Análises estrutural, nanoestrutural, e quantitativa de fases em materiais cerâmicos de interesse tecnológico, utilizando difração de raios X pelo método do pó

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

GEOLOGIA, GEOQUÍMICA E MINERALOGIA COMPARATIVA ENTRE AS INTRUSÕES DIAMANTÍFERAS CANASTRA-1 E ABEL RÉGIS (MINAS GERAIS)

Centenas de intrusões alcalino-ultrabásicas ocorrem na região sul-sudoeste de Minas Gerais. Duas destas intrusões, portadoras de diamantes e conhecidas como “Canastra-1” e “Abel Régis”, foram estudadas em detalhe visando seus aspectos geológicos, geoquímicos e mineralógicos. A segunda foi ainda objeto de datação LA-MC-ICP-MS em zircão. Em termos geológicos, tais intrusões exibem diferenças morfológicas significantes: a forma superficial do Canastra-1 é irregular e de pequena dimensão (150 m de comprimento maior), enquanto o Abel Régis é circular e de grande diâmetro (~1,4 km), as quais representam, respectivamente, fácies de raiz e de cratera. A geoquímica dessas intrusões apresentou características peculiares, principalmente quanto aos álcalis: o pipe Canastra-1 é empobrecido em Na2O e K2O, óxidos que possuem conteúdos significantes no pipe Abel Régis, este datado em 86,1 ±4,5Ma. Os aspectos mineralógicos das fases indicadoras de diamantes também são bastante distintos: a abundância em Cr-espinélio, bem como a presença de sanidina e a química mineral de ilmenita e diopsídio, são indicadores de uma possível “tendência” lamproítica para o pipe Abel Régis, enquanto o Canastra-1 possui aspectos geoquímicos e mineralógicos de um kimberlito clássico.

Processamento e propriedades magnéticas de manganitas multiferróicas = Mise en forme et propriétés magnétiques de manganites multiferróïques

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Síntese, caracterização estrutural, espectroscópica e análise do potencial fotocatalítico do aluminato de cobalto e potencial catalítico na preparação do biodiesel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese e caracterização de ferritas de manganês e zinco visando aplicação como agente de contraste em diagnóstico médico

This work aims to synthesize the manganese and zinc ferrite, by the polymeric precursor method, in order to obtain materials with appropriate characteristics for the application in medical diagnosis techniques. The manganese and zinc ferrite powders with the composition of Mn(1-x)ZnxFe2O4, where x=0,23, were prepared and calcined in air at different times and temperatures. The X-ray diffraction (XRD) data show that the sample calcined at 400°C crystallize as ferrite (monophase), but in an inverted spinel structure (high content of iron occupying manganese tetrahedral site and manganese occupying the iron octahedral site). The samples calcined at temperatures between 600°C and 900°C shows the secondary phase of hematite and the sample calcined at 1100oC shows to be monophase in ferrite with normal spinel structure. The monophase powders of ferrite showed a reduction in the surface area and an increasing in the pore size for higher calcination temperatures. The magnetic analysis show that the sample calcined at 400°C presents satisfactory magnetization at room temperature, however, it behaves as diamagnetic material at low temperatures (10K). The powder containing hematite, without the partial substitution of iron ions by manganese, showed to have low transition temperature, and consequently low magnetization at room temperature. The hematite, when partially substituted, provides materials with irregular magnetization at the saturation region. The powder calcined at 1100°C shows high magnetization either at room temperature or low temperature (10K)

Síntese e caracterização estrutural de pigmentos cerâmicos a base de cromita por método químico

The ceramic pigments are colored inorganic substances that during the process of dispersion in the ceramic glazes and subsequent calcination, are stable against physical and chemical attack. Therefore, they are crystalline compounds applied in the ceramic industry for coloring vitreous base. In this study, the Pechini method was used for obtaining the pigment CuCr2O4 with heat treatment at the temperatures of 800, 900 and 1000 ° C. The powder pigments were characterized on their structural, morphological and colorimetric aspects. The thermal analysis conducted on an amorphous precursor in a TG / DTA indicates the weight loss in the entire temperature range investigated, with characteristic exothermic peak of the elimination of the organic composition of the precursor around 300°C. The development of the crystalline phases were investigated by XRD, using a diffractometer with Cu Ka radiation and graphite monochromator, where it was observed the presence of crystalline phases corresponding to Cr2O3 and CuCr2O4.The measurements of the specific surface area of the powders pigments were carried out in an equipment Micromeritcs, model ASAP 2000, using N2 as gas of adsorption/desorption. The colorimetric measurements of the pigments were made in a colorimeter Gretac Macbeth Color-eye spectrophotometer 2180 / 2180UV in CIELAB standards. Based on the obtained results, it can be verified the thermal stability of the powder pigments of green coloration, which enables it as an alternative to the materials currently used in the manufacture of ceramic tiles.

Análise estrutural e morfológica de ferrita NiFe2O4 dopada com cromo

This paper reports on the effect of the substitution of Fe3+ for Cr3+ ions in the spinel lattice of the powders was investigated. Nickel ferrite powders with a NiFe2-xCrxO4 nominal composition (x = 0.0; 0.5; 1.0 and 1.5 mol of the chromium) were synthesized by combustion reaction using urea as fuel. The powders resulting were characterized by XRD, nitrogen adsorption by BET, SEM and Mössbauer spectroscopy (57Fe Mössbauer spectra). The results show that the substitution of the Fe3+ for Cr3+ions increased the crystalline degree of the phase, reduced the superficial area and consequently increased the particle size. The Mössbauer spectra of the samples also confirm the distribution of the particles size by the magnetic properties. Analyze of the spectra Mössbauer gives an estimate of the superparamagnetic and ferromagnetic particles behavior in each sample for several chromium concentrations.

Pigmentos a base de Cobalto para aplicação em revestimentos cerâmicos

Ceramic pigments that own mainly the spinel structure AB2O4 are becoming a matter of great scientific and technological interest due to the ability of accommodate different cations in its structure, allowing different dopings and thus obtaining different colors. Studies on ceramic pigments currently are being directed to the development of stable and pigments obtained at low temperatures and with greater reproducibility. This work aims at the use of inorganic pigments for applications in ceramic tiles, investigating the influence of doping and calcination temperature on the coloring pigments and ceramic glazes. the based pigments of CoCr2O4, CoAl2O4, Co0,8Zn0,2Cr2O4 and Co0,8Zn0,2Al2O4 were synthesized by a chemical route using commercial gelatin as organic precursor. The materials were characterized by thermogravimetric analysis (TG), X-ray diffraction (XRD), infrared spectroscopy (FTIR) spectroscopy scanning electron microscopy (SEM) in the UVVisible region and colorimetry. The results confirmed the feasibility of synthesis used, the route presented pigments crystal structures and the desired phases were obtained from 500 °C with increased crystallinity and the crystallite size. The pigments have hues ranging from green to violet according to their doping and calcination temperatures.

Transportadores sólidos de oxigênio à base de níquel e cobre suportados em aluminatos para combustão do metano pela tecnologia de recirculação química

In recent years, solid carriers suitable oxygen have been developed for use in different chemical processes recirculation. The success of this technology is directly related to the chemical reactivity and the oxygen storage capacity of the carrier. Thus, research into the development of new materials that can be applied to the process becomes extremely important. Possible candidates are the carriers based on nickel and copper for presenting favorable thermodynamic properties. In this work, aluminates type MAl2O4 (M = Mg and Ca) and M0,9B0,1Al2O4 (B = Ni and Cu) that are used as supports were synthesized by combustion reactions assisted by microwave and calcined at 900°C/2h. Then, the carriers were impregnated with 10% (m/m) of nickel or copper, and subsequently calcined at 600°C/2h to obtain the solid oxygen carriers, which were characterized by X-ray diffraction (XRD) Microscopy scanning electron microscopy (SEM) and temperature programmed reduction (TPR). Reactions simulating the combustion process by chemical recirculation were performed by cycles reduction/oxidation, in order to evaluate the reactivity of carriers. XRD analysis revealed diffraction peaks of the spinel type structures. In the doped substrates were verified the presence of secondary phases, suggesting that all the metal was incorporated into the spinel structure. In solid oxygen carriers, the NiO and CuO phases were observed after impregnation of active phases on different media. The results of evaluations of chemical cycles reduction/oxidation revealed that TSO's impregnated with nickel in various media were more active and are potential candidates for use in the chemical recirculation technology

Síntese e caracterizações estrutural e magnética das ferritas de cobalto-manganês (Co1-xMnxFe2O4 E Co1,2Fe1,8-xMnxO4)

The cobalt-manganese ferrites (Co1¡xMnxFe2O4 and Co1,2Fe1,8¡xMnxO4) has a mixed structure of spinel type and it has been regarded as one of candidates for petitive wide variety of applications in devices from ultrasonic generation and detection, sensors, transformers, as well as in medical industry. Ferrites cobalt-manganese nanostructured were produced via mechanical alloying with subsequent heat treatment and were characterized by X-ray diffraction, X-ray fluorescence, scanning electron microscopy and magnetization. Samples of Co1¡xMnxFe2O4 and Co1,2Fe1,8¡xMnxO4 were obtained from the precursor powders Fe3O4, Co3O4 and Mn3O4 which were stoichiometrically mixed and ground by 10h and heat treated at 900°C for 2h. The diffraction confirmed the formation of the pure nanocrystalline phases to series Co1,2Fe1,8¡xMnxO4 with an average diameter of about 94nm. It was found that the lattice parameter increases with the substitution of Fe3Å by Mn3Å. The x-ray fluorescence revealed that the portions of metals in samples were close to the nominal stoichiometric compositions. The microstructural features observed in micrographs showed that the particles formed show very different morphology and particle size. The magnetic hysteresis measurements performed at low temperature showed that the saturation magnetization and remanence increased as the concentration of manganese, while the coercive field decreased. The anisotropy constant (Ke f ), was estimated from the data adjustments the law of approaching saturation. It was found that the anisotropy decreases substantially with the substitution of Fe by Mn.

Pirometamorfismo em calcários da formação Jandaíra, bacia potiguar, nordeste do Brasil

The present study aims the characterization of thermally affected carbonate rocks from Jandaíra Formation in contact with Paleogene and Neogene basic intrusions in the region of the Pedro Avelino and Jandaíra municipalities (RN), northeastern Brazil. For this study, field, petrographic, x-ray diffraction, electron microprobe, and whole rock litogeochemistry data of carbonates were undertaken. The thermally unaffected limestones are classified like wackstones, grainstones and packstones. They may constitute carbonates grains of benthic foraminifera, echinoderm spines, ostracods, algae, corals, bivalves, gastropods, peloids and intraclasts. The porosities are classified like vug, intraparticle, interparticle, intercrystal and moldic types. The major minerals are calcite, ankerite and dolomite; the detrital are montmorillonite, pyrite, limonite, quartz and microcline. The thermally affected limestones are very coarse to very fine-grained and light to dark gray color. The fossiliferous components totally disappear, and the porosity tends to disappear. With the data obtained, it can be inferred that the carbonate protoliths would be calciferous to dolomitic limestones, both with small amount of clay minerals. Crystalline carbonates from dolomitic protolith have rhombohedral calcite and iron oxides / hydroxides, making the rocks much darker. The carbonates from calciferous protolith have a wide variation of grain size according to the recrystallization degree, increasing toward contact with the basic bodies. In this group, it was identified the minerals lizardite and spinel in weakly to moderately affected samples, and spinel and spurrite in strongly affected rocks, as well as calcite, that occur everywhere. The geological context (shallow level diabase intrusions), the crystallization of the pyrometamorphic minerals spurrite and olivine, and comparison with diagrams from the literature allow estimating temperatures and pressures around 1050-1200 °C and 0.5-1.0 kbar, respectively, for PTOTAL=PCO2. The post-intrusion cooling would have afforded the releasing of metasomatic / hydrothermal fluids, allowing the opening of the metamorphic system, with possible contribution of chemical elements from host units (sandstones, shales) and from basic intrusions. This would induce hydration of previous phases, allowing the formation of serpentine, chlorite and brucite. The results discussed here reveal the strong influence of the heat from basic intrusions within the sedimentary pile. Whereas in the offshore portion of the basin occur sills with up to 1000 m thickness, the understanding of pyrometamorphism might be useful for understanding and measuring the thermally affected rocks.

Pirometamorfismo em calcários da formação Jandaíra, bacia potiguar, nordeste do Brasil

The present study aims the characterization of thermally affected carbonate rocks from Jandaíra Formation in contact with Paleogene and Neogene basic intrusions in the region of the Pedro Avelino and Jandaíra municipalities (RN), northeastern Brazil. For this study, field, petrographic, x-ray diffraction, electron microprobe, and whole rock litogeochemistry data of carbonates were undertaken. The thermally unaffected limestones are classified like wackstones, grainstones and packstones. They may constitute carbonates grains of benthic foraminifera, echinoderm spines, ostracods, algae, corals, bivalves, gastropods, peloids and intraclasts. The porosities are classified like vug, intraparticle, interparticle, intercrystal and moldic types. The major minerals are calcite, ankerite and dolomite; the detrital are montmorillonite, pyrite, limonite, quartz and microcline. The thermally affected limestones are very coarse to very fine-grained and light to dark gray color. The fossiliferous components totally disappear, and the porosity tends to disappear. With the data obtained, it can be inferred that the carbonate protoliths would be calciferous to dolomitic limestones, both with small amount of clay minerals. Crystalline carbonates from dolomitic protolith have rhombohedral calcite and iron oxides / hydroxides, making the rocks much darker. The carbonates from calciferous protolith have a wide variation of grain size according to the recrystallization degree, increasing toward contact with the basic bodies. In this group, it was identified the minerals lizardite and spinel in weakly to moderately affected samples, and spinel and spurrite in strongly affected rocks, as well as calcite, that occur everywhere. The geological context (shallow level diabase intrusions), the crystallization of the pyrometamorphic minerals spurrite and olivine, and comparison with diagrams from the literature allow estimating temperatures and pressures around 1050-1200 °C and 0.5-1.0 kbar, respectively, for PTOTAL=PCO2. The post-intrusion cooling would have afforded the releasing of metasomatic / hydrothermal fluids, allowing the opening of the metamorphic system, with possible contribution of chemical elements from host units (sandstones, shales) and from basic intrusions. This would induce hydration of previous phases, allowing the formation of serpentine, chlorite and brucite. The results discussed here reveal the strong influence of the heat from basic intrusions within the sedimentary pile. Whereas in the offshore portion of the basin occur sills with up to 1000 m thickness, the understanding of pyrometamorphism might be useful for understanding and measuring the thermally affected rocks.

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Síntese e caracterização de espinélios a base de Cu, Fe e Cr para pigmentos cerâmicos

Inorganic pigment comprises a host lattice, which is part of the chromophore component (usually a transition metal cation) and possible components modifiers, which stabilize, add or restate the properties pigments. Among the materials with spinel, ferrites, and the chromite stand out, because they have broad technological importance in the area of materials, applicability, pigments, catalytic hydrogenation, thin film, ceramic tiles, among others. The present work, pigments containing CuFe2O4, CuCr2O4,e CuFeCrO4, were synthesized by a method that makes use of gelatin as organic precursor using their application to ceramic pigments. The pigments were characterized by X-ray diffraction (XRD), Infrared spectroscopy, scanning electron microscopy (SEM) spectroscopy in the UV-visible and Colorimetry. The results confirmed the feasibility of the synthetic route used, with respect to powders synthesized, there is the formation of spinel phase from 500°C, with an increase in crystallinity and the formation of other phases. The pigments were shown to be crystalline and the desired phases were obtained. The copper chromite have hues ranging from green to black according to the calcination temperature, while the copper chromite doped with iron had brownish. The ferrites showed copper color and darker brown to black, which may indicate an interesting factor because of the importance of black pigment

Síntese e caracterização de óxidos de cério e cobalto obtidos por gel-combustão e Pechini aplicados às reações de oxidação de n-hexano

Oxide type spinel AB2O4 presents structure adjusted for application in the automobile industry. The spinel of cobalt has many practical applications had its excellent physical and chemical properties such as catalyst in hydrocarbon oxidation reaction. The CeO2 has been used in many of these processes because it assigns to a material with excellent thermal resistance and mechanics, high capacity of oxygen stockage (OSC) among others properties. This work deals with the synthesis, characterization and catalytic application of spinel of cobalt and CeO2 with fluorita structure, obtained for method of Pechini and method of Gel-Combustion. The process of Pechini, the puff was obtained at 300 ºC for 2 h in air. In the process of Gel-Combustion the approximately at 350 ºC material was prepared and burnt for Pyrolysis, both had been calcined at 500 ºC, 700 ºC, 900 ºC and 1050 ºC for 2 h in air. The materials of the calcinations had been characterized by TG/DTA, electronic microscopy of sweepings (MEV), spectroscopy of absorption in the infra-red ray (FTIR) and diffraction of X-rays (DRX). The obtained material reaches the phase oxide at 450 oC for Pechini method and 500 °C for combustion method. The samples were submitted catalytic reaction of n-hexane on superficies of materials. The reactor function in molar ration of 0, 85 mol.h-1.g-1 and temperature of system was 450 °C. The sample obtained for Pechini and support in alumine of superficial area of 178,63 m2.g-1 calcined at 700 ºC, give results of catalytic conversions of 39 % and the sample obtained for method of gel-combustion and support in alumina of 150 mesh calcined at 500 ºC result 13 % of conversion. Both method were selective specie C1