L’aluminium est fabriqué en phase liquide à 1000°C dans une cuve à électrolyse par réduction de l’alumine dissoute dans un bain fluoré contenant essentiellement de la cryolithe Na3AlF6. Les parois latérales des cuves d’électrolyse sont revêtues par des briques réfractaires, dites « dalles de bordure », à base de SiC lié par Si3N4. Ces dalles, qui déterminent en grande partie la durée de vie de la cuve d’électrolyse, sont soumises à la corrosion par le bain, l’aluminium liquide et les gaz fluorés dégagés. Afin de contribuer à une meilleure connaissance des mécanismes de corrosion de ces dalles, l’étude des échantillons « post-mortem » prélevés des cuves industrielles a été effectuée. La mise au point d’un dispositif de simulation de corrosion en laboratoire a permis de suivre l’évolution du matériau en fonction de la composition de l’agent de corrosion. Ces études ont permis de mettre en évidence la forte réactivité de la phase liante de la dalle dans tous les zones de la cuve. Le rôle majeur de sodium, qui provient du bloc cathodique et la pâte de brasque, comme accélérateur de la corrosion de la dalle a été confirmé. La corrélation entre l’oxydation et la corrosion a été démontrée. La dissolution de SiO2 dans le bain fluoré a été étudiée par RMN haute température in situ et par RMN MAS à température ambiante sur les échantillons solidifiés. Nous avons montré la formation de phases aluminosilicatées (albite et néphéline) qui ont une solubilité non négligeable dans la cryolithe. / Aluminum is produced in liquid phase at 1000 °C in an electrolysis cell by reduction of alumina dissolved in a bath containing essentially cryolite Na3AlF6. The sidewalls of the electrolysis cells are lined with refractory bricks, called « edge slabs », based on Si3N4 bonded SiC. These slabs, which largely determine the lifetime of the electrolysis cell, are submitted to corrosion by the bath, the liquid aluminum and fluoride gas released. To contribute to a better understanding of the corrosion mechanisms of these slabs, the study of postmortem samples from industrial cells has been completed. A specific furnace for corrosion measurements in molten fluorides has been developed in order to characterize the evolution of the refractory with the composition of the corrosion agent. These studies highlight the high reactivity of the binding phase of the slab in all parts of the cell. The role of sodium, which comes from the cathode block and the ramming paste, and acts as an accelerator of corrosion has been confirmed. The correlation between oxidation and corrosion has been demonstrated. The dissolution of SiO2 in the cryolitic bath has been studied in situ by NMR at high-temperature and by NMR MAS on solidified samples at room temperature. We have shown the formation of aluminosilicate phases (albite and nepheline) which have a significant solubility in cryolite.

Dans ce travail, deux matériaux réfractaires à base de SiC et à liaison nitrurée sont caractérisés au niveau microstructural et thermomécanique. Ces matériaux sont utilisés dans les Unités de Valorisation Energétique d'Ordures Ménagères (U.V.E.O.M.). Dans cette application, les revêtements réfractaires sont soumis à de fortes sollicitations comme des hautes températures, des gradients thermiques, des gradients de composition chimique ainsi que de la corrosion. Les matériaux SiC-Si3N4 et SiC-SiAlON étudiés sont constitués d'agrégats de SiC reliés entre eux par une phase liante. Cette dernière présente un fort taux de porosité ouverte sous la forme d'un réseau complexe. L'analyse microstructurale de la phase liante a été réalisée par microscopie électronique à balayage et le comportement thermomécanique de chaque matériau a été caractérisé en flexion 4-points et par échographie ultrasonore. Lors de l'utilisation dans les U.V.E.O.M., les réfractaires sont exposés à des phénomènes d'oxydation, en particulier en présence d'humidité. Ainsi, le comportement à l'oxydation de ces matériaux a été étudié sur la plage 800°C - 1200°C sous air sec, sous air ambiant et sous air humide. Les évolutions microstructurales liées à l'oxydation montrent l'influence du réseau de porosité sur les régimes d'oxydation qui caractérisent ces matériaux en fonction du niveau de température et des conditions environnementales. Par ailleurs, le comportement thermomécanique a été déterminé après des vieillissements dans chacun de ces régimes. Cette démarche de caractérisation a permis l'établissement de relations entre le comportement thermomécanique et les évolutions microstructurales associées à l'oxydation. Des modèles phénoménologiques d'oxydation sont présentés. Pour finir, des traitements sont proposés afin d'améliorer la durabilité des réfractaires SiC-Si3N4 et SiC-SiAlON dans les U.V.E.O.M. / In this work, the microstructure and the thermomechanical behaviour of two SiC-based refractories are studied.In waste-to-energy plants, these materials are subjected to severe sollicitations such as thermal gradients, chemical composition gradients and corrosion. SiC-Si3N4 and SiC-SiAlON refractories are composed by SiC agregates bonded with silicon nitride based phases. A complex porosity network characterises the bonding phase. Its microstructure is analysed with Scanning Electron Microscopy (SEM). The thermomechanical behaviour of each refractory is characterised with 4-points bending tests and ultrasonic pulse echo measurement of the Young's modulus. During the running of waste-to-energy plants, refractories are exposed to oxidation phenomenons. They are more critical with an increase of a water content in the air. Thus, the oxidation behaviour is studied between 800°C and 1200°C under dry air, ambiant air and humid air. The microstructural evolutions due to oxidation are influenced by the porosity network, which leads to two oxidation stages depending on temperature level and environnemental conditions. Thermomechanical behaviour is also determined for each oxidation stage. This characterisation approach permits to establish relationships between the thermomechanical behaviour and the microstructural evolutions during oxidation. Phenomenological modellings are presented. Finally, thermal treatments are proposed in order to improve the durability of SiC-Si3N4 and SiC-SiAlON refractories in waste-toenergy plants.

Neste trabalho, foi realizado um estudo da caracterização elétrica dos ISFETs com estrutura Si/SiO2/Si3N4, utilizando pseudoeletrodos de Pt, Ag e Au como alternativas aos eletrodos convencionais para medições de pH. Primeiramente, foram empregados três métodos reportados na literatura (extrapolação linear para obtenção da tensão de limiar, segunda derivada para obtenção da tensão de limiar e corrente de sublimiar, respectivamente) com o objetivo de obter a sensibilidade dos ISFETs (mV/pH) e analisar a confiabilidade dos resultados utilizando eletrodo de referência padrão de Ag/AgCl. Posteriormente, tendo como base o eletrodo de Ag/AgCl, foram estudados os desempenhos de pseudoeletrodos de Pt, Ag e Au nas medidas de pH. Como resultado, observou-se que os pseudoeletrodos de Pt e Ag apresentaram sensibilidades compatíveis com o eletrodo de referência padrão de Ag/AgCl (~50mV/pH) para pH ácido na faixa de 1 a 3. Já o pseudoeletrodo de Au, manteve um comportamento aproximadamente linear ao longo de toda a faixa de pH estudada (1 a 10), porém, com sensibilidade inferior na faixa de 32 à 34mV/pH. / In this work, it is presented a study of the electrical characterization of Si/SiO2/Si3N4 estructured ISFETs using Pt, Ag and Au pseudoelectrodes as alternative references to the conventional ones for pH measurements. At first, it was used three different methods (linear extrapolation method to obtain the threshold voltage, second derivative method to obtain the threshold voltage and subthreshold-current method, respectively) having as objective to obtain the sensitivity of the ISFETs (mV/pH) and to analyze the reliability of the results using the standard Ag/AgCl reference electrode. Subsequently, using the Ag/AgCl electrode as a base for comparation, it was studied the performance of Pt, Ag and Au pseudoelectrodes for pH measurement. As a result, it was observed that the Pt and Ag electrodes presented sensitivity similar to the standard Ag/AgCl reference electrode (~50mV/pH) for pH in the range of 1 to 3. On the other hand, the Au pseudoelectrode presented an approximately linear behavior in all studied range of the pH (1 to 10), but, with lower sensitivity varying in the range of 32 to 34mV/pH.

Siliciumkarbid (SiC) und Siliciumnitrid (Si3N4) zeichnen sich durch hervorragende mechanische, thermische und chemische Materialeigenschaften und, insbesondere für das SiC, durch niedrige Kosten aus. Da beide Werkstoffe inkongruent schmelzen, können sie in reiner Form spritztechnisch nicht verarbeitet werden. Es werden metallurgische Lösungskonzepte erarbeitet, die darauf abzielen, die Hartstoffe zu benetzen und die Reaktivität herabzusetzen. Durch den Einsatz von Verbundpulvern besteht die Möglichkeit die Hartstoffpartikel gegen die rein thermisch induzierte Zersetzung beim spritztechnischen Verarbeiten weitgehend zu schützen. Zum Herstellen der Verbundpulver werden im Rahmen der experimentellen Untersuchungen unterschiedlichen Herstellungsverfahren eingesetzt. Unter Ausnutzen der prozessspezifischen Charakteristika der unterschiedlichen thermischen Spritzverfahren werden die so hergestellten Verbundpulver zu dichten, fest haftenden und hoch hartstoffhaltigen Spritzschichten verarbeitet. Neben der metallographischen Charakterisierung der Verbundschichten hinsichtlich Schichtmorphologie werden zudem die mechanisch-technologischen und chemisch-technologischen Eigenschaften untersucht.

In this work, a quantum well intermixing(QWI) technology, called impurity free vacancy diffusion(IFVD), is used to do the bandgap engineering in an optoelectronic monolithic integration. The monolithic integration of SOAs and EAMs is taken as an example. By IFVD, the transition energy levels of EAM quantum wells can be shifted to shorter wavelength region, while SOA quantum wells are kept the same. Therefore, the overall SOA-integrated EAM efficiency can be improved. We use dielectric film¡XSiO2 and Si3N4 to control the impurity free vacancy diffusion, both of these two dielectric layer will induce stress on the wafer, but they will come to the totally different result base on the difference atom chemistry with the substrate. Using Ga atom diffusion into SiO2 to relax stress, the IFVD will be operated to enhance quantum well intermixing, leading to energy bang transition change. On the other hand, with Si3N4 film, no significant intermixing is observed, implying atom chemistry dominates the whole process. Also, a super critical fluid technique by H2O2 is also employed to further improving SiO2 quality, a as large as 180nm blue shift is obtained, further improving such mechanism. Through difference properties between SiO2 and Si3N4 dielectric layers, different bandgap transitions in one single chip can be controlled in an area of 30£gm¡Ñ50£gm, leading to a planar bandgap engineering. Use these techniques, an EAM-SOA integration is designed and fabricated, obtaining an wavelength offset of 40nm with good quality of material structure. In the future, we can use this technique on large scale chip, tuning the bandgap to make photonic integration circuit without re-growth.

Ziel des Forschungsvorhabens war es, die Korrosionsbeständigkeit von gelöteten Metall-Keramik-Verbindungen gegenüber verschiedenen Medien mit geeigneten Untersuchungsmethoden zu bestimmen. Durch elektrochemische Messverfahren sind die Korrosionsvorgänge von metallischen Werkstoffen und ihren Fügeverbunden charakterisierbar. Es wird eine erhebliche Reduzierung der Prüfzeit gegenüber Prüfkammer- bzw. Realprüfungen erreicht. Die Auswertung der Untersuchungen ergab eine Korrelation zwischen Korrosionsbelastung und mechanischen Eigenschaften. Folgende Grundwerkstoffe und Aktivlote wurden für die Messungen verwendet: - Stähle: 1.0037, 1.4301, 1.4016 - Keramiken: Al2O3, ZrO2, SiC, Si3N4 - Lote: AgCu28-Basislot mit variierenden Titangehalten (Schwerpunkt Lot mit 3% Ti) Das Korrosionsverhalten der aktivgelöteten Metall-Keramik-Verbindungen wird entscheidend vom am stärksten korrosiv angegriffenen Teil der Probe bzw. des Bauteils bestimmt. Liegt ein chloridhaltiges Korrosionsmedium (3,5 % NaCl-Lösung) vor, dominiert der Metallpartner das Korrosionsverhalten. Die eingesetzten Stähle werden durch Lochfraß stark angegriffen. Dieser geht in flächigen Abtrag über und mit zunehmender anodischer Polarisation werden die Stähle regelrecht zerstört. In den Stählen enthaltene sulfidische Einschlüsse fördern den Korrosionsangriff. Dies wird besonders deutlich beim Stahl 1.4301, in dem sehr viele Mangansulfide zu finden sind. Die Korrosion der Lötnaht ist vergleichbar mit der des Stahles. Bei einem sulfathaltigen Korrosionsmedium (3,5 % Na2SO4-Lösung) wird zuerst die Lötnaht und dann der Stahl angegriffen. Dies wird neben der Lichtmikroskopie auch von den topographischen Messungen bestätigt. Im Falle der Verbindungen mit 1.4016 bewirken die Keramiken eine Verbreiterung des Passivbereiches im Vergleich zu Stahl, wenn auch bei höheren Stromdichten. Die Vorbelastung der Biegeproben durch anodische Polarisation bis 200 mV in 3,5 % NaCl-Lösung bewirkt die gleiche Schädigung wie die Exposition von 96 h im Salzsprühnebel gemäß DIN 50021 SS. Die Ergebnisse aus den Festigkeitsuntersuchungen an Verbindungen mit dem Stahl 1.4016 zeigen, dass gegenüber dem nichtkorrodierten Zustand die Festigkeit abnimmt. Dennoch erfolgt der Bruch in der Keramik und nicht in der Lötnaht. Mit der Bereitstellung von Stromdichte-Potential-Kurven steht ein Messverfahren zur schnellen und vergleichenden Bewertung von Metall-Keramik-Verbindungen hinsichtlich der Korrosionsanfälligkeit zur Verfügung. Die Schädigung der Verbindungen durch Korrosion bleibt im technisch beherrschbaren Bereich und steht somit dem Einsatz von Stahl als Verbindungspartner nicht entgegen.

For more than 50 years total hip replacements have been a common and successful procedure to increase patient mobility and quality of life. The 10-year implant survival rate is 97.8%. However, for longer implantation times there are limitations linked to the negative biological response to wear and corrosion products from the currently used biomaterials. In this thesis silicon nitride (SiNx) coatings were evaluated for use in total hip replacements, on the articulating bearing surface and modular taper connections. Homogeneous, dense SiNx coatings were deposited using reactive high power impulse magnetron sputtering (HiPIMS) up to a thickness of 8 µm. The N/Si atomic ratios ranged from 0.3 to 1.1 and the coatings showed a low surface roughness. The wear rate of a SiNx coated cobalt chromium molybdenum alloy (CoCrMo) was similar to that of bulk Si3N4, and less than one 46th of uncoated CoCrMo, an alloy that is commonly used in joint replacements. Wear debris generated from SiNx coatings was round in shape, with a mean size of 40 nm, and ranged between 10 and 500 nm. Model particles, similar in size and shape as the wear debris, were soluble in simulated body fluid. The dissolution rate was higher than the expected rate of debris generation. Along with the size of the debris, which is not in the critical range for macrophage activation, this dissolution may limit negative biological reactions. The SiNx coatings also dissolved in simulated body fluid. The coating with the highest N/Si ratio exhibited the lowest dissolution rate, of 0.2 to 0.4 nm/day, while CoCrMo under the same condition dissolved at a rate of 0.7 to 1.2 nm/day. SiNx-coated CoCrMo exhibited a reduced release of Co, Cr and Mo ions into the solution by two orders of magnitude, compared to uncoated CoCrMo. Si3N4 evaluated under micro-displacement in a corrosive environment, replicating the modular taper, showed a lower corrosion current compared to common biomedical alloys. SiNx coatings may also act beneficially to reduce issues associated with this type of contact. SiNx coatings have shown several properties in a laboratory environment that are hypothesised to increase the longevity of joint replacements. The promising results encourage further evaluation closer to the clinical application of total hip replacements, in particular in the articulating bearing surface and in modular tapers.

Submitted by Victor Hugo Albuquerque Rizzo (victor.rizzo@ufpe.br) on 2015-04-14T14:03:35Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO Carlos Augusto Bezerra Júnior.pdf: 10473836 bytes, checksum: 1b8127d28f4c0048aa1bc467c4862c15 (MD5) / Made available in DSpace on 2015-04-14T14:03:35Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO Carlos Augusto Bezerra Júnior.pdf: 10473836 bytes, checksum: 1b8127d28f4c0048aa1bc467c4862c15 (MD5) Previous issue date: 2013 / A garantia da integridade estrutural dos equipamentos na indústria passa necessariamente pela determinação das condições dos materiais e de suas propriedades mecânicas. Hoje em dia exigem-se materiais com propriedades específicas que deixam de ser atendidas pelo uso isolado das ligas metálicas, cerâmicas e poliméricas. Temos como exemplo casos como os da indústria eólica, aeronáutica, náutica e de transporte que, necessitam de materiais com baixa densidade, resistentes a corrosão, resistentes ao impacto e rígido. Nesta linha de pensamento, cada vez mais pesquisadores estão investindo tempo e tecnologia em busca de matérias compósitos que garantam uma distribuição homogênea de fases no seu reforço. A Metalurgia do Pó (MP) vem se destacando na promoção de uma melhor distribuição do reforço na matriz em relação ao processo convencional de fundição, obtendo-se então materiais com melhores propriedades mecânicas, dureza e resistência ao desgaste. O objetivo principal desse trabalho é produzir compósitos de matriz de liga de alumínio AA 2124, reforçado por nitreto de silício (Si3N4), utilizando o processo de metalurgia do pó (MP) e técnica de moagem de alta energia. Para tanto utilizou-se a caracterização por microscopia ótica (MO), microscopia eletrônica de varredura (MEV), difração de raios X (DRX), espectroscopia por dispersão de energia (EDS), difração a laser para avaliar e comparar as características de cada compósito, além de verificar as propriedades mecânicas inerentes. Os resultados de dureza apresentaram-se linearmente crescentes com o aumento da fração de reforço na matriz.

Neste trabalho, foi realizado um estudo da caracterização elétrica dos ISFETs com estrutura Si/SiO2/Si3N4, utilizando pseudoeletrodos de Pt, Ag e Au como alternativas aos eletrodos convencionais para medições de pH. Primeiramente, foram empregados três métodos reportados na literatura (extrapolação linear para obtenção da tensão de limiar, segunda derivada para obtenção da tensão de limiar e corrente de sublimiar, respectivamente) com o objetivo de obter a sensibilidade dos ISFETs (mV/pH) e analisar a confiabilidade dos resultados utilizando eletrodo de referência padrão de Ag/AgCl. Posteriormente, tendo como base o eletrodo de Ag/AgCl, foram estudados os desempenhos de pseudoeletrodos de Pt, Ag e Au nas medidas de pH. Como resultado, observou-se que os pseudoeletrodos de Pt e Ag apresentaram sensibilidades compatíveis com o eletrodo de referência padrão de Ag/AgCl (~50mV/pH) para pH ácido na faixa de 1 a 3. Já o pseudoeletrodo de Au, manteve um comportamento aproximadamente linear ao longo de toda a faixa de pH estudada (1 a 10), porém, com sensibilidade inferior na faixa de 32 à 34mV/pH. / In this work, it is presented a study of the electrical characterization of Si/SiO2/Si3N4 estructured ISFETs using Pt, Ag and Au pseudoelectrodes as alternative references to the conventional ones for pH measurements. At first, it was used three different methods (linear extrapolation method to obtain the threshold voltage, second derivative method to obtain the threshold voltage and subthreshold-current method, respectively) having as objective to obtain the sensitivity of the ISFETs (mV/pH) and to analyze the reliability of the results using the standard Ag/AgCl reference electrode. Subsequently, using the Ag/AgCl electrode as a base for comparation, it was studied the performance of Pt, Ag and Au pseudoelectrodes for pH measurement. As a result, it was observed that the Pt and Ag electrodes presented sensitivity similar to the standard Ag/AgCl reference electrode (~50mV/pH) for pH in the range of 1 to 3. On the other hand, the Au pseudoelectrode presented an approximately linear behavior in all studied range of the pH (1 to 10), but, with lower sensitivity varying in the range of 32 to 34mV/pH.

No description available.