X-ray photoelectron spectroscopy analysis of zirconium nitride-like films prepared on Si(100) substrates by ion beam assisted deposition

Thin zirconium nitride films were prepared on Si(l 00) substrates at room temperature by ion beam assisted deposition with a 2 keV nitrogen ion beam. Arrival rate ratios ARR(N/Zr) used were 0.19, 0.39, 0.92, and 1.86. The chemical composition and bonding structure of the films were analyzed with X-ray photoelectron spectroscopy (XPS). Deconvolution results for Zr 3d, Zr 3p(3/2), N 1s, O 1s, and C 1s XPS spectra indicated self-consistently the presence of metal Zr-0, nitride ZrN, oxide ZrO2, oxymnide Zr2N2O, and carbide ZrC phases, and the amounts of these compounds were influenced by ARR(N/Zr). The chemical composition ratio N/Zr in the film increased with increasing ARR(N/Zr) until ARR(N/Zr) reached 0.92, reflecting the high reactivity of nitrogen in the ion beam, and stayed almost constant for ARR(N/Zr) >= 1, the excess nitrogen being rejected from the growing film. A considerable incorporation of contaminant oxygen and carbon into the depositing film was attributed to the getter effect of zirconium. (C) 2007 Elsevier B.V. All rights reserved.

Synthesis, characterization and catalytic evaluation of cubic ordered mesoporous iron-silicon oxides

Iron was successfully incorporated in FDU-1 type cubic ordered mesoporous silica by a simple direct synthesis route. The (Fe/FDU-1) samples were characterized by Rutherford back-scattering spectrometry (RBS), small angle X-ray scattering (SAXS). N(2) sorption isotherm, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The resulting material presented an iron content of about 5%. Prepared at the usual acid pH of -0.3, the composite was mostly formed by amorphous silica and hematite with a quantity of Fe(2+) present in the structure. The samples prepared with adjusted pH values (2 and 3.5) were amorphous. The samples` average pore diameter was around 12.0 nm and BET specific surface area was of 680 m(2) g(-1). Although the iron-incorporated material presented larger lattice parameter, about 25 nm compared to pure FDU-1, the Fe/FDU-1 composite still maintained its cubic ordered fcc mesoporous structure before and after the template removal at 540 degrees C. The catalytic performance of Fe/FDU-1 was investigated in the catalytic oxidation of Black Remazol B dye using a catalytic ozonation process. The results indicated that Fe/FDU-1 prepared at the usual acid pH exhibited high catalytic activity in the mineralization of this pollutant when compared to the pure FDU-1. Fe(2)O(3) and Fe/FDU-1 prepared with higher pH of 2 and 3.5. (C) 2010 Elsevier B.V. All rights reserved.

On the Stabilization of Gold Nanoparticles over Silica-Based Magnetic Supports Modified with Organosilanes

The immobilization of gold nanoparticles (Au NPs) on silica is made possible by the functionalization of the silica surfaces with organosilanes. Au NPs could only be stabilized and firmly attached to silica-support surfaces that were previously modified with amino groups. Au NPs could not be stabilized on bare silica surfaces and most of the NPs were then found in the solution. The metal-support interactions before and after the Au NP formation, observed by X-ray absorption fine structure spectroscopy (XAFS), indicate a stronger interaction of gold-(III) ions with amino-modified silica surfaces than with the silanol groups in bare silica. An amino-modified, silica-based, magnetic support was used to prepare an active Au NP catalyst for the chemoselective oxidation of alcohols, a reaction of great interest for the fine chemical industry.

An investigation of the activation process of high temperature shift catalyst

The aim of this work is to address the activation process of a high temperature shift (HTS) catalyst, composed of Fe2O3/Cr2O3/CuO, by analyzing it before activation (HTS-V) and after activation (HTS-A) using complementary characterization techniques. The textural and morphological characterizations were done by transmission electron rnicroscopy (TEM) and nitrogen physisorption at 77 K; crystallographic structure was confirmed by X-ray diffraction (XRD); electronic structure was analyzed by X-ray absorption spectroscopy (XAS) and the chemical composition of the catalyst`s surface was obtained by X-ray photoelectron spectroscopy (XPS). The investigation pointed out that the HTS-V catalyst presents good textural and morphological properties, which are not deeply affected by the activation process (sample HTS-A). The iron oxide phase in the HTS-V catalyst is hematite whereas in HTS-A catalyst is magnetite with Fe2+/Fe3+ ratio close to the expected value (0.5). For both samples, the Cr ions seem to be incorporated in the iron oxide lattice with higher concentration at particle surface. In the HTS-V catalyst, the Cu ions have oxidation number II and occupy in average distorted octahedral sites; after the activation, the Cu ions are partially reduced, suggesting that the reduction of the Cu species is complex. (C) 2007 Elsevier B.V. All rights reserved.

Electrocatalysis of oxygen reduction on carbon-supported Pt-Co nanoparticles with low Pt content

The oxygen reduction reaction (ORR) was investigated on carbon-supported Pt-Co nanoparticle electrocatalysts with low Pt content in alkaline electrolyte. High resolution transmission electron microscopy, In situ X-ray absorption spectroscopy, and X-ray diffraction analysis evidenced large structural differences of the Pt-Co particles depending oil the route of the catalyst synthesis. It was demonstrated that although the Pt-Co materials contain low amounts of Pt, they show very good activities when the particles are formed by a Pt-rich shell and a Pt-Co core, which was obtained after submitting the electrocatalyst to a potential cycling in acid electrolyte. The high activity of this material was due to a major contribution from its higher surface area, as a result of the leaching of the Co atoms from the particle Surface. Furthermore, its high activity was ascribed to a minor contribution from the electronic interaction of the Pt atoms, at the particle surface, and the Co atoms located in the beneath layer, lowering the Pt cl-band center. As these electrocatalysts presented high activity for the ORR with low Pt content, the cost of the fuel cell cathodes could be lowered considerably. (c) 2009 Elsevier B.V. All rights reserved.

Ethanol electro-oxidation on carbon-supported Pt-Ru, Pt-Rh and Pt-Ru-Rh nanoparticles

This work investigates the effects of carbon-supported Pt, Pt-Ru, Pt-Rh and Pt-Ru-Rh alloy electrocatalysts oil the yields of CO2 and acetic acid as electro-oxidation products of ethanol. Electronic and structural features of these metal alloys were studied by in situ X-ray absorption spectroscopy (XAS). The electrochemical activity was investigated by polarization experiments and the reaction intermediates and products were analyzed by in situ Fourier Transform Infra-Red Spectroscopy (FTIR). Electrochemical stripping of CO. which is one of the adsorbed intermediates, presented a faster oxidation kinetics on the Pt-Ru electrocatalyst, and similar rates of reaction on Pt-Rh and Pt. The electrochemical current of ethanol oxidation showed a higher value and the onset potential was less positive oil Pt-Ru. However, in situ FTIR spectra evidenced that the CO2/acetic acid ratio is higher for the materials with Rh, mainly at lower potentials. These results indicate that the Ru atoms act mainly by providing oxygenated species for the oxidation of ethanol intermediates, and point out ail important role of Rh on the C-C bond dissociation. (C) 2007 Elsevier Ltd. All rights reserved.

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.

X-ray spectroscopy applied to radiation shielding calculation in mammography

The protective shielding design of a mammography facility requires the knowledge of the scattered radiation by the patient and image receptor components. The shape and intensity of secondary x-ray beams depend on the kVp applied to the x-ray tube, target/filter combination, primary x-ray field size, and scattering angle. Currently, shielding calculations for mammography facilities are performed based on scatter fraction data for Mo/Mo target/filter, even though modern mammography equipment is designed with different anode/filter combinations. In this work we present scatter fraction data evaluated based on the x-ray spectra produced by a Mo/Mo, Mo/Rh and W/Rh target/filter, for 25, 30 and 35 kV tube voltages and scattering angles between 30 and 165 degrees. Three mammography phantoms were irradiated and the scattered radiation was measured with a CdZnTe detector. The primary x-ray spectra were computed with a semiempirical model based on the air kerma and HVL measured with an ionization chamber. The results point out that the scatter fraction values are higher for W/Rh than for Mo/Mo and Mo/Rh, although the primary and scattered air kerma are lower for W/Rh than for Mo/Mo and Mo/Rh target/filter combinations. The scatter fractions computed in this work were applied in a shielding design calculation in order to evaluate shielding requirements for each of these target/filter combinations. Besides, shielding requirements have been evaluated converting the scattered air kerma from mGy/week to mSv/week adopting initially a conversion coefficient from air kerma to effective dose as 1 Sv/Gy and then a mean conversion coefficient specific for the x-ray beam considered. Results show that the thickest barrier should be provided for Mo/Mo target/filter combination. They also point out that the use of the conversion coefficient from air kerma to effective dose as 1 Sv/Gy is conservatively high in the mammography energy range and overestimate the barrier thickness. (c) 2008 American Association of Physicists in Medicine.

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

MAGNETIC RESONANT X-RAY DIFFRACTION APPLIED TO THE STUDY OF EuTe FILMS AND MULTILAYERS

In this work we use magnetic resonant x-ray diffraction to study the magnetic properties of a 1.5 mu m EuTe film and an EuTe/PbTe superlattice (SL). The samples were grown by molecular beam epitaxy on (111) oriented BaF(2) substrates. The measurements were made at the Eu L(2) absorption edge, taking profit of the resonant enhancement of more than two orders in the magnetically diffracted intensity. At resonance, high counting rates above 11000 cps were obtained for the 1.5 gm EuTe film, allowing to check for the type II antiferromagnetic order of EuTe. An equal population of the three possible in-plane magnetic domains was found. The EuTe/PbTe SL magnetic peak showed a satellite structure, indicating the presence of magnetic correlations among the 5 ML (monolayers) EuTe layers across the 15 ML PbTe non-magnetic spacers. The temperature dependence of the integrated intensities of the film and the SL yielded different Neel temperatures T(N). The lower T(N) for the SL is explained considering the higher influence of the surface atoms, with partial bonds lost.

Furan interaction with the Si(001)-(2 x 2) surface: structural, energetics, and vibrational spectra from first-principles

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of furan on the silicon (001) surface. A direct comparison of different adsorption structures with x-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), high resolution electron energy loss spectroscopy (HREELS), near edge x-ray absorption fine structure (NEXAFS), and high resolution spectroscopy experimental data allows us to identify the [4 + 2] cycloaddition reaction as the most probable adsorbate. In addition, theoretical scanning tunnelling microscopy (STM) images are presented, with a view to contributing to further experimental investigations.

Energy-dispersive X-ray fluorescence analysis of a pre-Columbian funerary gold mask from the Museum of Sican, Peru

A funerary gold mask from the Museum of Sican, Ferranafe, Peru was analyzed in 30 different areas using a portable equipment using energy-dispersive X-ray fluorescence. It was deduced from the measurements that the main sheet of the mask and the majority of the pendants have a similar composition and are made of tumbaga, which means a poor gold alloy enriched at the surface by depletion gilding, and have a similar `equivalent` gilding thickness of about 5 mu m. The nose, also on tumbaga, has different composition and a thickness of about 8 mu m. The clamps are on gilded or on silvered copper. The red pigment dispersed on the surface of the mask is cinnabar. Copyright (C) 2009 John Wiley & Sons, Ltd.

Root uptake and reduction of hexavalent chromium by aquatic macrophytes as assessed by high-resolution X-ray emission

Aquatic macrophytes Salvinia auriculata, Pistia stratiotes and Eichhornia crassipes were chosen to investigate the Cr(VI) reduced by root-based biosorption in a chromium uptake experiment, using a high-resolution XRF technique. These plants were grown in hydroponics medium supplied with non-toxic Cr concentrations during a 27-day metal uptake experiment. The high-resolution Cr-K beta fluorescence spectra for dried root tissues and Cr reference material (100% Cr, Cr(2)O(3), and CrO(3)) were measured using an XRF spectrometer. For all species of aquatic plant treated with Cr(VI), the energy of the Cr-K beta(2,5) line was shifted around 8 eV below the same spectral line identified for the Cr(VI) reference, but it was also near to the line identified for the Cr(III) reference. Moreover, there was a lack of the strong Cr-K beta"" line assigned to the Cr(VI) reference material within the Cr(VI)-treated plant spectra, suggesting the reduction of Cr(VI) for other less toxic oxidation states of Cr. As all Cr-K beta spectra of root tissue species were compared, the peak energies and lineshape patterns of the Cr-K beta(2,5) line are coincident for the same aquatic plant species, when they were treated with Cr(III) and Cr(VI). Based on the experimental evidence, the Cr(VI) reduction process has happened during metal biosorption by these plants. (C) 2009 Elsevier Ltd. All rights reserved.

X-ray spectrometry: a powerful tool for the measurement of complete fusion of weakly bound nuclei

We describe how the method of detection of delayed K x-rays produced by the electron capture decay of the residual nuclei can be a powerful tool in the investigation of the effect of the breakup process on the complete fusion (CF) cross-section of weakly bound nuclei at energies close to the Coulomb barrier. This is presently one of the most interesting subjects under investigation in the field of low-energy nuclear reactions, and the difficult experimental task of separating CF from the incomplete fusion (ICF) of one of the breakup fragments can be achieved by the x-ray spectrometry method. We present results for the fusion of the (9)Be + (144)Sm system. Copyright (c) 2008 John Wiley & Sons, Ltd.

Structure and optical properties of [Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders

[Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders with different yttrium concentrations (x = 0, 0.025 and 0.05) were prepared by solid state reaction. These powders were analyzed by X-ray diffraction (XRD). Fourier transform Raman scattering (FT-RS), Fourier transform infrared (FT-IR) and X-ray absorption near-edge (XANES) spectroscopies. The optical properties were investigated by means of ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. Even with the addition of yttrium, the XRD patterns revealed that all powders crystallize in a perovskite-type cubic structure. FT-RS and FT-IR spectra indicated that the presence of [YO(6)] clusters is able to change the interaction forces between the O-Ti-O and O-Zr-O bonds. XANES spectra were used to obtain information on the off-center Ti displacements or distortion effects on the [TiO(6)] clusters. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels (shallow or deep holes) within the band gap. The PL measurements carried out with a 350 nm wavelength at room temperature showed that all powders present typical broad band emissions in the blue region. (C) 2010 Elsevier Masson SAS. All rights reserved.