[pt] As ligas metálicas têm sido amplamente estudadas, visando atender aplicações onde propriedades físicas e químicas diferenciadas se fazem necessárias. Nesse sentido, merecem destaque as ligas voltadas ao recobrimento de substratos metálicos, tendo-se como objetivo a proteção do substrato em ambientes corrosivos. Sendo assim, a presente pesquisa propõe abordar um método de síntese de ligas de Cu-Ni em substratos de cobre através da decomposição térmica do nitrato de níquel, e subsequentemente a redução do óxido NiO formado, mediante redução com H2 a 350 graus Celsius e tratamento térmico na mesma atmosfera a 800 graus Celsius, com tempos variados (3, 4 e 5h), para estimular a difusão do níquel produzido no interior da matriz de Cu. Os filmes serão caracterizados via microscopia eletrônica de varredura (MEV), tanto em sessões transversais, quanto panorâmico, além da difração de raios-x (DRX) com incidência rasante, visando-se identificar a liga Cu-Ni produzida. Os resultados sugerem que o processo proposto foi bem-sucedido, permitindo um amplo recobrimento do substrato e a subsequente difusão do Ni produzido, o que permitiu a identificação, em todas as amostras, da liga de interesse. As amostras selecionadas serão futuramente utilizadas para ensaios de microdureza, bem como de eletro-corrosão, sendo o comportamento medido comparando-se com o substrato puro. Espera-se que a presença do recobrimento eleve a resistência à abrasão, bem como dificultar a corrosão do cobre presente. / [en] Metal alloys has been extensively studied to light upon applications where differentiated physical and chemical properties are required. In this context, its value highlighting the alloys for the coating of metallic substrates with the objective of protecting the substrate in corrosive environments. The present work proposes to approach a method of synthesis of Cu-Ni alloys in copper substrates through the thermal decomposition of nickel nitrate and subsequently to discount the NiO oxide formed by reduction with H2 at 350 degrees Celsius and heat treatment in the same atmosphere at 800 degrees Celsius with (3, 4 and 5h) to stimulate the diffusion of the nickel produced inside the Cu matrix. The films were then characterized by scanning electron microscopy (SEM) in both cross-sectional and panoramic sessions, in addition to X-ray diffraction (XRD) with low incidence, aiming to identify Cu-Ni alloy produced. The results suggest that the proposed process was successful, allowing a wide coating of the substrate and subsequent diffusion of Ni produced, which allowed the identification in all samples of the alloy of interest. Selected samples will be used in the future for microhardness tests, as well as for electro-corrosion, and the measured behavior is compared to that observed for pure substrate. The presence of the coating is expected to raise the abrasion resistance as well as to hinder the corrosion of the copper present.

[pt] Os materiais nanoestruturados têm se destacado nas pesquisas científicas relacionadas aos novos materiais por propriedades particulares, muitas vezes não presentes no mesmo material com constituição não nanométrica. O presente trabalho apresenta uma rota alternativa para síntese de liga de cobalto e níquel nanoestruturada. Esta rota tem como ponto de partida a obtenção de óxidos dos metais a partir da dissociação de seus respectivos nitratos e, subseqüente redução dos óxidos por hidrogênio. Os óxidos foram obtidos separadamente e também associados (co-formados) a partir da dissociação da mistura de seus nitratos à 400oC por três horas. Difração de raio-x foi utilizada para confirmar a formação de Co3O4 e NiO. Análises em MET (Microscópio Eletrônico de Transmissão) mostraram que, tanto o Co quanto o Ni, apresentavam partículas de dimensões nanométricas, com cerca de 20nm no caso do NiO e na faixa de 20-50nm no caso do Co3O4. As partículas de óxidos co-formados observadas apresentaram dimensões na faixa de 10nm a 50nm. Redução por H2 foi utilizada para obtenção dos metais Ni e Co e da liga. Estudos termodinâmicos preliminares foram realizados para confirmar a viabilidade do processo. As variáveis de processo analisadas foram temperatura (faixa de 200oC-500oC) e pressão parcial de H2 (0,4- 1,0atm). A redução do NiO mostrou um comportamento autocatalítico com Ea = 28,7kJ/mol, enquanto as reduções de Co3O4 e NiO+Co3O4 co- formados sugeriram modelo topoquímico, com Ea = 33,7kJ/mol e 29,7kJ/mol, respectivamente. Para a redução dos óxidos NiO+Co3O4 co-formados (obtenção da liga), a reação mostrou ser de 1a. ordem. Análises estruturais da liga realizadas em MET revelaram tamanhos médios de 20nm. / [en] It has been clear the increasing importance of nanostructured materials in the present scientific and technological developments due to their unique properties. It is also well established that properties of materials can be severely altered by making them to reach a nanostructured condition. The present work presents an alternative route for obtain nanoestructured nickelcobalt alloy. The methodology is based on the dissociation of the metal nitrates in a very small oxides particles, even nanometric ones, and subsequent hydrogen reduction of the obtained oxides. Thermodynamic studies have been developed to support the feasibility of the reactions carried out to obtain nickel and cobalt oxides as well as the metals particles. Nickel and cobalt oxides were produced, either isolated or co-formed, by dehydrating a water dissolved homogeneous solution of Ni (NO3)2 or/and Co(NO3)2 at 400oC for about three hours. X-ray diffraction has been carried out to confirmed the Co3O4 and NiO formation. Transmission Electron Microscopy (TEM) studies have shown nanoscale structures with different morphology and size distribution. Hydrogen reduction was applied to obtain Ni, Co and Ni0.5- Co0.5 alloy. The temperature and hydrogen partial pressure range studied were, respectively, 200oC-500oC and 0,4-1,0atm. The NiO reduction showed an autocatalytic behavior with Ea = 28,7kJ/mol while the isolated Co3O4 and the co-formed oxides reductions followed topochemical reaction model, with Ea = 33,7kJ/mol and 29,7kJ/mol, respectively. The Ni-Co alloy synthesis reaction showed a first order behavior. The TEM studies have revealed a Ni-Co alloy constituted by nanoscale single crystals of about 20nm in size.

[pt] A redução de deslocamentos e acelerações em edifícios é um aspecto de vital importância no projeto de estruturas sob a ação de sismos. Assim, o controle de vibrações de estruturas em regiões sujeitas a eventos sísmicos tem se tornado um importante tema de pesquisa em engenharia. Dentre os mecanismos propostos para a redução de vibrações em estruturas, encontram-se os amortecedores magnetoreológicos (MR). Amortecedores magnetoreológicos são dispositivos passivos ou semiativos que controlam as vibrações com um consumo mínimo de energia. Estes mecanismos são caracterizados por um comportamento histerético não linear que leva em geral a uma grande dissipação de energia. Neste trabalho estuda-se o efeito de um amortecedor MR e de seus parâmetros característicos na redução das vibrações de edifícios e torres esbeltas. Para isto, utiliza-se o modelo de Bouc-Wen. O edifício é descrito como um sistema discreto massa-mola-amortecedor do tipo shear-building e a torre como um pêndulo múltiplo, onde se leva em conta a possibilidade de grandes rotações e deslocamentos. Considera-se o amortecedor localizado na estrutura (primeiro andar) e como um sistema de isolamento de base, com o propósito de verificar a influência da localização do amortecedor na redução das respostas dinâmicas. Quando o dispositivo é usado como isolamento de base, ambos os modelos mostraram uma grande diminuição da resposta dinâmica, em comparação aos resultados com o dispositivo no primeiro andar. Estuda-se também a influência da relação entre as frequências da estrutura e o conteúdo de frequências da excitação na eficiência do amortecedor MR. Os resultados mostram que esta relação tem uma grande influência no grau de redução das vibrações da estrutura controlada. Em todos os casos analisados, observa-se que o amortecedor MR leva a uma redução das vibrações, em particular dos deslocamentos da estrutura. / [en] The reduction of displacements and accelerations in buildings is a vital aspect in the design of structures under an earthquake excitation. Thus, the vibration control of structures in areas subject to seismic events has become an important research topic in engineering. Among the proposed mechanisms to reduce vibrations in structures, are the magneto rheological dampers (MR). Magneto rheological dampers are passive or semi-active devices for vibration control characterized by small energy consumption. These mechanisms are characterized by a nonlinear hysteretic behavior that usually leads to large energy dissipation. In this paper the effect of an MR damper and its characteristic parameters in reducing the vibrations of buildings and slender towers is studied. For this, the Bouc-Wen model is adopted. The building is described as a discrete mass-spring-damper-type shear-building and the tower as a multiple pendulum, which takes into account large displacements and rotations. It is considered that the damper is located in the structure (first floor) or as a base isolation system, in order to verify the influence of the location of the damper in the reduction of dynamic responses. When the device is used as a base isolation, both models show a large decrease of the dynamic response as compared to the results with the device on the first floor. The influence of the relationship between the frequencies of the structure and frequency content of the excitation on the efficiency of MR damper is also investigated. The results show that this relation has a great influence on the degree of reduction of vibrations of the controlled structure. In all cases here analyzed, it is observed that the MR damper leads to a reduction of the vibration response, in particular the displacement of the structure.

[pt] O uso de abordagens de programação estocástica e redução de cenários tem se tornado imprescindível na análise e predição de comportamento de sistemas dinâmicos. Entretanto, tais técnicas não levam em conta o conhecimento prévio sobre domínio que o usuário possui. O presente trabalho tem por objetivo o desenvolvimento de uma abordagem visual e interativa para abordar o problema de redução de cenários com dados temporais. Para tanto, nós propomos a implementação de uma série de visualizações de dados temporais integradas. Também propomos a adaptação de um algoritmo de projeção multidimensional para lidar com dados temporais. Desta forma, podemos representar graficamente a evolução de um conjunto de cenários ao longo do tempo. Outra visualização proposta no presente trabalho é uma adaptação de Bump chart para lidar com dados temporais acumulados; através dele, um usuário pode comparar a evolução das distâncias entre os diferentes cenários e um cenário de referência. Para validar a nossa proposta, fizemos uma implementação das técnicas propostas e conduzimos um estudo com usuários de diferentes áreas do conhecimento e níveis de experiência. Os resultados obtidos até então indicam que uma abordagem visual para o problema de redução de cenários é viável, e permite a seleção de um conjunto razoável de cenários. Além disso, constatamos que essa abordagem pode ser útil em um contexto de exploração de dados visando a redução de cenários. O usuário também pode explorar visualmente os resultados de outras técnicas de redução de cenários usando nossa abordagem. Os usuários entrevistados reportaram facilidade em cumprir as tarefas propostas e comentaram positivamente sobre os mecanismos de interação fornecidos pelo nosso protótipo. Também testamos os cenários escolhidos usando nossa proposta contra outras abordagens encontradas tanto na literatura quanto em uso na indústria. Os resultados obtidos foram bons, indicando que nossa proposta é viável em casos de uso reais. / [en] Stochastic programming and scenario reduction approaches have become invaluable in the analysis and behavior prediction of dynamic systems. However, such techniques often fail to take advantage of the user s own expertise about the problem domain. This work provides visual interactive support to assist users in solving the scenario reduction problem with timeseries data. We employ a series of time-based visualization techniques linked together to perform the task. By adapting a multidimensional projection algorithm to handle temporal data, we can graphically present the evolution of the ensemble. We also propose to use cumulative bump charts to visually compare the ranks of distances between the ensemble time series and a baseline series. To evaluate our approach, we developed a prototype application and conducted observation studies with volunteer users of varying backgrounds and levels of expertise. Our results indicate that a graphical approach to scenario reduction may result in a good subset of scenarios and provides a valuable tool for data exploration in this context. The users liked the interaction mechanisms provided and judged the task to be easy to perform with the tools we have developed. We tested the proposed approach against state-of-the-art techniques proposed in the literature and used in the industry and obtained good results, thus indicating that our approach is viable in a real-world scenario.

[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.