Estudo sobre a redução aluminotérmica de Ta2O5 e TiO2 usando descarga de cátodo oco

In this study it was used two metallic oxides, Ta2O5 and TiO2, in order to obtain metallic powders of Ta and Ti through aluminothermic reduction ignited by plasma. Ta2O5 and TiO2 powders were mixed with Al in a planetary mill, using different milling times. A thermal analysis study (DTA and TG) was carried out, in order to know the temperature to react both the mixtures. Then, these mixtures were submitted to a hollow cathode discharge, where they were reacted using aluminothermic reduction ignited by plasma. The product obtained was characterized by XRD and SEM, where it was proven the possibility of producing these metallic particles, different from the conventional process, where metallic ingots are obtained. It was verified that the aluminothermic reduction ignited by plasma is able to produce metallic powders of Ta and Ti, and a higher efficiency was observed to the process with Ta2O5-Al mixtures. Among different microstructural aspects observed, it can be noted the presence of metallic nanoparticles trapped into an Al2O3 matrix, besides acicular structures (titanium) and dendritic structures (tantalum), which are a product characteristic from a fast cooling

Caracterização microestrutural e elétrica de La(FexNi1-x)O3 sintetizado pelo método da gelatina

The present work deals with the synthesis of materials with perovskite structure with the intention of using them as cathodes in fuel cells SOFC type. The perovskite type materials were obtained by chemical synthesis method, using gelatin as the substituent of citric acid and ethylene glycol, and polymerizing acting as chelating agent. The materials were characterized by X-ray diffraction, thermal analysis, spectroscopy Fourier transform infrared, scanning electron microscopy with EDS, surface area determination by the BET method and Term Reduction Program, TPR. The compounds were also characterized by electrical conductivity for the purpose of observing the possible application of this material as a cathode for fuel cells, solid oxide SOFC. The method using gelatin and polymerizing chelating agent for the preparation of materials with the perovskite structure allows the synthesis of crystalline materials and homogeneous. The results demonstrate that the route adopted to obtain materials were effective. The distorted perovskite structure have obtained the type orthorhombic and rhombohedral; important for fuel cell cathodes. The presentation material properties required of a candidate cathode materials for fuel cells. XRD analysis contacted by the distortion of the structures of the synthesized materials. The analyzes show that the electrical conductivity obtained materials have the potential to act as a cell to the cathode of solid oxide fuel, allowing to infer an order of values for the electrical conductivities of perovskites where LaFeO3 < LaNiO3 < LaNi0,5Fe0,5O3. It can be concluded that the activity of these perovskites is due to the presence of structural defects generated that depend on the method of synthesis and the subsequent heat treatment

Influência do método de síntese e caracterização de pós compósitos de NiO- Ce1-xEuxO2-δ para anodos catalíticos de células a combustível

Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 °C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800°C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases

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 de nanopartículas de magnetita via decomposição térmica em meio não-aquoso

This work aims at obtaining nanoparticles of iron oxide, the magnetite one (Fe3O4), via synthesis by thermal decomposition through polyol. Thus, two routes were evaluated: a simple decomposition route assisted by reflux and a hydrothermal route both without synthetic air atmosphere using a synthesis temperature of 260ºC. In this work observed the influence of the observe of surfactants which are generally applied in the synthesis of iron oxide nanoparticles decreasing cluster areas. Further, was observed pure magnetite phase without secondary phases generally found in the iron oxide synthesis, a better control of crystallite size, morphology, crystal structure and magnetic behavior. Finally, the introduction of hydroxyl groups on the nanoparticles surface was analyzed besides its employment in the polymer production with OH radicals. The obtained materials were characterized by XRD, DLS, VSM, TEM, TG and DSC analyses. The results for the magnetite obtainment with a particle size greater than 5 nm and smaller than 11 nm, well defined morphology and good magnetic properties with superparamagnetic behavior. The reflux synthesis was more efficient in the deposition of the hydroxyl groups on the nanoparticles surface

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 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

Obtenção de pós de tântalo metálico a partir da redução aluminotérmica com ignição a plasma

Metallic tantalum has a high commercial value due to intrinsic properties like excellent ductility, corrosion resistance, high melt and boiling points and good electrical and thermal conductivities. Nowadays, it is mostly used in the manufacture of capacitors, due to excellent dielectric properties of its oxides. In the nature, tantalum occurs in the form of oxide and it is extracted mainly from tantalite-columbite ores. The tantalum is usually produced by the reduction of its oxide, using reductants like carbon, silicon, calcium, magnesium and aluminum. Among these techniques, the aluminothermic reduction has been used as the industrial method to produce niobium, tantalum and their alloys, due to the easy removal of the Al and Al2O3 of the system, easing further refining. In conventional aluminothermic reduction an electrical resistance is used to trigger the reaction. This reaction self-propagates for all the volume of material. In this work, we have developed a novel technique of aluminothermic reduction that uses the hydrogen plasma to trigger the reaction. The results obtained by XRD, SEM and EDS show that is possible to obtain a compound rich in tantalum through this technique of aluminothermic reduction in the plasma reactor

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test

Estudo da viabilidade do processo de reciclagem do material descartado do sistema Zirkonzanh® de produção de próteses dentárias

At present, the material of choice for performing aesthetic dental prosthetic work is in the ceramic. Among them, the ceramic base of stabilized zirconia with 3% yttria (3Y - TZP) stand out for having excellent physical and mechanical properties. During the machining of blocks of zirconia in the laboratory to prepare the various types of prostheses, much of the material is given off in the form of powder, which is subsequently discarded. The waste of this material results in financial loss, reflecting higher final cost treatment for patients, as well as damage to the environment, thanks to the processes involved in the manufacture and disposal of the ceramic. This research, pioneered the recycling of zirconium oxide powder obtained during milling of dental crowns and bridges, we highlight the social and environmental aspects and aims to establish a protocol for the reuse of waste (powder of zirconia Zirkonzahn® system) discarded to obtain a new block of compacted zirconia to maintain the same mechanical and microstructural properties of commercial high-cost imported material. To compare with the commercial material, samples were uniaxially (20 MPa) and isostatically (100 MPa), and its mechanical and microstructural characterization was performed through tests of density, porosity, dilatometry, X-ray diffraction (XRD), hardness, fracture toughness, resistance to fracture electron microscopy (SEM) and analysis of grain size. The results observed in the samples were isostatically pressed similiares those obtained with samples from the commercial material demonstrating the viability of the process

Avaliação da corrosão em dutos por técnica gravimétrica e de resistência elétrica

With the increasing of demand for natural gas and the consequent growth of the pipeline networks, besides the importance of transport and transfer of oil products by pipeline, and when it comes to product quality and integrity of the pipeline there is an important role regarding to the monitoring internal corrosion of the pipe. This study aims to assess corrosion in three pipeline that operate with different products, using gravimetric techniques and electrical resistance. Chemical analysis of residues originated in the pipeline helps to identify the mechanism corrosive process. The internal monitoring of the corrosion in the pipelines was carried out between 2009 and 2010 using coupon weight loss and electrical resistance probe. Physico-chemical techniques of diffraction and fluorescence X-rays were used to characterize the products of corrosion of the pipelines. The corrosion rate by weight loss was analyzed for every pipeline, only those ones that has revealed corrosive attack were analyzed located corrosion rate. The corrosion potential was classified as low to pipeline gas and ranged from low to severe for oil pipelines and the pipeline derivatives. Corrosion products were identified as iron carbonate, iron oxide and iron sulfide

Adsorção de cobre e cromo utilizando fibra de sisal visando o tratamento da água produzida pela indústria petrolífera

Currently, the oil industry is the biggest cause of environmental pollution. The objective was to reduce the concentration of copper and chromium in the water produced by the oil industry. It was used as adsorbent natural sisal fiber Agave sp treated with nitric acid and sodium hydroxide. All vegetable fibers have physical and morphological properties that enablies the adsorption of pollutants. The basic composition of sisal is cellulose, hemicellulose and lignin. The features are typically found in the characterization of vegetable fibers, except the surface area that was practically zero. In the first stage of adsorption, it was evaluated the effect of temperature and time skeeking to optimize the execution of the factorial design. The results showed that the most feasible fiber was the one treated with acid in five hours (30°C). The second phase was a factorial design, using acid and five hours, this time was it determined in the first phase. The tests were conducted following the experimental design and the results were analyzed by statistical methods in order to optimize the main parameters that influence the process: pH, concentration (mol / L) and fiber mass/ metal solution volume. The volume / mass ratio factor showed significant interference in the adsorption process of chromium and copper. The results obtained after optimization showed that the highest percentages of extraction (98%) were obtained on the following operating conditions: pH: 5-6, Concentration: 100 ppm and mass/ volume: 1 gram of fiber/50mL solution. The results showed that the adsorption process was efficient to remove chromium and copper using sisal fibers, however, requiring further studies to optimize the process.

Avaliação de metodologia de preparo de amostra de petróleo por digestão ácida auxiliada por microondas para determinação de metais por ICP-OES

This project describes a methodology optimization that would allow for a more efficient microwave assisted digestion process for petroleum samples. With the possible chance to vary various factors at once to see if any one factor was significant enough in the answers, experimental planning was used. Microwave assisted digestion allows, through the application of potency, an increasing number of collisions between the HNO3 and H2O2 molecules, favoring sample opening for complex matrixes. For this, a 24 factorial experimental planning was used, varying potency, time and the volumes for HNO3 65% and H2O2 30%. To achieve the desired answers, several elements were monitored (C, Cu, Cr, Fe, Ni, Zn and V) through Inductively coupled plasma atomic emission spectroscopy (ICP-OES). With this initial study it was noticed that the HNO3 was not a significant factor for any of the statistical studies for any of the analytes and the other 3 factors and their interactions showed statistical significance. A Box Behnken experimental planning was used taking in consideration 3 factors: H2O2 volume, time (min) and Potency (W), Nitric Acid kept at 4mL for a mass of 0,1g of petroleum. The results were extremely satisfying showing higher efficiency in the digestion process and taking in a responsibility between the answers for each analyte and the carbon monitoring was achieved in the following conditions: 7mL of H2O2, 700 Watts of potency and a reaction time of 7 minutes with 4mL de HNO3 for a mass of 0,1g of petroleum. The optimized digestion process was applied to four different petroleum samples and the analytes determined by ICP-OES

Evolução diagenética e caracterização dos reservatórios da seção devoniana na Bacia do Rio do Peixe-Nordeste do Brasil

The Rio do Peixe Basin represents a main basin of northeastern Brazil and pioneering work positioned the rocks of this basin in the Early Cretaceous. However, a recent study, based on integrated pollen analysis from three wells, found an unprecedented siliciclastic sedimentary section, in the region, of early Devonian age. Therefore, the present study aims a detailed petrographic and petrological analysis of this devonian section, in the Rio do Peixe Basin and proposes a diagenetic evolution, to understand the characteristics of the porous system, identify the main reservoir petrofacies with the main factors impacting on the quality of these rocks as reservoirs and a quick study on the provenance of this section. The petrographic study was based on samples obtained from subsurface and surface. The diagenetic evolution of petrofacies and its identification were based only on subsurface samples and the study of provenance was based on surface samples. The thin sections were prepared from sandstones, pelites and sandstones intercalated with pelites. The original detrital composition for this section is arcosean and the main diagenetic processes that affected these rocks occur in various depths and different conditions, which resulted in extensive diagenetic variety. The following processes were identified: early fracture and healing of grains; albitization of K-feldspar and plagioclase; siderite; precipitation of silica and feldspar; mechanical infiltration of clay and its transformation to illite/esmectite and illite; autigenesis of analcime; dissolution; autigenesis of chlorite; dolomite/ferrous dolomite/anquerite; apatite; calcite; pyrite; titanium minerals and iron oxide-hidroxide. The occurrence of a recently discovered volcanism, in the Rio do Peixe Basin, may have influenced the diagenetic evolution of this section. Three diagenetic stages affected the Devonian section: eo, meso and telodiagenesis. This section is compositionally quite feldspathic, indicating provenance from continental blocks, between transitional continental and uplift of the basement. From this study, we observed a wide heterogeneity in the role of the studied sandstones as reservoirs. Seven petrofacies were identified, taking into account the main diagenetic constituent responsible for the reduction of porosity. It is possible that the loss of original porosity was influenced by intense diagenesis in these rocks, where the main constituent for the loss of porosity are clays minerals, oxides and carbonate cement (calcite and dolomite)

Aplicação de técnicas eletroquímicas na determinação do potencial de corrosividade de ligas de alumínio em água produzida

The resistance of aluminum and their alloys, to the corrosion phenomenon, in aqueous solutions, is a result of the oxide layer formed. However, the corrosion process in the aluminum alloy is associated with the presence a second phase of particles or the presence of chloride ions which promote the disruption of the oxide layer located producing the corrosion process. On the other hand, the term water produced is used to describe the water after the separation of the oil and gas in API separators. The volumes of produced water arrive around 5 more times to the volume of oil produced. The greatest feature of the water is the presence of numerous pollutants. Due to the increased volume of waste around the world in the current decade, the outcome and the effect of the discharge of produced water on the environment has recently become an important issue of environmental concern where numerous treatments are aimed at reducing these contaminants before disposal. Then, this study aims to investigate the electrochemical corrosion behavior of aluminum alloy 6060 in presence of water produced and the influence of organic components as well as chloride ions, by using the electrochemical techniques of linear polarization. The modification of the passive layer and the likely breakpoints were observed by atomic force microscopy (AFM). In the pit formation potential around -0.4 to -0.8 V/EAg/AgCl was observed that the diffusion of chloride ions occurs via the layer formed with the probable formation of pits. Whereas, at temperatures above 65 °C, it was observed that the range of potential for thepit formation was -0.4 to -0.5 V/EAg/AgCl. In all reactions, the concentration of Al(OH)3 in the form of a gel was observed