Properties of Va metal-B films prepared by r.f.-sputtering

Ta_100-x B _x alloy films were prepared by r.f.-sputtering in the chemical composition range 45 x 77. Ta_100-x B _x (45 x 58) films consist of the amorphous phase, while the TaB₂ crystal phase was observed in Ta_100-x B _x (66 x 77) films. A remarkable preferred orientation with the (001) plane of TaB₂ parallel to the film surface was observed in Ta₃₄B₆₆. The d.c. electrical conductivity of Ta_100-x B _x (45 x 77) films decreases with increasing boron content in the range 6.7 × 10³ to 1.3 × 10^3–1 cm^–1. The micro-Vickers hardness of Ta_100-x B _x (45 x 77) films was in the range 2200 to 2600 kg mm^–2.     

Monocarbonyl compounds from catalytic decomposition of autoxidized unsaturated fatty acid esters

Monocarbonyl compounds formed by the decomposition of autoxidized triolein, methyl linolenate, and methyl arachidonate were converted into their 2,4-dinitrophenylhydrazone derivatives and analyzed by thin layer and paper chromatographies. From decomposition of autoxidized triolein with acid-washed Fuller’s earth alkanals were the only monocarbonyl products found, whereas, with metal catalysts or heat, 2-alkenals were the primary products. Autoxidized methyl linolenate and methyl arachidonate decomposed with metal catalysts or heat yielded 23–55% of 2,4-alkadienals but minor amounts with acid-washed Fuller’s earth. The differences in distribution of monocarbonyl products were attributed to a selective course of scission of the hydroperoxides that depended upon the conditions of decomposition.     

Adhesive properties of cured epoxide resin containing the intermolecular compound of 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid

The intermolecular compound of 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid was synthesized, and the glass transition temperature and the adhesive properties of the cured epoxide resin containing the above compound were studied. Epoxide reacted with amino groups of 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid at the curing conditions of 150 to 180°C for 60 min and formed the cured compounds. The infrared spectra showed that epoxide reacted with isocyanuric acid in the presence of imidazole compounds and converted to 2-oxazolidinone compound on the curing process. The glass transition temperatures of the cured compounds having isocyanurate and 2-oxazolidinone rings in their structures were higher than that of the epoxide resin cured with imidazole and rise as the curing temperature rises, but fall as 2-oxazolidinone ring content increases in their cured compounds. The tensile shear and peel strengths of the steel and steel bonded with the cured compounds and the cured epoxide resin were measured at 25 and 150°C. The adhesive strengths were improved due to isocyanurate and 2-oxazolidinone rings formed in their cured compounds.     

Fat splitting by the twitchell process at low temperature

Summary A study was made of the degree of splitting of coconut and soybean oils by the Twitchell process at 35±0.1°C. with no shaking or stirring, using an agent consisting mainly of tetrabutyl naphthalene sulfonic acid with water or dilute sulfuric acid. The degree of splitting was greater with sulfuric acid than with water. In general, the degree of splitting of soybean oil was greater when the sulfonic acid was dissolved in the oil layer than when it was in water. The reverse was true with coconut oil. Although addition of glycerol had no effect on the degree of splitting, addition of glacial acetic acid to the coconut oil system decreased fat splitting to a considerable extent. Addition of coconut fatty acids to the coconut oil system had little effect, but soybean fatty acids added to the soybean oil system markedly increased the degree of splitting. For the first time it has been demonstrated that, at 35±0.1°C., splitting of a fat by the Twitchell process occurs in a stepwise way. Coconut oil in contact with 1N sulfuric acid containing the sulfonic acid, corresponding to 1% by the weight of the oil, was about 90% split in 15 to 30 days, depending on the area of contact of the two layers. The diglyceride concentration reached a maximum during the early days of the reaction and then decreased somewhat. Monoglyceride concentration appeared to reach a maximum more slowly and then continued at that level as the concentrations of free fatty acids and glycerol steadily increased. Presented at the symposia on fat of the Chemical Society of Japan, Nov. 10, 1954, and Nov. 8, 1955, Nagoya, Japan; and the 8th annual meeting of the Chemical Society of Japan, Apr. 2, 1955, Tokyo, Japan.     

Molecular association complex of urea with polyethylene: 3. Structural studies of the complex

The crystal structure of urea-polyethylene complex in the hexagonal form, obtained by one of our preparation methods, is analysed by X-ray power diffractometry. In this analysis, the fixed molecular parameters of urea are used, and three models with respect to rotational disorder of the guest polyethylene molecule are assumed. It is shown that the host lattice structure constructed by urea molecules is essentially the same as that of urea-n-paraffin complex. Effects of the disorder structure of the guest on X-ray scattering of the complex are presented. However, there is a difficulty in identifying the disorder structure by X-ray analysis. With the aid of a potential energy calculation between the hexagonal urea tunnel and the guest molecule, a rotational disorder model is preferred.     

Effect of Silicon Dioxide on the Thermal Diffusivity of Aluminum Nitride Ceramics

The thermal diffusivity of AlN ceramics was significantly decreased by the addition of SiO₂. The AlN ceramics with 4 wt% SiO₂ could not be densified by pressureless sintering in the temperature range 1400° to 1800°C. The thermal diffusivity of these samples was very low because of their porous structure. The AlN ceramics containing 2, 4, and 8 wt% SiO₂ were densified by hot-pressing and also had low thermal diffusivity. In these samples, the grains of the 27R polytype that resulted from the reaction between AlN and SiO₂ were dispersed, obstructing the conduction of heat. The relation between the amount of 27R polytype and the thermal diffusivity of the AlN ceramics was determined.     

In-situ monitoring of the stabilization with hydrogen of free radicals thermally induced from coal using high pressure e.s.r., d.t.a. and p.d.a. equipment

High temperature, high pressure e.s.r. measurements of the hydrogenation reaction of Taiheiyo coal in the presence of catalysts were carried out to understand the stabilization of thermally and/or catalytically induced free radicals. A decrease in free radical concentration with increasing temperature was observed for ZnCl₂ and SnCl₂ · 2H₂O catalysts at 10MPa under hydrogen gas. High pressure modified single-cell d.t.a. and p.d.a. equipment augmented the uniquely designed high temperature, high pressure e.s.r. cell. The hydrogenation reaction was monitored under the same experimental conditions as for e.s.r. From the results of the combination of high temperature, high pressure e.s.r. with high pressure d.t.a. and p.d.a., it was established that H₂ molecules can react efficiently with free radicals from coal molecules created by the presence of ZnCl₂ and SnCl₂ · 2H₂O catalysts.     

Effect of perchloric acid on the molecular weight and yield of poly-THF

Polytetramethylene glycol (molecular weight range 1000–8000) was prepared by the polymerization of tetrahydrofuran (THF) using a binary catalyst system of fuming sulfuric acid and perchloric acid. When 28% fuming sulfuric acid alone was used as the catalyst, the average molecular weight of polymer was low, the maximum value being 1000–1100. By the combination of fuming sulfuric acid with a small amount of perchloric acid, the average molecular weight of the polymer was increased to about 8000. Furthermore, the molecular weight was readily controlled in the range of 1000 to 8000 by varying the amount of the binary catalyst.     

Polymerization of propylene over metal oxides-supported TiCl3 catalysts

Summary Several metal oxides-supported TiCl₃ catalysts were prepared and propylene polymerization was conducted over them without cocatalysts. It was found that isotactic polymerization of propylene took place effectively over them.     

Polymerization of propylene over titanium exchanged Y-zeolite

Summary It was found that isotactic polymerization of propylene took place over titanium ion-exchanged Y-zeolite without organometallic compounds. The results obtained have led to the conclusions that Ti⁴⁺ species as well as Ti³⁺ species are active for the polymerization and that neither Ti-alkyl bonds nor Cl ligands are necessarily essential for polymerization of propylene.