Observation of 3‐D Structure of Bubbles in a Fluidized Catalyst Bed

The interface area between the bubble and emulsion phases in a fluidized catalyst bed is one of the important parameters used to analyze and design the fluidized bed reactor. We used a fast‐scanning X‐ray CT system to observe the bubble shape and structure. We then obtained the transient 2‐dimensional cross sectional gas‐phase distribution in a fluidized catalyst bed. Using image‐processing techniques, pseudo 3‐dimensional images of the bubbles were reconstructed. The bubble structure was studied based on the 3‐dimensional images and the previously obtained results in a 2‐dimensional fluidized bed. It was found that the bubble shape was not spherical but complicated, and that the bubbles ascending in a fluidized catalyst bed consisted of some smaller bubbles.     

Effects of Annealing on Dielectric Loss and Microstructure of Aluminum Nitride Ceramics

The effect of annealing on tan δ and microstructures of aluminum nitride (AlN) ceramics were explored. Yttria was added as a sintering additive to AlN powders, and the powders were pressureless-sintered at 1900°C for 2 h in a nitrogen flow atmosphere. In succession to sintering, AlN samples were annealed at 720, 970 and 1210°C for 2 and 4 h. Very low tan δ values between 2.6 and 6.0 × 10⁻⁴ at 28 GHz were obtained when the AlN samples were annealed for 4 h at all the annealing temperatures.     

Fracture Energies of Tape-Cast Silicon Nitride with β-Si3N4 Seed Addition

The fracture energies of the tape-cast silicon nitride with and without 3 wt% rod-like β-Si₃N₄ seed addition were investigated by a chevron-notched-beam technique. The material was doped with Lu₂O₃–SiO₂ as sintering additives for giving rigid grain boundaries and good heat resistance. The seeded and tape-cast silicon nitride has anisotropic microstructure, where the fibrous grains grown from seeds were preferentially aligned parallel to the casting direction. When a stress was applied parallel to the fibrous grain alignment direction, the strength measured at 1500°C was 738 MPa, which was almost the same as room temperature strength 739 MPa. The fracture energy of the tape-cast Si₃N₄ without seed addition was 109 and 454 J/m² at room temperature and 1500°C, respectively. On the contrary, the fracture energy of the seeded and tape-cast Si₃N₄ was 301 and 781 J/m² at room temperature and 1500°C, respectively, when a stress was applied parallel to the fibrous gain alignment. The large fracture energies were attributable primarily to the unidirectional alignment fibrous Si₃N₄ grains.     

Synergic effect of Pd/γ-alumina and Cu/ZSM-5 on the performance of NO x storage reduction catalyst

NO _x reduction with a combination of catalysts, Pd catalyst, NO _x storage reduction (NSR) catalyst and Cu/ZSM-5 in turn, was investigated to elucidate for the high NO _x reduction activity of this catalyst combination under oxidative atmosphere with periodic deep rich operation. The catalytic activity was evaluated using the simulated exhaust gases with periodically fluctuation between oxidative and reductive atmospheres, and it was found that the NO _x reduction activity with this catalyst combination was apparently higher than that of the solely accumulation of these individual activities, which was caused by the additional synergic effect by this combination. The Pd catalyst upstream of the NSR catalyst improved NO _x storage ability by NO₂ formation under oxidative atmosphere. The stored NO _x was reduced to NH₃ on the NSR catalyst, and the generated NH₃ was adsorbed on Cu/ZSM-5 downstream of the NSR catalyst under the reductive atmosphere, and subsequently reacted with NO _x on the Cu/ZSM-5 under the oxidative atmosphere.     

Microstructure and Thermal Shock Resistance of Molten Glass-Coated Carbon Materials Fabricated by Interfacial Control

Carbon substrates were coated completely with a molten silicate glass, where the wettability of carbon to glass was improved by infiltration and pyrolysis of perhydropolysilazane. Microstructures of the carbon–glass interface were dependent on P n ₂ during coating. Coating at lower P n ₂ induced the formation of cristobalite at the carbon–glass interface. When the coating was performed at higher P n ₂, the glass and carbon were strongly adhered, without the formation of cristobalite. Coating at higher P n ₂ improved the thermal shock resistance of the glass layer, because crack initiation was not induced by the phase transformation of cristobalite during the cooling process. In the case of coating at higher P n ₂, an oxynitride glass layer was formed at the glass subsurface by dissolution of N₂. A porous glass subsurface layer with uniform spherical micro-pores could be produced by soaking near the glass transition temperature in a steam environment. The porous layer with fine and homogeneous microstructure acts as a thermal shock absorbing layer, so that glass-coated carbon with a porous glass layer has excellent thermal shock resistance in addition to steam oxidation resistance.     

Continual conversion of free fatty acid in rice bran oil to triacylglycerol by immobilized lipase

Rice bran oil containing 30–50% free fatty acid was continually converted to an oil containing more than 75% of triacylglycerol (TG) by means of immobilized lipase. The reaction was carried out at 60°C for 24 h with dehydration and reactant mixing by dry nitrogen flow under a positive nitrogen atmosphere. Enzymatic TG synthesis with evaporation by heating was not suitable because of the increasing peroxide value of the oil. Part of this article was presented at the annual meeting of the Japan Oil Chemists' Society at Sendai, Japan, October, 16, 1990.     

Uniformly Porous Composites with 3-D Network Structure (UPC-3D) for High-Temperature Filter Applications

Uniformly porous composites with 3-D network structure (UPC-3D) have been recently developed via a pyrolytic reactive sintering process, which takes advantage of the evolved CO₂ gas from a decomposing carbonate source (e.g., dolomite, CaMg(CO₃)₂) and does not require any additional pore-forming agent nor long-time burning-out process. Through liquid formation via LiF doping, strong necks are formed between constituent particles before completion of the pyrolysis of carbonate, resulting in the formation of a strong 3-D network structure. The pore size distribution is very narrow (with typical pore size: ∼1 μm), and the porosity was controllable (∼30–60%) by changing the sintering temperature. This article presents the development details of UPC-3D, and reports the recent findings in CaZrO₃/MgAl₂O₄ system, which will be one of the more promising systems for practical applications.     

Tribological Characteristics of SiC Ceramics in High-Temperature and High-Pressure Water

The effects of temperature and sliding speed on the tribological behavior of a SiC ceramic by sliding on the same material in deoxygenated water were investigated from room temperature to 300°C under the corresponding saturated vapor pressures. The friction coefficient and specific wear rates of both plates and disks increased at elevated temperatures at all sliding speeds, but decreased with increasing sliding speed at 120° and 300°C. Fine mirrorlike worn surfaces were observed without wear debris under all sliding conditions. The wear mechanism appears to consist of hydrothermal oxidation of SiC and dissolution of reaction products such as silica.     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

Synthesis of High Density and Transparent Forsterite Ceramics Using Nano-Sized Precursors and Their Dielectric Properties

Forsterite (Mg₂SiO₄) ceramics were prepared using Mg(OH)₂ and SiO₂ as precursors, and the effect of powder characteristics of Mg(OH)₂ on calcination and sintering was investigated. The use of highly dispersed Mg(OH)₂ powder (HD powder) resulted in a lower calcination temperature. Forsterite powder of high homogeneity and small particle size prepared from the HD powder enabled synthesis of high-density forsterite ceramics by ordinary sintering without applying external pressure. Moreover, transparent forsterite ceramics were successfully synthesized through addition of excess Mg to the precursors to compensate for Mg evaporated during the sintering process. Subsequent dielectric measurements revealed that the transparent forsterite ceramics had a very low dielectric loss (tan δ<10⁻⁴).