[pt] A produção e o uso de DRI (Direct Reduction Iron) são cada vez maiores hoje em dia nos países desenvolvidos, essencialmente pela redução do preço do gás natural e do sucesso da tecnologia de extração de gás de xisto. Além disso, o menor teor de elementos contaminantes em DRI do que nas sucatas de aço, levou-o a ser considerado uma boa alternativa como carga metálica para o Forno Elétrico a Arco (FEA) e o processo no conversor LD /BOF. Os custos operacionais e os problemas ambientais, são atualmente dois fatores tecnológicos importantes a serem considerados na otimização da produção de DRI, afetando à produtividade, sustentabilidade e competitividade do processo industrial. O teor de carbono do DRI, por exemplo, tem se tornado cada vez mais importante, devido à sua capacidade de gerar energia química nas aciarias, complementando o uso de energia elétrica nos FEA e os inputs energéticos no LD. Este trabalho foi uma das partes do programa de cooperação entre a Companhia de Mineração Samarco e o Grupo de Siderurgia da Pontifícia Universidade Católica do Rio de Janeiro / PUC-Rio, que tratou especificamente do modelo cinético para a metalização e carburização simultâneas em fornos RD tipo cuba. No âmbito deste objetivo o reator foi dividido em três zonas: Redução, Transição e Resfriamento. Foram também consideradas mais três camadas concêntricas: periférica, media e central. Com base nos resultados obtidos em experiências que abrangeram diferentes tipos de pelotas, empregando misturas gasosas semelhantes às presentes nos processos industriais e obedecendo às suas correspondentes semelhanças fluidodinâmicas, foi desenvolvido um software, denominado METCARB, que incluiu na sua elaboração todas as equações e modelos cinéticos desenvolvidos experimentalmente nas três zonas do reator RD. A parte experimental foi, portanto, uma das partes principais do presente trabalho, conjuntamente com a concepção do modelo computacional e suas validações industriais. Com o METCARB, as previsões acerca da metalização e carburização simultâneas, em qualquer região interna do forno, se tornou possível, utilizando como entradas as dimensões do forno, medidas de temperaturas, composições dos gases, etc. Os resultados de metalização e carburização, também em formato gráfico, são gerados pelo sistema computacional, bem como as curvas cronométricas e tabelas de resultados. Estudos sobre dois casos reais foram realizados, a fim de validarem a ferramenta computacional desenvolvida. Constatou-se que a carburização do ferro metálico sempre ocorre simultaneamente com a redução dos óxidos de ferro e que, dependendo da temperatura e composição dos gases, pode ocorrer precipitação de finos de carbono. As simulações realizadas com o modelo METCARB mostraram que na periferia da ZR é gerado um DRI mais metalizado que na região do centro. Fenômeno contrário foi, entretanto, verificado com a carburização; Nas condições experimentais empregadas neste trabalho, os valores médios obtidos para a carburização e a metalização, no final da ZR, variam entre 0,4 - 0,7 por cento C, e 92 por cento - 97 por cento, respectivamente; Constatou-se não ocorrer progresso do grau de redução nas zonas de Transição (ZT) e de Arrefecimento (ZA), ou seja, mantiveram-se ao longo dessas zonas os valores de metalização obtidos no fundo da ZR; A influência do vapor de água no processo da carburização no caso estudado (0 - 4.25 por cento H2O) leva menor porcentagem de carburização (2,7 por cento C – 2,35). / [en] The production and the use of DRI (Direct Reduction Iron) are increasing today in developed countries, mainly by reducing the price of natural gas and the success of shale gas extraction technology. In addition, the lower level of contaminants in DRI than in metal scraps, led it to be considered a good alternative as metallic charge for the Electric Arc Furnace (EAF) and the process in LD / BOF converter. This work was one part of the cooperation program between Samarco Mining Company and Steel Group of the Pontifical Catholic University of Rio de Janeiro / PUC-Rio, which specifically dealt with the kinetic model for the metallization and carburization simultaneous in RD shaft furnaces. Under this purpose the reactor was divided into three zones: Reduction, Transition and Cooling. There were also three concentric regions considered: peripheral, media and center. Based on the results from experiments covering different types of pellets, using gas mixtures similar to those present in the industrial processes and obeying their corresponding fluid dynamic similarities, it developed a software called METCARB, which included in its preparation all kinetic equations and models developed experimentally in the three reactor zones of RD. The experimental part was therefore a major part of this work, together with the design of computational model and its industrial validations. With METCARB predictions about the simultaneous metallization and carburization in any internal region of the furnaces, it became possible, using as inputs the dimensions of the furnace, temperature measurements, compositions of gases, etc. The results of metallization and carburization also in graphic format are generated by the computer system, and the chronometric curves and results tables. Studies on two real cases were performed in order to validate the developed computational tool. It was found that the carburization always occurs simultaneously with the reduction of iron oxides and, depending on the temperature and composition of the gases; precipitation of fine carbon may occur. The simulations with METCARB model showed that the periphery of the ZR generated more DRI metallized than the center area. A contrary phenomenon has been verified with the carburization; With the experimental conditions used in this study, averages values obtained for the metallization and carburization in the final ZR vary between 0.4 - 0.7 percent C and 92 percent - 97 percent, respectively; It was not found that the progress of reduction degree occurred in the transition (ZT) and cooling (ZA) regions, in other words, it remained along these zones of the metallization values obtained at the bottom of ZR; The influence of water vapor in the carburization process in the case studies (0 - 4.25 percent H 2 O) takes a smaller percentage of carburization (2.7 percent C - 2.35).

[pt] Os materiais nanoestruturados têm sido estudados ao longo das últimas décadas, por apresentarem propriedades particulares, promissoras propriedades térmicas, mecânicas e catalíticas, que muitas vezes não estão presentes no material não manométrico. Alguns avanços recentes têm mostrado que estas propriedades podem ser reforçadas pela inclusão de materiais com propriedades diferentes na sua estrutura, formando assim nanocompósitos. Por exemplo, as ligas de CuNi são muito dúcteis, mas a presença de nanopartículas de Al2O3 depositadas na matriz pode melhorar consideravelmente a dureza do material. Tal nanocompósito pode ser obtido, por exemplo, através de decomposição térmica nitratos, seguido por redução seletiva com hidrogênio. Nesse contexto, o presente trabalho tem como foco a síntese de ligas de CuNi e CuNi com adição de nanoparticulas de Al2O3, baseados na redução seletiva de CuO e de NiO com H2, e óxidos coformados com o óxido de alumínio por meio da decomposição térmica de seus nitratos metálicos. Cálculos termodinâmicos mostraram que a redução de Cu e Ni pode ser realizada a temperaturas relativamente baixas (400 mais ou menos 5 Graus C), e também que o processo se desenvolve seletivamente (apenas os óxidos de Ni e de Cu reagem nas condições impostas), resultando em compósitos de CuNi/Al2O3, que consiste na formação de uma liga CuNi contendo 1 por cento de Al2O3 como finas nanopartículas distribuídas homogeneamente. Precursores e amostras reduzidas foram caracterizados por difração de raios x (DRX) para determinar a natureza das fases individuais presentes (óxidos e ligas), microscopia electrónica de varredura (MEV) como uma primeira aproximação da morfologia das partículas e microscopia eletrônica de transmissão (MET). Os resultados obtidos indicam que a via química proposta resultou satisfatória para a elaboração das ligas CuNi contendo nanopartículas de Al2O3 homogeneamente distribuídas. Os resultados obtidos também indicam que, para as condições experimentais impostas tanto a decomposição dos nitratos como as reações de redução alcançaram conversões de 100 por cento. / [en] Materials containing nanostructured particles have been studied over the last decades in order to take advantage of their promising thermal, mechanical and catalytic properties. Some recent progress has shown that these properties can be further enhanced by the inclusion of materials with different properties in their structure, thereby forming nanocomposites. For instance, Ni-Cu alloys are highly ductile, but the presence of Al2O3 nanoparticles deposited inside the alloy matrix can considerably improve the material s hardness. Such a nanocomposite can be obtained, for example, through nitrate solutions thermal decomposition followed by selective reduction with hydrogen. In this context, the present work focuses on the synthesis of CuNi alloys and CuNi/Al2O3 composites based on the selective reduction of copper and nickel oxides with pure H2, co-formed with aluminum oxide through thermal decomposition of aqueous solutions of their metal nitrates. Thermodynamic computations showed that the Cu and Ni reduction can be accomplished at relatively low temperatures (400 plus or minus 5 C degrees), and also that the process develops selectively (only the oxides of Ni and Cu react at the imposed conditions), resulting in Cu-Ni-Al2O3 composites, consisting in a Cu-Ni alloy crystals containing 1 percent of Al2O3 as fine homogeneously distributed nanoparticles. Both the original (co-formed) and reduced oxide samples were characterized using x ray diffraction (XRD) for determining the nature of the individual phases present (oxides and alloys) and scanning electron microscopy (SEM) as a first approach to the investigation of the morphology of the particles. The results indicate that the proposed chemical route resulted in composite materials containing CuNi alloy and Al2O3 particles of controllable composition and homogeneously distributed among the samples. The achieved results also suggest that for the imposed experimental conditions both the nitrate decomposition as well as the reduction reactions could be conducted to 100 percent conversion.

[pt] Este trabalho tem por objetivo investigar a redução do custo computacional associado ao cálculo das principais estatísticas das saídas dos modelos de propagação de incertezas. Para tal, apresentamos uma implementação alternativa ao método tradicional de Monte Carlo, chamado Caos Polinomial; que é adequado a problemas onde o número de variáveis de incerteza não é muito alto. No método Caos Polinomial, o valor esperado e a variância das saídas do simulador são diretamente estimados, como funções de distribuições de probabilidade de variáveis de incerteza na entrada do simulador. A principal vantagem do método de Caos Polinomial é que o número de pontos necessários para uma boa estimativa das estatísticas da saída de um simulador, comparado com Monte Carlo, é menor. Aplicações de Caos Polinomial em reservatórios de petróleo serão apresentadas para a propagação de até quatro variáveis, apesar do método poder ser aplicado a problemas de dimensões maiores. Nossos principais resultados são aplicados a dois modelos de reservatórios de petróleo sintéticos. / [en] In this work we investigate the reduction of the computational cost of the calculus of statistical moments of simulator s output in uncertainties propagation s models. For do that, we present an alternative s implementation to the traditional Monte Carlo s Method, called Polynomial Chaos; that is adequate to problems where the number of uncertain variables is not so high. In the Polynomial Chaos method, the expectation and the variance of the simulator s output are directly estimated, as functions of the probability distribuition of the uncertain variables in simulator input. The great advantage of Polynomial Chaos is that number of points necessary for a good estimation of the output statistics have smaller magnitude, compared to the Monte Carlo Method. Applications of Polynomial Chaos on oil reservoir simulations will be presented. As it is just a preliminar implementation, we just treat propagation s problems with at most four uncertainties variables, despite of the method being applicable to problems with more dimensions. Our main results are applied to two models of synthetic oil reservoirs.

[pt] Esta dissertação apresenta os resultados obtidos no processo de remediação de uma área contaminada por cromo hexavalente por meio da técnica de remediação química in situ (ISCR). A área de estudo localiza-se na cidade do Rio de Janeiro e foi ocupada por uma fábrica de vidros por cerca de quarenta anos e comprada para construção de condomínios residenciais. A área de estudo passou um processo de gerenciamento ambiental que contemplou diversos estudos ambientais para aquisição de dados e delimitar a contaminação, horizontal e verticalmente. O teste de bancada realizado com o reagente químico polissulfeto de cálcio demonstrou ser eficiente para reduzir as concentrações de cromo hexavalente em solo e água subterrânea. Com base nos dados adquiridos neste teste foi possível calcular a dose de injeção do polissulfeto de cálcio. Foram realizados setenta pontos de sondagem, pela técnica direct push, para injetar duzentos e cinquenta e dois mil e trinta litros de solução de polissulfeto de cálcio e água, sendo aproximadamente três mil e quinhentos litros por ponto de injeção. Os resultados após a injeção demonstraram que o polissulfeto de cálcio conseguiu remover o cromo hexavalente que estava adsorvido ao solo e reduziu a concentração de cromo hexavalente na água subterrânea entre quarenta e seis e sessenta e sete e noventa e nove e noventa e cinco por cento , após dezenove meses da injeção. Dessa forma, comprovou a eficiência deste reagente químico para remediação de áreas contaminadas por cromo hexavalente, assim como foi observado nos artigos técnicos de estudos de casos nos Estados Unidos e Europa. / [en] This dissertation presents the results obtained in the remediation process remediation of a contaminated area by hexavalent chromium applying the technology in situ chemical remediation (ISCR). The study area is located in the Rio de Janeiro city and was occupied by a glass factory for forty years and purchased for construction of residential condominiums. This dissertation presents the results obtained in the remediation process remediation of a contaminated area by hexavalent chromium applying the technology in situ chemical remediation (ISCR). The study area is located in the Rio de Janeiro city and was occupied by a glass factory for forty years and purchased for construction of residential condominiums. Chromium is an important metal for the industry and is used in various products and processes, such as electroplating, leather treatment, pulp, wood preservation, and refractory manufacturing. The trivalent chromium is essential from a nutritional point of view, non-toxic and poorly absorbed in the body, acting in the maintenance of some functions. Cr(III) is the most common being found and occurs naturally, since the element Cr(VI) can occur naturally, but in low concentrations, if the groundwater has geochemical conditions the Cr (III) can be oxidize to Cr (VI). The hexavalent chromium is the most dangerous valence state and, according to ATSDR (two thousand and twelve), have greater mobility in the groundwater, being carcinogenic by inhalation of high doses of soluble chromate salts. The mobility of hexavalent chromium is high in soil and groundwater because it is not adsorbed by the soil in that valence state, on the other hand when it is in trivalent form is strongly adsorbed by the soil, forming insoluble precipitates, having low mobility in soil and groundwater. The hexavalent chromium remediation by in situ chemical reduction using calcium polysulfide has been the subject of several field studies documented in the literature, both for soil and groundwater from the Chromite Ore Processing Residue (COPR) (Storch, et al., two thousand and two; Graham, et al., two thousand and six ; Charboneau, et al., two thousand and six ; Wazne, et al., two thousand seven a; Wazne, et al., two thousand seven b; Chrysochoou, et al., two thousand and ten ; Chrysochoou & Ting, two thousand and eleven ; Pakzadeh & Batista, two thousand and eleven ; Chrysochoou, et al., two thousand and twelve ). Calcium polysulfide is a fertilizer to soil and commercially available and has been used in some remediation studies cases for reducing hexavalent chromium in soil and groundwater. Being commercially available and used as fertilizer, it is a relatively cheap chemical reagent in comparison with other chemical compounds exclusively developed for this purpose. The stoichiometric demand and the chemical kinetics of the reduction of Cr (VI) by the calcium polysulfide in aqueous solution was studied by Graham et al. (two thousand and six) from the chromite ore processing residue (COPR). With this study it was reported that a molar ratio of a point sixty-six is required (close to the theoretical value of one point five) and a first-order kinetics with an initial concentration of twenty-six eight point mg/L and pH of the CPS solution around eleven point five, with the presence of oxygen. Thus, the hexavalent chromium is reduced to chromium hydroxide, slightly water soluble compound which is precipitated to the soil. The trivalent chromium has low solubility, toxicity, mobility, reactivity and is considered stable. There are various application techniques of chemical reagents in the underground environment, and choosing the most appropriate method for each area depends on the type of contaminant, geological environment, groundwater and surface interference, depth, thickness and size of the contaminated area. As described by Suthersan (mil novecentos ninety-six), the injection of chemical reagents has to achieve two objectives: (one) creating and maintaining an ideal redox environment and other parameters such as pH, presence or absence of dissolved oxygen, etc.; and (two) the delivery and distribution of the necessary reagents for a homogeneous way throughout the injection area, both horizontally and vertically. Thus, it is essential that the conceptual model of the study area is very detailed, so there is no doubt in the choice of chemical reagent application methodology. Although there are numerous laboratory studies on hexavalent chromium remediation using calcium polysulfide, there are few reports in the literature on the field application, especially case studies in Brazil, therefore, this case study becomes a demonstration applying calcium polysulfide as a remediation technique for hexavalent chrome, with geochemical data, which are important for monitoring chemical reduction. This case study shows the effectiveness, dosage and concentration of the study area, and may apply to other hexavalent chromium remediation projects. Materials and Methods A former glass factory (the Site ) operated in the North Zone of Rio de Janeiro / RJ, Brazil from the mid-thousand nine hundred and fifty s to two thousand and five. A portion of the facility was used to store raw material to produce glass, including arsenic oxide, and another portion of the Site was used to conduct industrial plating using hexavalent chromium (Cr(VI)) in the glass molds. In two thousand and nine, the Site was purchased for mixed use redevelopment, demanding an environmental assessment and subsequent remediation. Between two thousand and nine and two thousand and twelve several phases of site investigation was conducted. The results of the investigation indicated that Cr(VI) was present in soil at concentrations up to approximately twenty one mg/kg and in groundwater at concentrations up to approximately thirty mg/L. These concentrations exceeded regulatory criteria of three hundred mg/Kg for soil and zero point zero five mg/L for groundwater. A phased remedial approach was developed consisting of the following: (a) excavation and off-site disposal of two and four hundred ton of Cr(VI) impacted soil from the source area, performed in the unsaturated and saturated zone soils in the Cr(VI) source area; (b) post-excavation monitoring of the groundwater conditions; and (c) groundwater treatment following the excavation program. Hexavalent chromium concentrations in groundwater decreased significantly following the excavation, however, additional reduction of concentrations of Cr(VI) contaminant in groundwater was required. Then was designed and implemented a set of bench-scale treatability tests in order to evaluate groundwater remediation alternatives. Several proprietary and non-proprietary reductants for co-treatment of Cr(VI) were evaluated. Calcium polysulfide were selected to treat Cr(VI). To reduce residual Cr(VI) concentrations in the groundwater plume located downgradient of the former excavated source area, dois e seven hundred cubic meters were targeted for active treatment. The groundwater remediation approach consisted of the injection of thirty liters of CPS (twenty nine percent) diluted in two hundred and twenty liters of water, yielding a total of two hundred and fifty liters of solution injected using direct push technology into seventy two locations. Groundwater Monitoring As part of chemical reagent injection stage was performed the baseline monitoring with collection of soil and groundwater samples. The soil sampling was performed by direct push technique using PVC liner with two inches in diameter, to analyze the total and hexavalent chromium concentrations. Six months after the injection were installed sixteen monitoring wells, eight shallow wells (five meters) and eight deep wells (nine meters) spread upstream, side, middle and downstream of the injection area. Groundwater geochemical parameters (i.e., temperature, total solids dissolved, specific conductance, pH, oxidation-reduction potential, and temperature) were measured at the time groundwater samples were collected. Groundwater samples were collected and analyzed for total and dissolved chromium, hexavalent chromium, iron, arsenic, manganese, calcium, sulfate, and sulfide. Samples were field-filtered with disposable zero point forty-five μm polyethylene filter capsules prior to collecting samples for dissolved metals. Results and Discussion Dose calculations for the reduction of hexavalent chromium have been performed with the data obtained in the bench-scale treatability test and resulted in a stoichiometric demand of four mlCPS/kg soil to the treatment of the study area. Therefore thirty liters of solution was used containing twenty-nine percent calcium polysulfide and approximately two hundred and twenty two liters to perform their mixture, totaling two hundred and fifty-two thousand and thirty liters of solution. For solution injection were performed seventy two soil borings with eight point five meters deep, and the product was injected range between two point five and eightpoint five meters. The depth of injection was from two point five mbgl covered any change in water level due to seasonal variation. In each soil boring was injected chemical reagent solution comprised four hundred and seventeen liters of calcium polysulfide diluted in tree and eighty-three liters of water for a total volume of tree and a half liters of solution injected per point. The comparative analysis results of the third monitoring campaign ( eighteen months post-injection) with the baseline campaign (september/two thousand and twelve) indicated reduction of hexavalent chromium concentrations between forty-six point sixty-seven and ninety-nine and ninety-five percent. Regarding the second monitoring campaign (twelve months post-injection), the hexavalent chromium concentrations reduced between twenty-three point ninety-nine and ninety nine point seventy-nine percent in five of the fifteen monitoring wells that were sampled. In three of the fifteen monitoring wells the hexavalent chromium concentrations remained below the quantitation limit used by the analytical laboratory method. There was no increase in hexavalent chromium concentration, compared the results of the third and second monitoring campaign. The evaluation of the Eh and pH values measured in the monitoring campaigns showed that the pH value was in the acidic range (about four ) and after removal of contaminated soil with hexavalent chromium pH raised to between five and six, after the chemical reagent injection pH increased to the basic range (above seven point five). In the second and third campaign the pH reduced to acid range (below six point five), which can be regarded as the pH value of the area background. The Eh has inversely proportional behavior, increasing between the first and third campaign, and in the third campaign the measured values are in the ranges considered as moderately reducing (hundred to four hundred mV) and oxidizer (> four hundred mV). The pH variation also showed a relationship between increased concentrations of calcium, iron, manganese and sulfate (in some monitoring wells). There were also reductions in hexavalent chromium concentrations in monitoring wells. Conclusion This case study indicates that the use of different remediation techniques when applied together (excavation and chemical reduction), reducing the time required for remediation of a contaminated site without impacting the final cost of remediation. The chemical reduction of hexavalent chromium using calcium polysulfide was effective to reduce the concentration to less than the quantification limit of the analytical method used. Therefore, as presented it is necessary to carry out several studies to detail the hexavalent chromium concentration in the site, as well as understand the geochemistry of groundwater and performing bench-scale tests to evaluate the effectiveness of the chemical reagent in the site study hydrogeological environment and calculate the required dose. The treatability test with calcium polysulfide demonstrated the feasibility of using this chemical reagent by In Situ Chemical Reduction (ISCR) to reduce the hexavalent chrome concentration in soil and groundwater. The test resulted in a stoichiometric demand of four mlCPS /kg soil to the treatment of the study area. Soil samples collected six months after injection showed that the calcium polysulfide could desorb hexavalent chromium from the soil, since, contaminant concentrations were not detected in the samples. neteen months after the injection of the chemical reagent the groundwater concentrations of hexavalent chromium reduced from forty-six point sixty-seven to ninety-nine and ninety-five percent in relation to baseline campaign. And, of the fifteen monitoring wells in just three wells hexavalent chromium concentrations were detected. This demonstrates the effectiveness of using calcium polysulfide to remediate hexavalent chromium in soil and groundwater, confirming the studies by Storch et al. (two thousand and two), Graham et al (two thousand and six), Charboneau et al. ( two thousand and six), Wazne et al. (two thousand and seven a), Wazne et al. (two thousand and seven b), Chrysochoou et al. (two thousand and ten), Chrysochoou & Ting (two thousand and eleven), Pakzadeh & Batista (two thousand and eleven), Chrysochoou et al (2012) in several areas in United States and Europe.

[pt] O surgimento do fenômeno de estabilidade de tensão na operação dos sistemas elétricos motivou centenas de pesquisadores a desenvolverem métodos que permitam detectar a proximidade à instabilidade de tensão, com eficiência computacional, e tomar medidas acertadas para garantir a operação confiável e segura. Neste trabalho são analisados diferentes métodos que permitem transformar sistemas de grande porte em circuitos simples: o circuito equivalente entre geradores e cargas, baseado no cálculo de correntes de curto-circuito, na técnica de redução de rede pela eliminação de barras intermediárias e no equivalente de Thévenin. É analisada a utilização destes equivalentes na avaliação das condições de estabilidade de tensão com sistemas-testes de 3 e 4 barras. Através de diferentes testes verificou-se que o circuito equivalente entre geradores e cargas e a técnica de redução de rede não podem ser usados para o cálculo de índices de avaliação das condições de estabilidade de tensão, enquanto que, usando circuito equivalente de Thévenin encontrou-se um método que funciona corretamente para barra de carga terminal, barra não-terminal e barra de tensão controlada por gerador. / [en] The emergence of voltage stability phenomenon in the operation of power systems has motivated hundreds of researchers to develop methods to detect the proximity to voltage instability, with computational efficiency and to take all necessary and appropriate measures to ensure reliable and safe operation. In this work, different methods that allow transforming large systems into simple circuits were analyzed, such as the equivalent circuit between generators and loads, based on the calculation of short-circuit currents; the network reduction technique for eliminating intermediate buses; and the Thévenin equivalent. The application of these equivalents on voltage stability assessment of 3 and 4 bus testing systems were extensively tested. At the end, it was verified that that the equivalent circuit between the generator and load, and the network reduction technique, cannot be used for calculating the voltage stability conditions evaluation indexes. However, using Thévenin equivalent circuit, it was found a proper method, which works correctly for terminal buses, transit buses and voltage-controlled buses.

[pt] A formação de juntas metálicas / poliméricas estáveis é um enorme desafio nas ciências dos materiais. A adesão requer uma interface que é capaz de interagir especificamente com a fase metálica. As poliimidas apresentam grupos amino primários altamente reativos às superfícies metálicas. Os recobrimentos metal/polímero se utilizam principalmente como membranas de separação de gases (permeabilidade e permissividade) e como material de baixa constante dielétrica para dispositivos microeletrônicos. Este trabalho vem fornecer a síntese dos recobrimentos metal/polímero em poliimida e fita kapton, por redução com H2, com posterior compreensão dos mecanismos de quimio-absorção a base de catalisadores da base de paládio, prata, hipoclorito de sodio e da adição de solventes na poliimida PIR 003, que permite a adesão do cobre. Foram utilizados os precursores de cobre em CuSO(4).5H(2)O e do CuCl(2), sintetizados a partir do CuO, para uma posterior redução em atmosfera de H2 e obter cobre métalico no recobrimento, permitindo o desenvolvimento de novas abordagens para metalização de materiais baseados naredução por H2 em polímeros. A utilização de modelos matemáticos permitiu dar uma visualização aproximada do ajuste dos parâmetros na redução do cobre por H2. As medidas do ângulo de contato nas poliimidas funcionalizadas deram uma visualização da influenciada adesão com o cobre e as medidas das caracterizações foram realizadas a fim de mostrar consistência dos resultados dos diferentes tratamentos, entre as quais foram: FTIR, MEV-EDS, TGA, DRX. O presente estudo demostra que com o precursor de CuSO(4).5H(2)O e a funcionalização com o NaClO 50 ml/l na poliimida, apresentou o maior valor de tamanhode cristalito de 61.8 nm e também de maior espessura de recobrimento de 182 micrometros. Finalmente, os testes de adesão para a poliimida PIR 003-Cu com o precursor de CuSO4.5H2O, no recobrimento sem tratamento teve uma força de tração aproximada de 4MPa e no caso do tratamento Sn/Pd (0.1/0.2 g/l) uma média aproximada de 10 MPa. / [en] The formation of stable metallic / polymeric joints is a huge challenge in materialsscience. Adhesion requires an interface that is capable of specifically interacting with themetallic phase. Polyimides have primary amino groups that are highly reactive to metalsurfaces. The coatings of these metal/polymer are mainly used as gas separationmembranes (permeability and permittivity) and as a low dielectric constant material formicroelectronic devices. This work provides the synthesis of metal/polymer coatings inpolyimide and kapton tape, by reduction with H2, with further understanding of the chemoabsorption mechanisms based on catalysts based on palladium, silver, sodium hypochloriteand the addition ofsolvents in the polyimide PIR 003, which allows the adhesion of copper.Copper precursors in CuSO(4).5H2O and CuCl(2), synthesized from CuO, were used forfurther reduction in H2 atmosphere and to obtain metallic copper in the coating, allowingthe development of new approaches for metallization of materials based on H2 reductionin polymers. The use of mathematical models allowed an approximate visualization of theadjustment of the parameters in the reduction of copper by H2. The contact anglemeasurements in the functionalized polyimides gave a visualization of the influence ofadhesion with copper and the characterization measurements were carried out in order toshow consistency of the results of the different treatments, among which were: FTIR,MEV-EDS, TGA, DRX. The present study demonstrates that with the CuSO4.5H2Oprecursor and the functionalization with 50 ml/l sodium hypochlorite in the polyimide, itpresented the largest crystallite size value of 61.8 nm and also the largest coating thicknessof 182 micrometers. Finally, the adhesion tests for the polyimide PIR 003-Cu with the precursor ofCuSO4.5H2O, in the untreated coating had a tensile strength of approximately 4MPa andin the case of the Sn/Pd treatment (0.1/0.2 g/l) a approximate average of 10 MPa.

[pt] Em planejamento e operação de sistemas de energia elétrica, é necessário realizar diversas avaliações utilizando o algoritmo de fluxo de potência, para obter e monitorar o ponto de operação da rede em estudo. Em sua utilização determinística, devem ser especificados valores de geração e níveis de carga por barra, bem como considerar uma configuração especifica da rede elétrica. Existe, porém, uma restrição evidente em se trabalhar com algoritmo de fluxo de potência determinístico: não há qualquer percepção do impacto gerado por incertezas nas variáveis de entrada que o algoritmo utiliza. O algoritmo de fluxo de potência probabilístico (FPP) visa extrapolar as limitações impostas pelo uso da ferramenta convencional determinística, permitindo a consideração das incertezas de entrada. Obtém-se maior sensibilidade na avaliação dos resultados, visto que possíveis regiões de operação são mais claramente examinadas. Consequentemente, estima-se o risco do sistema funcionar fora de suas condições operativas nominais. Essa dissertação propõe uma metodologia baseada na simulação Monte Carlo (SMC) utilizando técnicas de amostragem por importância via o método de entropia cruzada. Índices de risco para eventos selecionados (e.g., sobrecargas em equipamentos de transmissão) são avaliados, mantendo-se a precisão e flexibilidade permitidas pela SMC convencional, porém em tempo computacional muito reduzido. Ao contrário das técnicas analíticas concebidas para solução do FPP, que visam primordialmente à elaboração de curvas de densidade de probabilidade para as variáveis de saída (fluxos, etc.) e sempre necessitam ter a precisão obtida comparada à SMC, o método proposto avalia somente as áreas das caudas dessas densidades, obtendo resultados com maior exatidão nas regiões de interesse do ponto de vista do risco operativo. O método proposto é aplicado nos sistemas IEEE 14 barras, IEEE RTS e IEEE 118 barras, sendo os resultados obtidos amplamente discutidos. Em todos os casos, há claros ganhos de desempenho computacional, mantendo-se a precisão, quando comparados à SMC convencional. As possíveis aplicações do método e suas derivações futuras também fazem parte da dissertação. / [en] In planning and operation of electric energy systems, it is necessary to perform several evaluations using the power flow algorithm to obtain and monitor the operating point of the network under study. Bearing in mind its deterministic use, generation values and load levels per bus must be specified, as well as a specific configuration of the power network. There is, however, an obvious constraint in running a deterministic power flow tool: there is no perception of the impact produced by uncertainties on the input variables used by the conventional algorithm. The probabilistic power flow (PLF) algorithm aims to solve the limitations imposed by the use of the deterministic conventional tool, allowing the consideration of input uncertainties. Superior sensitivity is obtained in the evaluation of results, as possible regions of operation are more clearly examined. Consequently, the risk of the system operating outside its nominal conditions is duly estimated. This dissertation proposes a methodology based on Monte Carlo simulation (MCS) using importance sampling techniques via the cross-entropy method. Risk indices for selected events (e.g., overloads on transmission equipment) are evaluated, keeping the same accuracy and flexibility tolerable by the conventional MCS, but in much less computational time. Unlike the FPP solution obtained by analytical techniques, which primarily aim at assessing probability density curves for the output variables (flows, etc.) and always need to have the accuracy compared to MCS, the proposed method evaluates only the tail areas of these densities, obtaining results with greater accuracy in the regions of interest from the operational risk point of view. The proposed method is applied to IEEE 14, IEEE RTS and IEEE 118 bus systems, and the results are widely discussed. In all cases, there are clear gains in computational performance, maintaining accuracy when compared to conventional SMC. The possible applications of the method and future developments are also part of the dissertation.

[pt] Esta dissertação tem como principal objetivo estudar aplicações da expansão ou decomposição de Karhunen-Loève em dinâmica de estruturas. Esta técnica consiste, basicamente, na obtenção de uma decomposição linear da resposta dinâmica de um sistema qualquer, representado por um campo vetorial estocástico, tendo a importante propriedade de ser ótima, no sentido que dado um certo número de modos, nenhuma outra decomposição linear pode melhor representar esta resposta. Esta capacidade de compressão de informação faz desta decomposição uma poderosa ferramenta para a construção de modelos reduzidos para sistemas mecânicos em geral. Em particular, este trabalho aborda problemas em dinâmica estrutural, onde sua aplicação ainda é bem recente. Inicialmente, são apresentadas as principais hipóteses necessárias à aplicação da expansão de Karhunen-Loève, bem como duas técnicas existentes para sua implementação, com domínios distintos de utilização.É dada especial atenção à relação entre os modos empíricos fornecidos pela expansão e os modos de vibração intrínsecos a sistemas vibratórios lineares, tanto discretos quanto contínuos, exemplificados por uma treliça bidimensional e uma placa retangular. Na mesma linha, são discutidas as vantagens e desvantagens de se usar esta expansão como ferramenta alternativa à análise modal clássica. Como aplicação a sistemas não-lineares, é apresentado o estudo de um sistema de vibroimpacto definido por uma viga em balanço cujo deslocamento transversal é limitado por dois batentes elásticos. Os modos empíricos obtidos através da expansão de Karhunen-Loève são, então, usados na formulação de um modelo de ordem reduzida, através do método de Galerkin, e o desempenho deste novo modelo investigado. / [en] This dissertation has the main objetive of studying applications of the Karhunen-Loève expansion or decomposition in structural dynamics. This technique consists basically in obtaining a linear decomposition of the dynamic response of a general system represented by a stochastic vector field. It has the important property of optimality, meaning that for a given number of modes, no other linear decomposition is able of better representing this response. This information compression capability characterizes this decomposition as powerful tool for the construction of reduced-order models of mechanical systems in general. Particularly, this work deals with structural dyamics problems where its application is still quite new. Initially, the main hypothesis necessary to the application of the Karhunen-Loève expansion are presented, as well as two existing techniques for its implementation that have different domains of use. Special attention is payed to the relation between empirical eigenmodes provided by the expansion and mode shapes intrinsic to linear vibrating systems, both discrete and continuous, exemplified by a bidimensional truss and a rectangular plate. Furthermore, the advantages and disadvantages of using this expansion as an alternative tool for classical modal analysis are discussed. As a nonlinear application, the study of a vibroimpact system consisting of a cantilever beam whose transversal displacement is constrained by two elastic barriers is presented. The empirical eigenmodes provided by the Karhunen-Loève expansion are then used to formulate a reduced-order model through Galerkin projection and the performance of this new model is investigated.

[pt] As companhias regionais de distribuição não são autossuficientes em energia elétrica para atender seus clientes, e requerem importar a potência necessária do sistema interligado. No Brasil, elas realizam anualmente o processo de contratação do montante de uso do sistema de transmissão (MUST) para o horizonte dos próximos quatro anos. Essa operação é um exemplo real de tarefa que envolve decisões sob incerteza com elevado impacto na produtividade das empresas distribuidoras e do setor elétrico em geral. O trabalho se torna ainda mais complexo diante da crescente variabilidade associada à geração de energia renovável e à mudança do perfil do consumidor. O MUST é uma variável aleatória, e ser capaz de compreender sua variabilidade é crucial para melhor tomada de decisão. O fluxo de potência probabilístico é uma técnica que mapeia as incertezas das injeções nodais e configuração de rede nos equipamentos de transmissão e, consequentemente, nas potências importadas em cada ponto de conexão com o sistema interligado. Nesta tese, o objetivo principal é desenvolver metodologias baseadas no fluxo de potência probabilístico via simulação Monte Carlo, em conjunto com a técnica da entropia cruzada, para estimar os riscos envolvidos na contratação ótima do MUST. As metodologias permitem a implementação de software comercial para lidar com o algoritmo de fluxo de potência, o que é relevante para sistemas reais de grande porte. Apresenta-se, portanto, uma ferramenta computacional prática que serve aos engenheiros das distribuidoras de energia elétrica. Resultados com sistemas acadêmicos e reais mostram que as propostas cumprem os objetivos traçados, com benefícios na redução dos custos totais no processo de otimização de contratos e dos tempos computacionais envolvidos nas estimativas de risco. / [en] Local power distribution companies are not self-sufficient in electricity to serve their customers, and require importing additional energy supply from the interconnected bulk power systems. In Brazil, they annually carry out the contracting process for the amount of transmission system usage (ATSU) for the next four years. This process is a real example of a task that involves decisions under uncertainty with a high impact on the productivity of the distributions companies and on the electricity sector in general. The task becomes even more complex in face of the increasing variability associated with the generation of renewable energy and the changing profile of the consumer. The ATSU is a random variable, and being able to understand its variability is crucial for better decision making. Probabilistic power flow is a technique that maps the uncertainties of nodal injections and network configuration in the transmission equipment and, consequently, in the imported power at each connection point with the bulk power system. In this thesis, the main objective is to develop methodologies based on probabilistic power flow via Monte Carlo simulation, together with cross entropy techniques, to assess the risks involved in the optimal contracting of the ATSU. The proposed approaches allow the inclusion of commercial software to deal with the power flow algorithm, which is relevant for large practical systems. Thus, a realistic computational tool that serves the engineers of electric distribution companies is presented. Results with academic and real systems show that the proposals fulfill the objectives set, with the benefits of reducing the total costs in the optimization process of contracts and computational times involved in the risk assessments.

[pt] Esta tese descreve a síntese de um óxido misto de Zn e Zr (ZnxZr1-xOy), mediante uma técnica ainda não reportada e a utilização deste material na síntese de acetona a partir de etanol. O objetivo foi desenhar um catalisador com propriedades óxido-redutoras e capacidade de se autorregenerar após cada ciclo. A zircônia monoclínica (m-ZrO2) é um óxido já usado em catálise devido às suas propriedades ácido-básicas, mas com fracas propriedades óxido-redutoras. Estas últimas poderiam ser promovidas mediante dopagem substitucional deste material. A inserção de pequeníssimas quantidades de Zn na rede da m-ZrO2, mostraram um incremento apreciável na sua redutibilidade. O material obtido foi caracterizado por diversas técnicas e testado na obtenção de acetona a partir de etanol. O resultado indicou que a dopagem permitiu a formação de vacâncias de oxigênio, as quais promoveram a mobilidade do oxigênio até a superfície e, com isso, aumentaram redutibilidade do material. A seletividade da reação de conversão de etanol teve como produto maioritário a acetona. Foi demostrado que a regeneração do catalisador se deve a espécies oxidantes provenientes da dissociação da água presente no médio reacional; esta dissociação ocorreu nas vacâncias superficiais. Assim, demonstrou-se que a técnica desenvolvida no presente estudo, além de simples, resultou efetiva na síntese do óxido misto de Zn e Zr, um catalisador de composição simples, capaz de conduzir os diferentes passos do mecanismo na síntese de acetona. Considera-se que esta é a primeira etapa na sua viabilização comercial. / [en] This thesis describes the synthesis process of a mixed oxide with Zn and Zr (ZnxZr1-xOy), through a not yet published technique, as well as the utilization of this material in the acetone synthesis from ethanol. The mean goal was to design a catalyst with enhanced oxy-reduction properties and capability for selfregeneration after each cycle. Monoclinic zirconia (m-ZrO2) is already used in catalysis due to its acidic-basic properties, although its oxy-reduction properties are negligible. The enhancement of the oxy-reduction properties can be reached by substitutional doping of this material with a lower oxidation state metal. The insertion of very small quantities of Zn in the m-ZrO2 lattice, showed a high increment of its reducibility. The mixed oxides obtained were characterized by several techniques and catalytically tested in the acetone synthesis from ethanol. The results showed that doping allows the formation of oxygen vacancies, which allow oxygen mobility and therefore, the enhancement of reducibility. The reaction selectivity had acetone as majority product. It was shown that water is also produced and that it is dissociated in the oxygen vacancies generating oxidant species. The catalysts regeneration occurs due to those oxidant species. Therefore, it was demonstrated that the technique developed in this study was easy and effective in the synthesis of the mixed oxide with Zn and Zr, a catalyst with simple composition able to conduct every step of the acetone synthesis. This is considered the first step in the commercial feasibility of this material.