<p> This thesis is concerned with the determination of the thermodynamics of the Fe-V-O system. </p> <p> In the first part the thermodynamics of liquid Fe-V-O alloys were studied in the temperature range of 1550-1700ºC using H₂O/H₂ equilibrium and/or an oxygen probe. 1st and 2nd order interaction parameters between V and O were determined, and the deoxidation reactions occurring when V is used as a deoxidizer were studied. Deoxidation diagrams are presented for V concentrations up to 12 wt. %. </p> <p> In the second part the thermodynamic equilibria between the lower oxides of vanadium (V - VO₀ٜ₂₋ₓ, VO₀ٜ₂₊ₓ - VO₁₋ᵧ, VO₁₊ᵧ - VO₁ٜ₅) were determined in the range 800-1400ºC using a solid state EMF technique, and the free energy of the formation of the oxides VO₀ٜ₂₊₍₋₎ₓ, VO₁₊₍₋₎ᵧ, VO₁ٜ₅ was estimated. </p> / Thesis / Doctor of Philosophy (PhD)

<P> A study has been made of the transformation of deoxidation products in the Fe-V-0 system in the temperature range 1545 -1640°C, using galvanic cells with solid electrolytes. The cells used were in the form of Zr02 (caO) immersion probes and Th02(Y2o2) crucible assemblies. The fields of study of Fev2o4(spinel) and v2o3 were established with respect to oxygen activity and temperature. </p> / Thesis / Master of Engineering (MEngr)

Materiais magnetostrictivos exibem deformação elástica na presença de um campo magnético aplicado e por isso são de grande interesse para aplicação em sensores e atuadores. Trabalhos publicados no ano 2000 mostraram que a adição de Ga e Al ao Fe resulta em ligas com elevada magnetostricção em campos baixos. A partir daí os esforços foram direcionados para a descoberta de novas ligas magnetostrictivas à base de Fe com propriedades similares às encontradas nas ligas Fe-Ga e Fe-Al. No presente trabalho foram adicionados o Sn e o V ao Fe com o objetivo de avaliar a magnetostricção e a microestrutura das ligas formadas. Para isso, foram produzidas por fusão a arco as ligas Fe-9%at.Sn, Fe-20%at.Sn e as ligas Fex% at.V para x = 20, 25 e 30. As ligas Fe-Sn foram submetidas a tratamentos térmicos em 550 e 750°C por 24 h e em 880°C por 6 h e depois resfriadas rapidamente para a retenção das fases (Fe?,Sn), FeSn, Fe3Sn2 e Fe5Sn3. Já as ligas Fe-V foram tratadas em 1100°C por 6 h para homogeneização da fase única (Fe?,V). A caracterização microestrutural e análise quantitativa das fases foram feitas por microscopia óptica e eletrônica de varredura, microanálise por energia dispersiva (EDS) e difratometria de raios X. Também foi medida a microdureza Vickers das amostras. A magnetostricção foi medida por dilatometria de capacitância usando um dilatômetro de placa inclinada inserido no equipamento Maglab da Oxford Instruments, em campos na faixa de -1,5 a 1,5 T e temperaturas próximas de 203 K. A magnetização de saturação das amostras foi obtida em 77, 203 e 300 K utilizando o PPMS 6000 da Quantum Design. A magnetostricção de saturação (?S) das amostras da liga Fe-9Sn foi negativa e o comportamento das curvas similar ao do Fe puro. As amostras da liga Fe- 20Sn apresentaram ?S positiva devido à presença das fases ferromagnéticas Fe3Sn2 e Fe5Sn3. A ?S das ligas Fe-V foi positiva e maior em módulo do que a das ligas Fe-Sn. Concluiu-se que a substituição do Fe por Sn e V de modo geral melhorou a magnetostricção do Fe, porém a melhora não foi tão relevante quanto a observada pela substituição por Ga. / Magnetostrictive materials exhibit elastic strain in the presence of an applied magnetic field and therefore are of great interest for use in sensors and actuators. Works published in 2000 showed that the addition of Ga and Al in Fe results in alloys with high magnetostriction at low fields. Since then efforts have been directed to the discovery of new magnetostrictive Fe based alloys with similar properties to those found in Fe-Ga and Fe-Al alloys. In the present work Sn and V were added to Fe with the purpose of evaluating the magnetostriction and microstructure of these alloys. Therefore, Fe-9at.%Sn, Fe-20at.%Sn alloys and Fexat.% V alloys for x = 20, 25 and 30 were produced by arc melting. The Fe-Sn alloys were heat-treated at the temperatures of 550 and 750°C for 24 h and 880°C for 6 h and then rapidly cooled to the retention of the (?Fe,Sn), FeSn, Fe3Sn2 and Fe5Sn3 phases. Fe-V alloys were heat-treated at the temperature of 1100°C for 6 h to homogenize the (?Fe,Sn) single phase. Microstructural characterization and quantitative analysis of the phases were made by optical and scanning electron microscopy, microanalysis by energy dispersive spectroscopy (EDS) and X-ray powder diffraction. The Vickers microhardness of the samples was also measured. The magnetostriction was measured by capacitance dilatometry using a tilted plate dilatometer inserted into the Maglab platform by Oxford Instruments, using applied field in the range from -1.5 to 1.5 T and at temperatures close to 203 K. The samples saturation magnetization was obtained at 77, 203 and 300 K using the Quantum Design PPMS 6000. The saturation magnetostriction (?S) of the Fe-9Sn alloy samples was negative and the ?S vs. H curves behavior are similar to the pure Fe. Fe-20Sn alloy samples had positive ?S due to the presence of Fe3Sn2 and Fe5Sn3 ferromagnetic phases. The Fe-V alloys ?S was positive and larger in module than the Fe-Sn alloys ?S. We concluded that the substitution of Fe by Sn and V in a general way improved the magnetostriction of Fe, but the improvement was not as significant as observed with the substitution by Ga.

Materiais magnetostrictivos exibem deformação elástica na presença de um campo magnético aplicado e por isso são de grande interesse para aplicação em sensores e atuadores. Trabalhos publicados no ano 2000 mostraram que a adição de Ga e Al ao Fe resulta em ligas com elevada magnetostricção em campos baixos. A partir daí os esforços foram direcionados para a descoberta de novas ligas magnetostrictivas à base de Fe com propriedades similares às encontradas nas ligas Fe-Ga e Fe-Al. No presente trabalho foram adicionados o Sn e o V ao Fe com o objetivo de avaliar a magnetostricção e a microestrutura das ligas formadas. Para isso, foram produzidas por fusão a arco as ligas Fe-9%at.Sn, Fe-20%at.Sn e as ligas Fex% at.V para x = 20, 25 e 30. As ligas Fe-Sn foram submetidas a tratamentos térmicos em 550 e 750°C por 24 h e em 880°C por 6 h e depois resfriadas rapidamente para a retenção das fases (Fe?,Sn), FeSn, Fe3Sn2 e Fe5Sn3. Já as ligas Fe-V foram tratadas em 1100°C por 6 h para homogeneização da fase única (Fe?,V). A caracterização microestrutural e análise quantitativa das fases foram feitas por microscopia óptica e eletrônica de varredura, microanálise por energia dispersiva (EDS) e difratometria de raios X. Também foi medida a microdureza Vickers das amostras. A magnetostricção foi medida por dilatometria de capacitância usando um dilatômetro de placa inclinada inserido no equipamento Maglab da Oxford Instruments, em campos na faixa de -1,5 a 1,5 T e temperaturas próximas de 203 K. A magnetização de saturação das amostras foi obtida em 77, 203 e 300 K utilizando o PPMS 6000 da Quantum Design. A magnetostricção de saturação (?S) das amostras da liga Fe-9Sn foi negativa e o comportamento das curvas similar ao do Fe puro. As amostras da liga Fe- 20Sn apresentaram ?S positiva devido à presença das fases ferromagnéticas Fe3Sn2 e Fe5Sn3. A ?S das ligas Fe-V foi positiva e maior em módulo do que a das ligas Fe-Sn. Concluiu-se que a substituição do Fe por Sn e V de modo geral melhorou a magnetostricção do Fe, porém a melhora não foi tão relevante quanto a observada pela substituição por Ga. / Magnetostrictive materials exhibit elastic strain in the presence of an applied magnetic field and therefore are of great interest for use in sensors and actuators. Works published in 2000 showed that the addition of Ga and Al in Fe results in alloys with high magnetostriction at low fields. Since then efforts have been directed to the discovery of new magnetostrictive Fe based alloys with similar properties to those found in Fe-Ga and Fe-Al alloys. In the present work Sn and V were added to Fe with the purpose of evaluating the magnetostriction and microstructure of these alloys. Therefore, Fe-9at.%Sn, Fe-20at.%Sn alloys and Fexat.% V alloys for x = 20, 25 and 30 were produced by arc melting. The Fe-Sn alloys were heat-treated at the temperatures of 550 and 750°C for 24 h and 880°C for 6 h and then rapidly cooled to the retention of the (?Fe,Sn), FeSn, Fe3Sn2 and Fe5Sn3 phases. Fe-V alloys were heat-treated at the temperature of 1100°C for 6 h to homogenize the (?Fe,Sn) single phase. Microstructural characterization and quantitative analysis of the phases were made by optical and scanning electron microscopy, microanalysis by energy dispersive spectroscopy (EDS) and X-ray powder diffraction. The Vickers microhardness of the samples was also measured. The magnetostriction was measured by capacitance dilatometry using a tilted plate dilatometer inserted into the Maglab platform by Oxford Instruments, using applied field in the range from -1.5 to 1.5 T and at temperatures close to 203 K. The samples saturation magnetization was obtained at 77, 203 and 300 K using the Quantum Design PPMS 6000. The saturation magnetostriction (?S) of the Fe-9Sn alloy samples was negative and the ?S vs. H curves behavior are similar to the pure Fe. Fe-20Sn alloy samples had positive ?S due to the presence of Fe3Sn2 and Fe5Sn3 ferromagnetic phases. The Fe-V alloys ?S was positive and larger in module than the Fe-Sn alloys ?S. We concluded that the substitution of Fe by Sn and V in a general way improved the magnetostriction of Fe, but the improvement was not as significant as observed with the substitution by Ga.

Les jonctions tunnel magnétiques épitaxiées sont des systèmes modèles permettant de confronter l'expérience à la théorie de l'effet tunnel polarisé en spin. Celles à barrière de MgO(001) font à ce titre l'objet de nombreuses études, dont certaines ont permis d'établir expérimentalement l'existence de phénomènes tunnel cohérents dépendant de la symétrie des états de Bloch. Les expériences réalisées au cours de cette thèse visent à identifier et contrôler plusieurs propriétés des interfaces, de la barrière et des électrodes qui s'expriment dans le transport tunnel. Nous étudions les conséquences d'un excès d'oxygène à l'interface Fe/MgO dans les jonctions Fe/MgO/Fe(001). La réalisation d'un empilement modèle Fe/p(1×1) O/MgO/Fe(001) nous permet de confirmer certains effets attendus, notamment la formation d'une barrière additionnelle à l'interface pour les états de symétrie Δ1. Cependant, et contre toute attente, la magnétorésistance dépend peu de la présence d'oxygène. Elle est en revanche très sensible à la qualité cristallographique des interfaces. Nous démontrons ainsi les influences néfastes du désordre et du désaccord paramétrique entre la barrière de MgO et l'électrode sous-jacente. L'emploi d'alliages Fe V de composition variable permet de réduire le désaccord paramétrique et de diminuer la densité de dislocations, ce qui conduit à une forte augmentation de la magnétorésistance. Nous étudions enfin comment les structures électroniques des alliages Fe Co et Fe V se manifestent dans le transport tunnel. Des mesures de photoémission résolue en spin nous permettent de sonder directement les bandes Δ et les états de résonnance interfaciale des surfaces (001) libres ou recouvertes de MgO.

With the progress of high alloy steelmaking processes, it is essential to minimize the loss of valuable metals, like chromium and vanadium during the decarburization process, from both economic as well as environmental view points. One unique technique to realize this aim, used in the present work, is the decarburization of high alloy steel grades using oxygen with CO2 in order to reduce the partial pressure of oxygen. In the present work, the investigation on the oxidation of iron-chromium and iron-vanadium molten alloys under CO2-O2 mixtures was carried out and presented in this dissertation. For oxidation study on Fe-Cr molten alloy with CO2-O2 mixtures, on the basis of thermodynamic analysis, energy balance calculation and modeling results, experimental validation in laboratory was carried out, and later on, the oxidation kinetics of Fe-Cr and Fe-Cr-C melts under controlled partial pressure of oxygen was investigated. Thermodynamics calculation and energy balance estimation demonstrated that, it is possible to use CO2 or CO2-O2 mixtures as decarburizers during EAF process and high initial carbon contents in the steel can be adopted at the beginning in order to reduce the cost. A generic model has been developed to describe the overall process kinetics prevailing in metallurgical reactors containing liquid metal and gas bubbles. This model is general and can be extended further to consider any gas liquid reactions in any chemical engineering reactor, and especially the metallurgical ones, like AOD. In the present dissertation, the model is applied in predicting the evolution of Cr and C contents in a Fe-C-Cr melt during injection of different O2-CO2 mixtures. The related simulation results illustrated that CO2 is efficient in Cr retention. In order to verify the modeling results, 1kg induction furnace experiments were carried out in the present laboratory. The results indicated that the predictions of the model are in good agreement with the experimental results. Meanwhile, the experimental results indicated that the Cr-losses can be significantly lowered by replacing the oxygen with CO2 in the injected gas, specifically for Fe-Cr-C melts with carbon levels higher than about 0.8 mass%. Subsequently, the oxidation kinetics of Fe-Cr and Fe-Cr-C melts was investigated under different CO2-O2 mixtures. It is indicated that, the oxidation rate is controlled by the chemical reaction at the initial stage and the reaction rate can be expressed as  at the Cr range of 11-21 mass% in the Fe-Cr melt. For oxidation study on Fe-V liquid alloy, the investigation of the oxidation kinetics was carried out under CO2-O2 mixtures, which is followed by the study on thermodynamic properties of vanadium containing slags. During oxidation of Fe-V melt, in the case of alloys with vanadium contents exceeding 10 mass%, there exists an incubation period before the chemical reactions prevail the process. In addition, the ‘incubation time’ increased with the increase of temperature and the vanadium content, whereas it decreased with the increase of oxygen partial pressure in the oxidant gas. High-temperature mass spectrometric method was used to determine the activity of the vanadium oxide in CaO-MgO-Al2O3-SiO2-V2O3 slags, whereas, the oxidation states of vanadium in the CaO-MgO-Al2O3-SiO2-VOxslag system was studied by XANES method. The results indicated that, higher basicities stabilize higher vanadium oxidation state, whereas, higher temperature stabilizes lower vanadium oxidation state. The present work, which was carried out within the ECO-STEELMAKING project funded by MISTRA via Jernkontoret is expected to lead to implementation of some modifications in high alloy steel production based on fundamental concepts towards more environment-friendly steel processing. / <p>QC20100628</p>

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