Multiplet splitting patterns exhibited by the first row transition metal oxides in X-ray photoelectron spectroscopy

High resolution photoelectron spectra from transition metal ions in TiO₂, V₂O₅, VO₂, V₂O₃, MnO, Mn₂O₃, MnO₂, Cr₂O₃, FeO, CoO, NiO, CuO, Cu₂O, FeSrO₃, and Cu doped CaTiO₃ were re-examined using a constrained curve fitting approach. Effective fits of the multiplet splitting present could be attained for the oxides with unfilled 3d bands if multiple final states were assumed. The type of transitions implied, also suggest the classification of these oxides during core level photoelectron emission as either; Mott–Hubbard (V₂O₅, VO₂, V₂O₃, Cr₂O₃, and FeO), intermediate (MnO, Mn₂O₃, and MnO₂) or charge transfer type compounds (FeSrO₃, CoO, NiO, CuO and Cu doped CaTiO₃). These transitions along with relationships defining the splitting energy with respect to the total spin and binding energy are discussed.     

Glass bead with minimized amount (11 mg) of sample for X‐ray fluorescence determination of archaeological ceramics

By using very small amount – 11‐mg – of sample powder, major oxides (Na₂O, MgO, Al₂O₃, SiO₂, P₂O₅, K₂O, CaO, TiO₂, MnO, and total Fe₂O₃) in ancient pottery (and igneous rocks) were determined with X‐ray fluorescence spectrometry. This minimized amount of sample was used to prepare a fused glass bead with 300 times the weight of lithium tetraborate as an alkali flux. Calibration standards were obtained by compounding chemical reagents (Na₂CO₃, MgO, Al₂O₃, SiO₂, Na₄P₂O₇, K₂CO₃, CaCO₃, TiO₂, MnO₂, and Fe₂O₃) and the flux. Fewer 11 mg of reagents as oxides were able to give reliable calibration curves with good linearity (correlation coefficient: r > 0.995). Fewer 11 mg of sample was able to give reliable analytical results with good precision (relative standard deviation: <3% for more than 10.0 mass% of analyte, <10% for 1.0–10.0 mass% of analyte, and <20% for 0.1–1.0 mass% of analyte). Lower limits of detection were roughly a sub‐percentage of analyte in an unprepared sample (e.g. 0.3 mass% for Na₂O, 0.5 mass% for MgO, 1.0 mass% for Al₂O₃, and 0.01 mass% for MnO). Composition of major oxides in artificial and natural aluminosilicate materials (including rock, stone, sand, sediment, and clay; and their products) should be fundamental information to be considered in detail. The present X‐ray determination based on very small amount of sample might be made readily accessible for destructive analysis of precious samples for archaeology (and geochemistry). Copyright © 2011 John Wiley & Sons, Ltd.     

The formation model of Ni-Cr oxides on NiCoCrAlY-sprayed coating

The atomic arrangement and distribution of oxides (Cr₂O₃, NiCr₂O₄ and NiO) on the sprayed-NiCoCrAlY coating after oxidation are analyzed. The formation and the growth model of Ni-Cr oxide phases are discussed according to the matching relationship between atoms. The outline character and a scale of spinel NiCr₂O₄ are discussed. The results show that Cr atoms can form two close-packed arrangements in the crystal plane of Cr₂O₃ perpendicular to 〈0 0 1〉 orientation. The atomic spacing in the first arrangement corresponds to double that of Ni/Ni₃Al in {1 1 1} crystal face. This suggests that Ni/Ni₃Al is the substrate for Cr₂O₃ to grow along 〈0 0 1〉 direction. The lattice mismatch between Cr₂O₃ and Ni/Ni₃Al is less than that of Al₂O₃, which indicates that Cr₂O₃ is easier to form than Al₂O₃ during the oxidation process. The atomic spacing in another close-packed arrangement of Cr₂O₃ perpendicular to 〈0 0 1〉 orientation is approximately equal to that of Ni or Cr in the plane of NiCr₂O₄ and NiO perpendicular to 〈1 1 1〉 orientation. So Cr₂O₃ can be the substrate for NiCr₂O₄ and NiO to grow in the 〈0 0 1〉 direction. NiCr₂O₄ and NiO can grow directly along the 〈1 1 1〉 orientation on each other. NiCr₂O₄ can grow outward in the planes of Cr₂O₃ perpendicular to 〈0 0 1〉 and grow inward along 〈1 1 1〉 orientation of NiO.     

Laser spectroscopy of spinel microcrystallites in a Cr3+ doped silicate glass

Laser spectroscopy of Cr³⁺ ions makes it possible to follow the crystallization process in a cordiente glass (52 SiO₂, 347 Al₂O₃, 12.5 MgO and 08 Cr₂O₃) Absorption and fluorescence are interpreted by structural considerations showing the variation of Cr³⁺ environment during heat treatment Fluorescence line narrowing is performed at 4 2 K giving information on the detailed crystal structure in MgAl₂O₄ spinel microcrystallites formed during heat treatment The splitting of the ²E level is close to 70 cm^?1 and the ¦2D¦ parameter ranges between 0 95 and 1 35 cm^?1 This wide distribution is associated with the well known disordered distribution of Mg²⁺ and Al³⁺ cations in MgAl₂O₄ spinels.     

Physical adsorption of nitric oxide on metal oxides

Adsorption isotherms have been measured at 77.5 K for nitric oxide and nitrogen on Al₂O₃, MgO, ZnO and NiO, and at 90.2 K. for nitric oxide on A1₂O₃ and NiO. Three isotherm measurements at 77.5 K were made on the Al₂O₃ sample for each adsorbate to examine the effect of different degrees of surface dehydroxylation. The latter was assessed by means of infrared absorption studies on an Al₂O₃ disc. Isosteric heats for NO adsorption on Al₂O₃ and NiO increase from ca. 8 kJ mol^?1 and 6 kJ mol^?1 (respectively) at half monolayer coverage to near the value of the enthalpy of sublimation (16.6 kJ mol^?1) at monolayer completion. These results are discussed in terms of adsorbate dimerisation. Anomalous adsorption-desorption behaviour for the NONiO system is discussed. Effective adsorbate molecular cross-sectional areas and results for N2 adsorption on preadsorbed NO do not support the existence of either localisation or micro-porosity.     

Factors affecting the formation of near infrared-emitting optical centers in Bi-doped glasses

The NIR-emitting optical centers in Bi₂O₃-doped MgO–Al₂O₃–SiO₂ glass were shown to be bismuth dimers formed in a reversible endothermic redox chemical reaction. The reaction enthalpy and the effective dimer charge were determined. It was also brought out that the red (～720 nm) emission band originates from the centers that are quite different from IR-emitting ones.     

Deposition and characterization of binary Al2O3/SiO2 coating layers on the surfaces of rutile TiO2 and the pigmentary properties

Binary Al₂O₃/SiO₂-coated rutile TiO₂ composites were prepared by a liquid-phase deposition method starting from Na₂SiO₃·9H₂O and NaAlO₂. The chemical structure and morphology of binary Al₂O₃/SiO₂ coating layers were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, TG-DSC, Zeta potential, powder X-ray diffraction, and transmission electron microscopy techniques. Binary Al₂O₃/SiO₂ coating layers both in amorphous phase were formed at TiO₂ surfaces. The silica coating layers were anchored at TiO₂ surfaces via Si-O-Ti bonds and the alumina coating layers were probably anchored at the SiO₂-coated TiO₂ surfaces via Al-O-Si bonds. The formation of continuous and dense binary Al₂O₃/SiO₂ coating layers depended on the pH value of reaction solution and the alumina loading. The binary Al₂O₃/SiO₂-coated TiO₂ composites had a high dispersibility in water. The whiteness and brightness of the binary Al₂O₃/SiO₂-coated TiO₂ composites were higher than those of the naked rutile TiO₂ and the SiO₂-coated TiO₂ samples. The relative light scattering index was found to depend on the composition of coating layers.     

Intriguingly high convective heat transfer enhancement of nanofluid coolants in laminar flows

We reported on investigation of the convective heat transfer enhancement of nanofluids as coolants in laminar flows inside a circular copper tube with constant wall temperature. Nanofluids containing Al₂O₃, ZnO, TiO₂, and MgO nanoparticles were prepared with a mixture of 55 vol.% distilled water and 45 vol.% ethylene glycol as base fluid. It was found that the heat transfer behaviors of the nanofluids were highly depended on the volume fraction, average size, species of the suspended nanoparticles and the flow conditions. MgO, Al₂O₃, and ZnO nanofluids exhibited superior enhancements of heat transfer coefficient, with the highest enhancement up to 252% at a Reynolds number of 1000 for MgO nanofluid. Our results demonstrated that these oxide nanofluids might be promising alternatives for conventional coolants.     

Solid state interactions in nano-sized oxides

Comparative study of reactivity of nano- and micro-sized alumina and nickel oxide, obtained by the electrical explosion of metal wires in oxidizing atmosphere, was carried out for the reactions NiO + MoO₃, NiO + Al₂O₃, and Al₂O₃ + Bi₂O₃ by coupled anneals of ceramics, measurements of the conductivity of individual oxides and raw oxide mixtures, X-ray diffraction and differential thermal analysis. The total conductivity of nano-structured oxides was found lower than that of micro-structured ceramics. Mixing bismuth oxide with nano-structured alumina leads to stabilization of the low temperature polymorph α-Bi₂O₃ up to 780 °C. The diffusion permeability of NiMoO₄ layer grown at the surface of NiO ceramics, having submicron grains, was found 2 times lower if compared to NiMoO₄ grown at micro-sized NiO ceramics. NiO and Al₂O₃ nano-powders preserve the high reactivity even when heated up to 1000 °C. The results are discussed in terms of size effects on the solid state reactivity of oxides.     

金属氧化物修饰对介孔纳米TiO2电极的染料敏化太阳能电池电化学性能的影响

将介孔TiO₂纳米粒子(m-TiO₂)多孔膜电极浸入相应的金属硝酸盐的500 oC热处理修饰金属氧化物(如Mg、ZnO、Al₂O₃或NiO).结果表明,金属氧化物修饰均可形成能垒对m-TiO₂膜电极的界面电荷传输过程产生影响,但外加偏压下其膜内电子传输和界面电荷复合均明显依赖于修饰氧化物的种类及其存在形态. 金属氧化物修饰的膜电极在电子传输和界面复合方面的变化与DSSCs的电流-电压特性曲线的变化规律具有明显的相关性,可不同程度地提高电池的光电压,而MgO、ZnO和NiO修饰的电池效率分别提高了23%、13%和6%. 上述结果表明调控电池的本征参数可以改善TiO₂-基DSSCs的性能.     

Fabrication of one-dimensional photonic crystals with Al2O3/TiO2 by pulsed laser deposition

One-dimensional photonic crystal (1D PC) mirrors consisting of Al₂O₃/TiO₂ stacks are theoretically and experimentally investigated at visible frequencies. In our experiments the refractive index of Al₂O₃ is tunable from 1.43 to 1.68. We found that the Al₂O₃/TiO₂ combination can be adopted to fabricate both broad- and narrow-band 1D PC mirrors: Substituting nanoporous Al₂O₃ for dense SiO₂ in an SiO₂/TiO₂ broad-band mirror yields the same spectral properties, while using dense Al₂O₃ in the combination can reduce the band-gap width to as low as 30 nm. The experimentally measured reflection and transmission spectra agree with the numerical results obtained by the transfer matrix method.     

Studies of two-dimensional condensation of water on hydroxylated ZnO,SnO2, and Cr2O3: Determination of two-dimensional critical temperature

The water physisorption isotherms on fully hydroxylated ZnO, SnO₂ and Cr₂O₃ were measured in a wide temperature range (248–298 K for ZnO, 268–333 K for SnO₂ and Cr₂O₃). The two-dimensional critical temperature of water was found to be 305 K on Cr₂O₃ and 236 K on ZnO, but could not be determined on SnO₂ because of poor uniformity of the surface. The entropy of the two-dimensionally condensed water on Cr₂O₃ was found to be 9.3 cal K^?1 mol^?1, which suggests that the condensed phase of water on Cr₂O₃ is ice-like.     

Electrical properties of Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-based composite systems

Composite electrolytes are well-known multiphase systems and exhibit maxima in the conductivity at certain second-phase concentration. An attempt has been made to investigate a number of sodium sulfate (Na₂SO₄)-based composite systems. The dispersoids that have been used are MgO, Al₂O₃, and SiO₂. The samples have been characterized using impedance spectroscopy, X-ray diffraction, and differential scanning calorimetry. The maximum conductivity has been observed for MgO dispersed system, and the percolation threshold has been observed at 30-mol% dispersoid, MgO concentration. Interestingly, two maxima have been observed in case of the Na₂SO₄–SiO₂ and Na₂SO₄–Al₂O₃ composite systems. In the Na₂SO₄–SiO₂ system, the first maximum occurs at lower concentration, i.e., in the range between 10 and 20 mol%, whereas the second occurs at the 40-mol% dispersoid concentration. For the Na₂SO₄–Al₂O₃ system, although slightly indistinguishable, two peaks in the conductivity vs composition plot have been observed around 12- and 30-mol% Al₂O₃ concentrations.     

X‐ray absorption study of the local structure at the NiO/oxide interfaces

This work reports an X‐ray absorption near‐edge structure (XANES) spectroscopy study at the Ni K‐edge in the early stages of growth of NiO on non‐ordered SiO₂, Al₂O₃ and MgO thin films substrates. Two different coverages of NiO on the substrates have been studied. The analysis of the XANES region shows that for high coverages (80 Eq‐ML) the spectra are similar to that of bulk NiO, being identical for all substrates. In contrast, for low coverages (1 Eq‐ML) the spectra differ from that of large coverages indicating that the local order around Ni is limited to the first two coordination shells. In addition, the results also suggest the formation of cross‐linking bonds Ni—O—M (M = Si, Al, Mg) at the interface.     

Metal oxide additives for the sintering of silicon carbide: Reactivity and densification

The effectiveness of sintering additives for β-SiC was examined based on thermodynamic calculations and experimental observations under hot pressing conditions of 1700–1800 °C. Various types of oxides, such as Al₂O₃, Fe₂O₃, MgO, TiO₂, WO₃ and Y₂O₃, were examined theoretically by considering the Gibbs formation free energy and vapor pressure. According to experimental observations expanded to their binary and ternary systems after hot pressing at 1750 °C and 20 MPa, Al₂O₃, MgO, Y₂O₃ and their mixed systems were found to be the only effective sintering additives that do not react with β-SiC at high temperatures. On the other hand, Fe₂O₃, TiO₂, WO₃ and their combinations with other oxides were not effective because of the reaction with β-SiC by forming the corresponding metal carbides and/or silicides, as predicted by thermodynamic simulations. Moreover, the experimental results for the additional possible components were also included.     

Esca investigations of some NiO/SiO2 and NiO—Al2 O3 /SiO2 catalysts

The ESCA spectra of a series of NiO/SiO₂ and NiO—Al₂ O₃/SiO₂ catalysts are reported, together with those of some reference compounds. The positions and shapes of the lines, in conjunction with a quantitative surface analysis from relative intensities, allow the identification of different surface phases, e.g. an NiO-like phase in the impregnated catalysts with very low catalytic activity and an Ni talc-like phase in the precipitated catalysts which have higher activity. The addition of Al₂O₃ has a great influence on the surface structure (formation of alumosilicate).     

Characterization of water exposed plasma sprayed oxide coating materials using XPS

The surface compositions and oxidation states of non-exposed and water exposed plasma sprayed oxide coatings were studied using X-ray photoelectron spectroscopy (XPS). Coating materials were TiO₂, Al₂O₃ and Cr₂O₃ and their mixtures. Water exposures were performed for free standing coating disks at mild electrolyte (1 mmol NaCl solution) at pH 4, 7 and 9. The exposure time was two weeks.It was observed that pure plasma sprayed TiO₂ material was chemically stable over whole experiment pH range and only slight surface hydroxylation was observed for this material.In case of plasma sprayed Al₂O₃ materials the surface O/Al ratio increased considerably during water exposure especially at exposure pH 7. This was probably result of surface conversion to hydrous form. No surface oxidation state changes were observed for this material.The non-exposed Cr₂O₃ materials contained both Cr(III) and Cr(VI) oxides. The water exposures increased the surface oxygen and Cr(VI) contents at the expense of Cr(III). The most probable reason for that was the dissolution of surface Cr(VI) oxide phase during water exposures and the (re)adsorption of dissolved Cr(VI) species back to the surface.     

Chemical modification of metal oxide carrier's surfaces with a silane coupling agent and an application of the method to catalyst preparation

Several metal oxides were modified with γ-anilinopropyltrimethoxysilane (AnPS). Variations in the physicochemical properties with the modification were investigated in detail. The adsorptivity of 12-tungstophosphate anion (PW12) was shown to be greatly improved in the carriers such as SiO₂, TiO₂, and Al₂O₃, which are porous and have a high surface area, but it was not increased in SnO₂ and MgO, which have a small surface area and a high isoelectric point. With TiO₂-carrier, quantitative studies on the adsorptivity were carried out further, and the interaction modes of PW12 on the AnPS-modified surfaces were discussed based on FT-IR and XPS analyses. The isotherm attained quite steeply to a monomolecular layer of PW12. The FT-IR bands ascribed to the anilino group deformed considerably and the N1s-peak in XPS shifted along with the PW12-adsorption. From the findings it was strongly suggested that PW12 was effectively fixed through an acid–base interaction on the AnPS-TiO₂. Catalytic activity of PW12 fixed on AnPS-TiO₂ for 2-propanol dehydration as a test reaction were examined; in the pretreatment at 300°C the activity was limited to a low level but after the treatment at 450°C it increased in proportion to the PW12-loading on the AnPS-TiO₂ surfaces. Thus, it was inferred that PW12 was quite regularly dispersed over the modified surface. In conclusion, it is suggested that the modification technique is applicable to the preparation of a metal oxide–supported heteropolyacid catalyst.     

Fabrication of surface relief gratings on transparent dielectric materials by two-beam holographic method using infrared femtosecond laser pulses

Fabrication of surface relief-type gratings in transparent dielectrics, which are hard to machine, has been achieved by a holographic technique using two infrared femtosecond (fs) pulses from a mode-locked Ti:sapphire laser. The present method can be applied for a variety of transparent dielectrics, Al₂O₃ (sapphire), TiO₂, ZrO₂, LiNbO₃, SiC, ZnO, CdF₂, MgO, CaF₂ crystals, and SiO₂ glass. It is found that the grating formation is due primarily to laser ablation processes. Planar surface relief gratings can be fabricated by colliding two fs laser pulses on the surface of substrates which move at a constant speed, synchronized with the laser repetition rate. Received: 1 March 2000 / Published online: 7 June 2000     

X‐ray fluorescence analysis of sludge ash from sewage disposal plant

Glass bead/x‐ray fluorescence spectrometry of the sludge incineration ashes generated in sewage processing was developed for the determination of ten major components (Na₂O, MgO, Al₂O₃, SiO₂, P₂O₅, K₂O, CaO, TiO₂, MnO, Fe₂O₃) and five minor elements (Zn, Cu, Cr, As, Pb). Sewage sludge ashes consisted of rock‐forming minerals and phosphate crystals that had been used for phosphorus removal. Ash samples were melted and molded with lithium tetraborate to 35 mm diameter glass disks in a Pt–Au crucible. Analytical results of ten major components and five minor elements agreed well with the recommended values of a phosphate rock standard reference material (NIST SRM 694). Elemental compositions of sewage sludge ash from seven sewage‐processing plants in Japan were determined using this method. Concentrations of Fe₂O₃, SiO₂, and CaO, along with loss of ignition in sewage sludge ash mutually differed among the sewage‐processing plant products. Seasonal variations in concentrations of ten major components and five minor components of ash samples produced from October 2001 to September 2002 were determined using the proposed method. Concentrations of SiO₂increased with the inflow of gravel by rainfall, thereby decreasing concentrations of P₂O₅ originating from excreta and microorganisms. Copyright © 2008 John Wiley & Sons, Ltd.