Dielectric relaxation study of hydrogen exposure as a source of two-level systems in Al2O3

An important question in the manufacture of superconducting electronics is how to control the two-level systems found in amorphous insulators. The present article shows that hydrogen has a marked impact on the two-level systems in thin films of reactively sputtered Al₂O₃, a standard tunnel oxide for Josephson junctions. The magnitude of dielectric relaxation current in Al₂O₃ films, believed to be caused by two-level systems, is shown to increase monotonically with the flow rate of H₂ into the chamber during deposition. This points toward a potential need for controlling hydrogen during the manufacture of superconducting electronics utilizing Al₂O₃.     

An investigation of the adducts of sulfur tetrafluoride (SF4) with BF3, AsF5, and SbF5

Three adducts SF₄·BF₃, SF₄·AsF₅, and SF₄·SbF₅ were studied in this work, in gas phase, DFT method was performed to study their molecular structures and thermodynamic properties. The heat of formation was studied at the high level DFT levels.

Crystal structures were predicted using the Dreiding force field and refined by DFT-GGA-RPBE method. All the obtained crystal structures belong to the P2₁/c space group. The lattice energies were predicted to be located between ?91.86 and ?693.73 kJ/mol at the GGA-RPBE level. Based on the optimized crystal structures, the band gap (ΔEg) and density of state (DOS) were predicted and the calculations indicate that they are semiconductors with the band gap between 2.22 and 2.43 ev.     

Advanced nanostructure Ti0.7In0.3O2 support enhances electron transfer to Pt: Used as high performance catalyst for oxygen reduction reaction

ABSTRACT

The slow rate of the oxygen reduction reaction (ORR) and the instability of Pt based catalysts are two of the most important issues which must be solved in order to make proton exchange membrane fuel cells (PEMFCs) a reality. Here, we present a new approach by exploring robust non-carbon Ti_0.7In_0.3O₂ used as a novel functionalised co-catalytic support for Pt. This approach is based on the novel nanostructure Ti_0.7In_0.3O₂ support with “electronic transfer mechanism” from Ti_0.7In_0.3O₂ to Pt that can modify surface electronic structure of Pt, owing to a shift in the d-band centre of the surface Pt atoms. The 20 wt% Pt/Ti_0.7In_0.3O₂ catalyst shows high activity than that of that of the commercial 20 wt% Pt/C (E-TEK). Our data suggest this enhancement is a result of both the electronic structure change of Pt upon its synergistic interaction with Ti_0.7In_0.3O₂ and the inherent structural and chemical stability and the corrosion-resistance of the Ti_0.7In_0.3O₂ in acidic and oxidative environments.     

Effect of ethylene carbonate in poly (methyl methacrylate)-lithium tetraborate based polymer electrolytes

Thin films composed of poly (methyl methacrylate) (PMMA), lithium tetraborate (Li₂B₄O₇) and ethylene carbonate (EC) were prepared by solution casting method. The highest ionic conductivity at room temperature was achieved for the composition PMMA:Li₂B₄O₇:EC (42:18:40) with the value 1.29 × 10⁻⁵ S cm⁻¹. The presence of plasticizer in the polymer complex is crucial in improving the ionic conductivity by increasing the concentration of free mobile ions through the structural conversion from crystalline to amorphous phase. This conversion lowers the viscosity of the polymer complex. Conductivity-temperature plots were found to obey Williams-Landel-Ferry (WLF) mechanism. Dielectric data was analyzed using the dielectric permittivity (ε′) and dielectric modulus (M′) of the samples. Fourier transform infrared (FTIR) studies confirmed that complexation occurs between PMMA, Li₂B₄O₇ and EC. Thermal stability of the polymer complex, which decreases with the addition of plasticizer (EC), was determined using thermal gravimetric analysis (TGA).     

Addition effects of bismuth oxide on Samaria-doped ceria based lithium carbonate composite electrolytes for intermediate temperature-solid oxide fuel cells

ABSTRACT

The effect of amounts (3, 5, 10, 20 wt%) of Bi₂O₃ on the sintering characteristics and porosity of Samaria-doped Ceria (SDC) based Lithium carbonate has been evaluated. The density had a maximum as high as 98.5% of theoretical density at 800°C with only 1wt%Li₂CO₃ and 3 wt%Bi₂O₃. The composite electrolytes showed high ion conductivity at evaluated temperatures. Composition and calcination temperature were found to affect the morphology and conductivity of the composite electrolytes greatly. The total conductivity closed to 3 orders of magnitude greater than pure SDC at operating temperature of 900°C and 3.5 orders of magnitude greater than pure SDC at operating temperature of 600°C. Especially, the best sample containing 3 wt% Bi₂O₃ sintered at 800°C for 2 h which had an ionic electrical conductivity of 0.17S cm^?1. According to fuel cell performance, these composite electrolytes are chemically stable, which is an attractive prospect in intermediate temperature solid oxide fuel cell applications.     

Crystal structure, vibrational spectra, and thermal decomposition and nitrogen adsorption behaviour of a new tetramanganese(II) dipyrophosphate decahydrate, Mn4(P2O7)2·10H2O

A new manganese(II) pyrophosphate, Mn₄(P₂O₇)₂·10H₂O, has been synthesized and characterized by single-crystal X-ray diffraction [orthorhombic space group Pnma, with unit cell parameters of a=9.3288(3) ?, b=25.9532(9) ?, c=8.4783(3) ?; Z=4]. All the pyrophosphate anions show non-linear P–O–P bonds with an average angle of 128.60°. The framework of this new pyrophosphate is made up of packed layers of MnO₆ octahedra connected by double-tetrahedra P₂O₇ groups and a layer of Mn(H₂O)₆ units. The [P₂O₇]⁴⁻ anions adopt a bent, near-staggered conformation. The absence of coincidences for the majority of the IR and Raman bands is in accord with the centrosymmetric structure of the material. The vibrational spectra have been interpreted in part on the basis of factor group effects. The structural changes occurring during heating have been investigated by TG-ATD. When Mn₄(P₂O₇)₂ ^.10H₂O is gradually heated, it decomposes into an intermediate hydrated salt at 96°C and then to anhydrous Mn₂P₂O₇ at 325°C. This thermal behaviour is different from that of Zn₄(P₂O₇)₂·10H₂O. The crystal structure of the new managenese(II) pyrophosphate is compared with the known structures of Zn₄(P₂O₇)₂·10H₂O, Mn₂P₂O₇·2H₂O and anhydrous Mn₂P₂O₇. The adsorption and desorption isotherms of Mn₄(P₂O₇)₂·10H₂O, Zn₄(P₂O₇)₂·10H₂O and MnKHP₂O₇·2H₂O have been investigated by BET measurements and the results show that the capacity for N₂ sorption of the Mn(II) salt is two times lower than is that of the Zn(II) isotype and two or three times higher than is that of MnKHP₂O₇·2H₂O.     

Synthesis of Hydrotalcite using Magnesium from Seawater and Dolomite

Abstract

Three methods of synthesizing hydrotalcite(HT) have been developed using magnesium from seawater and dolomite(MgCa(CO₃)₂). In the first process, 1.0M Na₂CO₃solution was added to calcium ion free artificial seawater containing AlCl₃ with an initial Mg/Al molar ratio of 2.0～3.7 until a pH of 10 was obtained. The solution was then continuously stirred for Ih at 60°C. CO₃ ^2--HT was precipitated as a single phase, and the initial Mg/Al molar ratio, which each recovery of Mg²⁺and Al³⁺ from the solution was above 98%, was 2.0–2.3. In the second process, a Ca(OH)₂ slurry was added to artificial seawater containing AlCl₃ with an initial Mg/Al molar ratio of 1.0～5.0 until a pH of 10.5 was obtained, and then was stirred for Ih at 60°C. HT was also precipitated as a single phase with initial Mg/Al molar ratio 2.0～4.0. The initial Mg/Al molar ratio, which each recovery of Mg²⁺ and Al³⁺ from the solution was above 98%, was 2.2～3.3, but SO₄ ^2- and Cl^? were contained in the precipitated HT. When HT was produced using initial Mg/Al molar ratio of 3.0 at 25°C, SO₄ ^2- and Cl^?in the HT were ion-exchanged with CO₃ ^2- in a 0.05M Na₂CO₃solution for 24h at 25°C, and SO₄ ^2- and Cl^? content of the HT were decreased to 0.5 and 0.05wt%, respectively. In the third process, dolomite calcined at 1000°C was added to an AlCl₃ solution with an initial Mg/Al molar ratio of 1.0～2.0, and the solution was stirred for 1～4h at 25～90°C. HT was precipitated with the smallest amount of MgO and Mg(OH)₂ when the initial Mg/Al molar ratio was 1.5 and the solution was stirred for 4h at 90°C.     

Growth of oxide fibers by the internal crystallization method

A new approach is developed for growing relatively inexpensive single-crystal and eutectic oxide fibers suitable for the fabrication of high-temperature composite materials. Sapphire (Al₂O₃), YAG (Y₃Al₅O₁₂), mullite (3Al₂O₃ · 2SiO₂), YAP (YAlO₃), and eutectic (Al₂O₃-Y₃Al₅O₁₂, Al₂O₃-ZrO₂ (Y₂O₃), and Al₂O₃-Gd₂O₃) fibers are produced by the internal crystallization method, and their mechanical strength and micro-structures are studied.     

High-quality silicon/insulator heteroepitaxial structures formed by molecular beam epitaxy using Al2O3 and Si

Heteroepitaxial growth of γ-Al₂O₃ films on a Si substrate and the growth of Si films on the γ-Al₂O₃/Si structures by molecular beam epitaxy have been investigated. It has been found from AFM and RHEED observations that, γ-Al₂O₃ films with an atomically smooth surface with an RMS values of ∼3 Å and high crystalline quality can be grown on Si (1 1 1) substrates at substrate temperatures of 650–750°C. Al₂O₃ films grown at higher temperatures above 800°C, did not show good surface morphology due to etching of a Si surface by N₂O gas in the initial growth stage. It has also been found that it is possible to grow high-quality Si layers by the predeposition of Al layer followed by thermal treatment prior to the Si molecular beam epitaxy. Cross-sectional TEM observations have shown that the epitaxial Si had significantly improved crystalline quality and surface morphology when the Al predeposition layer thickness was 10 Å and the thermal treatment temperature was 900°C. The resulting improved crystalline quality of Si films grown on Al₂O₃ is believed to be due to the Al₂O₃ surface modification.     

Structural and optical properties in gadolinium-aluminum-lead-germanate quaternary glasses

Glasses in the quaternary system 0.05Al₂O₃·0.95[xGd₂O₃·(100-x)(7GeO₂·3PbO)] with 0 ≤ x ≤ 40 mol% have been prepared from melt quenching method. In this paper, we investigated structural and optical properties in gadolinium-alumino-lead-germanate glasses through investigations of FTIR (Fourier-Transform Infrared Spectroscopy) and UV-VIS (Ultra-Violet) spectroscopy.The observations presented in these mechanisms show that by increasing Gd₂O₃ content up to 40 mol%, the glass network modification has taken place mainly in the germanate part, while the excess of oxygen can be accommodated in the host network by the creation of shorter rings of [Ge₂O₇] structural units and the formation of [AlO₄] structural units. The affinity pronounced of the gadolinium cations towards germanate structural units produces the formation of the Gd₂Ge₂O₇ crystalline phase.The UV-VIS spectroscopy data show the charge transfer transitions of Pb^+ 2-O^− 2, Al^+ 3-O^− 2 and Gd^+ 3-O^− 2, respectively. The additional absorption in the range of 300 to 600 nm was attributed to other types of defects such as: non-bridging oxygen ions, change in valency of ions and other color centers.The values of the direct optical band gap of the glasses are determined from the optical absorption spectra. By increasing Gd₂O₃ content in the glass matrix, the optical band gap energy increases indicating changes of the lattice parameters by Gd₂O₃ incorporation.     

Effect of alumina on the structure and properties of Li2O–B2O3–P2O5 glasses

The structure of glasses within the system Li₂O–Al₂O₃–B₂O₃–P₂O₅ has been studied through ³¹P, ¹¹B and ²⁷Al Nuclear Magnetic Resonance, and the effect of Al₂O₃ substitution by B₂O₃ and P₂O₅ network formers on the structure and properties investigated for a constant Li₂O content. Multinuclear NMR results reveal that substitution of Al₂O₃ for B₂O₃ and P₂O₅ network formers in a glass with composition 50Li₂O·15B₂O₃·35P₂O₅ produces a change in boron environment from four-fold to three-fold coordination. Meanwhile aluminum can be present in four-, five- and six-fold coordinations a higher amount of Al(IV) groups is found for increasing alumina contents. The behavior of the glass transition temperature and electrical conductivity of the glasses has been interpreted as a function of the structural changes induced in the glass network when alumina is substituted for B₂O₃, P₂O₅ or both. Small additions of alumina produce a drastic increase in glass transition temperature, while it does not change for [Al₂O₃] greater than 3 mol.%. However, the electrical conductivity shows very different behavior depending on the type of substitution; it can remain constant when B₂O₃ content decreases or sharply decrease when P₂O₅ is substituted by Al₂O₃, which is attributed to a higher amount of BO₃ and phase separation.     

Crystal Structure and Vibrational Spectra of Erbium Trisodium Bis(Cyclotriphosphate) Nonahydrate,ErNa<Subscript>3</Subscript>(P<Subscript>3</Subscript>O<Subscript>9</Subscript>)<Subscript>2</Subscript> · 9H<Subscript>2</Subscript>O

Abstract The cyclotriphosphate salt, ErNa₃(P₃O₉)₂ · 9H₂O, has been characterized by single-crystal X-ray diffraction [hexagonal, space group , with unit cell parameters of a = b = 30.8451(14), c = 12.8063(8) ?; Z = 18]. The structure consists of alternating layers of [P₃O₉]³⁻ groups, ErO₈ dodecahedra, Na(1)O₆ and Na(2)O₇ polyhedra linked together by water molecules. The P₃O₉ rings are grouped along the c-axis in a P₃O₉–ErO₈ arrangement thereby producing broad, hexagonal channels of diameter of 6.65 ? with a side dimension of 3.907 ?. The absence of coincidences for the majority of the IR and Raman bands observed for the cyclotriphosphate salt is in accord with the centrosymmetric structure of the material. The vibrational spectra have been interpreted on the basis of factor group effects. Graphical abstract We report the crystal structure and vibrational spectra of erbium trisodium bis(cyclotriphosphate)nanohydrate salt ErNa ₃ (P ₃ O ₉ ) ₂ · 9H ₂ O H. Assaaoudi, M. Ijjaali, A. Ennaciri, I. S. Butler* and J. A. Kozinski Crystal structure and vibrational spectra of erbium trisodium bis(cyclotriphosphate) nonahydrate,ErNa₃(P₃O₉)₂ · 9H₂O. Projection of the coordination polyhedra of ErNa₃(P₃O₉)₂ · 9H₂O down the c axis     

Structural and optical properties of TiO2:SnO2 thin films prepared by sol gel method

ABSTRACT

TiO₂:SnO₂ thin films were deposited on glass substrates, by using sol gel spin coating method with different ratio (3%, 5% and 7%) at 3200 rpm, to study their effect on different properties of TiO₂: SnO₂ thin films. The structural and optical properties of films have studied for different ratio. These deposited films have been characterized by various methods such as X-Ray Diffraction (XRD), Ultra Visible spectroscopy. The (XRD) can be used to identify crystal structure of as deposited films. The Transmission spectra have shown the transparent and opaque parts in the visible and UV wavelengths.     

Considerations on the structure and physical properties of B2O3-SiO2 and GeO2-SiO2 glasses

Data of density, refractive index and thermal expansion coefficient for B₂O₃-SiO₂ and GeO_2-SiO₂ glasses have been analyzed. The volumes of the structural units are the same found for the vitreous B₂O₃, GeO₂ and SiO₂. The volume of any structural unit is constant over the entire composition region of the glass system. The same has been found for the differential refraction and unit refraction of the structural units in these glasses. Different features are observed for the differential expansion of the structural units. There is a considerable change with composition in the differential expansion of BO₃, GeO₄ and SiO₄ units. The effect is attributed to a change in the asymmetry of vibrations with the number of Si-O-B or Si-O-Ge linkages in the matrix. The thermal expansion coefficient is mainly determined by the contribution of B₂O₃ or GeO₂ in the concerned glasses.     

Preparation of textured porous Al2O3 ceramics by slip casting in a strong magnetic field and its mechanical properties

The textured porous Al₂O₃ ceramics were prepared by slip casting in a strong magnetic field of 6 T and subsequently sintering. The c axis of Al₂O₃ grain was oriented parallel to the direction of the magnetic field and the textured porous microstructure with plate‐shape grains was formed. The porosity of textured porous Al₂O₃ ceramic was 30.37% and the relative density reached 66.29% when the sintering temperature is 1600°C. The textured porous Al₂O₃ green body showed the linear shrinkage anisotropy. The bending strength of the textured porous Al₂O₃ ceramics depended on the alignment direction of plate‐shape grains.     

Transport and Electrochemical Properties of Bi2Sr2CaCu2O8 Superconductors

Abstract

Electrical conductivity and thermoelectric power measurements (77–300K) of both the pure and electrochemically doped with lithium Bi₂Sr₂CaCu₂O₈ system, are presented. Clear correlation between transport and electrochemical properties of Li_xBi₂Sr₂CaCu₂O₈ was shown.     

Influence of Fe2O3 Doping on TiO2 Electrode for Enhancement Photovoltaic Efficiency of Dye-Sensitized Solar Cells

In this work, we report for the first time the improvement of the photovoltaic characteristics of dye-sensitized solar cells (DSSCs) by doping TiO₂ with Fe₂O₃. DSSCs were fabricated using various percentages of Fe₂O₃-doped TiO₂ composite nanoparticles. The Fe₂O₃-doped DSSCs exhibited a maximum conversion efficiency of 5.76% because of the effective electron transport. DSSCs based on Fe₂O₃-doped TiO₂ films showed better photovoltaic performance than cells fabricated with only TiO₂ nanoparticles. This result was attributed to the prevention of recombination between electrons in the TiO₂ conduction band with the dye or electrolytes. A mechanism was suggested based on impedance results, which indicated improved electron transport at the interface of the TiO₂/dye/electrolyte.     

One-step fabrication of Fe2O3/Ag core-shell composite nanoparticles at low temperature

The Fe₂O₃/Ag core-shell composite nanoparticles were successfully prepared via a simple method at low temperature. X-ray diffraction data revealed the formation of core-shell composite nanoparticles, with Fe₂O₃ as the core and silver as the shell. The results from the transmission electron microscopy and scan electron microscopy further indicated that the composite nanoparticles were spherical with a core diameter and shell thickness of 26.0 nm and 13.5 nm, respectively. Magnetic measurements showed that the composite nanoparticles exhibited a typical ferromagnetic behavior, a specific saturation magnetization of 0.95 emu/g and an intrinsic coercivity of 104.0 Oe at room temperature. For a standard two-probe analysis at room temperature, the composite nanoparticles showed a typical conductive behavior and its conductivity was about 3.41 S/m. Moreover, this present synthesis method of Fe₂O₃/Ag core-shell composite nanoparticles shows an easy processing and does not need high-temperature calcining to attain the final product, which can be applied in a variety of areas, including catalysis, medicine, photonics, and new functional device assemblies.     

Crystallization kinetics in Cu46Zr45Al7Y2 bulk metallic glass by differential scanning calorimetry (DSC)

Crystallization transformation kinetics in isothermal and non-isothermal (continuous heating) modes were investigated in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass by differential scanning calorimetry (DSC). In isochronal heating process, activation energy for crystallization at different crystallized volume fraction is analyzed by Kissinger method. Average value for crystallization in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass is 361 kJ/mol in isochronal process. Isothermal transformation kinetics was described by the Johnson-Mehl-Avrami (JMA) model. Avrami exponent n ranges from 2.4 to 2.8. The average value, around 2.5, indicates that crystallization mechanism is mainly three-dimensional diffusion-controlled. Activation energy is 484 kJ/mol in isothermal transformation for Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass. These different results were discussed using kinetic models. In addition, average activation energy of Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass calculated using Arrhenius equation is larger than the value calculated by the Kissinger method in non-isothermal conditions. The reason lies in the nucleation determinant in the non-isothermal mode, since crystallization begins at low temperature. Moreover, both nucleation and growth are involved with the same significance during isothermal crystallization. Therefore, the energy barrier in isothermal annealing mode is higher than that of isochronal conditions.     

Preparation and Characterization of [Zn(H2O)6][Zn2V10O28(H2O)10]?·?6H2O Single Crystals with a Novel Metallic Heteropolyoxoanion

Abstract  The compound investigated in this study contains a novel centrosymmetric heteroanion [Zn₂V₁₀O₂₈(H₂O)₁₀]²⁻. This cluster results from the connection between a V₁₀O₂₈ group and two Zn(2)O(OH₂)₅ octahedra. The Zn(1)O₆ octahedron and three water molecules associated with it are located between the different layers. The [Zn(H₂O)₆][Zn₂V₁₀O₂₈(H₂O)₁₀] · 6H₂O compound belongs to P-1 space group, with a = 8.967(2) ?, b = 10.390(4) ?, c = 12.338(13) ?, α = 108.31(7)°, β = 100.68(7)°, γ = 103.00(3)°, V = 1022(1) ?³ and Z = 1. Refinement gave R = 0.035 and wR(F²) = 0.098 for 3837 unique observed reflexions [I > 2σ(I)]. Index Abstract  The compound investigated in this study contains a novel centrosymmetric heteroanion [Zn₂V₁₀O₂₈(H₂O)₁₀]²⁻. This cluster results from the connection between a V₁₀O₂₈ group and two Zn(2)O(OH₂)₅ octahedra.