In some systems, including copper niobium, it has been found that as the scale of the two phases decreases, there is an anomalous increase in strength. Mechanisms of this strengthening have been postulated, but a general theory has yet to be developed. A model system to study the co-deformation of fine scale materials was developed and characterized. An aluminum 18.5at.% zinc alloy was selected and discontinuously precipitated to produce 100% transformation and an interlamellar spacing of 240nm.The material was tested using strain rate jump tests to determine the temperature sensitivity, tensile tested to determine work hardening and the temperature sensitivity, wire drawn to study the effect of large plastic deformation and finally tension compression tested to determine internal stresses. The bulk properties of the two phases are well known allowing for a detailed analysis of the composite properties when combined with the mechanical results. The material showed increased strength above the rule of mixture prediction from bulk properties due to a fine scale microstructure . Although the lamellar material had a much higher strength than the rule of mixtures would predict, the overall strength of the alloy did not approach that of more conventional high strength aluminum alloys. The material was found to be temperature and rate dependent, with an increased work hardening rate as the temperature was decreased. Temperature was found to play a key role in the stress partitioning between the two phases. Temperature dependent relaxation processes lowered the stress partitioning between the hard and soft phases as the temperature was increased. Therefore, stress relaxation must be minimized to maximize the strengthening found in fine scale materials.

In some systems, including copper niobium, it has been found that as the scale of the two phases decreases, there is an anomalous increase in strength. Mechanisms of this strengthening have been postulated, but a general theory has yet to be developed. A model system to study the co-deformation of fine scale materials was developed and characterized. An aluminum 18.5at.% zinc alloy was selected and discontinuously precipitated to produce 100% transformation and an interlamellar spacing of 240nm.The material was tested using strain rate jump tests to determine the temperature sensitivity, tensile tested to determine work hardening and the temperature sensitivity, wire drawn to study the effect of large plastic deformation and finally tension compression tested to determine internal stresses. The bulk properties of the two phases are well known allowing for a detailed analysis of the composite properties when combined with the mechanical results. The material showed increased strength above the rule of mixture prediction from bulk properties due to a fine scale microstructure . Although the lamellar material had a much higher strength than the rule of mixtures would predict, the overall strength of the alloy did not approach that of more conventional high strength aluminum alloys. The material was found to be temperature and rate dependent, with an increased work hardening rate as the temperature was decreased. Temperature was found to play a key role in the stress partitioning between the two phases. Temperature dependent relaxation processes lowered the stress partitioning between the hard and soft phases as the temperature was increased. Therefore, stress relaxation must be minimized to maximize the strengthening found in fine scale materials.

In some systems, including copper niobium, it has been found that as the scale of the two phases decreases, there is an anomalous increase in strength. Mechanisms of this strengthening have been postulated, but a general theory has yet to be developed. A model system to study the co-deformation of fine scale materials was developed and characterized. An aluminum 18.5at.% zinc alloy was selected and discontinuously precipitated to produce 100% transformation and an interlamellar spacing of 240nm.The material was tested using strain rate jump tests to determine the temperature sensitivity, tensile tested to determine work hardening and the temperature sensitivity, wire drawn to study the effect of large plastic deformation and finally tension compression tested to determine internal stresses. The bulk properties of the two phases are well known allowing for a detailed analysis of the composite properties when combined with the mechanical results. The material showed increased strength above the rule of mixture prediction from bulk properties due to a fine scale microstructure . Although the lamellar material had a much higher strength than the rule of mixtures would predict, the overall strength of the alloy did not approach that of more conventional high strength aluminum alloys. The material was found to be temperature and rate dependent, with an increased work hardening rate as the temperature was decreased. Temperature was found to play a key role in the stress partitioning between the two phases. Temperature dependent relaxation processes lowered the stress partitioning between the hard and soft phases as the temperature was increased. Therefore, stress relaxation must be minimized to maximize the strengthening found in fine scale materials. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Les alliages métalliques complexes (CMAs) sont des intermétalliques dont la structure est basée sur une maille unitaire géante pouvant contenir jusqu’à plusieurs milliers d’atomes. La maille unitaire est décorée par des clusters de haute symétrie, qui gouvernent les propriétés physiques de ces matériaux mais, jusqu’à présent, la réactivité chimique de ces matériaux a été peu étudiée. Le but de cette thèse était de comprendre l’influence de la complexité structurale et de la nature du métal de transition sur les premiers stades d’oxydation des alliages complexes Al-TM (TM= Co, Cu). L’influence de la complexité structurale a été examinée en étudiant des intermétalliques appartenant à la même famille (Al-Co) mais présentant une complexité structurale différente (Al9Co2, 22 atomes/maille unitaire et Al13Co4, 102 atomes/maille unitaire). L’influence du métal de transition a été étudiée en comparant les résultats obtenus sur Al9Co2, Al13Co4 et Al4Cu9 (52 atomes/maille unitaire). Les premiers stades d’adsorption, sous ultravide, d’oxygène moléculaire sur des surfaces propres Al4Cu9(110), Al9Co2(001) et Al13Co4(100) à différentes températures et dans une gamme de pression 10-8-10-7 mbar ont été suivis par LEED, XPS et STM.Pour les trois surfaces étudiées, seul l’aluminium est oxydé dans les conditions expérimentales utilisées. A température ambiante une couche désordonnée d’oxyde d’aluminium d’environ 1,34 nm est formée sur Al4Cu9, qui cristallise après chauffage à 650 °C pour former un film d’oxyde de structure sixton. Sur les surfaces d’alliages Al-Co, la couche désordonnée formée à température ambiante est plus fine (0,54 à 0,43 nm) et ne cristallise pas après recuit. Par contre, un oxyde de structure sixton est formé après oxydation de la surface de Al9Co2 à 500 °C. La formation de cette phase oxydée cristallisée est gouvernée par la compétition entre la ségrégation de l’aluminium et la diffusion de l’oxygène. Lorsque la ségrégation d’aluminium est insuffisante ou la diffusion d’oxygène trop rapide, cet oxyde n’est pas observé. La mobilité des atomes d’aluminium, liée au degré de covalence des liaisons intermétalliques, est donc le facteur prépondérant pour la structure du film d’oxyde formé. / Complex metallic alloys (CMAs) are intermetallics having a crystalline structure based on a giant unit cell which can contain up to several thousands of atoms. The cell structure is usually decorated with highly symmetric clusters which can affect the alloy physical properties. So far, very few studies of the chemical reactivity of these materials have been published. The aim of the thesis was to understand the influence of the structural complexity and of the nature of the transition metal on the oxidation of Al-TM (TM=Co, Cu). The influence of structural complexity was examined by studying intermetallics belonging to the same Al-Co family but showing different structural complexity (Al9Co2, 22 atoms/unit mesh and Al13Co4, 102 atoms/unit mesh). The effect of the transition metal was studied by comparing the results obtained on Al9Co2, Al13Co4 and Al4Cu9 (52 atoms/unit mesh) surfaces. The early stages of molecular oxygen adsorption on clean Al4Cu9(110), Al9Co2(001) and Al13Co4(100) surfaces at different temperatures and in the pressure range 10-8-10-7 mbar was followed using LEED, XPS and STM.For all surfaces studied, aluminum is the only element oxidised in our experimental conditions. At room temperature, a thin layer (1.34 nm thick) of disordered aluminium oxide is formed on Al4Cu9, which crystallises following annealing at 650 °C to form a sixton structure. On the Al-Co surfaces, the disordered oxide layer formed at room temperature is thinner (0.53 to 0.43 nm) and remains disordered after annealing at various temperatures. However, an ordered oxide with the sixton structure is formed after oxidation of the Al9Co2 surface at 500 °C. The formation of the ordered oxide layer is governed by the competition between aluminium segregation and oxygen diffusion. When aluminium segregation is too low or oxygen diffusion too fast, the ordered phase is not observed. Therefore, the aluminium atoms mobility, hence the degree of covalency of the intermetallic bonds, is the main parameter governing surface oxidation of these materials.

This thesis work is an experimental study of one type of Semi-Solid Metal casting (SSM) process which is called RheoMetalTM. This method is an efficient type of Rheocasting that creates a semi-solid slurry within 30 seconds that is used for a high pressure die casting machine. The purpose of using a slurry in a high pressure die casting machine is that the slurry has a higher viscosity due to its solid fraction. This makes the filling of the die cavity more laminar which reduces air entrapment in the casting. The difficulty with this type of casting is to control the process parameters to be able to insure a casting with desired properties. A few studies within RheoMetalTM has already been made but there is still a lack of knowledge of to what extent the process parameters affect the slurry. The goal in this work is to study how the different RheoMetalTM process parameters influence the primary α-Al solid fraction, shape and size. The process parameters that were studied in this work was the stirring rate, superheat and EEM amount. In this study, the so called growth layer has been removed to make more precise calculations of the primary α-Al. This work also aims to study how grain refinement affect the primary α-Al which is commonly used to improve the quality of castings. To be able to perform this study, both practical and theoretical work has been implemented. The casting process involved making of ladles and preparation of various equipment. The cast samples were then prepared by standard metallurgy procedure for optical analyse of the microstructure. A special etching reagent was used to analyse the microstructure in a microscope. The etching is called Weck’s reagent and its purpose is to differentiate the growth layer from the primary α-Al. The growth layer is formed during quenching and by excluding it, the calculation of the slurry’s primary α-Al becomes more precise. This is because the slurry is not quenched before it is inserted into the high pressure die casting machine, therefore no growth layer is formed. To analyse the cast samples, a special program was used to identify and to calculate the solid fraction, shape and size of the primary α-Al. The result from the calculations made by the program gave different tendencies when changing the EEM amount. The stirring rate showed a tendency to decrease the solid fraction and increase the shape factor. The superheat decreased the solid fraction and increased the shape factor. The grain refinement also decreased the solid fraction and increased the shape factor. There was no clear tendency showing that the equivalent circular diameter of the primary α-Al was affected by any of the parameters.

L'objectif premier de ce projet est la mise au point de procédés de fabrication microélectroniques/microtechnologiques compatibles avec l'utilisation d'un support papier. Pour cela, des techniques comme l'évaporation thermique sous vide, la photolithographie, l'électrodéposition et l'anodisation d'aluminium ont été développées et adaptées à ce support. Des bancs de caractérisations structurels, électriques et flexibles ont été aussi mis en œuvre pour étudier la fiabilité des couches déposées sur un tel substrat. En application, un capteur d'humidité à base d'oxyde d'aluminium flexible a été fabriqué et les tests en humidité ont montré d'excellents résultats permettant de valider le travail effectué. / The primary objective of this project is the implementation of microelectronics/microtechnology processes compatible with the use of paper-based substrate. For this purpose, techniques such as thermal vacuum evaporation, photolithography, electroplating and anodizing aluminum have been developed and adapted to this substrate. Structural, electrical and flexible characterizations benches have also been implemented to study the reliability of the layers deposited on such substrate. A moisture sensor based on flexible aluminum oxide was made and humidity tests have shown excellent results which validate the work.

Aluminiumfluorid (HS-AlF3), das mit Hilfe des Sol-Gel-Verfahrens unter nicht-wässrigen Bedingungen hergestellt wird, weist eine extrem große Oberfläche und eine hohe Lewis-Acidität auf, die mit den stärksten bekannten Lewis-Säuren wie SbF5 und ACF vergleichbar ist. Diese ungewöhnlichen Eigenschaften werden im Ergebnis einer neuen Sol-Gel-Synthese erhalten, die die Fluorolyse eines Aluminium-Alkoxids durch wasserfreien Fluorwasserstoff in organischen Lösungsmitteln zur Grundlage hat. Das zunächst in einer amorphen, katalytisch inaktiven Vorstufe mit großer Oberfläche gebildete Gel wird nach anschließender Trocknung mit gasförmigen Fluorierungsmitteln nachfluoriert, wobei die aktive Form des HS-AlF3 erhalten wird. Im Rahmen der vorliegenden Arbeit wurden alle Schritte dieses Syntheseweges untersucht und die Ergebnisse einschließlich einer detaillierten Analyse der erhaltenen Materialien diskutiert. Des Weiteren wurde HS-AlF3 durch eine Imprägnierungs-Methode auf das Trägermaterial Al2O3 aufgetragen, wobei verschiedene Beladungen mit HS-AlF3 getestet wurden. Die Eigenschaften des HS-AlF3/Al2O3 als Lewis-Säure-Katalysator wurden mittels der Dismutierung von CHClF2 und der Isomerisierung von CBrF2CBrFCF3 bestimmt. Die Herstellung von AlFyOx mit Hilfe des Sol-Gel-Verfahrens ist ebenfalls beschrieben, wobei das Produkt amorph ist und eine große Oberfläche von bis zu 240 m2/g aufweist. / Aluminum fluoride (HS-AlF3) prepared via sol-gel synthesis route under non-aqueous conditions exhibits high surface area and an extremely strong Lewis acidity, comparable with some of the strongest known Lewis acids such as SbF5 and ACF. The basis of its unusual properties is the sol-gel fluorination of aluminum alkoxide with anhydrous HF in organic solvents yielding first an amorphous catalytically inactive precursor with high surface area, which can be dried and eventually post-fluorinated to get HS-AlF3. In this thesis, all steps of the synthesis route were thoroughly investigated. The results of these investigations together with detailed analysis of the obtained materials are reported and discussed. HS-AlF3 supported on Al2O3 with different HS-AlF3 loadings was prepared by wet impregnation method. The properties of the HS-AlF3/Al2O3 samples as Lewis acid catalyst were evaluated for CHClF2 dismutation and CBrF2CBrFCF3 isomerization. The preparation of AlFyOx via sol-gel method is also reported. AlFyOx prepared is amorphous and have high surface are up to 240 m2/g.