[pt] O método EN baseia-se na quantificação do dano causado pela deformação decorrente do histórico de carregamento. O objetivo desse modelo consiste em estimar o número de ciclos para iniciar uma trinca por fadiga. Diferente do método SN o número de variáveis envolvidas nesse modelo é menor. Entretanto, requer um número maior de constantes, que nem sempre podem ser obtidas experimentalmente. Esse fato levou a formulação de diversos modelos que se propõem a estimar as constantes de Coffin-Manson, que na maioria dos casos levam a previsões de vida não conservativas, como visto em outros trabalhos. Contudo a maioria dos casos existentes na literatura não abordam o efeito de regiões de concentração de tensão e a influência de carregamentos com amplitudes variáveis. A metodologia usada nessas pesquisas consiste em avaliar a influência desses aspectos através da comparação entre a vida em fadiga experimental e a estimada segundo as constantes de Coffin-Manson medidas e estimadas segundo diferentes modelos. Esse estudo avalia o dano à fadiga segundo 2 tipos de concentradores de tensão e quatro históricos de carregamentos de amplitude variável. Considerando os modelos de Manson, Muralindhran-Manson, Bäumel-Seeger and Meggiolaro-Castro os resultados mostram que a vida em fadiga prevista usando os parâmetros de Coffin Manson obtidos segundo o método de Meggiolado-Castro e por Baumel-Segger são os que mais se aproximam das vidas estimadas baseada nas constantes experimentais. Nos demais casos nota-se que a regra de concentração de tensão exerce uma maior influência no resultado e levam a vidas à fadiga não conservativas. / [en] The strain-life designed is based on the damaged caused by the strain as a result of a loading history. The purpose of this approach is estimating the number of cycles to initiate a fatigue crack. Compared with the stress life method the EN needs a lower number of variables. However, it needs a large number of parameters that are not directly measurable properties of a material and conduct the necessary number of tests to obtain them is not always an option. This fact leads to the formulation of different models to estimate Coffin- Manson s constants, which in most of the cases can result in a non-conservative fatigue life prediction, as seen in several papers. However, in these studies, it is not considered a specimen with a stress concentration factor neither under a variable amplitude loading history. The methodology used in this research is evaluating the influence of these aspects by comparing the fatigue life experimental with the estimated by using the Coffin Manson s experimental constants and the fatigue life calculated with different models to estimate the Coffin-Manson s parameters. This study evaluated the fatigue damage based on four load histories and two types of samples with different stress risers. Considering the models of Manson, Muralidharan-Manson, Bäumel-Seeger, and Meggiolaro-Castro the results indicated that the fatigue life predicted using the Coffin Manson s parameter obtained by Meggiolaro-Castro and Baumel-Segger s model are more similar to the life calculated with the experimental constants. The other models are more influenced by the stress concentration s rule and can lead to not conservative fatigue life.

The glass-forming composition ranges in Al-La-Ni and Mg-TM (Cu, Zn)-Y alloys were predicted using Miedema’s model. Glass-forming abilities of Al-La-Ni alloys and Mg-Cu-RE alloys were studied in terms of reduced glass transition temperature (Trg), supercooled liquid region (∆Tx) and γ parameters. The glass-forming ability parameters of Mg-Cu-RE (RE: rare-earth) alloys were correlated with Mendeleev number. The Miedema model has been used to determine glass-forming composition range in binary Al-La, Al-Ni and La-Ni alloy systems and the ternary Al-La-Ni system by neglecting the ternary interactions. The glass-forming composition range for Al-La, Al-Ni and La-Ni alloy systems extends from 5 to 90 at% La, 30 to 80 at% Ni and 5 to 95 at% Ni, respectively. In these systems the predicted glass-forming composition range is wider than the experimentally observed range. Miedema model, restricting the difference of enthalpy of formation between the amorphous and solid solution phases to within –10000 J/mole to –55000 J/mole gives rise to better prediction of glass-forming composition range compared to the original models. The concept of mixing enthalpy and mismatch entropy has been used in order to quantify Inoue’s criteria of glass formation. The mixing enthalpy and normalised mismatch entropy of the ternary Al-La-Ni alloys, calculated by the extended regular solution model, vary between –12 to –40 kJ/mol and 0.16 to 0.65, respectively. The enthalpy contour plot has been constructed to distinguish the glass-forming compositions on the basis of the increasing negative enthalpy of the composition. Six Al rich Al-La-Ni alloys with nominal compositions Al89La6Ni5, Al85La10Ni5, Al85La5Ni10, Al82La8Ni10, Al80La10Ni10 and Al60La20Ni20 three La rich Al-La-Ni alloys with nominal compositions Al34La33Ni33, Al40La40Ni20 and Al25La50Ni25 have been chosen from the Al-La-Ni ternary phase diagram, to study the glass-forming ability of Al-La-Ni ternary alloy system and the correlation between La-based and Al-based glasses. All the alloys have been prepared using arc melting unit. All the alloy ribbons have been prepared using single-wheel vacuum melt-spinning unit. Two different wheel speeds of 20 m/s and 40 m/s were used for preparing ribbons of all the nine alloys. All the Al-La-Ni compositions, excluding equi-atomic composition (Al34La33Ni33) and Al60La20Ni20, give rise to amorphous phases. The supercooled liquid region and reduced glass transition temperature of this system increases with a decrease in Al content and an increase in La content. The glass-forming ability of the Al rich Al-La-Ni alloys is lower than that of the La-rich Al-La-Ni alloys. The glass-forming ability has been explained by taking into account the binary heat of mixing and the atomic radius mismatch of the constituent elements. Preferential crystallisation takes place during the heat treatment of glassy ribbons. The crystalline products are partially influenced by composition and binary heat of mixing between elements. Mg65Cu25Y10 alloy is a classical glass former of a family of Mg-based alloys. The partial or complete substitution of Y with other rare earth elements has been introduced to correlate the Mendeleev Number with the glass-forming ability parameters: reduced glass transition temperatures (Trg = Tg/Tl), supercooled liquid regions (∆Tx = Tx – Tg) and γ-criterion (TX/(Tg + Tm)). Mg-Cu-RE alloys with nominal compositions Mg65Cu25Y10, Mg65Cu25Y5Gd5, Mg65Cu25Y5Nd5, Mg65Cu25Gd10 and Mg65Cu25Nd10 were chosen for this work. The high reduced glass transition temperature, wider supercooled liquid region and higher γ value of Mg-Cu-Gd-Y amorphous alloy compared to Mg-Cu-Y and Mg-Cu-Nd-Y systems indicates that Mg-Cu-Gd-Y alloys possess higher glass-forming ability. The devitrification of all Mg-Cu-RE glassy alloys used for this work give rise to Mg2Cu (oF48) phase, which is known as anti-Laves phase. The glass-forming composition range for binary and ternary Mg-Cu-Y systems was calculated using Miedema’s model. The development of accurate methods of prediction of glass-forming ability in metallic systems is an important challenge. Pettifor has pioneered the Structure Mapping approach to binary intermetallics. The Pettifor approach can be adapted to the designing of bulk metallic glasses (BMGs). This method has been used to design Al-based and Mg-based BMG’s. Pettifor introduced an integer parameter to characterize the elements, which he called the Mendeleev Number. Essentially, Pettifor’s scheme orders the elements in a sequence of increasing electronegativity. With respect to Mendeleev Number, the Mg-Cu-RE system can be regarded as a binary system, because of the closeness of Mg and Cu (Mg:73, Cu:72, Y:25, Gd:27 and Nd:30). For this system, Mendeleev Number is a more effective parameter than atomic size (Mg: 1.60 Å, Cu: 1.27 Å), as a predictor of glass-forming ability. The effect of Y and rare earth elements on glass forming ability is similar. The atomic number of Y (39) is away from that of the rare earth elements and the Mendeleev Number of Y (25) comes in between those of the rare earth elements. Mg-Zn-Y system is an interesting system for researchers because of higher strength of these alloys. This system draws the crystallographers’ attention due to its composition-dependent structure variations. The Mg-rich RS/PM Mg-Zn-Y alloys yield superior mechanical properties. Therefore, the Mg-rich Mg-Zn-Y system has been chosen to study the microstructural evolution, even though the theoretical calculations for the glass-forming composition range for the Mg-Zn-Y system shows that this system is not a good glass former. Mg-Zn-Y system with nominal compositions Mg97Zn1Y2, Mg97Zn2Y1, Mg97−xZn1Y2Zrx and Mg92Zn6.5Y1.5 were chosen to study the microstructural evolution of these alloys. A small increase in Zn amount (above 2 at.%) in Mg-rich Mg-Y system results in quasicrystalline particles embedded in the matrix, whereas the addition of Zn up to 2 at.% leads to microstructural changes in the α-Mg solid solution.

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.

Ο χαρακτηρισμός της ποιότητας των χυτών κραμάτων αλουμινίου , γίνεται μέχρι σήμερα μέσω του χαρακτηρισμού της ποιότητας της μικροδομής, μετρήσεων σκληρότητας και πειραμάτων κρούσης και σε μικρότερο βαθμό, δοκιμών εκφυλισμού. Στην παρούσα διατριβή, προτείνεται ένας νέος εμπειρικός δείκτης για τον ποσοτικοποιημένο χαρακτηρισμό της ποιότητας χυτών κραμάτων αλουμινίου. Ο προτεινόμενος δείκτης αξιολογεί την ποιότητα ενός υλικού από την πλευρά του μηχανικού που σχεδιάζει ένα κατασκευαστικό στοιχείο και επομένως την αξιολογεί ως την ικανότητα του υλικού για μηχανικές επιδόσεις. Για την αξιολόγηση αυτή ο προτεινόμενος δείκτης συνεκτιμά την αντοχή και την ολκιμότητα του υλικού σε εκφυλισμό. Παράλληλα, για το χαρακτηρισμό της ποιότητας, ο δείκτης παίρνει υπόψη τη δυσθραυσότητα του υλικού καθώς και τη διασπορά των μηχανικών ιδιοτήτων του υλικού. Η διατύπωση του δείκτη στηρίχτηκε σε έναν ευρείας έκτασης πειραματικό χαρακτηρισμό της μηχανικής συμπεριφοράς σε εφελκυσμό καθώς και της μικροδομής των κυριότερων αεροπορικών χυτών κραμάτων αλουμινίου σε συνάρτηση με τη μεταβολή α) της χημικής σύστασης, β) του ρυθμού στερεοποίησης και γ) της θερμικής κατεργασίας αυτών καθώς και στη διατύπωση εμπειρικών συναρτήσεων για την εξάρτηση των μηχανικών ιδιοτήτων των κραμάτων που εξετάστηκαν από τις παραπάνω μεταβολές των παραμέτρων χύτευσης. Προκειμένου να διευκολυνθεί η αξιοποίηση του δείκτη, διατυπώθηκαν απλουστευμένες προσεγγιστικές εκφράσεις που επιτρέπουν τον υπολογισμό του από δεδομένα των απλών πειραμάτων της σκληρομέτρησης και της κρούσης. Τέλος προτάθηκε μεθοδολογία δημιουργίας χαρτών ποιότητας με βάση τον προταθέντα δείκτη για την υποστήριξη της επιλογής υλικού όταν είναι γνωστές οι απαιτήσεις σε μηχανικές επιδόσεις συγκεκριμένων κατασκευαστικών στοιχείων. / Quality evaluation of cast aluminum alloys is currently made mainly by means of the met- allographic characterization of the alloy’s niicrostructure, hardness measurements, impact tests and, to a lesser extend, tensile tests, are involved, as well. Yet, the overall decision is not a straight forward procedure, relies heavily on the experience of the quality engineer and involves an appreciable amount of subjective judgment. In the present Thesis, a new empirical quality index for the quantitative evaluation of the quality of cast aluminum alloys is introduced. The proposed index evaluates quality which is regarded as the ability of a material for mechanical performance. The index evaluates the quality of a cast alloy on the basis of a balance between the material’s tensile strength and ductility with regard also to the material’s toughness. In the proposed index the scatter in mechanical properties is also accounted. The formulation of the index has been based on an extensive experimental characterization of the tensile behavior and the microstructural features of the main aircraft aluminum cast alloys by varying chemical composition, solidification rate and artificial aging treat- ment. To facilitate the wide spread use of the index, simplified approximate expressions of the index have been formulated as well. These expressions allow for the calculation of the proposed quality index based on hardness measurements and impact test results. The index has been also exploited to devise quality maps, which may be used to support material selection with regard to the mechanical properties required by the design office for a certain application.

Submitted by Mery Piedad Zamudio Igami (mery@ipen.br) on 2017-03-10T14:37:28Z No. of bitstreams: 1 22056.pdf: 6258956 bytes, checksum: 5b6bd2c4bc8c6f66cd739d2ef10fe810 (MD5) / Made available in DSpace on 2017-03-10T14:37:28Z (GMT). No. of bitstreams: 1 22056.pdf: 6258956 bytes, checksum: 5b6bd2c4bc8c6f66cd739d2ef10fe810 (MD5) / A soldagem por fricção (Friction Stir Welding - FSW) é um processo eficiente de unir ligas de alumínio de alta resistência evitando defeitos que são usualmente criados quando técnicas convencionais de soldagem são utilizadas. A indústria aeronáutica tem mostrado grande interesse neste método de soldagem, tanto para a união de ligas similares como dissimilares. Entretanto, este processo causa modificações microestruturais dependentes das condições de tratamento térmico ou termomecânico. Contato elétrico entre zonas de microestruturas diferentes, por sua vez, pode resultar em acoplamento galvânico. No presente estudo, a soldagem por FSW foi usada para unir duas ligas de alumínio dissimilares, AA2024-T3 e AA7475-T651 e o efeito desta soldagem na resistência à corrosão das juntas soldadas e na microestrutura das ligas foi avaliada. Na investigação da resistência à corrosão foram utilizados ensaios eletroquímicos, especificamente, medidas de potencial de circuito aberto (OCP) em função do tempo de exposição ao meio corrosivo, ensaios de polarização e de espectroscopia de impedância eletroquímica, global (EIS) ou local (LEIS), em duas soluções, seja 0,1 M Na2SO4 ou 0,1 M Na2SO4 + 1 mM NaCl. Os ensaios eletroquímicos evidenciaram efeito de acoplamento galvânico nas juntas soldadas. A caracterização microestrutural foi realizada por microscopia ótica, microscopia eletrônica de varredura, microscopia eletrônica de transmissão e por calorimetria diferencial. As zonas afetadas pela solda tiveram importantes modificações na microestrutura indicadas pela precipitação e dissolução de precipitados que afetam a resistência à corrosão localizada. A resistência à corrosão intergranular e a resistência à esfoliação das juntas soldadas também foram avaliadas e comparadas com as das ligas AA2024-T3 e AA7475-T651 não soldadas. Os resultados mostraram aumento da suscetibilidade das juntas soldadas a estas formas de corrosão em comparação com as ligas não soldadas sendo observado ataque mais severo na liga AA7475-T651. A identificação das áreas anódicas e catódicas resultantes do acoplamento galvânico nas juntas soldadas foi realizada por teste que consistiu na deposição de camada de gel (ágar-ágar) com indicador universal na superfície das ligas soldadas. A liga AA2024-T3 atuou como cátodo, enquanto a AA7475-T651, como ânodo no par galvânico. Além disso, evolução de hidrogênio foi observada na região de interface entre a zona termomecanicamente afetada e a termicamente afetada da liga AA7475-T651 mostrando que reações catódicas também ocorreram localmente nesta última liga. Resultados de LEIS obtidos nas diferentes zonas das duas ligas soldadas por FSW mostraram acoplamento galvânico na interface entre elas para tempos curtos de ensaio e deslocamento da região mais ativa com o tempo de ensaio para a liga AA7475-T651, mais precisamente para a interface entre a zona termomecanicamente afetada e a térmicamente afetada desta liga. / Tese (Doutorado em Tecnologia Nuclear ) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

No presente trabalho quatro ligas Al-Si hipereutéticas, três das quais foram produzidas por conformação por \"spray\" e a outra por fundição, foram caracterizadas quanto a textura, dureza, microestrutura e resistência à corrosão em meio de condensado sintético automotivo (CSA). Duas das ligas conformadas por \"spray\" foram retiradas de camisas de cilindro e a outra de um pré-formado obtido em laboratório. A conformação por \"spray\" envolve a atomização de uma liga e a deposição de gotículas em um substrato, antes mesmo que todas se encontrem no estado sólido. Este processo permite a obtenção de materiais que se caracterizam por uma microestrutura livre de macrossegregações e bastante refinada, implicando melhor trabalhabilidade a quente. A caracterização da microestrutura das quatro ligas hipereutéticas revelou a presença de porosidades na liga obtida em laboratório, e microestrutura com distribuição homogênea de precipitados primários nas três ligas conformadas por \"spray\". A microestrutura de uma das ligas apresentou-se muito diferenciada, com a presença de eutético, sugerindo que esta foi fabricada por fundição. Nas camisas de cilindro foram feitas medidas de rugosidade, e em todas as ligas foram realizados ensaios de microdureza. A liga conformada por \"spray\" e obtida em laboratório foi laminada a quente e a frio. Foram realizados também estudos de textura, para tentar estabelecer uma correlação entre todas as ligas quanto ao processo de fabricação. A avaliação da textura indicou que a presença de fases de silício primário, finamente distribuídas impedem o aparecimento de texturas típicas de deformação de ligas de alumínio, mesmo após severas deformações, como as necessárias para a transformação de pré-formados em tubos que originam as camisas de cilindro. As medidas de rugosidade indicaram características próprias do acabamento superficial usado para a produção das camisas, por brunimento ou por ataque químico. Os ensaios de microdureza apresentaram variações de acordo com as rotas de fabricação sendo que a liga eutética apresentou os maiores valores de microdureza em comparação às ligas conformadas por \"spray\". Todas as ligas foram avaliadas quanto a resistência à corrosão por ensaios de espectroscopia de impedância eletroquímica em dois meios, CSA com pH 3,3 e CSA com pH 11. As quatro ligas hipereutéticas estudadas apresentaram mecanismo de corrosão similar em condensado sintético automotivo (CSA) pH 3,3. Em todas ocorreu o ataque intenso da matriz de alumínio e as partículas de silício primário atuaram como regiões catódicas. A liga 2 apresentou maior resistência à corrosão entre todas as ligas ensaiadas, tanto em CSA pH 3,3 como em pH 11. Neste último meio, uma camada de produtos de corrosão formou-se sobre todas as ligas, e os resultados indicaram mecanismos diferentes para o ataque da matriz de Al e para o crescimento da camada depositada na superfície das ligas estudadas. O ataque da matriz da liga 2 neste meio foi aparentemente mais lento do que sobre as demais ligas, com a formação de uma camada mais compacta de produtos de corrosão, estabelecendo um controle por difusão dos processos interfaciais para maiores períodos de ensaio. A camada formada sobre as demais ligas neste meio apresentou-se mais defeituosa, e nestas ocorreu também menor controle da velocidade das reações interfaciais por processos difusionais. / In the present study four hypereutectic Al-Si alloys, three produced by spray forming and one by casting, were characterized for microhardness, roughness, microstructure, texture and corrosion resistance in a synthetic automotive condensed solution (SACS). Two of the spray formed alloys tested were obtained from cylinder liners and the other was laboratory made. Spray forming involves alloy atomization and droplets deposition on a substrate, previous to the solidification of all of the droplets. This process favours the production of materials with a fine microstructure free of macrosegregation that is related to improved hot workability. The microstructure characterization of the four alloys revealed the presence of porosities in the laboratory made alloy. All the three alloys produced by spray forming showed a homogeneous distribution of primary precipitates. The microstructure of one of the alloys showed eutectic microstructure, indicating that this alloy was fabricated by casting. In the cylinder liners, the surface roughness was measured and the microhardness of all the alloys was also evaluated. Furthermore, the laboratory made alloy was hot and cold rolled. Texture determinations were carried out to investigate the correlation between the alloy type and their fabrication process. The texture investigation indicated that the fine distribution of primary silicon phase in the alloy hindered the development of texture typical of aluminium alloys deformation, even after severe mechanical work, such as those used in the conversion of pre-formed in cylinder liners. The surface roughness results indicated typical characteristics of the surface finishing used, honing or chemical etching. The microhardness results were dependent on the fabrication process used, with higher microhardness associated to the eutectic alloy comparatively to the spray formed ones. All hypereutectic alloys were tested for corrosion resistance using electrochemical impedance spectroscopy in two electrolytes, SACS with pH 3.3 and SACS with pH 11. The four tested alloys showed similar corrosion mechanisms in the acid electrolyte (SACS pH 3.3). The intense attack of the aluminium matrix occurred in ali tested alloys and the primary silicon phase was unattacked and appeared as emerging from the surface after corrosion immersion test. The primary silicon particles acted as cathodic sites. The alloy 2 showed the highest corrosion resistance among the tested alloys in both electrolytes, SACS pH 3.3 and SACS pH 11. In this last medium, a layer of corrosion products formed on all the alloys, and the results indicated different mechanisms for the aluminium matrix corrosive attack and growth of the deposited layer on the alloys surface. The kinetics of aluminium matrix attack was apparently slower in the alloy 2 than for the other alloys, resulting in the formation of a more compact layer of corrosion products, leading to diffusion controlled interfacial processes for longer test periods. The layer of corrosion products on the other three alloys (1, 3, and 4) had more defects and for these alloys diffusional controlled interfacial processes were not as significant as for alloy 2.

Dans un contexte normatif toujours plus sévère concernant les rejets automobiles polluants, la substitution des aciers par des alliages d’aluminium dans les structures des véhicules est en plein essor. Ce projet de thèse, qui s’inscrit dans un programme de développement de la société Constellium, cible plus précisément les alliages d’aluminium de la série 7xxx (Al-Zn-Mg) qui, malgré leurs propriétés mécaniques élevées, peuvent présenter une sensibilité à la corrosion sous contrainte (CSC) liée au phénomène de fragilisation par l’hydrogène (FPH). La compréhension des mécanismes mis en jeu dans ce type d’endommagement constitue donc une première étape vers une optimisation métallurgique en vue d’une industrialisation future de ces alliages dans le secteur automobile. La première partie de ces travaux est consacrée à l’étude de l’influence de l’état métallurgique de l’alliage 7046 sur son comportement en CSC et à l’identification des mécanismes de dégradation. Un lien direct a pu être mis en évidence entre l’abattement des propriétés mécaniques et les modes de rupture actifs et la quantité d’hydrogène dans l’alliage. Les deux modes d’endommagement observés, intergranulaire-fragile et transgranulaire-fragile, ont respectivement été attribués à un enrichissement en hydrogène aux joints de grains et au piégeage de l’hydrogène au niveau des précipités intragranulaires. Les interactions entre l’hydrogène et les précipités fins d’une part et les dislocations d’autre part, identifiés comme deux hétérogénéités microstructurales critiques vis-à-vis de la FPH, ont été étudiées à une échelle plus locale dans la seconde partie du travail de thèse. Les essais ont été réalisés sur des échantillons modèles, chargés en hydrogène en milieu H2SO4 sous polarisation cathodique et la profondeur de pénétration de l’hydrogène a été évaluée par SKPFM (Scanning Kelvin Probe Force Microscopy). L’ensemble des résultats obtenus met en évidence : 1/ un effet « barrière » des précipités fins et des dislocations sur la diffusion de l’hydrogène en relation avec un abattement des propriétés mécaniques moins important, 2/ un transport possible de l’hydrogène par les dislocations et 3/ l’efficacité du SKPFM pour déterminer précisément des coefficients de diffusion apparents de l’hydrogène. Ces résultats ouvrent ainsi de nouvelles pistes vers la compréhension des mécanismes de CSC dans les alliages Al-Zn-Mg. / Automotive industry is increasingly affected by standards requiring a major cut of polluting emissions, leading R&D policies to focus on replacing steel by aluminum alloys. This thesis project, initiated by the manufacturer Constellium, focuses on 7xxx (Al-Zn-Mg) aluminum alloys known to have high mechanical properties but also to be susceptible to stress corrosion cracking (SCC) partly attributed to hydrogen embrittlement (HE). Understanding the mechanisms involved would be a first step towards a metallurgical optimization and a future industrialization of these alloys. The first part focuses on the SCC behavior of the 7046 aluminum alloy, related to its microstructure, and the identification of degradation mechanisms involved. A hydrogen amount – loss of mechanical properties relationship was highlighted. The damage observed was explained by the presence of hydrogen in the grain boundaries and by a trapping effect of the intragranular hardening precipitates, limiting the hydrogen diffusion to the grain boundaries. Interactions between hydrogen and hardening precipitates and dislocations, both identified as critical microstructural heterogeneities for HE, are studied at a local scale in a second part. The hydrogen effect was characterized by penetration depth measurements made by SKPFM (Scanning Kelvin Probe Force Microscopy) on “model” samples cathodically charged in H2SO4. The whole results finally highlight: 1/ a “shielding” effect of fine precipitates and dislocations on hydrogen diffusivity related to a lower susceptibility to HE, 2/ hydrogen transport by dislocations and 3/ the efficiency of SKPFM to precisely measure effective diffusion coefficients of hydrogen. These results lead to new opportunities to understand SCC mechanisms in Al-Zn-Mg alloys.

In most casting applications, dendritic microstructure morphology is not desired because it leads to poor mechanical properties. Forced convection causing sufficient shearing in the mushy zone of the partially solidified melt is one of the means to suppress this dendritic growth. The dendrites formed at the solid-liquid interface are detached and carried away due to strong fluid flow to form slurry. This slurry, consisting of rosette or globular particles, provides less resistance to flow even at a high solid fraction and can easily fill the die-cavity. The stated principle is the basis of a new manufacturing technology called “semi-solid forming” (SSF), in which metal alloys are cast in the semi-solid state. This technique has numerous advantages over other existing commercial casting processes, such as reduction of macrosegregation, reduction of porosity and low forming efforts. Among all currently available methods available for large scale production of semisolid slurry, the cooling slope is considered to be a simple but effective method because of its simple design and easy control of process parameters, low equipment and running costs, high production efficiency and reduced inhomogeneity. With this perspective, the primary objective of the present research is to investigate, both experimentally and numerically, convective heat transfer and solidification on a cooling slope, in addition to the study of final microstructure of the cast billets. Some key process parameters are identified, namely pouring temperature, slope angle, slope length, and slope cooling rate. A systematic scaling analysis is performed in order to understand the relative importance of the parameters in influencing the final properties of the slurry and microstructure after solidification. A major part of the present work deals with the development of an experimental set up with careful consideration of the range of process parameters involved by treating the cooling slope as a heat exchanger. Subsequently, a comprehensive numerical model is developed to predict the flow, heat transfer, species concentration solid fraction distribution of aluminum alloy melt while flowing down the cooling slope. The model uses a variable viscosity relation for slurry. The metal-air interface at the top during the melt flow is tracked using a volume of fluid (VOF) method. Solidification is modeled using an enthalpy based approach and a volume averaged technique. The mushy region is modeled as a multi-layered porous medium consisting of fixed columnar dendrites and mobile equiaxed or fragmented grains. In addition, the solidification model also incorporates a fragmentation criterion and solid phase movement. The effects of key process parameters on flow behavior involving velocity distribution, temperature distribution, solid fractions at the slope exit, and macrosegregation, are studied numerically and experimentally for aluminium alloy A356. The resulting microstructures of the cast billets obtained from the experiments are studied and characterized. Finally the experimental results are linked to the model predictions for establishing the relations involving interdependence of the stated key process parameters in determining the quality of the final cast products. This study is aimed towards providing the necessary guidelines for designing a cooling slope and optimizing the process parameters for desirable quality of the solidified product.

Les directives de l'Union Européenne conditionnent la R&D du secteur automobile concernant l'utilisation de matériaux plus légers ayant pour but de réduire la consommation de carburant et une diminution de l’émission de gaz d’échappement. L’objectif est de mettre au point des aciers allégés d’au moins 10% (ρmax ≈ 7g/cm3). Les alliages fer-aluminium possèdent des propriétés physiques et mécaniques prometteuses mais présentent des défauts de surface appelés roping, apparaissant après l’emboutissage à froid. Cette étude a consisté à mieux comprendre les conditions de recristallisation au cours du laminage à chaud afin de contrôler la microstructure et ainsi limiter ces défauts. Il est généralement admis, lors d’une déformation à chaud, que les alliages ferritiques, à haute énergie de défaut d’empilement, donnent lieu aux processus de recristallisation dynamique géométrique (RDG) et de recristallisation dynamique continue (RDC). Dans cette étude, l’existence d’une transition entre les mécanismes de RDC et de recristallisation dynamique discontinue (RDD) a été mise en évidence pour des températures comprises entre 900 et 1100°C et des vitesses de déformation comprises entre 0,1 et 50s 1. La recristallisation post dynamique a aussi été étudiée afin d’observer l’évolution de la microstructure lors de maintiens en température. Un modèle développé antérieurement pour la RDC de l’aluminium a ensuite été utilisé afin de simuler une passe de laminage. Bien que la comparaison des résultats expérimentaux et simulés fasse apparaître un certain nombre de différences, ce modèle permet de reproduire qualitativement les évolutions de la microstructure. / The instructions of the European Union pilot the R&D in the automotive industry regarding the use of lightweight materials which aims at reducing fuel consumption and emission of exhaust gases.The objective is to develop steels of density reduced by at least 10% (ρmax ≈ 7g/cm3). Iron aluminum alloys display promising physical and mechanical properties but they often exhibit surface defects, referred to as roping, appearing after the deep drawing process. This study was carried out to better understand the conditions of recrystallization during hot rolling to control the microstructure and thereby limit these defects.During hot deformation, it is generally agreed that geometric dynamic recrystallization (GDRX) and continuous dynamic recrystallization (CDRX) operate in ferritic alloys with high stacking fault energy. In this study, the existence of a transition between CDRX and the mechanism of discontinuous dynamic recrystallization (DDRX) has been brought into evidence in the temperature range 900 1100°C and strain rate range 0.1-50s-1. Post-dynamic recrystallization was also studied to observe the evolution of microstructure during holding temperatures.A model formerly developed for the CDRX of aluminum was then used to simulate a rolling pass. Comparison of computed and experimental results shows some differences but this model can reproduce microstructural changes qualitatively.

A large number of advanced structural materials are based on metallic materials where alloying additions play a key role in imparting the required properties. Most of the commercially important aluminium alloys are classified by the nature of the alloying additions. Among them the 2219, 2618, 5086, and 7075 are important class of lightweight alloys that plays critical role in modern engineering application. However, despite having a series of commercially useful aluminum alloys for commercial applications the increasing need of improved performance requires newer development in particular for applications that require high strength at elevated temperatures and performance at extreme environments. Precipitations of the intermetallic compounds containing copper during thermal treatments play a very important role in developing high strength aluminium alloys. Although,these precipitates are stable at fairly high temperatures, the rapid coarsening of these second phase precipitates (e.g. Al2Cu), leads to loss of strength at elevated temperature. Several approaches are explored to overcome this problem. One of them is to utilize non-equilibrium solidification route, which can increase solid solubility and hence increasing the precipitate density. Nonequilibrium processing can also alter the selection pathway of the competitive phases and evolution of the microstructure. Recently, non–equilibrium solidification by suction casting technique is becoming increasingly popular for casting of metallic materials of any shape. In this technique solidification is effected by sucking the molten alloy into water cooled copper mold using a suction force resulting from the differences between the melting chamber in Argon gas pressure and casting chamber under vacuum. The present thesis aims to develop a set of newer alloys with small amount of alloying additions primarily based on nickel that can retain reasonable strength at high temperature by utilizing the non-equilibrium solidification route. In addition to Ni (≤ 0.10at.%), the thesis present results of the effect of minor addition of Sc and Zr as ternary and quaternary additions. Following a short review in chapter 2, Chapter 3 presents the experimental techniques adopted for both preparation of alloys and their characterization. Chapter 4 deals with the results of alloying of aluminum with minor amount of nickel. The Ni in the range of 0.05-0.20at% was used to develop a high temperature template, containing a set of hardening intermetallic compounds to increase the strength of the host matrix. The microstructural investigations of the suction cast alloys reveal a characteristic feathery microstructure. At higher magnification the microstructure reveals the presence of fine dispersions of a second phase. Both x-ray and transmission electron microscopy confirms the phase in the dispersions to be primarily crystalline Al9Ni2 phase having a monoclinic crystal structure. This phase does not exist in equilibrium phase diagram. Only at higher concentration one can observe equilibrium Al3Ni (Orthorhombic) particles. The size of the particle ranges from 50-200nm. Beyond~0.5at%Ni, the microstructure changes to normal cellular type solidification morphology with interdendritic space decorated by the eutectic network of Al-Al3Ni having a rod eutectic morphology. A careful observation of alloys with small amount of Ni reveals that the feathery structure is associated with the thin cells, which have grown by continuously splitting the tip yielding a fractal like dendritic morphology. The dispersoids form at the intercellular regions. We have presented clear evidence of their origin from the interdendritic liquid, which most likely underwent Rayleigh instability. The random distribution reflects the nature of the dendritic growth. We have argued that these inter-dendritic liquid droplets, which are enriched with Ni, get undercooled. The metastable Al9Ni2 phase nucleates and grows in this liquid. In order to confirm this scenario, we have carried out a phase field simulation for dendritic growth of aluminium solid solution in the alloy melt both under the condition of constraint growth and free growth. The observed distribution of the dispersoid is well reflected in the phase field simulation. The chapter also report the response of effect of direct ageing of suction cast alloy as one expect an extension solid solubility of Ni in Al. A small increase in hardness could be observed during ageing treatment. In order to determine the thermal stability of the intermetallic particles, the samples of the suction cast alloys were exposed at 200°C for 200h and 500°C for 100h respectively. No change in the microstructure could be observed excepting a slight coarsening indicating the dispersed particles are thermally stable. After exposure at two different temperatures the maximum retained hardness was measured to be 350MPa. We have also attempted to correlate the hardness with coarsening behavior of particles. The feathery morphology of the cast structures and fine dispersion of the intermetallic phase is expected to improve the tensile strength of the alloy. The tensile yield strength of cast alloys was determined to be 150MPa ± 20 for Al- 0.09at%Ni alloy. We have tried to estimate the expected strength of the alloy from quantitative microstructural parameters using possible hardening mechanism. The estimates are in good agreement to the observed values. The chapter 5 reports attempts to develop thermally stable precipitation strengthened aluminum alloys by retaining the dispersion template developed earlier alloyed with Ni. Then, the binary alloys were added with extremely low diffusivity element Zr. The element Zr is traditionally added in the aluminium alloys as grain refiner and as a powerful agent for inhibiting recrystallization especially for high strength aluminium alloys. However, in this work we have alloyed Zr for imparting precipitation hardening. An amount of 0.15at%Zr was added to the suction cast alloys of Al-0.05, 0.09 and 0.20at%Ni. The first two alloys exhibit the formation of metastable phase Al9Ni2 during solidification stage. Increase the concentration of the alloy to Al-0.20at% Ni with 0.15at%Zr additions exhibits combination of both stable Al3Ni and Al9Ni2 metastable phases. Microstructures of these alloys show columnar cells of ~200μm with dispersions of spherical nodules of Al9Ni2 and Al3Ni with varying size ranges from 200-500nm. Particle size distribution of Zr containing aluminium alloys with 0.05at% Ni is 595nm ± 20 while the alloy having the 0.09 at% Ni has the optimum size of 290nm. Further increase of Zr composition above 0.20at % led to columnar to equiaxed transition. The as cast alloys containing Zr does not show the improvement with limited yield strength of the order of 150MPa. The equivalent hardness of the samples has been measured to be about 370-420MPa. Heat-treated alloys however show the presence of Al3Zr (L12) precipitates with ~20nm size that are coherent with the matrix. Binary suction cast Al-0.15at%Zr alloy after ageing exhibits tensile yield strength of ~200MPa. With ternary aluminium alloy with minor additions Ni and Zr, The strength increases to ~300MPa. Additionally, the alloy continue retain a maximum hardness of 870-920MPa even after long hours of aging. The Zr containing alloys were proved to be stable. When the tests were carried out on a nominally alloyed sample of Al-0.09at%Ni-0.15at%Zr peak aged and exposed to 250°C for 200h, the yield strength under compression tests was found to be 280MPa. The chapter 6 of the thesis discusses the role of Sc with the ternary Al-alloys with Ni and Zr. Addition of small quantities 0.1 and 0.2at%Sc substantially reduces the inter-particle distance of precipitates by increasing volume fraction and number of nano-sized particles. It has been observed and presented in this thesis that the Sc addition provides the highest incremental strengthening per atom percent of any alloying element. Chill-suction cast samples show equiaxed cells in the samples with dispersions of particles inside and some segregated particles at the cell boundaries. To achieve a further increase in the number density of precipitates we processed the suction cast alloys with additional heat treatment at 375 and 450°C. All the suction cast alloys with varying Ni content and keeping the Sc and Zr constant at 0.10 and 0.15at% respectively exhibit formation of Al9Ni2 phase. The alloy Al-0.20at%Ni-0.10at%Sc-0.15at%Zr also contain stable phase of Al3Ni with an eutectic morphology. The DSC experiments in the dynamic mode with heating rate of 10°C min-1 exhibit two distinct exothermic peaks due to precipitates from solution at 375 and 450°C. The TEM analysis using STEMEDX has further confirmed the existence of nano-sized particles 30-50 nm of both phases of Al3Sc and Al3 (Sc, Zr). The tensile yield strength of the as cast alloy show 200MPa while after precipitation treatment, we observe improved yield strength 350-450MPa. Thermal stability of the alloys were tested after peak aged condition and exposed to 200°C for 250h. The results show that the yield strength is unaffected implying the coarsening resistance of the precipitate particles. Overall the thesis establishes that with minimum alloying additions, it is possible to design alloys that are expected to perform for high temperature applications by the formation of set of dispersions of Al9Ni2 (monoclinic) and precipitates of ordered cubic phases of (L12) structure of Al3Zr, Al3Sc and Al3 (Sc, Zr) with required number density of particles.