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Electric discharges in water and organic solutions
Klímová, Edita ; Brablec, Antonín (referee) ; Kozáková, Zdenka (advisor)
This work is focused on study of electrical discharges in liquids, especially in water solutions. Generation of the discharge in water solutions leads to simultaneous effect of UV radiation, shock waves, electrical field and most importantly, chemically reactive species. This can be utilized in many applications such as sterilization, degradation of organic waste products, lithotripsy or other medical applications. The experimental part is concentrated on a diaphragm arrangement of the reaction system. This means that the reactor is divided into two electrode reservoirs connected only through a small orifice in a dielectric barrier. This barrier is made of Macor® non-porous ceramics with thickness of 1 mm, with the diameter of the orifice 0.6 mm, in the first part of work. In the second part, ShapalTM-M ceramics of thickness 1.0 mm and orifice diameter 0.6 mm was used. The experimental part is divided into two sections. For both, NaCl is chosen as an electrolyte to set the initial conductivity of the tested solutions to the value of 400 S/cm. Supplied direct voltage is regulated to attain power of 100 W in the system. In the first part, effect of addition of chosen alcohols (ethanol, isopropylalcohol and glycerol) on the efficiency of the discharge in their water solutions is studied. For this purpose, a special glass reactor was designed and constructed. The efficiency of the discharge is measured by a spectroscopic determination of concentration of complex formed by a titanium reagent and hydrogen peroxide, which is generated during the discharge. The results show no positive effect of addition of extra OH group to the reaction through the alcohols. The use of isopropylalcohol causes even a significant decrease in the amount of hydrogen peroxide generated. The subject of the second part is a comparison of effect of different electrode materials on the discharge. The efficiency is measured by the same method as in the first part. Materials chosen were stainless steel, platinum, aluminium, copper and carbon. Each material shows different hydrogen peroxide production rate under the same parameters. The most perspective material seems to be carbon, as an inert material, that can be expected not to initiate any decomposition of hydrogen peroxide. The least favourable appears to be copper. When used, no production of hydrogen peroxide was observed in one of the electrode parts of the reactor.
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Study of influence of organic dye structure on their decomposition in the diaphragm discharge in liquids
Pajurková, Jana ; Fasurová, Naděžda (referee) ; Kozáková, Zdenka (advisor)
The main goal of presented thesis is to study the influence of organic dyes structure on its degradation in diaphragm discharge in liquids. Diaphragm discharge is a kind of non-thermal plasma that can be generated in liquids by the application of high voltage. In plasma channels (so-called streamers), many physical and chemical processes are formed. High electrical field, shock waves and last but not least emission of electromagnetic waves in the range of visible and ultra-violet radiation appear among physical processes. The most important chemical process is generation of active species. These species initiate chemical reactions and could attack molecules of organic compounds contained in water solution. The reason why organic dyes were chosen in this study is its visible destruction, because it is related to its decolouration. Further, UV-VIS spectroscopy for the determination of concentration during the experiment can be used. Organic dyes are good models of organic substance often contained in waste water and for which removal classical biological, chemical and physical methods aren’t sufficient. Selected dyes were mostly from the group of azo-dyes: Acid Red 14, Acid Red 18, Acid Yellow 23, Direct Blue 53, Direct Red 79, Direct Red 80, Direct Yellow 29, Food Yellow 3 and further, Acid Blue 74 (indigotic dye) and Direct Blue 106 (oxazine dye). Experiments were carried out in a special batch discharge reactor with the anode and the cathode spaces divided by a non-conductive barrier, where the diaphragm with a pin-hole was placed. Measurement showed different removal in the anode and cathode space. We have supposed it was caused by different streamers features and energetic conditions. Dyes were decomposed with higher efficiency in the anode space where the final concentration reached 40 % of the initial concentration while it remained about 90 % in the cathode space. In this thesis the influence of dyes structure on the dye decomposition by electrical discharge was investigated. Dyes consisted of small molecules and dyes with many substitutes bounded on aromatic ring were decomposed more easily than dyes consisted of big molecules. The shift of characteristic wavelength on both directions (to shorter as well as longer wavelength) was observed during the experiments especially when the Direct dyes were decomposed. This phenomenon was probably due to the formation of intermediate product, which have different characteristic wavelength than the primary compound. In general, colourfulness is given by long conjugated systems of double bonds with substitutes bounded on an aromatic ring. Each change in the molecule structure provides the colour change and this could be the possible reason of the shift of characteristic wavelength. The other task was the comparison of degradation process efficiency by the mean of electrolysis and diaphragm discharge. Results showed that electrolysis (30 W) was more convenient for degradation of dyes consisted of small molecules while diaphragm discharge (130170 W) suited for complex molecules. For degradation of small molecules, oxidation on the anode assumed to be the most effective process that is initiated by electrolysis. For degradation of big molecules, attack of active species produced by the discharge is necessary.
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Study of sterilization effect of diaphragm discharge in liquids
Holíková, Lenka ; Slámová, Jitka (referee) ; Kozáková, Zdenka (advisor)
The main objective of this thesis is to study the sterilizing effect of diaphragm discharge in liquids. Sterilization is a process, which can eliminate all forms of life. Generally, sterilization is divided into physical and chemical methods. Plasma sterilization is ranked among physical methods although the action of chemical processes participates in the decontamination as well. Effects of UV radiation, free radicals and temperature are utilized in these methods. Fungi spores of Aspergillus niger F8189 and bacteria spores of Bacillus subtilis are selected as model organisms. Aspergillus niger microorganism is suitable for its resistance to changes in pH and it is viable in a wide range of pH values. Bacillus subtilis is chosen because of a good heat resistance. Diaphragm discharge is one of the possible types of electrical discharges in generated liquids. It is a low-temperature plasma, which is generated using a high DC voltage. In the created plasma streamers various physical and chemical processes rise. The chemical processes are mainly the generation of active species and particles that initiate subsequent chemical reactions and attack mould spores and bacteria in liquids. The physical processes include shock waves, strong electric field and ultraviolet radiation. Experiments were conducted in a reactor with separate cathode and anode space. In the dielectric barrier PET diaphragm with a pin-hole (initial diameter of 0.4 mm) was attached. Enlargement of the hole was observed as a result of degradation of material at the edge of holes due to the discharge. Degradation of spores was observed, depending on the time and on the input power. Other parameters measured were pH, conductivity and temperature. Experiments did not show any difference of discharge activity in the cathode and anode area. The main factor in the removal of spores Aspergillus niger was probably the temperature because no demonstrable effect of sterilization by the diaphragm discharge operation had been observed when heat resistant Bacillus subtilis was used. Also, it was made an attempt, which has been studied only the temperature effect of the fungi spores of Aspergillus niger. The samples were placed in a thermoregulator, where it was simulated the same temperature increase as at the discharge. The experiment had a similar course as an attempt at the discharge.
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Study of electrolytic influence on organic dye decomposition in the diaphragm discharge in liquids
Davidová, Jaroslava ; Rašková, Zuzana (referee) ; Kozáková, Zdenka (advisor)
This Bachelor thesis is focused on study of chemical and physical influences which are proceed in diaphragm discharge in water solution. These processes could be used in water treatment. If DC non-pulsed voltage is applied, a significant influence of electrolysis must be taken into account. The main goal of this thesis is the estimation of electrolytic contribution to processes in the discharge. Theoretical part describes basic theory about creation of electrical discharges in water and electrolysis with emphasis on processes leading to destruction of organic compounds. Production of reactive particles (radicals, hydrogen peroxide, ozone, etc.) and electrochemical reactions on electrodes mainly belongs among these processes. This part describes analytical method (UV-VIS spectroscopy) which was used for determination of organic dyes concentration as well. Experimental part is oriented to experiment procedure which was carried out in an apparatus with separated anode and cathode area. Separation was made by dielectric diaphragm with a pinhole in the centre. Its initial diameter was 0.25 mm. Electrolytic decomposition was carried out at constant current of 30 mA and supplied power was about 14–32 W. Two Saturn dyes (Direct Blue 106 and Direct Red 79) were selected for experiments. As the decomposition was related to decoloration 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 remarkable effect on decomposition of organic dyes. These factors were: various polarities of electrodes, conductivity and pH of solution, applied power, kind of electrolyte and structure of organic dye. The electrolysis had the significant influence on decomposition of small organic molecules. Decomposition was running mainly in the anode area where so called negative discharge was created. Optimal conditions were set by NaCl electrolyte with concentration providing initial conductivity of 500 S·cm-1. By the NaNO3 electrolyte half decomposition efficiency was achieved and in Na3PO4 electrolyte, the decomposition even didn’t run. The decomposition in the anode area was stimulated by the low pH value, which was decreasing during electrolysis. Generally, higher decomposition was achieved by the discharge than by pure electrolysis but the electrolysis had higher efficiency. In pure electrolysis, high rate of removal can be achieved by the application of a relatively low power. When bigger organic molecules were decomposed, the efficiency was higher by applying the discharge.
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Diagnostics of Diaphragm Discharge in Water Solutions and its Application for the Nanomaterials Surface Treatment
Dřímalková, Lucie ; Brablec, Antonín (referee) ; Janda,, Mário (referee) ; Krčma, František (advisor)
The exact mechanism of the discharge in liquids ignition is not sufficiently known up to now. Although during the last years was achieved the great progress and overloading which some of them are written in this theoretical part of thesis. This thesis is divided into two experimental parts. When the first part deals with diagnostics of diaphragm discharge in electrolyte solutions and the second part is focused on its use for uncoiling (higher homogenization) of carbon nanotubes in solutions. In experiment 1, three different sized (4 l, 100 ml, 50 ml) diaphragm discharge configurations were used to diagnose diaphragm discharge in electrolyte solutions. Diagnostics is done through current and voltage waveforms with the addition of synchronized ICCD camera images that have been connected to a four-channel oscilloscope. The V-A characteristic can be described by three events occurring in the electrolyte solution with a gradual increase in voltage. Slowly increasing of the voltage in the solution leads first to electrolysis. The next phase is the formation of microbubbles or bubbles, which is characteristic of the curve by a slight decrease in the increase of the current passing between electrodes. The sudden increase in the current flow is characteristic of the last phase, namely the discharge phase. The distance of the electrodes from the diaphragm does not significantly affect the V-A characteristic. The higher diameter of the pin hole, therefore, has a higher voltage, but this does not affect the origin of bubble generation or breakdown. The higher thickness of diaphragm, the higher voltage is needed to the beginning of the bubbles generation, and consequently the discharge breakdown. Comparison of the voltage of the start generation of the bubbles and breakdown for PET diaphragms and diaphragms from the ceramic there was no mark able difference. One of the most important parameters is the conductivity of the electrolyte solution. The lower voltage is needed for the start generation of the bubbles at the higher solution conductivity, and also the discharge generation is observed at a lower breakdown voltage. The second experimental part is focused on the study of the diaphragm discharge effect on carbon nanotubes. A specially designed U-shaped reactor is used to modify carbon nanoparticles. Tap water and aqueous solutions of organic compounds are used as the electrolytic solutions. The discharge is generated by a non-pulsed DC high source with a voltage in the range of 0-2.8 kV supplied to platinum electrodes located in the electrolyte solution. The experimental results have shown that the diaphragm discharge has positive effects on the disintegration of clusters and agglomerates of carbon nanotubes. The primary effect on disintegration is probably the shock waves generated by the discharge. It turned out that it depends on the electrode configuration, where the treatment in anode space has far greater effects than the treatment in cathode half of the reactor. Effects of carbon nanotubes disintegration in solution are long-lasting and the treatment effect is not loosed after several months. There were detected no significant changes in the structure of plasma-treated nanotubes by Infra-red spectroscopy.
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Diagnostics of Diaphragm Discharge in Water Solutions and its Application for the Nanomaterials Surface Treatment
Dřímalková, Lucie ; Brablec, Antonín (referee) ; Janda,, Mário (referee) ; Krčma, František (advisor)
The exact mechanism of the discharge in liquids ignition is not sufficiently known up to now. Although during the last years was achieved the great progress and overloading which some of them are written in this theoretical part of thesis. This thesis is divided into two experimental parts. When the first part deals with diagnostics of diaphragm discharge in electrolyte solutions and the second part is focused on its use for uncoiling (higher homogenization) of carbon nanotubes in solutions. In experiment 1, three different sized (4 l, 100 ml, 50 ml) diaphragm discharge configurations were used to diagnose diaphragm discharge in electrolyte solutions. Diagnostics is done through current and voltage waveforms with the addition of synchronized ICCD camera images that have been connected to a four-channel oscilloscope. The V-A characteristic can be described by three events occurring in the electrolyte solution with a gradual increase in voltage. Slowly increasing of the voltage in the solution leads first to electrolysis. The next phase is the formation of microbubbles or bubbles, which is characteristic of the curve by a slight decrease in the increase of the current passing between electrodes. The sudden increase in the current flow is characteristic of the last phase, namely the discharge phase. The distance of the electrodes from the diaphragm does not significantly affect the V-A characteristic. The higher diameter of the pin hole, therefore, has a higher voltage, but this does not affect the origin of bubble generation or breakdown. The higher thickness of diaphragm, the higher voltage is needed to the beginning of the bubbles generation, and consequently the discharge breakdown. Comparison of the voltage of the start generation of the bubbles and breakdown for PET diaphragms and diaphragms from the ceramic there was no mark able difference. One of the most important parameters is the conductivity of the electrolyte solution. The lower voltage is needed for the start generation of the bubbles at the higher solution conductivity, and also the discharge generation is observed at a lower breakdown voltage. The second experimental part is focused on the study of the diaphragm discharge effect on carbon nanotubes. A specially designed U-shaped reactor is used to modify carbon nanoparticles. Tap water and aqueous solutions of organic compounds are used as the electrolytic solutions. The discharge is generated by a non-pulsed DC high source with a voltage in the range of 0-2.8 kV supplied to platinum electrodes located in the electrolyte solution. The experimental results have shown that the diaphragm discharge has positive effects on the disintegration of clusters and agglomerates of carbon nanotubes. The primary effect on disintegration is probably the shock waves generated by the discharge. It turned out that it depends on the electrode configuration, where the treatment in anode space has far greater effects than the treatment in cathode half of the reactor. Effects of carbon nanotubes disintegration in solution are long-lasting and the treatment effect is not loosed after several months. There were detected no significant changes in the structure of plasma-treated nanotubes by Infra-red spectroscopy.
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Preparation and characterization of plasma activated water
Lemonová, Hana ; Klímová, Edita (referee) ; Krčma, František (advisor)
This bachelor thesis deals with suitable methods for plasma activated water preparation. The plasma activated water is a new way of the indirect plasma application for the treatment of biological materials like food or even for the direct application for therapeutic purposes. The theoretical part is focused on getting acquainted with plasma activated water and methods for its preparation, using various plasma systems. The detailed description of the plasma-liquid systems used during this thesis is given later. The selected physical chemical properties, namely conductivity, pH value and stability of hydrogen peroxide are presented in the results part. An important aspect of this work was to find suitable storage conditions for plasma activated water.
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Study of Plasma - Liquid Interactions
Němcová, Lucie ; Brablec, Antonín (referee) ; Obradovic, Bratislav (referee) ; Krčma, František (advisor)
Disertační práce se zabývá detailním studiem vlastností různých elektrických výbojů generovaných ve vodných roztocích. Tyto výboje se staly v posledním desetiletí velmi populárním tématem, a to zejména díky mnoha praktickým využitím jako například v biomedicíně, čištění odpadních vod, ekologii nebo nanoinženýrství. Studium je zaměřeno na generaci peroxidu vodíku, jakožto jednu z nejvýznamnějších částic generovaných právě elektrickými výboji v kapalinách. Pro první část této práce byla využita speciální výbojová komora zkonstruovaná na Fakultě chemické Vysokého Učení Technického v Brně. Komora byla rozdělena tenkou diafragmovou přepážkou na dvě poloviny, přičemž uvnitř přepážky se nacházela malá dírka. V každé části komory se nacházela jedna elektroda, a obě dvě části komory byly vyplněny kapalinou. Ze zdroje bylo do kapaliny aplikováno vysokofrekvenční napětí (1 a 2 kHz), které tak vlastně upravovalo roztok chloridu sodného (1.5 l). Bylo zjištěno, že tento druh napětí, v porovnání s DC, nezpůsobuje nežádoucí přehřívání roztoku (počáteční vodivost 100 - 800 S/cm) během jeho úpravy při zachování účinnosti produkce peroxidu. Experimentální aparatura pro druhou část práce byla sestavena na Gentské Univerzitě v Belgii. Stejnosměrný výboj byl generován v bublinách plynů (He, Ar, N2, vzduch) v prostředí vodných roztoků. Byla studována generace peroxidu vodíku a odbourávání organických barviv přítomných ve zkoumaném roztoku. Ke generaci peroxidu vodíku byl použit roztok NaH2PO4 . 2H2O (5 microS/cm, V= 750 ml), ke zkoumání rozkladu barviv byly použity roztoky organických barviv Direct Red 79 (20 mg/l) a Direct Blue 106 (20 mg/l, V= 750 ml). Minimální koncentrace peroxidu vodíku byla naměřena při aplikaci proudu 10 mA, zatímco maximální koncentrace peroxidu vodíku byla zaznamenána při použití proudu 30 mA. Rozklad organických barviv vykazoval stejné vlastnosti. Čím vyšší byla dodávaná energie, tím více barviva se odbouralo. Třetí část práce probíhala ve spolupráci s Queen's University of Belfast, Centrum for Plasma Physics, UK. K realizaci experimentů bylo využito vysokofrekvenčního plazmového skalpelu (Arthrocar). Bylo zjištěno, že hodnota koncentrace peroxidu vodíku dosahovala maxima v roztocích s nepatrným přídavkem alkoholu (0.25 %). Celkem byly studovány čtyři 0.15 M roztoky BaCl2, Na2CO3, KCl a NaCl (V= 20 ml), jejichž počáteční vodivost se pohybovala kolem 13 mS/cm. Z výsledků bylo patrné, že největší rozdíl hodnot pH byl zaznamenán u roztoků s přídavkem ethanolu. V optických emisních spektrech byly identifikovány především radikály OH, které jsou prekurzory peroxidu vodíku. Výsledky ukázaly, že plazma v takovémto roztoku je stále tvořeno, což může být považováno za první krok generace plazmatu v organických sloučeninách. Poslední část práce byla zaměřena na tzv. mikroplazmatický jet v přímém kontaktu s kapalnou fází. Tato experimentální práce byla realizována na pracovišti Nanotechnology & Integrated Bio-Engineering Centre (NIBEC), University of Ulster, UK během studijní stáže. Jako vodivé médium byl použit roztok trihydrátu kyseliny chlorozlatité s různou počáteční vodivostí. Zajímavým zjištěním je fakt, že při tomto druhu měření bylo generováno stabilní plazma i při velmi malém výbojovém proudu (0.05 a 0.2 mA), a tedy i peroxid vodíku vznikal při velmi malé vstupní energii, což může být považováno za velmi dobrý výsledek.
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Electric discharges in water and organic solutions
Klímová, Edita ; Brablec, Antonín (referee) ; Kozáková, Zdenka (advisor)
This work is focused on study of electrical discharges in liquids, especially in water solutions. Generation of the discharge in water solutions leads to simultaneous effect of UV radiation, shock waves, electrical field and most importantly, chemically reactive species. This can be utilized in many applications such as sterilization, degradation of organic waste products, lithotripsy or other medical applications. The experimental part is concentrated on a diaphragm arrangement of the reaction system. This means that the reactor is divided into two electrode reservoirs connected only through a small orifice in a dielectric barrier. This barrier is made of Macor® non-porous ceramics with thickness of 1 mm, with the diameter of the orifice 0.6 mm, in the first part of work. In the second part, ShapalTM-M ceramics of thickness 1.0 mm and orifice diameter 0.6 mm was used. The experimental part is divided into two sections. For both, NaCl is chosen as an electrolyte to set the initial conductivity of the tested solutions to the value of 400 S/cm. Supplied direct voltage is regulated to attain power of 100 W in the system. In the first part, effect of addition of chosen alcohols (ethanol, isopropylalcohol and glycerol) on the efficiency of the discharge in their water solutions is studied. For this purpose, a special glass reactor was designed and constructed. The efficiency of the discharge is measured by a spectroscopic determination of concentration of complex formed by a titanium reagent and hydrogen peroxide, which is generated during the discharge. The results show no positive effect of addition of extra OH group to the reaction through the alcohols. The use of isopropylalcohol causes even a significant decrease in the amount of hydrogen peroxide generated. The subject of the second part is a comparison of effect of different electrode materials on the discharge. The efficiency is measured by the same method as in the first part. Materials chosen were stainless steel, platinum, aluminium, copper and carbon. Each material shows different hydrogen peroxide production rate under the same parameters. The most perspective material seems to be carbon, as an inert material, that can be expected not to initiate any decomposition of hydrogen peroxide. The least favourable appears to be copper. When used, no production of hydrogen peroxide was observed in one of the electrode parts of the reactor.
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Diagnostics of plasma generated in water solutions and its application
Holíková, Lenka ; Brablec, Antonín (referee) ; Kozáková, Zdenka (advisor)
This thesis deals with the study of parameters of diaphragm discharge in liquids. NaCl solution of different conductivity was used as a conductive medium. Conductivities were adjusted in the range from 220 to 1000 µS cm-1. Two diagnostic methods were used for the study of plasma parameters. The first one was employed in the laboratory of plasma chemistry at Faculty of Chemistry, Brno University of Technology, namely the optical emission spectroscopy. The second method used for plasma diagnostics was the time resolved ICCD camera at the Laboratoire de Physique des Plasmas at the École Polytechnique in Paris. The reactor for the diagnostics by optical emission spectroscopy had the volume of 4 l, and it was made of polycarbonate. PET diaphragm was placed in the barrier separating the cathode and the anode space. Electrodes were made of titanium coated with platinum. Electric power source supplied a constant DC voltage of maximum 5 kV and electric current up to 300 mA. Spectrometer Jobin Yvon TRIAX 550 with CCD detector was used during the experiments in order to measure overview spectra within the range from 200 to 900 nm as well as OH molecular spectra and Hß line spectra. All spectra were scanned in both discharge polarities, i.e. at the cathode and the anode part of reactor. The basic parameters of the discharge plasma were calculated from the spectra, that means rotational and electron temperature and electron density. Another part of experiment consisted of measurements by the ICCD camera iStar 734. Two types of reactors were used. The first one was the same as the reactor for the measurements by the optical emission spectroscopy. The second one was also made of polycarbonate, but the volume of conductive solution was 110 ml, only. HV electrodes made of stainless steel were placed in this reactor. Ceramic diaphragm (Shapal-MTM) was used in both reactors. Diaphragms had different thickness and diameter of holes. ICCD camera acquired photographs with details of processes of the bubbles generation and discharge operation (propagation of plasma channels), depending on solution conductivity, dimensions of the diaphragm, and with respect to the electrode part of the reactor.
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