Catalytic combustion of methane over Pt and PdO-supported CeO<Subscript>2</Subscript>–ZrO<Subscript>2</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

Catalytic combustion of methane was investigated on Pt and PdO-supported CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts prepared by a wet impregnation method in the presence of polyvinylpyrrolidone. The catalysts were characterized by X-ray fluorescence analysis, X-ray powder diffraction, X-ray photoelectron spectra, transmission electron microscopy, and BET specific surface area measurements. The Pt/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ and PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were selective for the total oxidation of methane into carbon dioxide and steam, and no by-products such as HCHO, CO, and H₂ were obtained. The catalytic activities of the PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were relatively higher than those of the Pt-supported catalysts, due to the facile re-oxidation of metallic Pd into PdO based on lattice oxygen supplied from the CeO₂–ZrO₂–Bi₂O₃ bulk. A decrease in the calcination temperature during the preparation process was found to be effective in enhancing the specific surface area of the catalysts, whereby particle agglomeration was inhibited. Optimization of the PdO amount and calcination temperature enabled complete oxidation of methane at temperatures as low as 320 °C on the 11.6 wt% PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalyst prepared at 400 °C.     

Optically stimulated luminescence of proton-irradiated α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> crystals

We present the results of the first domestic experimental investigation of the optically stimulated luminescence (OSL) in commercial thermoluminescence (TL) detectors based on proton-irradiated anion-defect corundum. It is demonstrated that the OSL and TL phenomena can, in principle, be jointly used for the dose diagnostics of accelerated particle beams. The observed phenomena have good prospects for application in radiation physics.     

Influence of Bi substitution on microwave dielectric properties of BaO–La<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

The influences of Bi substitution on microwave dielectric properties of Ba₄(La_0.5Sm_0.5)_9.33Ti₁₈O₅₄ solid solutions were investigated. Dielectric ceramics with general formula Ba₄(La_(0.5−z)Sm_0.5Bi _z )_9.33Ti₁₈O₅₄, z = 0.0–0.2 were prepared by conventional solid state route. The structural analysis of all the samples was carried out by X-ray diffraction and scanning electron microscopy. The dielectric properties were investigated as a function of Bi contents using open-ended coaxial probe method in the frequency range 0.3–3.0 GHz at room temperature. Dielectric constant varies from 83 to 88 and loss tangent from 2.1 × 10⁻³ to 5.5 × 10⁻³ at 3 GHz with temperature coefficient of resonant frequency changing from 106.7 to −8.4 ppm/oC as Bi contents increases from z = 0.00–0.20. It has been found that dielectric constant and temperature coefficient of resonant frequency improve whereas loss tangent is adversely affected with increase in Bi substitution.     

Synthesis of high-purity α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> from boehmite obtained by hydrothermal oxidation of aluminum

We demonstrate the possibility of obtaining high-purity aluminum oxide by successive processes of hydrothermal oxidation of aluminum and vacuum heat treatment of the solid oxidation product (boehmite). The results of studies of changes in the structural properties and chemical purity of alumina samples obtained in the different modes of vacuum heat treatment of boehmite are presented. Experiments have shown the ability to produce alumina with a purity of 99.997% (the total content of all impurities is approximately 30 ppm) of aluminum with a purity of 99.8%. It was shown that the chemical purity of the final product depends on not only the temperature and time of heat treatment but also a number of other parameters of the process.     

Reaction of CaAl<Subscript>4</Subscript>O<Subscript>7</Subscript> with (0001)-oriented α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Reactions between thin films of CA₂ and (0001)-oriented α-Al₂O₃ have been studied using a combination of microscopy techniques. Thin films of amorphous CA₂ were deposited on sapphire substrates by pulsed-laser deposition at 900 °C in an oxygen ambient atmosphere. After deposition, the reaction couples were heat treated in air for various times either at 1300 or 1400 °C. Atomic-force microscopy was used to monitor changes in the microstructure of the films. Interfaces between the different regions were examined by transmission electron microscopy (TEM) of cross-sectional samples prepared by focused ion-beam milling. The CA₂ films had dewetted the substrate surface as a result of the heat treatment. An interfacial reaction layer was observed between the dewetted CA₂ droplets and the substrate. The structure of this reaction layer was found to be consistent with γ-Al₂O₃ by computer analysis of high-resolution TEM images. There is a perfect epitaxy between the interfacial layer and the substrate. For the samples heat treated for longer times, hexagonal features were found on the substrate surface. The presence of these features on (0001)-oriented α-Al₂O₃ suggests that CA₆ platelets form by the transformation of the interfacial reaction layer. The results are discussed in relation to the crystallization behavior of the various calcium aluminate phases and the equilibrium-phase diagram of the CaO–Al₂O₃ system.     

Crystallization and microstructural evolution of MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>–La<Subscript>2</Subscript>O<Subscript>3</Subscript> glass-ceramics

Crystallization and microstructure of glasses with the molar compositions 1MgO·1.2Al₂O₃·2.8SiO₂·1.2TiO₂·xLa₂O₃ (x = 0.1 and 0.4) were thermally treated at different temperatures in the range from 950 to 1250 °C and then analyzed by X-ray diffraction and scanning electron microscopy, in combination with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. It was found that the microstructure is first homogeneous with the precipitation of randomly distributed crystals and then indialite domains with embedded perrierite and rutile crystals are formed. For higher temperatures or prolonged times, more domains appear and expand into the bulk of the sample. Finally, the entire sample consists of the indialite domains and the boundaries that are enriched in rutile, perrierite, and magnesium aluminotitanate. Nevertheless, very distinct differences are observed between the samples with different La₂O₃ concentrations. For the sample with x = 0.4, the domains were detected at lower temperatures, while the quantity and size of the domains increase faster due to the promoted precipitation of indialite. For the sample with x = 0.1, in addition to the domain boundaries, secondary boundaries between the “regions” (assemblages of the domains) are observed in a larger length scale. The average size of the crystalline phases found between the “regions” is larger than that typically observed at the domain boundaries. The sizes of the crystals at the boundaries decrease with higher concentrations of La₂O₃, and the crystals (especially perrierite) within the domains become larger, resulting in a more homogeneous microstructure. This results in better dielectric properties, i.e., much higher quality factor for the sample with x = 0.4 in comparison to that with x = 0.1 after heat-treatment at 1150 or 1250 °C.     

Preparation and bactericidal property of MgO nanoparticles on γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

After being impregnated in the solution containing Mg(NO₃)₂·6H₂O, -Al₂O₃ was dried and calcined at 500°C which results in the production of a bactericide, highly dispersed MgO loaded on the surface of -Al₂O₃. The threshold value of the monolayer dispersion of MgO on -Al₂O₃ is 14.97%, and MgO crystal formed when the load amount beyond this value. The samples with different load amount were characterized by X-ray Diffraction (XRD), Low-temperature N₂ adsorption-desorption, Inductively Coupled Plasma (ICP) and High Resolution Scan Electronic Microscope (SEM). The results showed that these MgO microcrystals are highly dispersed and have regular size in the range of 4 to 10.8 nm. The specific surface, pore volume and pore size of the sample decreases with the increase of load amount. It is demonstrated that -Al₂O₃ with highly dispersed MgO on the surface is efficient bactericide, and the one with 20% load amount of MgO can kill more than 99% bacteria and spore cells.     

Preparation,structure and microwave dielectric properties of 3MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–3TiO<Subscript>2</Subscript> ceramics

3MgO–Al₂O₃–3TiO₂ (MAT) ceramics were prepared by a conventional solid-state reaction method. The crystal structure, sintering behavior and microwave dielectric properties of ceramics were investigated using X-ray diffraction, scanning electron microscopy and network analyzer. MAT ceramics contained the coexistence of three phases, including MgAl₂O₄, MgTiO₃ and MgTi₂O₅. The ceramics sintered at 1350 °C for 4 h presented excellent comprehensive performances with relative permittivity (ε _r ) of 15.4, quality factor (Q × f) of 91,000 GHz and temperature coefficient of resonant frequency (τ _f ) about ?55.1 ppm/°C.     

A sol–gel-derived α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> crystal interlayer modified 316L porous stainless steel to support TiO<Subscript>2</Subscript>, SiO<Subscript>2</Subscript>, and TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> hybrid membranes

A homogeneous α-Al₂O₃ crystal membrane was fabricated by the sol–gel technique on 316L porous stainless steel (PSS) substrate with an average pore size of 1.0 μm. The preparation process was optimized by carefully choosing the binder, the concentrations of the casting solutions and the sintering temperatures of the membranes. Compared to methylcellulose and polyethylene glycol 20000, polyvinyl alcohol 1750 was found to be the most effective binder to fabricate a homogeneously structured Al₂O₃ membrane without defects. The concentration to prepare an uniform coverage membrane with a thickness of ~10 μm was 0.032 mol/L. When sintered at 1000 °C, γ-Al₂O₃ membrane with ~3 μm grains was obtained. When sintered at 1200 °C, γ-Al₂O₃ completely transformed into α-Al₂O₃ and the grains grew to ~5 μm. Accordingly, the process was applied to a bigger pore-sized PSS with an average pore size of 1.5 μm to fabricate an α-Al₂O₃ intermediate layer to initially modify its surface. A single α-Al₂O₃ crystal layer with a thickness of ~5 μm and an average pore size of 0.7 μm was achieved. Subsequently, TiO₂, SiO₂, and TiO₂–SiO₂ hybrid membranes were tried on the modified PSS. Defect-free microfiltration membranes with average pore sizes of ~0.3 μm were readily fabricated. The results indicate that the sol–gel method is promising to initially modify the PSS substrates and the sol–gel-derived α-Al₂O₃ crystal layer is an appropriate intermediate layer to modify the PSS and to support smaller grain-sized top membranes.     

System ZnO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>-CuO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>

Differential thermal analysis and x-ray diffraction data indicate that the ZnO B₂O₃-CuO B₂O₃ join of the ternary system CuO-B₂O₃-ZnO is pseudobinary, with eutectic phase relations and a liquid-liquid miscibility gap in the composition range 25–35 mol % CuO.Translated from Neorganicheskie Materialy, Vol. 41, No. 3, 2005, pp. 339–340.Original Russian Text Copyright © 2005 by Kasumova, Bananyarly.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Spectroscopic characterisation of local structure in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses doped with gadolinium

Gadolinium doped bismuth borate glasses containing up to 30 mol% Y₂O₃ were prepared by fast melt quenching method. The effect of yttrium on the local order in 3B₂O₃ · Bi₂O₃ and B₂O₃ · Bi₂O₃ glass matrices, particularly on the bismuth sites, was investigated by infrared (IR) spectroscopy and electron paramagnetic resonance (EPR) of Gd³⁺ ions. The IR results show that the local structure is more ordered in the glass system with higher bismuth content and the progressive addition of yttrium increases the local disorder in both bismuth–borate glass matrices. The EPR results indicate that Gd³⁺ ions occupy both bismuth and yttrium sites and reflect the same structural disorder like that suggested by IR results.     

Fabrication of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–SiO<Subscript>2</Subscript> Optical Fibers with a Perfect Step-Index Profile by the MCVD Process

An all-vapor phase MCVD process has been proposed for the fabrication of fiber preforms with a Yb₂O₃–Al₂O₃–P₂O₅–SiO₂ multicomponent glass core. We have investigated the tubular preform collapse into a rod and demonstrated approaches capable of preventing P₂O₅ losses in the central part of the core during the collapse process. Preforms with a flat, perfect step-index profile have been fabricated.     

BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript> films produced from BaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> heterostructures

BaFe₁₂O₁₉ hexaferrite films have been produced on thermally oxidized single-crystal silicon (SiO₂/Si) substrates by sequential ion-beam sputtering of BaFe₂O₄ and α-Fe₂O₃ targets in an argon-oxygen atmosphere. Their crystal structure has been studied, and the origin of the impurity phases forming during heat treatment has been identified. The results show that heat treatment may lead to the formation of eutectic melts. As a result, the hexaferrite films may contain spherulites.     

The influence of combustion synthesis conditions on the α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powder preparation

Fuel type and fuel/aluminium nitrate molar ratio proved to be of great importance during the preparation of α-Al₂O₃ powders. A stoichiometric amount of urea (U) enabled the formation of α-Al₂O₃ with a surface area of 24 m²/g directly from the combustion reaction. Monoethanolamine, triethylenetetramine, trishydroxymethylaminomethane, and triethanolamine yield amorphous powders. This behaviour was explained by the reaction mechanism, which requires the simultaneous decomposition of metal nitrate and fuel, as shown by thermal analysis. The use of 50% of the stoichiometric amount of U was unable to trigger a combustion reaction. The resulting powder was amorphous and had a surface area of 424 m²/g. A parabolic correlation between the surface area of combustion-synthesized powder and the U/aluminium nitrate molar ratio was found. Due to U consumption during the hydrolysis side-reaction, 50% of U excess above the stoichiometric ratio is required in order to maximize the exothermic effect of the combustion reaction. The use of U excess higher than 150% of the stoichiometric ratio not only increases the surface area of the powder, but also changes the phase composition: as the U excess increases the proportion of α-Al₂O₃ decreases and the amount of γ-Al₂O₃ increases.     

Fe effect on the process of intrinsic point defects in α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Fe is a common existing impurity in α-Al₂O₃, and thus the effect of Fe on the process of intrinsic point defects in α-Al₂O₃ has been investigated based on first-principles calculations. It is found that the formation, charge state, relative stability and equilibrium configuration of isolated intrinsic point defects in α-Al₂O₃ will be remarkably influenced by Fe, resulting in the variation of defect process, i.e., the formation of defect complex such as Schottky defect, Frenkel defect and antisite pair in α-Al₂O₃. Generally speaking, depending on the O-condition, the most stable configurations, types and relative proportions of defect complexes will be varied by Fe doping in α-Al₂O₃. From the viewpoint of defect formation energy, Fe is favorable for Frenkel defects and antisite pairs in α-Al₂O₃ under both O-rich and O-deficient conditions; while for Schottky defects, Fe is favorable for the defect formation under the O-rich condition, yet unfavorable under the O-deficient condition.     

Synthesis and characterization of TiO<Subscript>2</Subscript>–NiO and TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> nanocomposites

TiO₂–NiO and TiO₂–WO₃ nanocomposites were prepared by hydrothermal and surface modification methods. The samples were analyzed using X-ray diffraction, Scanning Electron Microscope images, Transmission Electron Microscope, Energy dispersive analysis, Zeta potential, Electrophoretic mobility and Photocatalysis activity measurement. XRD data sets of TiO₂–NiO, TiO₂–WO₃ powder nanocomposite have been studied for the inclusion of NiO, WO₃ on the anatase-rutile mixture phase of TiO₂ by Rietveld refinement. The cell parameters, phase fraction, the average grain size, strain and bond lengths between atoms of individual phases have been reported in the present work. Shifted positional co-ordinates of individual atoms in each phase have also been observed.     

Synthesis of <Emphasis Type="Italic">γ</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires through a boehmite precursor route

Crystalline γ-Al₂O₃ nanowires with diameter, 20–40 nm, length above 600 nm and aspect ratio above 30 have been successfully synthesized by thermal decomposition of boehmite (γ-AlOOH) precursors obtained via hydrothermal route by using AlCl₃, NaOH and NH₃ as starting materials. Thermogravimetric analysis (TG), differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscope (TEM), selected area electron diffraction (SAED) and high resolution transmission electron microscope (HRTEM) were used to characterize the features of the as-made γ-Al₂O₃ nanowires and their γ-AlOOH precursors. The pH value of the solution and the mixed precipitant play important roles in the formation of γ-AlOOH nanowires. After calcination at 500°C for 2 h, the orthorhombic γ-AlOOH transforms to cubic γ-Al₂O₃ and retains nanowire morphology.     

Increased mobility of an <Emphasis Type="Italic">α</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> grain boundary by electron-beam irradiation

When subjected to electron-beam irradiation in a transmission electron microscope, the grain boundary in an α-Al₂O₃ bicrystal is observed to migrate even at room temperature. The bicrystal is composed of grains with the same normal direction, and thus the difference in strain energy or surface energy between the two grains cannot explain the observed migration. We attribute this phenomenon to an increase in grain boundary mobility by electron-beam irradiation, especially by radiolysis effects.     

Variable—Range hopping in Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> glasses

The dc conductivity of the glasses in the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system was studied at temperatures between 223 and 393 K. At temperatures from 300 to 223 K, T^–1/4 (T is temperature) dependence of the conductivity was found, however, both Mott variable-range hopping and Greaves intermediate range hopping models are found to be applicable. Mott and Greaves parameters analysis gave the density of states at Fermi level N (E_F) = 3.13 × 10²⁰–21.01 × 10²⁰ and 1.93 × 10²¹–16.39 × 10²¹ cm^–3eV^–1 at 240 K, respectively. The variable-range hopping conduction occurred in the temperature range T = 300–223 K, since W_D was found to be large (W_D = 0.08–0.14 eV for these glasses) and dominated the conduction at T < 300 K.     

Comparative study of multilayered ZnO/TiO<Subscript>2</Subscript>/ZnO and TiO<Subscript>2</Subscript>/ZnO/TiO<Subscript>2</Subscript> thin films prepared by sol–gel dip coating method

The aim of this research work is to represent the comparative study of ZnO/TiO₂/ZnO (ZTZ) and TiO₂/ZnO/TiO₂ (TZT) thin films deposited by sol–gel dip coating on FTO substrates. After deposition, the films were annealed at 500 °C for 1 h. Structural, surface morphology, optical and electrical properties of these films were studied by X-ray diffractrometer (XRD), Raman spectra, atomic force microscope (AFM), photoluminescence spectra (PL) and four point probe technique respectively. XRD and Raman spectra confirmed the anatase, brookite phases of TiO₂ and cubic phase of ZnO. AFM confirmed the formation of nano particles with average sizes of 18.4 and 47.2 nm of TZT and ZTZ films respectively. According to PL spectra, both the multilayer films slowdown the electron hole recombination rate and enhances the optoelectronic properties of the materials. Also it showed the peaks in the visible region of spectrum. The four point probe results showed that the average sheet resistivity of the films is 450 and 120 (ohm-m) respectively.