Botryoidal platinum, palladium and potarite from the Bom Sucesso stream, Minas Gerais, Brazil: Compositional zoning and origin

Platinum-Pd nuggets from the Born Sucesso stream alluvium Minas Gerais, Brazil. have been investigated by electron-probe microanalysis. The nuggets attain 1 mm in maximum dimension and have a botryoidal habit, with pronounced compositional core-to-margin zoning of internal structures, Although there is a wide variation in internal morphology and individual zones vary markedly in thickness (<1-100 mum), a typical composite arborescent nugget comprises a broad irregular core region of massive auriferous Pd-Hg alloy (potarite delta-PdHg) or cavity space + relict potarite enclosed by a narrow zone of platiniferous, palladium or alloy of near Pt50Pd50 composition, and is progressively oscillatory zoned by palladian platinum, with growth eventually enveloping the whole botryoidal colony, to a narrow rim of palladian platinum or pure platinum. Other nuggets comprise an arborescent to dendritic core of auriferous potarite, a broad internal zone of either pure platinum or palladian platinum, and a narrow rim of platinum, the mineral palladium contains up to about 65 at.% Pd; this is the first detailed modern confirmation of palladium in its type locality. Auriferous potarite ranges in composition from similar toPd(3)Hg(2) to near Pd(Hg,Au). The origin of these nuggets remains unclear, but their mineralogy is broadly equivalent to that of palladian gold. potarite and platinum in alluvial sediments and overburden from Devon, England, which are considered to be detrital, and their platinum-group-clement geochemistry is consistent with precipitation from hydrothermal fluids. We suggest that the Bom Sucesso nuggets resulted from high-level episodic hydrothermal alteration of mafic and ultramafic rocks within the drainage basin, with the remobilized Pt and Pd precipitated in open spaces in the enclosing metaquartzites.

Investigations on the stability of plasma modified silicone surfaces

In this work it was investigated the effect of the exposure to different plasmas on the wettability of silicone samples. We have observed that oxygen. argon, and hydrogen glow discharges are quite effective in reducing the water contact angle of such polymer. However, indifferently to efficiency of the treatment, practically all the modified surfaces recovered great part of their original hydrophobicity. We have investigated this hydrophobic recovery using surface energy measurements and theoretical simulations based on the exponential decay of the population of polar groups on the surface. According to our results such recovery can be attributed to the decrease of polar species at the interface water-polymer surface.

Synthesis and characterization of a new platinum(II) complex with L-mimosine

Synthesis and characterization of a new Pt(II)-mimosine complex are described. Elemental, mass spectrometry and thermal analyses for the complex are consistent with the formula [PtCl2(C8H10N2O4)]center dot 1.5H(2)O. C-13 NMR, N-15 NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and O atoms in a square-planar geometry. The final residue after thermal treatment was identified as metallic Pt. The complex is soluble in dimethylsulfoxide.

Characterization of electrodes chemically modified with Mn(III) porphyrin/polypyrrole films as catalytic surfaces for an azo dye

In this study we describe the electrochemical behavior of 5,10,15,20-tetrakis(2'-aminophenylporphyrin)manganese(III) chloride supported on a glassy carbon electrode, as well as the electrochemical preparation and characterization of thin films based on pyrrole-3-carboxylic acid. The electrocatalytic action of the electrode modified with the Mn(III) porphyrin toward an azo dye was tested, and the characteristic strong interaction between the incorporated metalloporphyrin and RR120 dye was verified. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines.

Theoretical study of MgO(001) surfaces: Pure, doped with Fe, Ca, and Al, and with and without adsorbed water

Ab initio calculations of large cluster models have been performed in order to study water adsorption at the five-fold coordinated adsorption site on pure Mg(001) and MgO(001) surfaces doped with Fe, Ca, and Al. The geometric parameters of the adsorbed water molecule have been optimized preparatory to analysis of binding energies, charge transfer, preferential sites of interaction, and bonding distances. We have used Mulliken population analysis methods in order to analyze charge distributions and the direction of charge transfer. We have also investigated energy gaps, HOMO energies, and SCF orbital energies as well as the acid-base properties of our cluster model. Numerical results are compared, where possible, with experiment and interpreted in the framework of various analytical models. (C) 2001 John Wiley & Sons, Inc.

Crystal nucleation kinetics of a metastable phase on cordierite glass surfaces

The crystal nucleation rates of a metastable phase (chi) on the surface of a near stoichiometric cordierite glass were determined for temperatures between 839 and 910 degrees C (T-g similar to 800 degrees C). The surface nucleation kinetics of that phase on our glass, as well as on a stoichiometric glass (2 MgO-2Al(2)O(3)-5SiO(2)) studied by other authors, were analysed in terms of the classical nucleation theory; for the first time. It was shown that the effective interfacial energy for surface nucleation is substantially lower than that for homogeneous volume nucleation in silicate glasses, vindicating the assumption of heterogeneous nucleation on free glass surfaces. The average wetting angle between the nucleating crystals and the active solid particles was estimated to be around 46 degrees C. The pre-exponential constant was several orders of magnitude higher than the theoretical values as found for volume homogeneous nucleation in oxide glasses.

Changes of physical properties of glass surfaces exposed to KNO3 vapors

Modifications of glass surfaces were studied after exposure of samples to an atmosphere resulting from the decomposition of molten KNO3. The diffusion coefficient of K+ ions migrating into the surfaces of float glass and synthesized glasses doped with up to 5 wt% SnO2 was calculated by the Boltzmann-Matano technique. The Vickers hardness and the refractive index increase with exposure time. Infrared spectra show that the migration of K+ is responsible for an increase in the number of non-bridging oxygens in the exposed samples. The spectra of the synthesized glasses present evidences that their surfaces undergo crystallization during the exposure. All results lead to the conclusion that the presence of tin in the glasses hinders the diffusion of K+ ions, thus affecting the Vickers hardness, the refractive index and the infrared spectra. It is shown that the exposure method can be used as an alternative process to promote the K+ migration into glass surfaces. (c) 2006 Elsevier B.V. All rights reserved.

Crystal structure and infrared analysis of a new trinuclear platinum(II) complex with L-cysteine

A new trinuclear platinum(II) complex with cysteine of composition [Pt(C3H6NO2S)Cl](3)center dot(C2H6SO)(3) was obtained and structurally characterized by X-ray diffraction and infrared analysis. The compound crystallizes in the trigonal system, space group R3, and is described in a hexagonal cell with a=17.739(1), c=9.531(1) and Z=3. Cysteine is coordinated to Pt(II) through the nitrogen and sulphur atoms. Each cysteine sulphur bridges between two metal atoms. A square planar coordination sphere of platinum is completed by a chlorine atom. The complex is soluble in dimethyl sulfoxide.

Validity and reproducibility of a laser fluorescence system for detecting the activity of white-spot lesions on free smooth surfaces in vivo

The aim of the study was to determine the reproducibility and validity of DIAGNOdent in detecting active and arrested caries lesions on free smooth surfaces. Volunteers were selected from state schools of Piracicaba, São Paulo, Brazil. Overall, 220 lesions were clinically examined. Two specially trained ('calibrated') examiners performed both clinical and laser evaluations independently, and after a 1-week interval, the examinations were repeated, the intra-examiner agreement for the laser evaluation was substantial (kappa(ex1) = 0.79, kappa(ex2) = 0.71). There was almost perfect agreement between the two examiners for the clinical examination (kappa(ex1) = 0.95, kappa(ex2) = 0.85). The inter-examiner agreement showed substantial reproducibility (kappa = 0.77) for the laser examination and almost perfect agreement (kappa = 0.85) for the clinical evaluation. The validation criterion was the clinical examination of white spots, recorded as active or arrested. The sensitivity was 0.72 and the specificity was 0.73, which indicates that the DIAGNOdent was a good auxiliary method for detecting incipient caries lesions on free smooth surfaces. The utilization of both methods can improve the efficacy of caries diagnosis. Copyright (C) 2002 S. Karger AG, Basel.

Total secondary-electron yield of metals measured by a dynamic method

The secondary electron emission of dielectrics usually is measured by the pulse method, in which the dielectric is irradiated with short pulses of electrons. Attempts to use a dynamic method, in which the dielectric is irradiated continuously, have failed because the dielectric becomes charged and this charge interferes with the emission process. The dynamic method can, however, be applied to metals where volume charges are prevented. This article reports dynamic measurements of the total secondary emission yield from stainless steel, platinum, and aluminum and compares them with results from the current pulse method. In order to apply the dynamic method to metals a simple but important change in the setup was introduced: a dielectric slab was placed between the electrode and the metallic sample, which permitted the sample surface potential and therefore the energy of the incident electrons to change continuously. Unlike for dielectrics, the emission curves for metals are identical when obtained by the two methods. However, for a sample with deliberately oxidized surfaces the total secondary emission yield is smaller when measured with the dynamic method as compared with the pulse method, just as happens for dielectrics. (C) 2000 American Institute of Physics. [S0021-8979(00)03413-7].

Solid state reactions in the platinum-mercury system

Thermogravimetry, Differential Scanning Calorimetry and other analytical techniques (Energy Dispersive X-ray Analysis; Scanning Electron Microscopy; Mapping Surface; X-ray Diffraction; Inductively Coupled Plasma Atomic Emission Spectroscopy and Cold Vapor Generation Atomic Absorption Spectroscopy) have been used to study the reaction of mercury with platinum foils. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt to form intermetallic compounds each having a different stability, indicated by at least three mass loss steps. Intermetallic compounds such as PtHg4, PtHg and PtHg2 were characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of bulk mercury via thermal desorption. The Pt(Hg) solid solution formation caused great surface instability, attributed to the atomic size factor between Hg and Pt, facilitating the acid solution's attack to the surface.

Platinum Group Minerals in Eastern Brazil GEOLOGY AND OCCURRENCES IN CHROMITITE AND PLACERS

Brazil does not have working platinum mines, nor even large reserves of the platinum metals, but there is platinum in Brazil. In this paper, four massifs (mafic/ultramafic complexes) in eastern Brazil, in the states of Minas Gerais and Ceara, where platinum is found will be described. Three of these massifs contain concentrations of platinum group minerals or platinum group elements, and gold, associated with the chromitite rock found there. In the fourth massif, in Minas Gerais State, the platinum group elements are found in alluvial deposits at the Bom Sucesso occurrence. This placer is currently being studied.