The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

Mesoscale optical phenomena occur when light interacts with a number of different types of materials, such as biological and chemical systems and fabricated nanostructures. As a framework, mesoscale optics unifies the interpretations of the interaction of light with complex media when the outcome depends significantly upon the scale of the interaction. Most importantly, it guides the process of designing an optical sensing technique by focusing on the nature and amount of information that can be extracted from a measurement. Different aspects of mesoscale optics are addressed in this dissertation which led to the solution of a number of problems in complex media. Dynamical and structural information from complex fluids—such as colloidal suspensions and biological fluids—was obtained by controlling the size of the interaction volume with low coherence interferometry. With this information, material properties such as particle sizes, optical transport coefficients, and viscoelastic characteristics of polymer solutions and blood were determined in natural, realistic conditions that are inaccessible to conventional techniques. The same framework also enabled the development of new, scale-dependent models for several important physical and biological systems. These models were then used to explain the results of some unique measurements. For example, the transport of light in disordered photonic lattices was interpreted as a scale-dependent, diffusive process to explain the anomalous behavior of photon path length distributions through these complex structures. In addition, it was demonstrated how specialized optical measurements and models at the mesoscale enable solutions to fundamental problems in cell biology. Specifically, it was found for the first time that the nature of cell motility changes markedly with the curvature of the substrate that the cells iv move on. This particular work addresses increasingly important questions concerning the nature of cellular responses to external forces and the mechanical properties of their local environment. Besides sensing of properties and modeling behaviors of complex systems, mesoscale optics encompasses the control of material systems as a result of the light-matter interaction. Specific modifications to a material’s structure can occur due to not only an exchange of energy between radiation and a material, but also due to a transfer of momentum. Based on the mechanical action of multiply scattered light on colloidal particles, an optically-controlled active medium that did not require specially tailored particles was demonstrated for the first time. The coupling between the particles and the random electromagnetic field affords new possibilities for controlling mesoscale systems and observing nonequilibrium thermodynamic phenomena

En tant que technologie de projection thermique avancée, la projection plasma sous basse pression (LPPS) permet d'obtenir des revêtements de haute qualité et peut combler l'écart d'épaisseur entre les technologies de projection thermique conventionnelles et les procédés de couche mince standard. En outre, LPPS permet de construire des revêtements uniformes avec diverses microstructures; le dépôt a lieu non seulement à partir des éclaboussures liquides, mais aussi à partir des amas nanométriques ainsi que de la phase vapeur en fonction des conditions opérationnelles. Afin de continuer à améliorer et à développer le procédé LPPS, cette recherche vise à le combiner avec les procédés émergents de projection plasma en suspension et de projection plasma réactif. Il devait à la fois fournir deux nouveaux processus intégrés et réaliser des revêtements à structure fine avec des microstructures uniques et des performances élevées.Une torche à plasma bi-cathode (laboratoire LERMPS, UTBM, France) à mode d'injection axiale a été conçue et construite pour le LPPS, dont la puissance maximale en entrée du plasma a pu atteindre 80 kW. En utilisant cette nouvelle torche, soit la suspension à très fines particules, soit les poudres micrométriques ont pu être injectées dans le centre du plasma à basse pression. En conséquence, le transfert de chaleur et de masse entre le jet de plasma et les matériaux pulvérisés a été amélioré.La torche à plasma bi-cathode axiale a été appliquée d'abord pour pulvériser deux types de charges de YSZ, y compris la suspension de YSZ et les poudres agglomérées de YSZ. Les résultats ont indiqué que tous les revêtements YSZ présentaient des structures relativement denses en raison de la grande vitesse des particules sous faibles pressions. Les revêtements ont été composés des particules fondues, des particules agglomérées ainsi que du dépôt en phase vapeur. Il a été constaté que le degré de vaporisation de YSZ a été augmenté en utilisant une taille de particule plus fine, une pression ambiante plus basse, une distance de pulvérisation plus longue et une puissance de plasma plus élevée. En outre, tous les revêtements YSZ ont subi une transformation de phase significative d'une phase monoclinique à une phase tétragonale, et le degré de transformation était proportionnel au degré de vaporisation. Cependant, les propriétés mécaniques des revêtements résultants ont des comportements opposés. Les revêtements YSZ préparés à partir des particules agglomérées, qui avaient une plus grande taille de gouttelettes et moins de dépôt en phase vapeur, présentaient une dureté et un module de Young plus élevés que les revêtements YSZ fabriqués à partir d'une suspension fine.Une autre torche à plasma à haute énergie O3CP (Oerlikon Metco, Suisse) a été utilisée pour synthétiser in situ les revêtements de TiN sur des alliages de Ti-6Al-4V par projection de plasma réactive à très basse pression. Les poudres de Ti pur ont été pulvérisées dans une atmosphère de N2 sous une puissance de plasma d'entrée de 120 kW. Les revêtements TiN hybrides structurés ont été synthétisés, ce qui n'était pas le cas auparavant avec d'autres procédés de projection thermique. Il est connu que la réaction de nitruration se produisait non seulement dans le jet de plasma mais aussi sur le substrat. De plus, avec l'augmentation de la distance de pulvérisation, l'effet de nitruration a été affaibli et la structure hybride du revêtement de TiN a changé de laminaire dense en colonne poreuse, en function du degré de vaporisation supérieur, de la concentration de réactive inférieure et du substrat plus froid.. Néanmoins, ils ont également permis d'améliorer les propriétés mécaniques du substrat Ti-6Al-4V. / As an advanced thermal spray technology, low-pressure plasma spray (LPPS) allows obtaining high-quality coatings and can bridge the thickness gap between conventional thermal spray technologies and standard thin film processes. Moreover, LPPS permits to build uniform coatings with various microstructures; deposition takes place not only from liquid splats but also from nano-sized clusters as well as from the vapor phase depending on operational conditions. In order to further improve and develop the LPPS process, this research aims to combine it with the emerging suspension plasma spray and reactive plasma spray processes. It was expected to both provide two novel integrated processes and achieve fine-structured coatings with unique microstructures and high performance.A bi-cathode plasma torch (LERMPS lab, UTBM, France) with an axial injection mode was designed and built for LPPS, whose maximum input plasma power was able to reach to 80 kW. By using this new torch, either the very fine-particle suspension or the micro-sized powders was able to be injected into the plasma center under low pressures. As a result, the heat and mass transfer between the plasma jet and the sprayed materials were enhanced.The axial bi-cathode plasma torch was applied firstly to spray two kinds of YSZ feedstocks, including the YSZ suspension and the YSZ agglomerated powders. The results indicated that all the YSZ coatings exhibited relatively dense structures due to the high velocity of particles under low pressures. The coatings were composed of the melted particles, the agglomerated particles as well as the vapor deposition. It was found that the vaporization degree of YSZ was increased by using smaller particle size, lower ambient pressure, longer spraying distance and higher plasma power. In addition, all the YSZ coatings undergone a significant phase transformation from a monoclinic phase to a tetragonal phase, and the transformation degree was proportional to the vaporization degree. However, the mechanical properties of the resulting coatings had the opposite behaviors. The YSZ coatings prepared from the agglomerated particles, which had a bigger droplet size and less vapor deposition, showed a higher hardness and Young's modulus than the YSZ coatings fabricated from fine suspension did.Another high-energy plasma torch O3CP (Oerlikon Metco, Switzerland) was employed to in-situ synthesize the TiN coatings on Ti-6Al-4V alloys by reactive plasma spray under very low pressure. The pure Ti powders were sprayed into an N2 atmosphere under an input plasma power of 120 kW. The hybrid structured TiN coatings were synthesized, which was not previously achieved with other thermal spraying processes. It was known that the nitriding reaction occurred not only in the plasma jet but also on the substrate. Additionally, with increasing spraying distance, the nitriding effect was weakened, and the hybrid structure of TiN coating changed from dense laminar to porous columnar, according to the higher vaporization degree, lower reactant concentration and colder substrate. Nevertheless, they also were able to improve the mechanical properties of the Ti-6Al-4V substrate.

Ce travail de thèse est une étude par des méthodes de simulation de structure électronique du phénomène de dégradation en milieu aqueux de la zircone yttriée. La zircone yttriée est notamment utilisée pour la fabrication de prothèses dont la durée de vie dépend du matériau et de son environnement. Pour ces applications, la zircone yttriée est de structure tétragone, mais en fonction du dopage en yttrium et de l'environnement, cette phase est en compétition avec des structures monoclinique et cubique. Cette compétition est cruciale dans ce travail car elle peut à la fois, augmenter la résistance, ou favoriser la détérioration de ce matériau. L'étude réalisée se concentre sur des taux de dopage inférieurs à 20% mol. en oxyde d'yttrium Y2O3.Dans un premier temps, les structures atomiques d'équilibre à basse température ont été déterminées dans les trois phases en utilisant une méthode de calcul basée sur la Théorie de la Fonctionnelle de la Densité, dans l'approximation de la densité locale. Les résultats incluent de nouvelles structures qui n'ont jusqu'alors pas été discutées dans la littérature et qui sont cohérentes avec le diagramme de phase de la zircone yttriée à basse température. Une analyse plus détaillée suggère que le mécanisme de stabilisation de la zircone yttriée tetragonale est un effet du dépistage ionocovalent particulièrement efficace dans cette phase et dont la signature dans la structure s'exprime par la présence d'ions zirconium en coordination 7. Ceci représente un point important permettant de lier stabilité et structure dans ces systèmes. Une deuxième partie de ce travail est consacrée à l’effet de l'eau dans la zircone yttriée en volume. Pour conclure, ce manuscrit représente une contribution originale à la compréhension de mécanismes à l'échelle atomique qui sont à l'origine des propriétés de la zircone yttriée et de ses applications.yttriée et de ses applications. / This PhD thesis is an electronic structure simulation work to study the stabilization mechanism of yttria stabilized zirconia (YSZ) and the phenomena of the degradation of YSZ due to the presence of an aqueous media. YSZ is used especially in dental and orthopedics application sbut its service depends on the environment. For these biomedical applications a crystallographic tetragonal YSZ (t-YSZ) structure is used, but depending on the concentration of yttria (Y2O3) and the environment, this tetragonal structure is thermodynamically in competition with a monoclinic and cubic phases. This competition is crucial in this work, because it has both effects : increase the resistance or promote the degradation of this material. The study is conducted for Y2O3 concentrations less than 20% mol. First, atomic structures of the three phases at low temperature were determined using density functional theory (DFT)with the local density approximations (LDA). The results include new structures that were not discussed in the literature and which are consistent with the phase diagram of YSZ at low temperature. A more detailed analysis suggests that the stabilization mechanism in YSZ is due to an effective ionocovalent screening : particularly in t-YSZ phase, its signature is expressed in Zr-ions with a coordination number of 7. This represents an important point for linking stability and structure in these systems. A second part of this work is devoted to the effect of water on YSZ bulk systems which leads to low temperature degradation (LTD) of YSZ based bioceramics materials. In conclusion, this PhD thesis represents an original contribution to the understanding of the mechanism and properties of YSZ and its applications at the atomic scale.

No description available.

Les techniques de frittage ultrarapide « naturel » (sans charge) comme le frittage par micro-ondes ou par induction présentent de nombreux avantages. Toutefois, le développement de ces techniques passe par une compréhension et une maitrise des mécanismes mis en jeu. A la fois similaires et complémentaires, ces procédés de chauffage-frittage ont été étudiées par une approche expérimentale afin d’approfondir les connaissances dans le domaine du Frittage Ultrarapide Naturel (FUN). Au cours de cette thèse, l’étude du frittage par micro-ondes de composites céramiques Al2O3-(Y)ZrO2 (3 à 40%vol.) a été menée parallèlement à celle du frittage par induction d’une poudre métallique micronique de nickel. La démarche expérimentale adoptée a consisté à réaliser des expériences de frittage à vitesses de chauffage imposées (de 25 à 1000°C/min) sur ces matériaux modèles et des pièces de petites dimensions, en se référant aux comportements en frittage conventionnel tant au niveau macroscopique qu’au niveau microscopique. / The techniques of ultrafast pressureless sintering as microwave or induction sintering offer manyadvantages. However, the development of these techniques requires an understanding and a control ofthe mechanisms involved. Both similar and complementary, these processes of heating-sintering havebeen studied by an experimental approach to increase knowledge in the field of Ultrafast PressurelessSintering.In this thesis, the study of microwave sintering of Al2O3-(Y)ZrO2 composites has been conductedin parallel with induction sintering of a submicronic nickel powder. The experimental approach usedconsisted in carrying out sintering experiments at imposed heating rates (from 25 to 1000°C/min) onchosen materials and small parts, referring to conventional sintering behavior at the macroscopic andmicroscopic scale.

Tato doktorská práce se zabývala mikrostrukturálním vývojem vybraných oxidových keramických materiálů během konvenčního slinování (CS), rychlého slinování (RRS), flash slinování (FS) a slinování pomocí plazmatu (SPS). S ohledem na keramiku pro strukturální aplikace byly pomocí RRS připraveny relativně velké (1 cm3), bez defektní a téměř hutné pelety oxidu hlinitého a yttriem stabilizovaného oxidu zirkoničitého (YSZ) s homogenní mikrostrukturou. RRS bylo také shledáno jako optimální metoda pro přípravu vysoce hutné bezolovnaté piezoelektrické keramiky s podobnými vlastnostmi, jako byly získány po časově a energeticky náročnějším CS. Metoda SPS dále zlepšila vlastnosti bezolovnaté piezoelektrické keramiky a produkovala plně hutné vzorky, což je dobrým předpokladem pro translucenci a z níž vyplývajícím optoelektrickým vlastnostem. Nejoptimálnějších výsledků – plné hustoty a vysokých piezoelektrických vlastností – bylo dosaženo kombinací SPS a RRS. Analýzy provedené v této studii také poukázaly na důležitost eliminace těkavých nečistot před rychlým ohřevem. Jinak totiž dochází k zachycení těchto látek ve slinuté keramice, což ve výsledku limituje její konečnou hustotu. Ukázalo se, že nízké konečné hustoty RRS YSZ jsou spojeny se zachycením zbytkového chloru pocházejícího ze syntézy prášku. Pokud byl zbytkový chlor odstraněn vysokoteplotním žíháním keramických kompaktů před zahájením RRS, byly touto metodou získány téměř plně hutné YZS vzorky. Negativní vliv zbytkového chloru na zhutnění byl viditelný také u flash slinovaných YSZ vzorků. Navíc FS YSZ často vede ke zrychlení růstu zrn v jádře vzorku, v důsledku vyšší teploty a elektrochemické redukce. Ve spektru procesních parametrů použitých v rámci této práce dokonce došlo k abnormálnímu růstu zrna (AGG). Silně bimodální distribuce velikosti zrn ukázaná v této práci nebyla dříve nalezena u flash slinutého YSZ. AGG byl vysvětlen dvěma přispívajícími faktory – relativně velkou velikostí vzorku, která vedla k lokalizaci elektrického proudu a vzniku horkých míst (z angl. hot-spots), a celkově akcelerovanou kinetikou růstu zrn v jádře vzorku způsobenou elektrochemickou redukcí.