Microeletrodos: I. Construção e caracterização

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

Eletrodo modificado em filme de paládio para a determinação voltamétrica de fosfito

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

Microeletrodos: II. Caracterização eletroquímica

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

Síntese e reatividade de complexos platina-trifenilestibina: uma revisão bibliográfica

This article deals with synthesis and reactivity of complexes with triphenylstibine (SbPh3) as the ligand. A comparative study of analogous complexes of triphenylphosphine (PPh3) and triphenylarsine (AsPh3) with platinum in the oxidation states zero, two and four is included. The bibliographic revision includes publications since 1936, when the first Pt(II) complex with triphenylstibine was described.

Preparação de LiNbO3 e LiNbO3:Eu3+ pelo método dos precursores poliméricos

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

Sintering of tin oxide and its applications in electronics and processing of high purity optical glasses

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

Cerâmicas eletrônicas à base de SnO2 e TiO2

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

Filmes finos de SrBi2Ta2O9 processados em forno microondas

Filmes finos de SrBi2Ta2O9 foram depositados em substratos de Pt/Ti/SiO2/Si e, pela primeira vez, sinterizados em forno microondas doméstico. Os padrões de difração de raios X mostraram que os filmes são policristalinos. O processamento por microondas permite utilizar baixa temperatura na síntese e obter filmes com boas propriedades elétricas. Ensaios de microscopia eletrônica de varredura (MEV) e de Força Atômica (MFA) revelam boa aderência entre filme e substrato, com microestrutura de superfície apresentando grãos finos e esféricos e rugosidade de 4,7 nm. A constante dielétrica e o fator de dissipação, para freqüência de 100 KHz, à temperatura ambiente, foram de 77 e 0,04, respectivamente. A polarização remanescente (2Pr) e o campo coercitivo (Ec) foram 1,04 miC/cm² e 33 kV/cm. O comportamento da densidade de corrente de fuga revela três mecanismos de condução: linear, ôhmico e outro mecanismo que pode ser atribuído à corrente de Schottky. Dos padrões de DRX, análises das imagens por MEV e topografia de superfície por MFA observa-se que 10 min de tratamento térmico a 550 ºC, em forno microondas, é tempo suficiente para se obter a cristalização do filme.

The Ni-Cu-PGE sulfide ores of the komatiite-hosted Fortaleza de Minas deposit, Brazil: Evidence of hydrothermal remobilization

The Fortaleza de Minas Ni-Cu-PGE sulfide deposit is hosted by Archean komatiitic rocks of the Morro do Ferro greenstone belt, near the southwestern margin of the Sa (aFrancisco) over tildeo Francisco craton, Minas Gerais state, Brazil. The deposit contains 6 million tonnes of ore with an average grade of 2.2 wt% Ni, 0.4% Cu, 0.05% Co and 1.2 ppm PGE+Au, and comprises (i) a main orebody, which is metamorphosed, deformed and transposed along a regional shear zone, consisting mainly of disseminated, brecciated and stringer sulfide ores that are interpreted to be of early magmatic origin, and (ii) PGE-rich discordant veins that are hosted in N-S- and NE-SW-trending late faults that cross-cut the main orebody. The discordant PGE-rich ore (up to 4 ppm total PGE) is characterized by thin, discontinuous and irregular veins and lenses of massive sulfides hosted by serpentinite and talc schist, and is relatively undeformed if compared with the early types of ore. It is composed mainly of pyrrhotite, pentlandite, chalcopyrite, magnetite, carbonates, and amphiboles, with minor cobaltite-gersdorffite, sphalerite, ilmenite, and quartz, and rarely maucherite (Ni11Asg), tellurides and platinum-group minerals (PGM). Omeeite, irarsite, sperrylite, and Ni-bearing merenskyite are the main PGM, followed by minor amounts of testibiopalladite and an unknown phase containing Ru, Te, and As. The PGM occur either included in, or at the margins of, sulfides, sulfarsenides, silicates and oxides, or filling fractures in pyrrhotite, pentlandite, and chalcopyrite, suggesting that they started to precipitate with these minerals and continued to precipitate after the sulfides were formed. The mantle-normalized metal distribution of the two samples of discordant veins shows distinct patterns: one richer in Ni-Pd-Ir-Rh-Ru-Os and another with higher amounts of Cu-Pt-Bi. Both are strongly depleted in Cr if compared with the metamorphosed magmatic ore of this deposit, which follows the general Kambalda-type magmatic trend. on the basis of structural, mineralogical and geochemical evidence, we propose that the PGE-rich discordant ore may have formed by remobilization of metals from the deformed, metamorphosed magmatic orebody (which shows a depleted pattern in these elements) by reduced (pyrrhotite - pentlandite - pyrite are stable), neutral to alkaline and carbonic fluids (carbonate-stable). The PGE may have been transported as bisulfide complexes, and precipitated as tellurides (mainly Pd) and arsenides (Pt, Rh, Ru, Os, Ir) in the late N-S and NE-SW-trending faults owing to a decrease in the activity of S caused by the precipitation of sulfides in the veins.

Structure and crystallization of lanthanum fluorozirconate glasses

Glasses with compositions (1-x)ZrF4-xLnF(3), 0.2 less than or equal to x less than or equal to 0.4 and Ln = La or La, Eu have been synthesized and investigated using differential scanning calorimetry, X-ray diffraction, Raman scattering and Eu3+ optical spectroscopy. Single-phase polycrystalline lanthanum fluorozirconates with Zr/Ln ratio equal to 1, 2 and 3 have been investigated using the same techniques for comparison. The crystalline phases LnZrF(7), LnZr(2)F(11), LT-LnZr(3)F(15) (orthorhombic) and HT-LnZr(3)F(15) (trigonal) have been characterized in the recrystallized glasses and in samples spontaneously crystallized from the melt. Another phase has also been observed but remains undefined, the Raman scattering spectra of the vitreous samples are related to the vibration modes of [ZrF6] isolated octahedra, and of [ZrF7] and [ZrF8] structural units with bridging fluorine ions. The Eu3+ fluorescence data are related to a predominant local environment of the lanthanide ions in the glasses similar to that of the lanthanide in LnZrF(7).

Stress induced ordering due interstitials in Nb-4.7 at.%Ta

The presence of interstitial elements in metals cause strong changes in their physical, chemical or mechanical properties. These interstitial impurities interact with the metallic matrix atoms by a relaxation process known as stress induced ordering. Relaxation processes give rise to a peak in the internal friction spectrum, known as Snock effect. The presence of substitutional solutes has a strong influence on Snoek effect, particularly if the substitutional solute element is the one, which interacts with the interstitial element. Anelastic spectroscopy measurements provide information of the behavior of these impurities in the metallic matrix. In this paper, polycrystalline samples of Nb-4.7 at.%Ta alloy have been analyzed in the as-received condition. Measurements of anelastic spectroscopy were carried out using an inverted torsion pendulum, operating with frequency of 2.0-30.0 Hz and in a temperature range between 300 and 700 K. It was observed the presence of a relaxation structure that have been attributed to stress induced ordering due to interstitial atoms around atoms of the metallic matrix. The relaxation structure have been decomposed in its constituent peaks, what it allowed to identify the following relaxation processes: Ta-O, Nb-O and Nb-N. (c) 2005 Elsevier B.V. All rights reserved.

Development and testing of anode-supported solid oxide fuel cells with slurry-coated electrolyte and cathode

A laboratory setup was designed and put into operation for the development of solid oxide fuel cells (SOFCs). The whole project consisted of the preparation of the component materials: anode, cathode and electrolyte, and the buildup of a hydrogen leaking-free sample chamber with platinum leads and current collectors for measuring the electrochemical properties of single SOFCs. Several anode-supported single SOFCs of the type (ZrO(2):Y(2)O(3)+NiO) thick anode/(ZrO(2):Y(2)O(3)) thin electrolyte/(La(0.65)Sr(0.35)MnO(3)+ZrO(2):Y(2)O(3)) thin cathode have been prepared and tested at 700 and 800 degrees C after in situ H(2) anode reduction. The main results show that the slurry-coating method resulted in single-cells with good reproducibility and reasonable performance, suggesting that this method can be considered for fabrication of SOFCs. (c) 2005 Elsevier B.V. All rights reserved.

SrBi2Nb2O9 thin films crystallized using a low power microwave oven

SrBi2Nb2O9 thin films were produced by the polymeric precursor method using an aqueous solution. The crystallization of the films was carried out using a domestic microwave oven by means of a SiC susceptor in order to absorb the microwave energy and rapidly transfer the heat to the film. Low microwave power and short time have been used. The films obtained are well-adhered, homogeneous and with good specularity, even when treated at 600 degreesC for 10 min. The microstructure and the structure of the films can be tuned by adjusting the crystallization conditions. Depending on the direction of the heat flux it is possible to obtain preferential oriented or polycrystalline films in the microwave oven for 10 min. The microstructure presented a polycrystalline nature with spheroid small mean grain size when the susceptor is placed above the substrate. When the susceptor is placed below the substrate, the films presented platelet grains with mean grain size around 250 nm and a 001 orientation. For comparison, films were also prepared by the conventional method at 700 degreesC for 2 h. (C) 2003 Elsevier Ltd. All rights reserved.

THE ELECTROCHEMICAL OXIDATION OF (BENZYLIDENEACETONE)DICARBONYL(PHOSPHINE)IRON(0) AND (BENZYLIDENEACETONE)DICARBONYL(PHOSPHITE)IRON(0) COMPLEXES IN DIMETHYL FORMAMIDE

The electrochemical oxidation of (benzylideneacetone)dicarbonyl(phosphine)iron(0) and benzylideneacetone)dicarbonyl(phosphite)iron(0) complexes was studied by cyclic voltammetry and controlled potential electrolysis in 0.5 M NaClO4 (dimethyl formamide). The results suggest that the electrode process involves a complicated mechanism, the species formed in the first oxidation step being highly unstable and its decomposition producing free benzylideneacetone, free phosphine or phosphite, solvated iron(II) species and carbon monoxide which adsorbs on the platinum electrode. A linear relationship between E(p/2)ox and the ligand parameter P(L) was obtained with E(s) = 0.41 V and beta = 0.964, where E(s) and beta-denote electron-richness and polarizability of the metal centre, respectively.

Electrocatalysis of hydrogen evolution reaction on Pt electrode surface-modified by S-2 chemisorption

Kinetic studies of hydrogen evolution reaction (HER) at the surface of Pt in alkaline conditions, reported in this paper, show that electrocatalytic activity is enhanced after adsorption of S-2 ions. EIS and steady-state polarization curve data pointed to an undoubted improvement in performance with the Pt-S cathode that was attributed to higher adsorbed hydrogen coverage. Experimental findings suggested an increase in the electronic density of the modified surface sites that may strengthen the interaction between H2O and the adsorption site and, consequently, accelerates the Volmer step. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.