As propriedades mecânicas, de corrosão e a condutividade térmica e elétrica, aliadas à relativa facilidade de fundir atribuem grande relevância ao cobre e suas ligas. Algumas destas propriedades podem ser significativamente melhoradas com a diminuição do tamanho de grão da estrutura bruta de solidificação a partir do tratamento de inoculação do banho líquido. Este tratamento aumenta o número de núcleos sólidos, diminuindo assim o tamanho médio de grão. Neste trabalho, foi realizado um estudo do refino de grão da estrutura bruta de solidificação a partir da inoculação com adições de C, P e Zr a ligas do sistema Cu-Zn com teores de até 30% de Zn. Três séries de experimentos principais foram realizadas. Na primeira, o teor de Zr na liga Cu- 30%Zn foi gradativamente aumentado até 0,4% para mostrar o efeito do Zr. Na segunda, o teor de Zr foi mantido constante em 0,08%, enquanto o teor de Zn foi elevado gradativamente até 30% para mostrar o efeito do Zn. Na terceira foram testadas adições isoladas e conjuntas de C, P e Zr para verificar o efeito de cada elemento no refinamento de grãos. As amostras foram caracterizadas e analisadas por diferentes técnicas: (a) observação da macroestrutura de grãos; (b) análise química; (c) análise térmica; (d) microscopia óptica; (e) microscopia eletrônica de varredura; (f) microanálise EDS; g) microanálise WDS e h) difração de raios X. Os resultados mostram que o tamanho médio de grão diminui significativamente nas ligas do sistema Cu-Zn (6% <= Zn <= 30%) quando Zr e P são adicionados simultaneamente. Isoladamente, estes elementos quando adicionados, não reduzem significativamente o tamanho de grão. Nota-se também que o tamanho de grão é cada vez menor à medida que o teor de Zn aumenta de 0 a 30% com a adição de 0,08%Zr, porém não se observa uma correlação entre tamanho de grão e teor de Zn quando Zr não é adicionado. Uma análise da microestrutura dos lingotes utilizando as técnicas mencionadas mostra que a diminuição do tamanho médio de grão a partir de adições de Zr e P coincide com o aparecimento de precipitados facetados ricos em Zr e P. Esta análise indica que um possível mecanismo de inoculação dos latões é a nucleação heterogênea da fase sólida Cu-µ, com estrutura cristalina cúbica de faces centradas, sobre partículas sólidas de ZrP, com estrutura hexagonal compacta, formadas no banho líquido após as adições de Zr e P. / Good mechanical and corrosion properties, large thermal and electrical conductivities, as well as relatively large castability are characteristics that contribute to the importance of copper and copper alloys. Some of these properties are enhanced when the average grain size of the as-cast structure decreases by inoculation of the melt. The inoculation treatment increases the number of solid nuclei, causing a reduction in the average grain size. In the present work, an investigation of the grain refinement by inoculation with Zr and P additions to Cu-Zn melts with contents of Zn up to 30%(mass) was carried out. Three series of experiments were conducted. In one the Zr content of the Cu-30%Zn alloy was gradually increased up to 0.4% to reveal the effects of Zr, while in the second series, the concentration of Zr was constant, equal to 0.08%, but the Zn content was gradually increased to 30% to show the effect of Zn. The third one was to test separate and conjunct addition of C, P and Zr in order to understand each elements effect on grain refinement. The resulting samples were characterized and analyzed by several techniques: (a) visual observation of the grain macrostructure; (b) chemical analysis; (c) thermal analysis; (d) optical microscopy; (e) scanning electron microscopy; (f) EDS microanalysis; (g) WDS microanalysis; and (h) X-Ray diffraction. The results show that the average grain size of the Cu-Zn alloys (6% <= Zn <= 30% mass) decreases significantly when Zr and P are both added to the melt. Nevertheless, average grain size is not reduced significantly when either Zr or P are added separately to the melt. When 0.08%Zr is added, the average grain size decreases as the concentration of Zn increases from 0 to 30%Zn, but without Zr additions, the Zn content and the average grain size are uncorrelated. The microstructural analysis with the techniques listed before show that the decrease in average grain size caused by Zr and P additions coincide with the observation of faceted precipitates rich in Zr and P. This analysis indicates that the inoculation mechanism is probably the heterogeneous nucleation of solid Cu-µ, of face-centered-cubic lattice structure, on solid particles of ZrP, with hexagonal compact structure, formed in the melt after Zr and P additions.

O processo de reaproveitamento dos Resíduos de Construção e Demolição (RCD) na cidade de Londrina, Estado do Paraná, foi pesquisado. O objeto da investigação foi analisar a política sobre a reciclagem dos resíduos da construção na cidade. Constatou-se que o município tem observado as legislações atuais e que tem organizado e disciplinado a atuação dos grandes e pequenos gerdores. Também foram analisados os procedimentos adotados por uma empresa ambientalmente licenciada, identificando seu processo de produção do material reciclado e caracterizando o produto a ser reutilizado. O material reciclado é o resultado da rebritagem do resíduo da construção, que se transforma em pedras e areia resultantes da trituração de concreto puro ou da trituração conjunta de concreto, argamassa, pisos, revestimentos e tijolos cerâmicos. Foi analisado esse processo para verificar a existência de procedimentos de identificação de contaminação na empresa para a utilização dos resíduos na reciclagem e, principalmente, verificar a existência de contaminação no produto. Nos agregados produzidos foram identificados alumínio e cádmio em excesso e, para que possam ser utilizados livres destes contaminantes, foi proposta a técnica de estabilização por solidificação. No entanto, os resultados não foram os esperados, uma vez que observou-se aumento dos teores destes contaminantes após o encapsulamento usando a técnica à base de cimento Portland. Concluiu-se que, provavelmente, como já foi observado em pesquisas anteriores, a causa principal desse aumento é a contaminação do cimento, único material adicionado aos resíduos para a fabricação dos corpos de prova. Uma proposta de protocolo para a reutilização de resíduos de construção e demolição com resíduos industriais incorporados foi também apresentada, bem como recomendações para a produção e utilização de agregados reciclados. Como a contaminação do cimento parece ser recorrente, sugere-se que estudos sobre as possíveis causas da contaminação e desvios das normas técnicas sejam mais profundamente pesquisados. / The recycling process of construction and demolition residues (RCD) in the city of Londrina, Parana State, was searched. The object of the research was to analyze the policy on recycling of construction residues in the city. It was found that the city has noted the current legislation and has organized and disciplined the performance of large and small generators. Were also analyzed the procedures adopted by an environmentally licensed company, identifying its production process of recycled material and featuring the product to be reused. The recycled material is the result of rebritagem the residue of the construction, which turns into gravels and sand resulting from pure concrete grinding or joint grinding of concrete, mortar, floors, tiles and bricks. This process was analyzed to check for contamination identification procedures in the company for the use of residue recycling and especially check for contamination in the product. In produced clusters identified excess aluminum and cadmium, that can be used free of such contaminants, it has been proposed for stabilization/solidification technique. However, the results were not expected given that there was increase in levels of these contaminants after encapsulation technique using Portland cement-based. It was concluded that, probably, as has been observed in previous research, the main cause of this increase is contamination of the cement, only material added to the residue for the manufacture of test specimens. A proposed protocol for the reuse of construction and demolition residue with embedded industrial residue was also presented, as well as recommendations for the production and use of recycled aggregates. As cement contamination seems to be recurring, it is suggested that studies on the possible causes of contamination and technical norms deviations are more thoroughly researched.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1978. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / by Sindo Kou. / Ph.D.

Um modelo matemático para a transferência de calor no processo de refusão por eletroescória (ESR - \"electroslag remelting\") foi implementado a partir da equação diferencial de condução de calor transiente em coordenadas cilíndricas. A resolução numérica da equação diferencial foi facilitada através de uma mudança de variável que possibilitou fixar-se o tamanho do domínio de cálculo durante o período de crescimento do lingote. Duas análises foram conduzidas. Na primeira, uma análise paramétrica foi feita e na segunda um caso industrial foi analisado. Na primeira analise, a equação diferencial foi escrita na forma adimensional, indicando os parâmetros adimensionais importantes para o processo. Realizou-se um estudo paramétrico do modelo examinando-se o efeito de algumas variáveis de processo na geometria da poça de fusão, no tempo local de solidificação (LST) e no comprimento do lingote necessário para o sistema atingir um regime quase-estacionário. As variáveis de processo escolhidas para o estudo foram: (1) a taxa de refusão; (2) o tipo de material refundido e (3) as condições de extração de calor pelo molde. Os resultados mostraram que não é possível definir, para todas as condições industriais, uma única razão entre o comprimento e o raio do lingote no momento em que a poça de fusão atinge estado quase-estacionário. Observou-se ainda que o número de Stefan, que define o tipo de material, tem efeito desprezível na profundidade da poça de fusão e no tempo local de solidificação quando atinge valores maiores do que 0,5. Na segunda análise (caso industrial), o modelo foi usado para simular a refusão industrial de um lingote da liga ASTM F138. O perfil da poça de fusão e o fluxo de calor na interface metal-lingoteira foram medidos e apresentaram uma excelente aderência aos resultados do modelo. Os resultados apresentados permitem ainda a determinação (sob o ponto de vista microestrutural) do valor ótimo da taxa de refusão e do momento em que o processo atinge o estado quase-estacionário para uma ampla faixa de materiais, diâmetros de lingote e condições de transferência de calor adotadas industrialmente. / A mathematical model for heat transfer in the electroslag remelting process (ESR) was implemented using the transient heat conduction equation in cylindrical coordinates. The solution of the equations was facilitated by using a change of the axial coordinate, also known as the Landau transformation, which fixed the calculation domain size during the ingot growth period. Two analyses were carried out. In the first, a parametric study of the model was done, while in the second, the solidification of an industrial ingot was modeled. In the first analysis, the differential equation in dimensionless form indicated the important processing parameters, namely, the melting rate, the type of solidifying material, and the heat extraction to the mold. The effects of these parameters were examined on the pool profile geometry, local solidification time (LST) and length of ingot to reach quasi-steady state. The results showed that it is not possible to define, for all industrial conditions, a unique ratio of ingot length to ingot radius when the metal pool reaches the quasi-steady state. It was also observed that the Stefan number (Ste), which defines the type of solidifying material, had a negligible effect on the pool depth and on the LST for Ste > 0.5. In the second analysis, the model was used to simulate the solidification in the ESR process of an ingot made of the ASTM 138 steel. The geometric profile of the metal pool and the heat flux at the metal-mold interface were measured, showing reasonable agreement with the model results. Finally, the results given in the present work allow the definition (from a microstructural standpoint) of the optimum melting rate and the time to reach quasi steady-state for a wide range of industrial materials, ingot diameters and heat transfer conditions.

A produção de fundidos com baixo nível de defeitos e com propriedades mecânicas adequadas é facilmente alcançada com a previsão do comportamento do metal durante a solidificação. A transferência de calor entre o metal-líquido e o molde, nos primeiros instantes de contato, compromete definitivamente as propriedades mecânicas e a qualidade do produto final. O comportamento da transferência de calor entre o metal e o molde foi explorado através da análise térmica experimental e confrontado com o Modelo de Schwarz Modificado (MSM). Para comprovar experimentalmente os fenômenos previstos no MSM tais como: superesfriamento aparente, posição das interfaces líquido-superaquecido/líquido- superesfriado e da sólido/líquido durante a solidificação foram realizados experimentos com alumínio puro, gálio puro e estanho. Para a análise térmica foram utilizados dois sistemas de solidificação vertical descendente (Griffiths et al., 1993; Jinho et al., 1996; Jamgotchian et al., 1987). O sistema A e o sistema B, sendo que o sistema B também permitia a solidificação vertical ascendente. Em ambos os casos, o fluxo de calor foi direcionado através de uma barra de alumínio (na temperatura ambiente) que foi inserida verticalmente no banho (técnica do “dedo frio”). A barra extrai calor do líquido em função da diferença de temperatura entre a massa líquida e a massa sólida e simula o choque térmico do metal líquido com as paredes de um molde. Os resultados experimentais e os obtidos pela simulação foram confrontados. Apresenta-se a relação experimental entre o superesfriamento e a taxa de solidificação. Discute-se o redimensionamento da Ti (temperatura de interface) na solução de Schwarz e a comprovação experimental da solução do MSM. / The production of casting with low level of defects and adjusted mechanical properties can be obtained with the previous knowledge of the metal solidification behavior. The transference of heat between the metal-liquid and the mold, in the first instants of the contact, compromises definitively the mechanical properties and the final product quality. The behavior of the transference of heat between the metal and the mold was carried out through the experimental thermal analysis and the results were compared with the Modified Schwarz Model (MSM). To experimentally prove, the cooled phenomena in the MSM such as: apparent supercooling, liquid superheated/liquid supercooled interfaces position and of the liquid/solid during the solidification experiments had been carried out with pure aluminum, pure gallium and tins. Two systems A and B, one of descending vertical solidification and another one of descending and ascending solidification, had been used for the thermal analysis. In both systems, the heat flow was directed through a bar of aluminum (in the ambient temperature) that was inserted vertically in the bath (“cold finger” technique). The bar extracts heat of the liquid, had the difference of temperature between the liquid mass and the solid mass, and simulates the thermal shock of the metal with the mold walls. The experimental results were compared with simulated data. In this work are presented experimental relation between the supercooling and the rate of solidification. The new dimension of the Ti (temperature of interface) in the Schwarz equation and the experimental evidence of MSM solution, are considered.

A presente pesquisa realizou um estudo que investiga a viabilidade técnica para a reciclagem do resíduo sólido gerado pelo descarte das areias de fundição aglomeradas com argila, para aplicação no setor da construção civil. Para isso, o trabalho estabelece uma metodologia, a qual avalia a estabilização do resíduo em matrizes solidificadas de cimento Portland, melhoradas através de adições de argila bentonita sódica e/ou sílica ativa. A estabilização do resíduo foi verificada através de ensaio de solubilização, o qual submete as matrizes solidificadas a contatos dinâmico e estático com água destilada. Os desempenhos mecânico e físico das matrizes foram avaliados em ensaios de resistência à compressão, absorção de água e permeabilidade ao ar. Os resultados obtidos demonstram que, tanto a bentonita sódica, quanto a sílica ativa contribuem para o aumento da eficiência de fixação dos metais \'AL\', \'FE\' e \'CR\' por parte das matrizes de cimento Portland. As composições que obtiveram os melhores desempenhos mecânico, físico e químico foram utilizadas na confecção de tijolos maciços, visando aplicação na execução de alvenarias. Para a moldagem dos tijolos foi empregada uma prensa hidráulica, o que possibilitou manter a regularidade dimensional das faces. Ao mesmo tempo, o formato dos tijolos foi concebido com design diferenciado, proporcionando modulação e encaixes que podem reduzir significativamente o consumo da argamassa de assentamento. Os tijolos foram submetidos aos ensaios de solubilização, resistência à compressão e absorção de água, apresentando resultados satisfatórios e comprovando a viabilidade técnica para aplicação na execução de alvenarias. / In this research, a study that investigates the technical feasibility for the recycling of solid waste generated by the disposal of the foundry sands bonded with clay, for implementation in the construction industry, was conducted. For this reason, the work establishes a method, which assesses the stabilization of waste in solidified matrices of Portland cement, improved by the additions of sodium bentonite clay and/or silica fume. The stabilization of the waste was verified by solubilization test, which puts the solidified matrices in static and dynamic contacts with distiled water. The mechanical and physical performances of the matrices were evaluated in tests of resistance to compression, absorption of water and air permeability. The results show that both the sodium bentonite, and the active silica contribute to increase the fixation efficiency of the metals \'AL\', \'FE\' and \'CR\' by the matrices of Portland cement. The compositions that have the best mechanical, physical and chemical performance were used in the manufacture of massive bricks, seeking their use in the implementation of masonry. For the molding of bricks a hydraulic press was used, which allowed to keep the dimensional regularity of the faces. At the same time, the format of the bricks was designed with different shapes, providing modulation and fitting that can significantly reduce the consumption of settlement mortar. The bricks were subjected to tests of solubilization, resistance to compression and absorption of water, showing satisfactory results that confirm the technical feasibility for being used in the implementation of masonry.

Among all casting defects, shrinkage porosities could significantly reduce the strength of metal parts. As several critical components in aerospace and automotive industries are manufactured through casting processes, ensuring these parts are free of defects and are structurally sound is an important issue. This study investigates the formation of shrinkage-related defects in alloy solidification. To have a better understanding about the defect formation mechanisms, three sets of experimental studies were performed. In the first experiment, a real-time video radiography technique is used for the observation of pore nucleation and growth in a wedge-shaped A356 aluminum casting. An image-processing technique is developed to quantify the amount of through-thickness porosity observed in the real-time radiographic video. Experimental results reveal that the formation of shrinkage porosity in castings has two stages: 1-surface sink formation and 2- internal porosity evolution. The transition from surface sink to internal porosity is defined by a critical coherency limit of . In the second and third experimental sets, two Manganese-Steel (Mn-Steel) castings with different geometries are selected. Several thermocouples are placed at different locations in the sand molds and castings to capture the cooling of different parts during solidification. At the end of solidification, castings are sectioned to observe the porosity distributions on the cut surfaces. To develop alloys’ thermo-physical properties, MAGMAsoft (a casting simulation software package) is used for the thermal simulations. To assure that the thermal simulations are accurate, the properties are adjusted to get a good agreement between simulated and measured temperatures by thermocouples. Based on the knowledge obtained from the experimental observations, a mathematical model is developed for the prediction of shrinkage porosity in castings. The model, called “advanced feeding model”, includes 3D multi-phase continuity, momentum and pore growth rate equations which inputs the material properties and transient temperature fields, and outputs the feeding velocity, liquid pressure and porosity distributions in castings. To solve the model equations, a computational code with a finite-volume approach is developed for the flow calculations. To validate the model, predicted results are compared with the experimental data. The comparison results show that the advanced feeding model can accurately predict the occurrence of shrinkage porosity defects in metal castings. Finally, the model is optimized by performing several parametric studies on the model variables.

Measurements are carried out for dendrite tip growth of succinonitrile-acetone alloys solidifying freely in an undercooled melt. The current experimental investigation is conducted using the equiaxed dendritic solidification experiment (EDSE). This setup allows for precise measurements of the dendrite tip velocity, radius and shape for a range of undercoolings and solute concentrations. The collected data are compared to available theories of free dendritic growth, such as the Lipton-Glicksman-Kurz and Li-Beckermann models. It is found that for dilute succinonitrile-acetone alloys, the measured dendrite tip Péclet numbers agree well with previous theories of free dendritic growth, if the effects of melt convection are taken into account. The tip selection parameter deviates significantly from the pure succinonitrile value and is inversely related to the applied undercooling. Besides, the selection parameter shows no dependence on the solute concentration. These results are consistent with phase-field simulations and preceding experimental investigations. In addition, scaling relationships for the sidebranching shape were obtained in terms of the dendritic envelope, projection area and contour length. These new scaling relations agree well with previous measurements in pure succinonitrile dendrites by Li and Beckermann.

Low Pressure Die Casting (LPDC) process is one the most common casting process to produce structural automotive components, such as alloy wheels and suspension components. It has been identified that cavity filling and solidification process are two most critical aspects to produce premium quality casting components.During the solidification process of casting alloy, it is a well known phenomenon that metal experiences volumetric shrinkage due to its density difference between liquid and solid phase. When this volumetric shrinkage is not properly compensated, then a casting defect commonly known as solidification shrinkage occurs. The solidification shrinkage has very detrimental effects on structural integrity required for premium quality casting such as aluminium alloy wheels.Literature and practical experiences of foundry men show that it is critical to achieve unidirectional solidification pattern by avoiding an isolated hot spot in order to minimise the solidification shrinkage. However, it is found that the geometry of industrial casting applications is often constrained by other design factors that would not naturally avoid these isolated hot spots. The subject of this research, aluminium alloy wheels, is not excluded from this constraint.In aluminium alloy wheels, an isolated hot spot is commonly observed in an area known as rim and spoke junction due to its geometry constraints. Consequently, the solidification shrinkage is commonly experienced, which is undesirable due to its detrimental effects for the structural integrity of alloy wheels. In order to minimise the solidification shrinkage, forced cooling method is applied to avoid an isolated hot spot. The control of this forced cooling is achieved by cooling media, flow rate of cooling media and duration cooling circuit. Foundry experiments in industrial environment were conducted producing aluminium alloy wheels using commercially treated A356 (Al-Si) alloy, where different durations of cooling circuit were used to understand the sensitivity of solidification shrinkage formation to the duration of cooling circuit. This was followed by metallurgical structure analysis and numerical modelling to suggest the sensitivity of cooling circuit duration in controlling solidification shrinkage.The major finding conclusion of this research is that control of the shrinkage formation is not very sensitive to the duration cooling circuit. It is suggested that as casting solidifies initially from the mould wall, it retracts away from the cast-mould interface due to thermal contraction. Consequently, air gap is formed between casting and mould interface, creating an effective thermal resistance layer. Thereafter, heat transfer across the cast-mould interface is not sensitive to the change in the cooling channel which is a distance to the cast-mould interface.Some limitations of numerical modelling and metallurgical analysis were also identified during this research and recommendations were made to improve the accuracy of local hot spot prediction in production of aluminium alloy wheels. More specifically, numerical modelling of the effect of grain refinement and use of non homogeneous material property (particularly fraction of solid) for rapidly chilled area. Fraction of eutectic rather than secondary dendrites arm spacing is a proper microstructure parameter that can be used to locate the hot spot.

β-grain size is an influential microstructural parameter on the properties of titanium components. A reduction of β-grain size is generally associated with improvements to ductility, strength, corrosion and fatigue resistance of many α, α/β and β titanium alloys. During production of wrought titanium components, the β-grain size is carefully controlled during thermomechanical processing but there is currently no control of the β-grain size during solidification of cast components. As such, this inability to control the β-grain structure during solidification may limit the applications for solidification based technologies including casting, welding and direct metal deposition. Due to the limited knowledge of grain refinement practices and the lack of commercial grain refiners for the titanium system, this thesis investigates the mechanisms of β-grain refinement during solidification of cast titanium alloys. In this thesis, generalized theories for grain refinement that have been developed from research into other metallic systems are applied to the titanium system. Similar to the findings from aluminium and magnesium research, it is shown that grain refinement of cast titanium alloys requires the addition of growth restricting solutes which provide constitutional undercooling as well as the presence of potent nucleant particles. It is demonstrated that commercially pure titanium contains a natural distribution of nuclei particles which may originate from the mould wall and when powerful growth restricting solutes are introduced, significant prior-β grain refinement is achievable. All solutes investigated do not interact or poison the naturally occurring nucleants enabling the grain size of the titanium alloys to be predicted by an empirically determined relationship based on the growth restriction factor. A full list of growth restriction factors for various elements in titanium is determined and it is proven that growth restriction theory is valid in the titanium system. A further reduction in β-grain size is achievable by introducing additional nucleant particles to titanium castings in conjunction with growth-restricting solutes. Using a novel technique, titanium powder was introduced to the melt stream prior to solidification and was mixed throughout the liquid. The powder particles partially melted and the oxide surface layer dissolved allowing intimate substrate-liquid contact, enabling the titanium substrates to act as sites for heterogeneous nucleation. Using this technique, it was possible to grain refine commercially pure titanium without foreign elemental addition and when growth restricting solutes were present it was possible to obtain approximately an order of magnitude grain size reduction. The results and concepts developed from this work may aid the future development of a commercial grain refiner for titanium. If a grain refiner is developed, its application will not just be limited to the titanium casting industry but may also benefit other solidification based technologies such as welding, direct metal deposition and wrought billet production.