984 resultados para chemical evolution


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The metamorphosed banded iron formation from the Nogoli Metamorphic Complex of western Sierra de San Luis, Eastern Sierras Pampeanas of Argentina (Nogoli area, 32 degrees 55`S-66 degrees 15`W) is classified as an oxide facies iron formation of Algoma Type, with a tectonic setting possibly associated with an island arc or back arc, on the basis of field mapping, mineral and textural arrangements and whole rock geochemical features. The origin of banded iron formation is mainly related to chemical precipitation of hydrogenous sediments from seawater in oceanic environments. The primary chemical precipitate is a result of solutions that represent mixtures of seawater and hydrothermal fluids, with significant dilution by maficultramafic volcanic and siliciclastic materials. Multi-stage T(DM) model ages of 1670, 1854 and 1939 Ma and positive, mantle-like xi Nd((1502)) values of +3.8, +1.5 and +0.5 from the banded iron formation are around the range of those mafic to ultramafic meta-volcanic rocks of Nogoli Metamorphic Complex, which are between 1679 and 1765 Ma and +2.64 and +3.68, respectively. This Sm and Nd isotopic connection suggests a close genetic relationship between ferruginous and mafic-ultramafic meta-volcanic rocks, as part of the same island arc or back arc setting. A previous Sm-Nd whole rock isochron of similar to 1.5 Ga performed on mafic-ultramafic meta-volcanic rocks led to the interpretation that chemical sedimentation as old as Mesoproterozoic is possible for the banded iron formation. A clockwise P-T path can be inferred for the regional metamorphic evolution of the banded iron formation, with three distinctive trajectories: (1) Relict prograde M(1)-M(3) segment with gradual P and T increase from greenschist facies at M(1) to amphibolite facies at M(3). (2) Peak P-T conditions at high amphibolite-low granulite facies during M(4). (3) Retrograde counterpart of M(4), that returns from amphibolite facies and stabilizes at greenschist facies during M(5). Each trajectory may be regarded as produced by different tectonic events related to the Pampean? (1) and the Famatinian (2 and 3) orogenies, during the Early to Middle Paleozoic. The Nogoli Metamorphic Complex is interpreted as part of a greenstone belt within the large Meso- to Neoproterozoic Pampean Terrane of the Eastern Sierras Pampeanas of Argentina. (C) 2009 Elsevier Ltd. All rights reserved.

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This article reports a study of the thermal stability and morphological changes in tin oxide nanobelts grown in the orthorhombic SnO phase. The nanobelts were heat-treated in a differential scanning calorimetry (DSC) furnace at 800 degrees C for I It in argon, oxygen, or synthetic air atmospheres. The samples were then characterized by DSC, X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and high resolution field emission scanning electron microscopy (FE-SEM). The results confirmed that the orthorhombic SnO phase is thermodynamically unstable, causing the belts to transform into the SnO2 phase when heat-treated. During the phase transition, if oxygen is available in the furnace atmosphere, nanofibers grow at the edge of nanobelts at about 50 degrees of the belts' growth direction, while particles grow on the belt surface in the absence of oxygen. Although the decomposition process reduces the nanobelt cell volume by 22%, most belts remain monocrystalline after the heat treatment. The results confirm that phase transition is a decomposition process, which explains the morphological changes in the belts based on metallic tin generated in the process.

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

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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A lattice model is used to study mutations and compacting effects on protein folding rates and folding temperature. In the context of protein evolution, we address the question regarding the best scenario for a polypeptide chain to fold: either a fast nonspecific collapse followed by a slow rearrangement to form the native structure or a specific collapse from the unfolded state with the simultaneous formation of the native state. This question is investigated for optimized sequences, whose native state has no frustrated contacts between monomers, and also for mutated sequences, whose native state has some degree of frustration. It is found that the best scenario for folding may depend on the amount of frustration of the native structure. The implication of this result on protein evolution is discussed. (c) 2006 American Institute of Physics.

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Polycrystalline BaWO4 and PbWO4 thin films having a tetragonal scheelite structure were prepared at different temperatures. Soluble precursors such as barium carbonate, lead acetate trihydrate and tungstic acid, as starting materials, were mixed in aqueous solution. The thin films were deposited on silicon, platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and specular reflectance infrared Fourier transform spectroscopy, respectively. Nucleation stages and surface morphology evolution of thin films on silicon substrates have been studied by atomic force microscopy. XRD characterization of these films showed that BaWO4 and PbWO4 phase crystallize at 500 degreesC from an inorganic amorphous phase. FTIR spectra revealed the complete decomposition of the organic ligands at 500 degreesC and the appearance of two sharp and intense bands between 1000 and 600 cm(-1) assigned to vibrations of the antisymmetric stretches resulting from the high crystallinity of both thin films. The optical properties were also studied. It was found that BaWO4 and PbWO4 thin films have Eg = 5.78 eV and 4.20 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of BaWO4 and PbWO4 thin films. (C) 2003 Elsevier Ltd. All rights reserved.

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Stoichiometric CaWO4 and SrWO4 thin films were synthesized using a chemical solution processing, the so-called polymeric precursor method. In this soft chemical method, soluble precursors such as strontium carbonate, calcium carbonate and tungstic acid, as starting materials, were mixed in an aqueous solution. The thin films were deposited on glass substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Nucleation stages and surface morphology evolution of the thin films on glass substrates were studied by atomic force microscopy. The films nucleate at 300 degreesC, after the coalescence of small nuclei into larger grains yielding a homogeneous dense surface. XRD characterization of these films showed that the CaWO4 and SrWO4 phases crystallize at 400 degreesC from an inorganic amorphous phase. No intermediate crystalline phase was identified. The optical properties were also studied. It was found that CaWO4 and SrWO4 thin films have an optical band gap, E-gap=5.27 and 5.78 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity confirmed that this soft solution processing provides an inexpensive and environmentally friendly route for the preparation of CaWO4 and SrWO4 thin films. (C) 2003 Elsevier B.V. All rights reserved.

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Detailed room temperature micro-Raman scattering, X-ray diffraction, atomic force microscopy and specular reflectance infrared Fourier transform spectroscopy studies were carried out on soft chemical by processed Pb1-xBaxTiO3 thin films. The micro-Raman spectra pointed the existence of a stable tetragonal ferroelectric phase in the entire composition range (0 < x <= 1). The infrared reflectance spectra showed that the frequency of several peaks decreases as the Ba2+ concentration increases. These features are correlated to a decrease in the tetragonal distortion of the TiO6 octahedra as the Ba2+ concentration increases. Furthermore, as x increases from 0.70 to 1.0, the Raman spectrum shows an evolution towards the well-known Raman spectrum of the tetragonal BaTiO3. Therefore, we demonstrated that the combination of solid solution PbTiO3-BaTiO3 with a grain size in the order of 30-40 nm supports the tetragonal ferroelectric phase at room temperature. (C) 2007 Elsevier B.V. All rights reserved.

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This paper reviews the influence of particle size distribution, agglomerates, rearrangement, sintering atmospheres and impurities on the pore evolution of some commonly studied oxides. These factors largely affect sintering mechanisms due to modifications of diffusion coefficients or evaporation-condensation. Very broad particle size distribution leads to grain growth and agglomerates densify first. Rearrangement of particles due to neck asymmetry mainly in the early stage of sintering is responsible for a high rate of densification in the first minutes of sintering by collapse of large pores. Sintering atmospheres play an important role in both densification and pore evolution. The chemical interaction of water molecules with several oxides like MgO, ZnO and SnO2 largely affects surface diffusion. As a consequence, there is an increase in the rates of pore growth and densification for MgO and ZnO and in the rate of pore growth for SnO2. Carbon dioxide does not affect the rate of sintering of MgO but greatly affects both rates of pore growth and densification of ZnO. Oxygen concentration in the atmosphere can especially affect semiconductor oxides but significantly affects the rate of pore growth of SnO2. Impurities like chlorine ions increase the rate of pore growth in MgO due to evaporation of HCl and Mg(OH)Cl, increasing the rate of densification and particle cuboidization. CuO promotes densification in SnO2, and is more effective in dry air. The rate of densification decrease and pore widening are promoted in argon. An inert atmosphere favors SnO2 evaporation due to reduction of CuO. © 1990.

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Zinc oxide can be obtained by thermal decomposition of hydrozincite, a topochemical reaction. This work reports the relation between zinc oxide morphology and the precursor zinc hydroxide carbonate precipitation time. The morphological evolution was monitored by SEM, IR and XRD. Zinc oxide obtained from initially precipitated hydrozincite consists of porous spherical aggregates and shows a single Zn-O IR vibrational band. At longer periods of precipitation time the aggregates were transformed into spherulitic-shaped zinc oxide particles showing the Zn-O split vibrational band. X-ray patterns show that the hexagonal zinc oxide phase is substantially increased as a function of hydrozincite precipitation time. © 1997 Elsevier Science S.A.

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The structural evolution on the drying of wet sonogels of silica with the liquid phase exchanged by acetone, obtained from tetraethoxisilane sonohydrolysis, was studied in situ by small-angle x-ray scattering (SAXS). The periods associated to the structural evolution as determined by SAXS are in agreement with those classical ones established on basis of the features of the evaporation rate of the liquid phase in the obtaining of xerogels. The wet gel can be described as formed by primary particles (microclusters), with characteristic length a ∼ 0.67 nm and surface which is fractal, linking together to form mass fractal structures with mass fractal dimension D=2.24 in a length scale ξ∼6.7 nm. As the network collapses while the liquid/vapor meniscus is kept out of the gel volume, the mass fractal structure becomes more compacted by increasing D and decreasing ξ, with smoothing of the fractal surface of the microclusters. The time evolution of the density of the wet gels was evaluated exclusively from the SAXS parameters ξ, D, and a. The final dried acetone-exchanged gel presents Porod's inhomogeneity length of about 2.8 nm and apparently exhibits an interesting singularity D →3, as determined by the mass fractal modeling used to fit the SAXS intensity data for the obtaining of the parameters ξ and D.

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Cachaça is a traditional and popular Brazilian drink obtained by distilling fermented sugar cane juice. Among the steps involved in its production, natural aging in wood containers for a certain period of time can lead to alterations in the chemical composition, aroma, flavor and color of the beverage. The present work sought to determine the concentration of phenolic compounds after different periods of aging of the cachaça in an oak (Quercus sp.) barrel. Periodic collections during the aging period were performed, and thirteen selected phenolic compounds were determined by high performance liquid chromatography with a diode-array detector (HPLC-DAD). A progressive increase in the concentration of the compounds analyzed was observed, with syringaldehyde and gallic acid as the compounds encountered in the highest concentration.

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Neste trabalho realizou-se a caracterização química de fragmentos de artefatos cerâmicos encontrados em sítios arqueológicos com terra preta no Baixo Amazonas (Cachoeira-Porteira, Pará, Brasil), representativos da cultura Konduri (de 900 a 400 anos AP). Esses fragmentos são constituídos de SiO2, Al2O3, Fe2O3, Na2O e P2O5, sendo que SiO2 e Al2O3, juntos, perfazem mais de 80 % em peso. Os teores de P2O,5 são relativamente elevados (2,37 % em média) sob a forma de (Al,Fe)-fosfatos, incomuns em cerâmicas vermelhas primitivas, mas encontrados em algumas cerâmicas arqueológicas egípcias e romanas. As concentrações dos elementos traços são comparáveis ou mesmo inferiores ao nível crustal, embora a composição total seja próxima a mesma. A composição química (exceto P2O5) em conjunto com os dados mineralógicos e texturais indicam material saprolítico derivado de rochas ígneas félsicas ou rochas sedimentares como matéria-prima das cerâmicas. Os teores de K, Ca e Na mostram que os feldspatos e fragmentos de rochas foram adicionados ao material argiloso, como sugerido pela mineralogia. Os altos teores de sílica respondem pela presença de cauixi, cariapé e/ou areias quartzosas. Fósforo deve ter sido incorporadoà matriz argilosa da cerâmica, quando do cozimento de alimentos nos vasos cerâmicos, e ainda, em parte, durante a formação do perfil de solo tipo ABE sobre Latossolos Amarelos. A matéria prima e os temperos (cauixi, cariapé, rochas trituradas e fragmentos de vasos cerâmicos descartados) encontram-se disponíveis próximos aos sítios até a atualidade, e, portanto foram a área fonte dos mesmos para a confecção dos artefatos cerâmicos.

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