Oxidation behavior of TiAl coated with a fine-grain Co-30Cr-4Al film

The oxidation behavior of TiAl coupons coated with a fine-grain Co-30Cr-4Al (mass %) film of about 30-m thickness has been studied at 1100–1400 K in a flow of purified oxygen at atmospheric pressure for up to 500 ks. Three oxidation stages were recognized: initial transient, parabolic, and accelerated stages. However, at 1100 K a parabolic stage continues for more than 800 ks. The activation energy for parabolic oxidation agrees with reported values for the oxidation of alumina-former alloys, although the mass gains during the parabolic stages are relatively small at 1200 and 1300 K. Micropores developed mainly at the scale/coating and coating/substrate interfaces as oxidation proceeded. This is attributable to recrystallization of the coating during oxidation and a Kirkendall effect due to preferential diffusion of Co into the substrate. The accelerated oxidation can be explained in terms of the formation of rutile mounds on the scale.     

Characterization of the AIN–W Interface in a Cofired Multilayer AIN Substrate

The AIN–W Interfaces in a cofired multilayer AIN substrate were observed using an optical microscope, scanning electron microscope (SEM) and transmission electron microscope (TEM). Optical and SEM observations showed an intricate intricatelocking AIN-W grain structure at the interface. After the W pad was removed from the substrate with a NaOH etchant, the surface morphology of the W metal at the interface side was found to be very rough, with a small-grain microstructure compared with that at the free surface side. Electron microprobe analyses using SEM revealed that there was no diffusion of either W or Al at the interface at the order of a few micrometer's resolution. Bright-field images, dark-field images and selected area electron diffraction (SAD) patterns using TEM indicated there was no secondary phase between AIN and W. However, scanning transmission electron microscopy using an energy dispersive X-ray detector revealed that there was a 200-nm thick W diffusion layer from the interface into the AIN ceramics. It was concluded that the high adhesion strength between the W conductor and the AIN substrate (>20 MPa) was not due to any secondary phase but to mechanical interlocking of AIN and W during cofiring.     

Recovery of serum proteins using cellulosic affinity membrane modified by immobilization of CU2+ ion

An affinity membrane was prepared from a porous cellulose membrane, and adsorption and recovery of serum proteins were investigated from the viewpoint that affinity membranes are efficacious against separation and purification of biomaterials. Into the cellulose membrane, iminodiacetate (IDA) group that acts as a ligand to metal ions was introduced (Cell–IDA membrane), and then Cu²⁺ ion was immobilized (Cell–IDA–Cu membrane). Bovine serum albumin (BSA) and γ-globulin (BγG), which are the major proteins in blood, were adopted as model proteins to be separated. The Cell–IDA–Cu membrane had large adsorption capacity for these proteins despite the low degree of modification. The amounts of proteins adsorbed on the Cell–IDA–Cu membrane increased with increasing pH, and BγG was adsorbed more than BSA. High protein recoveries from the Cell–IDA–Cu membrane were obtained. The separation of these proteins was also conducted under the optimum conditions of adsorption and recovery, and BγG was concentrated more than BSA although the initial concentration of BγG was lower than that of BSA. © 1996 John Wiley & Sons, Inc.     

Selective isopentane formation from CH3OH on a new one-atomic layer ZrO2/ZSM-5 hybrid catalyst

A new one-atomic layer ZrO₂/ZSM-5 hybrid catalyst was prepared by using the repeated reactions between Zr(OC₂H₅)₄ and of the OH groups of the external surfaces of ZSM-5, followed by calcination. The one-atomic layer ZrO₂ attached on the ZSM-5 surface was characterized by means of X-ray diffraction, X-ray fluorescence and EXAFS. The ZrO₂ overlayer is suggested to epitaxially grow on the ZSM-5(001) plane in a [111] direction of tetragonal ZrO₂. The one-atomic layer ZrO₂/ZSM-5 is a unique catalyst which produces selectively isopentane from CH₃OH.     

Studies on chitin. IX. Crosslinking of water-soluble chitin and evaluation of the products as adsorbents for cupric ion

Water-soluble chitin was successfully crosslinked to varying extents with glutaraldehyde in homogeneous aqueous solutions to improve the properties as an adsorbent for metal cations, and the effects of crosslinking were discussed. Complete insolubilization was achieved with the fivefold excess aldehyde, but, in terms of adsorptivity of Cu²⁺, the chitin crosslinked at an aldehyde/amino group ratio of 1.0 was found to exhibit remarkable capacity and was much superior to others. The desorption of Cu²⁺ from the adsorption complex was also attained effectively at pH 2.0. These results indicated that the loose crosslinking was quite simple and efficient to produce high capacity adsorbents for practical use. Thermal behavior of the crosslinked chitin was examined by TMA and TGA; a softening phenomenon was observed at 145°C.     

Time-resolved DXAFS study on the reduction processes of Cu cations in ZSM-5

The time-resolved reduction process of copper cations in/on ZSM-5 during temperature-programmed reduction (300–700 K) was studied by energy-dispersive X-ray absorption fine structure (DXAFS) as well as transmission electron microscopy (TEM). Two Cu-ZSM-5 samples with different Cu loadings were prepared by an ion-exchange method. The Cu K-edge DXAFS spectra for isolated Cu₂₊ species in the channels of ZSM-5 and CuO particles on the outer surfaces of ZSM-5 were recorded at an interval of 1 s during the reduction. The curve fitting analysis of the EXAFS data and the XANES analysis revealed that the isolated Cu₂₊ species in the channels were reduced stepwise. They were reduced to isolated Cu₊ species at 400–450 K and the Cu₊ species to Cu₀ metallic clusters at 550–650 K. Small clusters like Cu₄ were initially formed, followed by particle growth. A small part of them went out to the outer surfaces of ZSM-5 during the reduction. In contrast, CuO particles on the outer surfaces were reduced directly to Cu₀ metallic particles around 450 K.     

Analysis of imazalil and its major metabolite in citrus fruits by GC-FTD

A simplified simultaneous analytical method of imazalil (IZ) and its major metabolite, alpha-(2,4-dichlorophenyl)-1H-imidazole-1-ethanol (IZM), in citrus fruits was developed, and commodities samples were investigated. A homogenate of citrus fruits was extracted with ethyl acetate under basic conditions. The crude extract was partitioned between 0.025 mol/L of sulfuric acid and ethyl acetate. The analytes were extracted from the aqueous fraction under basic conditions with ethyl acetate. The extract solution was purified with an ENVI-Carb cartridge, and then analyzed by GC-FTD and GC/MS. Recoveries of IZ and IZM added to grapefruit at the level of 0.05 microgram/g were 90.0 and 108.7%, and those in the case of lemon were 100.4 and 93.0%, respectively. The detection limits were 0.01 microgram/g in samples. By this method, IZ and IZM were analyzed in 46 citrus fruits on the market and were detected simultaneously in some samples.     

Desorption of carbon dioxide from supersaturated water in an agitated vessel

The rates of desorption of carbon dioxide from supersaturated water solutions into pure carbon dioxide or nitrogen gas stream were measured at 15,25, and 35°C in a baffled agitated vessel with a flat gas-liquid interface operated in a continuous manner. The volumetric liquid-phase mass transfer coefficients for the bubbles generated in the agitated liquid and the enhancement factors of the volumetric liquid-phase mass transfer coefficient for the free liquid surface due to the bubbling were calculated from the measured desorption rates and correlated as functions of the relative supersaturation of the solution and the liquid-phase Reynolds number.     

Graded‐index plastic optical fiber with high mechanical properties enabling easy network installations. I

A doped poly(methyl methacrylate) (PMMA)–based graded‐index plastic optical fiber (GI POF) with high mechanical strength is reported for the first time. Although the POF is generally believed to have a good mechanical flexibility even if it has a large‐core diameter, such a high mechanical strength has been provided by making the polymer chains in the POF highly oriented in its axial direction. If such an orientation of polymer chains is eliminated, the POF becomes brittle, which is similar to silica‐based fibers. On the other hand, too high an orientation of the polymer chains induces fiber deformation in a high‐temperature atmosphere resulting from orientation relaxation. This study reports how high mechanical strengths such as the tensile strength and the large elongation are provided to the GI POF. By selecting the optimum heat‐drawing conditions, the GI POF has a mechanical strength comparable to that of the commercially available step index (SI) POF. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 404–409, 2004     

Organocatalytic Enantioselective Decarboxylative Addition of Malonic Acids Half Thioesters to Isatins

The organocatalytic enantioselective decarboxylative addition of malonic acids half thioesters to isatins using a squaramide catalyst afforded the products with high enantioselectivity. These products are key intermediates in the synthesis of 3‐substituted 3‐hydroxy‐2‐oxindole derivatives. The first enantioselective synthesis of (−)‐flustraminol B has been accomplished.