Measurement of the melting points of oligomers obtained in the manufacture of poly(ethylene terephthalate)

The melting points (T_m) were measured for oligomers obtained by a direct continuous esterification process between terephthalic acid and ethylene glycol. Multiple regression analyses of data were carried out, and an equation was obtained for predicting melting points with correlation coefficient of ～0.99.     

Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.     

Self-aligned fabrication of single crystal diamond gated field emitter array

This paper describes a self-aligned fabrication process for diamond gated field emitter array (FEA). Utilizing the non-conformal coverage sputtering conditions of silicon oxide, an interesting “sphere on cone” structure is formed on diamond nano tip array, which is the key point of gate hole opening process. This structure causes shadowing at certain regions of side-wall during Ti / Au gate metal deposition. Removal of “sphere” by wet etching leads to the successful fabrication of a single crystalline diamond gated FEA. Scanning electron microscope observations reveal the fabrication of a uniform emitter array with tip radius of curvature (20 nm) and gate hole (1.4 μm). We also confirmed that no noticeable physical damage exists on tip. In field emission characteristics of the fabricated single crystal diamond gated FEA, gate voltage control of field emission current is realized.     

Production of dihomo-γ-linolenic acid byMortierella alpina 1S-4

The mycelial dihomo-γ-linolenic acid content of an arachidonic acid-producing fungus,Mortierella alpina 1S-4, was found to increase, with an accompanying marked decrease in its arachidonic acid content, on cultivation with sesame oil. The resultant mycelia were found to be a rich source of dihomo-γ-linolenic acid. This unique phenomenon was suggested to be due to specific repression of the conversion of dihomo-γ-linolenic acid to arachidonic acid by the oil. After fractionation of the oil with acetone into oil and non-oil fractions, it was found that the effective factor(s) was present in the non-oil fraction. In a study on optimization of the culture conditions for the production of dihomo-γ-linolenic acid byM. alpina 1S-4, a medium containing glucose, yeast extract and the non-oil fraction was found to be suitable for the production. Under the optimal conditions in a 50-1 fermentor, the fungus produced 107 mg of dihomo-γ-linolenic acid/g dry mycelia (2.17 g/l of culture broth). This value accounted for 23.1% of the total fatty acids in the lipids extracted from the mycelia. The mycelia were also rich in arachidonic acid (53.5 mg/g dry mycelia, 11.2%). Other major fatty acids in the lipids were palmitic acid (24.1%), stearic acid (7.0), oleic acid (20.1), linoleic acid (6.6) and γ-linolenic acid (4.1). On leave from Suntory Ltd.     

Photocatalysts using hexa- and octa-titanates with different tunnel space for water decomposition

Photocatalytic activities for water decomposition were examined for photocatalysts using hexa- and octa-titanates and TiO2(B) with different tunnel space in the structure. Using RuO2 as promoter, M2Ti6O13 (M = Li, Na, K, Rb) showed the stoichiometric production of Hz and O₂ except for Li, whereas H₂Ti₈O₁₇ and TiO₂(B) had very low activity producing only hydrogen as a product. The effects of promoters on Na₂Ti₆O₁₃ showed that the activity increased in the order of RuO₂ > RuO₂ + IrO₂ > IrO₂ > RuO₂ + Pt > MnO₂. These effects along with other related ones are discussed: it emerges that the presence of the tunnels is important for the achievement of high photocatalytic activity.     

Copolymerizations of macromonomer prepared by addition-fragmentation chain transfer polymerization of methyl acrylate trimer

Summary An oligomer of the methyl acrylate unsaturated trimer bearing 2-carbomethoxy-2-propenyl ω-end group (M _n = 1300, M _w/M _n = 1.7, and functionality > 0.7) was copolymerized as a macromonomer (0.02 mol/L) with styrene (1.0 mol/L) in benzene at 60 °C. The amounts of monomer and macromonomer in the feed simultaneously decreased with increasing time to indicate copolymer formation, and the macromonomer was found to be as reactive as styrene toward poly(styrene) radicals. The M _ns of the copolymers were 13900–22000 depending on conversion. No resonance due to the unsaturated <ω-end group bound to the poly(styrene) chain was detected by ¹H-NMR spectroscopy, indicating that no fragmentation of adduct radical of the end group to expel the poly(methyl acrylate trimer) radical. Polymerization of ethyl methacrylate (1.0 mol/L) in the presence of the macromonomer (0.02 mol/L) resulted in a mixture of the unreacted macromonomer and homopolymer of ethyl methacrylate. No end group bound to the poly(ethyl methacrylate) was detected by ¹H-NMR spectroscopy, excluding the possibility of addition fragmentation chain transfer to the macromonomer to expel an oligomer radical of the methyl acrylate trimer. Addition of the poly(methacrylate) radical to the macromonomer is extremely slow under the present conditions of copolymerization. Received: 27 March 2003/Revised version: 30 April 2003/ Accepted: 30 April 2003 Correspondence to Bunichiro Yamada     

Temperature Dependence of KIC for High-Pressure Hot-Pressed Si3N4 Without Additives

Temperature dependence of K_IC values for Si₃N₄ bodies sintered at high pressures without additives was studied from room temperature to 1400°C. Little change in K_K was found in this range.     

Redox properties of CeO2 and Pt-Rh/CeO2 studied by TAP method

Redox properties of CeO₂ and Pt-Rh/CeO₂ were studied by temporal analysis of products (TAP) method using alternative pulses of CO and O₂. A portion of pulsed CO was oxidized to CO₂ and a portion of CO was adsorbed on the surface. Pulsing ¹⁸O₂ onto the catalyst which has surface species derived from CO, evolved CO₂ contained no ¹⁸O suggesting that the surface species will be carbonate ions.     

Lysozyme requires fluctuation of the active site for the manifestation of activity

Mutations around His15 which lie far away from the active site,stimulated glycol chitin activity of lysozyme at physiologicaltemperature. Del-Argl4Hisl5 lysozyme, a mutant lysozyme whoseArgl4 and Hisl5 were deleted together, and has the highest activityamong these mutant lysozymes, had a similar binding abilityto a trimer of N-acetyl-glucosamine, a substrate analogue, relativeto native lysozyme. This suggests that the increased activitywas due to an increased k_cat in the catalysis reaction. TheH-D exchange rate of the N-1 proton in the Trp63 which is locatedin the active site cleft, was enhanced in the Del-Argl4Hisl5lysozyme, while 2-D proton NMR analysis revealed no conformationalchange around Trp63. We conclude that some sort of fluctuationat the active site might be required for the manifestation ofactivity. This theory is supported by the finding that the Del-Argl4Hisl5lysozyme showed a shift in temperature dependency of activityto lower temperatures compared with that of native lysozyme.     

Influence of reaction temperature on direct esterifications in a continuous recycling process between terephthalic acid and ethylene glycol

Simulations were carried out with a continuous recycle esterification model for the terephthalic acid–ethylene glycol (TPA–EG) system proposed previously. The influence of reaction temperatures, recycle ratios, and residence times on the oligomer characteristics was examined and the following results were obtained: (1) The main reactions proceed more under higher reaction temperatures, but the side reactions on diethylene glycol (DEG) proceed further than do the main reactions. (2) The higher residence time ratio of the first reactor to the total results in the proceeding of esterifications, which becomes remarkable as the temperature becomes high. (3) As the recycle ratio becomes high, the esterfications proceed, but in the very high degree of esterification, the tendency is reversed. (4) The characteristics of oligomer are almost the same at the same degree of esterification, independent of the reaction conditions. © 1994 John Wiley & Sons, Inc.