Magister Scientiae - MSc / The spectroscopic, SEM and Raman measurements on carbon nanotubes under the exact conditions of which OES analysis were made showed that at a pressure of 400 Torr and a flow rate of 200 sccm, the quality and quantity of single-walled carbon nanotubes was the highest. / South Africa

Le soudage à l’arc avec fil fusible est un procédé très utilisé, mais la compréhension des mécanismes régissant son fonctionnement comporte toujours quelques interrogations compte tenu de sa complexité. La composition du gaz de protection a une très forte influence sur le procédé : l’ajout de gaz actif modifie, par exemple, le courant nécessaire à la transition entre les différents régimes et est responsable de l’apparition d’oxyde de fer (gangue) à l’extrémité du fil fusible. Pour mener à bien l’étude du soudage MIG-MAG sous mélanges Ar-CO₂-O₂, plusieurs études sont réalisées pour caractériser et mieux comprendre les phénomènes physico-chimiques qui gouvernent le soudage MIG-MAG afin d’optimiser à terme le procédé. Un diagnostic spectroscopique, avec la mise en place d’un système d’acquisition composé de deux spectromètres qui permet d’enregistrer simultanément les raies spectrales de fer et d’argon, permet d’évaluer les distributions radiales de température et densité électronique dans la colonne de plasma. Une étude par cinématographie rapide est également menée pour tenter d’évaluer la formation et l’écoulement de la couche d’oxyde apparaissant en régime globulaire à la surface de l’anode fusible. Et enfin, des analyses micrographiques des électrodes sont réalisées pour étudier l’influence des modifications chimiques et structurales sur le comportement général du procédé pour différents types de paramètres utilisés. Les conséquences d’un changement de gaz de protection sont également appréhendées : Ar-CO₂, Ar-O₂ et Ar-CO₂-O₂. Il s’avère que la température électronique de l’arc évolue en présence d’oxygène dans le gaz de protection et que la modification du gaz actif modifie le type d’oxyde de fer formé. / The arc welding with consumable wire is a process widely used, but understanding the mechanisms governing its operation still has some questions given its complexity. The composition of the shielding gas has a very strong influence on the process: the addition of active gas changes, for example, the current necessary for the transition between the different metal transfers and is responsible for the appearance of an iron oxide (gangue) at the end of the consumable wire. To carry out the study of MIG-MAG welding under mixtures Ar-CO₂-O₂, several studies are performed to characterize and understand the physical and chemical phenomena that govern the MIG-MAG welding to optimize the process. A spectroscopic diagnosis, with the establishment of an acquisition system consisting of two spectrometers to record simultaneously the iron and argon spectral lines, allows to estimate the radial distributions of temperature and electron density in the plasma column. A study by rapid cinematography is also conducted to try to estimate the formation and flow of the iron oxide layer appearing in globular regime on the surface of the anode consumable. And finally, micrographic analyzes of the electrodes are made to study the influence of chemical and structural changes on the general behavior of the process for different types of parameters used. The consequences of a shielding gas change are also apprehended: Ar-CO₂, Ar-O₂ and Ar-CO₂-O₂. It turns out that the electron temperature of the arc changes in the presence of oxygen in the shielding gas and the change of the active gas modifies the type of iron oxide formed.

Measurement of absorption spectra of plasma during reactive ion etching enables characterization of etched species and control over the etching process. Aim of this diploma thesis is to design spectroscope with Czerny-Turner configuration for reactive ion etching system. Developed spectroscope achieves 1 nm resolution in 350-800 nm range. Device was tested during reactive ion etching of silicon.

The aim of this master thesis is the preparation and characterization of plasma activated water (PAW) prepared by dielectric barrier discharge at atmospheric pressure in air for the future applications in agriculture and medicine. The theoretical part is focused on plasma activated water and its effects on seeds and plants. The work also deals with the preparation and application of PAW in the world. Various types of plasma discharge configurations suitable for its preparation are described here. In the experimental part of the master thesis, distilled and tap water were chosen for activation. The concentrations of active particles in PAW generated by DBD such as nitrites, nitrates and hydrogen peroxide were determined. The value of the concentration of active particles changes probably due to mutual interactions when nitrites are oxidized by hydrogen peroxide to nitrates. Physical properties of PAW such as conductivity and pH were also characterized. After the preparation of PAW, the conductivity increases due to the increase in the concentration of active particles formed by dissociation and ionization of water molecules by plasma. The particles presented in the air, which are dissociated and ionized by plasma, also diffuse into the liquid, and contribute to this increase. The decrease in pH also corresponds to an increase in the concentration of hydrogen ions and the formation of nitric acids. Another aspect of this work was to study plasma activated water during the first eight hours after its preparation and to determine its properties. We have found that PAW prepared from tap water retains its characteristic properties for at least 8 hours and distilled water for 6 hours. In the master thesis, the analysis of plasma discharge was performed using optical emission spectroscopy. OES measurements were performed in the wavelength range 300 to 800 nm. The second positive nitrogen system (N2 (C 3u) N2 (B 3g)) and the first positive nitrogen system (N2 (B 3g) N2 (A 3+u)) were identified in the overview spectrum. Molecular nitrogen ions, OH· radicals, atomic oxygen and atomic hydrogen can be observed in the spectrum, too. The dielectric barrier discharge was also captured using a high-speed camera, and the recording shows the occurrence of multiple discharges that are spatially as well as temporary unstable.

The aim of the diploma thesis was the diagnostics of plasma generated in the atmosphere simulating conditions on Mars. This diploma thesis is focused on the simulation of Mars’ atmosphere at atmospheric pressure and normal laboratory temperature. Due to the similar conditions of Mars' atmosphere with Earth, this planet has been explored in the past as well as up to now. Mars' atmosphere is composed mostly of carbon dioxide, which makes up more than 90 % of Mars' atmosphere. A glow discharge generated in a special reactor at atmospheric pressure at a flow of pure CO2 was used to simulate the atmosphere of Mars. Part of the measurement was performed only in pure CO2 with changing current of 20, 25, 30, 35 and 40 mA. Part of the measurements was focused on the study of the effect of the addition of various gases, such as nitrogen, hydrogen and methane, at changes in their flow rates of 1, 2, 3, 4 and 5 sccm. The products formed in the special reactor were analysed using a mass spectrometer with proton ionization and with a flight time analyser. Optical emission spectrometry was used for plasma diagnostics and composition. Mainly simple aliphatic hydrocarbons, alcohols, aldehydes, and ketones were detected. With increasing flow rates of the individual gases, more complex aromatic compounds with higher molecular weights were formed. Corresponding mass and optical emission spectra were measured simultaneously.

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.

The decaying plasma was studied by the optical emission spectroscopy. DC discharge created at 45 – 200 mA in Pyrex and Quartz tubes in flowing regime was used. The emission of three nitrogen spectral systems (1st and 2nd positive and 1st negative) were studied in time evolution for pressures of 500 – 5 000 Pa at two wall temperatures – ambient and liquid nitrogen (150 K inside the decaying plasma). Results showed that all three nitrogen systems (respectively N2(B, v), N2(C, v) and N2+(B, v) states as their origins) had their population maxima called pink-afterglow in the afterglow part. These maxima decreased with the increase of pressure for all systems, and moved to the later decay time. Maxima increased with discharge current (respectively power) and moved to shorter time. Populations at temperature of 150 K were measured due to the experimental arrangement from 17 ms, only, and thus pink aftergow maximum wasn’t observed (only at 5 000 Pa some maximum was recognized). Populations were smaller at 150 K that populations measured at laboratory temperature at the middle decay time (50-100 ms). At the late time, the populations were higher at lower temperature at lower pressure. Higher shifts (in intensity and decaytime) of pink afterglow maxima were observed in Quartz tube in comparison with their values in Pyrex tube. Besides the populations, rotational temperatures of selected bands of three observed spetral systems (for 1st negative 0-0 band, 1st positive 2-0 band and for 2nd positive 0-2 band) were measured. Rotational temperatures were monitored from presumption that this kind of temperature is equal to temperature of neutral gas (at local thermodynamic equilibrium). Results from 1st negative and 1st positive system showed strong decreasing of rotational temperatures up to about 10 ms at post-discharge begin, then temperatures were constant up to 20 ms of decay time and after that they grew up. Temperatures increased with the increase of current. The part with decreased temperature correlated with pink-afterglow part of post-discharge. Unfortunately, rotational temperatures of 2nd positive system had bad reproducibility and the time profile shape was opposite. Experimental results were compared with numerical kinetic model created by group of prof. Vasco Guerra at Instituto Supetior Técnico in Portugal. Several sets of conditions for simulation at 500 and 1 000 K in active discharge were applicable for the calculation corresponding to the experiment. Comparison of numerical simulation and experimental data done for N2(B) state demonstrated that maxima populations in pink afterglow are depended on the temperature difference between active discharge and post discharge. Maxima populations were supposed in pink afterglow disappeared if the same temperatures in active and post discharges were supposed. Temperature in active discharge is higher at higher apllied power, as it was showed from rotational temperatures observation. The results clearly showed that real temperature profile must be included into the kinetic model.

The plasmachemical removal process of corrosion layers is based on a reduction effect of RF hydrogen low-pressure plasma, and it is used for archaeological objects. Incrustation layers on artifact surface become brittle and porous due to plasma processing. The structure and composition of corrosion layers is changed. Therefore, it is much easier to recover the original surface of the plasma treated artifacts in contrary to those treated by conventional ways. Moreover, we can save time on invasive and thus dangerous mechanical removal of corrosion layers as for example sanding is. After plasma treatment, we can observe fine details of the original surface and memory of tools used during its manufacturing. These details are important information on the origin and manufacturing methods of the artifacts. The plasma reduction process leads to the removal of impurities from cavities as well, and a function of mechanical components of archaeological object can be restored. Moreover, chlorides can be easily removed from the corrosion layers and thus any significant post-corrosion is protected. Each archaeological object is original and it has its own “corrosion history”. First, the object had been exposed to the atmosphere for a long time. Then, it had been often placed in a tomb or grave or it otherwise got into the soil or sea. Thus, each archaeological object was exposed to different corrosion stress (humidity, composition of corrosive environment, etc.). Due to these facts, any universal way of a corroded object treatment is very difficult or even impossible to propose. In this work, the problem was solved using model samples of common metals which were treated at various plasma treatment conditions. Archaeological objects made of iron are the most common artifacts, and the typical corrosion products on iron are akaganeite, rokuhnite, and szomolnokite. These three corrosion products were created on the model samples in laboratory and then, the plasmachemical reduction was applied for their removal. The experiment was done in a Quartz cylindrical reactor with capacitive coupled RF plasma created using outer electrodes. We used discharge power from 100 W to 400 W in a continuous or pulsed regime (duty cycle of 75 %, 50 % and 25 %). Flowing plasma was created in pure hydrogen at pressure of 150200 Pa. Sample temperature was monitored by a thermocouple, and it did not exceed 200C during all these experiments. This temperature is regarded as a limit temperature for metallographic changes of archaeological iron. Higher temperature can cause destruction of archaeological iron objects. The optical emission spectroscopy of OH radical was used for the process monitoring. We focused on the monitoring of OH-radicals generated in the plasma, which are characteristic species formed by this process. Each corrosion product has a different time evaluation of generated OH-radicals, which is closely related to the degradation of a given corrosion product. Corrosion layers were analyzed before and after the plasmachemical reduction by SEM-EDX. We have found that the plasmachemical reduction is not very suitable for the szomolnokite corrosion product, which is degraded with difficulty and at high applied powers, only. However, very good removal efficiency was obtained for the rokuhnite and akaganeite corrosion.

A huge number of experiments were carried out in the field of nitrogen post-discharges during the last 50 or 60 years and they were supported by many published theoretical works. Some papers were focused also on the nitrogen active discharge, post-discharge itself, or they focused mainly on the kinetic processes running during the post-discharge period. This experimental work shows how oxygen titration into post-discharge will influence nitrogen flowing post-discharge. Experimental data were obtained by optical emission spectrometry, Spectra were measured in the range 300 - 700 nm at laboratory temperature of 300K. Discharge current was kept constant at the value of 120 mA relating to the total discharge power of 145 W. Pressure was kept constant, too, at the value of 1000 Pa. The nitrogen of 99.9999 % purity (further purified by Oxiclear column) flow was adjusted at 0.8 l/min. Flow of oxygen (99.95 % purity) through he titration capillary introduced to post-discharge from down stream direction, was kept at 4 ml/min. Both gas flows were controlled by mass flow controllers. The optical emission spectrometer Jobin Yvon TRIAX 550 with 300 gr/mm grating equipped by liquid nitrogen cooled CCD detector was used for the spectra acquisition. The integration time of 1 s was used at all experiments. The position of titration tube end introduced into post discharge from the down stream side was set from 5 to 25 cm with respect to the end of the active discharge; the step of 1 cm was used. The optical emission spectra were measured at positions from 3 to 29 cm with respect to the active discharge end. The following nitrogen spectral systems were identified in the spectra: 1st positive, 1st negative and 2nd positive. Besides them, some bands of NO-beta system were found. The intensity profiles along the post discharge were obtained for selected vibrational spectral bands of these spectral systems and changes in the vibrational distributions of upper electronic states of these spectral systems were determined.

This work studies discharge plasma in a mixture of gases, similar to that used in the so-called CO2-lasers. This mixture consists of CO2, N2 and He. The effect of the mixture composition and discharge parameters (especially pressure, in the range of 266 Pa - 100 kPa) on the distribution of energy in the vibrational levels of nitrogen was examined. This is important parameter for modelling of the discharge plasma. The effect of the mixture composition on the degree of dissociation of the CO2 molecules was also studied. The relative concentration of CO was applied to find the conditions leading to a minimal dissociation of the carbon dioxide. Measurements of radial profiles were also made. Results from two discharge tubes made from different materials were compared. Two types of discharge were utilized to acquire a wide pressure range - low pressure DC glow discharge in the range of 266 Pa to 1330 Pa and dielectric barrier discharge in the range of 5 kPa to 100 kPa. Both discharges are used in commercial CO2-lasers. We observed a descending dependence of the vibrational temperature on the pressure and a big step caused by increased occurrence of standing ionizing waves in the mixtures with low nitrogen ratio. Vibrational temperature in the DBD was markedly lower than in the DC GD, because of the...