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.     

Modification of the ultrasound induced activity by the presence of an electrode in a sonoreactor working at two low frequencies (20 and 40 kHz). Part I: Active zone visualization by laser tomography

Sonoelectrochemical experiments differ from sonochemical ones by the introduction of electrodes in the sonicated reaction vessel. The aim of the study is to characterize the changes of the ultrasonic activity induced by the presence of an electrode located in front of the transducer. The scope of our investigations concerns two low frequencies vibration modes: 20 and 40 kHz. For this purpose, two laser visualization techniques have been used. The first part of the study, described in the present paper (part I), deals with the laser tomography technique which provides an accurate picture of the reactor actives zones, related to numerous cavitation events. For each frequency, two parameters were studied: the electrical power supplied to the transducer and the electrode transducer distance. At both frequencies, without electrode, we can observe distinct zones corresponding to cavitation production and stationary waves establishment. When increasing the input power, bubble clouds tend to form a unique cloud near the transducer. In presence of the electrode, bubble cavitation clouds are largely influenced by the obstacle. The second part of the paper (part II) will describe the Particle Image Velocimetry (P.I.V.) technique which allows to measure the velocity vector field in the fluid portion between the horn and the electrode.     

Large-scale ultrasonic cleaning system: Design of a multi-transducer device for boat cleaning (20kHz)

The present study is part of a global project which consists in the development of an automatic cleaning station for immersed boats (cockle, ninepin, etc.) in a self-service mode, associating an innovative ultrasonic device for cleaning with a specific water treatment. The originality of the process is that cleaning is performed by three transducers operating simultaneously at low frequency and moving along the surface, thanks to programmable logic controllers, and that it includes a suction to collect the dirt removed. Therefore, the time required for boat maintenance is shortened, ensuring high quality cleaning without the need for dry docks and avoiding additional pollution in the harbor areas. One of the key points was the evaluation of washing efficiency, as it is really hard to give a quantitative estimation of the dirt removed. To obtain the first design laws, feasibility tests have been carried out on dirty cockle samples and on real boat hulls with a laboratory ultrasonic device. The influence of a large number of parameters was tested such as transducer-probe distance, displacement speed and transmitted power. The obtained data allowed us to design an optimized cleaning device combining high efficiency and speed.     

Characterization of HIFU transducers designed for sonochemistry application: Cavitation distribution and quantification

Acoustic field distribution was determined in HIFU sonoreactors as well as localization of cavitation activity by crossing different techniques: modeling, hydrophone measurements, laser tomography and SCL measurements. Particular care was taken with quantification of this last technique by pixels or photon counting. Cavitation bubbles generated by HIFU are mainly located on the outer layer of the propagation cone in the post-focal zone. Greatest acoustic activity is not located at the geometrical focal, but corresponds to a high concentration of bubbles zone. On the contrary, the main sonochemical activity shifts slightly toward the transducer, whereas quenching of inertial cavitation is observed directly at the focal. Finally, SCL thresholds have been determined.     

A predictive model obtained by identification for the ultrasonic “equivalent” flow velocity at surface vicinity

In the specific applications of surface cleaning and electrochemistry which consist of processes implanting surface irradiation by ultrasound, design of large-scale devices requires us to understand acoustic field distribution together with its quantification. This observation allows systematic measurement of ultrasonic stirring throughout electrochemical determination of “equivalent” flow velocity versus various operating parameters (powers, electrode-horn distances, reactor geometry, frequencies, etc.). A numerical model was proposed to fit our curves and to identify some parameters by taking into account the characteristics of the ultrasonic wave (absorption coefficient, rate of cavitation bubbles and acoustic power). Nevertheless, the flicked behavior of the ultrasonic processes in the vicinity of the electrode as well as bubble presence which induce non-linearities in wave propagation lead us to propose a new approach based on parameter identification by methods currently used in chemical engineering. These parameters were related to physical criteria, and the global model was evaluated throughout analysis of its sensibility criteria.     

Respective contribution of cavitation and convective flow to local stirring in sonoreactors

The knowledge of respective parts of convection and cavitation to the stirring induced by ultrasound at one exact position into a sonoreactor is useful for all processes implementing surfaces exposed to sonication. PIV measurement allows real fluid motion determination, whereas the electrochemical technique gives an equivalent flow velocity considered as the sum of all stirring contributions to the electrode. Thus, by a simple subtraction between real fluid velocity and equivalent flow velocity, it is possible to identify the contribution of each phenomenon. Applied to low frequency reactors, it had been observed that cavitation is the preponderant phenomenon, with a contribution of stirring close to the electrode always more than 90%. High frequency reactors, frequently known to produce less cavitation, have shown that at the focal zone, if it concerns HIFU, cavitation becomes preponderant and reaches similar values to those close to the ultrasonic horn in low frequency sonoreactors.     

Visualisation and electrochemical determination of the actives zones in an ultrasonic reactor using 20 and 500 kHz frequencies

In this paper, active zones of an ultrasonic reactor are underlined by laser tomography and electrochemical measurements.     

Sonoelectrochemical recovery of silver from photographic processing solutions

This paper describes the effect of ultrasound upon the electrochemical recovery of silver from photographic processing solutions using a newly designed electrochemical cell--SonoEcoCell. Rates of deposition of silver (obtained potentiostatically) were studied in the model 'fix' solutions (dilute aqueous Na2S2O3/NaHSO3 at a stainless steel cylinder electrode in both the absence and the presence of ultrasound. Under silent conditions, the magnitude of the cathodic potential is a major factor in the removal of silver. Under 20 kHz sonication, the rate of deposition of silver increases with increasing ultrasonic intensity. The cathode efficiency is also enhanced under insonation. The position of the ultrasonic probe with respect to the rotating cylinder electrode (RCE) was studied. It was found that for a 'face-on' geometry (probe parallel to the electrode) led to higher rate constants compared with a 'side-on' geometry (probe perpendicular to the electrode). The effect of coupling an RCE with ultrasound upon these rate constants employing the two geometry was also investigated. It was found that, employing either the face-on or the side-on geometry alone, improved rate constants were obtained below approximately 1500 and 2000 rpm, respectively.     

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.     

Corrosion protection by sonoelectrodeposited organic films on zinc coated steel

A variety of coatings based on electrosynthesized polypyrrole were deposited on zinc coated steel in presence or absence of ultrasound, and studied in terms of corrosion protection. Cr III and Cr VI commercial passivation were used as references. Depth profiling showed a homogeneous deposit for Cr III, while SEM imaging revealed good surface homogeneity for Cr VI layers. These chromium-based passivations ensured good protection against corrosion. Polypyrrole (PPy) was also electrochemically deposited on zinc coated steel with and without high frequency ultrasound irradiation in aqueous sodium tartrate-molybdate solution. Such PPy coatings act as a physical barrier against corrosive species. PPy electrosynthesized in silent conditions exhibits similar properties to Cr VI passivation with respect to corrosion protection. Ultrasound leads to more compact and more homogeneous surface structures for PPy, as well as to more homogeneous distribution of doping molybdate anions within the film. Far better corrosion protection is exhibited for such sonicated films.