Les décharges Sparks sont des décharges électriques transitoires avec une courte durée de vie. Par rapport à son initiation en milieu gazeux, l’initiation de ce type de décharges dans un liquide diélectrique induit de nouveaux phénomènes physico-chimiques dans le plasma et aux interfaces plasma-liquide et plasma-électrodes. Depuis une vingtaine d’années, la recherche scientifique exploite les propriétés de ces décharges pour des applications diverses : dépollution de liquide, synthèse de nanoparticules, usinage par électro-érosion, etc. Dans ce contexte, ce mémoire a pour objectif d’apporter une meilleure compréhension de la physique des décharges Sparks dans les liquides diélectriques. Les décharges dans les liquides se caractérisent par un comportement stochastique fort. Des études statistiques d’un nombre important de décharges sur les caractéristiques électriques ont été effectuées en fonction de différents paramètres. Ces paramètres sont la distance inter-électrodes, la nature des électrodes ainsi que la polarité de la tension appliquée. L’acquisition des courbes courant-tension de chaque décharge permet de déterminer ses propriétés électriques, soient la tension de claquage, le courant de la décharge, le délai de claquage, la charge injectée, la probabilité de claquage, etc. L’influence d’un champ magnétique externe, en particulier son orientation par rapport à l’axe des électrodes, sur les caractéristiques de la décharge a ensuite été explorée. L’étude des interactions plasma-électrode en fonction de l’orientation du champ magnétique a été réalisée en analysant des images de la dispersion des impacts créés par les décharges sur la contre-électrode et de l’érosion de la pointe. De plus, nous avons démontré que la nature du matériau des électrodes, en particulier ses propriétés magnétiques, influe grandement le taux d’érosion de celles-ci. Les résultats rapportés dans ce mémoire contribueront non seulement à l’avancement de la physique des décharges dans les liquides, mais aussi au développement / optimisation des applications dans des différents domaines technologiques. / Spark discharges are transient electric discharges with a short lifetime. Compared to its initiation in a gaseous medium, the initiation of this type of discharges in a dielectric liquid induces new physico-chemical phenomena in the plasma and at the plasma-liquid and plasma-electrode interfaces. For about twenty years, scientific research has been exploiting the properties of these discharges for various applications: liquid depollution, nanoparticle synthesis, electro-erosion machining, etc. In this context, this thesis aims to provide a better understanding of the physics of Sparks discharges in dielectric liquids. Discharges in liquids are characterized by a strong stochastic behavior. Statistical studies of a large number of discharges on the electrical characteristics have been performed as a function of different parameters. These parameters are the inter-electrode distance, the nature of the electrodes and the polarity of the applied voltage. The acquisition of the current-voltage curves of each discharge allows to determine its electrical properties, i.e. the breakdown voltage, the discharge current, the breakdown delay, the injected charge, the breakdown probability, etc. The influence of an external magnetic field, in particular its orientation relative to the axis of the electrodes, on the characteristics of the discharge was then explored. The study of the plasma-electrode interactions as a function of the magnetic field orientation was performed by analyzing images of the dispersion of the impacts created by the discharges on the counter-electrode and the erosion of the tip. Furthermore, we have shown that the nature of the electrode material, in particular its magnetic properties, greatly influences the rate of electrode erosion. The results reported in this thesis will contribute not only to the advancement of the physics of discharges in liquids, but also to the development / optimization of applications in different technological fields.

This Diploma thesis was focused on the degradation of dyes Saturn Red L4B (Direct Red 79) and Saturn Blue LB (Direct Blue 106) by DC diaphragm discharge (DC-DD). Supplied power was between 160 and 180 W. Conductivity and pH were changing at each electrode area during the DC diaphragm discharge, therefore the effect of pH and conductivity changes on the dye solution itself were examined. All samples were measured by UV-VIS spectrometer in the wavelength range of 300–800 nm. No significant dependence of dye absorption spectra on conductivity was observed, while pH significantly affected the absorption curves of dyes. Ageing of dye spectra showed significant changes of Saturn Red L4B. Next task was the comparison of dyes destruction efficiency by DC-DD, audiofrequency diaphragm discharge (AF-DD) and electrolysis. Dye decomposition by AF-DD was not observed at set conditions (voltage of 80–120 V, current of 2.2 A and frequency of 2 kHz). In the case of DC diaphragm discharge the electrolysis played an important role. Decomposition efficiency of the dyes by electrolysis was up to 15 %. The pumping effect in the DC diaphragm discharge was also investigated. Although the individual electrode areas were linked only by a small pinhole in a nonconductive barrier (the pinhole diameter of 0.3 mm), solutions of the anode and cathode compartment interacted with each other up to 10 %. Finally, the degradation products of Saturn Red L4B treated by DC-DD in two electrodes parts are also described. Decomposition products were determined by high performance liquid chromatography (HPLC) combined with the mass spectrometer.

This Diploma thesis is focused on physical and chemical effects which contribute to the decomposition of organic dyes by diaphragm discharge generated in water solutions. Due to the application of DC high voltage source in continuous regime, there is an effect of electrolysis contributing to the dye decomposition by diaphragm discharge. The aim of this work was to find out when the electrolysis is running (or when is the moment of discharge breakdown) and which factors influence the breakdown. The other goal was decomposition of selected textile and food organic dyes by electrolysis itself. In the theoretical part, theory about creation of electrical discharges in aqueous solutions is noted and various types of underwater discharges are described. Background researches about underwater electrical discharges used in the world are mentioned as well as the use of diaphragm discharges and various ways how to remove organic dyes from wastewater. Finally, theories of electrolysis, UV-VIS spectroscopy and basis of other analytical methods useful for detection of organic molecules are described. Experimental part is oriented to experiment procedure which was carried out in a reactor with separated electrode areas. Separation was made by dielectric diaphragm with a pinhole in the centre. Its initial diameter was 0.4 mm. Used chemicals and course of experiments are described in this part, too. First, the breakdown moment in the reactor was investigated (i. e. determination, when only electrolysis was operating) by formation of hydrogen peroxide and measurement of dynamic (time resolved) electrical characteristics. Next, decomposition of selected dyes by electrolysis was carried out. As the decomposition was related to decolorization of the solution, UV-VIS spectroscopy in the range of 350–700 nm was used for determination of dye concentration. Next part focused on results presents various factors which had an effect on breakdown of diaphragm discharge. These factors are kind of used electrolyte, initial conductivity of solution, kind of dye, temperature of solution and type of reactor (or solution volume). From the result, the most important factor is initial solution conductivity. After the determination of the breakdown moment, the electrolysis of organic dyes was performed. The applied current was 10 mA, initial conductivity was 500 µS/cm and used electrolyte was NaCl. Moreover comparison of dye decomposition in dependence on the different applied power was realized. From this comparison one can assume, there is no significant contribution of electrolysis (the efficiency is approximately 15 %) to the diaphragm discharge in aqueous solution.