The need for environmentally friendly and energy efficient high temperature components that can operate under mechanical and/or thermal stress has prompted interest in the development of Fe-Cr-Al based alloys. These alloys have been widely investigated, because of their ability to form a protective layer of a - Al203, which is able to withstand further oxidation degradation. However, despite their superior oxidation qualities, alpha-alumina scales are highly susceptible to mechanical damage when subjected to aggressive environments. The origins of such failure can be attributed to the generation and relaxation of stresses during the scaling process. As such, this study has experimentally investigated the interaction between oxidation and stress on Fe-Cr-Al based alloy, Kanthal Al. Oxidation experiments of Kanthal Al were conducted in two parts. First, the alloy's scaling process at rest with respect to intrinsic growth stress and oxide morphology was examined. Second, external stress was applied during oxidation to obtain a comprehensive understanding of its effect on scale growth with comparison to experiments conducted without stress. The formation of compact α - Al203 scales was accompanied by compressive growth stresses on the order of 1 GPa. Prolonged oxidation decreased growth stresses resulting in increased scale porosity. Maximum scale porosity occurred under oxidation at 1300°C. Consequently, the protectiveness of the scale was heavily degraded, as indicated by scale morphology, implying that in-service operation at this temperature or above would be detrimental. Applied tensile stress showed a significant decrease in the development of intrinsic growth stress, suggesting a strong interdependency between scale growth stress and creep deformation at high temperature. There was no measurable change in the scale growth rate, as compared to experiments conducted at rest. Possible explanations include insufficient tensile load and/or drastic increase in spallation/rehealing, both of which simultaneously influences the lifetime of a material under aggressive operational conditions. / Thesis / Master of Applied Science (MASc)

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Classically 13% Cr is required for stable passivity of steel in acidic and neutral solutions. Some authors (Mansfeld, Fujimoto) have published potential cycling procedures that generate thick Cr-rich films. Fujimoto cycles right to the transpassivity potential and back in H2SO4 solution. Our idea is to work close to the reactivation potential where the passive film (Fe2O3) is reductively dissolved to Fe2+. While using an equimolar acetate buffer (pH 4.7), we have obtained new insights into the reactivation process. It is under a kind of thermodynamic control, in that the film cannot be reduced, and the metal cannot be dissolved, faster than would exceed the equilibrium concentration of Fe2+ at the electrode surface. Reductive dissolution leads to gel-like Cr-rich film, but Fe dissolution occurs through it, if formed in a single step. However alternating formation and reductive dissolution of a Fe-rich film assist the formation of a more robust Cr-rich film

Classically 13% Cr is required for stable passivity of steel in acidic and neutral solutions. Some authors (Mansfeld, Fujimoto) have published potential cycling procedures that generate thick Cr-rich films. Fujimoto cycles right to the transpassivity potential and back in H2SO4 solution. Our idea is to work close to the reactivation potential where the passive film (Fe2O3) is reductively dissolved to Fe2+. While using an equimolar acetate buffer (pH 4.7), we have obtained new insights into the reactivation process. It is under a kind of thermodynamic control, in that the film cannot be reduced, and the metal cannot be dissolved, faster than would exceed the equilibrium concentration of Fe2+ at the electrode surface. Reductive dissolution leads to gel-like Cr-rich film, but Fe dissolution occurs through it, if formed in a single step. However alternating formation and reductive dissolution of a Fe-rich film assist the formation of a more robust Cr-rich film

The oxidation behavior of model binary and ternary alloys in supercritical water (SCW) was examined. Binary alloys contained 9 or 14 at% Cr. Ternary alloys had 1.5 at% of one of the following elements: Si, Al, V, Mn or Ti. Samples with different surface finishes were exposed to SCW for up to 500 hours. The oxidized samples were characterized using gravimetry, SEM, HRTEM and EDX. After exposure, a uniform double layer oxide with outwardly grown magnetite inwardly grown Fe-Cr mixed oxide was detected on most of samples. Alloys contains 14 at% Cr or/and 1.5 at% Si showed a mixed oxidation mode, where relatively thick double layer oxides coexisted with thin protective oxide. The coverage with the thin oxide increased with the increase of deformation and/or Cr and/or Si content. A 20 nm thick Si-enriched layer was detected at such alloy/oxide interfaces. This behavior is very similar to “third element effect”.

The oxidation behavior of model binary and ternary alloys in supercritical water (SCW) was examined. Binary alloys contained 9 or 14 at% Cr. Ternary alloys had 1.5 at% of one of the following elements: Si, Al, V, Mn or Ti. Samples with different surface finishes were exposed to SCW for up to 500 hours. The oxidized samples were characterized using gravimetry, SEM, HRTEM and EDX. After exposure, a uniform double layer oxide with outwardly grown magnetite inwardly grown Fe-Cr mixed oxide was detected on most of samples. Alloys contains 14 at% Cr or/and 1.5 at% Si showed a mixed oxidation mode, where relatively thick double layer oxides coexisted with thin protective oxide. The coverage with the thin oxide increased with the increase of deformation and/or Cr and/or Si content. A 20 nm thick Si-enriched layer was detected at such alloy/oxide interfaces. This behavior is very similar to “third element effect”.

Generation and migration of helium and other point defects under irradiation causes ferritic steels based on the Fe-Cr system to age and fail. This is motivation to study point defect migration and the He equation of state using atomistic simulations due to the steels' use in future reactors. A new potential for the Fe-Cr-He system developed by collaborators at the Lawrence Livermore National Laboratory was validated using published experimental data. The results for the He equation of state agree well with experimental data. The activation energies for the migration of He- and Fe-interstitials in varying compositions of Fe-Cr lattices agree well with prior work. This research did not find a strong correlation between lattice ordering and interstitial migration energy

[pt] A crescente demanda mundial por energia e a necessidade do controle de emissão de gás carbônico (CO2), principal gás responsável pelo aquecimento global, exigem o desenvolvimento de novas tecnologias para a produção de energia com menor emissão de CO2. O uso de fontes alternativas na produção energética está aumentando, mas não é suficiente para suprir a demanda, portanto o uso de combustíveis fósseis ainda é necessário. Neste contexto, o uso da oxicombustão em usinas a carvão em conjunto com a captura e sequestro de carbono (CCS) surge como uma alternativa às usinas convencionais a carvão, pois não emite CO2 na produção de energia. O processo de oxicombustão difere basicamente do convencional pela queima de O2 puro e gás reciclado ao invés de ar. Com isso uma atmosfera rica em CO2 e H2O é formada no boiler, podendo aumentar a corrosão dos materiais em contato com o gás. Este trabalho teve como objetivo investigar o comportamento em corrosão em alta temperatura de ligas de ferro submetidas a condições simples e duplas em atmosferas ricas em CO2. Ligas experimentais e comerciais de ferro com diferentes teores de cromo, cobalto e carbono foram expostas a atmosferas contendo CO2, H2O e SO2 a 600 graus Celsius durante 1000 horas. As amostras foram analisadas em condição simples, onde a amostra é exposta a um mesmo gás em todas as faces e em condição dupla onde a amostra é exposta a vapor d água de um lado e um gás do outro, criando um gradiente de hidrogênio na amostra. As amostras foram caracterizadas por MEV, MET, EDS e microscópio ótico. Os resultados demonstraram que há maior corrosão em condição dual que em condição simples. A maioria das ligas experimentais apresentaram menor oxidação que o aço comercial VM12 em atmosferas ricas em CO2. Entretanto o aço VM12 apresentou melhores resultados quando exposto ao vapor d água. / [en] The world s increasing demand for energy and the need to control carbon dioxide (CO2) emissions, the main gas responsible for global warming, requires development of new technologies to produce energy with lower CO2 emission. Use of alternative renewable sources in energy production is increasing, but not enough to meet the demand. Thus, fossil fuel is still necessary. In this context, oxyfuel together with carbon capture and sequestration (CCS) arises as an alternative to conventional coal-fired power plants, because it does not emit CO2 during energy production. The oxyfuel process differs from the conventional process by burning pure O2 and recycled fuel gas instead of air. Therefore, a CO2-H2O-rich atmosphere is formed in the boiler, increasing the materials corrosion in contact with this atmosphere. The objective of this work was to investigate the high temperature corrosion behavior of iron alloys subjected to single and dual conditions in CO2-rich atmospheres. Model and commercial iron alloys with different chromium, cobalt and carbon content were exposed to atmospheres containing CO2, H2O and SO2 at 600 Celsius degrees for 1000 hours. The samples were analyzed in single atmosphere condition, when all sample faces were exposed to the same gas, and in dual atmosphere condition where the samples were exposed to water vapor on one side, to a gas on the other, creating an hydrogen gradient in the sample. The samples were characterized using TEM, SEM, EDS and light microscope. Results showed different corrosion rates according to chemical composition and microstructure of the samples and gases. Results showed that corrosion is higher in dual condition than in single condition. Most of the model alloys presented less corrosion than commercial steel VM12 in CO2-rich atmospheres. However, steel VM12 presented better results when exposed to water vapor.

Les aciers ferrito-martensitiques sont d’excellents candidats potentiels en tant que matériaux de structure dans les futurs réacteurs de fusion. A ce titre, ils devront résister à des flux intenses de neutrons de 14 MeV qui créeront des cascades de déplacements atomiques et des produits de transmutation tels que l’hélium. Afin de mieux comprendre le comportement de base de ces aciers sous irradiation en présence d’hélium, nous avons étudié les effets de l’hélium et ceux du chrome dans le cadre de ce travail de thèse. Du fer pur et un alliage modèle Fe-5,4%pds Cr ont ainsi été irradiés dans la plateforme JANNuS à 500°C en bi-faisceau avec des ions Fe+ et He+ et en mono-faisceau avec des ions Fe+. L’utilisation de cette plateforme a permis de suivre l’évolution du dommage jusqu’à des doses faibles (1 dpa) et de caractériser la microstructure après irradiation à forte dose (100 dpa). Elle a également permis l’observation in situ dans un MET couplé à deux accélérateurs des effets cinétiques d’implantation/irradiation. La nature et la répartition des défauts d’irradiation ont été déterminés : ce sont essentiellement des boucles de dislocations de vecteur de Burgers de type a<100> et des cavités/bulles. Nous avons montré que la co-implantation d’hélium et l’addition de chrome réduisent la mobilité des boucles. Par ailleurs, avec ou sans hélium, l’addition de chrome réduit le gonflement dans toutes les conditions étudiées. De plus, dans le fer pur irradié avec hélium, un phénomène original de germination hétérogène de cavités/bulles dans les plans des boucles a été mis en évidence. Enfin, nous avons également utilisé le code de dynamique d’amas CRESCENDO pour interpréter les résultats expérimentaux dans le fer pur irradié avec hélium. / Ferritic-martensitic steels are excellent potential candidates for a use as structural materials in future fusion reactors. For this application, they will have to withstand high fluxes of 14 MeV neutrons that will create atomic displacement cascades and transmutation reactions which will produce large quantities of helium. In order to understand the basic mechanisms under irradiation with helium, we have studied the effects of helium and those of chromium. Pure iron and a Fe-5.4 wt. % Cr model alloy were irradiated at the JANNuS platform in dual-beam mode with Fe+ and He+ ions and in single-beam mode with Fe+ ions at 500ºC. This platform enabled us to follow the evolution of damage up to low doses (1 dpa) and to characterize the microstructure at high doses (100 dpa). It also allowed us to observe in situ irradiation/implantation kinetic effects in a TEM coupled to two accelerators. The nature and distribution of irradiation defects was determined: they are essentially dislocation loops with a<100> Burgers vectors and cavities/bubbles. We have demonstrated that the co-implantation of helium and the addition of chromium both reduce the mobility of dislocation loops. The addition of chromium reduces swelling for all the irradiation conditions studied, with or without helium. In pure iron irradiated with helium, an original phenomenon was discovered for the first time: cavities/bubbles nucleate heterogeneously on the planes of the dislocation loops. We have also interpreted our experimental results in pure iron irradiated with helium using the cluster dynamics code CRESCENDO.

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.