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The microstructure and electrochemical behavior of boron doped and undoped ultra thin diamond film electrodes have been studied in this work. The ultra thin diamond films are deposited on porous silicon (PSi) by microwave plasma chemical vapor deposition (MPCVD). In order to enlarge the surface area of diamond electrodes, the deposition of nano structured diamond thin films is performed only in a short time deposition under a negative bias, so that diamond nuclei grew from the tips of PSi nano structures and the thin film surface remained rough and nano fine structured. Diamond thin films were analyzed by Raman spectroscopy and SEM, and then fabricated to the electrode device. From SEM analysis, the morphology of diamond thin films on PSi reveals in the shape of nano rods diamond crystallites. The electro-chemical response was evaluated by performing cyclic voltammetry in the inorganic K4[Fe(CN)6] and a K2HPO4 buffer solution. Boron doped diamond thin film on porous silicon has demonstrated a high redoxidation current of cyclic voltammetry, which may be due to the rough surface providing more electrochemical surface area and more sp2 conducting bonds exposed on the surface.

The favourable physical and mechanical properties of silicon carbide (SiC) nanopowders allow application across many areas, including high-power, high-frequency electronics and high-temperature technologies. Many different synthesis methods for the creation of SiC nanoparticles have been studied, including carbothermic reduction, pulsed laser deposition, sol-gel processes, microwave heating and various plasma techniques. Among the different synthesis methods reported in the literature, very few experiments investigate the microwave-induced plasma synthesis of SiC nanoparticles. The few reported studies show promising results with regard to particle size and production rate. In this work, the synthesis of SiC nanoparticles from methyltrichlorosilane (MTS) is reported using a microwave-induced plasma, operating at atmospheric pressure. The investigation was done experimentally using a 1 500 W power supply, a microwave generator operating at 2.45 GHz, a stub tuner, a waveguide and a sliding short. Quartz tubes were used, in which the plasma was generated and maintained. Hydrogen served as an added reductant for the conversion reaction, and argon served as the MTS carrier gas. The parameters studied were the H2:MTS molar ratio and the total enthalpy, in the ranges 0 to 10 and 70 to 220 MJ/kg respectively. X-ray diffraction studies confirmed the presence of β-SiC and optical emission spectrometry showed the majority of peaks to be that of elementary silicon, carbon and argon, indicative of MTS decomposition in the plasma. Scanning electron microscopy shows average individual particle sizes ranging between 50 and 135 nm, whereas transmission electron microscopy shows average individual particle sizes ranging from 15 to 140 nm. Larger agglomerates are also present, ranging in sizes from 460 to 1 800 nm. Through response surface methodology (RSM), it was shown that the optimum conditions for the production of nanoparticles lie within the range of enthalpy > 180 MJ/kg and H2:MTS ratio of > 5. / Dissertation (MEng)--University of Pretoria, 2015. / Mechanical and Aeronautical Engineering / MEng / Unrestricted

Low-temperature non–thermal plasmas are of growing interest due to their applications in various fields, such as plasma-assisted combustion, plasma medicine, material processing, etc. Hydroxyl radical (OH) is one of the key agents and most important reactive species generated in plasmas. We employ cavity ringdown spectroscopy (CRDS), both a pulsed laser and a continuous wave (cw) laser to measure absolute number densities of OH radicals in low-temperature plasmas. A 2.45 GHz microwave plasma source was used to excite two different types of plasma cavities: an atmospheric plasma jet and microwave plasma torch (MPT). The atmospheric microwave plasma jet was thoroughly explored and operated with different plasma gases. Plasma jets with argon (Ar), helium (He), Ar/N2, Ar/O2, He/N2, He/O2 and Ar/H2O were investigated. The absolute number densities of OH radicals were measured along the jet axis in all of plasma jets using pulsed CRDS. Effects of plasma power and gas flow rates on OH radical generation were also studied. We have reported for the first time that OH radicals exist in the far downstream region of a plasma jet axis. The far downstream is a location where the ratio of distance from the plasma jet orifice over the plasma jet column length is larger than 3. For an Ar plasma jet length of 3 mm, OH radicals were detected at a farthest distance ratio of 7.6. The OH density profiles along the axis in all the plasma jets indicate that OH radicals have the highest number density in the vicinity of the jet tip and gradually decreases in the downstream. Optical emission spectroscopy and digital imaging were simultaneously employed to identify the different radicals generated in plasma jets and to study the fine structures of the plasma jets. Pulsed CRDS was also employed to measure OH radical density in an Ar MPT. By using high temporal resolved imaging, it was observed that the widely reported converging point in Ar MPT is actually a time-averaged visual effect. Absolute number densities of OH radicals and water molecules were measured in an alternating current (AC) glow discharge using near infrared cw CRDS.

Le travail effectué dans le cadre de cette thèse porte sur l’étude des plasmas magnétisés et nonmagnétisés produits par des structures coaxiales qui font office à la fois de propagateur d’onde et de coupleur à impédance adaptée au plasma, mais aussi de sonde d’investigation et de caractérisation de la décharge. Une attention particulière est accordée à l’efficacité de couplage entre l’onde électromagnétique et la décharge et de production d’espèces, et ce pour différentes conditions opératoires : fréquence d’excitation (352 et 2450 MHz),configuration magnétique, géométrie de l’applicateur. L’analyse quantitative et comparative présentée dans ce travail s’appuie aussi bien sur une approche expérimentale que théorique. Les modèles analytiques développés etla simulation électromagnétique réalisée permettent d’extraire à partir des mesures expérimentales, d’une partl ’impédance du plasma décorrélée de celle de la structure de propagation de l’onde, et d’autre part, l’absorption globale et locale de l’onde. Du point de vue expérimental, des techniques et méthodes appropriées ont donc été développées et mises en oeuvre comme, par exemple la méthode de changement de plan d’impédance, ou encore l’auto-interférométrie. L’étude paramétrique, menée sur un domaine de pression étendu sur plusieurs décades(10-4 – 10 Torr) et pour une gamme de puissances allant de un à plusieurs centaines de watts, a permis une investigation minutieuse du type de couplage (capacitif, inductif, résistif) qui est fortement dépendant des caractéristiques de la décharge et donc des paramètres opératoires. Leur mise en corrélation, associée à l’analyse des modes de propagation dans un plasma magnétisé, a permis de localiser avec plus de précision les zones de couplage et d’identifier les principaux mécanismes d’absorption de l’onde mis en jeu. Les principaux résultats obtenus confirment une meilleure efficacité de production d’espèces chargées à une fréquence plus élevée (2450MHz), et la présence d’une population d’électrons chauds plus conséquente ainsi qu’une extension spatiale du plasma lorsque la fréquence est plus faible (352 MHz). Comme la technologie 352 MHz à état solide est plus avantageuse du point de vue du coût des composants, comparée à 2450 MHz, elle pourrait s’avérer intéressante pour des procédés visant la production d’espèces chimiquement actives. Toutefois, le couplage, peu efficace, de type capacitif induit par la diminution de la fréquence, requiert une attention accrue au niveau de la configuration du coupleur. Pour le développement en amont des coupleurs, les résultats issus de ce travail de thèse et les modèles analytiques développés devraient constituer un outil déterminant dans la conception de sources plasma micro-onde performantes. / The work done within the framework of this thesis focuses on the study of magnetized and nonmagnetizedplasmas produced by coaxial structures that serve both as wave propagator and as plasma matchedimpedance coupler but also as investigation and characterization probe of the discharge. Special attention isgiven to the efficiency of coupling between the electromagnetic wave and the discharge and of speciesproduction, for different operating conditions: excitation frequency (352 and 2450 MHz), magnetic configurationand geometry of the applicator. Quantitative and comparative analysis presented in this work is based both on anexperimental and a theoretical approach. Developed analytical models and conducted electromagnetic simulationare set in connection with the experimental measurements in order to determine, on the one hand, the plasmaimpedance de-embedded of the wave propagation structure and, on the other hand, the global and localabsorption of the wave. From the experimental point of view, appropriate techniques and methods have thereforebeen developed and implemented such as, for example, the impedance plane shift method, or autointerferometry.The parametric study, conducted on a pressure range extended over several decades (10-4 - 10Torr) and power ratings from one to several hundred watts, led to a thorough investigation of the coupling type(capacitive, inductive, resistive ) which is highly dependent on the discharge characteristics and thus of theoperating parameters. Their correlation, combined with the analysis of propagation modes in a magnetizedplasma, has helped locate more accurately the areas of coupling and to identify the main power absorptionmechanisms involved. The main results obtained for the two frequencies confirm a better production efficiencyof charged species at a higher frequency (2450 MHz), the presence of a more substantial hot electron populationand a spatial expansion of the plasma when the frequency is low (352 MHz). As the solid state 352 MHztechnology is more advantageous compared to that at 2450 MHz from the viewpoint of the cost of thecomponents, it could be interesting for processes aiming to produce active chemical species. However itsinefficient coupling, of capacitive type induced by frequency reduction, requires an increased attention at thelevel of coupler configuration. For upstream development of couplers, the analytical models and theexperimental results obtained in this thesis should be a key tool in the design of high-performance microwaveplasma sources.

Since their first observation in 1991, carbon nanotubes (CNTs) have attracted a lot of attention owing to their exceptional properties. Their excellent electrical and thermal conducting performances combined with their high toughness and transverse flexibility allow their use in a large range of varied applications. Offering at the same time a high aspect ratio (length-to-diameter) and a low density, carbon nanotubes show strong application potential in reinforced composite materials. Unfortunately, CNTs have the strong tendency to form bundles very difficult to dissociate and disperse in a majority of polymer matrices. Without efficient CNTs dispersion, nanocomposites can not present optimal mechanical, thermal and electrical properties. To overcome this drawback, one solution consists to graft polymer chains on the carbon nanotubes surface in order to disaggregate bundles and, in few cases, to improve interaction between the polymer matrix and nanotubes. The thesis work can be divided into three parts. The first is the one-step amination of multi-walled carbon nanotubes (MWNTs) via an original microwave plasma process. The MWNTs, placed in the post-discharge chamber in presence of H2, are subjected to a reactive flow of atomic nitrogen produced by the plasma. The results give evidence for efficient covalent grafting of primary amine groups along the sidewalls of MWNTs, avoiding any structural damage and alteration of properties. The so-grafted amine groups have been further consider as initiation sites for promoting the ring opening polymerization of lactone monomers yielding polyester-grafted MWNT nanohybrids. Finally, these nanohybrids have been used as highly filled masterbatches to be dispersed in the molten state within several polymer matrices, such as polycaprolactone (PCL) and high density polyethylene (HDPE), to obtain nanocomposites with largely improved properties. For instance, electrical measurements and morphological characterizations showed that the polyester surface-grafting allows for improving the dispersion state of the nanotubes in the different polymer matrices leading to enhanced electrical properties as well as thermal and mechanical performances.

The MP-AES 4200 using microwave plasma and an atomic emission spectroscopy detector provide a new and improved instrument to the analytical field. In this project will the performance of the equipment be evaluated in controlled NaCl-heavy matrices for selected metals (Cu, Zn, Li) and the result from this will be used to optimize a method for specific samples. These samples consist of combustion ashes from the incineration of hazardous waste and are provided by the company SAKAB AB. The sample preparation consisted of several cycles of L/S 10 followed by microwave assisted dissolution with concentrated HNO3, aqua regia or 18.2 MΩ. An extended amount of metals were quantified for these samples (Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Li, Mn, Na, Ni, Pb, V, Zn) and most (not Ca, Li, K or Na) were compared with an ICP-MS instrument equipped with a collision cell used for the elements As, Fe and V. A final experiment was made on an L/S 10 of the samples to attempt to separate the metals from the salt with ion exchange, something that would make it possible to recycle this otherwise unused waste. The detection limits were all in the low μg L-1 except for Cd, Mn and Zn, which were between 2-4 μg L-1. The MP-AES was found to be able to handle matrices up to 5 g L-1 NaCl without a significant loss of response and provided near identical results to the ICP-MS for the elements that could be compared, this did not included the elements not quantified with the ICP-MS or V which was the only element under the limit of detection for the MP-AES. The experiment where an attempt was made to separate the metals from the salt was proven successful after treatment of bark compost and another type of waste ash as cation exchangers.

La modélisation du rayonnement du CO2 à plus de 2000 K reste un défi pour la prédiction des transferts radiatifs à très haute température, en particulier pour le dimensionnement des protections thermiques des véhicules spatiaux entrant dans l’atmosphère de Mars. Le défi concerne aussi bien la constitution de bases de données que le développement de modèles permettant de réaliser des calculs couplés entre l’aérothermodynamique et les transferts radiatifs. Plusieurs bases de données spectroscopiques ont été développées dans les dernières décennies. Des simulations effectuées sur des mélanges CO2-N2 à l’équilibre ont montré que l’émission IR de CO2 reste importante, si ce n’est prédominante, jusqu’à 4000 K. Mais les données expérimentales permettant de vérifier leur précision à haute température sont peu nombreuses et limitées à la basse résolution spectrale, à des températures plus faibles, ou encore impliquent des incertitudes importantes. L’objectif principal de ces travaux est donc de fournir des données expérimentales à moyenne ou haute résolution spectrale et à haute température pour permettre de vérifier la précision des bases théoriques développées. Le mélange gazeux à très haute température dont nous mesurons les spectres d’émission est obtenu grâce à une décharge micro-ondes traversant un flux de CO2 pur. Aux températures atteintes (environ 6000 K), le mélange est à l’équilibre thermodynamique local (ETL) et contient principalement les espèces suivantes : CO2, CO, O2 et O. La mesure des spectres est effectuée grâce à un spectromètre à transformée de Fourier dans l’infrarouge. L’émission des bandes harmoniques de CO dans la région 3800-4400 cm puissance-1 permet la détermination précise du champ de température radial dans le plasma. L’émission théorique de CO2, que ce soit en coefficient d’émission ou en luminance intégrée sur un chemin optique, dans les régions de 2,7 _m et 4,3 _m, est alors calculée à partir des bases de données spectroscopiques et comparée aux mesures. Les bases de données spectroscopiques étudiées sont la base CDSD-4000 récemment publiée et EM2C-1994 qui est plus ancienne. Les résultats montrent que cette dernière est suffisante pour des applications classiques en combustion, nécessitant typiquement de faibles résolutions spectrales et des températures inférieures à 2500 K, pour lesquelles elle fut initialement développée. En revanche, la base CDSD-4000 est généralement en très bon accord avec les données expérimentales, en particulier dans les ailes de bandes ce qui indique sa fiabilité pour des applications à très haute température. Bien que des comparaisons aient révélé que les positions de raies pour les transitions à haute énergie manquent de précision dans cette base, le degré élevé de recouvrement des raies dans les régions 2,7 _m et 4,3 _m devrait grandement limiter l’impact de cette imprécision dans la pratique. L’autre objectif de ces travaux concerne la difficulté que pose la couplage entre les calculs d’aérothermodynamique et de transferts radiatifs. En effet, les calculs de transferts iv radiatifs impliquant des molécules polyatomiques doivent prendre en compte un nombre très important de transitions rovibroniques. Par conséquent, un modèle approché de propriétés radiatives (modèle Statistique à Bandes Etroites) a été développé et sa précision a été étudiée pour les systèmes électroniques optiquement épais des molécules carbonées diatomiques rencontrées dans les problèmes de rentrées atmosphériques martiennes. Ces systèmes sont CO 4eme positif, C2 Swan, et CN violet. Diverses conditions à l’ETL et hors ETL, ainsi que différents mélanges ont été étudiés pour différents régimes d’élargissement de raies. Les comparaisons effectuées avec les calculs "raie par raie" ont révélé d’excellents accords. Les paramètres de ce modèle ont été tabulés en fonction de deux températures, Tv (température vibrationnelle) et Tr (température rotationnelle). / Modeling of the radiation of CO2 above 2000 K remains a challenge for the prediction of radiative transfer at high temperatures, especially for the design of thermal protection of space vehicles entering the Martian atmosphere. The challenge for both the creation of databases that the development of models to perform calculations coupled between Aerothermodynamics and radiative transfer. Several spectroscopic databases have been developed in recent decades. Simulations of CO2-N2 mixtures at equilibrium showed that the IR emission of CO2 is important, if not predominant, up to 4000 K. But the experimental data to verify their accuracy at high temperature are few and limited to the low spectral resolution, at lower temperatures, or involve significant uncertainties. The main objective of this work is to provide experimental data at medium or high spectral resolution and high temperature in order to verify the accuracy of the theoretical foundations developed. The gas mixture at high temperature we measure the emission spectra is achieved through a microwave discharge through a stream of pure CO2. The temperatures reached (about 6000 K), the mixture is in local thermodynamic equilibrium (LTE) and mainly contains the following species: CO2, CO, O2 and O. The measurement of the spectra is carried out using a Fourier transform spectrometer in the infrared. The harmonic emission bands of CO in the region 3800-4400 cm-1 power allows accurate determination of the radial temperature field in the plasma. The theoretical CO2 emissions, both in emission coefficient or radiance integrated on an optical path, in the regions of 2.7 and 4.3 _m _m, is then calculated from the spectroscopic database and compared measures. The databases are based spectroscopic studied CDSD-4000 and recently published EM2C-1994 which is older. The results show that the latter is sufficient for combustion in conventional applications, typically requiring low spectral resolutions and temperatures below 2500 K, for which it was originally developed. However, based CDSD-4000 is generally in good agreement with experimental data, especially in the wings of bands indicating reliability for applications at very high temperatures. Although comparisons have revealed that the line positions for high energy transitions are unclear in this basis, the high degree of overlap of the lines in the regions 2.7 and 4.3 _m _m should greatly reduce the impact of this imprecision in practice. The other objective of this work concerns the difficulty of coupling between the calculations of radiative transfer and aerothermodynamics. Indeed, calculations of radiative transfer iv involving polyatomic molecules must take into account a large number of rovibronic transitions. Therefore, an approximate model of radiative properties (Statistics narrowband model) was developed and its accuracy has been studied for electronic systems optically thick carbon diatomic molecules encountered in problems of Martian atmospheric reentry. These systems are CO 4th positive, C2 Swan and CN violet. Various conditions to the non-LTE and LTE, and various mixtures have been studied for different regimes of line broadening. Comparisons with calculations "line by line" showed excellent agreement. The model parameters were tabulated in terms of two temperatures, Tg (vibrational temperature) and Tr (rotational temperature).

This thesis presents a Microwave Plasma Assisted Spray Deposition (MPASD) system design, characterization, and application to produce nano-sized particle coatings of metal oxides. A commercially available rectangular waveguide microwave power delivery system is utilized to initiate and sustain the plasma discharge within the customized plasma applicator where micron-sized droplets of a metal ion solution are heated to evaporate the solvent and thermally process the resulting nano-sized particles. The investigation of optimum conditions for oxygen, argon, and air plasma ignition in the MPASD system was presented. Measured electron temperature of the plasma was between 6000K and 40000K for the plasma conditions used in the MPASD process. Successful deposition of Y2O3:Eu nano-particles using the MPASD system was achieved. MPASD process allows control of the particle's properties, shown through XRD and photoluminescence studies of the Y2O3:Eu coatings. The MPASD process settings effect on particles activated doping concentration and, as a result, its photoluminescence was shown.

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