Evaluation of portable Raman spectroscopy and handheld X-ray fluorescence analysis (hXRF) for the direct analysis of glyptics

In archaeometry, the advantages of a combined use of Raman spectroscopy and X-ray fluorescence spectroscopy are extensively discussed for applications such as the analysis of paintings, manuscripts, pottery, etc. Here, we demonstrate for the first time the advantage of using both techniques for analysing glyptics. These engraved gemstones or glass materials were originally used as stamps, to identify the owner, for instance on letters, but also on wine vessels. For this research, a set of 64 glyptics (42 Roman glass specimens and 22 modern ones), belonging to the collection of the museum ‘Quinta das Cruzes’ in Funchal (Madeira, Portugal), was analysed with portable Raman spectroscopy and handheld X-ray fluorescence (hXRF). These techniques were also used to confirm the gemological identification of these precious objects and can give extra information about the glass composition. Raman spectroscopy identifies the molecular composition as well as on the crystalline phases present. On the other hand, hXRF results show that the antique Roman glass samples are characterised with low Pb and Sn levels and that the modern specimens can be discriminated in two groups: lead-based and non-lead-based ones.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.

Chemical ordering in As-Se glasses: X-ray absorption edge and XPES studies

X-ray absorption edge and X-ray photoelectron spectroscopic studies of As-Se glasses seem to support a chemical ordering model.

Investigations of oxide superconductors by x-ray absorption, photoemission and cognate spectroscopies

X-ray absorption spectra, X-ray photoelectron spectra and Auger spectra of cuprate superconductors are discussed. The studies establish the absence of Cu3+ for all practical purposes, but point out the importance of oxygen holes. X-ray photoelectron spectra of BaBi0.25Pb0.75O3 and related compounds are also examined.

New computational approaches for inelastic x-ray scattering

Inelastic x-ray scattering spectroscopy is a versatile experimental technique for probing the electronic structure of materials. It provides a wealth of information on the sample's atomic-scale structure, but extracting this information from the experimental data can be challenging because there is no direct relation between the structure and the measured spectrum. Theoretical calculations can bridge this gap by explaining the structural origins of the spectral features. Reliable methods for modeling inelastic x-ray scattering require accurate electronic structure calculations. This work presents the development and implementation of new schemes for modeling the inelastic scattering of x-rays from non-periodic systems. The methods are based on density functional theory and are applicable for a wide variety of molecular materials. Applications are presented in this work for amorphous silicon monoxide and several gas phase systems. Valuable new information on their structure and properties could be extracted with the combination of experimental and computational methods.

Nanoscale studies of materials using x-ray synchrotron radiation and mesoscopic modelling

X-ray synchrotron radiation was used to study the nanostructure of cellulose in Norway spruce stem wood and powders of cobalt nanoparticles in cellulose support. Furthermore, the growth of metallic clusters was modelled and simulated in the mesoscopic size scale. Norway spruce was characterized with x-ray microanalysis at beamline ID18F of the European Synchrotron Radiation Facility in Grenoble. The average dimensions and the orientation of cellulose crystallites was determined using x-ray microdiffraction. In addition, the nutrient element content was determined using x-ray fluorescence spectroscopy. Diffraction patterns and fluorescence spectra were simultaneously acquired. Cobalt nanoparticles in cellulose support were characterized with x-ray absorption spectroscopy at beamline X1 of the Deutsches Elektronen-Synchrotron in Hamburg, complemented by home lab experiments including x-ray diffraction, electron microscopy and measurement of magnetic properties with a vibrating sample magnetometer. Extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray diffraction were used to solve the atomic arrangement of the cobalt nanoparticles. Scanning- and transmission electron microscopy were used to image the surfaces of the cellulose fibrils, where the growth of nanoparticles takes place. The EXAFS experiment was complemented by computational coordination number calculations on ideal spherical nanocrystals. The growth process of metallic nanoclusters on cellulose matrix is assumed to be rather complicated, affected not only by the properties of the clusters themselves, but essentially depending on the cluster-fiber interfaces as well as the morphology of the fiber surfaces. The final favored average size for nanoclusters, if such exists, is most probably a consequence of these two competing tendencies towards size selection, one governed by pore sizes, the other by the cluster properties. In this thesis, a mesoscopic model for the growth of metallic nanoclusters on porous cellulose fiber (or inorganic) surfaces is developed. The first step in modelling was to evaluate the special case of how the growth proceeds on flat or wedged surfaces.

Metal-insulator transitions in metal clusters: a high-energy spectroscopy study of palladium and silver clusters

Bremsstrahlung isochromat spectroscopy (BIS) along with ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS) has been employed to investigate the electron states of Pd and Ag deposited on amorphous graphite at different coverages. The metal core level binding energies increase with decreasing cluster size while the UPS valence bands show a decrease in the 4d states at E(F) accompanied by a shift in the intensity maximum to higher binding energies. BIS measurements show the emergence of new states closer to E(F) with increase in the cluster size. It is pointed out that the observed spectral shifts cannot be accounted for by final-state effects alone and that initial-state effects have a significant role. It therefore appears that a decrease in cluster size is accompanied by a metal-insulator transition.

Influence of Si-C bond density on the properties of a-Si(1-x)C(x) thin films

Amorphous silicon carbide (a-Si(1-x)C(x)) films were deposited on silicon (100) and quartz substrates by pulsed DC reactive magnetron sputtering of silicon in methane (CH(4))-Argon (Ar) atmosphere. The influence of substrate temperature and target power on the composition, carbon bonding configuration, band gap, refractive index and hardness of a-SiC films has been investigated. Increase in substrate temperature results in slightly decreasing the carbon concentration in the films but favors silicon-carbon (Si-C) bonding. Also lower target powers were favorable towards Si-C bonding. X-ray photoelectron spectroscopy (XPS) results agree with the Fourier Transform Infrared (FTIR), UV-vis spectroscopy results. Increase in substrate temperature resulted in increased hardness of the thin films from 13 to 17 GPa and the corresponding bandgap varied from 2.1 to 1.8 eV. (C) 2011 Elsevier B.V. All rights reserved.

Platinum Ion-Doped TiO2: High Catalytic Activity of Pt2+ with Oxide Ion Vacancy in Ti1-x4+Ptx2+O2-x Compared to Pt4+ without Oxide Ion Vacancy in Ti1-x4+Ptx4+O2

Ti0.97Pt0.032+O1.97 and Ti0.97Pt0.034+O2 have been synthesized by a solution combustion method using alanine and glycine as the fuels, respectively. Both crystallize in anatase TiO2 structure with 15 nm average crystallite size. X-ray photoelectron spectroscopy (XPS) confirmed Pt ions are in the 2+ state in Ti0.97Pt0.03O1.97 (alanine) and 4+ state in Ti0.97Pt0.03O2 (glycine). The rate of CO oxidation occurring over Ti0.97Pt0.032+O1.97 (0.76 mu mol.g(-1).s(-1)) is similar to 10, times more than that over Ti0.97Pt0.034+O2 at 60 degrees C (0.08 mu mol.g(-1).s(-1)). A large shift in 100% hydrocarbons conversion to lower temperature was observed for Pt2+ ion-substituted TiO2 relative 10 that for Pt4+ ion-substituted TiO2. After reoxidation of the reduced compound by H-2 as well as CO, Pt ions are stabilized in mixed valences, 2+ and 4+ states. The role of oxide ion vacancy has been demonstrated by CO oxidation and H-2 + O-2 recombination reactions in the presence and absence of O-2. We analyze the activated lattice oxygens upon substitution of Pt2+ and Pt4+ ions in TiO2, using first-principles density functional theory (DFT) calculations with supercells of Ti31Pt1O63, Ti30Pt2O62, and Ti29Pt3O61 for Pt2+ ion substitution and Ti31Pt1O64, Ti30Pt2O62, and Ti29Pt3O61 for Pt4+ ion substitution in TiO2. We find that the local structure of Pt2+ ion has a distorted square planar geometry and that of Pt4+ ion has an octahedral geometry similar to that of Ti4+ ion in pure TiO2. The change in coordination of Pt2+ ion gives rise to weakly bonded oxygens, and these oxygens are involved in high rates of catalytic reaction. Thus, the high catalytic activity results from synergistic roles of Pt2+ ion and oxide ion vacancy and weakly bonded lattice oxygen.

Determination of Internal Structures of Heterogeneous Nanocrystals Using Variable-Energy Photoemission Spectroscopy

This article describes the determination of the internal structure of heterogeneous nanoparticle systems including inverted core-shell (CdS core and CdSe shell) and alloyed (CdSeS) quantum dots using depth-resolved, variable-energy X-ray photoelectron spectroscopy (XPS). A unique feature of this work is the combination of photoelectron spectroscopy performed at lower X-ray energies (400-700 eV), to achieve surface sensitivity, with bulk sensitive measurements at high photon energies (>2000 eV), thereby providing detailed information about the whole nanoparticle structure with a great accuracy. The use of high photon energies furthermore allows us to investigate nanoparticles much larger than those studied thus far. This capability is a consequence of the much-increased mean free path of the photoelectron achieved at high excitation energies. Our results show that the actual structures of the synthesized nanoparticles are considerably different from the nominal, targeted structures, which can be post facto rationalized in terms of the reactivity of different constituents.

Compositional dependence properties change in S40Se60-x,Sb-x alloys

Bulk samples of S40Se60,Sb-x (with x=10, 20, 30 and 40 at. %) were prepared from high purity chemicals by melt quenching technique. The samples compositions were confirmed by using energy dispersive analysis of X-rays. X-ray diffraction studies revealed that all the samples have poly-crystalline phase. The variation in optical properties with compositional has been investigated by X-ray photoelectron spectroscopy and Raman spectroscopy. The optical band gap of the thin films is found to be decreased with composition. Increasing Sb content was found to affect the structural and optical properties of bulk samples. The intensity of core level spectra changes with the addition of Sb clearly interprets the optical properties change due to compositional variation. The Raman shift and new peak formation in these samples clearly show the structural modifications due to Sb addition.

Photoluminescence enhancement of (NH4)(2)S-x passivated InP surface by rapid thermal annealing

Photoluminescence enhancement of (NH4)(2)S-x passivated InP surface followed by rapid thermal annealing (RTA) has been investigated by using photoluminescence (PL), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), An increase in PL intensity of up to 10 times was observed after sulfur passivation and RTA treatment compared to unpassivated InP surface. XPS measurement results show that introduction of RTA process can enhance the sulfur remaining on the passivated surface to bond to indium but no evidence of S-P bond is noticeable. Passivation enhancement mechanism is discussed.

PASSIVATION OF THE INP(100) SURFACE USING (NH4)(2)S-X

InP(100) surface treated with (NH4)(2)S-x has been investigated by using photoluminescence(PL), Auger electron spectroscopy and X-ray photoelectron spectroscopy. It is found that PL intensity increased by a factor of 3.3 after (NH4)(2)S-x passivation and the sulfur remained on the surface only bonded to indium, not to phosphorus. This suggests that the sulfur atoms replace the phosphorus atoms on the surface and occupy the phosphorus vacancies.

Preparation and electrical properties of new oxide ion conductors Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8)

Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8) were synthesized by modified sol-gel method. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The XRD patterns showed that the materials were single phase with a cubic fluorite structure. Impedance spectroscopy measurement in the temperature range between 350 degrees C and 800 degrees C indicated a sharp increase in conductivity for the system containing small amount of Dy2O3. The Ce5.6Dy0.4MoO15-delta detected to be the best conducting phase with the highest conductivity (sigma(t) = 8.93 x 10(-3) S cm(-1)) is higher than that of Ce5.6Sm0.4MoO15-delta (sigma(t) = 2.93 x 10(-3) S cm(-1)) at 800 degrees C, and the corresponding activation energy of Ce5.6Dy0.4MoO15-delta (0.994 eV) is lower than that of Ce5.6Sm0.4MoO15-delta (1.002 eV).

Preparation and Electrical Properties of New Oxide Ion Conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8)

A series of oxide ion conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8) have been prepared by the sol-gel method. Their properties were characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), Raman, IR, X-ray photoelectron spectroscopy (XPS), and AC impedance spectroscopy. The XRD patterns showed that the materials were single phase with a cubic fluorite structure. The conductivity of Ce6-xGdxMoO15-delta increases as x increases and reaches the maximum at x = 0.15. The conductivity of Ce4.5Gd1.5MoO15-delta is sigma(t) = 3.6 x 10(-3) S/cm at 700 degrees C, which is higher than that of Ce4.5/6Gd1.5/6O2-delta (sigma(t) = 2.6 x 10(-3) S/cm), and the corresponding activation energy of Ce4.5Gd1.5MoO15-delta (0.92 eV) is lower than that of Ce4.5/6Gd1.5/6O2-delta (1.18 eV).