31 resultados para EUSKADI TA ASKATASUNA. ETA
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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Impurity interstitial atoms present in metals with BCC structure can diffuse in the metallic matrix by jumps to energetically equivalent crystallographic sites. Anelastic spectroscopy (internal friction) is based on the measurement of mechanical loss or internal friction as a function of temperature. Due to its selective and nondestructive nature, anelastic spectroscopy is well suited for the study of diffusion of interstitial elements in metals. Internal friction measurements were made using the torsion pendulum technique with oscillation frequency of a few Hz, temperature interval from 300 to 700 K, heating rate of about 1 K/min, and vacuum better than 10-5 mbar. The polycrystalline Nb and Ta samples used were supplied by Aldrich Inc. The results obtained showed thermally activated relaxation structures due to stress-induced ordering of oxygen atoms around the Nb (or Ta) atoms of the metallic matrix. The results were interpreted by three methods and led to activation enthalpy values for the diffusion of oxygen in Nb and Ta of 1.15 eV and 1.10 eV, respectively.
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When metals that present bcc crystalline structure receive the addition of interstitial atoms as oxygen, nitrogen, hydrogen and carbon, they undergo significant changes in their physical properties because they are able to dissolve great amounts of those interstitial elements, and thus form solid solutions. Niobium and most of its alloys possess a bcc crystalline structure and, because Brazil is the largest world exporter of this metal, it is fundamental to understand the interaction mechanisms between interstitial elements and niobium or its alloys. In this study, mechanical spectroscopy (internal friction) measurements were performed on Nb-8.9wt%Ta alloys containing oxygen in solid solution. The experimental results presented complex internal friction spectra. With the addition of substitutional solute, interactions between the two types of solutes (substitutional and interstitial) were observed, considering that the random distribution of the interstitial atoms was affected by the presence of substitutional atoms. Interstitial diffusion coefficients, pre-exponential factors and activation energies were calculated for oxygen in this alloy.
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Density functional theory (DFT) calculations point out that the participation of water can effectively lower the barrier height for the isomerization process between hydrated oxide cation, MO(H2O)(+), and dihydroxide cation, M(OH)(2)(+), (M = V, Nb and Ta). The catalytic effect is achieved by a water-assisted mechanism in which water acts as proton donor and acceptor, via a transition structure corresponding to a six-membered ring. In the case of vanadium atom, the presence of two water molecules has been taken into account and the tautomerization becomes nearly barrierless, decreasing both the stability of the transition structures relative to intermediates and the depths of wells associated with the intermediates. (C) 2003 Elsevier B.V. All rights reserved.
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This paper reports on the phase transformation during the preparation of Ni-25Nb, Ni-25Ta, Ni-20Nb-5Ta and Ni-15Nb-10Ta (at-%) powders by high-energy ball milling from elemental powders. The milling process was performed in a planetary ball milling using stainless steel balls and vials, rotary speed of 300rpm, and a ball-to-powder of 10:1. To minimize contamination and spontaneous ignition the powders were handled under argon atmosphere in a glove box. The milled powders were characterized by means of X-ray diffraction techniques. Results indicated that the Ni atoms were preferentially dissolved into the Nb (and/or Ta) lattice at the initial milling times, which contributed to change the relative intensity on the diffraction peaks. After the dissolution of Nb (and/or Ta) into the Ni lattice, the Ni peaks were moved to the direction of lower diffraction angles in Ni-25Nb, Ni-25Ta, Ni-20Nb-5Ta, Ni-15Nb-10Ta powders, indicating that the mechanical alloying was achieved.
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Incoherent eta photoproduction in nuclei is evaluated at forward angles within 4 to 9 GeV using a multiple scattering Monte Carlo cascade calculation with full eta-nucleus final-state interactions. The Primakoff, nuclear coherent and nuclear incoherent components of the cross sections fit remarkably well previous measurements for Be and Cu from Cornell, suggesting a destructive interference between the Coulomb and nuclear coherent amplitudes for Cu. The inelastic background of the data is consistently attributed to the nuclear incoherent part, which is clearly not isotropic as previously considered in Cornell's analysis. The respective Primakoff cross sections from Be and Cu give Gamma(eta ->gamma gamma)=0.476(62) keV, where the quoted error is only statistical. This result is consistent with the Particle Data Group average of 0.510(26) keV and in sharp contrast (similar to 50%) with the value of 0.324(46) keV obtained at Cornell.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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A statistical law for the multiplicities of the SU(3) irreps (lambda, mu) in the reduction of totally symmetric irreducible representations {m} of U(N), N = (eta + 1) (eta + 2)/2 with eta being the three-dimensional oscillator major shell quantum number, is derived in terms of the quadratic and cubic invariants of SU(3), by determining the first three terms of an asymptotic expansion for the multiplicities. To this end, the bivariate Edgeworth expansion known in statistics is used. Simple formulae, in terms of m and eta, for all the parameters in the expansion are derived. Numerical tests with large m and eta = 4, 5 and 6 show good agreement with the statistical formula for the SU(3) multiplicities.
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The addition of different dopants affects the densification, mean grain size and electrical properties of TiO2-based varistor ceramics. This paper discusses the microstructural and electrical properties of (Ta, Co, Pr) doped TiO2 systems, demonstrating that some of these systems display electrical properties that allow for their use as low voltage varistor. Dopants such as Ta2O5 play a special role in the formation of barriers at the grain boundary and in the nonlinear behavior in TiO2-based systems. The higher values of nonlinear coefficient and breakdown electric field were obtained in the system just doped with Ta2O5 and CoO.
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It is well known that the interstitial elements present in solid solution in metals interact with the matrix by a relaxation process known as stress induced ordering. Traditionally this relaxation process is observed in the internal friction measurements. It is a common practice that researchers present the results of the frequency together with internal friction without giving any analysis. In this work we apply an expression which relates the variation of frequency with temperature and analyse the experimental results cited in the literature of the relaxation process due to the stress induced ordering of oxygen and nitrogen present in niobium and tantalum.
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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.
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The reactivity of the mer-[RuCl3(dppb)H2O] complex (1) with di-hydrogen shows that the products formed depend on the conditions of the reaction, i.e., solvents and presence or absence of a base. The new mixed-valence complexes [(diop)ClRu-(h-Cl)(3)-RuCl(dppb)] (3), [(binap)CIRu-(p-Cl)(3)-RuCl(dppb)] (4), [(PPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (6), [(dppn)ClRu-(mu-Cl)(3)-RuCl(dppb)] (7), [(P-ptol(3))(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (8), [(SbPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (9), [(eta(6)-C6H6)Ru-(mu-Cl)(3)-RuCl(dppb)] (11) and the known mixed-valence [(dppb)CIRu-(mu-Cl)(3)-RuCl(dppb)] (5) and [(diop)ClRu-(mu-Cl)(3)-RuCl(diop)] (10) were synthesized from complexes (1) or (2) using a methodology developed in our research group. The known complexes [(dppb)ClRu-(mu-Cl)(2)-RuCl(dppb)] (12), [(dppb)(CO)Ru-(mu-Cl)(3)-RuCl(dppb)] (13) and [H2NEt2][(dppb)ClRu-(mu-Cl)(3)-RuCl(dppb)] (14) were synthesized by changing the reaction conditions between mer-[RuCl3(dppb)H2O] (1) and dihydrogen. The crystal structures of (5) and (11) were determined by single-crystal X-ray diffraction. Some of the complexes described here are effective pre-catalysts for the hydrogenation of imines. Preliminary results on the homogeneous hydrogenation of the imines Ph-CH2-N=CH-Ph and Ph-N=CH-Ph are presented. (C) 2004 Elsevier Ltd. All rights reserved.
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The compounds [Fe(bda)(CO)(2)L] and [Fe(ch)(CO)(2)L], (bda=benzylideneacetone; ch=chalcone; L=CO, PPh3) were investigated by thermogravimetry and derivative thermogravimetry (TG and DTG). The fragmentation patterns suggest that the iron atom protects the enone fragment, so that the organic ligands break up with the loss of the pendant aromatic rings.
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Reaction of equimolar amounts of [Co-2(CO)(6)(dppm)] and [Cr(eta(6)-C6H5)(C=-CCH2NMe2)(CO)(3)] (1) in benzene gives the novel heterotrimetallic complex [Cr(eta(6)-C6H5){(mu(2)-eta(2)-C=CCH2NMe2)Co-2(CO)(4)(dppm)}(CO)(3)] (2) in 40% yield. The X-ray structure analysis of 2 reveals that the Cr(CO)(3) tripod adopts a nearly anti-eclipsed conformation. (C) 2002 Elsevier B.V. B.V. All rights reserved.