Low temperature (165°C) Wet Oxidation (WO) and Catalytic Wet Oxidation (CWO) of 12 organic compounds has been studied in highly alkaline, high ionic strength solution (simulating that encountered in the Bayer process used to refine alumina) for the first time. Most (11 out of 12) of the 12 organic compounds studied (formic, acetic, propionic, butyric, oxalic, malonic, succinic, glutaric, citric, lactic, malic and tartaric acids) have been identified in various worldwide Bayer liquors. The various aspects of WO and CWO studied for each of the above-mentioned compounds were as follows; -Extent of complete oxidation to carbonate (i.e. extent of removal of organic compound) -Extent of overall oxidation (i.e. extent of complete oxidation and partial oxidation to stable products) -The product(s) formed from partial (incomplete) oxidation -The reaction mechanism occurring -Why certain compounds undergo low temperature WO and/or CWO in highly alkaline, high ionic strength solution -The ability of various transition metal oxides to catalyse the WO of the selected organic compounds Of the 12 organic compounds studied only six (formic, malonic, citric, lactic, malic and tartaric acids) underwent appreciable (>2% overall oxidation) WO in isolation under the reaction conditions used (4.4 -7.0 M NaOH, 165°C, 500 kPa Po₂, 2 hours). Each of these six compounds underwent some complete oxidation and therefore can be partly removed from highly alkaline, high ionic strength solution using low temperature WO. The order of extent of complete oxidation determined was as follows tartaric> citric> malonic> formic> lactic> malic. All of these compounds also underwent some partial oxidation under the reaction conditions used, excluding formic acid, which only underwent complete oxidation. Oxalic acid was a major product of partial oxidation of all of the above-mentioned compounds (excluding formic acid), while acetic acid was a major product of partial oxidation of citric, lactic, malic and tartaric acids. The WO of formic, malonic, citric, lactic, malic and tartaric acids varied considerably with NaOH concentration over the NaOH concentration range studied (4.4 - 7.0 M). The extent of overall oxidation undergone by each of these compounds increased significantly with increasing NaOH concentration. All of the compounds that underwent appreciable WO under the reaction conditions studied contained hydrogen(s) significantly more acidic then the compounds that did not undergo appreciable WO, thus indicating that only organic compounds that contain acidic (albeit weakly acidic) hydrogens undergo low temperature (165°C) WO in highly alkaline, high ionic strength solution. Two different reaction mechanisms were identified to occur during low temperature WO in highly alkaline, high ionic strength solution. Malonic and formic acids underwent WO predominantly via a free radical based reaction mechanism, while citric, lactic, malic and tartaric acids underwent WO predominantly via an ionic based reaction mechanism. The six organic compounds that did not undergo appreciable WO in isolation (acetic, propionic, butyric, oxalic, succinic and glutaric acids) all underwent appreciable WO when in the presence of malonic acid undergoing low temperature WO. Hence, low temperature WO of all of the above-mentioned compounds can be initiated by free radical intermediates produced by malonic acid undergoing WO in highly alkaline, high ionic strength solution. The ability of several transition metal oxides to catalyse the WO of the chosen 12 organic compounds was investigated. Of the transition metal oxides studied CuO was clearly the most active. Five of the organic compounds studied (malonic, citric, lactic, malic and tartaric acids) were catalytically wet oxidised by CuO in highly alkaline, high ionic strength solution in isolation. The order of catalytic activity observed was malonic > tartaric> lactic> malic> citric. Two different catalytic reaction mechanisms were identified for CuO catalysed WO in highly alkaline solution for the organic compounds studied. CuO catalysed the WO of malonic acid predominantly by catalysing the formation of free radical intermediates. CuO catalysed the WO of citric, lactic, malic and tartaric acids predominantly via a complexation-based reaction mechanism.

High-temperature wet oxidation resistance of Type 310S stainless steel arises from the formation of a thin, adherent and compact external Cr2O3 scale that is more protective compared with the other oxides. Stability of the Cr2O3 scale is often at risk in the presence of water vapour at higher temperatures, which promotes the loss of oxidized Cr to volatilization. Continuous volatilization of the Cr2O3 scale accelerates the rate of oxidation and increases the risk of non-protective Fe-rich oxide formation that immensely contributes to the oxide thickening (breakaway oxidation). In this study, the possibility of surrogating high-pressure supercritical water with an ambient pressure air-10% H2O mixture is studied at temperatures associated with the predicted coolant outlet conditions in the current GEN IV design concepts. Factors influencing structure and composition of the Cr2O3 scale during wet oxidation are then examined in the wet environments. An increase in the total gas pressure, water vapour partial pressure and temperature is shown to accelerate the Fe-rich oxide formation by increasing the rate of oxidized Cr loss. A more complete physical description of the oxidation kinetics in terms of the evolution of the oxide scale structure and composition at the various exposure conditions is also reported. Presence of small amount of Mn in the alloy is shown herein to be beneficial as it assists the formation of a MnCr2O4 layer on top of the Cr2O3 scale, which serves to reduce the volatilization rate. It is shown however that the MnCr2O4 layer itself is only temporary protective and becomes prone to volatilization (loss of oxidized Cr) at relatively high temperatures, pressures and exposure times. The formation of a MnCr2O4 cap is therefore, only a temporary solution for delaying the onset of accelerated Fe-rich oxide formation. Addition of Si is proposed to be a more promising way of controlling the onset of the Fe-rich oxide formation. Increase in the Si content to ~6 wt.% results in the formation of a continuous SiO2 barrier layer under the Cr2O3 scale as well as Cr-rich silicide intermetallic phases in the starting microstructure that serve as effective Cr reservoirs in helping to maintain the structure and composition of the compact protective Cr2O3 scale despite the continued loss of oxidized Cr to volatilization. / Thesis / Doctor of Philosophy (PhD) / The effects of total gas pressure, water vapour partial pressure, temperature and minor alloying elements (Mn and Si in particular) on the wet oxidation performance of Type 310S stainless steel were examined within the context of the stability of the protective chromia (Cr2O3) scale formed. Focus was placed on examining factors that influence the onset of accelerated linear oxidation associated with the Fe-rich oxide formation and oxide thickening. Links between changes in structure and composition of the protective Cr2O3 scale and breakaway oxidation as exhibited in water vapour-containing environments are made using advanced electron microscopy techniques. Si addition up to ~6 wt.% assists the formation of a continuous silica (SiO2) barrier layer under the Cr2O3 scale as well as Cr-rich silicide intermetallic phases that act as reservoirs to supply for the oxidized Cr lost to volatilization. Si addition is proposed to be a promising way of prohibiting Fe-rich oxide formation albeit modifications to the morphology of the silicide intermetallic phases are required.

La carbonisation hydrothermale (HTC) est un procédé de conversion en énergie de la biomasse dans l’eau sous critique (180-250°C) à faibles pressions (10-40 bars). Ce procédé conduit à la production d’un matériau solide carboné appelé "hydro-char". L’objectif de ce travail est d’optimiser le procédé HTC par l’étude des performances de l’hydro-char comme source d’énergie. La biomasse étudiée est un résidu d’extraction d’huile d’olive dénommé grignons d’olive constitués de peau, de pulpe et de noyau (taux d’humidité de 70%). Ces grignons d’origine marocaine ont été préalablement séchés (GOS). Au cours de l’HTC, la biomasse est décomposée via des réactions de déshydratation et de décarboxylation. Les hydro-chars sont moins humides et plus riches en carbone que les GOS. Aussi, ils s’appauvrissent en cendres en les transférant dans la phase liquide. Les hydro-chars ont un PCS plus élevé que celui de la tourbe et de lignite. Les résultats montrent que le rendement et les propriétés de l’hydro-char dépendent surtout de la température du procédé. Pour mieux analyser l’effet des conditions opératoires, l’approche des plans d’expériences a été appliquée pour optimiser et modéliser le procédé HTC. Grâce au plan de Doehlert, on peut relier les propriétés de l’hydro-char avec son rendement massique et son comportement thermique de combustion. La représentation des surfaces de réponses a permis de définir les zones de production d’hydro-char avec ses propriétés permettant d’orienter l’élaboration de l’hydro-char pour répondre aux critères d’une application prédéfinie. Le liquide issu de l’HTC des GOS montre une sensibilité à la variation des conditions opératoires. Le carbone soluble dans ce liquide lui donne un pouvoir polluant. Pour le diminuer, deux procédés de traitement ont été testés: l’évaporation et l’oxydation en voie humide. Les résultats ont montré que la quantité d’eau utilisée pour le traitement est le facteur le plus influent sur le bilan énergétique du procédé HTC. / Hydrothermal carbonization (HTC) allows pre-treating humid biomass in subcritical water (180-250°C) and at low pressures (10-40 bars) in the absence of air. This process produces a carbonaceous solid material called "hydro-char". The main aim of this work is to optimize the HTC process by studying the potential of hydro-char to produce energy. The studied biomass is a by-product of the olive oil industry called olive pomace containing water, residual oil, olive skin, olive pulp, and olive stones (with 70% moisture content). The moroccan olive pomace was first air-dried (DOP) and characterized. During the HTC process, the biomass is decomposed via dehydration and decarboxylation reactions. The obtained hydro-char has much less moisture and higher carbon contents than that of untreated DOP. Also, the hydro-char becomes poor in ashes by transferring them into the liquid phase. Hydro-chars have a higher HHV than that of peat and lignite. The results show that hydro-char mass yield and its properties depend on the process temperature especially. For a better analysis of the effect of operating conditions, a Design of Experiments Response Surface Methodology (DoE/RSM) approach was applied to optimize the HTC process. The DoE/RSM allows identifying a relationship between hydro-char properties and its mass yield and thermal combustion behavior. Response-surface plots show defined areas of production of hydro-char which allows tailoring hydro-char elaboration to a specific application. The process liquid from the HTC treatment of DOP shows a sensibility to operating conditions. The soluble carbon in the HTC liquid increases its polluting power and to decrease it two treatment process have been tested: evaporation and wet oxidation. Finally, the results show that the amount of water used for the hydrothermal treatment is the most influential factor on the energy balance of the HTC process.

Ce travail de thèse porte sur la conception et la réalisation de capteurs optiques ultracompacts et sensibles utilisant le mode d’interrogation en intensité pour la détection d’analytes chimiques et biologiques. Deux approches, l’intégration hybride et l’intégration monolithique, ont été explorées durant cette thèse. Après un descriptif des outils d’analyse et de conception de guides d’onde et de micro résonateurs en anneaux, le manuscrit présente l’intégration hybride d’un laser Fabry-Perot en semiconducteur III-V avec un résonateur en anneau basé sur du matériau SOI. Le laser Fabry-Perot à faible coût fonctionnant en multimode longitudinal a été utilisé comme peigne de référence pour le résonateur en anneau en contact avec un échantillon liquide. L’effet Vernier a été implanté dans le système de détection en utilisant le mode d’interrogation en intensité. La largeur spectrale étroite du laser avec sa densité de puissance élevée ont permis d’obtenir un capteur de plus haute sensitivité en comparaison avec le capteur en double anneaux réalisé précédemment. Une étude numérique d’un capteur composé d’un laser Fabry-Perot et deux résonateurs en anneaux permettant de compenser la fluctuation de température a été ensuite présentée. Concernant l'intégration monolithique, l'interface entre oxyde et non-oxyde après l’oxydation de AlGaAs a été étudiée au Central de Technologies du LPN/CNRS. Un phénomène d’oxydation verticale de GaAs ou AlGaAs avec une faible teneur en aluminium activée par une couche voisine oxydée de AlGaAs avec une forte teneur en aluminium a été identifié expérimentalement. Afin de limiter l’oxydation verticale et de réduire la rugosité des interfaces, des guides d’onde basés respectivement sur une structure intégrant un super-réseau et sur une structure standard ont été fabriqués et caractérisés. L’impact de l'hydrogène sur l'activation du processus d'oxydation de GaAs ou AlGaAs avec une faible teneur en Al a été mis en évidence. Enfin, ce manuscrit décrit la réalisation et la caractérisation d’un laser Fabry-Perot fonctionnant en mode TM. Ce laser constitue une brique important vers l’intégration monolithique d’un capteur extrêmement sensible. / The objective of the thesis is to realize the integrated optical sensors with high sensitivity using intensity interrogation method for chemical and biological analyte detection. For this purpose, two approaches, hybrid integration and monolithic integration, have been explored theoretically and experimentally during this thesis. After a review of the design and analysis tools of optical waveguide and micro-ring resonators, the manuscript reports an experimental demonstration of a highly-sensitive intensity-interrogated optical sensor based on cascaded III-V semiconductor Fabry-Perot laser and silicon-on-insulator ring resonator. The low-cost easy-to-fabricate Fabry-Perot laser serves as a reference comb for the sensing ring in contact with liquid sample. The Vernier effet has been exploited in the detection scheme using intensity interrogation mode. The sharp emission peaks of the FP laser with high spectral power density result in a high sensitivity for the sensor compared to previously investigated all-passive double-ring sensor. The temperature compensation method has also been investigated numerically to improve the performance of the sensor. Concerning the potential monolithic integration of laser and sensing waveguide, the interface between oxide and non-oxide after wet oxidation of buried AlGaAs has been investigated at the Technology Centre of LPN/CNRS. The vertical oxidation of GaAs or AlGaAs with low Al content activated by a neighbouring oxidized Al-rich AlGaAs layer has been discovered experimentally. To limit the vertical oxidation and reduce the roughness of the interface, the waveguides with buried oxide layer on superlattice sample and standard sample have been fabricated and characterised. The key role of hydrogen incorporation in the activation of the oxidation process for GaAs or AlGaAs materials with low Al content has been shown experimentally. Finally, this thesis reports the fabrication and the characterisation results of a Fabry-Perot laser working on TM mode which is an important building block for highly-sensitive monolithically-integrated circuit.

Made available in DSpace on 2014-12-17T15:01:51Z (GMT). No. of bitstreams: 1 AristidesFSJ_TESE.pdf: 1616188 bytes, checksum: 162e291640cf71e1607267c17f431e17 (MD5) Previous issue date: 2010-10-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ? C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved. / A oxida??o ?mida de compostos org?nicos a CO2 e H2O tem demonstrado ser uma t?cnica interessante no tratamento de efluentes. Este trabalho tem como objetivo a s?ntese e caracteriza??o dos catalisadores Fe-MnO2/CeO2, K-MnO2/CeO2/paligorsquita e Fe/paligorsquita, assim como, a avalia??o na degrada??o oxidativa do fenol. Os experimentos foram realizados em um reator de leito de lama, com controle de temperatura, de press?o e de velocidade de agita??o e com coleta de amostras da fase l?quida. Os Experimentos foram executados nas seguintes condi??es operacionais: temperatura de 130 oC, press?o de 20,4 atm, concentra??o m?ssica do catalisador de 5 g/L e concentra??o inicial do fenol de 0,5 g/L. Os par?metros avaliados foram: teor de ferro impregnado (0,3; 7 e 10% em massa) e o pH do meio reacional (3,1; 6,8 e 8,7). Os resultados da caracteriza??o por DRX, MEV e FRX mostraram a dispers?o do ferro na paligorsquita, a pureza das fases e, finalmente, a composi??o dos elementos que constituem o catalisador. O uso da paligorsquita como suporte eleva a ?rea especifica superficial do catalisador que foi confirmada por an?lise BET. As curvas de degrada??o do fenol indicam que o catalisador Fe3+ suportado em paligorsquita tem um papel preponderante na convers?o de Carbono Org?nico Total (COT) quando comparado aos demais catalisadores. A diminui??o da alcalinidade do meio reacional favorece tamb?m a convers?o de COT. A convers?o m?xima de COT obtida com o catalisador 3% Fe/paligorsquita, foi em torno de 95 % para um tempo de rea??o de 60 minutos, reduzindo ao mesmo tempo a forma??o de ?cidos, em especial o ?cido ac?tico. Com os produtos obtidos da oxida??o ?mida do fenol, hidroquinona, p-benzoquinona, catecol e ?cido ox?lico, identificados e quantificados por Cromatografia L?quida de Alta Efici?ncia, foi poss?vel propor um mecanismo do processo reacional onde o fenol ? transformado em fase homog?nea e os demais em fase heterog?nea. Aplicou-se um modelo cin?tico, tipo Langmuir- Hinshelwood, com avalia??o das constantes cin?ticas das diferentes rea??es envolvidas

Indium-gallium-zinc oxide (IGZO) and zinc-tin oxide (ZTO) are investigated for thin-film transistor (TFT) applications. Negative bias illumination stress (NBIS) is employed for electrical stability assessment. Unpassivated IGZO and ZTO TFTs suffer from severe NBIS instabilities. Zinc-tin-silicon oxide is found to be an effective passivation layer for IGZO and ZTO TFTs, significantly improving the NBIS stability. NBIS instabilities in unpassivated TFTs are attributed to an NBIS-induced desorption of chemisorbed oxygen from the channel layer top surface, exposing surface oxygen vacancies. A ZTSO layer protects the channel layer top surface from adsorbed gas interactions and also appears to reduce the density of oxygen vacancies. The best device architectures investigated with respect to TFT electrical performance are found to be staggered with aluminum electrodes for unpassivated TFTs and coplanar with ITO electrodes for ZTSO-passivated TFTs. Annealing in wet-O₂ is not found to be effective for improving the performance of IGZO or ZTO TFTs or for reducing the post-deposition annealing temperature. / Graduation date: 2012

Le confinement électrique et optique par oxydation des couches minces d'AlGaAs est une étape essentielle dans la réalisation des composants photoniques actifs et passifs dans la filière de matériaux GaAs. La recherche de performances ultimes sur ces composants nécessite une meilleure maîtrise du procédé d'oxydation ainsi qu'une meilleure connaissance des propriétés optiques de l'oxyde d'aluminium (AlOx). Dans cette perspective, j'ai d'abord réalisé une étude expérimentale de la vitesse d'oxydation des couches d'AlGaAs en fonction de la température du substrat, de la composition en gallium des couches étudiées, de la pression atmosphérique et de la géométrie des mesas considérés. Puis, j'ai établi un modèle anisotrope permettant une meilleure résolution spatiale et temporelle de la forme du front d'oxydation de l'AlAs. Enfin, j'ai exploité ce procédé pour réaliser des composants d'optique guidée notamment des micro-résonateurs puis réalisé des guides optiques à fente et caractérisé leurs performances optiques. / Optical and electrical confinement using Al(Ga)As layer oxidation is a key milestone in the fabrication of active and passive GaAs-based photonic components. To optimize those devices, through the control of the optical and electrical confinements, a better modelling of oxidation process and a better understanding of optical properties of aluminum oxide (AlOx) is required. One part of this work is focusing on a throughout experimental study of AlGaAs oxidation kinetics, where I studied different important parameters such as wafer temperature, gallium composition, atmospheric pressure and mesa geometry. Then, I developed a new predictive model taking into account the process anisotropy, thus allowing a better temporal and spatial of AlAs oxidation front evolution. Finally, I could exploit this technological process to realize whispering gallery mode microdisks as well as slot optical waveguides, and I have characterized this latter photonic devices.