RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

Further characterisation of the 91500 zircon crystal

This paper reports the results from a second characterisation of the 91500 zircon, including data from electron probe microanalysis, laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS), secondary ion mass spectrometry (SIMS) and laser fluorination analyses. The focus of this initiative was to establish the suitability of this large single zircon crystal for calibrating in situ analyses of the rare earth elements and oxygen isotopes, as well as to provide working values for key geochemical systems. In addition to extensive testing of the chemical and structural homogeneity of this sample, the occurrence of banding in 91500 in both backscattered electron and cathodoluminescence images is described in detail. Blind intercomparison data reported by both LA-ICP-MS and SIMS laboratories indicate that only small systematic differences exist between the data sets provided by these two techniques. Furthermore, the use of NIST SRM 610 glass as the calibrant for SIMS analyses was found to introduce little or no systematic error into the results for zircon. Based on both laser fluorination and SIMS data, zircon 91500 seems to be very well suited for calibrating in situ oxygen isotopic analyses.

Raman scattering and photoluminescence analysis of silicon on insulator structures obtained by single and multiple oxygen implants

An analysis of silicon on insulator structures obtained by single and multiple implants by means of Raman scattering and photoluminescence spectroscopy is reported. The Raman spectra obtained with different excitation powers and wavelengths indicate the presence of a tensile strain in the top silicon layer of the structures. The comparison between the spectra measured in both kinds of samples points out the existence in the multiple implant material of a lower strain for a penetration depth about 300 nm and a higher strain for higher penetration depths. These results have been correlated with transmission electron microscopy observations, which have allowed to associate the higher strain to the presence of SiO2 precipitates in the top silicon layer, close to the buried oxide. The found lower strain is in agreement with the better quality expected for this material, which is corroborated by the photoluminescence data.

Growth, optical characterization, and laser operation of a stoichiometric crystal KYb(WO4)(2)

We present our recent achievements in the growing and optical characterization of KYb(WO4)2 (hereafter KYbW) crystals and demonstrate laser operation in this stoichiometric material. Single crystals of KYbW with optimal crystalline quality have been grown by the top-seeded-solution growth slow-cooling method. The optical anisotropy of this monoclinic crystal has been characterized, locating the tensor of the optical indicatrix and measuring the dispersion of the principal values of the refractive indices as well as the thermo-optic coefficients. Sellmeier equations have been constructed valid in the visible and near-IR spectral range. Raman scattering has been used to determine the phonon energies of KYbW and a simple physical model is applied for classification of the lattice vibration modes. Spectroscopic studies (absorption and emission measurements at room and low temperature) have been carried out in the spectral region near 1 µm characteristic for the ytterbium transition. Energy positions of the Stark sublevels of the ground and the excited state manifolds have been determined and the vibronic substructure has been identified. The intrinsic lifetime of the upper laser level has been measured taking care to suppress the effect of reabsorption and the intrinsic quantum efficiency has been estimated. Lasing has been demonstrated near 1074 nm with 41% slope efficiency at room temperature using a 0.5 mm thin plate of KYbW. This laser material holds great promise for diode pumped high-power lasers, thin disk and waveguide designs as well as for ultrashort (ps/fs) pulse laser systems.

Mineral inventory of continuously erupting basaltic andesites at Arenal volcano, Costa Rica: implications for interpreting monotonous, crystal-rich, mafic arc stratigraphies

Except for the first 2 years since July 29, 1968, Arenal volcano has continuously erupted compositionally monotonous and phenocryst-rich (similar to35%) basaltic andesites composed of plagioclase (plag), orthopyroxene (opx), clinopyroxene (cpx), spinel olivine. Detailed textural and compositional analyses of phenocrysts, mineral inclusions, and microlites reveal comparable complexities in any given sample and identify mineral components that require a minimum of four crystallization environments. We suggest three distinct crystallization environments crystallized low Mg# (<78) silicate phases from andesitic magma but at different physical conditions, such as variable pressure of crystallization and water conditions. The dominant environment, i.e., the one which accounts for the majority of minerals and overprinted all other assemblages near rims of phenocrysts, cocrystallized clinopyroxene (Mg# similar to71-78), orthopyroxene (Mg# similar to71-78), titanomagnetite and plagioclase (An(60) to An(85)). The second environment cocrystallized clinopyroxene (Mg# 71-78), olivine (<Fo(78)), titanomagnetite, and very high An (similar to90) plagioclase, while the third cocrystallized clinopyroxene (Mg# 71-78) with high (>7) Al/Ti and high (>4 wt.%) Al2O3, titanomagnetite with considerable Al2O3 (10-18 wt.%) and possibly olivine but appears to lack plagioclase. A fourth crystallization environment is characterized by clinopyroxene (e.g., Mg#=similar to78-85; Cr2O3=0.15-0.7 wt.%), Al-, Cr-rich spinel olivine (similar toFo(80)), and in some circumstances high-An (>80) plagioclase. This assemblage seems to record mafic inputs into the Arenal system and crystallization at high to low pressures. Single crystals cannot be completely classified as xenocrysts, antecrysts (cognate crystals), or phenocrysts, because they often contain different parts each representing a different crystallization environment and thus belong to different categories. Bulk compositions are mostly too mafic to have crystallized the bulk of ferromagnesian minerals and thus likely do not represent liquid compositions. On the other hand, they are the cumulative products of multiple mixing events assembling melts and minerals from a variety of sources. The driving force for this multistage mixing evolution to generate erupting basaltic andesites is thought to be the ascent of mafic magma from lower crustal levels to subvolcanic depths which at the same time may also go through compositional modification by fractionation and assimilation of country rocks. Thus, mafic magmas become basaltic andesite through mixing, fractionation and assimilation by the time they arrive at subvolcanic depths. We infer new increments of basaltic andesite are supplied nearly continuously to the subvolcanic reservoir concurrently to the current eruption and that these new increments are blended into the residing, subvolcanic magma. Thus, the compositional monotony is mostly the product of repetitious production of very similar basaltic andesite. Furthermore, we propose that this quasi-constant supply of small increments of magma is the fundamental cause for small-scale, decade-long continuous volcanic activity; that is, the current eruption of Arenal is flux-controlled by inputs of mantle magmas. (C) 2004 Elsevier B.V. All rights reserved.

Sensitivity of single-voxel 1H-MRS in investigating the metabolism of the activated human visual cortex at 7 T.

Proton magnetic resonance spectroscopy (1H-MRS) has been used in a number of studies to noninvasively assess the temporal changes of lactate in the activated human brain. However, the results have not been consistent. The aim of the present study was to test the sensitivity of 1H-MRS during functional experiments at the highest magnetic field currently available for human studies (7 T). Stability and reproducibility of the measurements were evaluated from LCModel analysis of time series of spectra measured during a visual stimulation paradigm and by examination of the difference between spectra obtained at rest and during activation. The sensitivity threshold to detect concentration changes was 0.2 micromol/g for most of the quantified metabolites. The possible variations of metabolite concentrations during visual stimulation were within the same range (+/-0.2 micromol/g). In addition, the influence of a small line-narrowing effect due to the blood oxygenation level-dependent (BOLD) T2* changes on the estimated concentrations was simulated. Quantification of metabolites was, in general, not affected beyond 1% by line-width changes within 0.5 Hz.

Mössbauer spectra of iron oxides in the bulk and nanocrystalline states

Magnetic nanoparticles are very important in modern industry. These particles are used in many different spheres of life. Nanoparticles have unusual physical and chemical properties connected both with quantum dimensional effects and with the increased role of the surface atoms. Most clearly the difference between the properties of bulk materials and nanoparticles can be seen in the magnetic properties of these materials. The most typical magnetic properties of nanomaterials are superparamagnetism with the size of the cluster from 1 to 10 nm; single-domain magnetic state of nanoclusters and nanostructures up to 20 nm; magnetization processes connected with magnetic cluster ordering and with its forms and sizes; quantum magnetic tunneling effects when magnetization changes by jumps and giant magnetoresistance effects. For research of the magnetic properties of iron-containing nanostructures, it is convenient to apply Mӧssbauer spectroscopy. In this work a number of nano-sized samples of iron oxides were examined by Mössbauer spectroscopy. The Mössbauer spectra of nanoparticles with various sizes were obtained. Mössbauer spectra of iron oxide nanoparticles were compared with the spectra of bulk samples. It was shown how the spectra of iron oxide nanoparticles change depending on the particle sizes.

Emission, kinetic and magnetic phenomena in rare-earth and transition metal doped ZnSe single crystals

In this work emission, optical, electrical and magnetic properties of the d- and f- elements doped zinc selenide crystals were investigated within a wide temperature range. Doping was performed in various technological processes: during the growth by chemical vapor transport method; by thermal diffusion from the Bi or Zn melt. Concentration of the doping impurity in the crystals was controlled by amount of the dopant in the source material or by its concentration in the doping media. Special interest in the work was paid to the influence of the different concentrations of Cr and Yb impurities on ZnSe crystals’ properties, correlations between observed effects and similarities with the Ni, Mn and Gd dopants are analysed. Possibility of formation of the excitons bound to the doping d-ions was shown. In contrast to this, it was observed that f-elements do not bound excitons, but prevent formation of excitons bound to some uncontrolled impurities. A mechanism of Cr doping impurity interaction with background impurities and zinc selenide structural defects was proposed based on experimental data. An assumption about resonant energy transfer between double charged chromium ions and complexes based on crystals’ vacancy defects was made. A correlation between emission and magnetic properties of the d- ions doped samples was established. Based on this correlation a mechanism explaining the concentration quench of the emission was proposed. It was found that f-ions bind electrically active shallow and deep donor and acceptor states of background impurity to electrically neutral complexes. This may be observed as “purification” of ZnSe crystals by doping with the rare-earth elements, resulting i tendency of the properties of f-ion doped crystals to the properties of intrinsic crystals, but with smaller concentration of uncontrolled native and impurity defects. A possible interpretation of this effect was proposed. It was shown that selenium substituting impurities decrease efficiency of the Yb doping. Based on this experimental results an attempt to determine ytterbium ion surroundings in the crystal lattice was made. It was shown that co-doping of zinc selenide crystals with the d- and f- ions leads to the combination of the impurities influence on the material’s properties. On the basis of obtained data an interaction mechanism of the d- and f-elements co-dopants was proposed. Guided by the model of the ytterbium ion incorporation in the selenide sublattice of the ZnSe crystals, an assumption about stabilization of single charged chromium ions in the zinc sublattice crystal nodes, by means of formation of the local charge compensating clusters, was made.

Phonon spectra and thermodynamic properties of rare gas solids based on empirical and semi-empirical (ab initio) two-body potentials : a comparative study /

We study the phonon dispersion, cohesive and thermal properties of raxe gas solids Ne, Ar, Kr, and Xe, using a variety of potentials obtained from different approaches; such as, fitting to crystal properties, purely ab initio calculations for molecules and dimers or ab initio calculations for solid crystalline phase, a combination of ab initio calculations and fitting to either gas phase data or sohd state properties. We explore whether potentials derived with a certain approaxih have any obvious benefit over the others in reproducing the solid state properties. In particular, we study phonon dispersion, isothermal ajid adiabatic bulk moduli, thermal expansion, and elastic (shear) constants as a function of temperatiue. Anharmonic effects on thermal expansion, specific heat, and bulk moduli have been studied using A^ perturbation theory in the high temperature limit using the neaxest-neighbor central force (nncf) model as developed by Shukla and MacDonald [4]. In our study, we find that potentials based on fitting to the crystal properties have some advantage, particularly for Kr and Xe, in terms of reproducing the thermodynamic properties over an extended range of temperatiures, but agreement with the phonon frequencies with the measured values is not guaranteed. For the lighter element Ne, the LJ potential which is based on fitting to the gas phase data produces best results for the thermodynamic properties; however, the Eggenberger potential for Ne, where the potential is based on combining ab initio quantum chemical calculations and molecular dynamics simulations, produces results that have better agreement with the measured dispersion, and elastic (shear) values. For At, the Morse-type potential, which is based on M0ller-Plesset perturbation theory to fourth order (MP4) ab initio calculations, yields the best results for the thermodynamic properties, elastic (shear) constants, and the phonon dispersion curves.

An application of cell-cluster theory to a rare gas crystal /|n[by] K. Westera. - 260 St. Catharines [Ont.] : Dept. of Physics, Brock University,

The Lennard-Jones Devonshire 1 (LJD) single particle theory for liquids is extended and applied to the anharmonic solid in a high temperature limit. The exact free energy for the crystal is expressed as a convergent series of terms involving larger and larger sets of contiguous particles called cell-clusters. The motions of all the particles within cell-clusters are correlated to each other and lead to non-trivial integrals of orders 3, 6, 9, ... 3N. For the first time the six dimensional integral has been calculated to high accuracy using a Lennard-Jones (6-12) pair interaction between nearest neighbours only for the f.c.c. lattice. The thermodynamic properties predicted by this model agree well with experimental results for solid Xenon.

The crystal and molecular structure of bis (pyridoxamine) copper (II) dinitrate monohydrate

The crystal structure of Cu(PM)2(N03hoH20 (where PM is pyridoxamine, CSHI2N202) has been determined from three dimensional x-ray diffraction data. The crystals are triclinic, space group pI, a = 14.248 (2), b = 8.568 (1), c = 9.319 (1) 1, a = 94.08 (1), e = 89.73 (1), y~~ 99.18 (1)°, z = 2, jl(MoK) = 10.90 em-I, Po = 1.61 g/cm3 and Pc = 1.61 g/em3• The structure a was solved by Patterson techniques from data collected on a Picker 4-circle diffractometer to 26max = 45°. All atoms, including hydrogens, have been located. Anisotropic thermal parameters have been refined for all nonhydrogen atoms. For the 2390 independent reflections with F ? 3cr(F) , R = 0.0408. The results presented here provide the first detailed structural information of a metal complex with PM itself. The copper atoms are located on centres of symmetry and each is chela ted by two PM zwitterions through the amino groups and phenolate oxygen atoms. The zwitterionic form found in this structure involves the loss of a proton from the phenolate group and protonation of the pyridine ring nitrogen atoms. The two independent Cu(PM)2 moieties are symmetrically bridged by a single oxygen atom from one of the nitrate groups. The second nitrate group is not coordinated to the copper atoms but is central to an extensive hydrogen bonding network involving the water molecule and uncoordinated functional groups of PM.

Crystal Growth and Characterization of Li0.9Mo6O17

Purple bronze Li0.9Mo6O17 has attracted researchers for its low dimensionality and corresponding properties. Although it has been studied for nearly two decades, there are still some unsolved puzzles with this unique material. Single crystals of Li0.9Mo6O17 were grown using the temperature gradient flux technique in this research. The crystal growth was optimized by experimenting different conditions and good quality crystals were obtained. X-ray diffraction results have confirmed the right phase of the crystals. Resistivity measurements and magnetic susceptibility measurements were carried out, and anomalous electronic behaviors were found. All of the samples showed the metal-insulator transition near 20K, followed by behavior that differs from sample to sample: either superconducting, metallic or insulating behavior was observed below 2K. Li0.9Mo6O17 was considered as a quasi-one-dimensional crystal and also a superconducting crystal, which implies a dimensional crossover may occur at the metal-insulator transition. A two-band scenario of the Luttinger liquid model was used to fit the resistivity data and excellent results were achieved, suggesting that the Luttinger theory is a very good candidate for the explanation of the anomalous behavior of Li0.9Mo6O17. In addition, the susceptibility measurements showed Curie paramagnetism and some temperature independent paramagnetism at low temperature. The absence of any anomalous magnetic feature near 20K where the resistivity upturn takes place, suggests that a charge density wave mechanism, which has been proposed by some researchers, is not responsible for the unique properties of Li0.9Mo6O17.

Anisotropy in elastic properties of lithium sodium sulphate hexahydrate single crystal—An ultrasonic study

The double sulfate family (ABSO4), where A and B are alkali metal cations, is the object of great interest owing to the complexity and richness of its sequence of phase transition induced by temperature variation. A new sulfate salt characterized by the presence of water molecule in the unit cell with the chemical formula, Li2Na3(SO4)2⋅6H2O (LSSW), was obtained. The ultrasonic velocity measurement was done with pulse echo overlap technique [PEO]. All the six second order elastic stiffness constants, C11 = C22, C33, C44 = C55, C12, C14 and C13 = C23 are reported for the first time. The anisotropy in the elastic properties of the crystal are well explained by the pictorial representation of the polar plots of phase velocity, slowness, Young’s modulus and linear compressibility in a–b and a–c planes.

Elastic constant measurements of super ionic LiKSO4:Na single crystals

Elastic properties of sodium doped Lithium potassium sulphate, LiK0.9Na0.1SO4, crystal has been studied by ultrasonic Pulse Echo Overlap [PEO] technique and are reported for the first time. The controversy regarding the type of crystal found while growth is performed at 35 °C with equimolar fraction of Li2SO4H2O, K2SO4 and Na2SO4 has been resolved by studying the elastic properties. The importance of this crystal is that it exhibits pyroelectric, ferroelectric and electro optic properties. It is simultaneously ferroelastic and superionic. The elastic properties of LiK0.9Na0.1SO4 crystal are well studied by measuring ultrasonic velocity in the crystal in certain specified crystallographic directions and evaluating the elastic stiffness constants, compliance constants and Poisson’s ratios. The anisotropy in the elastic properties of the crystal are well explained by the pictorial representation of the surface plots of phase velocity, slowness and linear compressibility in a-b and a-c planes.

Ultrasonic measurement of the elastic properties of benzoyl glycine single crystals

Certain organic crystals are found to possess high non- linear optical coefficients,often one to two orders of magnitude higher than those of the well known inorganic non-linear optical materials.Benzoyl glycine is one such crystal whose optical second-harmonic generation efficiency is much higher than that of potassium dihydrogen phosphate. Single crystals of benzoyl glycine are grown by solvent evaporation technique using N,N-dimethyl formamide as the solvent.All the nine second-order elastic stiffness constants of this orthorhombic crystal are determined from ultrasonic wave velocity measurements employing the pulse echo overlap technique.The anisotropy of elastic wave propagation in this crystal is demonstrated by plotting the phase velocity, slowness,Young's modulus and linear compressibility surfaces along symmetry planes.The volume compressibility, bulk modulus and relevant Poisson's ratios are also determined. Variation of the diagonal elastic stiffness constants with temperature over a limited range are measured and reported.