Magnetic interactions and spin-reversal mechanism in ErMn1-xCoxO3-delta samples

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

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.

Síntese e caracterização de componentes nanoestruturados de células a combustível de óxidos sólidos

Perovskite-like ceramic materials present the general formula ABO3, where A is a rare earth element or an alkaline metal element, and B is a transition metal. These materials are strong candidates to assume the position of cathode in Solid Oxide Fuel Cells (SOFC), because they present thermal stability at elevated temperatures and interesting chemical and physical properties, such as superconductivity, dieletricity, magnetic resistivity, piezoelectricity, catalytic activity and electrocatalytic and optical properties. In this work the cathodes of Solid Oxide Fuel Cells with the perovskite structure of La1-xSrxMnO3 (x = 0.15, 0.22, 0.30) and the electrolyte composed of zirconia-stabilized-yttria were synthesized by the Pechini method. The obtained resins were thermal treatment at 300 ºC for 2h and the obtained precursors were characterized by thermal analysis by DTA and TG / DTG. The powder precursors were calcined at temperatures from 450 to 1350ºC and were analyzed using XRD, FTIR, laser granulometry, XRF, surface area measurement by BET and SEM methods. The pellets were sintered from the powder to the study of bulk density and thermal expansion

Nanoparticles of octakis [3-(3-amino-1,2,4-triazole)propyl] octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands, for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters. (C) 2007 Elsevier B.V. All rights reserved.

Carbon-coated SnO2 nanobelts and nanoparticles by single catalytic step

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Factors to Achieve Aesthetics in All-Ceramic Restorations

The demand for aesthetic restorations has increased during the last years. Dental ceramics are a successful alternative for some cases because of aesthetics and biocompatibility. Therefore, the aim of this literature review was to present the factors necessary to fabricate all-ceramic restorations with aesthetics similar to natural dentition. A search of English-language peer-review literature was completed using MEDLINE database from 1975 to 2009 including the keywords "aesthetic," "metal-free crown," "all-ceramic," and "color." It was observed that several factors influence aesthetics of all-ceramic restorations. Color scale, light source during color evaluation, characteristic of core material, color of supporting tooth, presence of root post, and type of cement are clinical factors that may influence color of the restorations. Laboratorial factors as technique for ceramic condensation, thickness, temperature, and number of firing cycles also influence the result of these crowns. Although several clinical and laboratorial factors influence aesthetics of all-ceramic restorations, the aesthetic success and longevity of these restorations depend on the integration with surrounding periodontal tissue.

Cementation of Prosthetic Restorations: From Conventional Cementation to Dental Bonding Concept

The cementation procedure of metal-free fixed partial dentures exhibits special characteristics about the porcelains and cementation agents, which turns the correct association between these materials necessary. Our purpose in this literature review was to point the main groups of cements associated to metal-free restoration and discuss about the advantages, disadvantages, and recommendations of each one. Our search was confined to the electronic databases PubMed and SciELO and to books about this matter. There are essentially 3 types of hard cement: conventional, resin, or a hybrid of the two. The metal-free restorations can be fixed with conventional or resin cements. The right choice of luting material is of vital importance to the longevity of dental restorative materials. Conventional cements are advantageous when good compressive straight, good film thickness, and water dissolution resistance are necessary. However, they need an ideal preparation, and they are not acid dissolution resistant. Conventional cements are indicated to porcelains that cannot be acid etched. Resin cements represent the choice to metal-free restoration cementation because they present better physical properties and aesthetic than conventional agents.

In Vitro Study of Fracture Load and Fracture Pattern of Ceramic Crowns: A Finite Element and Fractography Analysis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis and characterization of TiO2 chemically modified by Pd(II) 2-aminothiazole complex for the photocatalytic degradation of phenol

An investigation was made into the photocatalytic activity of in situ synthesized TiO2 chemically modified by Pd(II) 2-aminothiazole complex for phenol degradation at different pH values. At longer reaction times, the bare titania presented far poorer pbotoactivity than the modified catalysts in the entire range of pH studied. The catalyst complexed with Pd(II) was more efficient than the metal-free Pd, irrespective of pH and reaction time, suggesting that metal plays an important role. A cooperative mechanism is proposed, involving the possible photoactivation of both TiO2 and sensitizer. (C) 2007 Elsevier B.V. All rights reserved.

The Water Effect on the Kinetics of the Bovine Liver Catalase

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Flexural Strength of Glass-Infiltrated Zirconia/Alumina-Based Ceramics and Feldspathic Veneering Porcelains

Purpose: To compare the flexural strength of two glass-infiltrated high-strength ceramics and two veneering glass-ceramics.Materials and Methods: Four ceramic materials were tested: two glass-infiltrated high-strength ceramics used as framework in metal-free restorations [In-Ceram Zirconia IZ (Gr1) and In-Ceram Alumina IA (Gr2)], and two glass-ceramics used as veneering material in metal-free restorations [Vita VM7 (Gr3) and Vitadur-alpha (Gr4)]. Bar specimens (25 x 5 x 2 mm(3)) made from core ceramics, alumina, and zirconia/alumina composites were prepared and applied to a silicone mold, which rested on a base from a gypsum die material. The IZ and IA specimens were partially sintered in an In-Ceram furnace according to the firing cycle of each material, and then were infiltrated with a low-viscosity glass to yield bar specimens of high density and strength. The Vita VM7 and Vitadur-alpha specimens were made from veneering materials, by vibration of slurry porcelain powder and condensation into a two-part brass Teflon matrix (25 x 5 x 2 mm(3)). Excess water was removed with absorbent paper. The veneering ceramic specimens were then removed from the matrix and were fired as recommended by the manufacturer. Another ceramic application and sintering were performed to compensate the contraction of the feldspar ceramic. The bar specimens were then tested in a three-point bending test.Results: The core materials (Gr1: 436.1 +/- 54.8; Gr2: 419.4 +/- 83.8) presented significantly higher flexural strength (MPa) than the veneer ceramics (Gr3: 63.5 +/- 9.9; Gr4: 57.8 +/- 12.7).Conclusion: In-Ceram Alumina and Zirconia were similar statistically and more resistant than VM7 and Vitadur-alpha.

Mechanism for interplay between electron and ionic fluxes in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds

This paper develops a framework for the interpretation of ionic insertion/deinsertion reactions in an aqueous environment taking place in transition-metal hexacyanoferrates of the general formula KhFek3+ [Fe2+ (CN)(6)](l)center dot mH(2)O, also called Prussian Blue. Three different processes were fully separated in the electrochemistry of these films. It was clearly identified that one of these electrochemical processes involves the insertion/deinsertion of H3O+ (hydrated protons) through the channels of the KhFek3+ [Fe2+ (CN)(6)](l) center dot mH(2)O structure to reach the film electroneutrality during the electron transfer between Everitt's Salt and Prussian Blue. The other electrochemical processes involve K+ or H+ (proton) exchange through the water crystalline structure existing in the channels of the KhFek3+ [Fe2+(CN)(6)](l)center dot mH(2)O structure.

Redox Behavior of molybdenum and tungsten in phosphate glasses

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.

A química supramolecular de complexos pirazólicos

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