60 resultados para Synthesis conditions

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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

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A polymeric precursor method based on the Pechini process was successfully used to synthesize zirconia-12 mol% ceria ceramic powders, the influence of the main process variables (citric acid-ethylene glycol ratio, citric acid-total oxides ratio and calcination temperature) on phase formation and powder morphology (surface area and crystallite size) were investigated. The thermal decomposition behavior of the precursor is presented. X-ray diffraction (XRD) patterns of powders revealed a crystalline tetragonal zirconia single-phase, with crystallite diameter ranging from 6 to 15 nm. The BET surface areas were relatively high, reaching 95 m(2) g(-1) Nitrogen adsorption/desorption on the powders suggested that nonaggregated powders could be attained, depending on the synthesis conditions. Copyright (C) 1999 John Wiley & Sons, Ltd.

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The understanding and control of ferromagnetism in diluted magnetic semiconducting oxides (DMO) is a special challenge in solid-state physics and materials science due to its impact in magneto-optical devices and spintronics. Several studies and mechanisms have been proposed to explain intrinsic ferromagnetism in DMO compounds since the theoretical prediction of room-temperature ferromagnetism. However, genuine and intrinsic ferromagnetism in 3d-transition metal-doped n-type ZnO semiconductors is still a controversial issue. Furthermore, for DMO nanoparticles, some special physical and chemical effects may also play a role. In this contribution, structural and magnetic properties of sonochemically prepared cobalt-doped ZnO nanoparticles were investigated. A set of ZnO samples was prepared varying cobalt molar concentration and time of ultrasonic exposure. The obtained results showed that single phase samples can be obtained by the sonochemical method. However, cobalt nanoclusters can be detected depending on synthesis conditions. Magnetic measurements indicated a possible ferromagnetic response, associated to defects and cobalt substitutions at the zinc site by cobalt. However, ferromagnetism is depleted at higher magnetic fields. Also, an antiferromagnetic response is detected due to cobalt oxide cluster at high cobalt molar concentrations. © 2012 Springer Science+Business Media, LLC.

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

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In this work, carbon-supported Pt70Co30 nanoparticles were prepared by a polyol process using a long-chain diol as reducer (hexadecanediol) and oleic acid and oleylamine as stabilizers. Depending on the synthesis conditions, Pt70Co30/C nanocatalysts with very small particle size (1.9 +/- 0.2 nm) and narrow distribution homogeneously dispersed on the carbon support and having a high degree of alloying without the need of thermal treatments were obtained. The as-prepared catalyst presents an excellent performance as proton exchange membrane fuel cells (PEMFC) cathode material. In terms of mass activity (MA), the Pt70Co30/C electrocatalysts produced single fuel cell polarization response superior to that of commercial catalyst. To analyze alloying effects, the result of thermal treatment at low temperatures (200-400 degrees C) was also evaluated and an increase of average crystallite size and a lower degree of alloying, probably associated to cobalt oxidation, were evidenced.

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In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO(3) with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.

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Hybrid transparent and flexible siloxane-polypropyleneglycol (PPG) materials with covalent bonds between the inorganic (siloxane) and organic (polymeric) phases were prepared by sol-gel process. In order to improve the quality of the mechanical properties of these materials, different amounts of methyltriethoxysilane (MTES) were added to the initial sol. The effect of MTES addition on the structure of the composites was studied by Small-Angle X-Ray Scattering (SAXS) and Si-29 Nuclear Magnetic Resonance (Si-29 NMR). In absence of MTES, SAXS spectra exhibit a peak that is assigned to spatial correlation due to short range order between the siloxane clusters embedded in the polymeric phase. The experimental results indicate that, for low MTES concentrations ([MTES]/[O] less than or equal to 0.8, O: ether-type oxygen of PPG), the silicon species resulting from hydrolysis and condensation of MTES fill the open spaces between polymeric chains, interacting with the ether-type oxygens. For larger MTES content ([MTES]/[O] greater than or equal to 0.8), the number of free ether-type oxygen sites avalaible for reaction with such silicon species is not large enough. Consequently, a fraction of silicon species resulting from MTES addition graft to siloxane clusters formed by hydrolysis and condensation of the hybrid precursor. For all MTES concentrations the condensation degree of the siloxane phase, determined from Si-29 NMR spectroscopy, is high (> 69%), as expected under neutral pH synthesis conditions.

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The thermoreversible sol-gel transition is well-known in biological and organic polymeric systems but has not been reported for inorganic systems. In this paper we put in evidence a thermoreversible sol-gel transition for zirconyl chloride aqueous solutions modified by sulfuric acid in the ratio 3:1 Zr:SO4. The synthesis conditions are detailed and a variety of experimental techniques (turbidimetry, dynamic rheology, and EXAFS) have been employed for investigating the thermal reversibility and the chemical structure of this new material. Turbidimetric measurements performed for solutions containing different concentrations of precursor have evidenced that the sol-gel transformation temperature increases from 50 to 80 degrees C as the concentration of zirconyl chloride decreases from 0.22 to 0.018 mol L-1. A more detailed study has been done for the sample with [Zr] = 0.156 mol L-1, in which the sol-gel-sol transformation has been repeated several times by a cyclic variation of the temperature. The mechanical properties of this sample, evaluated by measuring the storage and the loss moduli, show a change from liquid like to viscoelastic to elastic behavior during the sol-gel transition and vice versa during the gel-sol one. In situ EXAFS measurements performed at the Zr K-edge show that no change of the local order around Zr occurs during the sol-gel-sol transition, in agreement with the concept of physical gel formation. We have proposed for the structure of the precursor an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded in surface by complexing sulfate ligands, the sulfate groups act as a protective layer, playing a key role in the linking propagation among primary particles during sol-gel-sol transition.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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We report the structural and magnetic properties of Co2MnO 4, partially substituted by Bi at the octahedral site. Bismuth enhances ferromagnetism due to a decrease of the Co2+-Co2+ antiferromagnetic interactions and an increase of the Mn3+-Mn 4+ exchanges. Spurious phases (magnetic and/or nonmagnetic oxides) can easily form because of the large differences between the ionic radii of Bi3+ and Co3+, hiding or altering the intrinsic physical properties of the main BixCo2-xMnO4 phase. An easy way to eliminate the secondary phases is using acid reagents. Short-time etching of Bi0.1Co1.9MnO4 using nitric acid was successfully used, keeping most of the properties of the initial compound, with no alteration of the crystallographic structure. Final stoichiometry was respected (∼Bi0.08Co1.82MnO4), meaning that the material after etching definitely contains bismuth elements in its structure and the observed properties are intrinsic to the oxide spinel. Additional experiments were performed as a function of the synthesis conditions, showing that an optimal pH value of 7 allowed the best magnetic response of the non-doped material. © 2013 Elsevier B.V. All rights reserved.

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Pós-graduação em Ciência e Tecnologia de Materiais - FC