High-Temperature Fracture Mechanism of Low-Ca-Doped Silicon Nitride

High-purity Si₃N₄ (with 2.5 wt% glassy SiO₂) doped with 0 to 450 at.ppm of Ca was prepared as a model system to investigate the effects of grain-boundary segregants on fracture phenomenology at 1400°C. Subcritical crack-growth (SCG) resistance as well as creep resistance was degraded significantly by the presence of a small amount of Ca. The internal friction of the doped materials exhibited the superposition of a grain-boundary relaxation peak and a high-temperature background, and the apparent viscosity of the grain-boundary film was determined from the peak. Based on these experimental data, the fracture mechanism at 1400°C was divided into three regions: "brittle," SCG, and creep failure as a function of both external strain rate and Ca concentration, C _Ca. From the investigation of the C _Ca dependence of the critical strain rate for the transition from "brittle" to SCG fractures, the SCG phenomenon is suggested to be triggered by small-scale, grain-boundary sliding. The C _Ca dependence of "steady-state" creep rate was far from the theoretical dependence of diffusional creep via a solution-precipitation mechanism. The discrepancy was interpreted to be due to the presence of an impurity-insensitive creep component. This component may correspond to the lowest limit of the tensile creep rate in Si₃N₄ polycrystalline materials containing intergranular glassy-SiO₂ film.     

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.     

Rapid Quenching Technique Using Thermal-Image Furnace for Glass Preparation

A new technique combining a thermal-image furnace and a twin roller is described for quenching the melt to form glass. The technique was applied to the simple system Li₂O-SiO₂, since its fundamental parameters in the estimation of critical cooling rate are available. Glass flakes were obtained in the composition Li₄SiO₄, for which a very large critical cooling rate (∼10⁹ K·s⁻¹) was needed for glass formation.     

Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Effect of perchloric acid on the molecular weight and yield of poly-THF

Polytetramethylene glycol (molecular weight range 1000–8000) was prepared by the polymerization of tetrahydrofuran (THF) using a binary catalyst system of fuming sulfuric acid and perchloric acid. When 28% fuming sulfuric acid alone was used as the catalyst, the average molecular weight of polymer was low, the maximum value being 1000–1100. By the combination of fuming sulfuric acid with a small amount of perchloric acid, the average molecular weight of the polymer was increased to about 8000. Furthermore, the molecular weight was readily controlled in the range of 1000 to 8000 by varying the amount of the binary catalyst.     

Charged ultrafiltration membrane for permeation of proteins

Polyacrylonitrile-g-poly(N,N-dimethylaminoethyl methacrylate) was synthesized photochemically and quaternized. The positively charged membranes made from the quaternized graftcopolymer showed high ultrafiltration rate for water by adding poly(vinyl alcohol) to casting solution and washing it out after the casting. In buffered saline solution, the permeability of the membranes was very small at pH below isoelectric point of albumin but increased markedly at higher pH. On the other hand, the permeability for γ-globulin was very small and did not show any pH dependence.     

Validation of Platelet Counting Accuracy With the Celltac F Automated Hematology Analyzer

Rapid and accurate analysis of platelet count plays an important role in evaluating hemorrhagic status. Therefore, we evaluated platelet counting performance of a hematology analyzer, Celltac F (MEK-8222, Nihon Kohden Corporation, Tokyo, Japan), that features easy use with low reagent consumption and high throughput while occupying minimal space in the clinical laboratory. All blood samples were anticoagulated with dipotassium ethylenediaminetetraacetic acid (EDTA-2K). The samples were stored at room temperature (18^{^}C–22^{^}C) and tested within 4 hours of phlebotomy. We evaluated the counting ability of the Celltac F hematology analyzer by comparing it with the platelet counts obtained by the flow cytometry method that ISLH and ICSH recommended, and also the manual visual method by Unopette (Becton Dickinson Vacutainer Systems). The ICSH/ISLH reference method is based on the fact that platelets can be stained with monoclonal antibodies to CD41 and/or CD61. The dilution ratio was optimized after the precision, coincidence events, and debris counts were confirmed by the reference method. Good correlation of platelet count between the Celltac F and the ICSH/ISLH reference method (r = 0.99, and the manual visual method (r= 0.93) were obtained. The regressions were y = 0.90 x+9.0 and y=1.11x+8.4, respectively. We conclude that the Celltac F hematology analyzer for platelet counting was well suited to the ICSH/ISLH reference method for rapidness and reliability.     

Computer-aided reaction system synthesis based on structured process energy-exergy-flow diagram

A computerized thermodynamics-oriented procedure for reaction system synthesis is proposed. First, hierarchy structure of chemical reactions is discussed and the reaction system is categorized into three types; (1) combination with a heat source or sink, (2) combination with a reaction donor, and (3) decomposition of target reaction into subtargets. Then, the algorithm to find subtarget reactions and/or donor reactions is presented.     

E.s.r. study of annealing and melting effects on the molecular motion of spin trapped chain-end radicals located on the polyethylene surface

E.s.r. spectra of chain-end spin labels on the surface of polyethylene powder were obtained for high and low density polyethylene samples at various stages of heat treatment process. The subsequent crystalline structures of the samples were examined with wide angle and small angle X-ray diffraction spectra. The effects of annealing on the motion of the labels were dependent on annealing temperature and the type of the samples. Higher temperature annealing decreased the rotational correlation times (τ_c) and their activation energy in high density polyethylene but did not affect those of low density polyethylene. Melting decreases the values of τ_c and ΔE for both high an low density polyethylene samples. The cause of these decreases were attributed to the changing of the sites of the chain-end labels. The motion of the labels appeared to be influenced by the local segmental motion of the polymer main chains.     

The European,Japanese and US protective helmet,gloves and boots for firefighters: thermoregulatory and psychological evaluations

The purpose of this study was to investigate the physiological and subjective responses of the European, Japanese (JPN) and US firefighters' helmet, gloves and boots for international standardisation. Three experimental conditions were evaluated (clothing mass: 9.4, 8.2 and 10.1 kg for the three conditions, respectively) at the air temperature of 32°C and 60% relative humidity. The results showed that there was no significant difference among the three conditions in oxygen consumption, heart rate, total sweat rate, rectal temperature and mean skin temperature, whereas peripheral temperatures and subjective perceptions were lower in the JPN condition than in the other conditions (P < 0.05). These results indicate that a 0.5-kg reduction in helmet mass and a 1.1-kg reduction in boot mass during exercise resulted in a significant decrease in head and leg temperatures and subjective perceptions, while a 1.9-kg reduction in total clothing mass had insignificant influences on the metabolic burden and overall body temperature.