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Study of post-discharge in N2-H2 mixtures
Zedníčková, Petra ; Mazánková, Věra (referee) ; Krčma, František (advisor)
The presented Thesis deals on the nitrogen-hydrogen DC post-discharge observations by optical emission spectroscopy. The plasma was generated in Pyrex tube in flowing regime at pressure of 1 kPa at discharge current of 100 mA. The optical emission spectra were recovered at discharge times up to 50 ms in nitrogen containing 0 – 92 % of hydrogen; the gas mixture volume, i.e. the gas speed in the system was conserved for all mixtures. The experiments were carried out at two reactor wall temperatures at the spectra collecting point – at ambient temperature and at the wall temperature of liquid nitrogen (temperature in plasma was about 150 K). The nitrogen first and second positive and first negative spectral systems were identified in the spectra, the hydrogen atomic Balmer series lines were recorded, too. No molecular hydrogen emission was determined during the post-discharge. Some non-identified bands (but with high probability bands of nitrogen Herman infrared system) at 690 and 780 nm were detected, too, mainly at low temperature. The intensities of all determined radiating species decreased exponentially or more than exponentially with the decay time. The experimental data showed strong quenching of all nitrogen radiative states even at very a few percent hydrogen additions. The shape of the selected intensity dependencies on both hydrogen concentration, and the decay time are nearly the same for N2(C) and N2+(B) states, dependencies for N2(B) levels differs of them. The hydrogen line emission was nearly independent on the hydrogen content in the gas mixture up to about 50%, at highest hydrogen concentrations it slightly increased. The results obtained at the decreased wall temperature were very similar, only intensities of all nitrogen spectra increased by the factor about 3, the intensities of levels populated by the recombination of nitrogen atoms increased by factor about five. The atomic hydrogen alpha line (at 656 nm) was the most sensitive on temperature decrease; its intensity increased over one order in whole observed time interval. The obtained results will be confronted with numeric model of kinetic processes in the near future. After that, the specific conditions applicable for the technological applications of nitrogen-hydrogen gas mixtures under post-discharge conditions will be proposed.
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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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Reduction of bronze corrosion layers using hydrogen plasma
Miková, Petra ; Selucká, Alena (referee) ; Krčma, František (advisor)
This diploma thesis is focused to the plasma chemical reduction of model corrosion layers prepared on bronze samples. Bronze was the main material for production of the subjects in Bronze Age. First, it was very rare, and therefore was used only for making jewellery and other decorative subjects. Later, the objects of daily use and weapons were produced of bronze. These objects are found and it is necessary to restore him and preserve the cultural heritage for future generations. The research and the optimalization of plasmochemical reduction of model corrosion layers on bronze samples contributes to this. A metallographic grinder was used to create a defined surface, first with the sandpaper P 280 and then after sample 90 degree rotation with the sandpaper P 600. This ensured uniform surface at all bronze samples that is necessary to provide the same corrosion conditions. The grinded samples were washed by ethanol and dried by hot air stream. To prevent contact with the surrounding atmosphere and successive initiation of corrosion, the samples were stored in lockable polyethylene bags. This step was followed by the preparation of model corrosion layers. Hydrochloric and sulfuric acids were chosen as corrosive environments. Petri dish containing 20 ml of the selected acid was placed at the bottom of the desiccator. Samples were placed to the ceramic grate, over the dish, and they were corroded (in vapours of hydrochloric acid for 34 days and in vapours of sulfuric acid for 27 days). The corroded samples were treated using low-pressure hydrogen plasma excited by RF generator. Treatment of samples was carried out in quartz cylindrical reactor (length of 90 cm, inner diameter 9.5 cm) with copper electrodes placed outside. The pressure in the reactor was ranged around 160 Pa at hydrogen flow rate of 50 sccm during the experiments. The continuous and pulse modes (duty cycle of 25%, 50% or 75%) at peak power of 50–300 watts were used for the treatment of 90 minutes duration. The plasma treatment was monitored by optical emission spectroscopy of OH radical using compact Ocean Optics HR4000 spectrometer. Its integral intensity is proportional to the corrosion layer removal. The rotational temperatures of plasma were calculated using selected OH rotational lines, too. The sample temperature during the treatment was measured by thermocouple installed inside the additional non-corroded samples. The reduction of corrosion layer is successful when the maximum of relative intensity of OH radicals is produced and follow gradual decline. The samples which corroded in vapours of sulphuric acid and were treated in pulse modes with duty cycle of 25 % or with delivered power of 50 W has produced no maximum. To the remain samples the maximum although were observed, but reduced corrosion products on the surface were very cohesive. The maximum of relative intensity of OH radicals was observed at all samples corroded in vapours of hydrochloric acid. But there is problem with temperature of sample during experiment. The samples which layer of corrosion product was after experiment incoherent produced the layer of deposit tin. This effect formation at a higher temperature of sample during experiment and therefore with greater deliver energy.
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Diagnostics of plasma chemical deposition processes using organometallic precursors
Sahánková, Hana ; Dvořák, Pavel (referee) ; Krčma, František (advisor)
The aim of this work is diagnostic of plasma chemical deposition thin films based on organometallic precursors. Thin layers have recently become one of the most used methods for surface treatment of materials. They are used as a protective, functional layer, they improve surface properties of materials or increase or reduce the adhesion to various compounds. Plasma polymers are a modern trend in surface treatment technology. Their structure is different from classical polymers. The titanium (IV)isopropoxide was chosen as a monomer example, which is frequently used as a monomer for photocatalytic TiO2 films plasma deposition. These thin films are very promising for the removal of various air and water pollutants and thus they can significantly help in the increase of the environmental quality. Measurements took place on a commercial device Plasmatreater AS 400. The theoretical part describes the background needed for the study and diagnostics of plasma processes and technologies. The optical emission spectroscopy was chosen as a diagnostic method, and thus its principles are outlined in the theoretical part. Infrared spectroscopy and X-ray photoelectron spectroscopy were applied for the diagnostics of prepared thin films and they are also described in the theoretical part. The experimental part contains two sections. The first section is dedicated to the plasma diagnostics by optical emission spectroscopy. Discharge was generated in nitrogen or in the air. Measurements were performed at seven different duty cycles and at two different flow rates for each of the working gases. The molecular bands of nitrogen first negative and second systems, CN violet bands, and atomic lines of oxygen and nozzle elements (Cu, Cr) were identified in the spectra. The titanium lines, and bands of TiO were determined if the precursor was added. Electron temperature was calculated using chromium lines, and electron temperature maps were obtained for continuous mode and pulse mode with duty cycle 70% for nitrogen plasma with 500 sccm precursor flow. Similar discharge maps were also processed using the selected line of titanium (520 nm) TiO band (625 nm) again for the same discharge conditions. Furthermore, the dependences of the same quantities were obtained along the discharge axis as a function of duty cycle in both gases with precursor flow of 1000 sccm. The second part of results brings material analyzes of the deposited samples. The peaks of anatase and rutile have been identified by infrared spectroscopy. Using X-ray photoelectron spectroscopy, we found that our layers contain a significant amount of non-dissociated precursor. Moreover, a large number of radicals, which can interact with atmospheric gases, was determined on the surface. These radicals are removable by annealing or by ion etching. All results obtained during this research can significantly help us to improve the quality of deposited layers and allow us also some prediction of the thin film properties at given plasma conditions. Of course, further experimental as well as theoretical studies should be completed to obtain complete knowledge needed for the wide applications of these layers.
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Reduction of brass corrosion layers using hydrogen plasma
Řádková, Lucie ; Grossmannová, Hana (referee) ; Krčma, František (advisor)
The main topic of this Diploma thesis is the application of low-pressure low-temperature hydrogen plasma for the treatment model samples of rusted brass. Plasmachemical treatment of metallic artifacts is a relatively new way how to remove corrosion of artifacts. The temperature of an object should not exceed 150 °C during the treatment. Corrosion layers were prepared in an ammoniac corrosion atmosphere. The corrosion formation took two weeks. Energy Dispersive X-ray Microanalysis has shown that the corrosion layer was formed by carbon, oxygen, copper, zinc, and lead. The corrosion layers were blue-colored with white crystals on the surface. Except those two colors, brown color was observed on corrosion layers, too. The plasma reactor was a quartz tube with outer copper electrodes and supplied by the RF source of 13.54 MHz. The reactive atomic hydrogen was formed in plasma discharge. This atomic hydrogen reacted with the corrosive layer containing oxygen. This reaction created an unstable OH radical, which emitted light in the region of 305–320 nm. This radiation was detected by the optical emission spectroscopy and it was applied as process monitoring quantity. Rotational temperature and intensity of OH radicals were determined from obtained data. The sample temperature was measured by thermocouple installed inside the sample volume. Rusted samples were treated by low-pressure low-temperature hydrogen plasma. 16 samples were treated at different conditions – plasma power was 100 W, 200 W, 300 W, and 400 W at continuous mode and pulse mode with duty cycle of 25 %, 50 %, and 75 %. The pressure was between 140–160 Pa at hydrogen flow rate of 50 sccm. Samples after plasmachemical treatment were grey colored with white crystals on their surface. Corrosion layers were removed by spatula. The corrosion layers of some samples were easy removable, some others were difficult. Energy Dispersive X-ray Microanalysis, which was carried out after the treatment of 2 selected samples (400 W, 50% pulse mode and 400 W, 75% pulse mode), showed different amounts of carbon, oxygen, copper, zinc, and lead compared to the rusted sample. Other elements in the treated layer were silicon, sulfur, chlorine, and fluorine.
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Diagnostics of thin layer deposition using tetravinylsilane monomer
Flamíková, Kristýna ; Dvořák,, Pavel (referee) ; Krčma, František (advisor)
The aim of this work is plasma diagnostic during the deposition of thin films based on organosilicone compounds. These layers have a wide range of applications mainly as protective coatings or intermediate phase in composites reinforced by glass fibers. The theoretical part of this work gives a basic fundaments of optical emission spectroscopy and mass spectroscopy and describes procedures for rotational, vibrational, and electron temperature calculations. The RF capacitive coupled discharge in configuration with planar electrodes was used with tetravinylsilane (TVS) organosilicone monomer in this study. The optical emission spectroscopy and mass spectroscopy were applied for the plasma diagnostics. The deposition process was carried out in continuous regime with applied power of 20, 25, 40, 50, 60, and 70 W, some experiments were done also in pulsed regime with duty cycle 1:1, 1:4 and 1:9 at fixed power of 50 W and 10 W when discharge was on. The atomic lines of hydrogen Balmer series and many rotational lines of molecular hydrogen were identified in the spectra. Besides them, the molecular bands of SiH, CH and C2 species were observed. The rotational temperature calculated from 0-0 CH band was in the range of 600 – 1000 K depending on the discharge conditions. The electron temperature in the range of 3600-7500 K was calculated from hydrogen atomic lines. In situ mass spectra collected simultaneously with optical emission spectra showed TVS monomer fragmentation increase with the increase of applied power in continuous regime. This result well correlated with OES in case of CH radical and hydrogen species, the other particles were mainly non-measurable by emission spectroscopy. The same results were also obtained with respect to the duty cycle parameter. The presented results clearly demonstrated the increase of monomer fragmentation with the increase of mean applied discharge power. Determination of prepared layer properties is a subject of other works and their relation to the plasma parameters will be a subject of further studies.
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Diagnostics of thin layer deposition using dimethylphenylsilane monomer
Procházka, Michal ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The aim of this thesis is a study of processes during organosilicone thin film deposition via plasma polymerization. Recently, thin films are the most expanding way of surface modification of materials. They are used as protective coatings, functional layers, they can increase or decrease adhesion to different compounds (e.g. water), or just improve mechanical properties of bulk materials. Plasma polymers, which are not known so long, are a modern trend in evolution of thin film deposition. They have perfect adhesion to the substrate and they are highly resistant against most of chemical compounds. Their structure is quite different from the structure of classical polymers. Recently, organosilicon compounds are used as precursors for plasma polymers because silicon built in the structure of plasma polymer allows thin film deposition on glass substrate and the organic part of monomer gives us infinite possibilities of modification. In our case dimethylphenylsilane (DMPS) was used as a monomer. Various RF low pressure discharges were used during this study. Plasma diagnostic was performed by optical emission spectroscopy of inductive coupled plasma. This method allows us to determine plasma composition during the deposition process. Thus we can predict the composition of deposited thin film according to input parameters. From relative populations of fragments we are able to find out optimal conditions for deposition process. We can also calculate temperature of particles in plasma which gives us some information about particle energies. The first part of the study deals with the identification of particles (fragments) created by fragmentation of monomer in plasma environment. We successfully identified hydrogen atomic lines of Balmer’s series in the spectra. Many rotational lines of hydrogen molecule were also detected. Atomic carbon occurred only in small amount. Much more carbon was detected in the form of CH radical. We also found some weak lines connected to atomic silicon. When we used a mixture of DMPS and oxygen, OH radical and O2+ were present in spectra. Next, optimal settings of deposition were determined for particular fragments from relative intensities of these fragments in optical emission spectra. Using this information we are able to set up the process to deposit thin films of desired composition and properties. We calculated electron temperature from intensities of hydrogen lines in Balmer’s series. Rotational temperature was obtained from CH radical intensity. Unfortunately, there was no convenient radical from which intensity we would be able to calculate vibrational temperature. All results and information obtained during the research can be used in industrial plasma polymerization processes and development of new coatings and functional thin films. Other studies on DMPS or similar monomer may also be realized to get more knowledge about processes in plasma and this thesis could serve as a basis for further research. Moreover, this study is a part of an international project. The aim of this project is to study processes during plasma polymerization both theoretically and practically. Once finished, the project and its results will be presented in scientific literature and at international conferences.
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Optical emission spectoscopy of the nitrogen-argon post-discharge
Žáková, Marie ; Kudrle, Vít (referee) ; Krčma, František (advisor)
The study of plasmas generated in pure nitrogen and their afterglows are a subject of many hundreds works bringing a lot of information about the kinetic processes and energy transfer reactions. The effect of nitrogen pink afterglow has a specific position among the other kinds of discharges and post-discharges. The post-discharge, and especially the pink afterglow, is extremely sensitive to the presence of various impurities and experimental conditions (total gas pressure in a discharge tube, temperature, etc.) because of their significant influence on all kinetic processes. That is the reason, why it is so important to study this processes. The DC flowing afterglow (generated using the hollow molybdenum electrodes in the distance of 12 cm, power ± 290 W) was used for the experimental part of this work. The discharge was created in Pyrex discharge tube at different concentration ratio of nitrogen and argon. The total gas presure was in range from 500 Pa to 5000 Pa. The emission spectra of post-discharge were recorded by TRIAX 550 spectrometer with CCD detector in the range of 320-780 nm. The vibrational populations at individual vibrational levels were calculated using the emission bands of the first (N2 (B 3g) N2 (A 3u+)) and the second (N2 (C 3u) N2 (B 3g)) positive and the first negative (N2+ (B 2u+) N2+ (X 2g+) nitrogen spectral systems. The dependencies of intensity on decay time and relative vibrational populations on argon concentration and pressure were obtained. The pink afterglow was very sharp in pure nitrogen at low pressure. With the increasing total pressure it was shifted to the later decay times and it was visible for longer time, too. The same effect was observed with the increase of argon concentration in the gas mixture. At the highest argon concentrations, especially at lower pressure, the effect of pink afterglow dissapeared. The knowledge of these processes can give the solution of all kinetic reactions in plasma and this can be used in plasma chemistry and for development of new technologies. This will be a subject of further intensive studies.
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Study of plasmachemical reduction of corrosive layers on copper
Šimšová, Tereza ; Selucká, Alena (referee) ; Krčma, František (advisor)
The present diploma thesis concerns the research of plasmachemical reduction of copper corrosion layers. The process was based on using low pressure hydrogen RF plasma in which copper samples are treated for several hours. Four series of copper corrosion layers were prepared in four different corrosion atmospheres. The first two were prepared using saturated vapors of HCl and ammonium acetate that affected copper samples for one week. The second two sets were prepared by samples dipping in HNO3 and H2SO4. EDX analysis confirms visual composition of corrosion layers – chlorides, nitrides and sulphate, respectively. The ammonium acetate produced no corrosion layers and thus this set of samples was omitted. The optical emission spectroscopy was used to find out reactions in a hydrogen RF discharge. At the first, a character of plasma without samples was taken by measuring in continuous and pulsed regime. The integral spectrum intensity (300-700 nm) and intensities of hydrogen atomic lines were observed in the dependences on hydrogen flow, power and duty cycle. After that copper samples were treaded under various conditions in continual and pulse regime, typically at pressure of 170 Pa, 200 W power and hydrogen flow rate of 10.2 ml/min. The integral OH radical spectral intensity in the range of 305 – 330 nm was used as a monitor of plasma treatment process. The experimental results showed that intensities of OH radical depended strongly on the corrosion layer kind as well as on the RF discharge mode. Reduction of corrosion layers treated in the pulsed regime was not so satisfactory then in the continuous regime probably due to lower temperature of sample during the treatment. The total supplied energy into the system was also lower in this case. The sample sputtering was observed during the reduction in continuous regime. It means the corrosion was successfully removed but the process was not stopped at that moment, so it is necessary to propose another additional monitoring process besides observing OH radicals. Our experimental results are the first step in the spread research of plasmachemical treatment of copper made archaeological artifacts.
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Study of volatile hydrocarbon decomposition in non-thermal plasma of surface discharge at atmoapheric pressure
Věrná, Jana ; Rašková, Zuzana (referee) ; Kozáková, Zdenka (advisor)
The main goal of this thesis was to study plasma generated by surface discharge and its application in volatile organic compound destruction. Introduction of this thesis deals with the issue of volatile organic compound. The term of volatile organic compound was defined and explained. Summary of the most important sources of volatile organic compound emissions and possible technics for their elimination was presented. This thesis drew attention on negative aspects of volatile organic compounds on human organism and on the whole environment. The problems of surface discharge and its possible application in various branches are known only few years therefore construction of plasma reactor itself was the first independent step of this work. The plasma reactor was consisted of electrode, which was created from the series of metal stripes each other separated by dielectric barrier. On the surface of the electrode, discharge was regulated and distributed. For the reason of technical limits experiment time was limited up to one minute. The experimental part describes reactor for surface discharge and other parts of apparatus in which degradation volatile organic compound was carried out. Nitrogen was used as carrier gas and it was mixed with air before entering into the reactor. Samples of compounds after degradation process were taken from reactor for the subsequent analysis. Analysis of the products proceeded in a gas chromatogram linked to mass spectrometer. The decomposition products were adsorbed in the SPME filaments or in sorption tubes. The decomposition products were analysed also through the mean of Testo 350 M/XL. This apparatus provided the information on the concentration of small molecules such as CO, H2, NO, NO2 and CxHy Hexane, cyclohexane and xylene were used as VOC examples. Analysis of GC-MS showed decomposition products of hexane, cyclohexane and xylene. The decomposition products were especially various alcohols, ketones, aldehydes and benzene compounds. The apparatus Testo 350 M/XL was unable to detect any CxHy, only large quantity of NO2. This thesis was further focused on possible factors which could have an influence on degradation of compounds, for example input power or different flow of oxygen. It was found that increasing power declined the removal efficiency. The maximum removal efficiency was 87 % for degradation of hexane at the lowest input power. Next part of this thesis was focused on diagnostics of plasma generated in the surface discharge form. The optical emission spectroscopy has been chosen as the best method for plasma characterisation. By this method, various important discharge parameters can be determined, e.g. vibration and rotation temperature. The obtained numeric value of rotation temperature was 840±80 K and vibration temperature was 1880±140 K. The obtained results may be used as a fundament for further study of VOC decomposition in surface discharge.
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