Pesquisas anteriores sobre aÃos ferrÃticos experimentais com alto teor de molibdÃnio (Mo) constataram que embora o Mo seja responsÃvel por aumentar a resistÃncia à corrosÃo em meios ricos em Ãcidos naftÃnicos e em complexos de enxofre, teores acima de 5% Mo favorecem a formaÃÃo de fases deletÃrias e reduzem a tenacidade do aÃo. Para melhorar a tenacidade dessas ligas, mantendo-se a estabilidade da fase ferrÃtica, o presente trabalho adicionou nÃquel (Ni) à composiÃÃo, elevou o teor de cromo (Cr) para 25% e manteve o elevado teor de Mo. Essas novas ligas pertencem a uma famÃlia de aÃos denominados aÃos inoxidÃveis superferrÃticos, desenvolvidos inicialmente para uso em trocadores de calor e ambientes marinhos. Este trabalho faz parte de um estudo para adaptar a composiÃÃo de aÃos superferrÃticos comerciais para utilizaÃÃo em plantas petrolÃferas que refinam petrÃleos ricos em compostos de enxofre atravÃs do aumento do teor de Mo na liga. A cinÃtica de precipitaÃÃo de fases em ligas com composiÃÃes experimentais (Fe25%Cr5-7%Mo2-4%Ni) com adiÃÃo de niÃbio (Nb) e titÃnio (Ti) foi estudada para temperaturas de 400ÂC a 900ÂC em diferentes tempos de tratamento. Foi realizado o estudo termodinÃmico das ligas empregando o Thermo-Calc para determinar a temperatura de estabilidade da fase ferrÃtica e identificar as possÃveis fases intermetÃlicas precipitadas em condiÃÃes de equilÃbrio. As ligas foram envelhecidas a 400 e 475ÂC para estudar a precipitaÃÃo da fase alfa linha (αâ) e seus efeitos nas propriedades mecÃnicas, magnÃticas e de resistÃncia à corrosÃo. Foram realizados tratamentos isotÃrmicos de 600 a 900ÂC para estudar a cinÃtica de precipitaÃÃo das fases intermetÃlicas. As alteraÃÃes microestruturais, nas propriedades mecÃnicas e na resistÃncia à corrosÃo devido a variaÃÃo da composiÃÃo e do tratamento tÃrmico foram estudadas. Os resultados obtidos nas ligas experimentais tratadas a 400 e 475ÂC indicaram aumento na dureza e reduÃÃo da fase ferrita, acompanhada de aumento da suscetibilidade a corrosÃo por pite sendo mais crÃtico a 475ÂC, com melhor desempenho observado para a liga 5Mo4Ni. Para as amostras tratadas de 600 a 900ÂC a liga 7Mo2Ni apresentou a menor quantidade de fases deletÃrias precipitadas e menor suscetibilidade a corrosÃo por pite. Ocorreu precipitaÃÃo de austenita para as ligas contendo 4%Ni tratadas a 800ÂC e 900ÂC. A liga 7Mo4Ni apresentou pior desempenho comparada Ãs outras ligas experimentais em todas as condiÃÃes estudadas. / Previous research on experimental ferritic steel with high Mo content showed that Mo increases the resistance to naphthenic corrosion and sulfur complexes. However, Mo content above 5 wt% favored the formation of deleterious phases and reduced the toughness of the steel. To improve the toughness of these alloys and keep the ferrite phase stable, was added Ni, increased Cr content to 25% and maintained high Mo content. These new alloys belong to a family of steels known as superferritic stainless steels. They were originally developed for use in heat exchangers and marine environments. There is a current trend to use these alloys in the oil industry driving the research on the effect of the increase of Mo content on the microstructure of these steels. The kinetics of phase precipitation in experimental compositions (Fe25%Cr 5-7%Mo 2-4%Ni) with addition of Nb and Ti will be investigated for temperatures from 400  C to 900  C for different treatment times. In this first stage, Thermo-Calc software was used to determine the temperature stability of the ferritic phase and to identify possible intermetallic phases precipitated at thermodynamic equibrium. The alloys were aged at 400 and 475ÂC for study the alfa prime phase precipitation and their effects on the mechanical, magnetic and corrosion properties. Isothermal treatments were carried out 600 ÂC to 900  C to study the kinetics of precipitation of intermetallic phases. The microstructural changes on the mechanical and corrosion properties due to variation in composition and heat treatment were studied. The results obtained in the experimental alloys treated at 400 and 475ÂC indicated an increase in hardness, while wt% of ferrite had decreased, accompanied by increased susceptibility to pitting corrosion, the best performance observed for 5Mo4Ni alloy these conditions. For samples treated 600 to 900ÂC the 7Mo2Ni alloy showed the smallest amount deleterious phase precipitated and less susceptibility to pitting corrosion. Austenite phase precipitation occurred for the alloys containing 4%Ni treated at 800ÂC and 900ÂC. The 7Mo4Ni alloy showed worse performance compared to other experimental alloys in all conditions studied.

O presente trabalho teve como objetivo o estudo do estado sólido do ganciclovir (GCV) e suas diferentes formas polimórficas. O GCV é um fármaco antiviral útil no tratamento de infecções por citomegalovírus (CMV). Embora seja um fármaco amplamente usado, poucos estudos têm sido realizados sobre seu estado sólido. Atualmente, o GCV é conhecido por apresentar quatro formas cristalinas, duas anidras (Forma I e II) e duas hidratas (III e IV). Neste trabalho, nós reportamos a solução da estrutura cristalográfica da Forma I do GCV, que foi encontrado durante o screening de cristalização do fármaco, em que nove ensaios de cristalização (GCV-1, GCV-A, GCV-B, GCV-C, GCV-D, GCV-E, GCV-F, GCV-G e GCV-H) foram realizados e os materiais resultantes foram caracterizados por Difratometria de raios X (DRX), análise térmica (DTA/TG) e Hot Stage Microscopy. De todas as cristalizações realizadas foram obtidas quatro formas sólidas, denominadas como Forma I (GCV-1, GCV-B e GCV-H), Forma III (GCV-C, GCV-D, GCV-F e GCV-G), Forma IV (GCV-A) e Forma V (GCV-E). Esta última está sendo descrita pela primeira vez na literatura e indica a presença de outra forma hidratada de GCV. As Formas I, III e IV corresponderam a forma anidra e as duas formas hidratadas do fármaco, respectivamente. Além disso, foi evidenciado por experimentos de conversão de slurry e análise térmica que o cristalizado de GCV-1 (Forma I) foi o mais estável entre os materiais obtidos, e este deu origem ao monocristal da Forma I de GCV, estrutura cristalina anidra do fármaco. Neste trabalho, pela primeira vez, a estrutura cristalina deste composto foi definida por cristalografia de raios X de monocristal. A análise estrutural mostrou que a Forma I do fármaco cristaliza no grupo espacial monoclínico P21/c e está composta por quatro moléculas de GCV na sua unidade assimétrica. Cada molécula está unida intermolecularmente por ligações de hidrogênio, que dão lugar à formação de cadeias infinitas e estas por sua vez se arranjam de maneira a formar uma estrutura tridimensional. / This presented work aims to study the solid state of ganciclovir (GCV) and its different polymorphic forms. GCV is an antiviral drug useful in the treatment of cytomegalovirus (CMV) infections. Although it is a widely-used drug, few studies have been conducted on its solid state. Currently, GCV is known to have four crystalline forms, two anhydrous (Form I and II) and two hydrates (III and IV). In this investigation, we report a successful preparation of GCV Form I and its crystallographic structure, which was found during the crystallization of the drug, in which nine crystallization tests (GCV-1, GCV-A, GCV-B, GCV- D, GCV-E, GCV-F, GCV-G and GCV-H) were performed and the resulting materials were characterized by X-ray diffractometry (XRD), thermal analysis (DTA/TG) and Hot Stage Microscopy. Of all the crystallizations performed, four solid forms were obtained, denoted as Form I (GCV-1, GCV-B and GCV- H), Form III (GCV-C, GCV-D, GCV-F and GCV-G), Form IV (GCV-A) and Form V (GCV-E). The latter is being described for the first time in the literature and indicates the presence of another hydrated form of GCV. Forms I, III and IV corresponded to the anhydrous form and the two hydrated forms of the drug, respectively. In addition, it was evident by both the slurry conversion and the thermal analysis methods that the GCV-1 crystallized (Form I) was indeed the most stable amongst the materials obtained. This gave rise to GCV Form I monocrystal, anhydrous crystalline structure of the drug. The compound was characterized by monocrystal X-ray crystallography. The structural analysis showed that Form I of the drug crystallized in the monoclinic system space group P21/c is composed of four molecules of GCV in its asymmetric unit. Each molecule is linked intermolecularly by hydrogen bonds, which give rise to the formation of infinite chains arranged in a way that form a three-dimensional structure.

Previous experimental observations have shown that the pseudoelastic response of NiTi shape memory alloys (SMA) is localized in nature and proceeds through nucleation and propagation of localized deformation bands. It has also been observed that the mechanical response of SMAs is strongly affected by loading rate and cyclic degradation. These behaviors significantly limit the accurate modeling of SMA elements used in various devices and applications. The aim of this work is to provide engineers with a constitutive model that can accurately describe the dynamic, unstable pseudoelastic response of SMAs, including their cyclic response, and facilitate the reliable design of SMA elements. A 1-D phenomenological model is developed to simulate the localized phase transformations in NiTi wires during both loading and unloading. In this model, it is assumed that the untransformed particles located close to the transformed regions are less stable than those further away from the transformed regions. By consideration of the thermomechanical coupling among the stress, temperature, and latent heat of transformation, the analysis can account for strain-rate effects. Inspired by the deformation theory of plasticity, the 1-D model is extended to a 3-D macromechanical model of localized unstable pseudoelasticity. An important feature of this model is the reorientation of the transformation strain tensor with changes in stress tensor. Unlike previous modeling efforts, the present model can also capture the propagation of localized deformation during unloading. The constitutive model is implemented within a 2-D finite element framework to allow numerical investigation of the effect of strain rate and boundary conditions on the overall mechanical response and evolution of localized transformation bands in NiTi strips. The model successfully captures the features of the transformation front morphology, and pseudoelastic response of NiTi strip samples observed in previous experiments. The 1-D and 3-D constitutive models are further extended to include the plastic deformation and degradation of material properties as a result of cyclic loading. / Applied Science, Faculty of / Mechanical Engineering, Department of / Graduate

Ce travail a porté sur l'étude des phases métastables de l'alliage à mémoire de forme CuAlBe sous différents types de sollicitations mécaniques et thermiques par diffraction des neutrons. Il a permis de définir un protocole expérimental de caractérisation des transformations des phases métastables caractéristiques de l'effet mémoire de forme et de la superélasticité. Après élaboration par filage à chaud suivi d'une trempe à l'eau, le matériau est entièrement austénitique β1. Sa microstructure est composée de grains de taille relativement importante, de l'ordre de 400 µm. Ce procédé de fabrication génère une texture cristallographique de type fibre partielle <001>. L'étude de la superélasticité lors d'un essai de traction à température ambiante a mis en évidence le comportement pseudoélastique de l'alliage. L'étude de l'évolution des microdéformations a permis de mettre en avant la forte hétérogénéité de comportement du plan (400). Le pic de diffraction de ce plan présente également un fort élargissement dû aux fautes d'empilements qui est directement à relier à la transformation de phase de l'austénite en martensite. La martensite β'1 de structure monoclinique 18R complexe a été affinée à l'aide d'un modèle de type 6M. Ce modèle permet de rendre compte au mieux de la faible périodicité des fautes d'empilement caractéristiques de cette phase métastable à notre échelle d'analyse caractéristique d'un volume de l'ordre du centimètre cube. Après déformation plastique, la texture cristallographique du matériau a fortement évoluée. Le laminage à froid fait disparaitre la fibre partielle <001>. Aux plus forts taux de déformation plastique par laminage à chaud, la fibre <111> apparait. Cette forte déformation affecte également l'orientation des lattes de martensite. D'autre part, les températures des transformations de phases ainsi que l'hystérésis sont modifiées. Cependant, la structure cristallographique de la martensite générée par déformation plastique est identique à celle obtenue par refroidissement pour notre échelle d'observation. L'étude du retour à l'équilibre des phases métastables après recuit à haute température suivi d'une trempe sur un échantillon déformé plastiquement a montré la disparition totale de la martensite et l'apparition des phases stables α et γ2 pour des températures de recuit entre 500°C et 600°C. Au-delà de 600°C, ces deux phases disparaissent au profit de la phase β. On observe alors un fort grossissement du grain. La texture cristallographique est de nouveau caractérisée par la fibre partielle <001>. / This work deals with the study of metastable phases of CuAlBe shape memory alloy under mechanical and thermal solicitations by neutron diffraction. It enables to define an experimental protocol of characterization of metastable phase transformation.The raw material is fully austenitic at room temperature. Its microstructure is composed by huge grain size, close to 400 µm. The crystallographic texture is characterized by a <001> partial fibber.The study of the superelasticity during a tensile test at room temperature demonstrated the pseudoelastic behaviour of this material. The evolution of microdeformations showed the heterogeneous behaviour, especially for the (400) plane in axial direction. The diffraction peak of this plane family also has an important increase of the width. This increase can be linked to the transformation of the austenite into martensite.The crystallographic structure of the monoclinic martensite β'1 has been refined using the 6M model. This model enables to report the relatively low periodicity of stacking faults characterizing the martensitic transformation.After plastic deformation, the crystallographic texture evolved. The <001> partial fibber disappears. For the larger deformation rates, the <111> fibber appears.This large deformation also affects the martensite variant orientation and modifies the temperature of phase transformation.The return into equilibrium of metastable phases after annealing treatments between 500°C and 600°C followed by a quenching at room temperature on a plastically deformed sample has shown the disappearance of martensite and the growth of α and γ2 stable phases. Beyond 600°C, the grains grow largely. The crystallographic texture is characterized by the <001> partial fibber.

The operating efficiency and reliability of modern jet engines have undergone significant improvement largely owing to the advances of the materials science over the past 60 years. The use of both superalloys and TBCs in engine components such as turbine blades has made it possible for jet engines to operate at higher temperatures, allowing an optimal balance of fuel economy and thrust power. Despite the vast improvement in high temperature capability of superalloys, the utilization of TBCs has brought the concern of coating adhesion during their usage. TBCs are prone to spallation failure due to interfacial rumpling, which is driven primarily by thermal coefficient mismatch of the multi-layered structure. Although interfacial degradation of TBCs has been widely studied by detailed numerical and analytical models, the predicted results (i.e. stress state and rumpling amplitude) often deviate from that obtained by experiments. This is largely due to the lack of consideration of the influence of bond coat and substrate chemistry on the interfacial evolution of TBC systems. It is only in recent year that more and more study has been focused on studying the role of chemistry on the interfacial degradation of TBCs. The purpose of this PhD project is to clarify how the bond coat and substrate chemical compositions dictate the mechanisms of interfacial degradation, leading to the final spallation. A cross-sectional indentation technique was utilized to quantitatively characterize the adhesion of oxide-bond coat interface among 5 systematically prepared TBC systems. The adhesion of isothermally exposed oxide-bond coat interface was then correlated with different microstructure parameters, in an attempt to identify the key parameters controlling the TBC spallation lifetime. EBSD and EPMA analyses were conducted on the bond coat near the oxide-bond coat interface, in order to understand the relationship between the key parameters and specific alloying elements. The results clearly demonstrated that the phase transformation of bond coat near the oxide-bond coat interface plays the dominant role in the degradation of interfacial adhesion. Particularly, the co-existence of gamma prime and martensitic phases, each having very different thermomechanical response under thermal exposure, can generate a misfit stress in the TGO layer, and ultimately causes early TBC spallation. In addition, the phase transformation behavior has been closely associated with the inherent chemistry of the bond coat and substrate.

Objective: The goal of the present study was to investigate the effect of chairside surface treatments on biaxial flexural strength and subsurface damage of monolithic zirconia ceramics. Methods: Specimens (15x15x1.2 mm3) were prepared by sectioning from commercially available zirconia blanks (BruxZirTM) and sintering according to manufacturer's recommendations. Fully dense specimens were randomly divided into five groups (n=30) and treated as follows; 1) as-sintered (AS) 2) air abraded with 50 μm alumina fine particles (AAF), 3) air abraded with 250 μm coarse alumina particles (AAC), 4) ground (G), and 5) ground and polished (GP) to mimic chairside and dental laboratory treatments. Microstructural changes were thoroughly characterized by optical and scanning electron microscopy, surface profilometry and atomic force microscopy. Crystalline phases and their depth profile were investigated by x-ray diffraction (XRD) and grazing incidence x-ray diffraction (GIXRD). Results were analyzed by Kruskal-Wallis test and Tukey's adjustment for multiple comparisons. A 0.05 level of significance was used. Reliability was evaluated by Weibull analysis. Results: All treatment groups exhibited a significant difference in mean surface roughness (Rq) compared to the as-sintered group (p<0.05). The AAC group showed the highest surface roughness at 1.08 ± 0.17 μm, followed by the G, AAF and AS groups. The GP group exhibited the lowest surface roughness. The group air abraded with fine particles showed the highest mean biaxial flexural strength (1662.62 ± 202.58 MPa), but was not different from the ground and polished group (1567.19 ± 209.76 MPa). The groups air abraded with coarse particles or ground with diamond bur exhibited comparable mean biaxial flexural strength at 1371.37 ±147.62 MPa and 1356.98 ±196.77 MPa, respectively. The as-sintered group had the lowest mean biaxial flexural strength at 1202.29 ±141.92 MPa. The depth of compressive stress layer, measured by GIXRD was approximately 50 μm in the AAF group, followed by the AAC group with ~35 μm, ~10 μm for the ground group and ~5 μm for the ground and polished group. Deep subsurface cracks were observed in the AAC group (~80 μm in depth) and G group (~25 μm in depth), whereas shallower flaws were present in the AAF and GP groups at 10 and 3 μm, respectively. Weibull analysis represented a greater reliability in zirconia specimens treated with air abrasion groups. Conclusions: Surface treatments induced the t-m transformation in 3Y-TZP and associated development of compressive stresses to a depth that varied with the severity of the treatment performed. GIXRD revealed that AAF led to the thickest compressive stress layer, followed by AAC, G and GP. SEM revealed that subsurface damage was most severe with AAC, followed by G, AAF and GP. We propose that the flexural strength results can be explained by the difference between the depth of the compressive stress layer induced by the transformation and the depth of the subsurface flaws.

The relatively low oxidation resistance and subsequent surface embrittlement have often limited the use of titanium alloys in elevated temperature structural applications. Although extensive effort is spent to investigate the high temperature oxidation performance of titanium alloys, the studies are often constrained to complex technical titanium alloys and neither the mechanisms associated with evolution of the oxide scale nor the effect of oxygen ingress on the microstructure of the base metal are well-understood. In addition lack of systematic oxidation studies across a wider domain of the alloy composition has complicated the determination of composition-mechanism-property relationships. Clearly, it would be ideal to assess the influence of composition and exposure time on the oxidation resistance, independent of experimental variabilities regarding time, temperature and atmosphere as the potential source of error. Such studies might also provide a series of metrics (e.g., hardness, scale, etc) that could be interpreted together and related to the alloy composition. In this thesis a novel combinatorial approach was adopted whereby a series of compositionally graded specimens, (Ti-xMo, Ti-xCr, Ti-xAl and Ti-xW) were prepared using Laser Engineered Net Shaping (LENS™) technology and exposed to still-air at 650 °C. A suite of the state-of-the-art characterization techniques were employed to assess several aspects of the oxidation reaction as a function of local average composition including: the operating oxidation mechanisms; the structure and composition of the oxides; the oxide adherence and porosity; the thickness of the oxide layers; the depth of oxygen ingress; and microstructural evolution of the base material just below the surface but within the oxygen-enriched region. The results showed that for the Ti-Mo, Ti-Al and Ti-W systems a parabolic oxidation rate law is obeyed in the studied composition-time domain while Ti-Cr system experiences a rapid breakaway oxidation regime at low solute concentrations. The only titanium oxide phase present in the scale for all the binary systems was identified as rutile (TiO2) and formation of multiphase oxide scales TiO2+Al2O3 in Ti-Al system and TiO2+TiCr2 in Ti-Cr system was observed. A thermodynamic framework has been used to rationalize the oxygen-induced subsurface microstructural transformations including: homogeneous precipitation of nano-scaled β particles and discontinuous precipitation of +β phases in Ti-Mo and Ti-W system, evolution of TiCr2 intermetallic phase in Ti-Cr system and ordering phase transformation in Ti-Al system.

Two austenitic stainless steels of strongly different stacking fault energies (SFEs) and correspondingly different stabilities of the austenite phase were studied with respect to their very high cycle fatigue (VHCF) behavior. The metastable austenitic stainless steel 304L shows a very pronounced transient behavior and a fatigue limit in the VHCF regime. The higher SFE of the 316L steel results in a less pronounced transient cyclic deformation behavior. The plastic shear is more localized, and the formation of deep intrusions leads to microcrack initiation. However, the propagation of such microcracks is impeded by α'-martensite formed very localized within the shear bands. A comprehensive description of the microstructural changes governing the cyclic deformation including the transient resonant behavior was developed and transferred into a mechanism-based model. Simulation results were correlated with the observed deformation evolution and the change of the resonant behavior of specimens during VHCF loading providing a profound understanding of the VHCF-specific deformation behavior.

La fragilisation des aciers de cuve des réacteurs nucléaires sous irradiation aux neutrons est le facteur limitant la durée de vie des centrales nucléaires françaises. Ceci est dû au mouvement des dislocations qui se trouve être entravé par des amas de Cu, P, Si, Mn et Ni. Plus particulièrement, les amas induits de Mn et de Ni sont à l'origine d'un durcissement significatif à forte dose. Afin de prédire la dégradation des propriétés mécaniques, les expériences sont généralement réalisées à l'aide d'accélérateurs de particules. Cependant, les flux d'irradiation atteints sont compris entre 10⁻⁴ 10 ⁻ ⁶ dpa/s⁻ ¹, tandis qu'il est limité à 10⁻ ¹ ⁰ dpa/s⁻ ¹ dans les réacteurs de puissance actuels. Ce point est essentiel étant donné que le dommage d'irradiation dépend du flux de particules incidentes. La transférabilité ion/neutron constitue donc la problématique centrale. Celle-ci a été étudiée dans les alliages austénitiques seulement. Ce travail de thèse se propose donc d'étudier, dans des alliages ferritiques, l'effet du flux d'irradiation sur l'endommagement dans deux alliages différents : le Fe-Ni et le Fe-Mn, dans le but d'évaluer également l'effet de chaque soluté sur la microstructure obtenue après irradiation.Les alliages ont été analysés expérimentalement par Microscopie Electronique en Transmission (TEM), Microscopie Electronique à Balayage par Transmission (STEM) couplée à l'Analyse Dispersive en Energie des Rayons-X (EDS) et à la Spectroscopie de Perte d'énergie des Electrons (EELS), ainsi que par Sonde Atomique Tomographique (APT).Les irradiations ont été réalisées avec des ions Fe³⁺ de 2 MeV et des ions Fe⁹⁺ de 27 MeV, à 400°C, à des taux de dommage de 10⁻⁴ et 10⁻ ⁶ dpa/s⁻ ¹ respectivement, jusqu'à un même dommage de 1.2 dpa.Les résultats obtenus montrent que le Ni et le Mn ont des comportements sous irradiation très différents en termes de nature de nano-défauts créés.Des irradiations aux particules légères ont également été réalisées de manière à apprécier l'effet des cascades de déplacement.Enfin, une irradiation séquentielle, en deux étapes, a été effectuée à l'aide d'ions Fe⁹⁺ à température ambiante, puis de protons à 400°C, dans le but d'isoler la contribution au durcissement des amas de défauts ponctuels de celle des zones enrichies en soluté. / Reactor pressure vessel (RPV) steel embrittlement under neutron irradiation is the main lifetime limiting factor of nuclear reactors. This is due to the impeding of dislocation glide by nanometric clusters composed of Cu, P, Si, Mn and Ni. More specifically, radiation induced Mn and Ni enriched clusters cause a significant hardening at high dose. To predict this change in mechanical properties, particle accelerator based experiments are conducted. However, the achieved flux ranges between 10⁻⁴ and 10 ⁻ ⁶ dpa/s⁻ ¹, whereas it is limited to 10⁻ ¹ ⁰ dpa/s⁻ ¹ in modern nuclear power technologies. This point is of high importance since radiation damage highly depends on irradiation flux. The reproducibility ion-neutron is thus the key point. It has been studied in austenitic steels but little is known regarding any dose rate dependence in ferritic alloys. Therefore, this thesis focuses on the effect of ion fluxes on radiation damage in two different alloys : Fe-Ni and Fe-Mn in order to investigate, additionally, the effects of each solute on the microstructure after irradiation.The alloys were experimentally investigated using conventional Transmission Electron Microscopy, Scanning Transmission Electron Microscopy coupled to Energy Dispersive X-ray Spectroscopy and Electron Energy Loss Spectroscopy and by Atom Probe Tomography.Irradiations were performed with 2 MeV Fe³⁺ ions and 27 MeV Fe⁹⁺ ions at 400°C at a nominal damage rate of 10⁻⁴ and 10⁻ ⁶ dpa/s respectively, up to a nominal displacement damage of 1.2 dpa. The detailed analysis shows that Ni and Mn behave in a very different way in terms of nano-defects formed under irradiation.Besides, light particle irradiations were also performed in order to ascertain the cascade effects.Finally, a two-series irradiation was carried out using Fe ions at room temperature and protons at 400°C, to isolate the contribution of point defect clusters to hardening from that of solute enriched zones.

L’allègement dans le secteur de l’automobile revête un enjeu important du fait de normes d’émission de CO2 de plus en plus drastiques, de la nécessité de réduire la consommation en carburant des véhicules et d’une aspiration sociétale à une économie « plus verte ». Pour répondre à ces défis et dans un souci de sécurité et de contrôle des coûts, l’industrie automobile étudie actuellement la possibilité de développer et de produire une 3ème génération d'aciers à très haute résistance. Ils résultent de traitements thermomécaniques généralement innovants, possèdent des microstructures complexes et des propriétés mécaniques améliorées. Le procédé de Quenching and Partitioning (Q&P) est le traitement le plus prometteur, il consiste en une trempe sous la température de début de transformation martensitique Ms, puis, d'un réchauffage et d'un maintien au-dessus de la température initiale de trempe (QT). L'étape de maintien est appelée "étape de partition", car un enrichissement en carbone de l'austénite est attendu. Les propriétés mécaniques exceptionnelles des aciers Q&P sont dues à leur microstructure duplexe complexe : de très fins îlots d'austénite résiduelle imbriqués dans une matrice martensitique revenue et/ou fraîche. Bien que les mécanismes d'enrichissement en carbone de l'austénite résiduelle lors de l'étape de partition soient encore débattus dans la littérature, il existe des preuves tangibles qui attestent d’un phénomène de partition du carbone de la martensite vers l’austénite. Cependant, la formation de bainite et de carbures dans la martensite soulève la question de l’influence de ces réactions et de leurs interactions sur les mécanismes et les cinétiques d’enrichissement en carbone de l'austénite. Il s'agit clairement d'un sujet d'intérêt puisque les propriétés mécaniques de ces aciers reposent principalement sur la teneur en carbone des îlots d’austénite.Cette thèse qui repose sur une approche expérimentale multi-échelle couplée à une approche théorique en champ moyen, a pour ambition d’apporter des éléments de réponse aux mécanismes d’enrichissement en carbone de l’austénite dans un aciers duplex Q&P à très haute résistance de composition Fe-0,3 C-2,5Mn-1,5Si... / The need to reduce the fuel consumption of vehicles while increasing safety led the automotive industry to develop a 3rd generation of Advanced High Strength Steels. Such steels combine innovative processing routes, complex microstructures, improved mechanical properties and are a possible response in vehicle lightweighting. The Quenching and Partitioning (Q&P) process is the most promising route and involves quenching below the martensite start temperature followed by a reheatingand ageing above the initial quench temperature (QT). The ageing step is termed “partitioning step” since carbon enrichment in austenite is expected to occur during this stage. The exceptional mechanical properties of Q&P steels come from their complex duplex microstructure: very fine austenite island retained at room temperature embedded in both recovered and fresh martensite. Although the mechanisms of carbon enrichment in retained austenite during the partitioning step are still debated,strong evidences of carbon partitioning from martensite to austenite exist. However, both the formation of bainite and carbides into martensite raise the question of the effects of competitive reactions on the carbon enrichment in austenite. It is clearly a topic of interest since the benefits of such a treatment in terms of improved mechanical properties depends strongly on the austenite stability and thus on the level of carbon enrichment in austenite during the partitioning step.This thesis aims at combining an innovative multiscale experimental methodology with an original theoretical approach providing a unique opportunity to give some clarifications regarding the microstructure evolution and the mechanisms of carbon enrichment into austenite. After having determined the optimum Q&P parameters using dilatometric and XRD measurements, a Q&P treatment at three different QT (260, 230 and 200°C) and at a partitioning temperature of 400°C was applied to a model Fe-0.3 C-2.5Mn-1.5Si steel. The dilatometric data combined with an SEM image analysis study showed that bainite forms during the partitioning step. The presence of bainite was also confirmed by in-situ High Energy X-Ray Diffraction. While bainite was shown to appear as carbide free laths, tempered martensite showed an advanced state of intra-lath precipitation. The combination of atom probe tomography (APT) and TEM technics showed that theses carbides are transitional andboth η and ε carbides were observed. Their carbon content ranged from 20.0 to 27.7 at.%. APT measurements also highlighted carbon segregation on martensite defects during the initial quench and calculation of the evolution of the carbon excess concentration on laths boundaries suggest that desegregation occurs along the Q&P treatment. In-situ HEXRD permitted to follow the austenite lattice parameter evolution and it was shown that austenite is subjected to a sequence of tensile andcompression state induced by the formation of martensite. A model for the coefficient of thermal expansion of austenite taking into account its stress state was successfully developed. The evolutions of carbon content into austenite for the three QT were determined. Surprisingly the carbon enrichment into austenite was shown not to depend on QT. It was also shown that the increase of carbon content in austenite results from both carbon partitioning and bainite contributions. Lastly, an originaltheoretical approach was developed. It was evidenced that bainite continues to form while partitioning process is rapidly completed, thus bainite transformation controls the maximum austenite carbon enrichment at 400°C, independently of QT. The contribution of partitioning from martensite was shown to be larger with decreasing QT. The developed model successfully described the experimentally observed phase transformations and austenite carbon enrichment by taking into account theinteractions between carbon partitioning, bainite transformation and carbide precipitation.