Estudo da sinterização de eletrólito sólido de céria dopada com gadolínia

Fuel cells are electrochemical devices that convert chemical energy in electrical energy by a reaction directly. The solid oxide fuel cell (SOFC) works in temperature between 900ºC up to 1000ºC, Nowadays the most material for ceramic electrolytes is yttria stabilized zirconium. However, the high operation temperature can produce problems as instability and incompatibility of materials, thermal degradation and high cost of the surround materials. These problems can be reduced with the development of intermediate temperature solid oxide fuel cell (IT-SOFC) that works at temperature range of 600ºC to 800ºC. Ceria doped gadolinium is one of the most promising materials for electrolytes IT-SOFC due high ionic conductivity and good compatibility with electrodes. The inhibition of grain growth has been investigated during the sintering to improve properties of electrolytes. Two-step sintering (TSS) is an interesting technical to inhibit this grain growth and consist at submit the sample at two stages of temperature. The first one stage aims to achieve the critical density in the initiating the sintering process, then the sample is submitted at the second stage where the temperature sufficient to continue the sintering without accelerate grain growth until to reach total densification. The goal of this work is to produce electrolytes of ceria doped gadolinium by two-step sintering. In this context were produced samples from micrometric and nanometric powders by two routes of two-step sintering. The samples were obtained with elevate relative density, higher than 90% using low energy that some works at the same area. The average grain size are at the range 0,37 μm up to 0,51 μm. The overall ionic conductivity is 1,8x10-2 S.cm and the activation energy is 0,76 eV. Results shown that is possible to obtain ceria-doped gadolinium samples by two-step sintering technique using modified routes with characteristics and properties necessary to apply as electrolytes of solid oxide fuel cell

Síntese e caracterização de CuNb2O6 e CuNbC através de reação sólido- sólido e gás- sólido a baixa temperatura

The refractory metal carbides have proven important in the development of engineering materials due to their properties such as high hardness, high melting point, high thermal conductivity and high chemical stability. The niobium carbide presents these characteristics. The compounds of niobium impregnated with copper also have excellent dielectric and magnetic properties, and furthermore, the Cu doping increases the catalytic activity in the oxidation processes of hydrogen. This study aimed to the synthesis of nanostructured materials CuNbC and niobium and copper oxide from precursor tris(oxalate) oxiniobate ammonium hydrate through gas-solid and solid-solid reaction, respectively. Both reactions were carried out at low temperature (1000°C) and short reaction time (2 hours). The niobium carbide was produced with 5 % and 11% of copper, and the niobium oxide with 5% of copper. The materials were characterized by X-Ray Diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF), infrared spectroscopy (IR), thermogravimetric (TG) and differential thermal analysis (DTA , BET and particle size Laser. From the XRD analysis and Rietveld refinement of CuNbC with S = 1.23, we observed the formation of niobium carbide and metallic copper with cubic structure. For the synthesis of mixed oxide made of niobium and copper, the formation of two distinct phases was observed: CuNb2O6 and Nb2O5, although the latter was present in small amounts

Efeito da adição de grafite expandido por microondas nas propriedades térmicas, elétricas e mecânicas de nanocompósitos de matriz epóxi

Epoxy based nanocomposites with 1 wt % and 3 wt % of nanographite were processed by high shear mixing. The nanographite was obtained by chemical (acid intercalation), thermal (microwave expansion) and mechanical (ultrasonic exfoliation) treatments. The mechanical, electrical and thermal behavior of the nanocomposites was determined and evaluated as a function of the percentage of reinforcement. According to the experimental results, the electrical conductivity of epoxy was not altered by the addition of nanographite in the contents evaluated. However, based on the mechanical tests, nanocomposites with addition of 1 wt.% and 3 wt.% of nanographite showed increase in tensile strength of 16,62 % and 3,20 %, respectively, compared to the neat polymer. The smaller increase in mechanical strength of the nanocomposite with 3 wt.% of nanographite was related to the formation of agglomerates. The addition of 1 wt.% and 3 wt.% of nanographite also resulted in a decrease of 6,25 % and 17,60 %, respectively, in the relative density of the material. Thus, the specific strength of the nanocomposites was approximately 33,33 % greater when compared to the neat polymer. The addition of 1 wt.% and 3 wt.% of nanographite in the material increased the mean values of thermal conductivity in 28,33 % and 132,62 %, respectively, combined with a reduction of 26,11 % and 49,80 % in volumetric thermal capacity, respectively. In summary, it has been determined that an addition of nanographite of the order of 1 wt.% and 3 wt.% produced notable elevations in specific strength and thermal conductivity of epoxy

Efeito da Gália como aditivo de sinterização em eletrólitos cerâmicos à base de céria sintetizados pelo método de complexação de cátions

Fuel cells are considered one of the most promising ways of converting electrical energy due to its high yield and by using hydrogen (as fuel) which is considered one of the most important source of clean energy for the future. Rare earths doped ceria has been widely investigated as an alternative material for the electrolyte of solid oxide fuel cells (SOFCs) due to its high ionic conductivity at low operating temperatures compared with the traditional electrolytes based on stabilized zirconia. This work investigates the effect of gallium oxide (Gallia) as a sintering aid in Eu doped ceria ceramic electrolytes since this effect has already been investigated for Gd, Sm and Y doped ceria electrolytes. The desired goal with the use of a sintering aid is to reduce the sintering temperature aiming to produce dense ceramics. In this study we investigated the effects on densification, microstructure and ionic conduction caused by different molar fraction of the dopants europium (10, 15 and 20%) and gallium oxide (0.3, 0.6 and 0.9%) in samples sintered at 1300, 1350 and 1450 0 C. Samaria (10 and 20%) doped ceria samples sintered between 1350 and 1450 °C were used as reference. Samples were synthesized using the cation complexation method. The ceramics powders were characterized by XRF, XRD and SEM, while the sintered samples were investigated by its relative density, SEM and impedance spectroscopy. It was showed that gallia contents up to 0.6% act as excellent sintering aids in Eu doped ceria. Above this aid content, gallia addition does not promote significant increase in density of the ceramics. In Ga free samples the larger densification were accomplished with Eu 15% molar, effect expressed in the microstructure with higher grain growth although reduced and surrounded by many open pores. Relative densities greater than 95 % were obtained by sintering between 1300 and 1350 °C against the usual range 1500 - 1600 0 C. Samples containing 10% of Sm and 0.9% of Ga reached 96% of theoretical density by sintering at 1350 0 C for 3h, a gain compared to 97% achieved with 20% of Sm and 1% of Ga co-doped cerias sintered at 1450 0 C for 24 h as described in the literature. It is found that the addition of gallia in the Eu doped ceria has a positive effect on the grain conductivity and a negative one in the grain boundary conductivity resulting in a small decrease in the total conductivity which will not compromise its application as sintering aids in ceria based electrolytes. Typical total conductivity values at 600 and 700 °C, around 10 and 30 mS.cm -1 respectively were reached in this study. Samples with 15% of Eu and 0.9 % of Ga sintered at 1300 and 1350 °C showed relative densities greater than 96% and total conductivity (measured at 700 °C) between 20 and 33 mS.cm -1 . The simultaneous sintering of the electrolyte with the anode is one of the goals of research in materials for SOFCs. The results obtained in this study suggest that dense Eu and Ga co-doped ceria electrolytes with good ionic conductivity can be sintered simultaneously with the anode at temperatures below 1350 °C, the usual temperature for firing porous anode materials

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Determinação do perfil térmico em amostras de aço AISI M35 imersas em plasma

The heat transfer between plasma and a solid occurs mostly due the radiation and the collision of the particles on the material surface, heating the material from the surface to the bulk. The thermal gradient inside the sample depends of the rate of particles collisions and thermal conductivity of the solid. In order to study that effect, samples of AISI M35 steel, with 9,5 mm X 3,0 mm (diameter X thickness) were quenched in resistive furnace and tempereds in plasma using the plane configuration and hollow cathode, working with pressures of 4 and 10 mbar respectively. Analyzing the samples microstructure and measuring the hardness along the transversal profile, it was possible to associate the tempered temperature evaluating indirectly the thermal profile. This relation was obtained by microstructural analyzes and through the hardness curve x tempered sample temperature in resistive furnace, using temperatures of 500, 550, 600, 650 and 700°C. The microstructural characterization of the samples was obtained by the scanning electron microscopy, optic microscopy and X-ray diffraction. It was verified that all samples treated in plasma presented a superficial layer, denominated affected shelling zone, wich was not present in the samples treated in resistive furnace. Moreover, the samples that presented larger thermal gradient were treated in hollow cathode with pressure of 4 mbar

Estudo paramétrico da injeção de vapor em reservatórios delgados

Exploration of heavy oil reservoirs is increasing every year in worldwide, because the discovery of light oil reservoirs is becoming increasingly rare. This fact has stimulated the research with the purpose of becoming viable, technically and economically, the exploration of such oil reserves. In Brazil, in special in the Northeast region, there is a large amount of heavy oil reservoir, where the recovery by the so called secondary methods Water injection or gas injection is inefficient or even impracticable in some reservoirs with high viscosity oils (heavy oils). In this scenario, steam injection appears as an interesting alternative for recover of these kinds of oil reservoirs. Its main mechanism consists of oil viscosity reduction through steam injection, increasing reservoir temperature. This work presents a parametric simulation study of some operational and reservoir variables that had influence on oil recovery in thin reservoirs typically found in Brazilian Northeast Basins, that use the steam injection as improved oil recovery method. To carry out simulations, it was used the commercial software STARS (Steam, Thermal, and Advanced Processes Reservoir Simulator) from CMG (Computer Modeling Group) version 2007.11. Reservoirs variables studied were horizontal permeability, vertical and horizontal permeability ratio, water zone and pay zone thickness ratio, pay zone thickness and thermal conductivity of the rock. Whereas, operational parameters studied were distance between wells and steam injection rate. Results showed that reservoir variables that had more influence on oil recovery were horizontal permeability and water zone and pay zone thickness ratio. In relation to operational variables, results showed that short distances between wells and low steam injection rates improved oil recovery

Estudo da perda de carga e calor no poço injetor no processo De drenagem gravitacional assistida por vapor (SAGD)

The oil companies in the area in general are looking for new technologies that can increase the recovery factor of oil contained in reservoirs. These investments are mainly aimed at reducing the costs of projects which are high. Steam injection is one of these special methods of recovery in which steam is injected into the reservoir in order to reduce the viscosity of the oil and make it more mobile. The process assisted gravity drainage steam (SAGD) using steam injection in its mechanism, as well as two parallel horizontal wells. In this process steam is injected through the horizontal injection well, then a vapor chamber is formed by heating the oil in the reservoir and, by the action of gravitational forces, this oil is drained down to where the production well. This study aims to analyze the influence of pressure drop and heat along the injection well in the SAGD process. Numerical simulations were performed using the thermal simulator STARS of CMG (Computer Modeling Group). The parameters studied were the thermal conductivity of the formation, the flow of steam injection, the inner diameter of the column, the steam quality and temperature. A factorial design was used to verify the influence of the parameters studied in the recovery factor. We also analyzed different injection flow rates for the model with pressure drop and no pressure drop, as well as different maximum flow rates of oil production. Finally, we performed an economic analysis of the two models in order to check the profitability of the projects studied. The results showed that the pressure drop in injection well have a significant influence on the SAGD process.

Análise da recuperação em reservatório de gás com baixa permeabilidade (TIGHT GAS) através do fraturamento hidráulico

With the increasing of energetic consumption in the worldwile, conventional reservoirs, known by their easy exploration and exploitation, are not being enough to satisfy this demand, what has made necessary exploring unconventional reservoirs. This kind of exploration demands developing more advanced technologies to make possible to exploit those hydrocarbons. Tight gas is an example of this kind of unconventional reservoir. It refers to sandstone fields with low porosity, around 8%, and permeabilities between 0.1 and 0.0001 mD, which accumulates considerable amounts of natural gas. That natural gas can only be extracted by applying hydraulic fracturing, aiming at stimulating the reservoir, by creating a preferential way through the reservoir to the well, changing and making easier the flow of fluids, thus increasing the productivity of those reservoirs. Therefore, the objective of this thesis is analyzing the recovery factor of a reservoir by applying hydraulic fracturing. All the studies were performed through simulations using the IMEX software, by CMG (Computer Modelling Group), in it 2012.10 version

Ecologia do fitoplâncton em áreas de cultivo de Tilápia do Nilo, Oreochromis niloticus, em tanques-rede no açude Ministro João Alves, Parelhas, Rio Grande do Norte

The dams are limnic ecosystems of great importance for its multiple uses, among them, water supply for the public and to culture of artisanal fish are most relevant. The aim of the present study is to evaluate the physical-chemical characteristics and the phytoplankton community in two chosen sites (Point 1 littoral zone of point source; Point 2 pelagic zone of non-point source) of the Minister João Alves dam, which is also known as Boqueirão de Parelhas/RN. This represents the spatial distribution of the phytoplankton species in order to understand any possible alterations of the water quality and the phytoplankton composition in relation to the water quality originating from the impact of the tilapia, Oreochromis niloticus, culture. The study period also encompasses temporal variations exhibited in two seasons of an annual cycle, one during the dry season (Oct, Nov and Dec of 2008 and Jan of 2009), and the other rainy season (Mar, Apr, May and June of 2008) to extend the observation. The physicalchemical parameters, such as pH, temperature, electrical conductivity, concentration of dissolved oxygen were measured in situ and the values of the inorganic nutrients (nitrate, ammonium and orto-phosfato) and chlorophyll in the laboratory. The quali-quantitative analyses of the phytoplankton had been carried through sedimentation technique and the enumeration of the random of 400 cells, colonies and filaments counted using Sedgwick-Rafter counting chamber. The results of pH varied widely from the acidic to alkaline range with the minimum of 5.8 (± 0.8) and the maximum of 9.2 (± 0.7-0.8), at point 1 and 2. The dissolved oxygen content was higher in the rainy period than that in the dry period. The maximum electrical conductivity was of 1409 μScm-1 in point 1 and 431 minim of μScm-1, in point 2. There was a considerable alteration in the levels of inorganic nutrients such as nitrate-nitrogen, ammoniacal nitrogen and orthophosphate during the two cycles of study period. Phytoplankton assemblages presented a picture of alternate dominance among species Cyanobacteria, Bacillariophyceae and Chlorophyceae. The trophic state index diagnosed to the category of mesotrophic, which is based on the values of chlorophyll, total phosphorus and Secchi-disc measurements. The wind driven turbulence of the water column and the fresh inflow of water (flushing and dilution) during rainy season acted as constraint and did-not allow an exaggerated growth of the species of cyanobacteria. On the basis of the present we conclude that the culture of tilapias in cage-culture fails to produce pollution load that could compromise the quality of the water of the dam, probably be due to small dimension of the culture in relation to the size, volume of the water and the reservoir capacity support its own environment

Biologia alimentar e morfohistologia do tubo digestório do mussum, synbranchus marmoratus, bloch (osteichthyes: synbranchidae) no açude Marechal Dutra Gargalheiras , localizado no semi-árido brasileiro

Food habits and morpho-histology of the digestive tract of marbled swamp eel, Synbranchus marmoratus (Block, 1917) were investigated. The fish samples were captured during August, 2007 to July, 2008 in the Marechal Dutra reservoir, Acari, Rio Grande do Norte. The rain fall data was obtained from EMPARN. The fish captured, were measured, weighed, dissected, eviscerated and individual stomach weights were registered. The stomach contents analyses were carried out based on volumetric method, points, frequency of occurrence and applying the Index of Relative Importance. The degrees of repletion of the stomachs were determined besides the Index of Repletion relating to feeding activity variations and frequency of ingestion during the rainy and dry seasons. The rainfall varied from 0 mm a 335 mm with a mean value of 71.62 mm. Highest rainfall of 335.5 mm was registered in March, 2008 and August to December was the dry period. During the dry period the study species presented high degrees of repletion of the stomachs, with a peak value in the month of September (mean = 4.54; ± SD = 0.56). The minimum mean value of = 3.99 ± SD = 0.25 was registered in the month of May during the rainy period. The stomach contents of S. marmoratus registered show that this fish prefers animals, 78.22% of crustaceans 2.85% of mollusks, 3.25% of fish, 1.4% of insects and 13.5% of semi-digested organic matter, thus characterizing the study species as a carnivore with a preference for crustaceans. The morpho-histological aspects of the digestive tract of S. marmoratus indicate that the mouth is terminal adapted to open widely, thin lips with taste buds, small villiform teeth forming a single series on maxillas, four pairs of branchial arches with short and widely spaced branchial rays. The oesophagus is short and cylindrical with a small diameter. The oesophagus wall is thick with mucas surface and internal parallel folds. The stomach is retilinical in form, presenting cardiac, caecal and pyloric portions. The caecal portion is long and is intermediary in position between the cardiac and pyloric portions. The cardiac portion of the stomach is short and cylindrical formed of simple epithelial cylindrical mucus cells. The caecal portion is long with narrow walls, a big cavity and smaller folds which give rise to gastric glands. The phyloric portion has no glands and primary or secondary mucas folds. The morphohistological aspects of the digestive tract of S. marmoratus indicate its adaptation to a carnivorous feeding habit