A liga binária Al-Cu é a base para todas as ligas da série 2xxx que são de grande importância em diversas aplicações como na indústria aeronáutica, transporte, máquinas e equipamentos. No entanto, pouco se conhece sobre os efeitos do tipo de solidificação desta liga e da deformação plástica sobre sua resistência à corrosão em meio aquoso. O escopo deste trabalho foi procurar correlacionar microestruturas da liga Al-4,5%p.Cu solidificada de maneira convencional e unidirecional vertical ascendente (brutas de fusão, deformadas plasticamente por forjamento rotativo a frio, e tratadas termicamente visando recristalização), orientações preferenciais de grãos com as características de resistência à corrosão. Foram utilizadas técnicas de microscopia eletrônica de varredura e óptica, difratometria de raios X e ensaios eletroquímicos em soluções de NaCl 0,6 M e Na2SO4 0,1M por polarização potenciodinâmica e espectroscopia de impedância eletroquímica. A taxa de corrosão foi maior em solução de NaCl 0,6 M do que em Na2SO4 0,1M para todas as amostras. O aumento da redução por deformação plástica conduziu a uma diminuição da resistência à corrosão da liga devido ao aumento das tensões internas e ao aparecimento de orientações preferenciais dos grãos de menor densidade planar como (200) e (220). As amostras recristalizadas apresentaram de uma forma geral uma resistência maior quando comparada às amostras não recristalizadas, comportamento atribuído ao alívio de tensões internas e ao desaparecimento da orientação preferencial do plano menos denso (220). / The binary Al-Cu alloy is the basis for all AA2xxx alloys, being important in several applications as aeronautical industry, transportation, machines and equipments. However, few is known about the effect of the type of solidification of this alloy and plastic deformation on the corrosion resistance in aqueous medium. The scope of this work was to correlate microstructures of the Al-4.5 % wt. Cu alloy solidified under conventional and upward direct chilling conditions (as cast condition, plastic formed by cold swaging, and heat treated seeking recristallyzation), crystallographic orientations and corrosion resistance characteristics. Scanning electron microscopy and optical, X ray diffractometry techniques and electrochemical measurements in NaCl 0,6 M and Na2SO4 0,1 M potentiodynamic polarization and electrochemical impedance spectroscopy were used. The corrosion rate in NaCl 0,6 M was higher than in Na2SO4 0,1 M for all samples. The increase of the plastic deformation led to alloy corrosion resistance decrease, due to the internal stresses increase and the arising of less dense grain preferred orientations of lower planar density as (200) and (220) orientations. The recristallyzed samples presented in a general way a higher corrosion resistance, when compared to the non recristallyzed samples, being imputed to the internal tension relieve and the extinction of the plane (220) of lower planar density to a structure of random orientation.

Magnésio e suas ligas têm adquirido importância cada vez mais significativa como material estrutural de peso leve despertando um singular interesse pela indústria uma vez que oferece a melhor relação peso/resistência entre os metais. Os campos mais conhecidos de sua aplicação consistem na construção de veículos, na aeronáutica, manipulação industrial (robôs, automatização) e tecnologia de comunicação. Em particular, a indústria automobilística tem crescentemente ampliado a utilização de ligas de magnésio na produção de peças que vão desde caixas de câmbio até aros de rodas. As principais razões para este desenvolvimento são: mudanças na legislação ambiental, as exigências de cliente, e objetivos corporativos que requerem veículos mais leves diminuindo o consumo de combustível. O uso do magnésio para aplicações estruturais em altas temperaturas é limitado devido a sua baixa resistência à fluência. Isso se deve ao enfraquecimento do contorno de grão a partir da precipitação descontínua da fase b-Mg17Al12 de baixo ponto de fusão. Dentre as ligas de magnésio desenvolvidas para resistência à fluência, as ligas do sistema Mg-Al-RE-Ca oferecem ótimo desempenho com resultados similares à liga de alumínio ADC12. Muitos trabalhos sobre o sistema de ligas Mg-Al-RE-Ca foram realizados visando compreender a relação entre microestruturas e propriedades mecânicas. Entretanto, poucos estudos relacionaram a influência das variáveis de solidificação na formação das microestruturas. O presente trabalho tem como objetivo realizar um estudo em uma liga Mg-4%Al-3%La-1%Ca analisando a influência das variáveis térmicas tais como taxas de resfriamento, velocidade da isoterma liquidus e gradientes de temperatura, na formação de estruturas, na transição colunarequiaxial e espaçamento dendrítico durante o processo de solidificação. A previsão das distintas estruturas, tais como zona colunar e equiaxial é de grande interesse para avaliação e projeção das propriedades mecânicas dos fundidos. Dessa forma, a liga estudada foi submetida à solidificação unidirecional vertical ascendente e análise térmica. Foram realizadas análises metalográficas nos lingotes solidificados. Os resultados colaboram para uma melhor compreensão do fenômeno de solidificação da liga e serve como ferramenta no desenvolvimento de modelos de previsões de formação de micro e macroestruturas que influenciam diretamente nas propriedades mecânicas. / Due to their superior weight/resistance relation, magnesium and its alloys have been acquiring a great deal of importance in the modern industry, specially as lightweight structural materials in the fields of vehicle construction, aeronautics, industrial robotics, automation, and communication technologies. In particular, the automotive industry has been increasingly expanding the use of magnesium alloys in the production of auto-parts, ranging from gearbox housings to steering wheels. The main reasons for this developments are changes in environmental legislations, new customer requirements, and corporate policies regarding fuel consumption and weight/power relations. The use of magnesium alloys for structural applications at high temperatures is limited due to the precipitation of the discontinuous phase b-Mg17Al12, which in fact, weakens the grain boundary during service resulting in a low creep resistance. Among the magnesium alloys developed for creep resistance, the alloys of the system Al-Mg-RE-Ca offer optimum performance with results similar to the ADC12 aluminum alloy. Many studies on the Al-Mg-RE-Ca system alloys were aimed to understand the relationship between microstructure and mechanical properties. However, few studies undertake the influence of the solidification variables in the microstructure formation. This work aims to study the influence of some thermal variables such as temperature gradients, solidification and growth tip rate on the formation of microstructures, the columnar/equiaxial transition and dendrite arm spacing, during the solidification process of a Mg-4%Al-3%La- 1%Ca alloy. The prediction of the different structures, such as the columnar and the equiaxial regions is of great interest for the assessment and projection of the mechanical properties of the casts. Therefore, the alloy studied in this work were submitted to thermal analysis during an unidirectional vertical ascending solidification, as well as optical and scanning electron microscopy characterization. The results contribute to a better understanding of the solidification phenomena of the magnesium alloys, as well as a tool in the development of numerical models for the prediction of structures which directly influence the mechanical properties of the parts.

Modelling the ice accretion in glaze regime for the supercooled large droplets is one of the most challenging problems in the aircraft icing field. The difficulties are related to the presence of the liquid water film on the surface in the glaze regime and also the phenomena associated with SLD conditions, specifically the splashing and re-impingement. The steady improvement of simulation methods and the increasing demand for highly optimised aircraft performance, make it worthwhile to try to get beyond the current level of modelling accuracy. A semi-empirical method has been presented to characterize the thin water film in the icing problem based on both analytical and experimental approaches. The experiments have been performed at the Cranfield icing facilities. Imaging techniques have been used to observe and measure the features of the thin water film in the different conditions. A series of numerical simulations based on an inviscid VOF model have been performed to characterize the splashing process for different water film to droplet size ratios and impact angles. Based on these numerical simulations and the proposed methods to estimate the thin water film thickness, a framework has been presented to model the effects of the splashing in the icing simulation. These effects are the lost mass from the water film due to the splashing and the re-impingement of the ejected droplets. Finally, a new framework to study the solidification process of the thin water film has been explored. This framework is based on the lattice Boltzmann method and the preliminary results showed the capabilities of the method to model the dynamics, thermodynamics and the solidification of the thin water film.

<p>U radu je ispitana distribucija metala u sistemu sediment/voda na najugroženijim vodotocima u<br />AP Vojvodini. Na osnovu dobivenih podataka urađena je procena rizika na osnovu analize<br />porne vode, kiselog volatilnog sulfida i simultano ekstrahovanih metala i sekvencijalne<br />ekstrakcione procedure. Procena mobilnosti metala u sistemu sediment/voda određena je<br />promenom fizičko-hemijskih uslova u realnom sistemu (vodotok) i u laboratorijskim uslovima.<br />Ispitana je efikasnost in-situ (aeracijom sistema sediment/voda) i ex-situ remedijacije<br />sedimenta metodama termičkog tretmana i solidifikacije/stabilizacije.<br />Rezultati su ukazali da u svakom vodotoku i za&scaron;tićenoj zoni postoji lokacija u kojoj je sediment<br />barem po jednom metalu klasifikovan (holandski sistem klasifikacije sedimenata) kao zagađen<br />(klasa 3) ili izuzetno zagađen sediment (klasa 4). Generalno, kvalitet sedimenta manjih<br />vodotoka (Krivaja, Nadela, Kudo&scaron;, Veliki Bački kanal i Begej) je lo&scaron;iji u odnosu na ostale<br />ispitivane vodotoke.<br />Procena dostupnosti metala u sedimentu Velikog Bačkog kanala ukazala je da na svakom<br />ispitivanom profilu postoji minimum jedan metal i jedna metoda koja defini&scaron;e sediment kao<br />visoko rizičan. Takođe je zaključeno da je sediment na delu od 2+000 do 4+900 km zagađeniji,<br />jer postoji veći broj metala i metoda koji ga defini&scaron;u kao visoko rizičnim. Ovako dobijeni<br />rezultati ukazuju da nije dovoljan jednostavan i samo jedan pristup u oceni kvaliteta sedimenta<br />i proceni rizika koji metali mogu da ispolje u akvatičnom ekosistemu.<br />Ukazano je da pomeranje sedimenta (npr. otvaranja ustave), dovodi do promene fizičkohemijskih<br />uslova u sistemu sediment/voda, resuspenzije i transporta sedimenta. Usled ovih<br />promena povećava se dostupnost metala i dolazi do povećanja njihove koncentracije u vodenoj<br />fazi čime se znatno povećava rizik i mogućnost ispoljavanja negativnih efekata na akvatični<br />ekosistem.<br />U slučaju resuspenzije sedimenta u sistemu sediment/voda pronađena je zavisnost između<br />koncentracije metala u suspendovanim materijama i vodi od sadržaja određenih frakcija u<br />suspendovanim materijama (sadržaj organskih materija i frakcije do 63 &mu;m).<br />Remedijacione tehnike često su ekonomski neprihvatljive zbog velike zapremine zagađenog<br />sedimenta. Ukazano je da primena in-situ aeracije, omogućava smanjenje količine sedimenta<br />(čime se smanjuju tro&scaron;kovi eventualno naknadnog tretmana sedimenta), a da je tretman<br />solidifikacije/stabilizacije sedimenta sa glinom i termičke remedijacije zadovoljavjući sa<br />aspekta izluživanja metala. Dobijeni rezultati izvedenih testova izluživanja ukazali su na<br />moguću primenu ovih tretmana u pogledu re&scaron;avanja problema sedimenta koji je zagađen<br />metalima, bilo u pogledu sigurnog odlaganja na deponiju ili u smislu njegove upotrebe kao<br />dodatka pri proizvodnji građevinskog materijala (opeke), osnove za puteve, uređenje obale<br />(nasipa) itd. Na taj način mogu se znatno umanjiti tro&scaron;kovi izmuljivanja i manipulacije<br />kontaminiranog sedimenta, a sama remedijacija učiniti mnogo prihvatljivijom</p> / <p> This work investigates the distribution of metals in the sediment / water systems of the most<br /> endangered rivers in Vojvodina. Utilizing the data obtained, risk assessments are carried out<br /> based on analysis of pore water, acidic volatile sulphides and simultaneously extracted metals<br /> and sequential extraction procedure. The assessment of metal mobility in the sediment / water<br /> system is determined by the changing physical and chemical conditions in real systems<br /> (waterways) and under laboratory conditions. The effectiveness of in-situ (aeration of sediment<br /> / water) and ex-situ remediation of sediment by thermal treatment methods and solidification /<br /> stabilization are investigated.<br /> The results show that in each waterbody and protected area, certain locations have sediment<br /> which for at least one metal, is classified (by the Dutch system of sediment classification ) as<br /> polluted (class 3) or highly polluted (class 4). In general, the quality of sediment in smaller<br /> rivers (Krivaja, Nadela, Kudo&scaron;, Veliki Bački canal and Begej) is inferior to the other rivers<br /> studied.<br /> Assessment of the metals availability in the sediments of the Veliki Bački canal indicates that<br /> in each profile examined, at least one metal and one method defines the sediment as very<br /> hazardous. It is also shown that the sediment at the section from 2 +000 to 4 +900 km is the<br /> most polluted, with a number of metals and methods that define it as a high risk. The results<br /> indicate that it is inadequate to have a simple singular approach to sediment quality assessment<br /> and the assessment of the risks posed by metals detected in aquatic ecosystems.<br /> This work shows that sediment movement (e.g. from opening a sluice gate) leads to changes in<br /> the physical-chemical conditions of the sediment / water system, with resuspension and<br /> sediment transport. These changes increase metals availability and increase their<br /> concentrations in the aqueous phase, significantly increasing the posed risk and the possibility<br /> of adverse effects on aquatic ecosystems.<br /> In the case of sediment resuspension in the sediment / water system, a relationship was found<br /> between the concentration of metals in suspended matter and the concentration in the water for<br /> certain fractions of suspended matter (organic matter content and the fraction up to 63 &mu;m).<br /> Remediation techniques are often not economically viable due to the large volume of<br /> contaminated sediments involved. It is shown that the implementation of in-situ aeration<br /> reduces the amount of sediment (which reduces the costs of subsequent sediment treatment),<br /> and that solidification / stabilization treatment with clay and thermal remediation results in<br /> satisfactory remediation with respect to metals leaching. Leaching test results show the<br /> potential of these treatments to solve the problem of sediments which are contaminated with<br /> metals, either in terms of safe disposal in landfill or in terms of its use as a supplement in the<br /> production of building materials (brick), as road foundation, or for river bank reinforcement<br /> (dams), etc.. Thus, the costs of dredging and manipulating contaminated sediments can be<br /> significantly reduced, making remediation itself much more applicable.</p>

Dans le cas hypothétique d'un accident grave de réacteur nucléaire, le coeur pourrait fondre et former un mélange à haute température (2000-3000 K) appelé corium. Dans le cas du percement de la cuve, ce corium s'étalerait dans le puits de cuve, dans les pièces adjacentes ? comme cela s'est produit à Tchernobyl? ou dans un récupérateur dédié à cet effet ? comme pour le nouveau réacteur européen EPR. Cette thèse est consacrée à l'étude expérimentale de l'étalement du corium, en particulier à l'aide des expériences en matériaux prototypiques (contenant de l'oxyde d'uranium appauvri) réalisées sur l'installation VULCANO au CEA Cadarache. La première étape de l'analyse de ces essais consiste en l'interprétation des analyses matériaux à l'aide de modèles thermodynamiques de la solidification du corium. Connaissant pour chaque température, la répartition et les composition des phases présentes dans la coulée, on peut alors en estimer les propriétés physiques. L'arrêt de l'écoulement est contrôlé par les propriétés rhéologiques du corium, en particulier dans l'intervalle de solidification, ce qui nécessite de les étudier en détail. Les aspects hydrodynamiques, rhéologiques et thermodynamiques de l'écoulement de corium en cours de solidification ont pris en compte dans les modèles et codes de calcul qui sont validés à l'aide de ces essais et permettent de conforter le concept de récupérateur par étalement de l'EPR.

A la température de service (320°C), la ferrite des composants en acier inoxydable austéno-ferritique du circuit primaire des centrales nucléaires subit un vieillissement par transformations microstructurales. Cette phase devient alors fragile et la résilience du matériau chute.<br />L'objectif de ce travail est d'étudier les vitesses et les mécanismes de propagation de fissure par fatigue en fonction du vieillissement et de la température d'essai (20°C/320°C). Pour cela, deux aciers moulés (30 % de ferrite) sont testés. Dans le but de mieux comprendre le rôle joué par l'orientation cristallographique des phases dans le mécanisme de propagation, la microstructure du matériau est étudiée par diffraction des électrons rétrodiffusés (ESBD) et par Trempe en Solidification Dirigée. Des éprouvettes sont également prélevées de telle sorte que la fissure se propage au travers de structures de solidification équiaxes et basaltiques. Microstructure, propriétés mécaniques en fatigue / fissuration et mécanismes sont alors reliés. Pour la gamme de delta K balayée, la fissure avance sans chemin préférentiel par une rupture successive des lattes de chacune de phases. Le plan macroscopique de fissuration, déterminé par ESBD, est imposé par l'orientation cristallographique du grain ferritique. Ainsi, selon la structure de solidification, des fissures secondaires peuvent apparaître ce qui influe sur les vitesses de propagation.<br />La fermeture de fissure, mesurée afin d'estimer les vitesses de propagation intrinsèques au matériau, diminue avec le vieillissement ce qui s'explique par l'accroissement de la composante cinématique du comportement plastique cyclique. La pente de la droite de Paris déterminée à partir de vitesses intrinsèques augmente avec le vieillissement. Le domaine de vitesse peut alors être séparé en deux parties : celle pour laquelle les vitesses sont plus faibles dans le matériau non vieilli et celle pour laquelle la tendance est inversée.

Latent heat during recalesence and nucleation and post-recalesence temperature was analysed for refractory metals. An effect on latent heat was found by alloying the pure elements with other refractories. Latent heat was found to be 15-65% of tabulated values. Interface energy was evaluated from undercooling experiments. It was found that the dimensionless numbers β (σLs/ σLv) and α can be used to classify elements into distinctive groups and crystallographic structure. The phase diagrams for Al-Ti, Al-Ti-B and Al-Ti-C as well as inoculation were analysed. It was found that Al nucleates on Al3Ti which nucleates on TiB2. TiC was found to decompose into Al4C3 and Al3Ti. The inoculation of nodular cast iron with Mg, Ce; Ca and the formation of sulphides and oxides was analysed. The formation of new inclusions during the solidification as well as the formation of graphite is discussed. / QC 20100602

Modelling the ice accretion in glaze regime for the supercooled large droplets is one of the most challenging problems in the aircraft icing field. The difficulties are related to the presence of the liquid water film on the surface in the glaze regime and also the phenomena associated with SLD conditions, specifically the splashing and re-impingement. The steady improvement of simulation methods and the increasing demand for highly optimised aircraft performance, make it worthwhile to try to get beyond the current level of modelling accuracy. A semi-empirical method has been presented to characterize the thin water film in the icing problem based on both analytical and experimental approaches. The experiments have been performed at the Cranfield icing facilities. Imaging techniques have been used to observe and measure the features of the thin water film in the different conditions. A series of numerical simulations based on an inviscid VOF model have been performed to characterize the splashing process for different water film to droplet size ratios and impact angles. Based on these numerical simulations and the proposed methods to estimate the thin water film thickness, a framework has been presented to model the effects of the splashing in the icing simulation. These effects are the lost mass from the water film due to the splashing and the re-impingement of the ejected droplets. Finally, a new framework to study the solidification process of the thin water film has been explored. This framework is based on the lattice Boltzmann method and the preliminary results showed the capabilities of the method to model the dynamics, thermodynamics and the solidification of the thin water film.

Les aciers inoxydables austénoferritiques sont couramment utilisés dans l'industrie (nucléaire en particulier) pour leurs bonnes propriétés, notamment mécaniques. Cependant ces aciers sont susceptibles de "vieillir" en cours d'utilisation à des températures élevées. Comme ces propriétés (résilience, ténacité) sont souvent très dispersées et se dégradent lors du vieillissement, on cherche à les prévoir avec la plus grande précision possible. Pour ce faire on propose d'expliquer une partie de la dispersion observée sur la résilience par des paramètres mesurables, liés à la morphologie biphasée et bipercolée particulièrement complexe de ces aciers. Cette morphologie est d'abord caractérisée à partir de l'observation d'images en 2D et de la reconstitution d'une image en 3D. Parallèlement on précise la genèse de cette microstructure. Au vu des observations et analyses précédentes, les outils classiques de la morphologie mathématique peuvent être utilisés pour quantifier par analyse d'image cette structure et proposer des variables pertinentes. En utilisant un modèle paramétrique pour décrire le comportement de la résilience , on montre l'influence d'un paramètre morphologique -la finesse de la microstructure- sur cette dernière. Dans le cas des produits très vieillis -le plus important en pratique-, le manque de données disponibles ne permet pas de proposer un modèle de résilience qui tienne compte de cette variable morphologique. Un modèle mathématique de la structure 3D du matériau est enfin proposé: une chaîne de Markov homogène de processus spatiaux 3D dont l'évolution dans le temps mime la solidification. La morphologie de la microstructure est ainsi résumée à 8 paramètres. Ce modèle est susceptible d'être couplé avec un modèle de résilience pour élargir ses possibilités de prévision. Il pourrait également être utilisé pour servir de base à des modélisations ultérieures de l'endommagement et de la rupture de matériaux biphasés.

The mechanisms responsible for ice propagation on surfaces undergoing dropwise condensation have been determined and characterized. Based on experimental data acquired non-invasively with high speed quantitative microscopy, the freezing process was determined to occur by two distinct mechanisms: inter-droplet and intradroplet ice crystal growth. The inter-droplet crystal growth mechanism was responsible for the propagation of the ice phase between droplets while the intra-droplet crystal growth mechanism was responsible for the propagation of ice within individual droplets. The larger scale manifestation of these two mechanisms cooperating in tandem was designated as the aggregate freezing process. The dynamics of the aggregate freezing process were characterized in terms of the substrate thermal di usivity, the substrate temperature, the free stream air humidity ratio, and the interfacial substrate properties of roughness and contact angle, which were combined into a single surface energy parameter. Results showed that for a given thermal di usivity, the aggregate freezing velocity increased asymptotically towards a constant value with decreasing surface temperature, increasing humidity, and decreasing surface energy. The inter-droplet freezing velocity was found to be independent of substrate temperature and only slightly dependent on humidity and surface energy. The intra-droplet freezing velocity was determined to be a strong function of substrate temperature, a weaker function of surface energy, and independent of humidity. From the data, a set of correlational models were developed to predict the three freezing velocities in terms of the independent variables. These models predicted the majority of the measured aggregate, inter- and intra-droplet freezing velocities to within 15%, 10%, and 35%, respectively. Basic thermodynamic analyses of the inter- and intra-droplet freezing mechanisms showed that the dynamics of these processes were consistent with the kinetics of crystal growth from the vapor and supercooled liquid phases, respectively. The aggregate freezing process was also analyzed in terms of its constituent mechanisms; those results suggested that the distribution of liquid condensate on the surface has the largest impact on the aggregate freezing dynamics.