In this Thesis Ti-Al-C thin films deposited by cathodic arc at 700, 800 and 900 °C were investigated with respect to composition, structure and mechanical properties. The highest growth temperature resulted in close to single crystalline Ti2AlC MAX phase.   A high oxygen incorporation of 7-12 at.% was detected in all the films, likely originating from residual gas and the Al2O3 substrate. It was evident that the characteristic nanolaminated MAX phase structure was retained upon deflection from the ideal MAX phase stoichiometry.   Hardness and elastic modulus of the sample grown at 900 °C were 16 and 259 GPa, respectively, as determined by nanoindentation using a Berkovich tip. Nanoindentation measurements with a cube corner tip were also performed on all three samples in order to extract elastic moduli.   Analysis of loading-unloading curves and SPM images revealed no relation between pop-in events and pile-ups around the residual imprints, indicating that other mechanisms than formation of kink bands may be responsible for formation of pile-ups. This was also confirmed by cross-sectional TEM investigation of an indent: Ti2AlC MAX phase deformed without kinking and delamination, as opposed to the observations in single crystalline Ti3SiC2 films. Several possible reasons for the different deformation mechanism observed are discussed.    These results are of importance for the fundamental understanding of the origin of material characteristics, and serve as an initial study initiating further investigations of the influence of defects on MAX phase properties.

<p>In this Thesis Ti-Al-C thin films deposited by cathodic arc at 700, 800 and 900 °C were investigated with respect to composition, structure and mechanical properties. The highest growth temperature resulted in close to single crystalline Ti₂AlC MAX phase.</p><p> </p><p>A high oxygen incorporation of 7-12 at.% was detected in all the films, likely originating from residual gas and the Al₂O₃ substrate. It was evident that the characteristic nanolaminated MAX phase structure was retained upon deflection from the ideal MAX phase stoichiometry.</p><p> </p><p>Hardness and elastic modulus of the sample grown at 900 °C were 16 and 259 GPa, respectively, as determined by nanoindentation using a Berkovich tip. Nanoindentation measurements with a cube corner tip were also performed on all three samples in order to extract elastic moduli.</p><p> </p><p>Analysis of loading-unloading curves and SPM images revealed no relation between pop-in events and pile-ups around the residual imprints, indicating that other mechanisms than formation of kink bands may be responsible for formation of pile-ups. This was also confirmed by cross-sectional TEM investigation of an indent: Ti₂AlC MAX phase deformed without kinking and delamination, as opposed to the observations in single crystalline Ti₃SiC₂ films. Several possible reasons for the different deformation mechanism observed are discussed. </p><p> </p><p>These results are of importance for the fundamental understanding of the origin of material characteristics, and serve as an initial study initiating further investigations of the influence of defects on MAX phase properties.</p>

Many materials with complex crystal structures have attractive properties, including high specific strength, good creep resistance, oxidation resistance, often through high silicon or aluminium content. This makes them of interest for high temperature structural applications, but the use of many such phases is limited by low toughness. Even outside structural applications, brittle failure is a primary cause of failure in coatings and device materials and, therefore, improved toughness is desirable. In complex crystals plasticity, and hence toughness, is limited by the energy increases that occur as linear defects, dislocations, move. This is known as the lattice resistance. By understanding the factors controlling the lattice resistance in complex crystal structures, it is hoped that a general method for tailoring the flow stress of a material might be found. Present ductile-brittle criteria are based on simple ratios of polycrystalline elastic constants and are too limited to accurately capture flow behaviour. There are complex materials which, despite such criteria predicting brittle behaviour, exhibit low flow stresses, though on a limited number of slip systems: MAX phases, Mo$_2$BC, Nb$_2$Co$_7$ and Ta$_4$C$_{3-x}$ are examples of this. Where plastic flow is limited by the lattice resistance we must consider the effect of crystal structure on dislocation motion more directly. Aspects which are lost by considering bulk polycrystalline properties are elastic heterogeneity, elastic anisotropy and contributions to the energy changes by other interactions, such as electrostatic interactions. In this work examples of each of these are presented and modelled using an adapted version of the Peierls model. A Peierls model generalised to use the entire stiffness tensor has been implemented in Python; this allows the investigation of the effect of varying anisotropy on the yield stress of materials that would not be picked up by the use of polycrystalline elastic constants. Calculations using the changing elastic tensor during hydrogen loading of cementite suggest that hydrogen loading causes a dramatic reduction in the flow stress, consistent with experiments and associated with hydrogen embrittlement of steel. Materials for which empirical potentials can provide more insight than linear elasticity are explored with the example of ionic materials. This is done with a Peierls dislocation configuration and a molecular statics energy calculation. A simple model built electrostatic and Lennard-Jones interactions was used for the rocksalt structure, this model was found to describe the hard slip system well, but was insufficient to describe the softer slip system. Local heterogeneity in elastic properties is explored in the MAX phases where local variation in chemical environment, characterised by electronegativity, produces pronounced variation in the local stiffness within the unit cell. These local variations have been modelled with density functional theory and have been shown to be consistent with the macroscopic elastic properties while also explaining the apparent scatter in the elastic properties. These non-uniform strains are shown to have a dramatic effect on the flow stress of the MAX phases. The face-centred cubic Ti$_2$Ni structure has been used to experimentally demonstrate this effect of heterogeneity softening. The slip system was characterised by micropillar compression and the slip planes were found to be the {1 1 1} planes. The hardness of a range of alloys with the Ti$_2$Ni structure was characterised by nanoindentation of the {1 1 1} faces of single crystals. The hardness was found to decrease as the chemical, and thus elastic, heterogeneity of the unit cell increased, as expected. This effect of heterogeneity softening presents a potential route to tailoring the yield stress of crystals.

Les phases MAX sont des carbures et / ou des nitrures ternaires avec un fort potentiel dans des applications diverses. Cette étude a porté sur deux phases MAX, Ti3SiC2 et Ti2AlC qui sont les plus connues dans ce groupe de matériaux. La première partie de ces travaux était dédiée à l’élaboration des poudres et des matériaux frittés. L’objectif était d’obtenir une variété de matériaux présentant différentes caractéristiques microstructurales, en termes de composition chimique et de taille de grains. Ainsi, des poudres commerciales et synthétisées par SHS ont été densifiées à l'aide de deux techniques de frittage sous charge, i.e. SPS et HP. La deuxième partie du travail a été consacrée à une meilleure compréhension de l’influence de la composition chimique et de la taille des grains sur le comportement thermomécanique des phases MAX. Des informations supplémentaires ont été fournies en couplant deux techniques expérimentales, la flexion quatre points et l’émission acoustique, et en les associant à des observations SEM post-mortems. L’approche expérimentale développée, basée sur la comparaison des réponses mécaniques des matériaux Ti3SiC2 (contenant la phase MAX et des phases secondaires) et de Ti2AlC (phases MAX uniquement), a permis d’approfondir la compréhension des mécanismes de déformation et d’endommagement induits. Il était également montré que les phases sécondaires et la taille de grains influence la manière dont les différents endommagements sont accumulées dans le matériaux. Les résultats d’EA sont fourni les informations supplémentaires sur les type d’endommagements rencontrées et leur chronologie qui résultent avec le comportement nonlinéaire de phases MAX. La dérnière partie de cette thèse a montré que le température de transition fragile-plastique est autour de 1200˚C et que la taille de grains l’abaisse. / MAX phases are ternary carbide and/or nitride with a great potential in various application. This study concerned two MAX phase compounds, namely Ti3SiC2 and Ti2AlC, which are on the most studied among all known MAX phases. The first part dealt with materials elaboration which includes both synthesis and sintering stages. The objective was to obtain a variety of materials with different microstructural features, i.e. phase composition and grain size. For this purpose, both commercial and SHS-derived powders were densified with two pressure-assisted sintering technique, i.e. SPS and HP. The second part of work was devoted to deeper understanding of the influence of phase composition and grain size to thermomechanical behavior of MAX phases. More information was provided when two experimental techniques, four-point bending and AE monitoring, were coupled together with post-mortem SEM observations. The developed experimental approach based on comparison of mechanical responses of Ti3SiC2 (MAX phase and secondary phases) and Ti2AlC (containing only MAX phases) compounds, is implemented to investigate the induced deformation and damage mechanisms. It was shown that higher quantity of MAX phases in the material improves flexural strength with corresponding more pronounce nonlinear behavior and high dissipated energy. When MAX phase grains are coarser the mechanical strength lowers but the nonlinear part becomes more significative, which results in higher values of dissipated energy. It was also shown that the secondary phases and the grain size impact the way in which the damage is accumulated within the sample. AE data provided more information on possible damage mechanisms and their chronology leading to hysteretic behavior of MAX phases. The last part has shown that the BPTT for Ti3SiC2 is ≈1200˚C and the grain size of MAX phases lowers this BPTT.

<p>The technique of Nanoindentation <em>in situ</em> Transmission Electron Microscope has been implemented on a Philips CM20. Indentations have been performed on Si and Sapphire (<em>α-Al</em><em>2</em><em>O</em><em>3</em>) cut from wafers; Cr/Sc multilayers and <em>Ti</em><em>3</em><em>SiC</em><em>2</em> thin films. Different sample geometries and preparation methods have been evaluated. Both conventional ion and Focused Ion Beam milling were used, with different ways of protecting the sample during milling. Observations were made of bending and fracture of samples, dislocation nucleation and dislocation movement. Basal slip was observed upon unloading in Sapphire. Dislocation movement constricted along the basal planes were observed in <em>Ti</em><em>3</em><em>SiC</em><em>2</em>. Post indentation electron microscopy revealed kink formation in <em>Ti</em><em>3</em><em>SiC</em><em>2</em> and layer rotation and slip across layers in Cr/Sc multilayer stacks. Limitations of the technique are presented and discussed.</p>

The technique of Nanoindentation in situ Transmission Electron Microscope has been implemented on a Philips CM20. Indentations have been performed on Si and Sapphire (α-Al2O3) cut from wafers; Cr/Sc multilayers and Ti3SiC2 thin films. Different sample geometries and preparation methods have been evaluated. Both conventional ion and Focused Ion Beam milling were used, with different ways of protecting the sample during milling. Observations were made of bending and fracture of samples, dislocation nucleation and dislocation movement. Basal slip was observed upon unloading in Sapphire. Dislocation movement constricted along the basal planes were observed in Ti3SiC2. Post indentation electron microscopy revealed kink formation in Ti3SiC2 and layer rotation and slip across layers in Cr/Sc multilayer stacks. Limitations of the technique are presented and discussed.

No description available.

L'allègement des structures est devenu un enjeu majeur pour les industries du transport. Afin de répondre à cette demande, une stratégie de recherche d'élaboration de nouveaux matériaux, présentant des propriétés spécifiques égalant a minima les propriétés des matériaux en service, a été mise en place. C'est dans ce contexte général que s'inscrivent ces travaux sur la phase MAX Ti3AlC2. La tenue à l'oxydation et les propriétés en traction et en fluage traction à haute température (800-1000°C) ont été évaluées pour des échantillons élaborés au cours de cette étude par métallurgie des poudres (frittage naturel + frittage flash). Les différents essais menés en oxydation ont montré l'existence de deux comportements (oxydation passivante ou catastrophique suivant la nature des oxydes formés) majoritairement contrôlés par les caractéristiques microstructurales des échantillons (taille de grains, nature des éléments en site A, rugosité et porosité). Les premiers essais de fluage traction réalisés sur la phase MAX Ti3AlC2 ont souligné la bonne ductilité de ces matériaux. De plus, les propriétés spécifiques sont comparables, voire dépassent, celles de superalliages polycristallins et d'aluminures de titane. Une étude multi-échelle a mis en évidence une déformation se produisant par glissement aux joints de grains à 900 et 1000°C et par mouvement de dislocations à 800°C. Un endommagement de type cavitation accompagné par des phénomènes d'oxydation de fissures en surface des fûts a été mis en lumière. / The lightening of structures has become a major challenge for transport industries. New materials with, at least, equivalent specific properties to currently used materials have been designed in order to cope with this challenge. In this regard, Ti3AlC2 MAX phase has been studied. The high temperature (800-1000°C) oxidation resistance and tension and tensile creep properties were assessed for Ti3AlC2 samples elaborated using a powder metallurgy process (pressureless sintering + spark plasma sintering). The various oxidation tests pointed out two different behaviors (protective oxidation or catastrophic one depending on the grown oxides nature) mainly controlled by samples microstructural features (grains size, elements on A site, roughness and porosity). The first tensile creep tests ever performed on Ti3AlC2 MAX phase indicates the high ductility of these materials whose specific properties reach or surpass those of polycrystalline superalloys and titanium aluminides. A multi-scale study highlights deformation mechanisms occurring through intergranular sliding at 900 and 1000°C and through dislocations glide at 800°C. Damage mechanisms occurring through cavitation supported by crack oxidation phenomena on gauge length surface were also underlined.

Les phases MAX sont des carbures ou des nitrures ternaires nano-lamellaires comportant un métal de transition (M), un élément des colonnes 13-16 (A), X=C ou N.Ces phases combinent certaines des meilleures propriétés des céramiques à celles des métaux. Leurs propriétés physiques (rigidité, résistance aux chocs mécaniques et thermiques, bonnes conductivités thermique et électrique), associées à la possibilité d’usinage, les rend très attractives en termes d’applications technologiques potentielles.En 2011, il a été établi qu’un traitement à l’acide fluorhydrique (HF) des phases MAX comprenant de l’aluminium permet une élimination sélective des plans d’atomes Al, avec pour résultat la formation de matériaux bi-dimensionnels (2D) appelés MXènes pour souligner la perte des atomes de Al. Ces nouveaux membres de la famille des matériaux 2D sont plus résistants, chimiquement plus polyvalents et possèdent une conductivité supérieure à nombre d’autres matériaux. Ils se révèlent par conséquent très intéressants pour de nouvelles applications, par exemple pour des systèmes de délivrance de médicaments in vivo, le stockage d’hydrogène, ou pour remplacer d’autres matériaux dans des batteries, le traitement des eaux usées ou divers capteurs.Dans cette thèse, nous présentons notre travail sur la synthèse, la caractérisation structurale et le transport électronique dans les phases MAX et leurs dérivés 2D, les MXènes. En ce qui concerne les phases MAX, et motivés par les propriétés fortement anisotropes attendues de tels matériaux nano-lamellaires, produire des monocristaux massifs est le moyen le plus naturel d’obtenir des échantillons où l’anisotropie des propriétés physiques peut être sondée expérimentalement. En utilisant avec succès la méthode de croissance en solution à haute température associée à un refroidissement lent, nous avons obtenu des monocristaux de divereses phases MAX, incluant Cr2AlC, V2AlC, Ti3SiC2, etc.La caractérisation structurale confirme le caractère mono-cristallin des échantillons. Expérimentalement, nous avons acquis un jeu exhaustif de mesures de magnéto-transport de monocristaux en fonction de la température et du champ magnétique. De plus, nous obtenons un rapport d’anisotropie très important entre la résistivité dans le plan ab et celle parallèle à l’axe c, allant de plusieurs centaines à plusieurs milliers. A partir des courbes de magnétorésistance et d’effet Hall, nous avons étudié en détail le comportement du transport dans le plan basal. D’un point de vue théorique, nous avons proposé un modèle général mais simple pour décrire les propriétés de magnéto-transport d’électrons presque libres dans des métaux 2D hexagonaux. Ce modèle a été modifié pour être appliqué aux propriétés de transport des phases MAX nano-lamellaires.En ce qui concerne les MXènes, nous avons synthétisé avec succès des écailles de MXènes V2CTx de grande surface à partir du traitement HF conventionnel de monocristaux de V2AlC. La délamination mécanique de ces écailles multi-couches de V2CTx en échantillons comportant peu de monocouches a aussi été réalisée. Nous avons établi la morphologie typique de ces couches à partir d’images de microscopies MEB ou TEM. A partir d’analyse EDX, nous concluons que les terminaisons -OH dominent et sont les plus stables énergétiquement. Nous détaillons ensuite le procédé de fabrication des dispositifs électriques utilisés pour obtenir les résultats de mesures de transport électrique jusqu’à basse température. Nous avons obtenu avec succès des résultats originaux sur les MXènes V2CTx, avec une valeur moyenne de résistivité de l’ordre de 2 × 10-5 ohmm. La mesure d’effet de champ indique une mobilité de 22.7 cm2/Vs. Du fait de l’intensité des recherches portées actuellement sur les MXènes, nous espérons que ces résultats contribueront de manière significative à une meilleure compréhension de cette classe de matériaux et de la façon dont leurs propriétés peuvent être contrôlées. / MAX phases are layered early transition metal ternary carbides and nitrides so called because they are composed of M, an early transition metal, A, a group A element and X is C and/or N. MAX phase structure is composed of near close-packed planes of M atoms with the X atoms occupying all the octahedral sites between them. Their physical properties (stiffness, damage and thermal shock resistance, high thermal and electrical conductivity) along with the fact they are readily machinable, make them extremely attractive in terms of the potential technological applications.In 2011, it was discovered that by immersing Al-containing MAX phases in HF acid, it was possible to selectively etch the Al, resulting in two-dimensional (2D) materials, that were labeled MXene to denote the removal of the A-group element and make the connection to another conducting 2D material, graphene. This new member of 2D materials family owns stronger, more chemically versatile, and have higher conductivity than other materials. As such they are highly interesting on new applications, e.g. specialized in vivo drug delivery systems, hydrogen storage, or as replacements of common materials in e.g. batteries, sewage treatment, and sensors.In this thesis, as its self-telling title indicated, we present our work on the synthesis, structural characterization and the electron transport in the MAX phases and their 2D derivatives, MXenes.For MAX phase: motivated by the theoretically expected anisotropic properties of these layered materials, producing bulk single crystals is a natural way to obtain samples where the anisotropy of the physical properties can be experimentally probed. Also, knowledge of low-temperature behavior of single crystal is vital because it can provide insight into MAX intrinsic physical properties. Using high temperature solution growth and slow cooling technique, several MAX phases single crystals have been successfully grown, including Cr2AlC, V2AlC, Ti3SiC2, etc. Structural characterization confirms the single crystalline character of the samples. Experimentally, a set of experimental data was obtained from single crystals of V2AlC and Cr2AlC as a function of temperature and magnetic field. In particular, we obtain a very high ratio between the in-plane and parallel to the c-axis resistivity, which is very substantial, in the range of a few hundreds to thousands. From MR and Hall effect measurement, in-plane transport behaviors of MAX phases have been studied. The extracted mobility is in the range from 50 to 120 cm2/V·s, which is the same order of magnitude of polycrystalline sample. Theoretically, a general, yet simple model was proposed for describing the weak field magneto-transport properties of nearly free electrons in two-dimensional hexagonal metals. It was then modified to be applicable for the transport properties of layered MAX phases.For MXene: Large scale V2CTx MXene flakes was successfully synthesized by conventional HF-etching of V2AlC single crystals. Mechanical delamination of multilayered V2CTx flakes into few layer flakes and transfer on Si/SiO2 substrate was also achieved. Structural characterization demonstrated an enlarged interplane distance, while prior DMSO intercalation seems to have no effect on this type of MXenes. From EDS results, we concluded that -OH terminations on V2CTx is the dominated, and the most energetically favorable, compared to -F and -O functional groups. We then detail the electrical device fabrication process and proceed with electrical measurements results, performed down to low temperature, with the aim to extract useful information on charge carrier behavior. We successfully obtained some first hand transport data on V2CTx MXenes, the average value for the resistivity of V2CTx MXenes is 2 × 10-5 Ω ∙m, which is in consistent with reported other MXene samples. The mobility, 22.7 cm2/V·s , which stays in the same order of magnitude as its parent MAX phase.

Les phases MAX sont des carbures ou nitrures ternaires dont les propriétés sont généralement décrites comme la combinaison exceptionnelle des meilleures propriétés des métaux et des céramiques. Sous forme de couches minces, ces matériaux sont prometteurs en tant que contact ohmique sur des substrats de SiC pour la microélectronique de puissance. Des approches originales dédiées à l'obtention de films minces épitaxiés des phases MAX Ti2AlN, Ti3SiC2 et Ti3(Si,Ge)C2 sont développées dans ce travail. Des recuits à 750°C de systèmes multicouches (Ti+Al)/AlN permettent ainsi de former des couches de Ti2AlN fortement texturées sur des substrats de SiC ou Al2O3. La seconde approche consiste à recuire à 1000°C des couches de TixAly ou TixGey, déposés sur 4H-SiC, pour obtenir des films minces épitaxiés de Ti3SiC2 et Ti3(Si,Ge)C2. Ces derniers présentent les caractéristiques d'un contact ohmique sur SiC. / MAX phases are a family of ternary carbides or nitrides which properties are generally described as an exceptional combination of the best properties of metals and ceramics. Thin films of MAX phases being considered as good candidates for ohmic contacts on SiC substrates for power microelectronics devices, thin films of Ti2AlN and Ti3(Si,Ge)C2 were synthesized by using original approaches. Highly textured Ti2AlN thin films were so obtained by thermal annealing at 750°C of (Ti+Al)/AlN multilayers whereas epitaxial thin films of Ti3SiC2 on 4H-SiC were achieved after an annealing at 1000°C of TixAly or TixGey layers. Good ohmic contact behaviors of Ti3SiC2 layers were confirmed in this work whereas Ti2AlN thin films behave as Schottky barriers.