Defect structures and dopant solution states of Hf-doped Si3N4 ceramics

Transition-metal-doped silicon nitride ceramics have attracted much attention as gate materials for semiconductors because of their electrical properties as well as chemical and thermal stability. The present study aims to clarify the defect structures of Hf-doped β-Si₃N₄ by theoretical calculations and scanning transmission electron microscopy (STEM). First-principles calculations based on a hybrid functional method were performed. It was found that Hf dopants are mainly substituted for the Si sites and can be occasionally located at interstitial sites in the lattice of β-Si₃N₄. The substitution sites of Hf dopants predicted by the first-principles calculations were also confirmed by the high-resolution STEM images.     

Weighting matrix of quadratic performance index and design method of optimal deadbeat control system

A method of determination of the weighting matrix of the quadratic performance index and a method of design of an optimal deadbeat control system are discussed. First, the relationship between the weighting matrix of the quadratic performance index and the extra poles of the overparametrized pulse transfer function model is indicated. Next, a method of design of an optimal deadbeat control system is explained. Lastly, to demonstrate the effectiveness of the proposed method, some numerical examples are presented. © 2000 Scripta Technica, Electr Eng Jpn, 133(1): 53–63, 2000     

Usefulness of Permanent Power Fuse in Control Centers with Molded Case Circuit Breakers

The increase in electric power consumption in industry has led to the development of modern distribution systems such as control centers having high kVA ratings and high prospective fault current. In such a situation, the improvement of the system usefulness such as reliability and cost effectiveness is the essential requirement. An index is presented to evaluate the system usefulness using the cost effectiveness for fault protection in a system of given bank kVA. The index is estimated on four different system structures of control centers, including one which utilizes Permanent Power Fuses (PPF). It is presented that the PPF combined with molded case circuit breaker in main circuit effectively improves the cost effectiveness in control centers with high fault current. Operating principles of the PPF and the control center utilizing the PPF are briefly outlined.     

Non-linear current–voltage characteristics related to native defects in SrTiO3 and ZnO bicrystals

SrTiO₃ and ZnO bicrystals with various types of boundaries were fabricated in order to examine their current–voltage characteristics across single grain boundaries. Their grain boundary structures were also investigated by high-resolution transmission electron microscopy. In Nb-doped SrTiO₃, electron transport behaviors depend on the type of boundaries. Random type boundaries exhibit highly non-linear current–voltage characteristics, while low angle boundaries show a slight non-linearity. On the contrary, undoped ZnO does not exhibit non-linear current–voltage characteristics in any type of boundaries including random ones. It is suggested that the differences observed in current–voltage properties between the two systems are mainly due to the difference in the accumulation behavior of acceptor-like native defects at grain boundaries. A clear non-linearity is obtained by means of Co-doping even for the highly coherent Σ1 boundary in a ZnO bicrystal. This is considered to result from the production of acceptor-like native defects by Co-doping.     

Magnetization measurement of 3He film adsorbed on sintered silver powder

The static magnetization of ³He film adsorbed on sintered silver powder has been measured for coverages from 0.10 to 0.54 atoms/»² in steps of 0.02 atoms/»² and at a coverage of 4.5 atoms/»². Below 0.20 atoms/»² the magnetization well obeys the Curie law, while above that coverage a ferromagnetic tendency appears. The coverage dependence of the magnetization greatly differs from that for graphite. At 0.23 atoms/»² the magnetization has apeak like that for graphite; however, the magnitude of the peak is not so large. Furthermore, a multipeak structure is found in the isotherm of the magnetization at 0.2 mK. It has two prominent peaks at 0.23 and 0.29 atoms/»², and two other peaks are found at 0.35 and 0.41 atoms/»². These appear periodically with an interval of 0.06 atoms/»², which is nearly equal to the coverage of one liquid layer.     

Mesoporous Co3O4 for low temperature CO oxidation: effect of calcination temperatures on their catalytic performance

Mesoporous Co3O4 particles are prepared by using mesoporous silica KIT-6 (with double gyroid Ia-3d symmetry) as a hard-template and Co(No3)2 x 6H2O as an inorganic precursor. In the former section, we investigate the effect of the calcination temperatures at which the Co salts are converted into Co3O4 inside the mesopores on the textural parameters of the products. The results of N2 adsorption-desorption analysis indicates that the calcination temperatures do not obviously affect the textural parameters such as the surface areas and pore volumes. However, when the calcination temperature reaches 800 degrees C, the mesostructural ordering is dramatically decreased, resulting in the reduction of the surface areas and pore volumes. After 800 degrees C calcination, the formation of large Co3O4 grains is partially confirmed on the particle surface by SEM observation. The grain size is much larger than the mesopore size of the original KIT-6, meaning the crystal growth is continuously occurred by breaking the rigid silica frameworks. In the latter section, we discuss the effect of the calcination temperatures and textural parameters on the catalytic activity for CO oxidation by both steady state and kinetic measurements. All mesoporous Co3O4 particles show a high catalytic activity, for example, -72 degrees C for sample calcined at 450 degrees C. Only 10 degrees C difference in T50 (the temperature of 50% conversion of CO) is found between the samples with the highest and lowest catalytic activity. The values of activation energy (Ea) and pre-exponential factor (A) per unit area are almost the same between two samples calcined at 450 degrees C and 800 degrees C. It is demonstrated that calcination process can not alter the essential catalytic property of mesoporous Co3O4 particles.     

Kinetic and morphological study of a magnesium ethoxide‐based Ziegler–Natta catalyst for propylene polymerization

BACKGROUND: Kinetic and morphological aspects of slurry propylene polymerization using a MgCl₂‐supported Ziegler–Natta catalyst synthesized from a Mg(OEt)₂ precursor are investigated in comparison with a ball‐milled Ziegler–Natta catalyst. RESULTS: The two types of catalyst show completely different polymerization profiles: mild activation and long‐standing activity with good replication of the catalyst particles for the Mg(OEt)₂‐based catalyst, and rapid activation and deactivation with severe fragmentation of the catalyst particles for the ball‐milled catalyst. The observed differences are discussed in relation to spatial distribution of TiCl₄ on the outermost part and inside of the catalyst particles. CONCLUSION: The Mg(OEt)₂‐based Ziegler–Natta catalyst is believed to show highly stable polymerization activity and good replication because of the uniform titanium distribution all over the catalyst particles. Copyright © 2008 Society of Chemical Industry     

Effect of oxide film on oxygen reduction current for the platinum-cobalt alloy electrodes in PEFC

Effect of surface oxide on Pt-Co alloy electrodes on the oxygen reduction reaction (ORR) was investigated in 0.5 M sulfuric acid solution by electrochemistry, ellipsometry, laser Raman scattering spectroscopy, and XPS. The oxide as thick as 1-2 nm increases the overpotential of ORR and falls down efficiency of PEFC. The thickness of the oxide films is precisely determined by ellipsometry. The oxide film 1.9 nm thick was formed on Pt-50 mol% Co electrode by constant potential oxidation at 1.20 V and the film 1.5 nm thick remains on the electrode at 0.6 V at which ORR already starts. The remaining oxide decreases the current density of ORR and increases the overpotential. On pure Pt electrode, the similar influence of the oxide film was observed.