A comparative study of hydrosilane compounds as cocatalysts in the metathesis of 1-hexene

The selectivity of I-hexene metathesis using WCI6 as catalyst was evaluated with a series of hydrosilane-compounds as cocatalysts: Ph3SiH, Ph2SiH2, PhSiH3 and polymethylhydrosiloxane (PMHS). The metathesis reaction is favored by the addition of promoters. When in the presence of WCl4(OAr)(2), OAr = 2,6-dichlorophenoxide, 2,6-difluorophenoxide, olefin metathesis occurs with good selectivity without the use of promoters. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Compostos heterometálicos. Interação do tricarbonil com ligação W-Hg, [WCl(CO)3(bipy)(HgCl)], com tiouréias

Reactions of [WC1(CO)(3)(bipy)(HgCl)], [bipy = 2,2 -bipyridine], with thioureas were performed giving compounds of the type [WCl(CO)(3)(bipy)(HgCl)L], [L = thiourea (tu); N-methylthiourea (mtu); N,N-dimethyithiourea (dmtu)] in which the coordination sphere of the tungsten atom remained unchanged. The coordination of the thioureas to mercury atom was proved to occur in accord to infrared spectra, through the sulphur atom.

Determination of selenium in nutritionally relevant foods by graphite furnace atomic absorption spectrometry using arsenic as internal standard

A method has been developed for the direct determination of Se in nutritionally relevant foods by graphite furnace atomic absorption spectrometry. Tungsten/rhodium carbide coating on the integrated platform of a transversely heated graphite atomizer or W coating with co-injection of Pd(NO3)(2) were used as a permanent modifiers. Samples and reference solutions were spiked with 500 mu g L-1 As and absorbance variations due to changes in experimental conditions were minimized. For 20 mu L aqueous analytical solutions delivered into the graphite tube, analytical curves in the 5.0-40 mu g L-1 with good linear correlation were established. Pyrolysis and atomization temperatures were evaluated using pyrolysis and atomization curves, respectively. The optimized heating program (temperature, ramp time, hold time) of the graphite tube of the Perkin-Elmer SIMAA 6000 atomic absorption spectrometer was: dry steps (110 degrees C, 5 s, 10 s; 130 degrees C, 15 s, 15 s); air-assisted pyrolysis step (600 degrees C, 20 s, 40 s; 20 degrees C, 1 s, 40 s); pyrolysis step (1300 degrees C, 10 s, 20 s); atomization step (2100 degrees C, 0 s, 4 s); clean step (2550 degrees C, 1 s, 5 s). The method was applied for Se determination in coconut water, coconut milk, soybean milk, cow milk, tomato juice, mango juice, grape juice and drinking water samples and four standard reference materials and results were in agreement at 95% confidence level. The lifetime of the tube was 500 firings and the relative standard deviations of measurements of typical samples containing 25 mu gL(-1) Se were 3.0% and 6.0% (n = 12) with and without internal standardization, respectively. The limits of detection were in the 0.35 mu g L-1-0.7 mu g Se L-1 range. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values were in the 98-109% range. (c) 2004 Elsevier Ltd. All rights reserved.

Coating residual stress effects on fatigue performance of 7050-T7451 aluminum alloy

The tendency of the aircraft industry is to enhance customer value by improving performance and reducing environmental impact. In view of availability, aluminum alloys have a historically tendency to faster insertion due to their lower manufacturing and operated production infrastructure. In landing gear components, wear and corrosion control of many components is accomplished by surface treatments of chrome electroplating on steel or anodizing of aluminum. One of the most interesting environmentally safer and cleaner alternatives for the replacement of hard chrome plating or anodizing is tungsten carbide thermal spray coating, applied by the high velocity oxy fuel (HVOF) process. However, it was observed that residual stresses originating from these coatings reduce the fatigue strength of a component.An effective process as shot peening treatment, considered to improve the fatigue strength, pushes the crack sources beneath the surface in most of medium and high cycle cases, due to the compressive residual stress field induced. The objective of this research is to evaluate a tungsten carbide cobalt (WC-Co) coating applied by the high velocity oxy fuel (HVOF) process, used to replace anodizing. Anodic films were grown on 7050-T7451 aluminum alloy by sulfuric acid anodizing, chromic acid anodizing and hard anodizing. The influence on axial fatigue strength of anodic films grown on the aluminum alloy surface is to degrade the stress-life performance of the base material. Three groups of specimens were prepared and tested in axial fatigue to obtain S-N curves: base material, base material coated by HVOF and base material shot peened and coated.Experimental results revealed increase in the fatigue strength of Al 7050-T7451 alloy associated with the WC 17% Co coating. on the other hand, a reduction in fatigue life occurred in the shot peened and coated condition. Scanning electron microscopy technique and optical microscopy were used to observe crack origin sites, thickness and coating/substrate adhesion. (c) 2007 Elsevier B.V. All rights reserved.

Photochromic properties of tungstate-based glasses

Vitreous samples were prepared in the NaPO(3)-BaF(2)WO(3) ternary system with high WO(3) concentrations. These glasses exhibit a strong absorption in the visible due to the presence of reduced tungsten species and the use of oxidizing species is required. The couple Sb(2)O(3)/NaNO(3) was introduced in the composition and allowed to obtain transparent glasses. These oxidized samples were illuminated by visible laser radiation and showed an efficient volumetric photochromic effect. The photosensitive effect appeared as a dark spot throughout the entire volume of the glasses. The effect was investigated by several techniques such as, U-V-visible absorption, Raman and XANES at the L(1) and L(3) tungsten absorption edges. The results suggest a photoreduction of tungsten atoms without structural changes of the viteous network. Finally, the photochromic effect can be erased by thermal treatment at 200 degrees C for a few minutes. (C) 2007 Published by Elsevier B.V.

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Direct determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by simultaneous GFAAS using integrated platforms pretreated with W-Rh permanent modifier together with Pd plus Mg modifier

A method is proposed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by electrothermal atomic absorption spectrometry (ETAAS) using W-Rh permanent modifier together with Pd(NO3)(2) + Mg(NO3)(2) conventional modifier. The integrated platform of a transversely heated graphite atomizer (THGA) was treated with tungsten, followed by rhodium, forming a deposit containing 250 mug W + 200 mug Rh. A 500-muL, volume of fuel ethanol was diluted with 500 muL, of 0.14 mol L-1 HNO3 in an autosampler cup of the spectrometer. Then, 20 muL, of the diluted ethanol was introduced into the pretreated graphite platform followed by the introduction of 5 mug Pd(NO3)(2) + 3 mug Mg(NO3)(2). The injection of this modifier was required to improve arsenic and iron recoveries in fuel ethanol. Calibrations were carried out using multi-element reference solutions prepared in diluted ethanol (1 + 1, v/v) acidified to 0. 14 mol L-1 HNO3. The pyrolysis and atomization temperatures of the heating program were 1200degreesC and 2200degreesC, respectively, which were obtained with multielement reference solutions in acidic diluted ethanol (1 + 1, v/v; 0. 14 mol L-1 HNO3). The characteristic masses for the simultaneous determination in ethanol fuel were 78 pg Al, 33 pg As, 10 pg Cu, 14 pg Fe, 7 pg Mn, and 24 pg Ni. The lifetime of the pretreated tube was about 700 firings. The detection limits (D.L.) were 1.9 mug L-1 Al, 2.9 mug L-1 As, 0.57 mug L-1.Cu, 1.3 mug L-1 Fe, 0.40 mug L-1 Mn, and 1.3 mug L-1 Ni. The relative standard deviations (n = 12) were 4%, 4%, 3%, 1.5%, 1.2%, and 2.2% for Al, As, Cu, Fe, Mn, and Ni, respectively. The recoveries of Al, As, Cu, Fe, Mn, and Ni added to the fuel ethanol samples varied from 81% to 95%, 80% to 98%, 97% to 109%, 85% to 107%, 98% to 106% and 97% to 103%, respectively. Accuracy was checked for the Al, As, Cu, Fe, Mn, and Ni determination in 10 samples purchased at a local gas station in Araraquara-SP City, Brazil. A paired t-test showed that at the 95% confidence level the results were in agreement with those obtained by single-element ETAAS.

New tungstate fluorophosphate glasses

\A new class of tungstate fluorophosphate glasses was identified in the NaPO3-BaF2-WO3 ternary system. The variation of several physical properties was determined with respect to chemical composition. Characteristic temperatures, density and refractive index increase as tungsten oxide content increases. The optical transmission range and specially the energy bandgap depend of the WO3 amount. No crystallization could be observed for the Most WO3 concentrated vitreous samples (greater than or equal to20% molar). Color and optical properties of the glasses depend of the melting time because of the presence of reduced tungsten species like W5+ and W4+. In addition, photodarkening is observed in tungsten rich glass samples under UV laser illumination and this phenomenon can be reversible by heat treatment near the glass transition temperature. (C) 2004 Published by Elsevier B.V.

Towards an insight on the photoluminescence of disordered CaWO4 from a joint experimental and theoretical analysis

A joint experimental and theoretical study has been carried out to rationalize for the first time the photoluminescence (PL) properties of disordered CaWO4 (CWO) thin films. From the experimental side, thin films of CWO have been synthesized following a soft chemical processing, their structure has been confirmed by X-ray diffraction data and corresponding PL properties have been measured using the 488 nm line of an argon ion laser. Although we observe PL at room temperature for the crystalline thin films, the structurally disordered samples present much more intense emission. From the theoretical side, first principles quantum mechanical calculations, based on density functional theory at B3LYP level, have been employed to study the electronic structure of a crystalline (CWO-c) and asymmetric (CWO-a) periodic model. Electronic properties are analyzed in the light of the experimental results and their relevance in relation to the PL behavior of CWO is discussed. The symmetry breaking process on going from CWO-c to CWO-a creates localized electronic levels above the valence band and a negative charge transfer process takes place from threefold, WO3, to fourfold, WO4,. tungsten coordinations. The correlation of both effects seems to be responsible for the PL of amorphous CWO. (c) 2005 Elsevier B.V. All rights reserved.

Glasses in the SbPO4-WO3 system

Glasses in the binary system (100 - x)SbPO4-xWO3 (20 <= x <= 60, x in mol%) have been prepared and characterized. Differential thermal analysis (DTA) shows that the glass transition temperature, T-g increases from 412 degrees C, for samples containing 20 mol% of WO3 to 481 degrees C observed for glass containing 60 mol%. Sample containing 40 mol% in WO3 were observed to be the most stable against devitrification. The structural organization of the glasses has been studied by using Fourier transform infra-red (FTIR), Raman, P-31 Magic angle spinning (MAS) and spin echo nuclear magnetic resonance (NMR) spectroscopies. Results suggest two distinct networks comprising the glass structure, one with high SbPO4 content and the other characteristic of the highest WO3 content samples. The glasses present photochromic properties. Colour changes are observed for samples after exposure to ultraviolet or visible laser light. XANES, at L-1 absorption edge of tungsten, suggests partial reduction from W6+ to W5+ species during the laser irradiation. The photochromic effects and the colour changes, promoted by laser excitation, are reversible and easily removed by heat for during 1 h at 150 degrees C. Subsequent 'write/erase' cycles can be done without degradation of the glasses. (C) 2007 Elsevier B.V. All rights reserved.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (&GE; 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Antimony oxide based glasses

Glass formation has been investigated in binary systems based on antimony oxide as the main glass former: (100-x)Sb2O3-xWO3, (5 < x < 65), (100 - x)Sb2O3-xSbPO(4), (5 < x < 80) and (100 - x)Sb2O3-x[Sb(PO3)(3)](n), (10 < x < 40). Ternary systems derived from the Sb2O3-WO3 binary glass have also been studied: Sb2O3-WO3-BaF2 Sb2O3-WO3-NaF and Sb2O3-WO3-[Sb(PO3)(3)](n). Glass transition temperature ranges from 280 degreesC to 380 degreesC. It increases as the concentration in tungsten oxide or antimony phosphate increases. Refractive index is larger than 2. Tungsten-containing glasses are yellow in transmission and turn green at the largest WO3 content. Optical transmission and temperatures of glass transition, T-g, onset of the crystallization. T-x, and maximum of crystallization, T-p, have been measured using differential scanning calorimetry (DSC). These glasses have potential photonic applications. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Tungstate fluorophosphate glasses as optical limiters

Nonlinear absorption measurements were performed on fluorophosphate glasses with high concentrations of tungsten oxide. Large two-photon absorption coefficients, alpha(2), were determined at 660 nm using nanosecond laser pulses. It was observed that alpha(2) increases for increasing tungsten oxide concentrations and, hence, the optical limiting performance of this glass composition can be controlled. (C) 2002 American Institute of Physics.

Crystallographic properties of KSr2Nb5O15

Nanostructured KSr2Nb5O15 oxide was synthesized by the polymeric precursor method, a chemical synthesis route based on the Pechini's method. The X-ray diffraction (XRD) pattern of the calcined powder at 1150 degreesC were performed in the angular range 5 less than or equal to 20 less than or equal to 120degrees with a 0.02degrees step and a fixed counting time of 30 s. The XRD data were analyzed by the Rietveld refinements using the FullProf software. The results C showed a tetragonal system with the tetragonal tungsten bronze structure (TTB) type (a = 12.4585 (2) Angstrom and c = 3.9423 (6) Angstrom, V = 611,90 (2) Angstrom). In this work, the sites occupancy by the K+ and Sr2+ cations on the TTB type structure were determined. The thermal parameters (B) were analyzed. (C) 2004 Elsevier B.V. All rights reserved.

Thin films prepared from tungstate glass matrix

Vitreous samples containing high concentrations of WO3 (above 40% M) have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. These films were characterized by X-ray diffraction (XRD), perfilometry, X-ray energy dispersion spectroscopy (EDS), M-Lines and UV-vis absorption spectroscopy. In this work, experimental parameters were established to obtain stable thin films showing a chemical composition close to the glass precursor composition and with a high concentration of WO3. These amorphous thin films of about 4 mu m in thickness exhibit a deep blue coloration but they can be bleached by thermal treatment near the glass transition temperature. Such bleached films show several guided modes in the visible region and have a high refractive index. Controlled crystallization was realized and thus it was possible to obtain WO3 microcrystals in the amorphous phase. (C) 2007 Elsevier B.V. All rights reserved.