Ferritisch/martensitische Cr-Stähle und deren oxiddispersionsverfestigte Varianten gehören zu den potenziellen Konstruktionswerkstoffen für Komponenten zukünftiger kerntechnischer Einrichtungen, wie z. B. Fusionsreaktoren und Spalt-reaktoren der IV. Generation, die Strahlungsfeldern mit hohem Neutronenfluss aus-gesetzt sind. Ein Hauptproblem dieser Materialgruppen ist das Auftreten des Spröd-duktil-Übergangs und dessen maßgeblich durch die Strahlenhärtung verursachte Verschiebung zu höheren Temperaturen. In der vorliegenden Arbeit wird das Bestrahlungsverhalten von binären Fe-Cr-Modelllegierungen untersucht, die ein vereinfachtes Modell für ferritisch/martensitische Cr-Stähle darstellen. Dabei werden Bestrahlungen mit Eisenionen zur Simulation der durch Neutronen hervorgerufenen Schädigung verwendet. Die auf wenige Mikrometer begrenzte Eindringtiefe der Ionen macht es erforderlich, dass für dünne Schichten geeignete Charakterisierungsmethoden ein-gesetzt werden. Im Rahmen dieser Arbeit sind das Nano¬härte¬messungen und Transmissions¬elektronen¬mikroskopie (TEM). Im Ergebnis liegen die bestrahlungsinduzierte Härteänderung der Schicht in Ab-hängig¬keit von Chromgehalt, Bestrahlungsfluenz und –temperatur sowie, für aus-gewählte Zustände, quantitative TEM-Analysen vor. Zusammen mit begleitenden Ergebnissen von Neutronenkleinwinkelstreuexperimenten an neutronen-bestrahlten Proben der gleichen Werkstoffe ermöglichen sie die Identifizierung von bestrahlungsinduzierten Versetzungsringen und nm-großen α’-Ausscheidungen als Quellen der Strahlenhärtung. Im Rahmen eines vereinfachten Modells, das auf Orowan zurückgeht, werden die Hindernis¬stärken dieser Gitterbaufehler für das Gleiten von Versetzungen abgeschätzt. Darauf aufbauend erfolgt ausblickartig eine Erweiterung des Untersuchungsgegenstands auf komplexere Situationen hinsichtlich der Bestrahlungs-bedingungen und des Werkstoffs. Durch das Einbeziehen simultaner und sequentieller Bestrahlungen mit Eisen- und Heliumionen kann gezeigt werden, dass der Effekt von Helium auf die Strahlenhärtung von der Bestrahlungs-reihenfolge abhängt und dass der simultane Eintrag fusionsrelevanter Mengen von Helium zu einer Verstärkung der Strahlenhärtung führt, die auf einem synergistischen Effekt beruht. Für Cr-Stähle mit 9 % Cr und deren oxiddispersions-verfestigte Varianten wird kein grundlegend anderes Bestrahlungsverhalten beobachtet als für binäres Fe-9at%Cr. Es gibt jedoch Hinweise, dass Oxid-dispersionsverfestigung die Strahlenhärtung unter bestimmten Bedingungen reduzieren kann. Im Ergebnis der Arbeit zeigt sich, dass Ionenbestrahlungen in Kombination mit Nanohärtemessungen zu einem vertiefenden Verständnis der Strahlenhärtung in Werkstoffen auf Fe-Cr-Basis sowie zu einer effektiven Materialvorauswahl beitragen können. Voraussetzung ist, dass der Eindruckgrößeneffekt und der Substrateffekt auf geeignete Weise in Rechnung gestellt werden.

[pt] A redução na emissão de CO2 na atmosfera é um dos desafios atuais mais importantes enfrentados por diferentes indústrias no mundo. A geração de energia através da queima de combustíveis fósseis utilizando oxigênio puro [1], também chamada de tecnologia de oxicombustão, é uma opção utilizada pelas indústrias de geração de energia para minimizar os índices de concentração de CO2 até emissão ZERO [1,2]. Inevitavelmente, as tubulações dos trocadores de calor que conformam aquelas plantas de energia, sofrem corrosão em contato com os gases de combustão (H2O-CO2) em altas temperaturas. Estas tubulações, fabricadas com aço ou com ligas ferro-cromo vem sendo utilizadas no intuito de reduzir a corrosão. Tubulações com revestimentos/recobrimentos protetores tem sido também considerados para aumentar a resistência a processos corrosivos sem requerer o emprego de ligas de alto custo. Um revestimento adequado deve ser inerte e estável em altas temperaturas como é o caso dos materiais cerâmicos. A alumina, sendo um material estável em ambientes característicos do processo de oxicombustão apresenta características favoráveis para esta proteção [3]. Amostras de Fe-Cr foram oxidadas sob condições que simularam processos de Oxicombustão nos laboratórios do Bundesanstalt Für Materialforschung Und-Prüfung (BAM) Berlim-Alemanha. O processo ocorreu a 650 graus Celsius durante 2000 h, em atmosfera contendo 60 por cento CO2,30 por cento H2O, 7 por cento N2, 2 por cento O2 e 1 por cento SO2. A caracterização microestrutural das amostras oxidadas foi realizada nos laboratórios do instituto Nacional de Tecnologia (INT), utilizando técnicas de Microscopia Eletrônica de Varredura (MEV) e Espectroscopia por Dispersão de Energia de Raios-X (EDS). Foram produzidos riscos na superfície do revestimento de Al2O3, previamente aos testes de oxidação, para simular falhas no revestimento; além da eficácia do revestimento de alumina, foi também avaliado o papel do cromo como meio protetor contra a corrosão e de outros elementos de liga no processo de oxidação do aço P92, buscando identificar o mecanismo de oxidação. Como resultado do fluxo dos gases de oxicombustão há formação de camadas de Fe3O4, Fe2O3 e cromo-espinélio nas ligas sem revestimento. As amostras que possuíam o revestimento de alumina apresentaram ótima proteção, com resultados de uma alta eficácia, enquanto as amostras que tinham riscos apresentaram uma oxidação interna de oxidação cromo-espinélio protetor na matriz logo abaixo da região afetada. / [en] The reduction in the emission of CO2 in the atmosphere is one of the most important problems faced by different industries in the world. The generation of energy from oxyfuel oxygen, [1], also called Oxyfuel technology, is a matter of CO2 emission for ZERO [1,2]. Inevitably, as pipes of the heat exchangers that make up these power plants, they suffer corrosion in contact with the flue gases (H2O-CO2) at high temperatures. These pipes, made of steel or iron-chromium alloys, are not used instead of reducing corrosion. Pipes with protective coatings have already been submitted to increase resistance to corrosive processes without requiring the use of high cost alloys. One which must be inert and static at high temperatures is the case of ceramic materials. An alumina, being a suitable material to the environments characteristic of the Oxyfuel process, presents characteristics favorable to the protection [3]. Fe-9Cr samples were oxidized under conditions that simulated Oxyfuel processes in the laboratories of the Bundesanstalt Für Materialforschung Und-Prüfung (BAM) Berlin-Germany. The process occurred at 650 degree Celsius for 2000 h, in an atmosphere containing 60 percent CO2, 30 percent H2O, 7 percent N2, 2 percent O2 and 1 percent SO2. The microstructural characterization of the oxidized samples was performed in the laboratories of the National Institute of Technology (INT), using Scanning Electron Microscopy (SEM) and X-ray Energy Dispersion Spectroscopy (EDS) techniques. Risks were produced on the Al2O3 coating surface, prior to the oxidation tests, to simulate coating failures; besides the effectiveness of the alumina coating, the role of chromium as a protective medium against corrosion and other alloying elements in the oxidation process of P92 steel was also evaluated, in order to identify the oxidation mechanism. As a result of the flow of oxyfuel gases, Fe3O4, Fe2O3 and chromium-spinel layers are formed in the alloys without coating. The samples that had the alumina coating presented optimum protection, with results of a high efficiency, while the samples that had scratches presented an internal oxidation of protective chromium-spinel oxidation in the matrix just below the affected region.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O objetivo deste trabalho foi avaliar a influÃncia da porcentagem em massa de Mo em ligas Fe-Cr-Mo frente à corrosÃo por CO2 em Ãgua artificial de tanque de armazenamento de petrÃleo e propor uma liga experimental para ser usada em dutos suscetÃveis a esse tipo de corrosÃo. Foram estudados o aÃo carbono 1020, para comparaÃÃo, e dois tipos de ligas Fe-Cr-Mo, uma comercial, denominada P9 (Fe-9Cr-1Mo); e uma liga experimental, E (Fe-9Cr-5Mo). Foram feitas medidas de PLP com tempo de Eca de 1 h. As curvas mostraram que, no aÃo 1020, ocorre apenas a dissoluÃÃo do Fe, enquanto que, com o aumento da porcentagem de Mo, ocorre passivaÃÃo. O monitoramento da corrosÃo foi feito por espectroscopia de impedÃncia eletroquÃmica, ao longo de 168 h de imersÃo. Os diagramas de Nyquist mostraram que o aumento na quantidade de Mo aumenta a impedÃncia das ligas estudadas. Jà as representaÃÃes de Bode mostraram que hà apenas um processo na corrosÃo no aÃo 1020, enquanto que hà dois para as ligas P9 e E. A caracterizaÃÃo da superfÃcie foi feita por MEV. A distribuiÃÃo dos produtos de corrosÃo foi homogÃnea no aÃo 1020 e heterogÃnea nas demais ligas. A identificaÃÃo dos produtos de corrosÃo foi feita por espectroscopia RAMAN, mostrando que houve a formaÃÃo de produtos de corrosÃo protetores apenas para as ligas Fe-Cr-Mo e que apenas a liga E apresentou produtos contendo Mo. Isso està em acordo com os resultados obtidos nas curvas de polarizaÃÃo e nos diagramas de impedÃncia, uma vez que o Mo pode estabilizar filmes de passivaÃÃo. Assim, a liga experimental E pode ser usada em substituiÃÃo à liga comercial P9 em plantas de exploraÃÃo de petrÃleo suscetÃveis a corrosÃo por CO2. / The objective of this work was to evaluate the influence of the percentage in mass of Mo in Fe-Cr-Mo alloys against CO2 corrosion in artificial water of oil storage tank and to propose an experimental alloy to be used in susceptible to this kind of corrosion pipes. They had been studied the 1020 carbon steel, for comparison, and two types of Fe-Cr-Mo alloys, one advertising, called P9 (Fe-9Cr-1Mo); and one experimental alloy, E (Fe-9Cr-5Mo). They had been made measurements of LSP with time of Eoc of 1 h. The curves had shown that, in 1020 steel, the dissolution of Fe occurs only, whereas, with the increase of the percentage of Mo, occurs passivation. Monitoring of the corrosion was made by electrochemical impedance spectroscopy, throughout 168 h of immersion. Nyquist diagrams had shown that the increase of Mo content increased the impedance of the studied alloys. Although, the Bode representations showed that there is only one process in the corrosion of 1020 steel, while there are two ones for P9 and E alloys. The characterization of the surface was made by SEM. The distribution of the corrosion products was homogeneous in the 1020 steel and heterogeneous one in the other alloys. The identification of the corrosion products was made by RAMAN spectroscopy, showing that there was protective corrosion products formation only to Fe-Cr-Mo alloys and that only the E alloy presented Mo-containing products. This is in agreement with the results obtained in polarization curves and in impedance diagrams, once Mo can stabilizes passivation films. So, experimental E alloy can be used in substitution of P9 alloy in oil exploration plants susceptible to CO2 corrosion.

Ferritisch/martensitische Cr-Stähle und deren oxiddispersionsverfestigte Varianten gehören zu den potenziellen Konstruktionswerkstoffen für Komponenten zukünftiger kerntechnischer Einrichtungen, wie z. B. Fusionsreaktoren und Spalt-reaktoren der IV. Generation, die Strahlungsfeldern mit hohem Neutronenfluss aus-gesetzt sind. Ein Hauptproblem dieser Materialgruppen ist das Auftreten des Spröd-duktil-Übergangs und dessen maßgeblich durch die Strahlenhärtung verursachte Verschiebung zu höheren Temperaturen. In der vorliegenden Arbeit wird das Bestrahlungsverhalten von binären Fe-Cr-Modelllegierungen untersucht, die ein vereinfachtes Modell für ferritisch/martensitische Cr-Stähle darstellen. Dabei werden Bestrahlungen mit Eisenionen zur Simulation der durch Neutronen hervorgerufenen Schädigung verwendet. Die auf wenige Mikrometer begrenzte Eindringtiefe der Ionen macht es erforderlich, dass für dünne Schichten geeignete Charakterisierungsmethoden ein-gesetzt werden. Im Rahmen dieser Arbeit sind das Nano¬härte¬messungen und Transmissions¬elektronen¬mikroskopie (TEM). Im Ergebnis liegen die bestrahlungsinduzierte Härteänderung der Schicht in Ab-hängig¬keit von Chromgehalt, Bestrahlungsfluenz und –temperatur sowie, für aus-gewählte Zustände, quantitative TEM-Analysen vor. Zusammen mit begleitenden Ergebnissen von Neutronenkleinwinkelstreuexperimenten an neutronen-bestrahlten Proben der gleichen Werkstoffe ermöglichen sie die Identifizierung von bestrahlungsinduzierten Versetzungsringen und nm-großen α’-Ausscheidungen als Quellen der Strahlenhärtung. Im Rahmen eines vereinfachten Modells, das auf Orowan zurückgeht, werden die Hindernis¬stärken dieser Gitterbaufehler für das Gleiten von Versetzungen abgeschätzt. Darauf aufbauend erfolgt ausblickartig eine Erweiterung des Untersuchungsgegenstands auf komplexere Situationen hinsichtlich der Bestrahlungs-bedingungen und des Werkstoffs. Durch das Einbeziehen simultaner und sequentieller Bestrahlungen mit Eisen- und Heliumionen kann gezeigt werden, dass der Effekt von Helium auf die Strahlenhärtung von der Bestrahlungs-reihenfolge abhängt und dass der simultane Eintrag fusionsrelevanter Mengen von Helium zu einer Verstärkung der Strahlenhärtung führt, die auf einem synergistischen Effekt beruht. Für Cr-Stähle mit 9 % Cr und deren oxiddispersions-verfestigte Varianten wird kein grundlegend anderes Bestrahlungsverhalten beobachtet als für binäres Fe-9at%Cr. Es gibt jedoch Hinweise, dass Oxid-dispersionsverfestigung die Strahlenhärtung unter bestimmten Bedingungen reduzieren kann. Im Ergebnis der Arbeit zeigt sich, dass Ionenbestrahlungen in Kombination mit Nanohärtemessungen zu einem vertiefenden Verständnis der Strahlenhärtung in Werkstoffen auf Fe-Cr-Basis sowie zu einer effektiven Materialvorauswahl beitragen können. Voraussetzung ist, dass der Eindruckgrößeneffekt und der Substrateffekt auf geeignete Weise in Rechnung gestellt werden.

Ferritisch/martensitische Cr-Stähle und deren oxiddispersionsverfestigte Varianten gehören zu den potenziellen Konstruktionswerkstoffen für Komponenten zukünftiger kerntechnischer Einrichtungen, wie z. B. Fusionsreaktoren und Spaltreaktoren der IV. Generation, die Strahlungsfeldern mit hohem Neutronenfluss ausgesetzt sind. Ein Hauptproblem dieser Materialgruppen ist das Auftreten des Spröd-duktil-Übergangs und dessen maßgeblich durch die Strahlenhärtung verursachte Verschiebung zu höheren Temperaturen. In der vorliegenden Arbeit wird das Bestrahlungsverhalten von binären Fe-Cr-Modelllegierungen untersucht, die ein vereinfachtes Modell für ferritisch/martensitische Cr-Stähle darstellen. Dabei werden Bestrahlungen mit Eisenionen zur Simulation der durch Neutronen hervorgerufenen Schädigung verwendet. Die auf wenige Mikrometer begrenzte Eindringtiefe der Ionen macht es erforderlich, dass für dünne Schichten geeignete Charakterisierungsmethoden eingesetzt werden. Im Rahmen dieser Arbeit sind das Nanohärtemessungen und Transmissionselektronenmikroskopie (TEM). Im Ergebnis liegen die bestrahlungsinduzierte Härteänderung der Schicht in Abhängigkeit von Chromgehalt, Bestrahlungsfluenz und –temperatur sowie, für ausgewählte Zustände, quantitative TEM-Analysen vor. Zusammen mit begleitenden Ergebnissen von Neutronenkleinwinkelstreuexperimenten an neutronenbestrahlten Proben der gleichen Werkstoffe ermöglichen sie die Identifizierung von bestrahlungsinduzierten Versetzungsringen und nm-großen α’-Ausscheidungen als Quellen der Strahlenhärtung. Im Rahmen eines vereinfachten Modells, das auf Orowan zurückgeht, werden die Hindernisstärken dieser Gitterbaufehler für das Gleiten von Versetzungen abgeschätzt. Darauf aufbauend erfolgt ausblickartig eine Erweiterung des Untersuchungsgegenstands auf komplexere Situationen hinsichtlich der Bestrahlungsbedingungen und des Werkstoffs. Durch das Einbeziehen simultaner und sequentieller Bestrahlungen mit Eisen- und Heliumionen kann gezeigt werden, dass der Effekt von Helium auf die Strahlenhärtung von der Bestrahlungsreihenfolge abhängt und dass der simultane Eintrag fusionsrelevanter Mengen von Helium zu einer Verstärkung der Strahlenhärtung führt, die auf einem synergistischen Effekt beruht. Für Cr-Stähle mit 9 % Cr und deren oxiddispersionsverfestigte Varianten wird kein grundlegend anderes Bestrahlungsverhalten beobachtet als für binäres Fe-9at%Cr. Es gibt jedoch Hinweise, dass Oxid-dispersionsverfestigung die Strahlenhärtung unter bestimmten Bedingungen reduzieren kann. Im Ergebnis der Arbeit zeigt sich, dass Ionenbestrahlungen in Kombination mit Nanohärtemessungen zu einem vertiefenden Verständnis der Strahlenhärtung in Werkstoffen auf Fe-Cr-Basis sowie zu einer effektiven Materialvorauswahl beitragen können. Voraussetzung ist, dass der Eindruckgrößeneffekt und der Substrateffekt auf geeignete Weise in Rechnung gestellt werden.

Orientador: Paulo Roberto Mei / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-12T11:09:37Z (GMT). No. of bitstreams: 1 Bubani_FrancodeCastro_M.pdf: 7334881 bytes, checksum: 9cc4f96ceff0972bc2552404b4ccee84 (MD5) Previous issue date: 2008 / Resumo: Os efeitos da adição de níquel e da temperatura em ligas ferro-cromo foram estudados. Sete ligas de base ferro, com 18% Cr e teores de níquel variando entre zero e 60%, foram utilizadas no estudo (0, 10, 20, 30, 40, 50 e 60% Ni). Foram realizados ensaios de tração em temperatura ambiente, 350 e 700 ºC; simulação por termodinâmica computacional; microscopia ótica no estado recozido, nas amostras de quick stop, após deformação a frio, a 350 e a 700 ºC; difração de raios X no estado recozido, após deformação a 350 e a 700 ºC; ensaio de dureza a quente a 100, 200, 300 e 400 ºC; ensaio de impacto Charpy em temperatura ambiente e a -196 ºC; e ensaio de quick stop; análise térmica por DTA; ensaios de dureza no estado recozido, nos cavacos obtidos em torneamento, após deformação a 350 e 700 ºC. Os resultados dos ensaios de tração a 350 ºC foram correlacionados com os dados obtidos por Marques (2007), visando relacionar propriedades mecânicas e usinabilidade. A tendência geral de redução da usinabilidade com o aumento do teor de níquel foi relacionada com o aumento da resistência mecânica e da ductilidade a quente, proporcionados pelo níquel. A alta usinabilidade observada na liga 30% Ni foi relacionada com a presença de inclusões com cálcio nesta liga, o que proporcionou ganhos muito expressivos em usinabilidade, mas sem prejudicar as propriedades mecânicas avaliadas. / Abstract: The effects of nickel addition and temperature in iron-chromium alloys have been studied. Seven iron-base alloys with 18% Cr and nickel content varying from zero to 60% were used in the study (0, 10, 20, 30, 40, 50 and 60% Ni). The alloys were submitted to tension tests at room temperature, 350 and 700 ºC; computational thermodynamics simulations; optical metallography observations in annealed state, after deformation at room temperature, 350 and 700 oC, and in quick stop samples; x-ray diffraction, annealed and after deformation at 350 and 700 ºC; hot hardness test at 100, 200, 300 and 400 ºC; Charpy impact tests at room temperature and at -196 ºC; quick stop test; differential thermal analysis tests; Vickers hardness tests: annealed, on chips, after deformation at 350 and 700 ºC. The results of the tension tests at 350 ºC were correlated with the data obtained by Marques (2007), aiming at reaching a relationship between mechanical properties and machinability. The general tendency of reduction in machinability with the increase of nickel content was related to the increase in mechanical strength and hot ductility provided by nickel. The high machinability observed in the 30% Ni alloy was related with the presence of calcium inclusions in this alloy, which allowed for significant gains in machinability, but without loss to the evaluated mechanical properties. / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

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>

Cette étude s’inscrit dans le cadre du stockage de l’hydrogène pour des applications mobiles de faibles puissances électriques. Elle a été réalisée dans le cadre du projet FUI HyCAN. L’objectif était la formulation et la fonctionnalisation d’un alliage métallique de structure cubique corps centrée. Ces solutions solides désordonnées sont à base de vanadium qui présente initialement une bonne réactivité vis-à-vis de l’hydrogène.Cependant la thermodynamique du système V-H ne permet pas une utilisation pour des températures inférieures à 40°C, son coût est prohibitif et sa mise en oeuvre en milieu industriel nécessite quelques précautions. Nous avons travaillé sur trois grandes familles d’alliages à base de vanadium. Les alliages de Ti-V-Cr ont été étudiés au rayonnement synchrotron par diffraction X in operando dans le but de comprendre les transformations structurales observables lors de l’hydruration et de les relier à la thermodynamique des composés. Dans unsecond temps, le cahier des charges du projet nous a orienté vers des composites à base de vanadium dans lesquels nous développons une structure intergranulaire permettant une meilleure activation et une déstabilisation contrôlée de l’hydrure pour atteindre des températures de fonctionnement proche de 0°C.L’utilisation du ferro-vanadium en tant que précurseur a motivé l’étude des alliages de type Ti-V-Fe et Ti-V-Fe-Cr. La viabilité des solutions de stockage sur la base de ces matériaux est discutée. Tout au long de ces travaux la relation microstructure/propriété de sorption de l’hydrogène est systématiquement discutée et des modèles empiriques décrivant l’équilibre de l’hydrure sont systématiquement confrontés à la base bibliographique.Enfin, une partie de l’étude est consacrée à l’étude et à la modélisation des réservoirs en condition de fonctionnement, d’un point de vue de la thermique, du respect des normes de sécurité et des contraintes mécaniques générées par le lit de poudre réactif. / This study has been carried out in the framework of solid state hydrogen storage for mobile applications withlow electrical power. It was conducted under the FUI project HyCAN. The objective was to develop andfunctionalize a bcc alloy. Such disordered solid solutions are based on vanadium, which initially has a goodreactivity in relation to hydrogen. However, the thermodynamics of V-H system does not allow applicationsbelow 40 ° C, the cost is prohibitive and its implementation in industrial environments is not straightforward.We worked on three major families of vanadium alloys. Alloys Ti-V-Cr have been studied by in operandosynchrotron radiation X-ray diffraction in order to understand the observable structural transformations that takeplace during hydrogenation and then to link them to the thermodynamics of compounds. In a second step, thespecifications of the project directed us towards vanadium composites in which we develop an intergranularstructure for a better controlled activation and destabilization of the hydride so as to reach operatingtemperatures near 0 ° C. The use of ferro-vanadium as a precursor prompted the study of alloys in the Ti-V-Feand Ti-V-Cr-Fe systems. The viability of storage solutions on the basis of these materials is discussed.Throughout the course of this work the relationship between microstructure and hydrogen sorption properties issystematically discussed and empirical models describing the hydride equilibrium are routinely faced with thebibliographic database.Finally, part of the study is devoted to the study and modeling of reservoirs in operating condition, from thepoint of view of heat exchange, compliance with safety standards and mechanical stresses generated by the bedreactive powder.

L’acier inoxydable est un alliage important pour le développement technique d’une société moderne; cela a été découvert au début du 20ème siècle. Cependant, leur système d'alliage de base, Fe-Cr, est affecté par une lacune de miscibilité à basse température (<600 °C) présent dans le diagramme de phases. Les alliages présentant une lacune de miscibilité dans leur diagramme de phase ont tendance à se décomposer. Ce phénomène également connu sous le nom de "fragilisation à 475 °C", est d’une importance technique, car la décomposition modifie les propriétés mécaniques de ces alliages; dans ce cas présente, par la perte de ductilité et de résistance aux chocs. La tendance à la décomposition augmente avec la diminution de la température, ce qui limite la température de service supérieure à environ 300 °C, limitant ainsi la durée de vie de ces alliages. Étant donné que la fragilisation peut provoquer une défaillance soudaine de ces alliages, cet aspect nuit à leur utilisation en tant que composants structurels dans les secteurs du transport et de l’énergie. La décomposition des alliages Fe-Cr pose un défi aux techniques de caractérisation traditionnelles, car les variations de composition se produisent à l'échelle nanométrique. Par conséquent, la sonde atomique tomographique de pointe a été utilisée pour étudier ces variations de composition à l'échelle atomique en 3D. La modélisation atomistique corrélative a été utilisée pour améliorer davantage la compréhension du processus de décomposition dans ces alliages ; ce modèle était basé sur la théorie de la fonction de densité atomique. Pour émuler la décomposition améliorée du matériau, causée par la température et/ou une charge externe, la décomposition dans ce projet est stimulée par une température de service supérieure à la normale. Dont la nécessité de connaître la limite exacte de la lacune de miscibilité. Ainsi, la nécessité d'évaluer la limite supérieure de température de cette décomposition dans le système Fe-Cr est née de résultats non concluants des analyses de la littérature existant. Par conséquent, un four de haute précision en combinaison avec une sonde atomique tomographique a été utilisé pour étudier la décomposition et l’agglomération dans le système Fe-Cr d’une manière plus précise que jamais. En outre, d’explorer en détail l’emplacement de la limite de la lacune de miscibilité. La décomposition de ces alliages au cours du vieillissement modifie les propriétés mécaniques. Ainsi, en raison de leur utilisation en tant que composants structurels, le comportement de décomposition dû au vieillissement a été étudié, ainsi que le vieillissement dû à la charge externe. Cette dernière situation se rencontre également dans des applications réelles pendant le service, émulées par le vieillissement dû à la pression en utilisant une simple force de traction. Afin d'examiner en détail l'effet de la pression externe, l'orientation du grain par rapport à la direction de traction a été prise en compte lors d'un simple vieillissement thermique et lors de l’application d’une force de traction continue. Ainsi, l'orientation cristallographique et les niveaux de charge ont été pris en compte pour leur effet sur le processus de décomposition/dégradation. / Stainless steel is an important alloy for the technical development of a modern society, they were discovered in the early 20th century. However, their base alloying system, Fe-Cr, is affected by a low temperature (<600°C) miscibility gap present in the phase diagram. Alloys with a miscibility gap in their phase diagram tend to decompose. This phenomenon is also known as the “475°C embrittlement”, it is of technical importance as decomposition alters the mechanical properties of these alloys, in this specific case, by loss of ductility and impact toughness. The tendency to decompose increases with decreasing temperature, restricting the upper service temperature to around 300°C and limiting the service lifetime of these alloys. Because embrittlement can cause sudden failure of these alloys, this phenomenon is detrimental to their use as structural components in transportation and energy industry. The decomposition of Fe-Cr alloys poses a challenge for traditional characterisation techniques, as composition variations occur at the nanoscale. Therefore, the state-of-the-art atom probe tomography have been utilised to study these composition variations at the atomic scale in 3D. Correlative atomistic modelling has been used to further enhance the understanding of the decomposition process in these alloys, this model was based on atomic density function theory. To emulate enhanced decomposition of the material, caused by temperature and/or an external load, decomposition in this work is stimulated by a higher than the normal service temperature. Hence, a need to know the exact limit of the miscibility gap. Thus, a need to evaluate the upper-temperature limit of this decomposition in the Fe-Cr system arose from inconclusive results in the literature. Hence, a high precision furnace in combination with atom probe was utilised to study decomposition and clustering in the Fe-Cr system more accurately than ever before. Furthermore, to explore in detail the location of the limit of the miscibility gap. The decomposition of these alloys during ageing alter the mechanical properties. Thus, due to their use as structural components, the decomposition behaviour during ageing was investigated, as well as ageing during external load. This last situation is also encountered in real applications during service, mimicked by stress-ageing using a simple tensile force. In order to in detail investigate the effect of the external stress, grain orientation with respect to the tensile direction was considered during simple thermal ageing, and during the constantly applied tensile force. Thus, crystallographic orientation and load levels were considered for their effect on the decomposition process.

Stainless steels are very important engineering materials in a variety of applications such as in the food industry and nuclear power plants due to their combination of good mechanical properties and high corrosion resistance. However, ferrite-containing stainless steels are sensitive to the so-called ‘475°C embrittlement’, which is induced by phase separation of the ferrite phase, where it decomposes into Fe-rich ferrite (α) and Cr-rich ferrite (α'). The phase separation is accompanied with a severe loss of toughness. Therefore, the upper service temperature of ferrite-containing stainless steels in industrial applications has been limited to around 250°. In the present work, Fe-Cr based steels were mainly investigated by atom probe tomography. A new method based on the radial distribution function (RDF) was proposed to quantitatively evaluate both the wavelength and amplitude of phase separation in Fe-Cr alloys from the atom probe tomography data. Moreover, a simplified equation was derived to calculate the amplitude of phase separation. The wavelength and amplitude was compared with evaluations using the auto-correlation function (ACF) and Langer-Bar-on-Miller (LBM) method, respectively. The results show that the commonly used LBM method underestimates the amplitude of phase separation and the wavelengths obtained by RDF shows a good exponential relation with aging time which is expected from the theory. The RDF is also an effective method in detecting the phenomena of clustering and elemental partitioning. Furthermore, atom probe tomography and the developed quantitative analysis method have been applied to investigate the influence of different factors on the phase separation in Fe-Cr based alloys by the help of mainly mechanical property tests and atom probe tomography analysis. The study shows that: (1) the external tensile stress during aging enhances the phase separation in ferrite. (2) Phase separation in weld bead metals decomposes more rapidly than both the heat-affected-zone metals and the base metals mainly due to the high density of dislocations in the welding bead metals which could facilitate the diffusion. (3) The results show that Ni and Mn can enhance the phase separation comparing to the binary Fe-Cr alloy whereas Cu forms clusters during aging. (4) Initial clustering of Cr atoms was found after homogenization. Two factors, namely, clustering of Cr above the miscibility gap and clustering during quenching was suggested as the two responsible mechanisms. (5) The homogenization temperatures significantly influence the evolution of phase separation in Fe-46.5at.%Cr. / <p>QC 20140910</p> / Spinodal Project