As origens dos elementos residuais (trace element) nas ligas à base de Ni provém basicamente de duas fontes: (1) minérios e (2) sucatas. O controle da concentração destes elementos residuais é muito importante, pois afetam as propriedades mecânicas dessas ligas. Alguns estudos mostram que os elementos Pb e Bi têm um sério impacto negativo nos resultados dos ensaios de fluência das ligas a base de Ni. A presença dessas impurezas causa o aumento da quantidade de cavidades nos contornos de grão que resultam em fracasso prematuro na vida útil desse material. Dessa forma, este trabalho tem como objetivo estudar a cinética da remoção de elementos residuais, tais como Pb e Bi da liga VAT32 através da aplicação de vácuo durante a elaboração da liga. Os resultados obtidos demonstraram que a taxa de remoção dos residuais Pb e Bi no refino a vácuo atingiram percentuais de 99,6% e 96,1% respectivamente. Fatores como volume do cadinho, elevação de temperatura, níveis de vácuo abaixo de 10-4 mbar, limpeza do sistema que compreende câmara e cadinho (residuais de corridas anteriores), contribuem significativamente para as taxas acima descritas. Por outro lado, quanto maior o volume de liga fundida, diminuição de temperatura, vácuo deficiente ou contaminação do sistema, a taxa de remoção de Pb e Bi são prejudicadas. / The origins of trace elements in Ni-based alloys come basically from two sources: (1) minerals and (2) scrap. Control of the concentration of trace elements is very important because they affect the mechanical properties of these alloys. Some studies show that the elements Pb and Bi have a serious negative impact on the results of creep tests of Ni based alloys. The presences of these impurities cause the increase of the number of cavities at grain boundaries that result in premature failure of this material. Thus, this work aims to study the kinetics of removal of trace elements such as Pb and Bi in alloy VAT32 by applying vacuum during the preparation of the alloy. The results showed that the rate of removal of residual Pb and Bi in the vacuum refining reached 99.6% and 96.1% respectively. Parameters such as the crucible volume, high temperature, vacuum levels below 10-4 mbar, cleaning of the system which comprises chamber and crucible (residual from previous races), contribute significantly to the rates described above. Moreover, the higher the volume of molten alloy, low temperature, vacuum system contamination and low vacuum pressure decrease, refining degree of Pb and Bi.

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The 40 kg melt was degassed by two methods: Immersion of a degassing tablet in a melt by an immersion bell and an argon degassing through a lance with a porous plug. Up-gassing tablets were also used during the experiment. The method of double weighing was used for evaluation. No technically significant degassing was achieved using degassing tablets. After degassing with tablets was observed a decrease in DI (Dichte Index) value with increasing residence time. Excessive dosing of the tablet does not ensure a higher degassing effect, it only ensures a higher turbulence of the reaction. Preheating the degassing tablets before use does not affect degassing. By preheating the up-gassing tablets, their reactivity is reduced. Two immersion bells with different proportions were tested. The bells do not ensure a homogeneous dispersion of bubbles in the melt. By argon degassing through the porous plug, the melt was degassed to a value DI = 1,87 %. The consumption of argon for degassing smaller amounts of melt is higher than for degassing larger amounts of melt. Argon refining is more efficient than using tablets.

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In the oxidative refining of metallurgical grade silicon the loss of Si to the slag in the form of SiO2 is an economical concern. The purpose of this report is to investigate the possibility of using SiO2 and mechanical stirring to remove Ca and Al as a substitute to the oxidative refining. In the experiments graphite crucibles were used in a vertical resistance furnace and controlled argon atmosphere. The removal rate of Ca and Al are measured by X-ray fluorescence and the slag is examined in a scanning electron microscope. The slag formation kinetics are examined and a calculation of the activities of Ca, Al and their respective oxides in the slag phase is conducted. The driving forces of creating CaO and Al2O3 in this system is calculated to better understand the behavior of the Ca and Al removal. The results show that removal of dissolved Ca and Al by mechanical stirring is possible and in this setup a stirring time of 20 minutes is sufficient since no more refining can be obtained by increasing it.

The growth and removal of inclusions in stirred ladles hasbeen studied. First, the importance of different growthmechanisms suggested in the literature were studied. Simulationresults from a fundamental model of an induction-stirred ladlehave been used as input in the calculations. Based on thegrowth calculations it was concluded that four of the growthmechanisms need not to be considered since they contribute solittle: i) diffusion of oxygen and aluminum to the inclusionsurface, ii) diffusion coalescence, iii) Brown motioncollision, and iv) laminar shear collision. The majorcontributor to inclusion growth is turbulent collision. Growthdue to Stoke's collisions is also somewhat important if largedifferences among inclusion sizes exist. Growth of inclusions in gas stirred ladles was studied usinga similar approach as the one for induction stirred ladles, butwith use of simulation results from a fundamental mathematicalmodel of a gas-stirred ladle. Similarly to what was found inthe case of induction stirring, it was found that turbulentcollisions and Stokes collisions appeared to be the majormechanisms for inclusion growth. The contribution of laminarshear collisions to growth was deemed negligible compared tothat of turbulent collisions. For the gas stirred ladle different removal mechanisms werealso studied, based on input data from a mathematical model ofa gas-stirred ladle. It was found that different modelssuggested to predict the inclusion removal due to bubbleflotation gave very different results. Also, all models assumeda spherical shape of the gas bubbles, which was found to beless realistic. Therefore, a new model for inclusion removal byspherical cap bubble flotation was developed. In the newcalculations, the most important mechanisms of inclusionremoval were found to be removal to the top slag and removal bybubble flotation, assuming spherical-cap bubbles and planecontact. When the bubbles were assumed to be spherical,resulting removal rates were lower than when they were assumedto be spherical caps. Based on these results it is concludedthat more research is needed to obtain a better understandingof the importance of bubble flotation on inclusion removal.Experiments are clearly needed to determine which modelconcepts produce predictions in best agreement withcorresponding data from actual steelmaking processes. / NR 20140805

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The purpose of this work aims to develop and explore a nonlinear multiperiod petroleum refinery model based on a real-world model. Due to the inherent complexity and interconnected nature of petroleum refineries, various studies are implemented to describe the multiperiod model. The model is based around maximizing the profit of a petroleum refinery, starting from the crude inputs through the crude distillation unit, to the intermediate product processing through various unit operations, and finally to the blending of the final products. The model begins as a single period model, and is re-formulated as a multiperiod model by incorporating intermediate product tanks and dividing the model into partitions. In solving the multiperiod model, the termination criteria for convergence was varied in order to investigate the effect on the solution; it was found that it is acceptable to terminate at a relaxed tolerance due to minimal differences in solution. Several case studies, defined as deviations from normal operation, are implemented in order to draw comparisons between the real-world model and the model studied in this thesis. The thesis model, solved by CONOPT and IPOPT, resulted in significant gains over the real-world model. Next, a Lagrangean decomposition scheme was implemented in an attempt to decrease computation times. The decomposition was unable to find feasible solutions for the subproblems, as the nonlinear and nonconvex nature of the problem posed difficulty in finding feasibilities. However, in the case of a failed decomposition, the point where the decomposition ends may be used as an initial guess to solve the full space problem, regardless of feasibility of the subproblems. It was found that running the decomposition fewer times provided better initial guesses due to lower constraint violations from the infeasibilities, and then combined with the shorter decomposition time resulted in faster computation times. / Thesis / Master of Applied Science (MASc) / Petroleum refineries consist of complex units that serve a certain purpose, such as separating components of a mixed stream or blending intermediate products, in order to create final commercial products, e.g. gasoline and diesel. Due to the complexity and interconnectivity in a refinery, it is difficult to determine the optimal mode of operation. Thus, by formulating the refinery in mathematical form, optimization techniques may be used to find optimal operation. Furthermore, optimization problems can be formulated in a multiperiod fashion, where the problem is repeated over a set time horizon in partitions. The advantage is a higher detail in the operation of the refinery but this comes at a cost of higher computation time. In this work, a multiperiod refinery is formulated and studied by exploring model size, computation times, comparison of solvers, and solution strategies such as decomposition.

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