En esta tesis se ha estudiado en una primera parte el efecto del hidrógeno sobre el sistema bimetálico B2 FeAl con defectos puntuales. En este caso se determinó la ubicación de la impureza en un sitio intersticial octaédrico y los resultados se compararon con cálculos de densidad funcional y con algunos resultados experimentales de la literatura. En una segunda parte se estudio el efecto de diferentes adsorbatos (H y CO) en la superficie (110) del compuesto intermetálico PdGa. Se determinaron las geometrías de adsorción y el enlace químico. Además, se computaron las frecuencias de vibración metal-adsorbato. Finalmente, se estudio el efecto del hidrógeno sobre las superficies de bajo índice (100), (111) y (1 1 1) de PdGa; determin ándose geometrías de adsorción, enlace químico y frecuencias de vibración. Todos los cálculos fueron realizados utilizando la teoría del funcional de la densidad (DFT). La optimización de la geometría, la estructura electrónica y frecuencias de vibración se obtuvieron con el código VASP. Los cambios en el enlace químico del hidr´ogeno adsorbido/ absorbido y el CO adsorbido se computaron con el código SIESTA. Se analizó el rol de los orbitales s, p y d en el mecanismo de enlace para todos los sistemas metálicos así como el efecto del hidrógeno y CO sobre la fuerza cohesiva metal-metal. / In this thesis, it has been studied the hydrogen e↵ect on the bimetallic system B2 FeAl with single defects, as a first part. The impurity location has been determined as an octahedral interstitial site and the results were compared with density functional calculations and some experimental data from literature. In a second part, it has been studied the e↵ect of di↵erent adsorbates (H and CO) on the (110) surface of the intermetallic compound PdGa. The adsorption geometries and chemical bond were computed. In addition, the metal-adsorbate vibrational frequencies were calculated. Finally, the hydrogen e↵ect on the low-index surface (100), (111) and (1 1 1) of PdGa has been studied. The adsorption geometries, chemical bond and vibrational frequencies were also computed. All the calculations have been performed using density functional theory (DFT). The optimized geometry, electronic structure and vibrational frequencies have been obtained using the VASP code. The changes in the chemical bond of the adsorbed/ absorbed hydrogen and CO adsorbed have been computed with the SIESTA code. The role of s, p and d orbitals in the bonding mechanism for all metallic systems has been analyzed as well as the hydrogen and CO e↵ect on the metal-metal cohesive interaction.

Ordered intermetallics based on transition metal aluminides have been proposed as structural materials for advanced aerospace applications. The development of these materials, which have the advantages of low density and high operating temperatures, have been focused on the aluminides of titanium, nickel and iron. Though these materials exhibit attractive properties at elevated temperatures, their utilization is limited due to their propensity for low temperature fracture and susceptibility to decreased ductility due to environmental effects. A major embrittlement mechanism at ambient temperatures in these aluminides has been by the loss of cohesive strength at the interfaces (intergranular failure). This study focuses on this mechanism of failure, by undertaking a systematic study of the energies and structures of specific grain boundaries in some of these compounds. The relaxed atomistic grain boundary structures in B2 aluminides, FeAl, NiAl and CoAl and <I>L</I>1₀ γ-TiAl were investigated using molecular statics and embedded atom potentials in order to explore general trends for a series of B2 compounds as well as TiAl. The potentials used correctly predict the proper mechanism of compositional disorder of these compounds. Using these potentials, point defects, free surface energies and various grain boundary structures of similar energies in three B2 compounds, FeAl, NiAl and CoAl were studied. These B2 alloys exhibited increasing anti-phase boundary energies respectively. The misorientations chosen for detailed study correspond to the Σ5(310) and Σ5(210) boundaries. These boundaries were investigated with consideration given to possible variations in the local chemical composition. The effects of both boundary stoichiometry and bulk stoichiometry on grain boundary energetics were also considered. Defect energies were calculated for boundaries contained in both stoichiometric and off-stoichiometric bulk. The surface energies for these aluminides were also calculated so that trends concerning the cohesive energy of the boundaries could be studied. The implications of stoichiometry, the multiplicity of the boundary structures and possible transformations between them for grain boundary brittleness are also discussed. / Ph. D.

This study is mainly aimed at interstital-free and dual-phase steels, analyzing the compositions and distribution of selective surface oxides after annealing and then to know the influence of these oxidation for the formation of FeAl inhibition layer in hot-dip galvanizing. Interstital-free and dual-phase steels were first annealed at 800 oC for 1-200 s in a 10% H2-N2 protected atmosphere of -70 oC and 0 oC dew point respectively and then dipped in zinc bath with Al content 0.12-0.18 wt% for 0-20 s. Using this combined SEM, Auger electron spectroscopy(AES), X-ray photoelectron spectroscopy(XPS) and ICP-AES etc. instruments, it is shown that the MnAl2O4 spinels were the major oxidation on the surface of IF steel after annealing. The average oxidation thickness was about 5-15 nm. Annealing times has little effect on the thickness. On the other hand, MnO were observed on DP steel surface after anneaing. The MnO paticles mainly distributed at the grain boundaries ,and the average oxdaiton thickness increase rapidly from 20 nm(10 s) to 110 nm(200 s) with annealing times. The growth of the FeAl inhibition layer can separate to nucleation in initial stage and diffusion growth later. The Fe2Al5 nucleation times were all about 0.1 s in both steels , and average thicknesses were approximately 20 nm. For IF steels , Al uptake in the zinc bath and steel interface was depleted in nucleation stage with 0.12 wt% Al content, so that delayed the growth of Fe2Al5, and the rate determining step was the diffusion of Al in zinc bath. When Al content raise up to 0.14 wt%, the phenomenon of growth delay was not happened, and the rate determining step of Fe2Al5 growth changed to the solid-state diffusion of Fe in Fe2Al5. For DP steels, when Al content up to 0.14 wt%, the growth mechanism was similar to IF steels, but the rate determining step of Fe2Al5 growth was mainly in the grain boundary diffusion of Fe in Fe2Al5. Moreover, where the MnO paticles was rich could obviously observe the delay of Fe2Al5 growth. It was probably because of consuming a great deal of Al to reduce the MnO oxides.

La fusion sélective par laser (Selective Laser Melting, SLM), une des techniques de la fabrication additive (AM), permet la production de pièces en trois dimensions (3D) de formes complexes directement à partir de poudres métalliques. Elle présente de nombreux avantages significatifs par rapport aux méthodes traditionnelles de fabrication mais se heurte encore à une faible disponibilité des matériaux en poudre.Le travail effectué dans cette étude a donc consisté à étudier et à développer un nouveau moyen pour réaliser in situ des pièces en alliages et en composites à partir de mélanges de poudres.Au niveau expérimental le choix s’est porté sur le système Fer-Aluminium et sur un renforcement par des particules de SiC.Les essais ont permis de constater que dans le processus de fabrication de pièces par SLM la puissance du laser et la vitesse de balayage déterminent au premier chef la densité, la microstructure, la composition de phase et les propriétés mécaniques.À partir d’un mélange de poudres, des phases intermétalliques ont été obtenues en contrôlant les paramètres SLM. Un traitement thermique ultérieur influence les paramètres cristallins, le degré d’ordre et les propriétés mécaniques des pièces ainsi formées.Avec l’utilisation de poudres préalliées, un phénomène de texture a été observé prenant la forme de grains allongés/colonnaires orientés dans la direction de construction.Le renforcement de la matrice de fer par des particules de SiC de différentes tailles conduit à une modification structurale avec la formation de produits d’interaction, perlitie et martensite, conduisant à une amélioration de la résistance à la traction par rapport au Fe pur. / Selective laser melting (SLM), as one of the additive manufacturing (AM) technologies, enables the production of three dimensional (3D) complex parts directly from metal powders. It offers many significant advantages compared with traditional manufacturing methods; however it faces a limited availability of powder materials.The work done during this study consisted in investigating and developing a new way of in situ producing alloys and composites from powder mixtures.The iron-aluminum system and reinforcement by SiC particles were considered.Experiments have shown that the laser power and scanning speed primarily determine the density, microstructure, phase composition and mechanical properties in the manufacturing process of SLM parts.Using pre-alloyed powders, a phenomenon of texture was observed in the form of elongated/columnar grains oriented in the building direction.Using powder mixtures, intermetallic phases were obtained by controlling the SLM parameters. A heat treatment influences the crystal parameters, the degree of order and the mechanical properties of the formed parts.The reinforcement of the iron matrix by SiC particles of several sizes leads to a structural change with the formation of interaction products, perlite and martensite, leading to an improvement in tensile strength compared to pure Fe.

La fusion sélective par laser (Selective Laser Melting, SLM), une des techniques de la fabrication additive (AM), permet la production de pièces en trois dimensions (3D) de formes complexes directement à partir de poudres métalliques. Elle présente de nombreux avantages significatifs par rapport aux méthodes traditionnelles de fabrication mais se heurte encore à une faible disponibilité des matériaux en poudre.Le travail effectué dans cette étude a donc consisté à étudier et à développer un nouveau moyen pour réaliser in situ des pièces en alliages et en composites à partir de mélanges de poudres.Au niveau expérimental le choix s'est porté sur le système Fer-Aluminium et sur un renforcement par des particules de SiC.Les essais ont permis de constater que dans le processus de fabrication de pièces par SLM la puissance du laser et la vitesse de balayage déterminent au premier chef la densité, la microstructure, la composition de phase et les propriétés mécaniques.À partir d'un mélange de poudres, des phases intermétalliques ont été obtenues en contrôlant les paramètres SLM. Un traitement thermique ultérieur influence les paramètres cristallins, le degré d'ordre et les propriétés mécaniques des pièces ainsi formées.Avec l'utilisation de poudres préalliées, un phénomène de texture a été observé prenant la forme de grains allongés/colonnaires orientés dans la direction de construction.Le renforcement de la matrice de fer par des particules de SiC de différentes tailles conduit à une modification structurale avec la formation de produits d'interaction, perlitie et martensite, conduisant à une amélioration de la résistance à la traction par rapport au Fe pur.