Direct ethoxylation of fatty methyl ester over Al-Mg composite oxide catalyst

For the purpose of estimating the reaction mechanism of the direct ethoxylation of a fatty ester in the presence of an Al-Mg composite oxide catalyst, a labeled fatty methyl ester C₁₁H₂₃CO¹⁸OCH₃ containing ¹⁸O isotope was synthesized and directly ethoxylated. The product was evaluated by gas chromatography-mass spectrometry (GC-MS). The GC-MS spectra showed that the ¹⁸O isotope label was present only in the methoxy group at the molecular end of the ethoxylated fatty methyl ester. This supports the reaction mechanism of coordination anionic polymerization where the bond between the acyl and methoxy groups of the fatty methyl ester molecule was broken, caused by the bifunctional effect of the acid-base active sites; an intermediate chemisorption species was formed; and then ethylene oxide was addition-polymerized sequentially, in parallel.     

Humidity Sensor Characteristics of Woodceramics

The humidity sensor characteristics of Woodceramics were investigated. The Woodceramics used in this experiment were prepared at 650–900°C. The size of specimens selected was 1 × 1 × 10 mm . One was used as-cut and the other was polished. Above 700°C, the resistance of the specimen was below 50 and the decrease of resistance with increasing relative humidity was small. The specimen prepared at 650°C had a resistance of about 1 k. The resistance of as-cut specimens decreased with increase in relative humidity, but that of the polished specimen did not change significantly. The difference between as-cut and polished samples was explained by the differences in surface micro-structure.     

Prediction of the biologically active sites in eclosion hormone from the silkworm, Bombyx mori

The structure-activity relationship of eclosion hormone from the silkworm, Bombyx mori, was analyzed. First, the probable active residues in silkworm eclosion hormone and also tobacco hornworm eclosion hormone were predicted by the average distance map method. To examine the contributions of those residues to the activity of silkworm eclosion hormone, Gly-substituted mutants for those predicted residues were produced by site-directed mutagenesis and their activities were evaluated by a bioassay. Finally, Glu12, Met24 and Phe25 were estimated to be the crucial residues for the eclosion hormone activity. The possibility of the development of a blocker of an eclosion hormone receptor on the basis of the present work is also discussed.      

Hydrodesulfurization activity of highly dispersed Co sulfide clusters prepared in zeolite cages

Zeolite-supported highly dispersed Co sulfide clusters are synthesized using Co(CO)₃ (NO) as a precursor. The amount of Co inCoS_x/zeolite anchored by a CVD technique increases as the Al/Si ratio of the zeolite increases, whereas the activity per Co atomdecreases for thiophene hydrodesulfurization (HDS). When an Na-exchanged USY zeolite is used, the Co sulfide catalyst shows a muchhigher HDS activity than a conventional Co—Mo/Al₂ O₃ catalyst. It is considered from XAFS and NO adsorption techniques that thehigh HDS activity of CoS_x/USY-Na is due to an extremely high dispersion of Co sulfide clusters. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure and Viscosity of Grain Boundary in High-Purity SiAlON Ceramics

Three high-purity SiAlON materials (Si_{6− z} Al _z O _z N_{8− z} , z = 1, 2, 3) were characterized with respect to both structure and viscous behavior of internal grain boundaries. Internal friction experiments provided a direct measure of the intrinsic viscosity of grain boundaries and concurrently revealed the occurrence of a grain-boundary interlocking mechanism that suppressed sliding. A residual glass phase (consisting of aluminum-rich SiO₂) and nanometer-sized mullite residues were found at glassy triple-grain junctions of the z = 1 SiAlON. A low-melting intergranular phase dominated the high-temperature behavior of this material and caused grain-boundary sliding at temperatures as low as 1100°C. A quantitative analysis of the grain-boundary internal friction peak as a function of oscillation frequency indicated an intergranular film viscosity of log η∼ 7.5 Pa · s at 1100°C. Glass-free grain boundaries were a characteristic of SiAlON materials with z ≥ 2, which yielded a significant improvement in refractoriness as compared to the z = 1 SiAlON material. In these materials, relaxation resulting from grain-boundary sliding was suppressed, and the internal friction curve simply experienced an exponential-like increase.     

Formation Mechanism of Hydrous-Zirconia Particles Produced by Hydrolysis of ZrOCl2 Solutions: II

The primary and secondary particle sizes of monoclinic hydrous-ZrO₂ particles produced by the hydrolysis of various ZrOCl₂ solutions, with and without the addition of NaCl, CaCl₂, or AlCl₃, were measured using X-ray diffraction and transmission electron microscopy in order to clarify the formation mechanisms of primary and secondary particles. The primary particle size of hydrous ZrO₂, under a constant ZrOCl₂ concentration, decreased monotonously with increasing Cl⁻-ion concentration. On the contrary, the secondary particle size increased monotonously with increasing Cl⁻-ion concentration. The present experimental results revealed that the primary and secondary particle sizes of hydrous ZrO₂ are controlled primarily by the concentrations of H⁺ and Cl⁻ ions produced during hydrolysis, and are independent of the type of added metal ions. The formation mechanisms of the primary and secondary particles of hydrous ZrO₂ were determined on the basis of the present experimental results.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

Effect of metallic wire inserted in nozzle in high-speed melt spinning of poly(ethylene terephthalate)

High-speed melt spinning of poly(ethylene terephthalate) was performed using a spinning nozzle with an inserted metallic wire of various lengths (0, 8, 30, and 45 mm). The molecular orientation of as-spun fibers increased with the increase in the wire length at all the take-up velocities examined. Along with the enhanced molecular orientation, the longer wire length led to the starting of orientation-induced crystallization at lower take-up velocities. The structure of crystallized fibers obtained at low speeds can be characterized by high crystallinity and relatively low molecular orientation. From the on-line measurement of the diameter and temperature profiles of the spin line with the 30-mm metallic wire, it was revealed that the spin-line had a maximum diameter of about 6 mm at the wire end. The spin-line temperature at this position was about 190°C. The solidification of the spin-line occurred at positions much closer to the spinneret in comparison with ordinary high-speed spinning. These results show that high-speed spinning with a wire inserted in the nozzle corresponds to a spinning process operated at extremely low extrusion temperature using a nozzle with an extremely large diameter. From the starting of orientation-induced crystallization at lower levels of birefringence in comparison with ordinary high-speed spinning, the alteration of the inherent fiber structure that cannot be represented by birefringence was also suggested. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 665–674, 1998     

Novel functional polymers: Poly(dimethylsiloxane)–polyamide multiblock copolymer. III. Synthesis and surface properties of disiloxane–aromatic polyamide multiblock copolymer

Disiloxane–aromatic polyamide(aramid) multiblock copolymers(2SiPASs) were synthesized using 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane(BATS) as an analog of aramidsilicone resin consisting of aromatic polyamide and poly(dimethylsiloxane) (PDMS). 2SiPASs afford a transparent and toughened plastic film. The surface properties of 2SiPAS were investigated by X-ray photoelectron spectroscopy (xps) and static contact angle measurement. The results of surface analysis suggested that BATS content of the 2SiPAS surface increased with increasing BATS content in bulk. The interaction between the platelets and the 2SiPAS surface was found to be very weak when the BATS content reached 26 wt % in bulk. © 1996 John Wiley & Sons, Inc.