Role of tungsten in promoting selective reduction of NO with CO over Ir/WO3–SiO2 catalysts

Catalytic hydrogenation of naphthalene to decalin was studied over a carbon-supported rhodium catalyst in supercritical carbon dioxide solvent at 333 K, and the results were compared with those in an organic solvent. cis-, trans-Decalin and tetralin were formed from the beginning of the reaction in supercritical carbon dioxide. Higher concentration of hydrogen in carbon dioxide solvent and on the active site, and also the suppression of desorption of partially hydrogenated tetralin molecules from the active site would be responsible for higher selectivity to cis-decalin in supercritical carbon dioxide than that in an organic solvent.     

Prostaglandin-like substances formed during autoxidation of methyl linolenate

Prostaglandin-like substances other than 3-(2-ethyl-5-hydroxy-3-oxo)-cyclopentanyl-2-propenal (compound I), which upon reacting with amino acids form reddish pigments, were purified, and their chemical structures were determined. Three red pigment-forming substances (RPS) in autoxidized methyl linolenate were purified successively by gel chromatography on Sephadex LH-20, column chromatography and thin layer chromatography on Silica Gel 60, and by high performance liquid chromatography on μ-Porasil. IR spectra of the RPS showed the absorption of an ester group (νC=O 1730 cm⁻¹ in CHCl₃) and of a longer branched chain (νC-H 2800–3100 cm⁻¹), in addition to the absorption bands observed in compound I. Electron impact mass spectra of the trimethylsilyl ethers obtained after reduction with NaBH₄ and NaBD₄ were analyzed in detail and compared with those of compound I. The structures of the RPS were identified as stereoisomeric methyl 8-[2-(2-formylvinyl)-3-hydroxy-5-oxo-cyclopentanyl]-octanoates derived from methyl 12-hydroperoxy-linolenate. Presented at the general meeting of the Japanese Society of Scientific Fisheries, held at Tohoku University, Sendai, Japan, October 1984.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Separation of surfactant mixtures and their homologs by high performance liquid chromatography

A technique for separating similar and diverse ionogenic mixtures into their individual homologs was studied by high performance liquid chromatography on an octadecyl-silica (TSK Gel LS-410) column. Conditions used for the separation were: column size, 6 mm id×200 mm; mobile phase, water/methanol (15:85, v/v) containing (a) 1.0 M sodium perchlorate and adjsting to pH 2.5 with phosphoric acid, (b) 0.1 M and pH 3.5; column temp., 50 C. By using 2 mobile phase conditions, various surfactant mixtures were separated into their individual homologs and simultaneously distinguished from each other, regardless of their ionogenic properties.     

Differential scanning calorimetric studies on the glass transition temperature of polyhydroxystyrene derivatives containing sorbed water

Poly(4-acetoxystyrene) (PAS) and poly(4-acetoxy-3-methoxystyrene) (PAMS), poly(4-hydroxystyrene) (PHS) and poly(4-hydroxy-3-methoxystyrene) (PHMS) have been prepared. The effects of hydrogen bonding on the glass transition temperatures (T_g) of these polymers have been studied by differential scanning calorimetry. The T_g′s of partially hydrolyzed PAS and PAMS increased with the degree of hydrolysis. Partially hydrolyzed PAS and PAMS are estimated to be random copolymers, judging from the correspondence between the calculated and observed T_g′s of these polymers. The effect of water on the glass transition was also studied, and it was clarified how water adsorbed on the polymers acts as a hydrogen-bond breaker. The ‘critical water content’ is calculated from the decrease of T_g by water absorption, and the relation between hydrogen bonding and T_g is discussed.     

Vertical pneumatic conveying: An experimental study with particles in the intermediate and turbulent flow regimes

Vertical pneumatic conveying was studied in a 3-inch diameter riser 30 feet in length using solids ranging in particle Reynolds number from 100 to 3500. Particle to gas mass flow ratios varied from 0 to 8 and pipeline conditions extended from dilute flow down into the choking region. Average particle hold-up was determined by means of a series of quick-closing valves and particle slip velocity was often found to be greater than the calculated terminal velocity. The reasons for this are examined. Frictional pressure losses in the riser were also determined and compared with literature data. The phenomenon of choking is considered briefly.     

Efficient usage of highly dispersed Pt on carbon nanotubes for electrode catalysts of polymer electrolyte fuel cells

A Pt-deposited carbon nanotube (CNT) shows higher performance than a commercial Pt-deposited carbon black (CB) with reducing 60% Pt load per electrode area in polymer electrolyte fuel cells (PEFCs) below 500 mA/cm². K₂PtCl₄ and H₂PtCl₆·6(H₂O) are used for the Pt deposition onto multi-walled CNTs (MWCNTs), which are produced by the catalytic decomposition of hydrocarbons. The electric power densities produced using the Pt/CNT electrodes are greater than that of the Pt/CB by a factor of two to four on the basis of the Pt load per power. CNTs are thus found to be a good support of Pt particles for PEFC electrodes. TEM images show 2–4-nm Pt nanoparticles dispersed on the CNT surfaces. These high performances are considered to be due to the efficient formation of the triple-phase boundaries of gas–electrode–electrolyte. The mechanisms of Pt deposition are discussed for these Pt-deposited CNTs.     

Effects of 6-anilino-1,3,5-triazine-2,4-dithiol,zinc stearate,and barium stearate on the thermal stabilization of PVC

Individual action and synergistic effect in the combination of 6-anilino-1,3,5-triazine-2,4-dithiol (AF), zinc stearate, and barium stearate on the color stabilization of PVC were investigated. In this system, AF selectively reacts with allylic chlorine atoms in PVC. Consequently, unstable allylic chlorine units were converted to thermally stable allylic structures, thus retarding the development of polyene sequences. Zinc stearate accelerated the reaction of AF with allylic chlorine atoms in PVC, forming the zinc salts of AF (AFZ_nSt, St?C₁–H₃₅COO? ) by reacting with AF. Barium stearate reacted with ZnCl₂ which is formed in the above reaction to give St₂Zn and BaCl₂. Consequently, barium stearate led to the selective reaction of AF with allylic chlorine atoms in PVC and the remarkable retarding effect of discoloration of PVC.     

Formation and Properties of Ln-Si-O-N Glasses (Ln = Lanthanides or Y)

Homogeneous Y-Si-O-N glasses containing 15 or 20 eq% nitrogen (N) were prepared from compositions with Y/Si ratios in the vicinity of that of the lowest eutectic point on the Y₂O₃–SiO₂ phase diagram. The liquidus on the phase diagram shifted toward lower temperatures by incorporation of N. The density, the elastic moduli, and the glass transition temperature of the Y-Si-O-N glasses increased with incorporation of N. This is due to the closer packing of atoms in the glasses by the substitution of N, which is in three-fold coordination with Si, for O which is in two-fold coordination, and the stronger covalent nature of the Si–N bond compared with the Si–O bond. The coefficient of thermal expansion of the Y-Si-O-N glasses increased with increasing Y content, because the discontinuity of the glass network developed with increasing nonbridging anions by the introduction of Y. In contrast, the glass transition temperature and the elastic moduli increased with Y content due to the high coordination of Y for O, and the relatively high cationic field strength of Y. Furthermore, the effect of cationic field strength on properties of Ln-Si-O-N glasses (Ln = lanthanides or Y) is discussed.