Showing papers on "Oxide published in 1998"

Self-organized formation of hexagonal pore arrays in anodic alumina

Abstract: The conditions for the self-organized formation of ordered hexagonal structures in anodic alumina were investigated for both oxalic and sulfuric acid as an electrolyte. Highly ordered pore arrays were obtained for oxidation in both acids. The size of the ordered domains depends strongly on the anodizing voltage. This effect is correlated with a voltage dependence of the volume expansion of the aluminum during oxidation and the current efficiency for oxide formation. The resulting mechanical stress at the metal/oxide interface is proposed to cause repulsive forces between the neighboring pores which promote the formation of ordered hexagonal pore arrays.

Article having transparent conductive oxide thin film and its production

Abstract: PROBLEM TO BE SOLVED: To obtain an oxide film having excellent transmitting property for blue light while reducing the amt. of In2O3 which is a scarse mineral resource by using an oxide having a specified compsn. of Zn, Al and Ba, In as a target and specifying the substrate temp. and pressure. SOLUTION: An oxide expressed by the general formula of ZnxMyInzO(x+3y/2+3z/2) is used as a target to form an oxide film by sputtering or laser ablation method under the conditions of from room temp. to 300 deg.C substrate temp. and 1×10-2 to 10 (Pa) pressure. In the formula, M is at least one element of Al and Ga, the proportion x/y ranges 0.2 to 12, the proportion z/y ranges 0.4 to 1.4. The conductivity of the oxide of the target is good when the carrier electron density in the conductive band ranges about 1×1018 to 1×1022/cm3. By injecting actions to the oxide, carrier electrons are injected to the conductive band to develop the conductivity.

Catalytic Decomposition of Hydrogen Peroxide on Iron Oxide: Kinetics, Mechanism, and Implications

Abstract: This research describes the heterogeneous catalytic reactions of H2O2 with granular size goethite (α-FeOOH) particles in aqueous solution under various experimental conditions. This is an important reaction for the environment since both H2O2 and iron oxides are common constituents of natural and atmospheric waters. Furthermore, iron oxides function as catalysts in chemical oxidation processes used for treatment of contaminated waters with H2O2. The results of this study demonstrated that the decomposition rate of H2O2 over goethite surface can be described by the second-order kinetic expression −d[H2O2]/dt = k[FeOOH][H2O2], where k = 0.031 M-1 s-1, at pH 7 in the absence of any inorganic or organic chemical species. The apparent reaction rate was dominated by the intrinsic reaction rates on the oxide surfaces rather than the mass transfer rate of H2O2 to the surface. The activation energy of the reaction of H2O2 with the iron oxide surface was determined to be 32.8 kJ/M. The reaction mechanism for the de...

Tin doped indium oxide thin films: Electrical properties

Abstract: Tin doped indium oxide (ITO) films are highly transparent in the visible region, exhibiting high reflectance in the infrared region, and having nearly metallic conductivity. Owing to this unusual combination of electrical and optical properties, this material is widely applied in optoelectronic devices. The association of these properties in a single material explains the vast domain of its applicability and the diverse production methods which have emerged. Although the different properties of tin doped indium oxide in the film form are interdependent, this article mainly focuses on the electrical aspects. Detailed description of the conduction mechanism and the main parameters that control the conductivity is presented. On account of the large varieties and differences in the fabrication techniques, the electrical properties of ITO films are discussed and compared within each technique.

Determination of the concentration of surface hydroxyl groups on metal oxide films by a quantitative XPS method

Abstract: Quantitative XPS has been used to determine the surface concentration of hydroxyl groups in native air-formed oxide films on metals having low surface areas. A mathematical expression has been derived to give the concentration of surface hydroxyl groups as a function of the intensity ratio of the OH to O2− contributions to the O 1s photopeak. This expression is based on modeling the oxide film on a metal to be a multilayer system consisting of an outermost layer of organic contamination, a layer of chemisorbed water, a surface hydroxylated region of the oxide film and the inner portion of the oxide film. The average values of the experimentally determined concentrations of surface hydroxyl groups are 15, 13, 11, 6 and 8 OH nm−2 for oxide-covered aluminum, chromium, titanium, tantalum and silicon, respectively. X-ray photoelectron spectroscopy depth profiles using argon ion sputtering and variable-angle XPS have been utilized in this work. Surface treatments have employed either ultrasonic cleaning with organic solvents or argon plasma treatment. © 1998 John Wiley & Sons, Ltd.

On the Growth of Highly Ordered Pores in Anodized Aluminum Oxide

Abstract: It is now established that hexagonally ordered domain structures can be formed in anodic alumina films by repeated anodization and stripping of the porous oxide. We find that the domain size is a linear function of time and increases with temperature. The pore density is initially high but decreases with anodizing time, as dominant pores deepen. Very small pores exist in native oxide in air or nucleate after electropolishing. Pore growth may start when the electric field increases at the pore bottoms, and acid dissolves the oxide locally.

Quasi-ideal strontium titanate crystal surfaces through formation of stontium hydroxide

Abstract: In recent years, well-defined and nearly perfect single crystal surfaces of oxide perovskites have become increasingly important. A single terminated surface is a prerequisite for reproducible thin film growth and fundamental growth studies. In this work, atomic and lateral force microscopy have been used to display different terminations of SrTiO3. We observe hydroxylation of the topmost SrO layer after immersion of SrTiO3 in water, which is used to enhance the etch-selectivity of SrO relative to TiO2 in a buffered HF solution. We reproducibly obtain perfect and single terminated surfaces, irrespective of the initial state of polished surfaces and the pH value of the HF solution. This approach to the problem might be used for a variety of multi-component oxide single crystals. True two-dimensional reflection high-energy electron diffraction intensity oscillations are observed during homo epitaxial growth using pulsed laser deposition on these surfaces.

New insights in the relation between electron trap generation and the statistical properties of oxide breakdown

Abstract: In this paper it is demonstrated in a wide stress field range that breakdown in thin oxide layers occurs as soon as a critical density of neutral electron traps in the oxide is reached. It is proven that this corresponds to a critical hole fluence, since a unique relationship between electron trap generation and hole fluence is found independent of stress field and oxide thickness. In this way literature models relating breakdown to hole fluence or to trap generation are linked. A new model for intrinsic breakdown, based on a percolation concept, is proposed. It is shown that this model can explain the experimentally observed statistical features of the breakdown distribution, such as the increasing spread of the Q/sub BD/-distribution for ultrathin oxides. An important consequence of this large spread is the strong area dependence of the Q/sub BD/ for ultrathin oxides.

Characterization of Iron Oxides Commonly Formed as Corrosion Products on Steel

Abstract: For fundamental studies of the atmospheric corrosion of steel, it is useful to identify the iron oxide phases present in rust layers. The nine iron oxide phases, iron hydroxide (Fe(OH)2), iron trihydroxide (Fe(OH)3), goethite (α-FeOOH), akaganeite (β-FeOOH), lepidocrocite (γ-FeOOH), feroxyhite (δ-FeOOH), hematite (α-Fe2O3), maghemite (γ-Fe2O3) and magnetite (Fe3O4) are among those which have been reported to be present in the corrosion coatings on steel. Each iron oxide phase is uniquely characterized by different hyperfine parameters from Mossbauer analysis, at temperatures of 300K, 77K and 4K. Many of these oxide phases can also be identified by use of Raman spectroscopy. The relative fraction of each iron oxide can be accurately determined from the Mossbauer subspectral area and recoil-free fraction of each phase. The different Mossbauer geometries also provide some depth dependent phase identification for corrosion layers present on the steel substrate. Micro-Raman spectroscopy can be used to uniquely identify each iron oxide phase to a high spatial resolution of about 1 µm.

Coaxial Nanocable: Silicon Carbide and Silicon Oxide Sheathed with Boron Nitride and Carbon

Abstract: Multielement nanotubes comprising multiple phases, with diameters of a few tens of nanometers and lengths up to 50 micrometers, were successfully synthesized by means of reactive laser ablation. The experimentally determined structure consists of a β-phase silicon carbide core, an amorphous silicon oxide intermediate layer, and graphitic outer shells made of boron nitride and carbon layers separated in the radial direction. The structure resembles a coaxial nanocable with a semiconductor-insulator-metal (or semiconductor-insulator-semiconductor) geometry and suggests applications in nanoscale electronic devices that take advantage of this self-organization mechanism for multielement nanotube formation.

Chemical vapor deposition of gold on Al2O3, SiO2, and TiO2 for the oxidation of CO and of H2

Abstract: In order to clarify the effect of metal oxide support on the catalytic activity of gold for CO oxidation, gold has been deposited on SiO2 with high dispersion by chemical vapor deposition (CVD) of an organo-gold complex. Comparison of Au/SiO2 with Au/Al2O3 and Au/TiO2, which were prepared by both CVD and liquid phase methods, showed that there were no appreciable differences in their catalytic activities as far as gold is deposited as nanoparticles with strong interaction. The perimeter interface around gold particles in contact with the metal oxide supports appears to be essential for the genesis of high catalytic activities at low temperatures.

Prevention of Protein Adsorption by Tethered Poly(ethylene oxide) Layers: Experiments and Single-Chain Mean-Field Analysis

Abstract: Prevention of protein adsorption by the surface-grafted poly(ethylene oxide) (PEO) chains has been well-known. We have examined the mechanisms of how the grafted PEO prevents protein adsorption. PEO−poly(propylene oxide)−PEO (PEO−PPO−PEO) triblock copolymers were used to graft PEO to the trichlorovinylsilane (TCVS)-modified glass by γ-irradiation. The surface density of the PEO chains was varied up to 60 pmol/cm2 and the number of the ethylene oxide (EO) units of the PEO segment was varied from 75 to 128. The adsorption of lysozyme and fibrinogen to the PEO-grafted glass was examined using radiolabeled proteins. The surface protein concentration decreased as the surface density of the grafted PEO increased, but surface protein concentration never reached zero. The experimental data were compared with the predictions by the single-chain mean-field theory. There was very good agreement between the predictions of the theory and the experimental observations. It was found that the mechanism for prevention of ...

Reduction characteristics of copper oxide in cerium and zirconium oxide systems

Abstract: The reduction of CuO dispersed on fluorite-type oxide catalysts, namely La-doped CeO2 and Y-doped ZrO2 was studied in this work. On both supports distinct copper species were identified as a function of copper content by temperature-programmed reduction (TPR) by H2 and CH4, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and scanning transmission electron microscopy/energy dispersive X-ray (STEM/EDX) analyses. At low copper loading ( 15 at%), in addition to clusters, larger CuO particles are present which are reduced at higher temperature close to the reduction temperature of bulk CuO. At copper loading lower than ca. 5 at%, copper is present as highly dispersed clusters or isolated Cu ions, which interact strongly with the fluorite-type oxide, thus requiring higher reduction temperature. However, the latter is still below the bulk CuO reduction temperature. Copper is more stabilized when dispersed in Ce(La)O2 than in Zr(Y)O2 matrix, so that reduction of copper oxide species requires lower temperatures on the Zr(Y)O2-based catalysts. The reducibility of the doped ceria is enhanced by the presence of copper in both H2- and CH4-TPR. On the other hand no such interaction is present in CuZr(Y)O2 system. The activity of various copper species for methane oxidation is discussed.

Superconductivity at 25.5 K in electron-doped layered hafnium nitride

Abstract: The electronic properties of crystals with a layered structure can be radically altered by the intercalation, between the layers, of guest species that act as electron donors or acceptors. Such studies have been performed extensively on graphite, transition-metal dichalcogenides and oxide bronzes1. Interest in redox intercalation reactions2 has increased recently because the high-transition-temperature (high-Tc) superconductors based on copper oxide also have layered structures, the superconductivity occurring within two-dimensional CuO2 planes separated by charge-reservoir oxide layers3. Similarly, in metal-doped fullerenes, which show relatively high transition temperatures, the electron donor atoms sit in the interstitial sites between adjacent fullerene balls4. In a previous study5, we described a layered nitride, β-ZrNCl, consisting of Zr–N double layers sandwiched between two close-packed chlorine layers. On lithium intercalation, the crystal changed from a semiconductor to a metal, and became a superconductor at 13 K. Here we report the properties of the isostructural compound β-HfNCl. After electron-doping the crystal by lithium intercalation, we observe superconductivity with a Tc of up to 25.5 K. This transition temperature is higher than that observed in any intermetallic compound, and suggests that layered nitride structures may offer transition temperatures comparable to those observed in layered copper oxide structures.

Hydrogen gas-extraction module and method of fabrication

Abstract: A hydrogen gas-extraction module includes an intermediate layer bonded between a porous metal substrate and a membrane layer that is selectively permeable to hydrogen. The metal substrate includes a substantial concentration of a first metal at a surface of the metal substrate, and the intermediate layer includes an oxide of this first metal. In one embodiment, where the module is designed to selectively extract hydrogen at high temperatures, the porous metal substrate comprises stainless steel, and the membrane layer includes palladium or a palladium/silver alloy. A method for fabricating a hydrogen gas-extraction membrane includes reacting the porous metal substrate with an oxidizing agent to form a ceramic intermediate layer on a surface of the porous metal substrate and covering the ceramic coating with the membrane layer that is selectively permeable to hydrogen.

Bacterial reduction of crystalline Fe (super 3+) oxides in single phase suspensions and subsurface materials

Abstract: Microbiologic reduction of synthetic and geologic Fe{sup 3+} oxides associated with four Pleistocene-age, Atlantic coastal plain sediments was investigated using a dissimilatory Fe reducing bacterium (Shewanella putrefaciens, strain CN32) in bicarbonate buffer. Experiments investigated whether phosphate and anthraquinone-2,6-disulfonate, (AQDS, a humic acid analogue) influenced the extent of crystalline Fe{sup 3+} oxide bioreduction and whether crystalline Fe{sup 3+} oxides in geologic materials are more or less reducible than comparable synthetic phases. Anaerobic incubations (10{sup 8} organisms/mL) were performed both with and without PO{sub 4} and AQDS that functions as an electron repository and shuttle. The production of Fe{sup 2+} (solid and aqueous) was followed with time, as was mineralogy by X-ray diffraction. The synthetic oxides were reduced in a qualitative trend consistent with their surface area and free energy: hydrous ferric oxide (HFO) > goethite > hematite. Bacterial reduction of the crystalline oxides was incomplete in spite of excess electron donor. Biogenic formation of vivianite [Fe{sub 3}(PO{sub 4}){sub 2}{center_dot}8H{sub 2}O] and siderite (FeCO{sub 3}) was observed; the conditions of their formation was consistent with their solubility. The geologic Fe{sup 3+} oxides showed a large range in reducibility, approaching 100% in some materials. The natural oxides were equally or more reducible thanmore » their synthetic counterparts, in spite of association with non-reducible mineral phases (e.g., kaolinite). The reducibility of the synthetic and geologic oxides was weakly effected by PO{sub 4}, but was accelerated by AQDS. CN32 produced the hydroquinone form of AQDS (AHDS), that, in turn, had thermodynamic power to reduce the Fe{sup 3+} oxides. As a chemical reductant, it could reach physical regions of the oxide not accessible by the organism. Electron microscopy showed that crystallite size was not the primary factor that caused differences in reducibility between natural and synthetic crystalline Fe{sup 3+} oxide phases. Crystalline disorder and microheterogeneities may be more important.« less

Raman spectroscopy of monolayer-type oxide catalysts: Supported Mo oxides

Abstract: Oxides of the group VIb metals (Cr, Mo, W) and oxides of vanadium, rhenium, and niobium supported on a second high-surface-area metal oxide such as Al2O3, TiO2, Si02, ZrO2, and so forth are recognized as industrially important catalysts or catalyst precursors for various reactions [1–11], These materials frequently have been described as so-called monolayer catalysts based on a structural model which assumed spreading of the active oxide over the support surface. These catalysts have been investigated by a variety of techniques, conventional bulk sampling techniques as well as by surface-sensitive electron and ion spectroscopies, in an attempt to elucidate the nature of the catalyst surface species, and to study the coordination environment of the active metal center(s). Electronic spectroscopy gives rise to broad bands and the spectra are less informative than vibrational spectra. In addition, although techniques such as Auger electron spectroscopy (AES) and x-ray photoelectron spectroscopy (XPS...

Propylene Oxidation on Copper Oxide Surfaces: Electronic and Geometric Contributions to Reactivity and Selectivity

Abstract: Cu2O is an efficient catalyst in the partial oxidation of propylene to acrolein, while propylene oxidation on CuO leads to complete combustion. The interaction of propylene at elevated temperature (>300 K) and elevated pressure (5 Torr) with cuprous and cupric oxide has been investigated with core level XPS, resonant photoemission, and temperature-programmed desorption. Reduction of the copper oxide surfaces was examined as a function of temperature and revealed that cupric oxide has a greater reactivity toward propylene oxidation than cuprous oxide (Ea = 5.9 versus 11.5 kcal/mol for cuprous oxide (24.7 and 48.1 kJ/mol)). This variable temperature oxidation of propylene was also monitored via core level and resonant photoemission and was found to occur by a similar mechanism on both surfaces. Reaction at lower temperature produces a surface intermediate which exhibits carbon 1s XPS peaks at 284.0 and 285.5 eV binding energy in a 2:1 intensity ratio. This is consistent with an allyl alkoxide surface specie...

Rapid Deswelling Response of Poly(N-isopropylacrylamide) Hydrogels by the Formation of Water Release Channels Using Poly(ethylene oxide) Graft Chains

Abstract: Poly(ethylene oxide) (PEO) chains are introduced as graft chains maintaining freely mobile ends in thermo-responsive cross-linked poly(N-isopropylacrylamide) (PIPAAm) hydrogels by copolymerization of IPAAm with α-acryloyl-ω-methoxy-PEO. The deswelling response on raising the temperature of this gel above the gel phase transition temperature (TP) takes place within 10 min, whereas a conventionally cross-linked PIPAAm gel of the same dimensions requires 1 month for deswelling. This difference is due to the formation of water release channels within the skin layer by the hydrophilic PEO graft chains. The rapid deswelling of the grafted gel is compared with the deswelling changes of random copolymer gels composed of IPAAm and hydrophilic acrylic acid (AAc), which also accelerates gel deswelling. Deswelling is fastest in copolymers containing 1.3 wt % AAc and in grafted gels containing 13 wt % PEO. These results were interpreted as reflecting the gel structure.

Oxidation of sulfur dioxide to sulfur trioxide over supported vanadia catalysts

Abstract: The objectives of this research are to establish the fundamental kinetics and mechanism of sulfur dioxide oxidation over supported vanadia catalysts and use these insights to facilitate the design of SCR DeNOx catalysts with minimal sulfur dioxide oxidation activity. A series of supported vanadia catalysts were prepared on various metal-oxide supports: ceria, zirconia, titania, alumina and silica. Raman spectroscopy was used to determine the coordination of surface species. At low vanadia loadings, vanadia preferentially exists on oxide support surfaces as isolated tetrahedrally coordinated (M‐O)3V a5 aO species. At higher vanadia loadings, the isolated (M‐O)3V a5 aO species polymerize on the oxide support surface breaking two V‐O‐M bonds and forming two V‐O‐V bridging bonds. The turnover frequency for sulfur dioxide oxidation was very low, 10 ˇ4 to 10 ˇ6 s ˇ1 at 4008C, and was independent of vanadia coverage suggesting that only one vanadia site is required for the oxidation reaction. As the support was varied, sulfur dioxide oxidation activity of the supported vanadia catalysts varied by one order of magnitude (Ce>Zr, Ti>Al>Si). The basicity of the bridging V‐O‐M oxygen appears to be responsible for influencing the adsorption and subsequent oxidation of the acidic sulfur dioxide molecule. Over the range of conditions studied, the rate of sulfur dioxide oxidation is zero-order in oxygen, first-order in sulfur dioxide and inhibited by sulfur trioxide. The turnover frequency for sulfur dioxide oxidation over WO3/TiO2 was an order of magnitude lower than that found for V2O5/TiO2, and no redox synergism between the surface vanadia and tungsten oxide species was evident for a ternary V2O5/ WO3/TiO2 catalyst. This suggests that WO3 promoted catalysts may be suitable for low-temperature SCR where minimal sulfur dioxide oxidation activity is required. # 1998 Elsevier Science B.V. All rights reserved.

Effect of modification of oxide layer on NiTi stent corrosion resistance.

Abstract: Because of its good radiopacity, superelasticity, and shape memory properties, nickel-titanium (NiTi) is a potential material for fabrication of stents because these properties can facilitate their implantation and precise positioning. However, in vitro studies of NiTi alloys report the dependence of alloy biocompatibility and corrosion behavior on surface conditions. Surface oxidation seems to be very promising for improving the corrosion resistance and biocompatibility of NiTi. In this work, we studied the effect on corrosion resistance and surface characteristics of electropolishing, heat treatment, and nitric acid passivation of NiTi stents. Characterization techniques such as potentiodynamic polarization tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to relate corrosion behavior to surface characteristics and surface treatments. Results show that all of these surface treatments improve the corrosion resistance of the alloy. This improvement is attributed to the plastically deformed native oxide layer removal and replacement by a newly grown, more uniform one. The uniformity of the oxide layer, rather than its thickness and composition, seems to be the predominant factor to explain the corrosion resistance improvement.

Photorefractive waveguides in oxide crystals: fabrication, properties, and applications

Abstract: , LiTaO3, BaTiO3, KNbO3, SrxBa1-xNb2O6 (0.25≤x≤0.75, SBN), and Bi12(Si,Ti,Ge)O20 (BSO, BTO, BGO) waveguides are discussed. Furthermore, the suitability of photorefractive waveguides for nonlinear optical components is demonstrated in some examples.