Diploma thesis on Corrosion and Strenght Properties of Al – Cu Alloys. The thesis deals about aluminum, copper and alloys of these metals. It describes the production and processes, composition and it´s utilization. Furthermore, the thesis focuses on corrosion and rust prevention. The text concludes with the metodology of tensile tests which were used in the practical part of the thesis. The practical part of the thesis consists of description of operations before measurement, the measurement and subsequent evaluation

Les mécanismes de formation de phases dans des films minces du système ternaire Al-Cu-Fe et des systèmes binaires Al-Cu, Al-Fe et Cu-Fe ont été étudiés. Dans chacun des systèmes, plusieurs échantillons avec des compositions distinctes ont été préparés par pulvérisation cathodique. Des couches d’aluminium, de cuivre et de fer ont été déposées séquentiellement sur des substrats de silicium oxydé et ont été traités thermiquement par différentes méthodes puis caractérisés. Des mesures de diffraction de rayons X et de résistivité in-situ ont été effectuées pour suivre la formation des phases. Des recuits thermiques suivis de trempe ont été réalisés et les échantillons ont été caractérisés par diffraction des rayons X. L’analyse enthalpique différentielle a également été utilisée ainsi que des mesures simultanées in-situ de résistivité et de diffraction des rayons X. L’ensemble des résultats obtenus nous a permis de proposer des mécanismes de formation de phases pour chacun des échantillons étudiés et en utilisant des modèles théoriques de croissance de phases nous avons pu déterminer des données cinétiques sur la formation de phases dans ces films. / The mechanisms of phase formation in thin films have been studied in the Al-Cu, Al-Fe, Fe-Cu and Al-Cu-Fe systems. Several samples with different compositions have been prepared by sputtering. Aluminium, copper and iron layers were deposited onto oxidized silicon substrates, they were heat treated and characterized by using several techniques. In situ X-ray diffraction and resistivity measurements were used to follow the phase formation. Thermal annealings followed by quenching have also been carried out to get additional information.Differential Scanning Calorimetry and coupled in-situ resistivity and X-ray diffractionmeasurements were performed. The whole results allowed us to suggest a mechanism of phase formation for each sample and by using theoretical models of growth we determined kinetic data on the phase formation.

Made available in DSpace on 2016-03-15T19:36:33Z (GMT). No. of bitstreams: 1 Nilton Inacio Domingues Junior.pdf: 2643612 bytes, checksum: 326f49f818932a8e26d3dc25d8e43064 (MD5) Previous issue date: 2011-08-23 / Fundo Mackenzie de Pesquisa / Aluminum alloys present low specific density, good strength, and high corrosion resistance under common environments. Aluminum-Copper 2024 alloy is one of the most widely used alloy in aircraft fuselage structures due to its good mechanical properties. The microstructure of the alloy was observed by optical microscopy showing elongated grains caused from the rolling process. Solution heat treatment was performed at 495, 505, and 515°C followed by water quenching. Afterwards, artificial aging was carried out at 190 and 208°C. Hardness measurements and tensile tests were performed to determine the mechanical properties of this material after heat treatments. Tensile and hardness tests exhibited similar mechanical properties for the alloy in the three solution temperatures (495, 505, and 515°C). In general, the increase of the strength due to aging was accompanied by a decrease in ductility of the alloy. The highest values of yield and ultimate strength were obtained in the solubilized alloy at 505°C and artificially aged at 208ºC/2h. A fatigue study on Al-2024 alloy was conducted under symmetric tension-compression at room temperature, using a rotating bending testing machine. S-N curve has not shown a typical fatigue limit, but a drop steadily with decreasing stress cycle. Specimen reached up to 7.8 x 106 cycles before fracture at 110.23 MPa. The fracture surfaces of specimens submitted to high stress and low number of cycles showed large quantity of precipitates and microvoids, while in specimens submitted to low stress and high number of cycles were observed the presence of cracks along the periphery of the fracture surface. The presence of pores was intercepted and pulled out of the matrix precipitates in the fracture surface during crack propagation of high cycle fatigue. / Ligas de alumínio apresentam baixa massa específica, relativamente alta resistência mecânica e elevada resistência à corrosão. A liga alumínio-cobre 2024 tem sido uma das ligas mais amplamente utilizada, principalmente em estruturas de aeronaves, devido às suas boas propriedades mecânicas. A microestrutura da liga observada por microscopia óptica apresentou grãos alongados decorrentes do processo de laminação. O tratamento térmico de solubilização na liga 2024 foi executado em três temperaturas diferentes a 495, 505 e 515°C seguido por resfriamento em água. Após a solubilização, envelhecimento artificial foi executado nas temperaturas de 190 e 208°C. Medidas de dureza e ensaios de tração foram feitos para determinar as propriedades mecânicas deste material após tratamentos térmicos. Ensaios de tração e medidas de dureza revelaram propriedades mecânicas similares para a liga 2024 nas três temperaturas de solubilização (495, 505 e 515°C). Em geral, o aumento na resistência mecânica decorrente do envelhecimento foi acompanhado pela diminuição da ductilidade da liga. Os valores mais elevados de limite de escoamento e de resistência foram obtidos na liga solubilizada a 505°C e envelhecida a 208°C/2h. Esta condição foi escolhida para a execução dos ensaios de fadiga e levantamento da curva S-N. O estudo de fadiga da liga 2024 foi conduzido sob ciclo reverso tensão-compressão à temperatura ambiente, utilizando uma máquina de fadiga flexo-rotativa. A curva S-N não apresentou um patamar de limite de fadiga típico dos aços, mas caiu continuamente com a diminuição do ciclo de tensão. O corpo-de-prova suportou mais de 7,8x106 ciclos antes de romper para ciclo de tensão de 110,23 MPa. As superfícies de fratura dos corpos-de-prova submetidos a tensões elevadas e baixo número de ciclos mostraram basicamente precipitados e microcavidades, enquanto que nas fraturas dos corpos-de-prova submetidos a tensões baixas e elevado número de ciclos observou-se a presença de trincas ao longo de toda a borda da superfície de fratura. Houve a presença de poros interceptados e precipitados arrancados da matriz na superfície da fratura durante a propagação da trinca por fadiga de alto ciclo.

Après un chapitre d’introduction à propos des alliages métalliques complexes et leurs surfaces, le manuscrit est divisé en deux parties distinctes. La première partie (Chap.II) porte sur la détermination structurale de la surface d’ordre 2 de la phase décagonale Al-Cu-Co par LEED et STM. Les conclusions de ce chapitre indiquent (i) que la surface observée expérimentalement correspond à des terminaisons denses et riches en l’élément de plus faible énergie de surface (Al) et (ii) que la phase serait stabilisée par le terme entropique de l’énergie libre de Helmotz. Dans la deuxième partie de la thèse (Chap.III, IV et V), on applique une approche originale de science des surfaces pour résoudre un problème applicatif : l’adhérence des revêtements quasicristallins sur les substrats métalliques. On propose d’insérer une couche d’accrochage entre le revêtement et le substrat. L’alliage ?-Al4Cu9 est un bon candidat pour réaliser cette interface car il possède des propriétés structurales et électroniques intermédiaires entre un métal et un quasicristal. On élabore donc par MBE des interfaces modèles par adsorption puis recuit de Cu sur le quasicristal i-Al-Cu-Fe, puis d’Al sur Cu(111). Les expériences de photoémission, STM et LEED, ainsi que les calculs de DFT, démontrent la faisabilité d’une interface cohérente entre l’alliage de surface ?-Al4Cu9 et le Cu d’une part, et entre ?-Al4Cu9 et le quasicristal, d’autre part. Ces résultats fondamentaux sont reproduits avec succès dans le domaine applicatif, par l’élaboration de revêtements de phase ? par pulvérisation cathodique magnétron (Chap.V) / After an introductive chapter on complex metallic alloys and surfaces, the thesis is divided into two distinct parts. The first part (Chap.II) concerns the structural determination of the 2-fold surface of d-Al-Cu-Co quasicrystal, by using LEED and STM. The results show (i) that the experimental terraces correspond to dense and Al-rich terminations -the element with the lowest surface energy- and (ii) that this decagonal phase could be entropically stabilized. In the second part of the manuscript (Chap.III, IV and V), we apply a surface science approach to solve a technological bottleneck: the adherence of quasicrystalline coatings on metallic substrates. We propose to grow a buffer layer that would accommodate the differences between the two materials. For that purpose, the ?-Al4Cu9 phase is a good candidate as it shares electronic and structural properties with both substrate and coating. Hence, we synthesize model interfaces by using MBE, first by adsorption and annealing of Cu on the 5-f surface of i-Al-Cu-Fe quasicrystal and then in the Al on Cu(111) system. Photoemission, STM and LEED experiments, along with DFT calculations show that a coherent interface can be grown between the ?-Al4Cu9 surface alloy and both the Cu and the quasicrystal. Those fundamental results are successfully reproduced in the real world, by growing similar interfaces using magnetron sputterring (Chap.V)

Cette thèse est consacrée à l'étude des structures atomiques des phases icosaédriques de type F et leurs dislocations.<br /><br />Dans cette étude nous avons d'abord construit une structure générique permettant de traiter dans un seul schéma les phases icosaédriques de type F connues. Afin de valider ce modèle nous avons synthétisé quelques compositions suggérées par ce dernier. Ces synthèses ont permis entre autres de découvrir deux nouvelles phases quasipériodiques à la stoechiométrie Al66,08Cu21,35Mn8,29Fe4,28 , l'une icosaédrique (métastable) de type F et l'autre décagonale (stable). Elles ont montré, à une composition au-delà de celles déjà étudiées dans le système (Al,Pd,Fe), l'existence d'une phase F-IQC.<br /><br /> Globalement, ces résultats expérimentaux d'études de nouvelles phases icosaédriques ont permis de montrer la fiabilité du modèle : sur les trois essais de nouvelles compositions, deux ont montré l'existence de phases icosaédriques de type F et la troisième a mis en évidence une phase décagonale en relation d'épitaxie canonique avec la phase icosaédrique brut métastable (axe 10 confondu avec un axe 5).<br /><br />Possédant un modèle fiable nous avons donc pu y introduire des dislocations. Nous avons ainsi précisé la géométrie des dislocations à l'échelle atomique, hors de la zone de cœur, dans les phases F-IQC. Dans cette structure nous avons aussi identifié les mouvements des phasons et tenté d'apporter des éléments de réponse aux mouvements de ces dislocations.

Le procédé de soudage par friction malaxage (FSW) entraîne, d’une manière générale, une importante chute de dureté à travers le joint soudé. Dans le but de concevoir des structures aéronautiques soudées par FSW en fatigue, il est nécessaire de connaître l’impact de cette chute de dureté dans le comportement mécanique global de la soudure. Dans ces travaux, l’alliage d’aluminium à durcissement structural 2198-T8 est considéré. Une chaîne de calcul de durée de vie en fatigue d’une structure soudée par FSW est mise en place. Elle intègre un couplage de calculs et d’expériences grâce auxquels le comportement mécanique de la structure est modélisé. Dans un premier temps, le gradient de comportement mécanique de la soudure est étudié. Des essais mécaniques de traction et cycliques sont réalisés à température ambiante. La méthode de corrélation d’images numériques (DIC) est utilisée dans le but de mesurer les champs de déplacements localement dans et au voisinage du joint soudé. À partir des résultats expérimentaux, les paramètres mécaniques d’un modèle de comportement sont identifiés à partir d’un élément de volume, zone par zone à travers le joint soudé. En parallèle, une quantification des précipités durcissants T1 (Al2CuLi) est menée dans différentes zones du joint soudé à l’aide d’un Microscope Electronique en Transmission (MET). Un lien entre l’évolution de la microstructure à travers la soudure et l’évolution des paramètres mécaniques est recherché. Le modèle de comportement mécanique est utilisé sur des calculs de structure utilisant la méthode des éléments finis pour simuler le joint soudé. En parallèle, des essais de fatigue sont réalisés sur des éprouvettes uniaxiales et cruciformes soumises à des chargements uniaxiaux et multiaxiaux. À l’aide des simulations du gradient de comportement mécanique du joint soudé ainsi que des résultats mesurés en fatigue, les paramètres d’un modèle d’endommagement sont identifiés. Ce modèle est utilisé pour prédire les durées de vie en fatigue et les zones d’amorçages de fissure pour une structure soudée soumise à des chargements multiaxiaux. / The Friction Stir Welding (FSW) process generally induces a critical hardness decrease inside the welded joint. To design aeronautical structure welded by FSW in fatigue, it is then necessary to know the impact of this hardness drop on the constitutive behaviour of the junction. In this study, the hardening structural aluminium alloy 2198-T8 is considered.A fatigue lifetime assessment loop of a welded structure is implemented. It integrates a calculations and experiments coupling which is used to model the structure’s mechanical behaviour. The gradient mechanical behaviour of the weldment is initially studied.Monotonic and cyclic mechanical tests are carried out to room temperature. Digital Image Correlation (DIC) is used to measure local displacement fields around the junction. Based on this experimental data, mechanical parameters for a constitutive model are identified on a volume element, zone by zone across the welded joint. In parallel, a quantification of the T1 (Al2CuLi) strengthening precipitates is realized in different region of the joint with a Transmission Electron Microscope. A connection between the microstructure evolution and the mechanical parameters is researched. The gradient mechanical behaviour of the joint is assessed on a 3D structure by Finite Element Analysis. Furthermore, fatigue tests are carried out on uniaxial and multiaxial loadings welded specimen. Thanks to the mechanical behaviour model and the fatigue lifetime measured, a damage model is used to predict the fatigue lifetime and the crack initiation zone for a welded structure which is subjected to higher multiaxial loads.

Les mécanismes de formation de phases dans des films minces du système ternaire Al-Cu-Fe et des systèmes binaires Al-Cu, Al-Fe et Cu-Fe ont été étudiés. Dans chacun des systèmes, plusieurs échantillons avec des compositions distinctes ont été préparés par pulvérisation cathodique. Des couches d'aluminium, de cuivre et de fer ont été déposées séquentiellement sur des substrats de silicium oxydé et ont été traités thermiquement par différentes méthodes puis caractérisés. Des mesures de diffraction de rayons X et de résistivité in-situ ont été effectuées pour suivre la formation des phases. Des recuits thermiques suivis de trempe ont été réalisés et les échantillons ont été caractérisés par diffraction des rayons X. L'analyse enthalpique différentielle a également été utilisée ainsi que des mesures simultanées in-situ de résistivité et de diffraction des rayons X. L'ensemble des résultats obtenus nous a permis de proposer des mécanismes de formation de phases pour chacun des échantillons étudiés et en utilisant des modèles théoriques de croissance de phases nous avons pu déterminer des données cinétiques sur la formation de phases dans ces films.

In this thesis, the effect of mechanical deformation on structure, thermal stability and hardness of a single-phase spray-deposited quasicrystalline alloy with composition Al62.5Cu25Fe12.5 has been investigated in detail. The purpose of the investigation was to study the effect of mechanical milling at different milling speeds (which approximately scale with the milling intensity) on mechanically-induced phase transformations during milling and on the phase evolution during subsequent heating. The results of the milling experiments indicate that, irrespective of the milling speeds used, mechanical milling of Al62.5Cu25Fe12.5 quasicrystals leads to the formation of a disordered CsCl-type ß phase with grain size of about 10 – 20 nm. The analysis of the kinetics of the QC–to–ß phase transformation reveals that the milling intensity has a considerable effect on the characteristics of the transformation. The increase of the milling speed considerably shortens the incubation time needed to start the QC–to–ß phase transformation. Also, the overall transformation is much faster for milling at high speeds. The QC–to–ß phase transformation starts when the grain size of the quasicrystals is reduced to about 10 nm irrespective of the milling speed used and clearly indicates that a critical grain size of the quasicrystals for initiating the transformation exists. On the other hand, no critical value of lattice strain was found for the QC–to–ß transformation. This indicates that the phase transformation is controlled by the local length scale (i.e. the grain size) and by the corresponding grain boundaries rather than by the energy stored in the lattice. Energetic considerations obtained through a simple model based on the mass and velocity of the milling balls reveal that the energy needed for the QC–to–ß transformation increases with increasing the milling speed, that is, the energetic efficiency of the process decreases with increasing the milling intensity. This indicates that part the extra energy supplied during milling at high intensities is not used to induce the phase transformation but it is dissipated by heat. During heating, the milled powder displays a multi-step thermal behavior characterized by the grain growth of the disordered ß phase at low temperatures, followed, at higher temperatures, by its transformation into the original icosahedral quasicrystalline phase. The transformation is gradual and the quasicrystals and the disordered ß phase coexist over a temperature interval of more than 250 K. The phase transformations occurring during milling and subsequent annealing have a remarkable effect on the hardness, which can be tuned within a wide range of values (7–9.6 GPa) as a function of the volume fraction of the different phases. This suggests that a composite material with optimized mechanical properties can be produced by an appropriate thermo-mechanical treatment. The quasicrystals milled at a very low speed show a transition between Hall-Petch to inverse Hall-Petch behavior at a grain size of about 40 nm, which represents the critical value for grain size softening of the present Al62.5Cu25Fe12.5 quasicrystals. This behavior may be attributed to the complexity of the quasicrystalline structure and to its peculiar deformation mechanism at room temperature (i.e. shear banding), where meta-dislocation-assisted deformation is almost absent. In order to analyze the effectiveness of the Al62.5Cu25Fe12.5 quasicrystals as reinforcing agent in metal matrix composites, Al-based composites were synthesized by hot extrusion of elemental Al blended with different amounts of Al62.5Cu25Fe12.5 quasicrystalline particles. The work was focused on two specific aspects: evaluation of the mechanical properties through room temperature compression tests and modeling of the resulting properties. The addition of the quasicrystalline reinforcement is very effective for improving the room temperature mechanical properties of pure Al. The compressive strength increases from 155 MPa for pure Al to 330 and 407 MPa for the composites with 20 and 40 vol.% of reinforcement, respectively, reaching an ultimate strain of 55 % and 20 % before fracture occurs. These results indicate that the addition of the QC reinforcement leads to composite materials with compressive strengths exceeding that of pure Al by a factor of 2 – 2.5, while retaining appreciable plastic deformation. The mechanical properties of the composites have been modeled by taking into account the combined effect of load bearing, dislocation strengthening and matrix ligament size effects. The calculations are in very good agreement with the experimental results and reveal that the reduction of the matrix ligament size, which results in a similar strengthening effect as that observed for grain refinement, is the main strengthening mechanism in the current composites. Finally, the interfacial reaction between the Al matrix and the QC reinforcement has been used to further enhance the strength of the composites through the formation of a new microstructure consisting of the Al matrix reinforced with Al7Cu2Fe w-phase particles. The optimization of the structure-property relationship was done through the systematic variation of the processing temperature during consolidation. The mechanical behavior of these transformation-strengthened composites is remarkably improved compared to the parent material. The yield strength of the composites significantly increases as the Al + QC -> ω transformation progresses from 195 MPa for the sample reinforced only with QC particles to 400 MPa for the material where the Al + QC -> ω reaction is complete. These results clearly demonstrate that powder metallurgy, i.e. powder synthesis by ball milling followed by consolidation into bulk specimens, is an attractive processing route for the production of novel and innovative lightweight composites characterized by high strength combined with considerable plastic deformation. In addition, these findings indicate that the mechanical behavior of Al-based composites reinforced with Al62.5Cu25Fe12.5 quasicrystalline particles can be tuned within a wide range of strength and plasticity depending on the volume fraction of the reinforcement as well as on the extent of the interfacial reaction between Al matrix and QC reinforcing particles.

Dans ce travail, Al-Cu échantillons modèle en alliage ont été chauffés sous vide ultra élevé, et on a trouvé que l'oxyde Al grandi et Cu pertage inceased en fonction de l'exposition à l'O2 en raison de l'oxydation préférentielle de Al. échantillons ont ensuite été recuits à 540 °C sous vide poussé et vieilli à 300 °C dans l'air, et corrodés en peu de temps dans l'électrolyte neutre et l'électrolyte alcalin contenant des ions Cl- en utilisant le système à trois électrodes, respectivement. Après immersion dans l'électrolyte neutre, corrosion morphologies (creusement de tranchées sur l'échantillon poli vs fosses creuses sur l'échantillon vieilli) se distinguent. Cependant, dans un électrolyte alcalin, la corrosion a à deux phases en raison de la dissolution de l'aluminium et de l'oxyde d'aluminium dans une solution alcaline: d'une part, un oxyde d'Al et la matrice d'Al ont été dissous en général, ce qui entraîne riche en Cu intermétalliques étant laissé isolément sur la surface; d'autre part, la corrosion générale a ensuite accompagné la dissolution préférentielle du substrat environnant riche en Cu intermétalliques résultant dans des tranchées autour des particules. Formation des mixtes Al-Cu oxydes riche en Cu2O et CuO dépôts ont été trouvés sur la surface corrodée. En outre, les échantillons Al-Cu recouvertes de revêtements Al2O3 déposés par procédé ALD à la surface ont été corrodés dans des conditions similaires. Comme on s'y attendait, une amélioration significative de la résistance à la corrosion des échantillons d'alliages revêtus a été observée, mais la couche d'ALD dans l'électrolyte alcalin est pas aussi stable que dans les électrolytes neutres. / In this work, Al-Cu model alloy samples were heated in ultra high vacuum (UHV), and it was found that the Al oxide grew and Cu percentage increased as a function of exposure to the O2 owing to the preferential oxidation of Al. Then samples were annealed at 540 °C in high vacuum and aged at 300 °C in air, and corroded in short time in the neutral electrolyte and the alkaline electrolyte containing Cl- ion using the three-electrode system, respectively. After immersion in the neutral electrolyte, corrosion morphologies (trenching on the polished sample vs. hollow pits on the aged sample) are distinguished due to the different distributions of Cu-rich intermetallics in the polished sample (distributed homogeneously) and the aged sample (mostly beneath the oxide layer). However, in alkaline electrolyte, corrosion went at two stages owing to the dissolution of aluminium and aluminium oxide in an alkaline solution: firstly, Al oxide and the Al matrix were dissolved generally, resulting in Cu-rich intermetallics being left isolatedly on the surface; secondly, general corrosion went on accompanied with the preferential dissolution of substrate surrounding Cu-rich intermetallics resulting in trenching around particles. Formation of mixed Al-Cu oxides/hydroxides layer rich in Cu2O and CuO deposits were found on the corroded surface. Furthermore, Al-Cu samples covered with Al2O3 coatings deposited by ALD process on the surface were corroded under similar conditions. As expected, a significant improvement of corrosion resistance of the coated alloy samples was observed, but the ALD layer in alkaline electrolyte is not as stable as in neutral electrolytes, and undergoes dissolution.

Selective laser melting (SLM) is an additive manufacturing technology. In this thesis, a heat-treatable Al-3.5Cu-1.5Mg-1Si alloy and related materials (composites and hybrid materials) have been successfully fabricated by selective laser melting and characterized in terms of densification, microstructure, heat treatment, mechanical properties as well as tribological and corrosion behavior. Firstly, the fully dense SLM Al-Cu-Mg-Si alloy was fabricated by SLM successfully. The alloy shows a higher yield strength than SLM Al-12Si alloy, and lower wear resistance and corrosion rate than commercial 2024 alloy before and after T6 heat treatment. Secondly, with the aim of designing new alloy compositions and to examine the phases and microstructures of SLM Al-Cu alloys and to correlate their microstructures with the observed mechanical properties, Al-xCu (x = 4.5, 6, 20, 33 and 40 wt. %) alloys have been synthesized in-situ by SLM from mixtures of Al-4.5Cu and Cu powders. The results indicate that the insufficient Cu solute diffusion during the layer-by-layer processing results in an inhomogeneous microstructure around the introduced Cu powders. With increasing Cu content, the Al2Cu phase in the alloys increases improving the strength of the material. These results show that powder mixtures can be used for the synthesis of SLM composites but the reaction between the matrix and the second-phase should be considered carefully. Thirdly, the TiB2/Al-Cu-Mg-Si composite was also designed and fabricated successfully by SLM and it shows a higher strength than the unreinforced SLM alloy before and after T6 heat treatment. Finally, an Al-12Si/Al-3.5Cu-1.5Mg-1Si hybrid with a good interface was fabricated successfully. This hybrid alloy shows a good yield strength and elongation at room temperature, indicating an effective potential of selective laser melting in the field of hybrid manufacturing.