Gibbs Energy Change of Carbothermal Nitridation Reaction of Al2O3 to Form AlN and Reassessment of Thermochemical Properties of AlN

The experimental method for the high-temperature reaction equilibria in the AlN-Al₂O₃ system has been established. The equilibrium N₂-CO gas compositions coexisting with AlN- Al₂O₃-graphite have been successfully measured by quadrupole mass spectrometry and gas chromatography. From the obtained results, the standard Gibbs energy change of the forming reaction of AlN by carbothermal nitridation is determined at temperatures ranging from 1723 to 1899 K:
From the obtained result, the standard Gibbs energy of formation of AlN and the third-law enthalpy of formation of AlN at 298.15 K are derived as
The disagreement between the present results and values in the NIST–JANAF thermodynamic table is discussed.     

Evaluation of the pseudocapacitance in RuO2 with a RuO2/GC thin film electrode

The pseudocapacitance of nanocrystalline RuO₂ with BET surface area of 42 m² g⁻¹ was evaluated using a RuO₂ modified Glassy Carbon (RuO₂/GC) thin film electrode. The charge storage behavior of the RuO₂/GC thin film electrode was studied from fast to slow scan cyclic voltammetry between various potential windows. The utilization of the thin film electrode method for nanocrystalline RuO₂ with known specific surface area allowed a semi-quantitative understanding of the electric double-layer capacitance (C_dl), adsorption related charge (C_ad), and the irreversible redox related charge (C_irr) per unit mass and surface area of RuO₂. Comparison of the cyclic voltammograms between different voltage windows revealed that the contribution from C_irr is especially dominant below 0.4 V (versus RHE) at slow scan rates.     

Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10⁻⁴ to 10⁻³ S cm⁻¹ at room temperature. Gelation was found to cause little change in the diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids.     

Visualization of Knoop Indentation Damage of Silicon Nitride by Plasma Etching

A visualizing technique for indentation damage of ceramics was developed. Plasma etching was used to enhance the view of cracks and the subsurface microcracking crush zone following Knoop indentation of hot pressed Si₃N₄. The microcracking zone was readily identified from the surface view of the indented surface as a grain-falling-off region (GFOR), defined as a region in which grains were removed by preferential etching using CF₄ gas, followed by ultrasonic cleaning. A fissure-like opening corresponding to the indentation cracks was also observed. It is inferred that the formation of the GFOR region and the fissure-like opening were caused by the etching/cleaning treatment. Meanwhile, the etching on a section which included diagonals of the impression provided a section view of the microcracking zone.     

Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature

Using multi-anvil high-pressure devices and synchrotron radiation, X-ray in situ observations of HfO₂ under high pressure and high temperature have been performed to investigate its phase relations and compression behavior. An orthorhombic phase (orthoI) is stable from 4 to 14.5 GPa below 1250°–1400°C and transforms to a tetragonal phase, which is one of the high-temperature forms of HfO₂, above these temperatures. Another orthorhombic phase (orthoII) with a cotunnite-type structure appears above 14.5 GPa. OrthoII is stable up to 1800°C at 21 GPa. OrthoII is quenchable to ambient conditions. The orthoI-to-orthoII transition is accompanied by ∼8 vol% decrease. The bulk moduli of orthoI and orthoII at room temperature are 220 and 312 GPa, respectively. This low compressibility of orthoII indicates that it is a potential candidate for very hard materials.     

Candidate Biomarkers for Genetic and Clinicopathological Diagnosis of Endometrial Cancer

The recent increase in the frequency of endometrial cancer has emphasized the need for accurate diagnosis and improved treatment. The current diagnosis is still based on conventional pathological indicators, such as clinical stage, tumor differentiation, invasion depth and vascular invasion. However, the genetic mechanisms underlying endometrial cancer have gradually been determined, due to developments in molecular biology, leading to the possibility of new methods of diagnosis and treatment planning. New candidate biomarkers for endometrial cancer include those for molecular epigenetic mutations, such as microRNAs. These biomarkers may permit earlier detection of endometrial cancer and prediction of outcomes and are likely to contribute to future personalized therapy for endometrial cancer.     

Reinvestigation of the Oxidative Folding Pathways of Hen Egg White Lysozyme: Switching of the Major Pathways by Temperature Control

It has been well established that in the oxidative folding of hen egg white lysozyme (HEL), which has four SS linkages in the native state (N), three des intermediates, i.e., des[76–94], des[64–80], and des [6–127], are populated at 20 °C and N is dominantly formed by the oxidation of des[64–80] and des[6–127]. To elucidate the temperature effects, the oxidative folding pathways of HEL were reinvestigated at 5–45 °C in the presence of 2 M urea at pH 8.0 by using a selenoxide reagent, DHS^ox. When reduced HEL was reacted with 1–4 equivalents of DHS^ox, 1S, 2S, 3S, and 4S intermediate ensembles with 1–4 SS linkages, respectively, were produced within 1 min. After the oxidation, 3S was slowly converted to the des intermediates with formation of the native structures through SS rearrangement. At 5 °C, des[76–94] was populated in the largest amount, but the oxidation to N was slower than that of des[64–80] and des[6–127]. At 35 °C, on the other hand, des[64–80] and des[6–127] were no longer stable, and only des[76–94] was populated. The results suggested that the major folding pathways of HEL can be switched from one to the other by temperature control.     

Regio‐ and Stereochemical Controlled Koenigs–Knorr‐Type Monoglycosylation of Secondary Hydroxy Groups in Carbohydrates Utilizing the High Site Recognition Ability of Organotin Catalysts

The catalytic regio‐ and stereoselective monoglycosylation of carbohydrates using organotin catalysts is demonstrated. The one‐step reaction affords various oligosaccharides linked at the secondary hydroxy group in high chemical yield and good regio‐ and stereoselectivities. The regioselectivity of the glycosylation is shown to depend on the spatial arrangement of the hydroxy groups in the carbohydrates.

     

Theoretical model for flash generation

Reduction of flash generated in a gas vent is of great concern for manufacturers of electronic parts. The present study proposes a theoretical model for flash generation through consideration of flow characteristics in a gas vent. The model predicts the factors controlling flash, i.e., material parameters such as zero‐shear viscosity, crystallization temperature, thermal conductivity, and heat capacity, and process parameters such as injection and mold wall temperatures, packing pressure, and the clearance of a gas vent. On the other hand, we measure the amount of flash generated in the molding of poly(phenylene sulfide) (PPS) composites containing glass fiber and spherical fillers (CaCO₃ or Al₂O₃). Flash reduces with decreasing size of spherical fillers. These experimental data are successfully interpreted using the flash model. Polym. Eng. Sci., 45:198–206, 2005. © 2005 Society of Plastics Engineers     

Surface properties of carbon micro-coils oxidized by a low concentration of oxygen gas

Vapor-grown carbon micro-coils were oxidized under a low O₂ flow-rate for introducing oxygen-containing functional groups on the surface. The surface characteristics were then examined. The O1s/C1s intensity ratios of the XPS spectra measured on the surface increased on using the oxidation treatment. The maximum O1s/C1s ratio of 11.4 at.% was obtained under the following conditions: (a) the flow-rate of the mixed gas of O₂+Ar (O₂/Ar=1/10) was 82.5 sccm; (b) the oxidation temperature was 600°C; and (c) the treatment time was 30 min. The maximum O1s/C1s ratio is about 3.5 times that of the source carbon coils. The specific surface area significantly increased due to the oxidation treatment and attained a maximum value of 1050 m² g⁻¹, which is about 10 times that of the source carbon coils. As the specific surface area increased, the surface morphology of the carbon coils became more complicated on a nanometer scale.