<p>A supply shortage of solar-grade silicon in recent years resulted from a rapid expansion of the solar cell industry. Therefore, many efforts have been done to obtain reliable metallurgical methods for production of SoG silicon from metallurgical grade silicon.</p> <p>In this research, refining of metallurgical grade silicon by chlorination treatment with the emphasis on Al removal was investigated. Thermodynamic calculations through Factsage confirmed the feasibility of Al removal in repeated steps of chlorination. Therefore, an Ar+SiCl₄ gas mixture with different flow rates was applied to the silicon melt by blowing and injection methods at different temperatures and the ICP-OES was used for analysis of the impurities in silicon.</p> <p>Results revealed that Al removal from silicon by chlorination treatment under the conditions employed in this study is first order reaction with respect to Al. By increasing the temperature in the chlorination process, the rate constant increases which is related to an increase in the liquid mass transfer rate. Also the observed higher rates of Al removal under injection conditions appear to be the result of improved stirring in the melt rather than an increase in the interfacial area.</p> / Master of Applied Science (MASc)

This thesis deals with peritectic reactions and transformations that occur during the solidification of many alloys. Peritectics are believed to be a major cause of crack-formation in many steels, thus, good knowledge of the mechanisms by which these phenomena occur is essential for preventing such defects. The thesis also handles the behaviour of metals, in particular cast structures, during hot forming. Grain size and microstructure are of most importance in determining the strength, toughness and performance of a steel. For achieving enhanced mechanical and microstructural properties, good understanding of the phenomena occurring during hot forming is required. Peritectic reactions and transformations were studied in Fe-base and steel alloys through differential thermal analysis (DTA) experiments and micrographic investigation of quenched DTA samples. The effect of the ferrite/austenite interface strain during the peritectic reaction on equilibrium conditions was thermodynamically analysed, and the results were related to temperature observations from DTA experiments conducted on Fe-base alloys and low-alloy steels. Massive transformations from ferrite to austenite were observed in the micrographs of a number of quenched low-alloy steel samples and it was proposed that these transformations are uncontrolled by diffusion, and occur in the solid state as a visco-plastic stress relief process. DTA study of an austenitic stainless steel indicated that the alloy can exhibit primary precipitations to either ferrite or austenite. A continuously-cast breakout shell of the steel was analyzed and it was suggested that the observed irregularities in growth were due to alternating precipitations of ferrite and austenite; parts of the shell with higher ratios of primary-precipitated ferrite shrink in volume at the peritectic temperature and experience reduced growths. An experimental method for studying the behaviour of metals during hot forming developed, and hot compression tests were conducted on cast copper and ball-bearing steel samples. Flow stress curves were obtained at varying temperatures and strain rates, and the results showed good agreement with earlier observations reported in literature. Micrographic analysis of quenched samples revealed variations in grain size and a model was fitted to describe the grain size as a function of deformation temperature and strain. Solidification growth during continuous casting of stainless steel and copper was numerically modelled. A varying heat transfer coefficient was proposed to approximate the experimentally measured growth irregularities in the continuously-cast stainless steel breakout shell. Solidification growth of pure copper was also modelled in the Southwire continuous casting process. Temperature measurements from the chill mould were used to approximate the temperature gradient and the heat extraction from the solidifying strand, and the results were used in a two-dimensional model of solidification. / QC 20100803

Η επεξεργασία των νικελιούχων λατεριτικών μεταλλευμάτων της χώρας μας για την παραγωγή σιδηρονικέλιου στη Λάρυμνα συνοδεύεται με την εκπομπή 200000t/y λεπτομερούς σκόνης που συλλέγεται στα συστήματα αντιρρύπανσης των περιστροφικών κάμινων (Π/Κ), μέσης περιεκτικότητας 1.2-1.5% σε Ni και 4-5% σε C. Η διατριβή αυτή συνέβαλε στην ανάπτυξη μεθόδου ανακύκλωσης της σκόνης αυτής με απευθείας αναγωγική της τήξη σε ηλεκτρική κάμινο συννεχούς ρεύματος (DC-HEP) με εμφυσησή της μέσω του κεντρικού διάτρητου γραφιτικού ηλκετρόδιου. Την προκαταρκτική θεωρητική διερεύνηση και τις εργαστηριακές προδοκιμές ακολούθησαν βιομηχανικές δοκιμές στην κάμινο 125t DC-HEP στη χαλυβουργία Georgsmarienhutte της Γερμανίας, όπου έλαβε χώρα τήξη 70t σκόνης και 2.5t φιλομερούς μεταλλεύματος.Η ανάκτηση Ni ήταν πολύ υψηλή 93-99%. Παρήχθησαν χάλυβες χαμηλής κραμάτωσης σε σε Ni καθώς και ποικίλοι τύποι σκωρίας προς διερεύνηση της χρήσης τους στην παραγωγή σύνθετων τσιμέντων Portland και σκωριωτσιμέντων. Πραγματοποιήθηκε μεταλλουργική αξιολόγηση των δοκιμών και αναπτύχθηκε μοντέλο προσομοίωσης της αναγωγικής τήξης της σκόνης. / The tratment of the laterite nickel ferrous ores in Hellas for the production of ferronickel at Larymna is associated with the emission of 200000t/y of fine dust collected in the gas cleaning systems of the rotary kilns (R/Ks), with 1.2-1.5% and 4-5% . Average Ni and C contents respectively . This thesis contributed to the development of a method for the recycling of this dust by means of its direct reduction smelting in a DC-HEP furnace (Direct Current-Hollow Electrode Powder) by its injection through the central hollow graphite electrode. The preliminary theoretical study and the laboratory trials were followed by industrial heat campaigns in the 12st DC-HEP furnace at georgsmarienhutte steelwork in Germany, where around 70t of dust and 2.5t of ore fines were smelted. The Ni-recovery was very high 93-99.9%. Low Nickel alloyed steel grades were produced and various slag types for the investigation of their utilization for the production of composite-portland cements and slag cements. The metallurgical evaluation of the trials was performed and model for the dust reduction smelting process was developed.

<p>Sampling of liquid steel to control the steel making process is very important in the steel industry. However, there are numerous types of disposable samplers and no united standard for sampling. The goal in this study is to investigate the effect of slag protection type and sample geometry on sampling parameters and sample homogeneity. Three sample geometries were selected: i) Björneborg ii) Lollipop with a 6 mm thickness and iii) Lollipop with a 12 mm thickness. These sample geometries have been tested with two types of slag protection: metal-cap-protection and argon-protection. The filling velocity and solidification rate of steel samples have been experimentally measured during plant trials. The sample homogeneity with respect to total oxygen content and inclusion size distribution has been determined in different parts of the samples. The study shows that argon-protected samplers have lower, more even, filling velocities (0.19±0.09 m/s) compared to metal-cap-protected samplers (1.28±2.23 m/s). The solidification rate measurements of the different samplers show that the 6 mm thick Lollipop has the highest solidification rate (99~105 °C/s).  Measurements of total oxygen content in argon-protected samples showed little variation between different zones of the samples. However, metal-cap-protected samples contained much higher total oxygen contents. Light optical microscope studies showed that the increase in total oxygen content was probably caused by entrapment of top slag during sampling. Furthermore, it was found that the contamination of top slag in the metal samples increased with a decreased sample weight. Determination of inclusion size distribution in argon-protected Lollipop samples showed that a larger number of primary inclusions are found in the top part compared to the middle and the bottom part of the samples.</p><p> </p>

O presente estudo, desenvolvido no Programa de Pós-Graduação em História Social da Universidade de São Paulo, vincula-se, também, por seus objetivos e condição de sua orientadora, ao Programa de Pesquisas em História da Cultura Material do Museu Paulista da USP, que vem se configurando, nas últimas duas décadas, como centro emergente neste campo. Constitui, outrossim, aprofundamento de pesquisa em torno do comércio e fabricação de brinquedos na cidade de São Paulo nas primeiras décadas do século XX, na qual, das 77 fábricas e fabriquetas de brinquedos mapeadas, ativas entre 1901 e 1937, sobressaiu-se a Seção de Brinquedos da Metalúrgica Matarazzo METALMA, que por uma conjunção de características relativas a porte, duração, tipologia fabril e, sobretudo, por participar de momento histórico marcado por um pensamento industrial de ideologia nacionalista e anseio de modernização, mostra-se como objeto de pesquisas de interesse, até então não realizado. É objetivo da pesquisa esmiuçar e concretizar os modos como os ideais do nacionalismo e modernização puderam se desenvolver nos meandros da fabricação de brinquedos voltados ao mercado consumidor brasileiro de objetos de uso doméstico, desde os materiais e métodos fabris utilizados até o produto final brinquedos de lata com temáticas variadas, que são recuperados e analisados enquanto parte do corpus documental (seja no plano da informação textual e iconográfica, seja no exame de exemplares ainda existentes), tornando-se o objeto como documento, na perspectiva da História da Cultura Material. / The present study, developed at the Post-Degree Program at the São Paulo University (USP), is also related, due to its goals and supervisors status, to the History of Material Culture Research Program at the Paulista Museum, from the same university, a center which, in the last two decades, has become an emerging center of research in the field. Therefore, the present study is a deeper research on toys trade and manufacturing in the city of Sao Paulo during the first decades of the 20th century. From the 77 plants and small factories which have been mapped, actives between 1901 and 1937, the Seção de Brinquedos da Metalúrgica Matarazzo METALMA (Matarazzo Metallurgical Section of Toys) is of special interest. Owing to a group of traits related to size, activity period, factoring type and, especially, for taking part of a historical moment of a nationalistic industrial mindset and an urge for modernization, this company is the object of this research. The goal of this research is to scrutinize and actualize the way in which the ideology of nationalism and modernization could develop at the core of toy manufacturing targeted to the Brazilian end consumer, from materials and factoring procedures adopted to the final product differently themed tin toys which have been retrieved and analyzed as part of the documental corpus (both as textual and iconographical information and as analyses of remaining objects), and have become the documents for this research on perspective to the History of Material Culture.

No presente trabalho foram estudados os fenômenos de encruamento e, principalmente, transformação de fases, recuperação e recristalização, presentes na liga U-7,5Nb-2,5Zr (Mulberry alloy) e no urânio não ligado. Realizou-se a fusão da liga por dois métodos: plasma (menor massa) e indução (maior massa). A caracterização microestrutural das ligas resultantes nos estados bruto de fundição e homogeneizado (tratado termicamente na região da fase &#947; seguido de resfriamento rápido em água), assim como do urânio em seu estado inicial, foi realizada com auxílio de várias técnicas complementares de análise microestrutural. No estado gama estabilizado, a liga U-7,5Nb-2,5Zr foi deformada na temperatura ambiente por dois métodos: laminação a frio, dividida em vários estágios (20%, 50%, 60% e 80%), e limagem, sendo o pó resultante de alto grau de deformação. As amostras deformadas foram posteriormente recozidas em tratamentos isócronos (1 hora) e isotérmicos (200ºC, 450ºC e 700ºC). O urânio não ligado foi deformado em aproximadamente 60% e 80% de redução em espessura, e em seguida submetido a tratamentos isócronos (1 hora) e isotérmicos (400ºC e 650ºC). Os fenômenos de encruamento, recuperação, recristalização e transformação de fases foram estudados predominantemente por microscopia óptica, dureza e difração de raios X, com auxílio do método de Rietveld. Adicionalmente, técnicas de análise térmica (dilatometria e calorimetria diferencial) foram utilizadas para acompanhamento da cinética de transformação de fase e energia armazenada na deformação. Com relação à deformação, a liga U-7,5Nb-2,5Zr mostrou ser capaz de sofrer reduções da ordem de 70% na temperatura ambiente, sem necessidade de recozimentos intermediários e com um baixo grau de encruamento. Similarmente, o urânio não ligado mostrou ser capaz de sofrer graus de deformação mais altos na temperatura ambiente, entretanto, este material apresentou alto grau de encruamento e, mesmo após considerável grau de deformação, ainda apresentava muitas heterogeneidades de deformação, como bandas de deformação e maclas. Foi observado que a recristalização do urânio não ligado teve início a aproximadamente 454ºC. Para a liga no estado deformado e supersaturado, a precipitação de fases tende a ocorrer antes da recristalização. Assim, o comportamento desta liga sob aquecimento pós-deformação pode ser resumido da seguinte forma: ~200°C (Recuperação) ---> 300-575°C (Precipitação de fases) ---> 575°C (Recristalização). O rápido aquecimento para temperaturas acima de 650ºC, ou a manutenção desta temperatura por longos tempos, gera uma estrutura &#947; recristalizada com grãos equiaxiais. Uma estrutura de grãos finos (~8,3µm) foi obtida no recozimento a 700ºC/1h tanto para baixo como para alto grau de deformação. Uma taxa de aquecimento lenta, ou recozimento na faixa de 300-575ºC, gera precipitação da fase antes da recristalização. Consequentemente, a transformação eutetóide &#947;&#8594;&#945;+&#947;&#8323; ocorre de modo a herdar a orientação do grão &#947; deformado, o que pode gerar uma textura de transformação. Na faixa de temperaturas de 575-650ºC ocorre a interação entre os fenômenos de precipitação de fase e recristalização. Em recozimentos a 200ºC foi possível observar a predominância da recuperação para graus de deformação intermediários (60%) e altos (80%), mas para grau de deformação baixo (20%) prevaleceu endurecimento por precipitação da fase &#945;\'\'. Com auxílio da análise em um calorímetro diferencial (DSC) foi observado que a energia armazenada na deformação e liberada durante o processo de recristalização da liga U-7,5Nb-2,5Zr foi de 6,5J/g. Tal valor é relativamente alto se comparado aos metais comuns, o que leva à suposição de que uma linha de discordância no urânio representa uma maior energia. Este fato tem influência direta no processo recristalização. Este experimento demonstrou também que os fenômenos de precipitação de fase e recristalização interagem entre si, com relação à energia disponível para o processo. A textura da liga U-7,5Nb-2,5Zr foi estudada por difração de raios X (DRX) nas condições com fase &#947; estabilizada (obtida através de fusão, coquilhamento e homogeneização seguida de têmpera) e no estado deformado (laminado a temperatura ambiente). A liga na condição com &#947; estabilizado apresentou textura moderada com apenas as componentes (023) e (032). Após a deformação de 80%, o material apresentou uma textura de fibra (001)&#60;uvw&#62;, pouco comum nos metais CCC, além da fibra &#947; (111)&#60;uvw&#62;, com intensidade intermediária. / In this work it was studied the phenomena of work hardening, mainly phase transformation, recovery and recrystallization in the U-7.5Nb-2.5Zr alloy (Mulberry alloy) and unalloyed uranium. The alloy was melted by two methods: plasma (smaller mass) and induction (larger mass). Microstructural characterization of the samples in the as-cast and homogenized states (the last one was heat treated in the &#947; phase region and then quenched in water), as well as uranium in its initial state, was performed using several complementary techniques for microstructural analysis. In the gamma stabilized state, the U-7.5Nb2.5Zr alloy was deformed at room temperature by two methods: cold rolling in several stages (20%, 50%, 60% and 80%), and then filed, resulting in a powder with high degree of deformation. Deformed samples were subsequently annealed by isochronal (1 hour) and isothermal (200°C, 450°C, 700°C) treatments. Unalloyed uranium was deformed by approximately 60% and 80% reduction in thickness, and then subjected to isochronous (1 hour) and isothermal (400°C and 650°C) treatments. The phenomena of work hardening, recovery, recrystallization and phase transformation were studied by optical microscopy, hardness testing and X-ray diffraction, using the Rietveld method. Additionally, thermal analysis techniques (differential calorimetry and dilatometry) were used to measure the kinetics of phase transformation and energy stored during deformation. With regard to deformation, the U-7.5Nb-2.5Zr alloy was reduced of approximately 70% at room temperature without intermediate annealing and with a low degree of work hardening. Similarly, unalloyed uranium was reduced of high degrees of deformation at room temperature. However, this sample showed a higher degree of work hardening, and even after significant deformation still showed lots of inhomogeneities of deformation, such as deformation bands and twins. It was observed that recrystallization of unalloyed uranium started at about 454°C. For the alloy in the supersaturated and deformed states, the phase precipitation tends to occur before recrystallization. Thus, the behavior of this alloy under heat treatments after deformation can be summarized as follows: ~200°C (Recovery) ---> 300-575°C (Phase precipitation) ---> 575°C (Recrystallization). Rapid heating to temperatures above 650°C, or maintain this temperature for a long time, generates a &#947; recrystallized structure with equiaxed grains. Fine grain structure (~8.3 µm) was obtained for annealing at 700°C/1 h for both lower and higher deformation degrees. Slow heating rate or annealing treatment in the range of 300 to 575ºC, causes precipitation before recrystallization. Consequently, the eutectoid transformation &#947;&#8594;&#945;+&#947;&#8323; occurs in order to inherit orientation from the &#947; deformed grain, which may generate a transformation texture. The interaction between the phenomena of phase precipitation and recrystallization was observed in the temperature range of 575-650°C. At the annealing temperature of 200°C it was possible to observe the predominance of recovery at intermediate (60%) and higher (80%) degrees of deformation, while at lower deformation degree (20%) &#945; phase precipitation hardening has predominated. The results obtained using a differential calorimeter (DSC) showed that the energy stored during deformation and released during the recrystallization of the U-7.5Nb-2.5Zr alloy was 6.5 J/g. That value is relatively high compared to common metals, which leads to the conclusion that dislocation lines in uranium alloys possess higher energy. This fact has a direct influence in the recrystallization process. This experiment also demonstrated that the phenomena of phase precipitation and recrystallization interact with each other with regard to energy available for the process. The texture of the U-7.5Nb-2.5Zr alloy was studied by X-ray diffraction (XRD) in the &#947;-phase stabilized condition (obtained by melting, casting, homogenization and then quenching) and in deformed state (rolled at room temperature). The first condition generated moderate texture with the components (023) e (032). After 80% of deformation, the samples showed a fiber texture (001)&#60;uvw&#62;, uncommon in the BCC metals, as well the &#947; fiber (111)&#60;uvw&#62; with intermediate intensity.

The use of composites materials in aerospace applications can provide significant weight reduction. However, in airframe designs composites are frequently required to be joined to metal components, which is a challenging issue owing to the very different thermo-physical properties of the two classes of materials. In many cases adhesive bonding has insufficient durability and the requirement for large lapped areas and mechanical fasteners adds considerable weight, reducing the mass savings associated with the introduction of composite structures. A promising approach for improving joint performance is to surface engineer locking features on to the metal part which then integrate with the composite laminate to increase shear load transfer, both via better adhesion and also by mechanical "fit" throughout the thickness of the composite. Such hybrid joints are known as "hyper-joints". For this work, three main techniques are currently being investigated for generating the required surface features. These are; (i) sculpting surfaces using power beam local surface melting techniques (Surfi-Sculpt), (ii) building surface protrusions by additive layer manufacturing (AM) and (iii) arc percussive welding process. The present work aims to provide understanding of the critical metallurgical interactions during the growth/production of the surface engineered features and how some build parameters might affect the eventual joint integrity, durability and performance. To enable the use of the arc-percussive welding process as a viable manufacturing route for these hyper-joints, optimisation of its process parameters were studied in the course of this work. Further work on the effect of process parameters such as voltage, travel velocity, gap setting and time delay on the quality of the weld were also investigated in this study. Of the above mentioned process parameters, the voltage across the capacitor and travel velocity of the actuator have been found to have far greater effect on the weld quality. More importantly, the travel velocity of the actuator was also found to help determine the shape, size and distribution of the melt pool. Based on the systematic study and analysis of all of the process parameters involved, an optimised process window has now been proposed. Microstructural characterisations of hyper-joint samples made via the three manufacturing routes were performed in the course of the work. The observed microstructures were related to the process history and the process parameters. Most importantly it was for found that in common with most welding and AM processes, columnar prior β grains developed in all the samples studied by epitaxial-regrowth either along the build or weld directions. It was also found that the fusion zone of the similar titanium alloy (Ti-6Al-4V to Ti-6Al-4V) arc-percussive welded samples were characterised by extremely fine acicular alpha' martensitic platelets formed as a result of the high cooling rate associated with the process. On the other hand, the fusion zone of the dissimilar titanium alloy (Ti-6Al-4V to β21S) arc-percussive welded samples was characterised by an extremely fine cellular structure prompted by constitutional supercooling. Finally the microstructures observed in the Surfi-Sculpt samples were found to be dependant on the swipe pattern and duration. In order to assess the performance of hyper-joints made via two of the candidate manufacturing routes, tensile testing of standard and modified tensile samples was performed. The result indicated that on average the strength of these hyper-joint pins were within nominal values expected of the Ti-6Al-4V and β21S alloys. It was also found that with optimum weld conditions, failure occurred only along the gauge length for the arc-percussive welded samples whilst the strength of the AM samples degrade as the gauge diameter decreases as the effect of surface defects became prominent. Results are also reported on a novel method for testing the shear strength and properties of individual hyper-pins manufactured via this process. Interpretation of the shear test was assisted by finite element modelling. The shear test results indicated that the arc-percussive welded samples outperformed the SLM-AM samples thereby giving credence to the process as a viable means for making the pins.

Les principaux objectifs étaient d'évaluer la stabilité de l'environnement des scories métallurgiques de Cu résultant de différentes périodes d'activités industrielles et de différentes technologies de fusion. Parmi les scories étudiées, on retrouve: les scories historiques cristallines (SH) ainsi que modernes: les scories de four vertical (SFS), les scories granulées (GS) et les scories de plomb (LS). Les différentes approches adoptées dans ce travail de thèse ont tenu compte de: i) la composition chimique et la phase minérale des scories, ii) la sensibilité à la lixiviation des scories sous l’exposition à différentes conditions de pH en mode statique, iii) l’altération des scories sous exposition aux acides organiques couramment trouvés dans l'environnement du sol, iv ) la bio-altération des scories par les bactéries (Pseudomonas aeruginosa) et v) l’application future de la récupération des métaux provenant des scories étudiées en mettant en œuvre la méthode de lixiviation biologique. Résultats cruciaux: Les résultats des tests de lixiviation dépendant du pH ont montré une libération de métal plus élevée dans des conditions fortement acides (pH 2 et 4), alors que la lixiviation dans des conditions alcalines (pH 10.5) était moins importante pour toutes les scories analysées. L'effet de l’altération par le sol a été démontré, la dissolution des scories est notamment sensible à la présence d'exsudats racinaires artificiels (ARE), d’acides humiques (HA) et d’acides fulviques (FA), la contribution des ARE étant la plus forte. Selon les données recueillies, la dissolution relative des scories est strictement liée à leurs caractéristiques (composition chimique et minéralogique) en fonction des différentes conditions étudiées. L'étude concernant l’effet de l’altération biologique a révélé que Pseudomonas aeruginosa améliore considérablement la libération des éléments majeurs (Si et Fe) et métalliques (Cu, Zn, Pb) par rapport aux effets des facteurs abiotiques, indépendamment de la chimie et de la structure des scories. En outre, une récupération élevée (jusqu'à 90%) des métaux (Cu, Zn, Fe) pourrait être obtenue grâce à la lixiviation avec Acidithiobacillus thiooxidans dans des conditions de laboratoire. Conclusions générales : La stabilité des scories dans l'environnement dépend à la fois des caractéristiques chimiques et de la minéralogie. Cependant, les phases minérales hébergeant les métaux sont les facteurs les plus déterminants concernant l'intensité de la lixiviation des métaux. Pour cette raison, l'examen individuel du comportement des scories est important pour empêcher la contamination de l'environnement et devrait être considéré comme une priorité pour la gestion durable des scories. L’optimisation des paramètres de fonctionnement pour le biolessivage et le développement de la technologie à l'échelle industrielle pourrait permettre une bien meilleure gestion (voir l’exploitation) des scories métallurgiques de Cu / Problem statement: Copper pyrometallurgical slags are inevitable waste by-products of Cu smelting operations. These waste are considered to be important due to their production volume and high residual metal content that are inefficiently recovered during industrial process. Due to the lack of sustainable practices in the past, tremendous volumes of Cu-slags have been disposed in many industrial districts, regardless of the weathering and associated environmental risk. Consequently, there are many areas where slags have been proven to be a source of metallic pollution for the surrounding environment. At the present time, the outstanding contradiction between the sustainable development and environmental pollution encourages to undertake the action regarding this aspect. For this reason, slags are currently being used as supplementary materials for civil engineering purposes (e.g. cement and concrete additives, road bed filling materials, hydraulic construction materials) rather than disposed. Additionally, modern-day management strategies require slags to be thoroughly evaluated with respect to their environmental stability prior undertaking any reuse action. Main objectives were to evaluate environmental stability of Cu-metallurgical slags resulting from different periods of industrial activities and different smelting technologies. Those included: historical crystalline slag (HS) as well as modern: shaft furnace slag (SFS), granulated slag (GS) and lead slag (LS). Different approaches undertaken in this PhD work considered: i) chemical and mineral phase compositions of slags, ii) leaching susceptibility of slags under exposure to different pH-stat conditions, iii) slags weathering under exposure to organic acids commonly found in soil environment, iv) bacterially (Pseudomonas aeruginosa) mediated weathering of slags and v) future application of studied slags for metal recovery by implementing the bioleaching method. Crucial results: The results of the pH-dependent leaching tests showed a higher metal release in strong acidic conditions (pH 2 and 4), whereas leachability at alkaline conditions (pH 10.5) revealed a lower importance for all the slags analyzed. The study considering soil weathering scenario demonstrated that Cu-slags are susceptible to dissolution in the presence of artificial root exudates (ARE), humic (HA) and fulvic acids (FA), whereby ARE were found to have stronger contribution than HA and FA. According to data collected, the different behavior of individual slags is strictly related to their characteristics (chemical and phase composition) reflecting various susceptibilities to dissolution under the investigated conditions. The study considering bio-weathering scenario revealed that Pseudomonas aeruginosa considerably enhances the release of major (Si and Fe) and metallic (Cu, Zn, Pb) elements compared to the effects of abiotic factors, regardless of the slags chemistry and structure. Furthermore, a high gain (up to 90%) of metals (Cu, Zn, Fe) could be credited to bioleaching with Acidithiobacillus thiooxidans under laboratory conditions. General conclusions: The environmental stability of slags depends on both, their bulk chemistry and mineralogy. However, mineral phases harbouring the metals are the key players in metal leachability intensity. For, this reason consideration of individual slags behaviour is important for preventing environmental contamination and should be regarded as priority branch of sustainable slag management. Optimization of operating parameters for bioleaching following development of industrial scale technology is an incentive scheme for future management of Cu-metallurgical slags

Foi efetuada a caracterização microestrutural de 10 ligas dos sistemas urânio-nióbio (U-10Nb; U-15Nb; U-20Nb), urânio-zircônio (U- 10Zr; U-15Zr, U-20Zr) e urânio-nióbio-zircônio (U-2,5Nb-2,5Zr; U-5Nb- 5Zr; U-7,5Nb-7,5Zr; U-10Nb-10Zr), no canto rico em urânio. As ligas estudadas são candidatas ao uso como elementos combustíveis tipo placa, utilizados tanto em reatores nucleares de pesquisa como em reatores nucleares de potência. As ligas foram preparadas por fusão a plasma em forno com eletrodo não consumível de tungstênio. Após várias fusões, as amostras sofreram tratamento térmico de homogeneização a 1000ºC por 96 horas, com resfriamento em água. Em seguida, as amostras homogeneizadas foram recozidas a 700 e a 500ºC, com resfriamento em água. No total, foram estudadas 40 amostras de 10 ligas diferentes em 4 condições diferentes: bruto de fundição, homogeneizadas a 1000ºC e envelhecidas a 700 e a 500ºC. Foram utilizadas várias técnicas complementares de caracterização microestrutural: microscopia óptica, microscopia eletrônica de varredura com auxilio de microanálise por dispersão de energia de raios X, difração de raios X com auxílio do método de análise de Rietveld, e medidas de microdureza Vickers. Os resultados mostraram que os elementos de liga Nb e Zr estabilizam a fase alotrópica &#947 do urânio e atrasam a transformação de &#947; para &#946;. Neste aspecto, o Nb é mais eficaz que o Zr. Além disto, podem ocorrer durante o resfriamento transformações martensíticas &#947;&#8594;&#945;\', &#946;&#8594;&#945;&#8242; e possivelmente &#947;&#8594;&#947;°. A temperatura de início de transformação martensítica (Ms) formadora da fase diminui com a adição dos elementos de liga estudados. Ms intercepta a temperatura ambiente entre as composições U-5Nb-5Zr e U-7,5Nb-7,5Zr. Foi verificado também que a reação peritetóide &#945; + &#947;2&#8594; &#948; do sistema U-Zr possui uma cinética lenta e não pode ser detectada nos tempos e temperaturas estudados. Em algumas ligas foi possível reter na temperatura ambiente ligas com microestrutura martensítica dúcteis, que permitem a conformação mecânica a frio, o que é de significativo interesse tecnológico. / The microstructures of 10 uranium-rich alloys of the uraniumniobium (U-10Nb; U-15Nb; U-20Nb), uranium-zirconium (U-10Zr; U- 15Zr;U-20Zr) and uranium-niobium-zirconium (U-2.5Nb-2.5Zr; U-5Nb-5Zr; U-7.5Nb-7.5Zr; U-10Nb-10Zr)systems have been characterized. The studied alloys are considered for plate-type nuclear fuels fabrication used both in nuclear research reactors and in nuclear power reactors. The alloys were melted by arc plasma methods employing nonconsumable tungsten cathode. After several fusions, samples were subjected to homogenizing heat treatment at 1000ºC for 96 hours and then quenched in water. Then the samples were annealed at 700 and 500ºC. The microstructural characterization encompassed 40 samples of 10 different alloys composition in four different conditions: as cast, homogenized at 1000°C and aged at 700 and 500ºC. Microstructural characterization was performed using several complementary techniques: optical microscopy; scanning electron microscopy with energy-dispersive X-ray analysis; X-ray diffraction with the aid of the Rietveld analysis method; and Vickers microhardness measurements. The results showed that the Nb and Zr additions have stabilized the uranium &#947;-phase and delayed the &#947; and &#946; phase transformation. In this regard, Nb was more effective than Zr. However, during cooling martensitic transformations &#947;&#8594;&#945;\', &#946;&#8594;&#945;\' and possibly &#947;&#8594;&#947;° may occur. The martensitic transformation start temperature (Ms), which produces the phase , decreased with Nb and Zr additions. Ms intersected room temperature between the compositions U-5Nb-5Zr e U- 7,5Nb-7,5Zr. It was found that the peritectoid reaction &#945; + &#947;2 &#8594; &#948; of the U-Zr system showed a very slow kinetics and could not be detected in the range of the studied times and temperatures. An important result of the technological point of view is that in some alloys it was possible to retain at room temperature a ductile martensitic microstructure, allowing cold forming.

Foi efetuada a caracterização microestrutural de 10 ligas dos sistemas urânio-nióbio (U-10Nb; U-15Nb; U-20Nb), urânio-zircônio (U- 10Zr; U-15Zr, U-20Zr) e urânio-nióbio-zircônio (U-2,5Nb-2,5Zr; U-5Nb- 5Zr; U-7,5Nb-7,5Zr; U-10Nb-10Zr), no canto rico em urânio. As ligas estudadas são candidatas ao uso como elementos combustíveis tipo placa, utilizados tanto em reatores nucleares de pesquisa como em reatores nucleares de potência. As ligas foram preparadas por fusão a plasma em forno com eletrodo não consumível de tungstênio. Após várias fusões, as amostras sofreram tratamento térmico de homogeneização a 1000ºC por 96 horas, com resfriamento em água. Em seguida, as amostras homogeneizadas foram recozidas a 700 e a 500ºC, com resfriamento em água. No total, foram estudadas 40 amostras de 10 ligas diferentes em 4 condições diferentes: bruto de fundição, homogeneizadas a 1000ºC e envelhecidas a 700 e a 500ºC. Foram utilizadas várias técnicas complementares de caracterização microestrutural: microscopia óptica, microscopia eletrônica de varredura com auxilio de microanálise por dispersão de energia de raios X, difração de raios X com auxílio do método de análise de Rietveld, e medidas de microdureza Vickers. Os resultados mostraram que os elementos de liga Nb e Zr estabilizam a fase alotrópica &#947 do urânio e atrasam a transformação de &#947; para &#946;. Neste aspecto, o Nb é mais eficaz que o Zr. Além disto, podem ocorrer durante o resfriamento transformações martensíticas &#947;&#8594;&#945;\', &#946;&#8594;&#945;&#8242; e possivelmente &#947;&#8594;&#947;°. A temperatura de início de transformação martensítica (Ms) formadora da fase diminui com a adição dos elementos de liga estudados. Ms intercepta a temperatura ambiente entre as composições U-5Nb-5Zr e U-7,5Nb-7,5Zr. Foi verificado também que a reação peritetóide &#945; + &#947;2&#8594; &#948; do sistema U-Zr possui uma cinética lenta e não pode ser detectada nos tempos e temperaturas estudados. Em algumas ligas foi possível reter na temperatura ambiente ligas com microestrutura martensítica dúcteis, que permitem a conformação mecânica a frio, o que é de significativo interesse tecnológico. / The microstructures of 10 uranium-rich alloys of the uraniumniobium (U-10Nb; U-15Nb; U-20Nb), uranium-zirconium (U-10Zr; U- 15Zr;U-20Zr) and uranium-niobium-zirconium (U-2.5Nb-2.5Zr; U-5Nb-5Zr; U-7.5Nb-7.5Zr; U-10Nb-10Zr)systems have been characterized. The studied alloys are considered for plate-type nuclear fuels fabrication used both in nuclear research reactors and in nuclear power reactors. The alloys were melted by arc plasma methods employing nonconsumable tungsten cathode. After several fusions, samples were subjected to homogenizing heat treatment at 1000ºC for 96 hours and then quenched in water. Then the samples were annealed at 700 and 500ºC. The microstructural characterization encompassed 40 samples of 10 different alloys composition in four different conditions: as cast, homogenized at 1000°C and aged at 700 and 500ºC. Microstructural characterization was performed using several complementary techniques: optical microscopy; scanning electron microscopy with energy-dispersive X-ray analysis; X-ray diffraction with the aid of the Rietveld analysis method; and Vickers microhardness measurements. The results showed that the Nb and Zr additions have stabilized the uranium &#947;-phase and delayed the &#947; and &#946; phase transformation. In this regard, Nb was more effective than Zr. However, during cooling martensitic transformations &#947;&#8594;&#945;\', &#946;&#8594;&#945;\' and possibly &#947;&#8594;&#947;° may occur. The martensitic transformation start temperature (Ms), which produces the phase , decreased with Nb and Zr additions. Ms intersected room temperature between the compositions U-5Nb-5Zr e U- 7,5Nb-7,5Zr. It was found that the peritectoid reaction &#945; + &#947;2 &#8594; &#948; of the U-Zr system showed a very slow kinetics and could not be detected in the range of the studied times and temperatures. An important result of the technological point of view is that in some alloys it was possible to retain at room temperature a ductile martensitic microstructure, allowing cold forming.