Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Crack opening displacement of a through-wall crack in a plate subjected to bending load

This study was performed in order to clarify crack opening displacement (COD) of through-wall cracks in a plate subjected to bending load. The former COD evaluation methods were mainly developed corresponding to tensile load, but there has been nothing that has been developed corresponding to bending load. Therefore, the authors evaluated CODs of the through-wall cracks in plates which were subjected to a bending load using finite element method (FEM) analyses, and proposed a simplified COD evaluation method accounting for both tensile and bending loads. The proposed method is useful for leakage evaluation at a crack opening of an elbow crown or in the vicinity of the coolant surface of a vessel in which the bending stress is relatively large.     

An entropy model for shear deformation of granular materials

A statistical mechanical analogy for characterization of granular materials is discussed by using such notions as the state of the material, the density of states, entropy, canonical distribution and the partition function. The transition law of states during shear deformations of the material is microscopically investigated in the case of two-dimensional model granular materials. The assumption of entropy growth is shown to characterize the dilatancy of the material. A rough proof is given by assuming the measure preserving property of the transition and showing its ergodicity.     

Magnetic breakdown phenomena in quasi-two dimensional organic conductors

Magneto-oscillation phenomena of the magnetization in low dimensional organic conductors (BEDT-TTF)₂X, are investigated theoretically, focusing on the magnetic breakdown (MB) occured in high fields. Our full quantum mechanical theory reproduces various oscillations, including the interference difference oscillation, which is prohibited in the so-called network model of semi-classical theory, and demonstrates a smooth crossover to the MB orbit oscillation, or MB phenomenon. This is interpreted in terms of the recursive band structures.     

Effect of the addition of NH4F on anodic behaviors of DSA-type electrodes in H2SO4-(NH4)2SO4 solutions

The effect of NH₄F addition on the high-anodic behaviors of various DSA-type electrodes was investigated in a mixture of sulfuric acid and ammonium sulfate. The pronounced effect of NH₄ addition was observed on DSA-type Ti/RuO₂, Ti/IrO₂?TiO₂ electrodes, but not observed on the other electrodes studied. The close relationship was found between the increment of the electrode potential caused by the NH₄ addition and the quantity of F^? adsorbed on the electrode surface. The effect of NH₄F addition was considered to be resulted from the adsorption of F^? on the electrode surface, and the presence of adsorbed F^? was directly proved.     

Activation of a Au/TiO2 Catalyst by Loading a Large Amount of Fe–Oxide: Oxidation of CO Enhanced by H2 and H2O

Catalytic activity of a 1 wt% Au/TiO₂ catalyst is markedly improved by loading a large amount of FeO_x, on which the oxidation of CO in excess H₂ is selectively promoted at temperature lower than 60 °C. Oxidation of CO with O₂ on the FeO_x/Au/TiO₂ catalyst is markedly enhanced by H₂, and H₂O moisture also enhances the oxidation of CO but its effect is not so large as the promotion by H₂. We deduced that activation of Au/TiO₂ catalyst by loading FeO_x is not caused by the size effect of Au particles but a new reaction path via hydroxyl carbonyl intermediate is responsible for the superior activity of the FeO_x/Au/TiO₂ catalyst.     

Two-stage pyrolysis of heavy oils. 3. Pyrolysis of tar-sand bitumens. Relation between ethylene yield and structural characteristics of heavy oils

Thermal cracking of tar-sand bitumens has been carried out using a two-stage pyrolysis reactor with temperature zones of 440°C and 750–800°C, respectively. Feedstocks were pyrolysed in the first stage into cracked oils, which were carried to the second stage for subsequent pyrolysis. Only 12–14 wt% of ethylene was obtained from tar-sand bitumens at the residence time of 1.2 s in the second stage, although 27 and 16 wt% were obtained from Taching and Iranian heavy vacuum residues, respectively. The tar-sand bitumens contain shorter paraffinic straight-chains and have more branched molecules than the vacuum residues of petroleum. A straight-chain paraffin index is proposed, with which a good correlation was obtained between ethylene yield and the fraction of straight-chain paraffin carbons in the heavy oil.     

Influence of activated carbon pore structure on oxygen reduction at catalyst layers supported on rotating disk electrodes

Carbon materials are often used as catalyst supports, and for catalysts in electrodes of a polymer electrolyte fuel cell, carbon black has been used. Recently, it was found, however, that activated carbon could replace carbon black and besides, significantly improve the activity of the electrode catalyst layer for oxygen reduction. In the present study, to optimize the pore structure of activated carbon for further activity improvement, the influence of the pore structure on the activity was investigated using activated carbon of various specific surface areas and mean pore diameters. A catalyst layer was formed from activated carbon loaded with platinum and a polymer electrolyte. The activity of the layer was measured in an oxygen-saturated perchloric acid solution, supporting the layer on a rotating glassy carbon disk electrode. We found that increases in the specific surface area and mean pore diameter increased the activity and that the latter was more effective than the former mainly due to the enhanced mass-transfer in the pores; the catalyst layer formed from activated carbon with the largest mean pore diameter was the most active. Unless pores excessively develop and lose connections between particles, a large pore diameter is therefore desired for the fuel cell electrodes.     

Decomposition of Carbon Dioxide to Carbon with Active Wustite at 300°C

Active wustite (FeδO, with a δ value of 0.98) was prepared by keeping normal wustite (δ value of 0.94) in a N₂ atmosphere at 300°C for 10 min. This reaction is given by (4δ₂–3)Fe_δ1O→(4δ₁–3)Fe_δ2O + (δ₂–δ₁)Fe₃O₄ where δ₁= 0.94 and δ₂= 0.98. The equation indicates that the normal wustite undergoes eutectoid decomposition into active wustite and stoichiometric magnetite (Fe₃O₄). Carbon dioxide (1.013 × 10⁵ Pa) was almost completely (100%) decomposed into carbon (zero valence) by the active wustite at the low temperature of 300°C, which was associated with the transformation of the active wustite into the stoichiometric magnetite. The internal pressure of the reaction cell eventually became a vacuum.     

Preparation of plasma-polymerized membranes from I-(trimethylsilyl)-I-propyne and gas permeability through the membranes

Summary Plasma-polymerized membranes for gas separation were prepared from 1-(trimethylsilyl)-1-propyne. The permeation data of He, H₂ 0₂, N₂, CO₂, and CH₄ through the membranes showed plasma-polymerized 1-(trimethylsilyl)-1-propyne had high permselectivity but low permeability compared with poly[l-(trimethylsilyl)-1-propyne]. This behavior is considered to be due to the crosslinking structure of the plasma-polymerized membrane. The correlation between plasma polymerization conditions and the membrane performance was studied. The optimum condition at which the deposition rate of the plasma polymer is maximized agreed with the optimum value to yield maximum separation factor of gases through the membrane.