High Thermal Conductivity in Silicon Nitride with Anisotropie Microstructure

Silicon nitride was fabricated by tape casting of α-Si₃N₄ powder with 5 wt% Y₂O₃ and 5 vol% rodlike β-Si₃N₄ seed particles, followed by tape stacking, hot pressing under 40 MPa, and annealing at 1850°C for 2-66 h under a nitrogen pressure of 0.9 MPa. Silicon nitrides fabricated by this procedure exhibited a highly anisotropic microstructure with large elongated grains (developed from seed particles) uniaxially oriented parallel to the casting direction. Thermal conductivities parallel to the grain alignment were much higher than those measured in other directions and exhibited high values of up to 120 W/(m.K). The anisotropic thermal conductivity of the specimen could be explained by the rule of mixture, considering that large elongated grains developed from seeds have higher thermal conductivity than a small-grained matrix.     

Some properties of mullite powders prepared by chemical vapour deposition

The sinterability of mullite (3Al₂O₃·2SiO₂) powder prepared by chemical vapour deposition was examined to improve the conditions for fabricating dense mullite ceramics. The starting powder contained not only mullite, but also a small amount of -Al₂O₃ (Al-Si spinel) and amorphous material. Although the compressed powder was fired at a temperature between 1550 and 1700 °C for 1, 3 and 5 h, the relative densities of the sintered compacts were limited to 90%: (i) due to the creation of pores/microcracks during the solid state reaction (1100–1350 °C), and (ii) due to restriction on the rearrangement of grains because the amount of liquid phase (1550–1700 °C) was insufficient. Calcination of the starting powder was effective for preparation of easily sinterable powder with homogeneous composition. When the compact formed by compressing the calcined powder at 1400 °C for 1 h was fired at 1650 °C for 3 h, the relative density was raised up to 97.2%; moreover, mullite was the only phase detected from the sintered compact. The sintered compact was composed of polyhedral grains with sizes of 1–2 m and elongated grains with long axes of 6 m.     

Environmentally friendly coloured materials: cellulose/titanium dioxide/inorganic pigment composite spherical microbeads prepared by viscose phase-separation method

In order to develop environmentally friendly coloured materials, cellulose composite spherical microbeads hybridised with titanium dioxide (TiO₂) particles and inorganic pigment were prepared by a phase-separation method using viscose and an aqueous solution containing sodium polyacrylate. Findings regarding the relationships between cellulose xanthate and the electronic characteristics of TiO₂ particles used in the cellulose/inorganic material composite sphering process are also reported. These findings suggest that the location of TiO₂ particles in cellulose microbeads is related to electrical repulsion between the xanthate (CSS⁻) group and TiO₂. The use of TiO₂ powder as colour pigment is limited, as its colour is white. The cellulose composite spherical microbeads covered with TiO₂ and Fe₂O₃ particles were developed by addition of iron oxide (Fe₂O₃). Their surfaces were viewed by laser microscope and using SEM images. These composite microbeads retained the photocatalytic property of TiO₂. Cellulose/TiO₂/Fe₂O₃ composite spherical microbeads with both colour function and photocatalytic properties were successfully prepared.     

Preparation of new redox-active polyionenes with porphyrin units in the main chain

Quaternization of trans-dipyridylporphyrin with 1,4-butaneditrifluoromethane-sulfonate affords new polyionenes containing porphyrin units in the main chain. The polymers exhibit chemical and electrochemical reversible redox activities. Weitz-type two-step redox processes similar to those of viologens account for the redox properties of the polymers. Received: 26 November 1996/Revised: 24 January 1997/Accepted: 10 February 1997     

Application results of a prototype ultrasonic liquid film sensor to a 7 MPa steam–water two-phase flow experiment

A prototype ultrasonic liquid film sensor was applied to a high-temperature steam–water two-phase flow experiment. The liquid film sensor was vertically installed in a loop which was connected to HUSTLE, a multi-purpose steam source test facility. The hydraulic diameter of the measurement section was 9.4 mm. The output waveforms of the sensor were acquired with a digital oscilloscope. The fluid temperature and system pressure were kept at 288 °C and 7.2 MPa, respectively, during the experiment. The pulse-echo method was used to calculate the liquid film thickness. The cross-correlation calculation was utilized to determine the time difference between the pulse reflected at the sensor surface and the pulse reflected at the liquid film surface. The time-averaged liquid film thicknesses were less than 0.055 mm in the annular flow condition. The increase of the time-averaged thickness was small with the change of the gas momentum flux. The film thicknesses measured with the sensor were compared with the past experimental results; the former were smaller than one-fourth of the thickness estimated as the mean film thickness. The comparison results suggested that the continuous liquid sublayer thickness was measured with the liquid film sensor.     

Structural characterization of photoreduced complete and incomplete cubane-type molybdenum oxide clusters in CO and their catalytic behavior in propene metathesis reaction

SiO2-impregnated complete and incomplete cubane-type molybdenum oxide clusters such as [(RhCp*)₄Mo₄O₁₆] (I) and [(RhCp*)₂Mo₃O₉(OMe)₄] (II) were photoreduced with a UHP-Hg lamp (> 365 nm) in CO, resulting in the formation of catalytically active species for propene metathesis at 300 K. The CO-photoreduced Mo oxide clusters were characterized by EXAFS, IR, XPS and TPD technique. The results suggest that the Mo-O_4c (four-centered bridging oxygens) in I were specifically reduced with CO under the illumination to produce two sets of subcarbonyl species, e.g., those characteristic of the IR bands at 2061 and 2021 cm^–1, which were thermally inactive for the¹³CO exchange reaction but very active under illumination at 300 K, possibly assignable to Mo(CO)x (x = 2, 3), whereas those at 2092 and 2035 cm^–1 due to Rh(CO)₂, which were readily exchangeable with¹³CO at 300 K in dark. Removal of both carbonyls attached on Rh and Mo in photoreduced I and II by evacuation at 375–440 K led to the formation of oxygen-deficient Mo⁴+/Mo⁵⁺ sites, which exhibited high catalytic activities in propene metathesis at 300 K to produce an equimolar mixture of ethene and 2-butenes. The CO-photoreduced incomplete cubane Mo oxide cluster (II) exhibited higher activities and higher trans/cis ratios of 2-butenes in the reaction, compared with those on the photoreduced I.     

Combustion synthesis of LaSi3N5:Eu2+ phosphor powders

LaSi₃N₅:Eu²⁺ phosphor powders were prepared by a highly efficient combustion synthesis method. It was found that the compositions of the raw powder mixtures had great influences on the phase compositions and particle morphologies of the synthesized powders. By selecting appropriate starting compositions and combustion parameters, single phase LaSi₃N₅:Eu²⁺ phosphors could be synthesized. When excited by a UV light, the LaSi₃N₅:Eu²⁺ phosphors emitted green light. The wavelength and intensity of the emission spectra were affected by the amount of Eu²⁺ dopant. With increasing amount of Eu²⁺ dopant, concentration quenching could occur and emission spectra shifted to longer wavelengths.     

The effect of lutein supplementation on visual fatigue: A psychophysiological analysis

We used psychophysiological technology to examine the effect of an oral supplement, a combination of lutein, zeaxanthin and blackcurrant extract (LUT), on visual fatigue, within the context of a randomized, double-blind, placebo-controlled cross-over trial. The LUT supplement and placebo samples were randomly assigned to thirteen participants, who took the samples for two LUT (and vice versa) for another 2 week. Each participant completed visual proof reading tasks for 2 h during each of four testing sessions. Saccade tests were administered before and after the proof reading task, during which the participants moved their eyes back and forth between two targets positioned in the center of two checkerboards. We recorded EEG, EOG, heart rate, and facial muscle potential/performance during the saccade tests. Blood pressure was measured and subjective fatigue and stress scores were collected before and after the proof reading task. We averaged EEG starting at saccade offset in order to analyze eye fixation related potentials (EFRP). Our results suggested that the proof reading task induced visual fatigue. An analysis of EFRP and other psychophysiological data revealed significant differences between the LUT and placebo conditions. These results suggest that supplementation with LUT could help to reduce symptoms of visual fatigue.     

Decomposition and regeneration of methane in the absence and the presence of a hydrogen-absorbing alloy CaNi5

Suitable catalysts for the decomposition of methane into carbon and hydrogen and for the regeneration of methane by hydrogenation of the carbon have been looked for in a series of transition metals and precious metals supported on various carriers. The most active catalyst for both reactions was Ni/SiO₂. The carbon formed on this catalyst was thermodynamically less stable than graphite. The different rate equations for the decomposition of methane obtained for the fresh and carbon deposited Ni/SiO₂ suggest that the rate-determining steps are different for the two catalysts. The highest number of carbon atoms deposited per one Ni atom was 31 at 773 K. However, the number of methane molecules recovered easily at 773 K was limited to 1.5 per Ni atom.

A physical mixture of Ni/SiO₂ and CaNi₅, a hydrogen-absorbing alloy, enhanced the decomposition rate of methane, enabling the complete conversion of methane at 773 K beyond the thermodynamic limitation. The presence of CaNi₅ at 273 K separated from the catalyst in a reaction system further enhanced the decomposition of methane due to an increased hydrogen-absorbing capacity of the CaNi₅ at low temperatures. The carbon deposited on Ni/SiO₂ in this case was reactive to be hydrogenated back to methane at 773 K, giving an average 7.5 CH₄ molecules per one Ni atom.     

Microstructural Design of Silicon Nitride with Improved Fracture Toughness: II, Effects of Yttria and Alumina Additives

Significant improvements in the fracture resistance of self-reinforced silicon nitride ceramics have been obtained by tailoring the chemistry of the intergranular amorphous phase. First, the overall microstructure of the material was controlled by incorporation of a fixed amount of elongated ß-Si₃N₄ seeds into the starting powder to regulate the size and fraction of the large reinforcing grains. With controlled microstructures, the interfacial debond strength between the reinforcement and the intergranular glass was optimized by varying the yttria-to-alumina ratio in the sintering additives. It was found that the steady-state fracture toughness value of these silicon nitrides increased with the Y:Al ratio of the oxide additives. The increased toughness was accompanied by a steeply rising R -curve and extensive interfacial debonding between the elongated ß-Si₃N₄ grains and the intergranular glassy phase. Microstructural analyses indicate that the different fracture behavior is related to the Al (and O) content in the ß´-SiAlON growth layer formed on the elongated ß-Si₃N₄ grains during densification. The results imply that the interfacial bond strength is a function of the extent of Al and Si bonding with N and O in the adjoining phases with an abrupt structural/chemical interface achieved by reducing the Al concentration in both the intergranular phase and the ß´-SiAlON growth layer. Analytical modeling revealed that the residual thermal expansion mismatch stress is not a dominant influence on the interfacial fracture behavior when a distinct ß´-SiAlON growth layer forms. It is concluded that the fracture resistance of self-reinforced silicon nitrides can be improved by optimizing the sintering additives employed.