Effect of cavitation intensity control on self-assembling of alkanethiols on gold in room temperature ionic liquids.

This study investigates the effect of cavitation intensity on self-assembling of alkanethiol molecules on gold in room temperature ionic liquids (RTILs) under low frequency ultrasound irradiation (20 kHz). The use of RTILs, with low vapor pressure, enabled cavitation activity to be controlled up to quenching through pressure decrease within an argon-saturated atmosphere. This control possibility was used to acquire deeper insights into the role of cavitation on self-assembling processes. It was shown by electrochemical, contact angles and Polarization Modulation - Infrared Reflection Absorption Spectroscopy (PM-IRRAS) measurements that cavitation activates orientation and organization of self-assembled monolayers (SAM). X-ray Photoelectron Spectroscopy (XPS) revealed that, even if chemical adsorption of molecules is highly activated under ultrasound irradiation, it is not dependent on acoustic cavitation intensity.

Use of ultrasound irradiation during acid etching of the 2024 aluminum alloy: Effect on corrosion resistance after anodization.

While aluminum alloys are widely used in industrial applications, their protection by anodization as surface treatment always requires a preparation step by alkaline or acid etching. In this paper, use of ultrasound during the acid etching step on the 2024 aluminum alloy was investigated. Etching rate, calculated as of weight loss, was measured under ultrasound irradiation, and compared to silent conditions. The etched surface was characterized by Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM/EDS) and X-Ray Diffraction (XRD). Surface treatment was performed up to the final anodization step samples, and their final properties were evaluated as a function of various pre-treatments, including acid etching under ultrasound. The main evaluation concerned anticorrosion properties through electrochemical tests: polarization measurements and electrochemical impedance spectroscopy (EIS) in NaCl solution. Finally, use of ultrasound irradiation during acid preparation induced a beneficial effect on the corrosion performance of the anodic layer.

Influence of pressure on ultrasonic cavitation activity in room temperature ionic liquids: An electrochemical study.

This paper provides proofs of the respective contributions of dissolved gases and solvent vapor on cavitation activity in sonoreactors. This activity can be detected by electrochemistry because the fluctuating events measured at the electrode surface are only linked to physical effects of cavitation. As ionic liquids present very low volatilities, their vaporization is reduced, and cavitation bubbles only depend on the presence of gases. Then, cavitation activity may be trigged by reactor atmosphere control. Applying severe depression within an irradiated ionic liquid medium contributes to removing dissolved gases, thus quenching cavitation activity. A specific sonoelectrochemical cell was developed for this purpose. These first results show, through electrochemical experiments, that cavitation activity markedly decreases from atmospheric pressure down to 26 kPa. Below 26 kPa, it remains very low and stable. The same experiments were carried out in acetonitrile as a witness. As expected, no depression effect is observed on cavitation activity as it is supported by the volatile solvent contribution.

Synthesis of sub-micronic and nanometric PMMA particles via emulsion polymerization assisted by ultrasound: Process flow sheet and characterization.

PMMA particle synthesis was performed from MMA (methyl methacrylate) and water mixtures, exposed to different ultrasonic systems and frequencies. The sonication sequence was 20kHz→580kHz→858kHz→1138kHz, and the solution was sampled after each irradiation step for polymerization. Effects of sonication parameters (time, power), polymerization method (thermo-initiated or photo-initiated), use of small amounts of surfactant (Triton X-100™ or Tween® 20) and initial MMA quantity were investigated on particle size and synthesis yields. Particle size and size distribution were measured by DLS (Dynamic Light Scattering), and confirmed via SEM (Scanning Electron Microscopy) images. Synthesis yield was calculated using the dry weight method. Particle composition was estimated using FTIR (Fourier Transform Infra-Red) spectroscopy. PMMA (polymethylmethacrylate) monodispersed particles were successfully synthesized, with a possibility of control in the 78-310nm size range. These sized-controlled particles were synthesized with a 7.5-85% synthesis yield (corresponding to 7.5-40g/L particle solid content), depending on operational parameters. Furthermore, a trade-off between particle size and synthesis yield can be proposed: 20kHz→10min waiting time→580kHz→858kHz leading to 90nm particles diameter with 72% yield in less than 40min for the whole sequence. Thus, the synthesis under ultrasound can be found easy to implement and time efficient, ensuring the success of the scale-up approach and opening up industrial applications for this type of polymeric particles.

Characterization of HIFU transducers designed for sonochemistry application: Acoustic streaming.

Cavitation distribution in a High Intensity Focused Ultrasound sonoreactors (HIFU) has been extensively described in the recent literature, including quantification by an optical method (Sonochemiluminescence SCL). The present paper provides complementary measurements through the study of acoustic streaming generated by the same kind of HIFU transducers. To this end, results of mass transfer measurements (electrodiffusional method) were compared to optical method ones (Particle Image Velocimetry). This last one was used in various configurations: with or without an electrode in the acoustic field in order to have the same perturbation of the wave propagation. Results show that the maximum velocity is not located at the focal but shifted near the transducer, and that this shift is greater for high powers. The two cavitation modes (stationary and moving bubbles) are greatly affect the hydrodynamic behavior of our sonoreactors: acoustic streaming and the fluid generated by bubble motion. The results obtained by electrochemical measurements show the same low hydrodynamic activity in the transducer vicinity, the same shift of the active focal toward the transducer, and the same absence of activity in the post-focal axial zone. The comparison with theoretical Eckart's velocities (acoustic streaming in non-cavitating media) confirms a very high activity at the "sonochemical focal", accounted for by wave distortion, which induced greater absorption coefficients. Moreover, the equivalent liquid velocities are one order of magnitude larger than the ones measured by PIV, confirming the enhancement of mass transfer by bubbles oscillation and collapse close to the surface, rather than from a pure streaming effect.

Effects of high frequency ultrasound irradiation on incorporation of SiO2 particles within polypyrrole films.

This paper deals with the effect of ultrasound on polypyrrole/SiO2 composite film elaboration through various steps (particle dispersion, electrosynthesis). Experiments were carried out on stainless steel in phosphoric acid solution. An efficient method for dispersion of SiO2 particles prior to electropolymerization, based on low frequency irradiation (20kHz), was proposed. It was shown that mechanical effects of high frequency ultrasound (i.e. mass transfer improvement) led to enhancement of electropolymerization kinetics. Scanning electron microscopy imaging and glow discharge optical emission spectroscopy revealed localization of SiO2 particles in the outer region of the films as well as better incorporation of particles under high frequency ultrasound irradiation. Finally, anticorrosion behavior of formed films was investigated in sodium chloride solution by Open Circuit Potential and anodic polarization methods. The results showed that polypyrrole/SiO2 films elaborated under ultrasound irradiation exhibit the best protective performances.

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.

Doping properties of PEDOT films electrosynthesized under high frequency ultrasound irradiation.

The present study presents the use of high frequency ultrasound (500 kHz, 25 W) for 3,4-ethylenedioxythiophene (EDOT) electropolymerization in aqueous medium in order to investigate its effects on conducting polymer properties. It was shown that mass transfer increases under ultrasound irradiation which improved electropolymerization and the comparison with experiments carried out at the same mass transfer level (4.6 × 10(-5) ms(-1)) puts in evidence that stirring effect is not the only phenomenon induced by ultrasound during electrodeposition. PEDOT films elaborated under ultrasonication present increased doping levels revealed by X-ray Photoelectron Spectroscopy (XPS) analysis, especially in the case of thick films (measured by mechanical probe), thanks to better incorporation of counter ions within polymer matrix as another consequence of mass transport improvement under ultrasound and probably film heating by wave absorption for the highest thicknesses. A dilation of the film under sonication leading to an increase in film thickness was also highlighted. Finally, a refining of the surface structure was also observed via SEM imaging.

Electrosynthesis and characterization of conducting polypyrrole elaborated under high frequency ultrasound irradiation.

The effects of high frequency ultrasound (500kHz) on pyrrole electropolymerization in sodium perchlorate aqueous medium have been investigated. Cyclic voltametry studies showed that there is no influence on pyrrole oxidation potential. Scanning Electron Microscopy (SEM) imaging, and mechanical and optical profiling, revealed thinner, denser and more homogeneous surface structure for polypyrrole films elaborated under ultrasound irradiation. This is attributed to cavitation bubble asymmetric collapse close to the interface, which should induce changes in the nucleation-growth mechanism during the first polymerization stage. An increase of approximately 27% in doping level for sonicated films was revealed by X-ray Photoelectron Spectroscopy (XPS) analyses.

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.

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.

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.

Effect of ultrasounds on the electrochemical synthesis of polypyrrole, application to the adhesion and growth of biological cells.

In this study, a new way to synthesize polypyrrole films is presented. This original way consists in the electropolymerization of polypyrrole under high frequency ultrasonic irradiation on conductive fluorine-doped tin oxide surfaces. The polypyrrole films obtained are then compared, in terms of chemical structure and morphology, to polypyrrole films synthesized by standard electrochemical methodology. Next, these polymer films are tested as an alternative to biomaterials that are commonly used as cell culture substrates. Thus, the adhesion and growth of osteoblastics cells and microbial cells on polymer-modified surfaces are investigated by using qualitative observation and quantitative tests. These studies proved the non-toxicity of the polymer films for osteoblastic and microbial cells but also a different behaviour of osteoblastic cells and microbial cells with polypyrrole films.

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.

Modification of the ultrasound induced activity by the presence of an electrode in a sono-reactor working at two low frequencies (20 and 40 kHz). Part II: Mapping flow velocities by particle image velocimetry (PIV).

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 in the ultrasonic activity induced by the presence of an electrode located in front of the transducer. The scope of our investigations concerns two low frequency vibration modes: 20 and 40 kHz. For this purpose, two laser visualization techniques have been used. The first part of the study, described in a previous paper (Part I), deals with the laser tomography technique which provides an accurate picture of the reactor active zones, related to numerous cavitation events. The second part of the paper (Part II) will describe the particle image velocimetry (PIV) technique used to measure the velocity vector field in the fluid portion between the horn and the electrode. As for the previous study, two parameters were studied: the electrical power supplied to the transducer and the electrode/transducer distance. The velocity vector fields show a main flow in the reactor axis. This flow seems to correspond to the conical cavitation bubbles structure which is observed on the laser tomography pictures. When an electrode is introduced into the reactor, two additional symmetric transversal flows can be quantified on both sides of the electrode.

Energetic balance in an ultrasonic reactor using focused or flat high frequency transducers.

In order to undertake irradiation of polymer blocks or films by ultrasound, this paper deals with the measurements of ultrasonic power and its distribution within the cell by several methods. The electric power measured at the transducer input is compared to the ultrasonic power input to the cell evaluated by calorimetry and radiation force measurement for different generator settings. Results obtained in the specific case of new transducer types (composites and focused composites i.e., HIFU: high intensity focused ultrasound) provide an opportunity to conduct a discussion about measurement methods. It has thus been confirmed that these measurement techniques can be applied to HIFU transducers. For all cases, results underlined the fact that measurement of radiation pressure for power evaluation is more adapted to low powers (<15 W) and that measurement by calorimetry is a valid technique for global energy measurements. Composites and monocomponent transducers were compared and it appears that the presence of an adaptation glass plate reduces the efficiency of the monocomponent transducers. The distribution of ultrasonic intensity is qualitatively depicted by sono-chemiluminescence of luminol. Finally, the quantity of energy absorbed by samples placed in the sound field is determined and the temperature distribution monitored as a function of wall distance. This energetic balance allows us to understand the global behaviour of all experimental set-ups made up of a generator-transducer-liquid and sample.

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).

Effects of ultrasonic irradiation on the properties of coatings obtained by electroless plating and electro plating.

This paper deals with the effects of ultrasonic irradiation on electroless copper coating i.e. metallic deposition on non-conductive substrates and on electroplating on metallic substrates. Ultrasonic irradiation was both applied during activation (surface preparation for the electroless coating) and during plating steps in both cases. Several parameters were monitored, such as plating rates, practical adhesion, hardness, internal stress versus varying acoustic powers and frequencies. Optimum conditions for irradiation time, frequency and power were determined for each step. It appears clearly that ultrasound use affects deposit properties. Then, changes in the coating mechanisms can be discussed, and several parameters will be explored in this paper, to explain enhancement of deposit properties: increase in catalyst specific area, stirring dependence, surface energy evolution, dihydrogen desorption, structure of coating.

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.

Influence of ultrasound power and frequency upon corrosion kinetics of zinc in saline media.

This paper is devoted to zinc corrosion and oxidation mechanism in an ultrasonically stirred aerated sodium sulfate electrolyte. It follows a previous study devoted to the influence of 20 kHz ultrasound upon zinc corrosion in NaOH electrolytes [Ultrason. Sonochemis. 8 (2001) 291]. In the present work, various ultrasound regimes were applied by changing the transmitted power and the wave frequency (20 and 40 kHz). Unlike NaOH electrolyte which turns the zinc electrode into a passive state, Na2SO4 saline media induces soft corrosion conditions. This allows a study of the combined effects of ultrasonically modified hydrodynamic and mechanical damage (cavitation) upon the zinc corrosion process. A series of initial experiments were carried out so as to determine the transmitted power and to characterize mass transfer distribution in the electrochemical cell. Zinc corrosion and oxidation process were subsequently studied with respect to the vibrating parameters. When exposed to a 20 kHz ultrasonic field, and provided that the electrode is situated at a maximum mass transfer point, the corrosion rate reaches values six to eight times greater than in silent conditions. The zinc oxidation reaction, in the absence of competitive reduction reactions, is also activated by ultrasound (20 and 40 kHz) but probably through a different process of surface activation.