be due to the increase of the moving speed or to the acceleration of the particle in the solution.     

Effects of ultrasound on the electrochemical cementation of cadmium by zinc powder

This work is devoted to a kinetics study of cadmium electrochemical cementation on zinc powder under ultrasonic low-frequency field (20 kHz). Compared to mechanical stirring with a Rushton turbine and for the same suspension quality, ultrasound lead to a lower kinetics during the major part of the reaction but to final conversion rate near 100%. Pointing out a thermal modification in the deposit morphology due to acoustic cavitation, gives explanation to these processes changes. Besides several acting parameter effects, such as temperature, metallic ion concentrations or ultrasonic power have been observed and analysed.     

Improvement of leaching process of Geniposide with ultrasound

The effect of ultrasound on the leaching process, in which Geniposide is leached from the Gardenia fruit by deionized water at 20 degrees C, was investigated. The phase equilibrium and the dynamics were measured at static, stirring, and ultrasonically assisted conditions, respectively. The experimental results show that the extraction yield of Geniposide with ultrasound at 0.1533 W cm(-2), is increased by 16.5%, in comparison with that without ultrasound when the ratio of the solvent volume to the fruit weight is 40 ml/g. A model for mass transfer, based on the intraparticle diffusion and the external mass transfer, was developed. And the dynamic curves calculated by the model are in a good agreement with the experimental data. The external mass transfer coefficient k(f)/R and intraparticle diffusion coefficient D(e)/R2 were obtained by fitting of the experiment data. The external mass transfer coefficient with ultrasound at 0.1533 W cm(-2) is 1.63 times higher than that in static process, and the intraparticle diffusion coefficient with ultrasound at 0.1533 W cm(-2) is 3.25 times higher than that in static process.     

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.     

A new sono-electrochemical method for enhanced detoxification of hydrophilic chloroorganic pollutants in water

A new method for detoxification of hydrophilic chloroorganic pollutants in effluent water was developed, using a combination of ultrasound waves, electrochemistry and Fenton's reagent. The advantages of the method are exemplified using two target compounds: the common herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its derivative 2,4-dichlorophenol (2,4-DCP). The high degradation power of this process is due to the large production of oxidizing hydroxyl radicals and high mass transfer due to sonication. Application of this sono-electrochemical Fenton process (SEF) treatment (at 20 kHz) with quite a small current density, accomplished almost 50% oxidation of 2,4-D solution (300 ppm, 1.2 mM) in just 60 s. Similar treatments ran for 600 s resulted in practically full degradation of the herbicide; sizable oxidation of 2,4-DCP also occurs. The main intermediate compounds produced in the SEF process were identified. Their kinetic profile was measured and a chemical reaction scheme was suggested. The efficiency of the SEF process is tentatively much higher than the reference degradation methods and the time required for full degradation is considerably shorter. The SEF process maintains high performance up to concentrations which are higher than reference methods. The optimum concentration of Fe²⁺ ions required for this process was found to be of about 2 mM, which is lower than that in reference techniques. These findings indicate that SEF process may be an effective method for detoxification of environmental water.     

Electroless copper coating of epoxide plates in an ultrasonic field.

This paper reports the study of ultrasonic irradiation effects on electroless copper coating on an epoxide resin. Several parameters were monitored, such as plating rates, practical adhesion and internal stress, versus varying acoustic powers at a constant frequency of 530 kHz. Exposure conditions were characterised by both transmitted power and interfacial mass transfer coefficients. Optimum conditions expressed in irradiation time and power were determined. The use of ultrasound during electroless copper plating affects the plating rates and the deposits properties, particularly the practical adhesion which increases whereas the internal stress decreases. Then, the changes in the coating mechanisms are discussed.     

Potential-modulated electrochemiluminescence of a tris(2,2′-bipyridine)ruthenium(II) / lidocaine system under 430 kHz ultrasound irradiation

The electrochemiluminescence (ECL) of tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)₃²⁺) in the presence of lidocaine was investigated under ultrasound (US) irradiation. The sonoelectrochemical experiments are conducted by indirect irradiation of ultrasound with a piezoelectric transducer operating at 430 kHz. In a supporting electrolyte at pH 11, the Ru(bpy)₃²⁺/lidocaine system gave weak ECL peaks around +1.2 V and +1.45 V, respectively. The ECL signal at +1.2 V was attributed to redox reactions of the oxidative intermediates of Ru(bpy)₃²⁺ and lidocaine, while the signal at +1.45 V was assumed to be caused by an advanced oxidation process due to the generation of hydroxyl radicals (OH) at the electrode surface. In this study, the potential modulation approach is employed in the study of ECL process upon US irradiations because it can suppress the noise components from sonoluminescence effectly and improve the resolution of ECL-potential profiles. It is found ECL signals were greatly enhanced upon US irradiation at the output power of 30 W, however, the relative intensity of ECL signal at +1.2 V was larger than that obtained with a rotating disk electrode even though the mass transport effect is equilvalent. The experiment results suggest that the chemical effect (i.e., generation of OH) by 430 kHz US becomes remarkable in the electrochemical process. Detailed ECL reaction routes under US are proposed in this study.     

Sulfur removal from bauxite water slurry (BWS) electrolysis intensified by ultrasonic

Effects of ultrasonic on desulfurization ratio from bauxite water slurry (BWS) electrolysis in NaOH solution were examined under constant current. The results indicated that ultrasonic improved the desulfurization ratio at high temperatures because of the diffusion and transfer of oxygen gas in electrolyte. However, due to the increase in oxygen gas emission, ultrasonic could not improve the desulfurization ratio obviously at low temperatures. Additionally, the particle size of bauxite became fine in the presence of ultrasonic, indicating that the mass transfer of FeS₂ phase was improved. According to the polarization curves, the current density increased in the presence of ultrasonic, indicating that the mass transfer of liquid phase was improved. The apparent activation energy (AAE) of electrode reaction revealed that ultrasonic did not change the pathway of water electrolysis. However, ultrasonic changed the pathway of BWS electrolysis, converting indirect oxidation into direct oxidation. The AAE of BWS electrolysis in the presence of ultrasonic was higher than that in the absence of ultrasonic. And the low AAEs (less than 20 kJ/mol) clearly indicated the diffusion control during BWS electrolysis reaction.     

High-frequency sonoelectrochemical processes: mass transport, thermal and surface effects induced by cavitation in a 500 kHz reactor

The use of high frequency ultrasound in electrochemical systems is of major interest for the optimisation of electrosynthetic and electroanalytical procedures, especially when the strong mechanical effects of 20 kHz ultrasound are detrimental. The characterisation of a 500 kHz ultrasound reactor for sonoelectrochemical experiments by voltammetric and potentiometric measurements revealed the presence of considerable thermal, as well as mass transport, effects depending on geometric parameters and the material used for the construction of the working electrode. Micromixing and cavitation processes govern the mass transport to and from the electrode surface and are shown by atomic force microscopy (AFM) to cause erosion on the electrode surface. Electrochemically active films of Prussian blue are shown to be gradually removed by cavitation erosion. Degassing the solution prior to sonication increases the efficiency of cavitation processes.     

Effect of ultrasound on the solubility limit of a sparingly soluble solid

The influence of power ultrasound (20 kHz) on the rate of attainment of saturation of sparingly soluble benzoic acid in distilled water and in 24% (w/w) aqueous glycerol was experimentally investigated at 30 °C. The importance of proper temperature control of process vessel contents when it was irradiated with high ultrasonic power level settings was demonstrated. A method was proposed to calculate the volumetric mass transfer coefficient under non-isothermal conditions.     

Electrochemical study of silver thiosulphate reduction in the absence and presence of ultrasound

The electrochemical reduction of silver thiosulphate was studied potentiostatically on platinum electrodes in the absence and presence of ultrasound (20 kHz). This system is irreversible and the reaction is both diffusion and kinetically controlled. The slowest step is the kinetic reaction especially the chemisorption of ions at the electrode surface. Ultrasound greatly improves the mass transport, which can be explained by changing from diffusion to mainly convection. This paper reports the effect of ultrasound upon electrode kinetic and mass-transport parameters at various RDE rotation speeds and ultrasonic intensities. It was found that the heterogeneous rate constant (kf) is improved in the presence of ultrasound due to the increase in the formal or standard heterogeneous rate constant (k0) (approximately by 10-fold under sonication).     

Study on the changes of ultrasonic parameters over supercritical Ni-Co electroplating process

This work discusses the influence of changes to ultrasound (US) parameters over the nickel cobalt (Ni-Co) metal thin film properties produced by supercritical CO₂ (SC-CO₂) electroplating. Additionally, Ni-Co films were produced by conventional electroplating and silent SC-CO₂ and compared against each other.The discussion on metal thin film properties revolves around variations to the bath type ultrasonic power (15 W and 20 W) and frequency (42 k Hz and 72 kHz) during experiments. The properties provided by the three electroplating processes and analyzed include: grain sizes, film elemental content analyses, surface microstructures, film hardness, corrosion resistance, surface roughness, crystalline structure and preferential growth, etc. From the results it was clear that quality of films produced by US-SC-CO₂ was improved compared to that of films produced by silent SC-CO₂, which itself was better than those produced by conventional electroplating. However, when US power was varied we observed a decline in the mechanical properties of the produced films.The combination of ultrasonic agitation with SC-CO₂ allows for improved mechanical properties such as: lower surface roughness, finer grain size and surface morphologies, increased corrosion resistance and film hardness. The ultrasound agitation applied to SC-CO₂ electroplating enhanced the formation of alloyed metal as ultrasonic agitation increased the electrolyte flowability during electroplating process resulting in increased mass transfer while at the same time achieving a surface cleaning effect which removed metal ions with poor adhesion and other unwanted particles. Moreover, application of ultrasonic agitation avoids the use of surfactants so only changes to the physical phenomena and no changes to the chemical composition of the deposited thin films were observed, meaning less pollution to the electrolyte and higher purity of the deposited films.The US-SC-CO₂ electroplating method described in this work effectively enhanced the mechanical properties of the deposited thin films compared to those produced by both silent SC-CO₂ and conventional electroplating processes.     

Ultrasonically enhanced electrochemical oxidation of ibuprofen

A hybrid advanced oxidation process combining sonochemistry (US) and electrochemistry (EC) for the batch scale degradation of ibuprofen was developed. The performance of this hybrid reactor system was evaluated by quantifying on the degradation of ibuprofen under the variation in electrolytes, frequency, applied voltage, ultrasonic power density and temperature in aqueous solutions with a platinum electrode. Among the methods examined (US, EC and US/EC), the hybrid method US/EC resulted 89.32%, 81.85% and 88.7% degradations while using NaOH, H₂SO₄ and deionized water (DI), respectively, with a constant electrical voltages of 30 V, an ultrasound frequency of 1000 kHz, and a power density of 100 W L⁻¹ at 298 K in 1 h. The degradation was established to follow pseudo first order kinetics. In addition, energy consumption and energy efficiencies were also calculated. The probable mechanism for the anodic oxidation of ibuprofen at a platinum electrode was also postulated.     

Assessment of the beneficial combination of electrochemical and ultrasonic activation of compounds originating from biomass

The electro-oxidation of organic molecules at the anode with simultaneous generation of hydrogen at the cathode in electrosynthesis reactors is considered as a promising and efficient process for the co-production of hydrogen and bio-sourced value-added chemicals. In this study and for the first time, we investigated the electro-oxidation of glucose and methylglucoside in 0.1 mol L⁻¹ NaOH on polycrystalline Pt (real surface area = 14.5 ± 0.5 cm², roughness ≈ 5) in the potential range [0; +1.20 V vs. rhe] under silent and ultrasonic (bath, 45 kHz, P_acous = 11.20 W) conditions. A series of linear sweep voltammograms, chronoamperograms and high-performance liquid chronoamperograms were generated. It was found that higher current densities were obtained under ultrasonic conditions over the potential range of +0.25 V to +1.10 V vs. rhe, indicating that higher oxidation rates were provided under ultrasonication. It was observed that the desorption of species from the Pt surface in the medium potential region was favoured, allowing free catalytic Pt sites for further adsorption and oxidation of reactants; and in the high potential region, high peak current densities in the presence of ultrasound was due to enhanced mass transport of the electroactive species from the bulk electrolyte to the Pt-polycrystalline electrode surface. HPLC studies confirmed that higher electrochemical activity was obtained in the presence of ultrasound than in the absence. In our conditions, it was also found that low frequency ultrasound did not change the selectivity of the glucose and methylglucoside electro-oxidation reactions but instead, a significant increase in the rate of conversion was observed.