It is well known that within materials science and engineering, the advancement of steels is subject to the conflicting objectives of achieving high strength, energy absorption, and ductility within a single material. Multilayer metal composites (MLMCs), combining multiple advanced high strength steels (AHSSs), are promising candidates for designing materials that can achieve these mechanical property combinations which are unattainable by monolithic steels. However, the mechanical behaviour and corresponding properties of MLMCs are challenging to predict, due to the number of variables within the design space of the composite. Variables such as alloy design, number, thickness, configuration of layers, and interfacial bonding strength, all impact the potential mechanical properties. Accordingly, this work addressed the fracture behaviour of a multilayer AHSS composite, consisting of carbide-free bainitic (CFB) steel and high Mn twinning-induced plasticity (TWIP) steel, in both sequential deformation and co-deformation of layers to determine the potential advantages of a multilayer structure. In tensile deformation, a balanced combination of high strength (ultimate tensile strength (UTS) of 1290 MPa) and high ductility (total elongation (TE) of 23%) was achieved with a sandwich structure configuration consisting of two outer layers of the TWIP steel and an inner core layer of the CFB steel. The composite consisted of equal volume fractions of each constituent steel. The TE achieved by this structure exceeds that which previous studies would predict, which suggest that the elongation of a composite is controlled by the elongation limits of the monolithic hard layer (which in the case of the CFB steel is 13%). In the sandwich configuration, the soft outer layers contributed to increased ductility of the composite by inhibiting crack formation in the hard layer and exerting a compressive stress on the inner CFB core. The increased compression caused the CFB to yield at a lower stress (than it would in monolithic conditions), allowing it to plastically deform further, and the composite to have a greater total elongation. This was attributed to the strong interfacial bond, which enabled the layers to co-deform without any delamination. A bilayer composite consisting of the same volume fractions (as the sandwich configuration), demonstrated the same UTS, but a total elongation of 13%. The reduced ductility is a result of smaller compressive forces on the CFB, as well as, crack formation in the CFB at the 13% elongation (the TE of monolithic CFB), which led to immediate fracture of the sample. In tensile deformation with a pre-existing crack (double-edge notched tension (DENT)), the bilayer composite exhibited a high essential work of fracture (EWF)/cracking resistance. In the sandwich configuration, the outer TWIP layers exerted a compressive stress on the inner CFB core, which was possible due to the strong interfacial bond. This compressive stress and the thin layer configuration caused the CFB core to fracture in a ductile manner. The impact energy absorption of the sample was investigated by Charpy impact testing, and the procedure of crack propagation analyzed by three-point bending. High energy absorption was achieved with a notch positioned in the TWIP layer, in which the composite exceeded the energy absorption of either monolithic steel. The sample absorbed the energy through plastic deformation of the two layers, as the interface prevented crack formation in the CFB layer. When the notch was positioned in the CFB layer, the impact energy absorption was nearly equal to that of the monolithic TWIP steel. In this configuration, the composite absorbed the energy through dissipation of the propagating crack along the interface, causing delamination and subsequent bending of the TWIP layer. In assessing the experimental results in this work, it was determined that in both deformation conditions (sequential and co-deformation), the composite is sensitive to the layer configuration. To produce an optimal and balanced combination of mechanical properties (strength, energy absorption, and ductility), it is critical to inhibit or at minimum, delay crack initiation within the CFB (hard steel) layer. Overall, this research shows that the experimental multilayer composite is promising for developing an AHSS structure that can demonstrate properties unattainable by monolithic steels. / Thesis / Master of Applied Science (MASc) / Advanced high strength steels are generally limited by competing mechanical properties of strength and impact energy absorption. Combining hard and soft phase microstructures within one material (i.e. dual-phase steel) thermodynamically restricts the material by the composition and the possible heat treatment conditions. It also leads to large strain gradients resulting in void formation and failure. Instead, multilayer composites can be designed with each layer independently exhibiting a monolithic microstructure that optimizes each desired mechanical property. The bonding strength between the layers can also be adjusted, altering the distribution of stresses when the material is deformed. This research aimed to analyze a multilayer metal composite that combined a soft-phase austenitic steel exhibiting high energy absorption with a hard-phase carbide-free bainitic steel exhibiting high strength. The material was evaluated in two conditions: i) under co-deformation where the layered structure was deformed parallel to the interface and ii) under sequential deformation, where stress was applied to one layer at a time. The results indicated that in both conditions, the composite was sensitive to the configuration of the layers. It demonstrated the potential to exhibit a combination of high strength and high energy absorption capabilities in sequential deformation. In co-deformation, certain configurations of the composite were able to exhibit increased ductility and fracture resistance (improved from the monolithic hard steel). In both cases, the critical design factor was that crack initiation and propagation must be restricted in the hard material to achieve balanced mechanical properties of strength and energy absorption.

Le couplage des propriétés ferromagnétiques et semiconductrices représente une perspective prometteuse, afin de réaliser des technologies qui exploitent le spin des électrons. Ceci permettra de stocker et traiter des bits informatiques de façon instantanée dans le même dispositif, plutôt que dans des dispositifs séparés (mémoire et processeur). La Spintronique pourrait alors révolutionner la technologie de l'information. Un candidat potentiel pour la fabrication d'hétérostructures métal ferromagnétique/semiconducteur pour des applications en Spintronique, est le système Mn-Ge. Ce système qui est compatible avec la technologie CMOS, présente une phase intéressante pour la Spintronique qui est Mn5Ge3, avec une possibilité d'épitaxie sur le Ge(111). Afin d'intégrer cette phase dans des procédés de fabrication, nous étudions la diffusion réactive à l'état solide entre un film de Mn et un substrat de Ge (comme dans le cas de la formation des siliciures dans la technologie CMOS). L'accent a été mis sur la séquence de formation de phases lors de la réaction entre un film nanométrique de Mn et le Ge, l'influence de l'interface sur cette réaction, et sur la diffusion du Mn dans le Ge. L'incorporation du carbone dans des films minces de Mn5Ge3 a montré une augmentation notable de la température de Curie : nous présentons alors l'effet du carbone sur la réaction Mn-Ge, et sa redistribution dans les couches minces MnxGey. / Coupling ferromagnetic and semi-conducting properties represents a pathway toward producing technologies that exploit the spin of electrons. That would allow store and process computer bits instantly in a same device, rather than separate devices (memory and CPU). The Spintronics could then revolutionize the information technology. A potential candidate for the fabrication of heterostructures ferromagnetic metal / semiconductor for Spintronics applications is the Mn-Ge system. This system is compatible with CMOS technology, and presents an interesting phase for Spintronics which is Mn5Ge3 phase, which is able to be grown epitaxially on Ge(111). To integrate this phase in the manufacturing process, we study the solid state reactive diffusion between a thin Mn film and Ge substrate, to form a germanide upon the Ge substrate (as in the case of the formation of silicides in CMOS technology). Emphasis was placed on the sequence of phase formation during the reaction between a 50 nm thick Mn film and Ge, the influence of the interface on the reaction, and the diffusion of Mn in Ge. Incorporation of carbon in thin Mn5Ge3 films showed a significant increase in the Curie temperature, we then present the effect of carbon on the reaction Mn-Ge and its redistribution in thin MnxGey films.

Die vorliegende Arbeit untergliedert sich in drei aufeinander aufbauende Themenkomplexe. Der erste Komplex umfasst Untersuchungen zum Nachweis und zur Quantifizierung von Beugungsanteilen in der ioneninduzierten Elektronenemission (IILEED). Dazu wurden bei der streifenden Streuung schneller He und H -Ionen an Cu(001) energiedispersive zweidimensionale Winkelverteilungen emittierter Elektronen aufgenommen. Es konnten reflexartige Intensitäten in der ioneninduzierten Elektronenemission nachgewiesen werden, deren Raumwinkeländerungen in Abhängigkeit von Anregungsrichtung und Detektionsenergie mittels einer modifizierten Ewaldkonstruktion quantitativ nachvollziehbar sind. Die beobachteten Beugungsstrukturen geben Aufschluss über den ursächlichen elektronischen Anregungsprozess an der Oberfläche. Im zweiten Teil wird die ioneninduzierten Elektronenemission beim Wachstum ultradünner 3d-Übergangsmetallfilme (Co, Fe, Mn) auf Cu(001) untersucht. Die streng zum jeweiligen Wachstumsstadium korrelierten Änderungen der Energiespektren und Anzahlverteilungen emittierter Elektronen (SEE-Oszillationen), sind hauptsächlich auf binäre Stossprozesse der Projektile mit Stufenkanten zurückzuführen. Die SEE-Oszillationen können zur in-situ Wachstumsanalyse und Bedeckungsbestimmung ultradünner Filme herangezogen werden. Im dritten Abschnitt wird eine neue Messmethode zur Analyse komplex rekonstruierter Oberflächenstrukturen vorgestellt. Die Methode der „Ionenstrahltriangulation“ (IST) basiert auf der relativen Änderung der Anzahlverteilung emittierter Elektronen bei azimutaler Drehung der Probenoberfläche. Bestimmt werden die azimutale Richtung und die relative Breite von Oberflächenkanälen in der obersten atomaren Lage. Die Registrierung der pro Streuprozess emittierten Elektronenanzahl eröffnet erstmalig eine quantitative Simulation von IST-Messkurven. Auf dieser Grundlage können mittels IST die lateralen Atompositionen langreichweitig geordneter Oberflächenstrukturen auf mehrere hundertstel Angström genau festgelegt werden. Das hohe strukturanalytische Potential dieser Messmethode demonstrieren IST-Untersuchungen an den Strukturphasen der Systeme Mn/Cu(001) und Fe/Cu(001). / H+ and He+ ions with an energy of 25 keV are scattered under a grazing angle of incidence from a clean and flat Cu(001) surface. For specific azimuthal orientations of the crystal surface with respect to low index directions in the surface plane we observe the ion induced emission of electrons with a conventional LEED (low energy electron diffraction) setup. By operating the instrument in an energy dispersive mode we find intensity distributions of emitted electrons which can unequivocally be ascribed to diffraction effects at the target surface. From this ion induced LEED-reflexes (IILEED) we get important information about the electron excitation- and emission effects during the scattering process. In the second part of this work we investigate the correlation between thin-film growth (Co, Fe, Mn on Cu(001)) and electron emission in the regime of grazing ion scattering. The “rough” surface of uncompleted layers increase the probability of binary collisions of incident ions with individual atoms at the surface. The energy spectras and the number distribution of emitted electrons are substantially influenced by these “violent” collisions and allow us to monitor growth of thin films via simple measurements of target current or from energy spectra of emitted electrons. The method provides excellent signals and is also applicable in the regime of poor layer growth. By making use of ion beam triangulation (IBT), direct information on the atomic structure of thin films and substrate surfaces is obtained. We discuss in the third part of this work a new variant of this method based on the detection of the number of emitted electrons. The data are analyzed via computer simulations using classical mechanics which provides a quantitative analysis with respect to projectile trajectories. This new detection scheme allows the determination of the in-plane structure of reconstructed thin films and surfaces with high precision. The impressed potential of this method is demonstrated by quantitative analysis of the structural phases of Fe and Mn on Cu(001).

Nesta tese, analisamos dois sistemas de semicondutores magnéticos: um semicondutor magnético cristalino de EuTe e uma heteroestrutura formada por um poço quântico de GaAs/AlGaAs ao lado uma barreira tipo delta de Mn, que, ao difundir-se, forma o semicondutor magnético diluído de (Ga,Mn)As. Nossos estudos foram focados na possibilidade de manipularmos oticamente a orientação magnética de ambos os sistemas. No semicondutor magnético de EuTe, a indução de magnetização se dá pela formação de polarons magnéticos ao redor de elétrons fotoexcitados. Para o estudo dos polarons, um modelo teórico elaborado foi adaptado para a construção de um sistema computacional baseado no método de Monte Carlo. Essa sistema permitiu o cálculo do momento magnético e do raio do polaron em temperaturas finitas, muito acima da temperatura de Néel. O modelo foi elaborado para reproduzir tanto as propriedades do EuTe sem o polaron (temperatura de Néel e campo crítico), quanto o deslocamento da linha de fotoluminescência devido a formação do polaron. Além do desenvolvimento do próprio método computacional, que pode ser utilizado para estudar outros sistemas, o conhecimento adquirido com o estudo do EuTe serviu como base para o estudo de um sistema mais complexo, que é a heteroestrutura de GaAs/AlGaAs + dMn. O estudo da heteroestrutura de GaAs/AlGaAs + dMn foi feito em cima de medidas experimentais de rotação de Kerr com resolução temporal. O sistema de medição construído permite, também, medidas de rotação de Kerr com resolução espacial, que servem para o estudo de transporte e hélice de spin em semicondutores, e está detalhadamente descrito em um dos capítulo desta tese. Na amostra estudada, o controle da magnetização dos íons de Mn é feito através da interação de troca com o elétron fotoexcitado no poço quântico. Os resultados obtidos das medidas de rotação de Kerr mostram uma frequência de precessão dependente do tempo, que revela a existência de dois processos com dinâmicas diferentes: uma primeira orientação do spin dos íons de Mn devido à polarização do par elétron-buraco no poço quântico, seguida por um realinhamento desses spins com o campo magnético externo, a partir do momento em que a coerência dos spins dos buracos desaparece. Esse resultado sugere que a interação entre os elétrons fotoexcitados e os íons de Mn ocorre por intermédio dos buracos fotoexcitados, ao contrário do que havia sido proposto em estudos anteriores de estruturas similares, mas de acordo com o modelo de interação sp-d, utilizado para explicar o ferromagnetismo do (Ga,Mn)As. / In this thesis we analyzed two magnetic semiconductor systems: one intrinsic magnetic semiconductor crystal of EuTe and one GaAs-based heterostructure with a GaAs/AlGaAs quantum well close to delta-type Mn barrier, that forms a diluted magnetic semiconductor of (Ga,Mn)As after diffusion. Our studies on both systems were focused on the possibility of optical manipulation of magnetic order. In EuTe pure semiconductor, the magnetization control occurs due to de formation od magnetic polarons around photo-excited electrons. To study magnetic polarons we adapted a theoretical model to build a computer simulation system based on Monte Carlo\'s method. This system allowed us to calculate the magnetic moment and radius of the polaron at finite temperatures fair above Néel Temperature. The computational model was tested to reproduce EuTe properties without polarons (Néel Temperature and critical magnetic field) and with polarons (photoluminescence line shift). Beside the development of this computational model, that can be used to study other systems, the knowledge acquired during the studies on EuTe helped us to better understand the more complex system of the GaAs/AlGaAs +dMn heterostructure. The studies about the GaAs/AlGaAs + dMn heterostructure were based on experimental measurements of time-resolved Kerr rotation. The measurement system we built also allows us to perform spatial-resolved Kerr rotation measurements to study spin transport and spin helix on semiconductors and it is described in details in one chapter of this thesis. The optical manipulation of Mn ions magnetization on the studied sample is consequence of the exchange interaction with the photoexcited electron inside the quantum well. The results of Kerr rotation measurements show a time-dependent precession frequency that reveals the existence of two process with distinct dynamics: the initial orientation of Mn ions spins with the photoexcited electron-hole pair, followed by the realignment of these spins with the external magnetic field, as soon as the photoexcited hole spins loose its coherence. These results indicate that the exchange interaction between the photoexcited electron inside the quantum well and the Mn ions is mediated by the photoexcited holes, in opposition of what was being proposed in previous studies of similar structures, but in agreement with the sp-d model, used to explain the (Ga,Mn)As ferromagnetism.

Ce travail de thèse a été consacré à l'étude à la fois théorique et expérimentale de la dynamique de l'aimantation assistée par un champ électrique dans un dispositif à base de (Ga,Mn)As. Une couche de (Ga,Mn)As, dont l’anisotropie magnétique est complexe, est un matériau de choix pour la manipulation de l’aimantation par un champ électrique.J’ai présenté une stratégie de retournement précessionnel de l'aimantation qui tire partie de la réduction transitoire de l'anisotropie cubique provoquée par une courte impulsion de champ électrique. A l’aide d’un modèle macrospin, j’ai démontré notamment qu'une impulsion de champ électrique de quelques ns de durée est suffisante pour basculer l'aimantation entre deux positions d'équilibres.L'aspect expérimental est basé sur l'utilisation d'une jonction p-n tout semi-conducteur dont la région dopée p est formée par une couche mince de (Ga,Mn)As. La déplétion des porteurs de charge dans le canal semi-conducteur provoquée par l'application d'un train d'impulsions de tension de courte durée induit une forte diminution du champ d'anisotropie cubique. L'étude expérimentale du renversement de l'aimantation en champ magnétique a conduit à la mise en évidence d'un retournement de l'aimantation via la nucléation et la propagation de parois et d’une distribution large des champs de piégeage. L'inhomogénéité magnétique au sein de la couche de (Ga,Mn)As a empêché l'observation d'une résonance ferromagnétique induite par un champ électrique. Néanmoins, des mesures de retournement avec une ou plusieurs impulsions de tension de grille ont permis de proposer un processus de renversement de l'aimantation induit par un champ électrique. / This work has been devoted to the study of both theoretical and experimental electric field induced magnetization dynamics in a (Ga,Mn)As based device. A layer of (Ga,Mn)As, whose magnetic anisotropy is complex, is of particular interest for magnetization manipulation by electric fields.I proposed a scheme for the precessional switching of the magnetization using cubic anisotropy field reduction triggered by electric field pulse. Using a model macrospin, I demonstrated that a ns-pulse is sufficient to switch the magnetization between two equilibrium positions.An all-semiconductor epitaxial p-n junction based on low-doped (Ga,Mn)As was fabricated. Gating effects triggered by low voltage pulses induced a strong decrease of the cubic anisotropy field. I demonstrated that magnetization reversal is dominated by the nucleation and the propagation of domain walls. The distribution of pinning fields was found to be broad. Due to a magnetic inhomogeneity of the (Ga,Mn)As layer, it was not possible to observe any ferromagnetic resonance induced by an electric field. However, I proposed a magnetization reversal scenario based on single or multiple gate voltage pulses measurements

Le développement d’une troisième génération d’aciers Fe-Mn-Al-C à structure duplex, pour des teneurs en Mn et Al inférieures à 8 %mass, pourrait être une réponse prometteuse aux objectifs d’allègement de 20% des véhicules automobiles, tout en garantissant des propriétés de haute résistance mécanique et haute formabilité.Le choix des nuances et l’optimisation des conditions d’élaboration nécessitent de prévoir en particulier les compositions et proportions des phases existantes en fonction de la route métallurgique. Une base de données thermodynamiques fiable et précise est donc requise. Cependant les données de la littérature sur le système quaternaire Fe-Mn-Al-C, dans les domaines de composition envisagés, sont limitées.Ce mémoire est consacré à l’établissement des équilibres de phases ferrite-α, austénite-γ et carbure-κ (Fe,Mn)3AlC entre 700 et 1000°C par une approche couplée d’expériences ciblées et de modélisation thermodynamique. Pour appuyer l’évolution expérimentale des fractions de phases et des compositions, une modélisation cinétique (DICTRA) est proposée. La cinétique de formation de l’austénite en fonction de la composition de l’alliage et de la température de maintien dans le domaine intercritique a été caractérisée. Les phases en équilibre, caractérisées par DRX, MEB, microsonde, sont représentées sous forme de conodes α/γ, γ/κ, α/γ/κ, ce qui permet de définir les domaines de stabilité de l’austénite et du carbure κ. Ces données expérimentales sont utilisées pour affiner la description thermodynamique du système quaternaire mais il est nécessaire de réviser la modélisation du carbure κ. / A third generation of Fe-Mn-Al-C steels with a duplex structure, for Mn and Al contents less than 8%mass, could be a promising response to the 20% weight lightening of automotive vehicles, by keeping a high strength and a high formability.The knowledge of the corresponding quaternary phase diagram serves as a roadmap for the choice of compositions and the optimization of elaboration conditions. A reliable and precise thermodynamic database is therefore required. However, the literature data on the Fe-Mn-Al-C quaternary system in the targeted domains are limited.This study is devoted to the establishment of phase equilibria involving ferrite-α, austenite-γ and carbide-κ (Fe,Mn)3AlC between 700 and 1000°C by a coupled approach of experiments and thermodynamic modeling. A kinetic model (DICTRA) is proposed to support the experimental evolution of phase fraction and composition. The kinetics of austenite formation as a function of the alloy composition and of the maintaining temperature in the intercritical domain have been calculated. The phases in equilibrium, characterized by XRD, SEM, EPMA, are represented as α/γ, γ/κ, α/γ/κ tie-lines in order to specify the stability fields of γ and κ. These data are used to refine the thermodynamic description of the quaternary system but it is necessary to revise the modeling of κ carbide.

En tant que nouveau matériau magnétique à mémoire de forme, les alliages basés sur le système Ni-Mn-Sn possèdent de multiples propriétés physiques telles que l'effet de mémoire de forme des alliages polycristallins, l'effet magnétocalorique géant, l'effet de magnétorésistance et l'effet de polarisation d'échange. Jusqu'à présent, la plupart des études ont été axées sur l'amélioration des multifonctionnalités de ces alliages, mais l'information fondamentale qui est fortement associée à ces propriétés n'est toujours pas claire. Ainsi, une étude approfondie sur les structures cristallines de la martensite et de l'austénite, les caractéristiques microstructurales et cristallographiques de la transformation martensitique a été menée dans le cadre du présent travail de doctorat. Il a été confirmé que l'austénite de Ni50Mn37.5Sn12.5 possède une structure cubique L21 (Fm3 ̅m, No.225). Le paramètre de réseau de l'austénite dans Ni50Mn37.5Sn12.5 est aA = 5.9813 Å. La martensite possède une structure orthorhombique (4O) à quatre couches (Pmma, No.51). Les paramètres de réseau de la martensite dans Ni50Mn38Sn12 et Ni50Mn37.5Sn12.5 sont a4O = 8.6068 Å; b4O = 5.6226 Å and c4O = 4.3728 Å, and a4O = 8.6063 Å, b4O = 5.6425 Å, and c4O = 4.3672Å, respectivement. La martensite 4O Ni-Mn-Sn présente une microstructure hiérarchiquement maclée. La martensite est organisée en larges plaques dans le grain d'austénite d'origine. Les plaques contiennent des colonies à forme irrégulière avec deux modèles caractéristiques de microstructures : le motif lamellaire classique et le motif en arête de poisson. Dans chaque colonie, il existe quatre variantes d'orientation (A, B, C et D) et elles forment trois types de macles (Type I, Type II et macles composées). Les interfaces entre les variantes correspondantes sont en coincidence avec leur plan de maclage K1. Les plans d'interface des paires de macles composées A-D et B-C peuvent avoir une ou deux orientations différentes, ce qui conduit aux deux modèles microstructuraux. Les variantes correspondantes dans les colonies voisines dans une même large plaque (colonies intra-plaques) possèdent des orientations proches et le joint de colonie est courbé, tandis que la limite de colonie inter-plaques est relativement droite. La relation d’orientation de Pitsch (Orientation Relation OR), spécifiée comme {1 0 1} A//{22 ̅1}4O and <1 0 1 ̅> A//<1 ̅2 2>4O, a été exclusivement déterminée à être une OR effective entre l'austénite cubique et la martensite modulée 4O. Sous cette OR, 24 variantes peuvent être générées dans un grain d'austénite. Ces 24 variantes sont organisées en 6 groupes et chaque groupe correspond à une colonie de martensite. La structure de martensite finement maclée (microstructure sandwich) est le composant microstructural de base produit par la transformation martensitique. Une telle structure assure une interface de phase invariante (plan d'habitat) pour la transformation. Au cours de la transformation, les variantes de la martensite sont organisées en clusters en forme de diamant composés de colonies de variantes et avec des structures en forme de coin au front de transformation. Chaque coin est composé de deux structures sandwich séparées par un plan de nervure médiane {1 0 1}A. Les paires de variantes dans chaque coin devraient avoir le même type de macles avec une relation de Type I ou de Type II pour garantir de bonnes compatibilités géométriques des variantes à l'interface de phase et au plan de la nervure centrale. Dans les diamants, les colonies sont séparées par des frontières présentant des marches à faible énergie interfaciale qui évoluent vers les joints des colonies intra-plaques et par des joints droits qui deviennent les joints entre les plaques. Les diamants s'allongent le long de la direction presque parallèle aux plans de la nervure centrale des coins et la forme de la plaque de la martensite est finalement formée. [...] / Being a novel magnetic shape memory material, Ni-Mn-Sn based alloy systems possess multiple physical properties, such as shape memory effect of polycrystalline alloys, giant magnetocaloric effect, large magnetoresistance effect and exchange bias effect. So far, most studies have been focused on the improvement of the multifunctionalities of these alloys, but the fundamental information which is highly associated with these properties is still unclear. Thus, a thorough study on the crystal structures of martensite and austenite, microstructural and crystallographic features of martensitic transformation has been conducted in the present PhD work. The austenite of Ni50Mn37.5Sn12.5 was confirmed to possess a L21 cubic structure (Fm"3" ̅m, No.225). The lattice parameter of austenite in Ni50Mn37.5Sn12.5 is aA=5.9813 Å. The martensite possesses a four-layered orthorhombic (4O) structure (Pmma, No.51). The lattice parameters of martensite in Ni50Mn38Sn12 and Ni50Mn37.5Sn12.5 are a4O = 8.6068 Å; b4O = 5.6226 Å and c4O = 4.3728 Å, and a4O = 8.6063 Å, b4O = 5.6425 Å, and c4O = 4.3672Å, respectively. The 4O Ni-Mn-Sn martensite exhibits a hierarchically twinned microstructure. The martensite is organized into broad plates in the original austenite grain. The plates contain irregularly shaped colonies with two characteristic microstructural patterns: classical lamellar pattern and herring-bone pattern. In each colony, there are four orientation variants (A, B, C and D) and they form three types of twins (Type I, Type II and compound twin). The interfaces between the corresponding variants are in coincidence with their twinning plane K1. The interface planes of the compound twin pairs A-D and B-C can have one or two different orientations, which leads to the two microstructural patterns. The corresponding variants in the neighboring colonies within one broad plate (intra plate colonies) possess close orientations and colony boundary is curved, whereas the inter plate colony boundary is relatively straight. The Pitsch OR, specified as "{1 0 1}" A//"{2 " "2" ̅" " "1" ̅"}" 4O and "<1 0 " "1" ̅">" A//"<" "1" ̅" " "2" ̅" 2>" 4O, was uniquely determined to be an effective OR between the cubic austenite and 4O modulated martensite. Under this OR, 24 variants can be generated within one austenite grain. Such 24 variants are organized into 6 groups and each group corresponds to a martensite colony. The finely twinned martensite structure (sandwich microstructure) is the basic microstructural constitute produced by martensitic transformation. Such a structure ensures an invariant phase interface (habit plane) for the transformation. During the transformation, martensite variants are organized into diamond shaped clusters composed of variant colonies and with wedge shaped structures at the transformation front. Each wedge is composed of two sandwich structures separating by a midrib plane {1 0 1}A. The variant pairs in each wedge should have the same twin type with either Type I or Type II relation to ensure good geometrical compatibilities of the variants at phase interface and at the midrib plane. Within the diamonds, colonies are separated by step-like boundaries with low interfacial energy that evolve into the intra plate colony boundaries and by straight boundaries that become the inter plate colony boundaries. The diamonds elongates along the direction nearly paralleled to the midrib planes of the wedges and plate shape of martensite is finally formed. Such features of the diamond structure in Ni-Mn-Sn alloys are realized by self-accommodation of transformation strains for energy minimization. The present work provides comprehensive microstructural and crystallographic information on martensite and on martensitic transforamtion of Ni-Mn-Sn alloys and it is useful for understanding their multi functionalities associated with martensitic transformation and helpful on property optimization

Nesta tese, analisamos dois sistemas de semicondutores magnéticos: um semicondutor magnético cristalino de EuTe e uma heteroestrutura formada por um poço quântico de GaAs/AlGaAs ao lado uma barreira tipo delta de Mn, que, ao difundir-se, forma o semicondutor magnético diluído de (Ga,Mn)As. Nossos estudos foram focados na possibilidade de manipularmos oticamente a orientação magnética de ambos os sistemas. No semicondutor magnético de EuTe, a indução de magnetização se dá pela formação de polarons magnéticos ao redor de elétrons fotoexcitados. Para o estudo dos polarons, um modelo teórico elaborado foi adaptado para a construção de um sistema computacional baseado no método de Monte Carlo. Essa sistema permitiu o cálculo do momento magnético e do raio do polaron em temperaturas finitas, muito acima da temperatura de Néel. O modelo foi elaborado para reproduzir tanto as propriedades do EuTe sem o polaron (temperatura de Néel e campo crítico), quanto o deslocamento da linha de fotoluminescência devido a formação do polaron. Além do desenvolvimento do próprio método computacional, que pode ser utilizado para estudar outros sistemas, o conhecimento adquirido com o estudo do EuTe serviu como base para o estudo de um sistema mais complexo, que é a heteroestrutura de GaAs/AlGaAs + dMn. O estudo da heteroestrutura de GaAs/AlGaAs + dMn foi feito em cima de medidas experimentais de rotação de Kerr com resolução temporal. O sistema de medição construído permite, também, medidas de rotação de Kerr com resolução espacial, que servem para o estudo de transporte e hélice de spin em semicondutores, e está detalhadamente descrito em um dos capítulo desta tese. Na amostra estudada, o controle da magnetização dos íons de Mn é feito através da interação de troca com o elétron fotoexcitado no poço quântico. Os resultados obtidos das medidas de rotação de Kerr mostram uma frequência de precessão dependente do tempo, que revela a existência de dois processos com dinâmicas diferentes: uma primeira orientação do spin dos íons de Mn devido à polarização do par elétron-buraco no poço quântico, seguida por um realinhamento desses spins com o campo magnético externo, a partir do momento em que a coerência dos spins dos buracos desaparece. Esse resultado sugere que a interação entre os elétrons fotoexcitados e os íons de Mn ocorre por intermédio dos buracos fotoexcitados, ao contrário do que havia sido proposto em estudos anteriores de estruturas similares, mas de acordo com o modelo de interação sp-d, utilizado para explicar o ferromagnetismo do (Ga,Mn)As. / In this thesis we analyzed two magnetic semiconductor systems: one intrinsic magnetic semiconductor crystal of EuTe and one GaAs-based heterostructure with a GaAs/AlGaAs quantum well close to delta-type Mn barrier, that forms a diluted magnetic semiconductor of (Ga,Mn)As after diffusion. Our studies on both systems were focused on the possibility of optical manipulation of magnetic order. In EuTe pure semiconductor, the magnetization control occurs due to de formation od magnetic polarons around photo-excited electrons. To study magnetic polarons we adapted a theoretical model to build a computer simulation system based on Monte Carlo\'s method. This system allowed us to calculate the magnetic moment and radius of the polaron at finite temperatures fair above Néel Temperature. The computational model was tested to reproduce EuTe properties without polarons (Néel Temperature and critical magnetic field) and with polarons (photoluminescence line shift). Beside the development of this computational model, that can be used to study other systems, the knowledge acquired during the studies on EuTe helped us to better understand the more complex system of the GaAs/AlGaAs +dMn heterostructure. The studies about the GaAs/AlGaAs + dMn heterostructure were based on experimental measurements of time-resolved Kerr rotation. The measurement system we built also allows us to perform spatial-resolved Kerr rotation measurements to study spin transport and spin helix on semiconductors and it is described in details in one chapter of this thesis. The optical manipulation of Mn ions magnetization on the studied sample is consequence of the exchange interaction with the photoexcited electron inside the quantum well. The results of Kerr rotation measurements show a time-dependent precession frequency that reveals the existence of two process with distinct dynamics: the initial orientation of Mn ions spins with the photoexcited electron-hole pair, followed by the realignment of these spins with the external magnetic field, as soon as the photoexcited hole spins loose its coherence. These results indicate that the exchange interaction between the photoexcited electron inside the quantum well and the Mn ions is mediated by the photoexcited holes, in opposition of what was being proposed in previous studies of similar structures, but in agreement with the sp-d model, used to explain the (Ga,Mn)As ferromagnetism.

Lors d’un recuit inter-critique d’un acier dit « Medium Manganèse », dont la teneur en Mn est située entre 4 et 12 %, avec une microstructure initiale complètement martensitique, la formation de l’austénite obéit à un mécanisme spécifique qui porte le nom d'ART - « Austenite Reverted Transformation » (transformation inverse de l’austénite). L’objectif de ce travail de thèse était d’étudier et de modéliser les évolutions microstructurales en lien avec les propriétés mécaniques lors d’un recuit ART. Il a été déterminé que la microstructure finale se compose de phases de nature (ferrite, austénite résiduelle et martensite de trempe) et morphologie (en forme d’aiguille et polygonale) différentes. Une attention particulière a été accordée aux cinétiques de dissolution des carbures et de formation de l’austénite. Une vision complète de ces processus a été construite. En outre, le mécanisme de stabilisation de l’austénite résiduelle à la température ambiante a été étudié et discuté. Enfin, des essais de traction ont été réalisés afin d’évaluer le comportement mécanique de l’acier après différents recuits ART et établir le lien avec la microstructure. Une analyse plus détaillée du comportement de chaque constituant de la microstructure a été effectuée. A l'issue de cette thèse, un modèle complet est disponible pour calculer les courbes de contrainte vraie - déformation vraie d’un acier Medium Mn / During the intercritical annealing of fully martensitic Medium Mn steel, containing from 4 to 12 wt.% Mn, the formation of austenite happens through the so-called “Austenite Reverted Transformation” (ART) mechanism. In this PhD work, the evolution of both microstructure and tensile properties was studied as a function of holding time in the intercritical domain. The microstructure evolution was studied using a double experimental and modeling approach. The final microstructure contained phases of different natures (ferrite (annealed martensite), retained austenite and fresh martensite) and of different morphologies (lath-like and polygonal). A particular attention was paid to the kinetics of austenite formation in connection with cementite dissolution and to the morphology of the phases. A mechanism was proposed to describe the formation of such microstructure. The critical factors controlling thermal austenite stability, including both chemical and size effects, were determined and discussed, based on the analysis of the retained austenite time-evolution. At last, tensile properties of the steel were measured as a function of holding time and the relation between microstructure and mechanical behavior was analyzed. Advanced analysis of the individual behavior of the three major constituents was performed. As a final output of this work, a complete model for predicting the true-stress versus true-strain curves of medium Mn steels was proposed

Ce travail est consacré à la recherche et au développement de nouvelles molécules à viséepharmacologique en série naphtoquinonique en utilisant des réactions par transfert monoélectroniquede type SRN1 et des cyclisations radicalaires oxydatives induites par l'acétate de manganèse(III). Lapremière partie décrit l’étude de la réactivité SRN1 de la 2-(chlorométhyl)-3-méthoxynaphtoquinoneavec divers anions nitronates conduisant à la formation de produits de C-alkylation avec de bonsrendements. Ces derniers ont fait l’objet d’une réaction de réduction-cyclisation permettant la synthèsede nouveaux dérivés benzo[g]indol-5(3H)-ones. Dans la seconde partie, une nouvelle réactiond’oxydation initiée par l’acétate de manganèse(III) a été développée sur la 2-hydroxy-3-méthylnaphtoquinone dans des conditions opératoires douces. En effet, la réactivité originale de la 2-hydroxy-3-méthylnaphtoquinone avec divers alcènes aromatiques en présence de Mn(OAc)3 et dedioxygène, a permis pour la première fois en série naphtoquinonique, l’obtention de nouveaux dérivésoriginaux dihydronaphto[2,3-c][1,2]dioxine-5,10(3H,10aH)-diones sous forme d’un mélange dediastéréoisomères à potentialités antipaludiques. Un mécanisme réactionnel original a été proposé pourla formation de ces produits. / This work is focused on the research and development of new pharmacologicalmolecules in naphthoquinonic series, synthesized by single electron transfer reaction SRN1 ormanganese(III) acetate catalyzed oxidative radical cyclization. The first part describes the SRN1reactivity of 2-(chloromethyl)-3-methoxynaphthoquinone with various nitronate anions leading to theC-alkylation products. The reduction-cyclization reaction of the latter derivatives allowed us to obtainnew benzo[g]indol-5(3H)-one derivatives. In the second part, a new reaction initiated by Mn(OAc)3 on2-hydroxy-3-methylnaphthoquinone was developed under mild conditions. Indeed, the original reaction of2-hydroxy-3-methylnaphthoquinone with various aromatic alkenes in presence of dioxygen led to newdihydronaphtho[2,3-c][1,2]dioxine-5,10(3H,10aH)-dione derivatives as a mixture of diastereoisomerswith antimalarial potential. An original mechanism was proposed in order to explain the formation ofthese products.