Síntese e caracterização de tungstatos de cério e estrôncio para fins catalíticos

The main goal of this work was to produce nanosized ceramic materials of the family of the tungstates (tungstates of cerium and strontium), and test them for their catalytic activity in processes involving the transformation of methane (CH4). The methodology used for the synthesis of the ceramic powders involved the complexation combining EDTA-citrate. The materials characterization was performed using simple and differential thermogravimetry, x-ray diffraction, transmission electron microscopy, and energy dispersive spectroscopy (EDS). The microstructure analysis was performed using the refinement by the Rietveld method, and the crystallite size and distribution of the materials was elucidate by the Scherrer and Williamson-Hall methods. The conditions of the synthesis process for the three envisaged materials (SrWO4, SrWO4 using tungsten oxide concentrate as raw material, and Ce2(WO4)3) were adjusted to obtain a single phase crystalline material. The catalytic tests were carried out in the presence of methane and synthetic air, which is composed of 21% O2 and 79% N2. The analysis of the conversion of the reaction was done with the aid of an fourier transform infrared device (FTIR). The analysis showed that, structurally, the SrWO4 produced using raw materials of high and poor purity (99% and 92%, respectively) are similar. The ideal parameters of calcination, in the tested range, are temperature of 1000 °C and time of calcination 5 hours. For the Ce2(WO4)3, the ideal calcination time and are temperature 15 hours and 1000°C, respectively. The Williamson-Hall method provided two different distributions for the crystallite size of each material, whose values ranged between the nanometer and micrometer scales. According to method of Scherrer, all materials produced were composed of nanometric crystallites. The analyses of transmission electron microscopy confirmed the results obtained from the Williamson- Hall method for the crystallite size. The EDS showed an atomic composition for the metals in the SrWO4 that was different of the theoretical composition. With respect to the catalytic tests, all materials were found to be catalytically active, but the reaction process should be further studied and optimized.

Propriedades magnéticas de ortoferritas de lantânio dopadas com estrôncio

Samples of lanthanum Ortoferrites doped with strontium were synthesized in a single phase by the sol-gel method. Two samples were prepared, one by varying the concentration of strontium in lanthanum ortoferrites La1−xSrxFeO3−δ with (0 ≤ x ≤ 0.5), and another batch of samples of type, La1/3Sr2/3FeO3−δ, now varying only the temperature of calcination. Our samples were obtained by Pechini method and sintered in air and oxygen atmospheric. Their crystal structures were determined by x-ray diraction (XRD), scanning electron microscopy (SEM), where we observed that the samples (0 ≤ x ≤ 0.3) have orthorhombic symmetry and the volume of the single cell decreases with the increasing of concentration of strontium. For x = 0.5 it is only observed the simple phase when that is sintered in O2 atmospheric. Their magnetic characteristics were obtained by the Mössbauer spectroscopy and magnetic measurements. The magnetization measurements for samples La1−xSrxFeO3−δ with (0 ≤ x ≤ 0.5) revealed that the magnetization decreases with increasing concentration of strontium, but for the sample x = 0.4 the magnetization shows a high coercive field and a ferrimagnetic behavior, which is attributed to a small amount of strontium hexaferrite. As for the samples La1/3Sr2/3FeO3−δ calcined between 800 oC e 1200 oC. The hysteresis curves revealed two distinct behaviors: an declined antiferromagnetic behavior (Canted) for samples calcined between 800 oC and 1000 oC and a paramagnetic behavior for the samples calcined at 1100 oC e 1200 o C. Thermal hysteresis and sharp peaks around the Néel temperature (TN), over the curves of specific heat as a function of temperature was only observed in calcined samples with 1100 oC and 1200 oC. This eect is attributed to the charge ordering. These results indicate that the charge ordering occurs only in the samples without oxygen deficiency. Magnetic measurements as a function of temperature are also in agreement with this interpretation

Ordenamento de cargas e propriedades magnéticas de ortoferritas de lantânio dopadas com estrôncio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ordenamento de cargas e propriedades magnéticas de ortoferritas de lantânio dopadas com estrôncio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese e caracterização de catalisadores nanométricos de LaSrNiO4 para aplicação em dessulfurização de tiofeno

The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nanosized catalyst of nickelate of lanthanum doped with strontium (La(1-x)SrxNiO4-d; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300ºC/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000°C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N2 by BET method, X-ray diffraction (XRD), scanning electron microscopy (HR_SEM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700ºC have crystalline structure. The results of SEM evidenced the obtainment of nanometric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m2/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200ºC, the relation F/W equal to 0,7 mol h-1mcat -1. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%

Síntese citrato-hidrotermal e caracterização eletroquímica de LSCF para aplicação como catodo em célula a combustível de temperatura intermediária

The lanthanum strontium cobalt iron oxide (La1-xSrxCo1-yFeyO3 LSCF) is the most commonly used material for application as cathode in Solid Oxide Fuel Cells (SOFCs), mainly due to their high mixed ionic electronic conductivity between 600 and 800ºC. In this study, LSCF powders with different compositions were synthesized via a combination between citrate and hydrothermal methods. As-prepared powders were calcined from 700 to 900°C and then characterized by X-ray fluorescence, X-ray diffraction, thermal analyses, particle size analyses, nitrogen adsorption (BET) and scanning electronic microscopy. Films of composition La0,6Sr0,4Co0,2Fe0,8O3 (LSCF6428), powders calcined at 900°C, were screen-printed on gadolinium doped ceria (CGO) substrates and sintered between 1150 and 1200°C. The effects of level of sintering on the microstructure and electrochemical performance of electrodes were evaluated by scanning electronic microscopy and impedance spectroscopy. Area specific resistance (ASR) exhibited strong relation with the microstructure of the electrodes. The best electrochemical performance (0.18 ohm.cm2 at 800°C) was obtained for the cathode sintered at 1200°C for 2 h. The electrochemical activity can be further improved through surface activation by impregnation with PrOx, in this case the electrode area specific resistance decreases to values as low as 0.12 ohm.cm2 (800°C), 0.17 ohm.cm2 (750°C) and 0.31 ohm.cm2 (700°C). The results indicate that the citrate-hydrothermal method is suitable for the attainment of LSCF particulates with potential application as cathode component in intermediate temperature solid oxide fuel cells (IT-SOFCs)

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

Petrologia do magmatismo tardi-brasiliano no Maciço São José de Campestre(RN/PB), com ênfase no Plúton Alcalino Caxexa

The area studied is located on the north-easternmost portion of the Borborema Province, on the so-called São José de Campestre Massif, States of RN and PB, Northeast Brazil. Field relations and petrographic, geochemical and isotope data permitted the separation of five suites of plutonic rocks: alkali-feldspar granite (Caxexa Pluton), which constitutes the main subject of this dissertation, amphibole-biotite granite (Cabeçudo Pluton), biotite microgranite, gabbronorite to monzonite (Basic to Intermediate Suite) and aluminous granitoid. The Caxexa Pluton is laterally associated to the Remígio Pocinhos Shear Zone, with its emplacement along the mylonitic contact between the gneissic basement and the micashists. This pluton corresponds to a syntectonic intrusion elongated in the N-S direction, with about 50 km2 of outcropping surface. It is composed exclusively of alkali-feldspar granites, having clinopyroxene (aegirine-augite and hedenbergite), andradite-rich garnet, sphene and magnetite. It is classified geochemically as high silica rocks (>70 % wt), metaluminous to slightly peraluminous (normative corindon < 1%), with high total alkalis (>10% wt), Sr, iron number (#Fe=90-98) and agpaitic index (0.86-1.00), and positive europium anomaly. The Cabeçudo Pluton is composed of porphyritic rocks, commonly containing basic to intermediate magmatic enclaves often with mingling and mixing textures. Petrographically, it presents k-feldspar and plagioclase phenocrysts as the essential minerals, besides the accessories amphibole, biotite, sphene and magnetite. It is metaluminous and shows characteristics transitional between the calc-alkaline and alkaline series (or monzonitic subalkaline). Its REE content is greater than those ones of the Caxexa Pluton and biotite microgranite, and all spectra have negative europium anomalies. The biotite microgranites occur mainly on the central and eastern portion of the mapped area, as dykes and sheets with decimetric thickness, hosted principally in orthogneisses and micashists. Their field relationships as regards the Caxexa and Cabeçudo plutons suggested that they are late-tectonic intrusions. They are typically biotite granites, having also sphene, amphibole, allanite, opaques and zircon in the accessory assemblage. Geochemically they can be distinguished from the porphyritic types because the biotite microgranites are more evolved, peraluminous, and have more fractionated REE spectra. The Basic to Intermediate rocks form a volumetrically expressive elliptical, kilometric scale body on the Southeast, as well as sheets in micashists. They are classified as gabbronorites to monzonites, with the two pyroxenes and biotite, besides subordinated amounts of amphibole, sphene, ilmenite and allanite. These rocks do not show a well-defined geochemical trend, however they may possibly represent a monzonitic (shoshonitic) series. Their REE spectra have negative europium anomalies and REE contents greater than the other suites. The aluminous granitoids are volumetrically restricted, and have been observed in close association with migmatised micashists bordering the gabbronorite pluton. They are composed of almandine-rich garnet, andalusite, biotite and muscovite, and are akin to the peraluminous suites. Rb-Sr (whole rock) and Sm-Nd (whole-rock and mineral) isotopes furnished a minimum estimate of the crystallization (578±14 Ma) and the final resetting age of the Rb-Sr system (536±4 Ma) in the Caxexa Pluton. The aluminous granitoid has a Sm-Nd garnet age similar to that one of the Caxexa Pluton, that is 574±67 Ma. The strong interaction of shear bands and pegmatite dykes favoured the opening of the Rb-Sr system for the Caxexa Pluton and biotite microgranite. The amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer indicate minimum conditions of 560°C and 7 kbar for the Cabeçudo Pluton, 730°C and 6 kbar for the microgranite and 743°C and 5 kbar for the basic to intermediate suite. The Zr saturation geothermometer reveals temperatures of respectively 855°C, 812°C and 957°C for those suites, whereas the Caxexa Pluton shows temperatures of around 757°C. The Caxexa, Cabeçudo and microgranites suites crystallized under high fO2 (presence of magnetite). On the other hand, the occurrence of ilmenite suggests less oxidant conditions in the basic to intermediate suite. Field relations demonstrate the intrusive character of the granitoids into a tectonically relatively stable continental crust. This is corroborated by petrographic and geochemical data, which suggest a late- or post-collisional tectonic context. It follows that the generation and emplacement of those granitoid suites is related to the latest events of the Brasiliano orogeny. Finally, the relationships between eNd (600 Ma), TDM (Nd) and initial Sr isotope ratio (ISr) do not permit to define the precise sources of the granitoids. Nevertheless, trace element modelling and isotopic comparisons suggest the participation of the metasomatised mantle in the generation of these suites, probably modified by different degrees of crustal contamination. In this way, a metasomatised mantle would not be a particular characteristic of the Neoproterozoic lithosphere, but a remarkable feature of this portion of the Borborema Province since Archaean and Paleoproterozoic times.

Incrustação em poço produtor de petróleo e gás natural: um estudo de caso

Water and gas is a common by - product of the oil production process. Production may be compromised by the precipitation of inorganic salts in both the reservoir and producing well, through scale formation. This precipitation is likely the cause of the formation damage. High temperatures and h igh pressures (HTHP) may favor the precipitation of insoluble salts. The most common types of scale in oil fields are calcium carbonate and calcium sulphate, strontium and barium sulphate. New types of scale formation have attracted special attention such as zinc sulphide and lead. This precipitation may occur in the pores of reservoir rocks, in the production string and in equipment, causing obstructions and consequent production losses. In this study, the influence of well depth on incrustation compositio n was investigated to design removal treatments and assess the behavior of these deposits along the string, through the analysis of pressure and temperature. Scale residues were recovered from the inside of the production string of an oil and gas well duri ng the string removal operation. A total of 10 samples from different depths (15.4 m to 4061.5 m) were obtained. Initially a dissolution test was conducted in weak acid, similar to that used in removal operations with this type of scale formation. Majority composition was defined and confirmed by dissolution tests using X - Ray Fluorescence Spectroscopy (XRF), X - Ray Diffraction (XRD) and Scanning Electron Microscope (SEM) techniques. Residues with distinct characteristics were observed in different proportion s, showing a tendency toward increased and/or decreased mass with depth. In the samples closest to the surface, typical sandstone residues were found, with calcium (45% Ca) as the metal of highest concentration. The obtained results indicate correlations o f the scale types studied with the depth and, consequently, with the thermodynamic conditions of pressure and temperature.

Síntese e caracterização de catalisadores nanométricos de LaSrNiO4 para aplicação em dessulfurização de tiofeno

The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nanosized catalyst of nickelate of lanthanum doped with strontium (La(1-x)SrxNiO4-d; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300ºC/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000°C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N2 by BET method, X-ray diffraction (XRD), scanning electron microscopy (HR_SEM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700ºC have crystalline structure. The results of SEM evidenced the obtainment of nanometric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m2/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200ºC, the relation F/W equal to 0,7 mol h-1mcat -1. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%