Phase relations and activities in the Co Ni O system at 1373 K

The tie-lines delineating equilibria between CoO-NiO and Co-Ni solid solutions in the ternary Co-Ni-O system at 1373 K have been determined by electron microprobe andedax point count analysis of the oxide phase equilibrated with the alloy. The oxygen potentials corresponding to the tie-line compositions have been measured using a solid oxide galvanic cell with calcia-stabilized zirconia electrolyte and Ni + NiO reference electrode. Activities in the metallic and oxide solid solution have been derived using a new Gibbs-Duhem integration technique. Both phases exhibit small positive deviations from ideality; the values ofG E/X 1 X 2 are 2640 J mol−1 for the metallic phase and 2870 J mol−1 for the oxide solid solution.

Electrical conductivity of Ca-doped YFeO3

Electrical conductivity and Seebeck coefficient of calcium-doped YFeO3, a potential cathode material in solid oxide fuel cells (SOFC), are measured as function of temperature and composition in air to resolve conflicts in the literature both on the nature of conduction (n- or p-type) and the types of defects (majority and the minority) present. Compositions of Y1-xCaxFeO3-delta with x = 0.0, 0.025, 0.05 and 0.1 are studied in the temperature range from 625 to 1250 K. All Y1-xCaxFeO3-delta samples show p-type semiconducting behaviour. Addition of Ca up to 5% dramatically increases the conductivity of YFeO3; increase is more gradual up to 10%. A second phase Ca2Fe2O5 appears in the microstructure for Ca concentrations in excess of 11%.

Investigation on the Sr-doped ceria Ce1-xSrO2-delta (x=0.05-0.2) as an electrolyte for intermediate temperature SOFC

The effect of Sr doping in CeO2 for its use as solid electrolytes for intermediate temperature solid oxide fuel cells (IT-SOFCs) has been explored here. Ce1-xSrxO2-delta (x = 0.05-0.2) are successfully synthesized by citrate-complexation method. XRD, Raman, FT-IR, FE-SEM/EDX and electrochemical impedance spectra are used for structural and electrical characterizations. The formation of well crystalline cubic fluorite structured solid solution is observed for x = 0.05 based on XRD and Raman spectra. For compositions i.e., x > 0.05, however, a secondary phase of SrCeO3 is confirmed by the peak at 342 cm(-1) in Raman spectra. Although the oxygen ion conductivity was found to decrease with increase in x, based on ac-impedance studies, conductivity of Ce0.95Sr0.05O2-delta was found to be higher than of Ce0.95Gd0.1O2-delta and Ce0.8Gd0.2O2-delta. The decrease in conductivity of Ce1-xSrxO2-delta with increasing dopant concentration is ascribed to formation of impurity phase SrCeO3 as well as the formation of neutral associated pairs, Se `' Ce V-o. The activation energies are found to be 0.77, 0.83, 0.85 and 0.90 eV for x = 0.05, 0.1, 0.15 and 0.20, respectively. (C) 2014 Elsevier B.V. All rights reserved.

An electrochemical method for the synthesis of few layer graphene sheets for high temperature applications

We demonstrate an electrochemical technique for the large scale synthesis of high quality few layer graphene sheets (FLGS) directly from graphite using oxalic acid (a weak acid) as the electrolyte. One of the interesting observations is that the FLGS are stable at least up to 800 degrees C and hence have potential application in solid oxide fuel cells as a gas diffusion layer.

Effect of the A cation size disorder and synthesis conditions on the properties of an iron perovskite series

Póster presentado en The Energy and Materials Research Conference - EMR2015 celebrado en Madrid (España) entre el 25-27 de febrero de 2015

Mo的掺杂对Ce_(0.8)Gd_(0.2)O_(1.9)烧结温度及电性能的影响

掺杂的CeO2基固体电解质因其在中低温条件下(500￣700℃)具有高氧离子电导率而成为有希望的IT-SOFCs(intermediate temperature-solid oxide fuel

Investigation into the effect of Fe-site substitution on the performance of Sr2Fe1.5Mo0.5O6-δ anodes for SOFCs

Ni-substituted Sr₂Fe_1.5-xNi_xMo_0.5O_6-δ (SFNM) materials have been investigated as anode catalysts for intermediate temperature solid oxide fuel cells. Reduced samples (x = 0.05 and 0.1) maintained the initial perovskite structure after reduction in H₂, while metallic nickel particles were detected on the grain surface for x = 0.2 and 0.3 using transmission electron microscopy. Temperature programmed reduction results indicate that the stable temperature for SFNM samples under reduction conditions decreases with Ni content. In addition, X-ray photoelectron spectroscopy analysis suggests that the incorporation of Ni affects the conductivity of SFNM through changing the ratios of Fe³⁺/Fe²⁺ and Mo⁶⁺/Mo⁵⁺. Sr₂Fe_1.4Ni_0.1Mo_0.5O_6-δ shows the highest electrical conductivity of 20.6 S cm^-1 at 800 °C in H₂. The performance of this anode was further tested with electrolyte-supported cells, giving 380 mW cm^-2 at 750 °C in H₂, hence demonstrating that Ni doping in the B-site is beneficial for Sr₂Fe_1.5Mo_0.5O_6-δ anode performance. 

Clinopyroxene based glasses and glass-ceramics for functional applications

As piroxenas são um vasto grupo de silicatos minerais encontrados em muitas rochas ígneas e metamórficas. Na sua forma mais simples, estes silicatos são constituídas por cadeias de SiO3 ligando grupos tetrahédricos de SiO4. A fórmula química geral das piroxenas é M2M1T2O6, onde M2 se refere a catiões geralmente em uma coordenação octaédrica distorcida (Mg2+, Fe2+, Mn2+, Li+, Ca2+, Na+), M1 refere-se a catiões numa coordenação octaédrica regular (Al3+, Fe3+, Ti4+, Cr3+, V3+, Ti3+, Zr4+, Sc3+, Zn2+, Mg2+, Fe2+, Mn2+), e T a catiões em coordenação tetrahédrica (Si4+, Al3+, Fe3+). As piroxenas com estrutura monoclínica são designadas de clinopiroxenes. A estabilidade das clinopyroxenes num espectro de composições químicas amplo, em conjugação com a possibilidade de ajustar as suas propriedades físicas e químicas e a durabilidade química, têm gerado um interesse mundial devido a suas aplicações em ciência e tecnologia de materiais. Este trabalho trata do desenvolvimento de vidros e de vitro-cerâmicos baseadas de clinopiroxenas para aplicações funcionais. O estudo teve objectivos científicos e tecnológicos; nomeadamente, adquirir conhecimentos fundamentais sobre a formação de fases cristalinas e soluções sólidas em determinados sistemas vitro-cerâmicos, e avaliar a viabilidade de aplicação dos novos materiais em diferentes áreas tecnológicas, com especial ênfase sobre a selagem em células de combustível de óxido sólido (SOFC). Com este intuito, prepararam-se vários vidros e materiais vitro-cerâmicos ao longo das juntas Enstatite (MgSiO3) - diopsídio (CaMgSi2O6) e diopsídio (CaMgSi2O6) - Ca - Tschermak (CaAlSi2O6), os quais foram caracterizados através de um vasto leque de técnicas. Todos os vidros foram preparados por fusão-arrefecimento enquanto os vitro-cerâmicos foram obtidos quer por sinterização e cristalização de fritas, quer por nucleação e cristalização de vidros monolíticos. Estudaram-se ainda os efeitos de várias substituições iónicas em composições de diopsídio contendo Al na estrutura, sinterização e no comportamento durante a cristalização de vidros e nas propriedades dos materiais vitro-cerâmicos, com relevância para a sua aplicação como selantes em SOFC. Verificou-se que Foi observado que os vidros/vitro-cerâmicos à base de enstatite não apresentavam as características necessárias para serem usados como materiais selantes em SOFC, enquanto as melhores propriedades apresentadas pelos vitro-cerâmicos à base de diopsídio qualificaram-nos para futuros estudos neste tipo de aplicações. Para além de investigar a adequação dos vitro-cerâmicos à base de clinopyroxene como selantes, esta tese tem também como objetivo estudar a influência dos agentes de nucleação na nucleação em volume dos vitro-cerâmicos resultantes á base de diopsídio, de modo a qualificá-los como potenciais materiais hopedeiros de resíduos nucleares radioactivos.

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

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

Síntese e caracterização de componentes nanoestruturados de células a combustível de óxidos sólidos

Perovskite-like ceramic materials present the general formula ABO3, where A is a rare earth element or an alkaline metal element, and B is a transition metal. These materials are strong candidates to assume the position of cathode in Solid Oxide Fuel Cells (SOFC), because they present thermal stability at elevated temperatures and interesting chemical and physical properties, such as superconductivity, dieletricity, magnetic resistivity, piezoelectricity, catalytic activity and electrocatalytic and optical properties. In this work the cathodes of Solid Oxide Fuel Cells with the perovskite structure of La1-xSrxMnO3 (x = 0.15, 0.22, 0.30) and the electrolyte composed of zirconia-stabilized-yttria were synthesized by the Pechini method. The obtained resins were thermal treatment at 300 ºC for 2h and the obtained precursors were characterized by thermal analysis by DTA and TG / DTG. The powder precursors were calcined at temperatures from 450 to 1350ºC and were analyzed using XRD, FTIR, laser granulometry, XRF, surface area measurement by BET and SEM methods. The pellets were sintered from the powder to the study of bulk density and thermal expansion

Desenvolvimento de componentes nanométricos para aplicação em células a combustível à base de sólidos estruturados e filmes finos

The present work aims the preparation of filmes of strontium-doped lanthanum manganite (perovskita) yttria-stabilized zirconia (LSM-SDC) films deposited on substrate of YSZ by means of spin coating technique having as principal objective their application to solid oxide fuel cells of intermediate temperature. La0,8Sr0,2MnO3 and Ce0,8Sm0,2O1,9 were obtained by modified Pechini method by use of gelatin which act as polymerization agent. The powders obtained were characterized by Xray fluorescence, X ray diffraction, electronic scanning microscopy and the superficial area by BET method. The results obtained by X-ray fluorescence showed that the route adopted for obtention of powders was effective in the obtention of the compositions with close values to the stoichiometrics. Ethyl cellulose was used as pore-forming agent and mixed with the LSM-SDC powders in weight proportions of 1:24, 2:23 and 1:9. The films were sintered at 1150 °C for 4 h and characterized by X-ray diffraction and scanning electron microscopy technique (SEM) and atomic force. The phases quantification of the precursory powders and of the obtained films was carried through Rietveld method. According with the analysis of SEM, as the content of ethyl cellulose was increased, the pore distribution in films become more uniform and the pore size reduced. The methodology used for the obtention of the films was very efficient, considering a material was obtained with characteristics that were proper to the application as electrolyte/cathode system to solid oxide fuel cells

Síntese e caracterização de pós Ba(x)Sr(1-x)Co0,8Fe0,2O3- através do método de coprecipitação via oxalato

Ceramic powders based on oxides of perovskite-type structure is of fundamental interest nowadays, since they have important ionic-electronic conductivity in the use of materials with technological applications such as gas sensors, oxygen permeation membranes, catalysts and electrolytes for solid oxide fuel cells (SOFC). The main objective of the project is to develop nanostructured ceramic compounds quaternary-based oxide Barium (Br), Strontium (Sr), Cobalt (Co) and Iron (Fe). In this project were synthesized compounds BaxSr(1-x)Co0, 8Fe0,2O3- (x = 0.2, 0.5 and 0.8) through the oxalate co-precipitation method. The synthesized powders were characterized by thermogravimetric analysis and differential thermal analysis (TGADTA), X-ray diffraction (XRD) with the Rietveld refinement using the software MAUD and scanning electron microscopy (SEM). The results showed that the synthesis technique used was suitable for production of nanostructured ceramic solid solutions. The powders obtained had a crystalline phase with perovskite-type structure. The TGA-DTA results showed that the homogeneous phase of interest was obtained temperature above 1034°C. It was also observed that the heating rate of the calcination process did not affect the elimination of impurities present in the ceramic powder. The variation in the addition of barium dopant promoted changes in the average crystallite size in the nanometer range, the composition being BSCF(5582) obtained the lowest value (179.0nm). The results obtained by oxalate co-precipitation method were compared with those synthesis methods in solid state and EDTA-citrate method

Análise do 'LA''CR'O IND.3' dopado com 'SR' e 'CO',preparados via reação de combustão, utilizando difração de raios X com aplicação do método de Rietveld

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