The direct determination of rare earth elements in basaltic and related rocks using ICP-MS: Testing the efficiency of microwave oven sample decomposition procedures

Tests are described showing the results obtained for the determination of REE and the trace elements Rb, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and U with ICP-MS methodology for nine basaltic reference materials, and thirteen basalts and amphibolites from the mafic-ultramafic Niquelandia Complex, central Brazil. Sample decomposition for the reference materials was performed by microwave oven digestion (HF and HNO(3), 100 mg of sample), and that for the Niquelandia samples also by Parr bomb treatment (5 days at 200 degrees C, 40 mg of sample). Results for the reference materials were similar to published values, thus showing that the microwave technique can be used with confidence for basaltic rocks. No fluoride precipitates were observed in the microwave-digested solutions. Total recovery of elements, including Zr and Hf, was obtained for the Niquelandia samples, with the exception of an amphibolite. For this latter sample, the Parr method achieved a total digestion, but not so the microwave decomposition; losses, however, were observed only for Zr and Hf, indicating difficulty in dissolving Zr-bearing minerals by microwave acid attack.

Can mass dissociation patterns of transition-metal complexes be predicted from electrochemical data?

The Cooks kinetic method has been very convenient to correlate the relative dissociation rates obtained by collision-induced fragmentation experiments with the energies of two related bonds in molecules and complexes in the gas phase. Reliable bond energy data are, however, not always available, particularly for polynuclear transition-metal complexes, such as the triruthenium acetate clusters of the general formula [Ru(3) (mu(3)-O)(mu-CH(3)COO)(6)(py)(2)(L)](+), where L = ring substituted N-heterocyclic ligands. Accordingly, their gas-phase collision-induced tandem mass spectrometry (CID MS/MS) dissociation patterns have been analyzed pursuing a relationship with the more easily accessible redox potentials (E(1/2)) and Lever`s E(L) parameters. In fact, excellent linear correlations of In(1/2A(L)/A(py)), where A(py) and A(L) are the abundance of the fragments retaining the pyridine (py) and L ligand, respectively, with E(1/2) and E(L) were found. This result shows that those electrochemical parameters are correlated with bond energies and can be used in the analysis of the dissociation data. Such modified Cooks method can be used, for example, to determine the electronic effects of substituents on the metal-ligand bonds for a series of transition-metal complexes. Copyright (C) 2008 John Wiley & Sons, Ltd.

Early and post transition metal complexes as a single of combined components in the ethylene and isoprene polynerization

In this work is reported, in a first step, the effect of different experimental parameters and their relation with polymer properties using the homogeneous binary catalyst system composed by Ni(α-diimine)Cl2 (α-diimine = 1,4-bis(2,6-diisopropylphenyl)- acenaphthenediimine) and {TpMs*}V(Ntbu)Cl2 (TpMs* = hydridobis(3-mesitylpyrazol-1- yl)(5-mesitylpyrazol-1-yl)) activated with MAO. This complexes combination produces, in a single reactor, polyethylene blends with different and controlled properties dependent on the polymerization temperature, solvent and Nickel molar fraction (xNi). In second, the control of linear low density polyethylene (LLDPE) production was possible, using a combination of catalyst precursors {TpMs}NiCl (TpMs = hydridotris(3- mesitylpyrazol-1-yl)) and Cp2ZrCl2, activated with MAO/TMA, as Tandem catalytic system. The catalytic activities as well as the polymer properties are dependent on xNi. Polyethylene with different Mw and controlled branches is produced only with ethylene monomer. Last, the application group 3 metals catalysts based, M(allyl)2Cl(MgCl2)2.4THF (M = Nd, La and Y), in isoprene polymerization with different cocatalysts systems and experimental parameters is reported. High yields and polyisoprene with good and controlled properties were produced. The metal center, cocatalysts and the experimental parameters are determinant for the polymers properties and their control. High conversions in cis-1,4- or trans-1,4-polyisoprene were obtained and the polymer microstructure depending of cocatalyst and metal type. Combinations of Y and La precursors were effective systems for the cis/transpolyisoprene blends production, and the control of cis-trans-1,4-microstructures by Yttrium molar fraction (xY) variation was possible.

Investigation of microwave dielectric relaxation solid state process in the antiferroelectric phase of NaNbO3 ceramics

This letter reports microwave dielectric measurements performed in the antiferroelectric phase of NaNbO3 ceramics from 100 to 450 K. Remarkable dielectric relaxation was found within the antiferroelectric phase and in the vicinity of the ferroelectric-antiferroelectric phase transition. Such dielectric relaxation process was associated with relaxations of polar nanoregions with strong relaxor-like characteristic. In addition, the microwave dielectric measurements also revealed an unexpected and unusual anomaly in the relaxation strength, which was related to a disruption of the antiferroelectric order induced by a possible AFE-AFE phase transition. (C) 2004 Elsevier Ltd. All rights reserved.

A comparative solid state C-13 NMR and thermal study of CO2 capture by amidines PMDBD and DBN

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

Rare earth centers properties and electron trapping in SnO2 thin films produced by sol-gel route

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis and thermal studies of solid state 2-chloro-benzylidenepyruvic acid and its compounds with sodium, aluminium (III), gallium (III) and indium (III) cations

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

Solid-state compounds of 2-methoxybenzylidenepyruvate and 2-methoxycinnamyllidenepyruvate with thorium (IV) Preparation and thermal studies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation of strip rolling directly from the semi-solid state

defect metal alloy strip when thixorolling directly from the semi-solid state. To facilitate the study lead/tin alloys were chosen for their relatively low operating temperature. The objective is to extrapolate these findings to the higher temperature aluminium, alloys. Three alloys (70%Pb30%Sn, 60%Pb-40%Sn, 50%Pb-50%wtSn) were used particularly to study the influence of the solidification interval. The equipment consists of a two roll mill arranged as an upper and lower roller, where both rollers are driven at a controlled speed. The lower roller is fed with semi solid alloy through a ceramic nozzle attached to the lower end of a cooling slope. Several types of nozzle and their position at the roller were tested. This produced different solidifications and consequently different finished strip. The alloys were first cast and then poured onto the cooling slope through a tundish in order to create a continuous laminar flow of slurry and uniformity of metal strip quality. The pouring was tested at different positions along the slope. The cooling slope was coated with colloidal graphite to promote a smooth slurry flow and avoid the problem of adherence and premature solidification. The metallic slurry not only cools along the slope but is also initially super-cooled to a mush by the lower roller whilst at room temperatures, thus enabling thixorolling. It was also found that the nozzle position could be adjusted to enable the upper roller to also contribute to the solidification of the metallic slurry. However the rollers and the cooling slope naturally heat up. Temperature distribution in these zones was analysed by means of three thermocouples positioned along the cooling slope and a fourth in the base of the semi solid pool within the nozzle. The objective being to design an optimum pouring and cooling system. The formed strip was cooled down to room temperature with a shower of water. Microstructures of the thixorolling process were analysed. The differences in solidification conditions resulted in differing qualities of finished strip and corresponding defect types, all of which are a serious quality issue for the rolled product.

Dielectric response features and oxygen migration on rare earth modified lead titanate ferroelectric ceramics

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

Partial purification and properties of cellulase-free alkaline xylanase produced by Rhizopus stolonifer in solid-state fermentation

Rhizopus stolonifer was cultivated in wheat bran to produce a cellulase-free alkaline xylanase. The purified enzyme obtained after molecular exclusion chromatography in Sephacryl S-200 HR showed optimum temperature as 45 degrees C and hydrolysis pHs optima as pH 6.0 and 9.0. Xylanase presented higher Vmax at pH 9.0 (0.87 mu mol/mg protein) than at pH 6.0 and minor Km at pH 6.0 (7.42 mg/mL)than at pH 9.0.

Microbial rennet produced by Mucor miehei in solid-state and submerged fermentation

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

Pectinase production by Penicillium viridicatum RFC3 by solid state fermentation using agricultural wastes and agro-industrial by-products

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

Pectinase production by a Brazilian thermophilic fungus Thermomucor indicae-seudaticae N31 in solid-state and submerged fermentation

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

Purification and characterization of an exo-polygalacturonase produced by Penicillium viridicatum RFC3 in solid-state fermentation

The pectinolytic enzyme obtained from Penicillium viridicatum RFC by solid-state fermentation was purified to homogeneity by pretreatment with kaolin (40 mg mL(-1) ) and ultrafiltration. followed by chromatography on a Sephadex G50 column. The apparent molecular weight of the enzyme was 24 kDa. Maximal activity occurred at pH 6.0 and at 60 degrees C. The enzyme proved to be an exo-polygalacturonase, releasing galacturonic acid by hydrolysis of highly esterified pectin. The presence of 10 mM Ba2+ increased the enzyme activity by 96% and its thermal stability by 30%. besides increasing its stability at acid pH. The apparent K-m with apple pectin as substrate was 1.82 mg mL(-1) and the V-max was 81 mu mol min(-1). (c) 2007 Elsevier Ltd. All rights reserved.