Nous étudions la fragilisation par l'hydrogène de l'alliage d'aluminium 7108. Une technique expérimentale spécifique a été développée : Un pré-chargement en hydrogène des échantillons, à travers un dépôt de nickel de quelques dizaines de microns, qui empêche la dissolution du substrat d'aluminium, est utilisé. Il permet la comparaison de la résistance à la fragilisation de différentes microstructures modèles. Nous étudions l'effet du traitement thermique et de la précipitation sur la sensibilité à l'hydrogène pour des vitesses de déformation macroscopiques imposées variables. Différents modes de rupture sont observés ainsi que des transitions entre eux. Au moyen de simulations numériques à l'échelle mésoscopique, l'effet de taille des précipités intergranulaires pré-fragilisés sur la ténacité des joints de grains est estimé, en utilisant un modèle de zone cohésive. Nous analysons la compétition entre la diffusion de l'hydrogène vers la pointe de la fissure et la vitesse de fissuration par un couplage mécanique - diffusion basé sur la diffusion de l'hydrogène assistée par la contrainte hydrostatique. Une vitesse critique au-delà de laquelle l'hydrogène ne peut plus suivre la fissure, est mise en évidence. L'influence de la microstructure du joint de grains sur cette vitesse est analysée. La valeur est comparée à une estimation des vitesses de propagation expérimentales obtenues pour différentes vitesses de déformation macroscopiques. Nous analysons l'effet du piégeage de l'hydrogène par les précipités intergranulaires et la désorption sur la répartition de l'hydrogène le long du joint de grains en imposant un flux au niveau de l'interface précipités - matrice. / We study the hydrogen embrittlement of the 7108 aluminum alloy. A specific experimental technique was developed : A hydrogen pre-charging, through few tens of microns of deposit of nickel, which prevents the dissolution of the aluminum substrate is used. It allows a comparison of the resistance to embrittlement of different model microstructures. We study the effect of heat treatment and intergranular precipitation on the susceptibility to hydrogen embrittlement for several macroscopic strain rates. Different failure modes and transitions between them are observed. Through numerical simulations, at the mesoscopic scale, the effect of the size of pre-weakened intergranular precipitates on the grain boundary toughness is estimated using a cohesive zone model. We further analyze the competition between the hydrogen diffusion toward the crack tip and crack velocity. For this purpose, a mechanical – diffusion coupling based on the hydrogen diffusion assisted by hydrostatic stress is elaborated. A critical crack velocity, beyond which hydrogen can no longer follow the crack, is highlighted. The influence of the grain boundary microstructure on this critical crack velocity is evaluated and its value is compared with an estimate of velocities obtained for different experimental macroscopic strain rates. We analyze the effect of hydrogen trapping by intergranular precipitates and hydrogen desorption by imposing a flux at the precipitates – matrix interfaces.

Nous étudions la fragilisation par l'hydrogène de l'alliage d'aluminium 7108. Une technique expérimentale spécifique a été développée : Un pré-chargement en hydrogène des échantillons, à travers un dépôt de nickel de quelques dizaines de microns, qui empêche la dissolution du substrat d'aluminium, est utilisé. Il permet la comparaison de la résistance à la fragilisation de différentes microstructures modèles. Nous étudions l'effet du traitement thermique et de la précipitation sur la sensibilité à l'hydrogène pour des vitesses de déformation macroscopiques imposées variables. Différents modes de rupture sont observés ainsi que des transitions entre eux. Au moyen de simulations numériques à l'échelle mésoscopique, l'effet de taille des précipités intergranulaires pré-fragilisés sur la ténacité des joints de grains est estimé, en utilisant un modèle de zone cohésive. Nous analysons la compétition entre la diffusion de l'hydrogène vers la pointe de la fissure et la vitesse de fissuration par un couplage mécanique - diffusion basé sur la diffusion de l'hydrogène assistée par la contrainte hydrostatique. Une vitesse critique au-delà de laquelle l'hydrogène ne peut plus suivre la fissure, est mise en évidence. L'influence de la microstructure du joint de grains sur cette vitesse est analysée. La valeur est comparée à une estimation des vitesses de propagation expérimentales obtenues pour différentes vitesses de déformation macroscopiques. Nous analysons l'effet du piégeage de l'hydrogène par les précipités intergranulaires et la désorption sur la répartition de l'hydrogène le long du joint de grains en imposant un flux au niveau de l'interface précipités - matrice.

Les alliages d'aluminium de la série 7xxx sont des alliages à durcissement structural, principalement utilisés dans des applications aéronautiques en raison de leurs propriétés mécaniques spécifiques élevées. Le composant principal de leur résistance mécanique est leur microstructure de précipitation, obtenue par le biais de traitements thermomécaniques complexes. Ceux-ci induisent cependant des contraintes internes à longue distance, susceptibles de générer des distorsions sévères dans les pièces aéronautiques. Certains traitements thermomécaniques comme le grenaillage (shot peening), le formage laser (laser forming) et le formage revenu (age-forming), des procédés respectivement purement mécanique, purement thermique et thermomécanique, permettent de réduire les distorsions de pièces usinées. Ils modifient cependant la microstructure, et, par conséquent, les propriétés mécaniques. La présente étude, portant sur les couplages entre ces traitements thermomécaniques, la microstructure et les propriétés mécaniques d'un alliage 7xxx, comprend un travail de caractérisation expérimentale et de modélisation à base physique. L'effet de la précipitation sur l'écrouissage du matériau est ainsi examiné, et un modèle d'écrouissage destiné à être implémenté dans un modèle éléments finis de simulation du grenaillage est proposé. L'étude du formage laser aboutit quant à elle à un modèle prédictif de l'état de précipitation et des propriétés mécaniques locales induits par ce procédé. La dernière partie est consacrée à l'étude de l'effet du formage revenu – procédé combinant déformation plastique et traitement thermique simultanés – sur la précipitation.

Casting, Solidification, Aluminum, Physical Metallurgy, Mechanical Metallurgy, Strengthening Model, Aluminum Wrought Alloys, Aluminum 7xxx Series, Al-Zn-Mg-Cu / Over the past decades, researchers in casting fields, especially in semi-solid metal state, have endeavored to find new ways to enable the Al wrought alloys of casting using the conventional casting processes; mainly in order to improve the product properties and decrease the product cost. The thixoforming and rheocasting processes have been presented as ways by which the microstructure of Al-base wrought alloys can be changed into non-dendritic, which in turn can lead to improvement to the mechanical properties. This can be because the effect of the non-dendritic microstructure on the mechanical properties of the material. Unfortunately, these processes have proved to be cost prohibitive and be a bit complicated for commercial applications. Further, conventional casting of Al-base wrought alloys along with their superior properties and performance have been a challenge for foundry industry due to the main disadvantage of hot tearing or hot cracking during solidification process. This can render the cast component ineffective. To overcome the disadvantages of thixoforming and rheocasting processes, Controlled Diffusion Solidification (CDS) process was innovated mainly to enable casting of aluminum wrought alloys with a non-dendritic morphology of the primary Al phase in the resultant cast microstructure and thus alleviating the problem of hot tearing and obtaining a cost effective product with improved mechanical properties. The CDS is a simple process involving mixing of two precursor alloys of different thermal masses (temperature and solute) and subsequently casting the resultant mixture of the desired solute composition and temperature as a near net shaped cast product. The process can easily be commercialized with a marginal capital cost required for set up such as the addition of an extra holding furnace. Further, the CDS process would prove itself to be unique in its ability to cast Al-based wrought alloys into near net shaped components without additional processes and cost. The originality of this study is to present a viable casting process for the Al-7xxx wrought alloys (Al-Zn-Mg-Cu); by which the Al-7xxx family alloys are presented in cast condition to have an acceptable uniaxial property range that is comparable with their wrought counterparts. This study presents the process and alloy parameters necessary for the casting of Al-7xxx wrought alloys (Al-Zn-Mg-Cu), by using the CDS process coupling with tilt pour gravity casting (TPGC) machine. The uniaxial tensile mechanical properties of several Al-7xxx CDS castings under various heat treatment conditions, namely, solutionizing (T4), peak aged (T6) and annealing (O), necessary for development of an ageing process on the material were investigated and presented. The tilt pour gravity casting process coupled with the CDS technology was employed to demonstrate the ability to cast Al-7xxx wrought alloys into high integrity components with high strength and ductility. The microstructure characterization was carried out by Electron Microscopy (TEM, SEM and EDS) and DSC test experiments for all the as cast (F), T4, T6 and anneals (O) conditions of the CDS cast components. Also, the predictive capabilities for the yield strength of Al 7xxx alloys CDS cast components was investigated using structural-properties modeling for the various strengthening effects that are recently proposed specifically for the Al-7xxx wrought counterparts. The study has successfully led to a more in-depth understanding of the innovative CDS casting process by applying it to several compositions of Al-7xxx wrought alloys in an industrial scale CDS casting experiments, using tilt pour gravity casting (TPGC) machine. This will hopefully lead us to a clearer path towards commercializing the CDS process and obtaining a viable casting process for Al-base wrought alloys into near net shape components without much change to economics of the casting process. / Dissertation / Doctor of Philosophy (PhD) / Casting, Solidification, Aluminum, Physical Metallurgy, Mechanical Metallurgy, Strengthening Model, Aluminum Wrought Alloys, Aluminum 7xxx Series, Al-Zn-Mg-Cu

This project was funded by Automotive Partnership Canada (APC), an initiative created by the Government of Canada in an attempt to support significant, collaborative R&D activities in order to benefit the entire Canadian automotive industry. / High strength Al-Zn-Mg-Cu alloys have been increasingly employed in the transportation industry due to the increased demands for light structural components. However, their applications have been limited to relatively expensive wrought products. Application of the shape cast Al-Zn-Mg-Cu parts has never been the focus of attention due to their poor castability and mechanical properties. Improving the casting quality is expected to increase their utilization within the automotive industry. The poor castability and mechanical properties of some alloys in this family may be effectively improved through optimized chemistry control and melt treatment including grain refinement. The primary objective of this project is to optimize the chemistry and heat treatment of the Al-Zn-Mg-Cu alloy family that results in improved strength with acceptable level of ductility and casting quality relative to other shape cast Al alloys. The Taguchi experimental design method was used to narrow down the number of required casting experiments required to meet the research objective. Three levels across four elements yielded a total of 9 Al-Zn-Mg-Cu alloys, which were cast using a tilt pour permanent mold process. The effect of each major alloying element on the microstructure, and mechanical properties was investigated. Tensile measurements were made on the 9 alloys subjected to two steps solution treatments. Mechanical properties such as yield strength (YS), ultimate tensile strength (UTS), and elongation at fracture (El.%) were experimentally measured and statistically analyzed. An ANOVA analysis was employed to quantify the percentage contribution of the alloying elements on the material properties. Grain refinement was found to play a significant role in improving the hot tearing resistance and, thereby ameliorating quality. The alloying element that affected the YS and UTS to the greatest extent was Cu, followed by Zn. In contrast, the effect of Mg and Ti on YS and UTS was insignificant. Moreover, a decrease in Mg content had the greatest effect in enhancing the El.%. A regression analysis was used to obtain statistical relationships (models) correlating the material properties with the variations in the content of the major alloying elements. The R-square values of YS, UTS, and El.% were 99.7 %, 98 %, and 90 %, respectively, showing that the models replicated the experimental results. Verification measurements made on shape cast Al-6Zn-2Mg-2Cu alloy revealed that the material property model predictions were in agreement with the experimentally measured values. The results show that secondary and over ageing treatments of the shape cast Al-Zn-Mg-Cu alloys lead to superior combination of YS and El.%. The ongoing advances in shape casting of Al-Zn-Mg-Cu alloys with high will make them suitable choices for commercial load-bearing automotive components, when it comes to the selection of a material meeting the minimum requirements for strength, damage tolerance, cost and weight. / Thesis / Master of Applied Science (MASc)

Al-Zn-Mg-Cu-Zr based AA7010 aluminum alloy belongs to the class of heat treatable alloys and the semi-finished products are generally produced by hot rolling, forging or extrusion processes. It is well known that the thermo-mechanical processing parameters strongly influence both the evolution of texture as well as microstructure in the material. As a result, the semi-finished products exhibit anisotropy in mechanical properties causing legitimate concerns on the applicability of the alloys. In the present thesis, a systematic study on the evolution of texture and microstructure and its implications on the mechanical properties anisotropy of AA7010 alloy has been attempted. A brief introduction on the development of texture and its influence on the anisotropy of the mechanical properties of 7xxx series aluminum alloys is presented first with a view to explore the scopes for further investigation. An overview of the relevant literature is described subsequently. The development of texture and microstructure in an Al-Zn-Mg-Cu-Zr based 7010 aluminum alloy during uneven, hot cross-rolling is presented. Materials processing involves three different types of uneven cross-rolling. The variations in relative intensity of the β-fibre components as a function of cross rolling modes have been investigated. It has been shown that the main attributes to the texture evolution in the present study are (a) cross-rolling and inter-pass annealing that reduce the intensity of Cu component following each successive pass, (b) recrystallization resistance of Bs oriented grains, (c) stability of Bs texture under cross-rolling, and (d) Zener pinning by Al3Zr dispersoids. The stability of the unique single, rotated Brass-{110}(556) component developed in the present alloy, during long term thermal annealing and cold rolling deformation has been systematically investigated further. Subsequently, the influence of development of microstructure and texture on the in-plane anisotropy (AIP) of yield strength, work hardening behavior and yield locus anisotropy has been presented. The AIP and work hardening behavior are evaluated by tensile testing at 0o, 45o and 90o to the rolling direction, whilst yield loci have been generated by Knoop hardness method. It has been observed that in spite of having strong rotated Brass texture, the specimens show low AIP especially in peak aged temper. The in-plane anisotropy (AIP) of yield strength, and work hardening behavior of a heat treated 7010 aluminum alloy sheet having strong, rotated Brass-{110}556 component with different texture intensity and volume fraction of recrystallization has been further evaluated. It is observed that the AIP increases with increase in texture intensity and volume fraction of recrystallization. In the subsequent chapter, the tensile flow and work hardening behavior are described using constitutive equations. Room temperature tensile properties have been evaluated as a function of tensile axis orientations in as-hot rolled as well as peak aged conditions. It has been found that both the Ludwigson and a generalized Voce-Bergström relation adequately describe the tensile flow behavior in all conditions compared to the Hollomon relation. The Voce-Bergström parameters define the slope of - plots in the stage-III regime when the specimens show a classical linear decrease in hardening. Further analysis of work hardening behavior throws light on the effect of texture on the dislocation storage and dynamic recovery. An overall summary of the experimental results and the scopes for future studies have been presented at the end.

Les alliages d'aluminium de la série 7000 à hautes caractéristiques mécaniques, constitués principalement des éléments d'addition Zn, Mg, et Cu, sont notamment utilisés dans l'industrie aéronautique civile. Néanmoins, les traitements thermiques et/ou thermomécaniques appliqués pour maximiser les propriétés mécaniques de ces alliages, peuvent les sensibiliser à divers modes de corrosion structurale dont la corrosion feuilletante, dont les mécanismes sont encore mal compris. En outre, les nouvelles générations d'alliages, développées en vue d'augmenter les propriétés mécaniques, contiennent toujours plus d'éléments d'addition, ce qui est susceptible de modifier leur sensibilité à ce phénomène. <br />Ce travail s'attache à faire progresser la compréhension des mécanismes de corrosion feuilletante des alliages 7000, en cherchant à identifier le rôle des principaux éléments d'alliage. Pour cela nous avons caractérisé finement les états de précipitation d'un grand nombre de microstructures, comme la composition des précipités durcissants nanométriques et de la matrice, par ASAXS et 3DAP. En parallèle, nous avons développé de nouvelles techniques électrochimiques permettant de quantifier la sensibilité de ces mêmes microstructures à la corrosion feuilletante. <br />Les résultats de l'étude mettent en évidence l'existence de deux mécanismes de corrosion : endommagement par dissolution intergranulaire et par rupture intergranulaire, dont la prédominance dépend de la composition de l'alliage et du traitement thermique. Nous proposons une explication au comportement en corrosion des différentes microstructures, faisant intervenir la composition chimique des différentes entités microstructurales.

As altas concentrações de aerossol fino e ultrafino observadas na atmosfera de áreas urbanas possuem um importante papel no clima local e global, devido sua interação com a radiação solar e também pela característica de formação dos núcleos de condensação de nuvens (CCN). Essas altas concentrações de partículas são responsáveis pela poluição do ar, atualmente considerada como o principal problema ambiental para a saúde pública no mundo, sendo relacionada ao câncer, doenças respiratórias, cardiovasculares e o mal de Alzheimer. Nesse contexto, o presente trabalho almejou a caracterização e discriminação de fontes poluentes para o aerossol atmosférico da cidade de São Paulo, utilizando os isótopos de Pb, Zn e Cu simultaneamente. Além disso, nesse estudo também foi realizada a avaliação do efeito das fontes locais e remotas para a ativação do CCN na atmosfera dessa região. São Paulo é a maior cidade da Região Metropolitana de São Paulo (RMSP), que por sua vez é a maior megacidade da América do Sul, e está entre as dez maiores do mundo. Amostras de aerossol urbano foram coletadas no inverno de 2013 e verão de 2014 na cidade de São Paulo. Ao mesmo tempo foram coletadas, em São Paulo e Cubatão, amostras de fontes poluentes importantes para a RMSP, como aquelas relacionadas ao tráfego veicular (combustíveis, pneu, poeira de rua e aerossol de túnel), construção civil (cimento) e à área industrial de Cubatão (aerossol). Adicionalmente, foram medidas no inverno de 2014 a concentrações de CCN, a distribuição por tamanho e a concentração em número das partículas. As determinações das composições isotópicas de Pb, Zn e Cu foram realizadas com um novo procedimento analítico, desenvolvido para a separação sequencial e purificação desses elementos, a partir de uma mesma solubilização de amostra, seguida pelas análises por espectrometria de massas empregando MC-ICP-MS e TIMS. A validação da exatidão e precisão desse procedimento foi realizada pela análise de amostras de materiais de referência, aerossol e fontes poluentes. Com base nos dados isotópicos das fontes poluentes, o tráfego veicular foi diferenciado da área industrial de Cubatão utilizando as assinaturas isotópicas de Pb dessas fontes, que demonstraram grande reprodutibilidade quando comparadas com estudos anteriores. Adicionalmente, as assinaturas isotópicas da poeira de rua e dos pneus foram discriminadas das emissões veiculares em um diagrama \'delta\'66ZnJMC vs 206Pb/207Pb. As assinaturas isotópicas de Zn e Cu da poeira de rua, emissões veiculares e cimento foram discriminadas em um diagrama \'delta\'65CuNIST vs \'delta\'66ZnJMC. As contribuições das fontes para as composições isotópicas de Pb e Zn, determinadas no aerossol da cidade de São Paulo, foram quantificadas utilizando modelos de mistura ternária. Nesses modelos o tráfego veicular (57 a 66%) foi predominante, seguido pela fonte não-caracterizada (25 a 32%), que mostrou uma assinatura isotópica de Pb e Zn específica observada nas duas campanhas. A área industrial de Cubatão apresentou contribuições de 11 a 17%, enquanto a poeira de rua contribuiu em até 18% para as assinaturas de Pb e Zn no aerossol. No inverno de 2014, o tráfego veicular local, o sal marinho e a queima de biomassa foram identificadas nas amostras de aerossol por análises de PMF, trajetórias de massas de ar e pelo sistema lidar. Também foram observados eventos de formação de aerossol secundário em 35% dos dias de medição. A ativação de CCN foi menor durante o dia em relação ao período noturno, sendo esse padrão associado principalmente as emissões do tráfego veicular local. Comparando os dias com contribuições das fontes remotas, pôde-se concluir que o material particulado proveniente do tráfego veicular durante o dia mostrou o maior efeito nos parâmetros de ativação de CCN em comparação com as fontes remotas de sal marinho e queima de biomassa. / Fine and ultrafine aerosol particles in high concentrations found in the atmosphere of urban areas, play an important role in local and global climate through interaction with solar radiation and cloud condensation nuclei (CCN) formation. These high concentrations of particles are related to the air pollution, which is the major environmental problem to the public health in the world, related with cancer, cardiovascular, respiratory and Alzheimer diseases. In this context, this study reports the simultaneous use of Pb, Zn and Cu to characterize and discriminate pollutant sources of the atmospheric aerosol from São Paulo City and evaluate the effect of local and remote sources to CCN activation in the atmosphere of this area. São Paulo is the main city of Metropolitan Area of São Paulo (MASP), which is the largest megacity in South America and rank among the ten most populous in the world. Urban aerosol samples were collected during winter of 2013 and summer of 2014 in the São Paulo city. At the same time, samples of the main pollutant sources of MASP, were sampled in São Paulo and Cubatão, such as vehicular traffic (fuels, tyres, road dust and tunnel aerosol), construction (cement) and aerosol from Cubatão industrial area. In addition, CCN concentrations, particle number concentrations and size distributions were measured during the winter of 2014 in the same sampling site. The Pb, Zn and Cu isotopic composition were determined by a new analytical procedure, developed to sequential separation of these elements, using a unique sample dissolution, followed by mass spectrometry analysis by MC-ICP-MS and TIMS. Analytical procedure validation of Accuracy and precision was carried with reference materials, aerosol and pollutant source samples. Based on isotopic data obtained on the pollutant sources, vehicular traffic was differentiated from Cubatão industrial area, using Pb isotopic fingerprints of this sources, which showed long term reproducibility when compared with previous studies. In addition, road dust and tyre isotopic signatures were discriminated from vehicular emissions in a \'delta\'66ZnJMC vs 206Pb/207Pb four isotope plot. Interestingly, Zn and Cu isotopic fingerprints of road dust, vehicular emission and cement was distinguished in a \'delta\'65CuNIST vs \'delta\'66ZnJMC four isotope plot. In order to quantify contributions of sources to Pb and Zn isotopic compositions determined in aerosol from São Paulo city, ternary mixing models were performed. In these models, vehicular traffic accounted to the main contribution (57 to 66%), followed by non-characterized source (25 to 32%), with a specific Pb and Zn isotopic signature identified in aerosol during the two campaigns. Cubatão industrial area showed contributions of 11 to 17%, whereas road dust contributed 18% to Pb and Zn isotopes in aerosol. In the winter of 2014, local vehicular traffic, sea salt and biomass burning were identified in aerosol by PMF, air masses trajectories and lidar analysis. Some new particle formation (NPF) events were identified on 35% of the sampling days. CCN activation was lower during the daytime compared to nightime periods, a pattern that was found to be associated mainly with local road-traffic emissions. Comparing the days with remote sources events, we concluded that particulate matter from local vehicular emissions during the daytime have a greater effect on CCN activation parameters than that from sea salt and biomass burning remote sources.