Pseudo-binary system Bi2O3-TeO2 in air

The phase equilibria in the pseudo-binary system Bi₂O₃-TeO₂ at 600° 950° C in air were examined by solid-state reaction techniques and X-ray powder diffraction method. Four pseudo-binary compounds appeared, i.e., -Bi₂O₃ type solid solution having a compositional range of (1-x)Bi₂O₃·xTeO₂ wherex=0 0.4 a new compound Bi₆Te₂O₁₅ which has an orthorhombic cell of a=2.27(4) nm, b=1.06(1) nm and c = 0.539(8) nm, 2Bi₂O₃ · 3TeO₂, and an unidentified phase Bi₂O₃·2TeO₂. The formation of the phase Bi₆Te₂O₁₅, in which all the Te ions are hexavalent, was confirmed by the thermogravimetry and by the Mössbauer spectra. The liquidus curves for whole system were determined by DTA method.     

Modification of mesophase pitch by blending Part 2 Modification of mesophase pitch fibre precursor with thermoresisting polyphenyleneoxide (PPO)

Polyphenyleneoxide was blended in amounts of 5 or 10 wt% into petroleum-derived mesophase pitch to reinforce the pitch fibre before the oxidative stabilization to achieve better handling properties. Although polyphenyleneoxide was fusible but hardly soluble in the mesophase pitch even at a spinning temperature of 350° C, blended pitch could be smoothly spun into pitch fibre 10m diameter, as could the parent pitch. Fibrous polyphenyleneoxide of less than 1m diameter was homogeneously dispersed in the pitch fibre, being arranged along the fibre axis. Such fibrous polyp henyleneoxide reinforced the pitch fibre considerably. The fibrous substances at the centre of the fibre disappeared in the carbonized fibre at 1300° C after oxidation at 250° C, although some short ones were observed in the skin region of the fibre, suggesting that polyphenyleneoxide was co-carbonized to be assimilated with mesophase pitch at the centre of the fibre, where the effects of oxidation may be rather limited. The oxidation reactivity and its mechanical strength after carbonization were slightly lower in comparison with those of the parent mesophase pitch.     

Collective modes and a theory of response ofd-wave superconductors

We present a theory of the response ofd-wave superconductors to weak applied fields, by taking account of the Coulomb interaction and all the collective degrees of freedom as well as crystal symmetry. We choose two representative phases: the d phase, which has point nodes in the energy gap, and theY _2–1 phase, which has line as well as point nodes. The former is a self-consistent solution for cubic as well as spherical symmetries and the latter is one for spherical, cubic, and hexagonal symmetries. We obtain obviously gauge-invariant expressions for the order-parameter fluctuations and the currents, having forms common not only to thed-wave states, but also to thep-wave states studied earlier. We also investigate the collective excitations; in the long-wavelength limit for spherically symmetric systems, there are, on the frequency-temperature plane, seven branches for eachd-wave phase considered, in addition to the common plasma mode and orbital Goldstone modes resulting from the spontaneous breakdown of the rotational invariance. In theY _2–1-phase two eigenmodes are found to become gapless at a finite temperature, below which they are purely imaginary. This implies instability of the phase. The effect of crystal anisotropy on the collective spectra is also studied.A preliminary report on the present work was published inJpn. J. Appl. Phys. Suppl. 26-3, 167 (1987).     

Carbonization of coals to produce anisotropic cokes. 1. Modifying activities of some additives in the co-carbonization of low-rank coals

Using low-rank coals, the modifying activities of some petroleum, coal tar and aromatic hydrocarbon additives have been examined to find procedures for their utilization in the preparation of blast furnace coke. Petroleum pitch, especially after hydrogenation, exhibited excellent modifying activity even with non-fusible coals. In contrast, the activity of coal tar was very limited with such coals. The napththenic component, revealed by n.m.r. of the additives, appears to be important in the co-carbonization by inducing fusibility and anisotropic development in such coals. Co-carbonization to recover the dehydrogenated additives was attempted. However, there was no development of the anisotropy in the resultant coke by dissolution of the coal particles although the coal particles were firmly fixed in the matrix. Acid-refluxing treatment of non-fusible coals was found to enhance their modification susceptibility, indicating that some of the acid-soluble mineral matter is important in the thermal depolymerization or fusion process of the coal.     

Influence of Metal Ions on the Order-Disorder Transition Temperature of the Ba-M-O (M: La, Y, In, or Ga) System

Preparation of BaLa₂O₄, B_a3,Y₄O₉, B_a,In₂O₅, and Ba₃Ga₂O₆ powders and their sintering were investigated in Ar or air. These sintered bodies with perovskite-related structure were synthesized by reaction sintering, using mixed powders in the atomic ratios of Ba/La = 1, Ba/Y = 0.75, Ba/In = 1, and Ba/Ga = 1.5. The order-disorder transition temperatures of the BaLa₂O₄, Ba₃Y₄O₉, Ba₂In₂O₅, and Ba₃Ga₂O₆ sintered bodies were 270°, 350°, 880°, and 123O^oC, respectively. It was found that the temperatures were influenced by the ionic radius of cations in B sites, and the transition temperatures decreased with increasing ionic radius.     

Aspects of gasification and structure in cokes from coals

Cokes were prepared from nine coals of different rank and characterized by surface area measurement, reactivity to carbon dioxide at 1473K and Raman-laser spectroscopy. Rates of gasification of cokes on a unit surlface area basis (K¹ = g m^?2 min^?1) decreased with increasing rank of parent coal based on maximum oil reflectances. However rates of gasification could not be related to coke structure as measured by Raman-laser spectroscopy.     

Poly(p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO₂, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.     

Novel method of preparing Ag–Hg alloy on polyacrylamide films and their structure

A novel method is proposed of preparing thin Ag–Hg alloy on PAAm film surface at room temperature: The film of interest is formed by holding PAAm aqueous solution with AgNO₃ in Hg-saturated atmosphere. Two kinds of films, one of which is a conductor and the other an insulator, can be selectively formed with pH-controlled PAAm solution by ammonia. The conducting surface is assigned to the α phase of Ag–Hg alloy by means of X-ray analysis. Potentiometric titration and IR spectral studies suggest the existence of PAAm–Ag⁺ complexes. On the basis of their structure and the oxidation and reduction potential of Ag⁺ and Hg²⁺, the mechanism of film formation is also discussed.     

A facile chemical synthesis of cholest-4-en-3-one. Carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and cholest-5-en-3-one

This paper presents a simplified method for the chemical synthesis of cholest-4-en-3-one, which is a naturally occurring steroid and a salient intermediate in steroid chemistry. Pyridinium chlorochromate (PCC) in refluxing benzene has been found to be an effective and convenient reagent for the oxidation and concomitant isomerization of cholest-5-en-3β-ol (cholesterol) to cholest-4-en-3-one in high yield. Also described are the carbon-13 nuclear magnetic resonance spectral properties of cholest-4-en-3-one and of the isolated reaction intermediate cholest-5-en-3-one. Based on a paper presented at the Symposium on Plant and Fungal Sterols: Biosynthesis Metabolism and function held at the AOCS Annual Meeting, Baltimore, MD, April 1990.     

Aggregation arrestant pheromone of the German cockroach,Blattella germanica (L.) (Dictyoptera: Blattellidae): Isolation and structure elucidation of blattellastanoside-A and -B

The aggregation pheromone of the German cockroach,Blattella germanica, consists of attractant and arrestant, which can be detected by olfactometer and choice-chamber assay, respectively. Both were extracted from the frass-contaminated filter paper being used as a shelter. They were separated by solvent partition withn-butanol and water. The arrestant from then-butanol phase was purified by open column chromatography and then successive HPLC isolated two major arrestant components. Spectral evidence from SI-MS, HR-EI-MS, and NMR experiments with pulse techniques provided possible structures as 1-(6-chloro-4,5-epoxy-5-stigmast-3-yl)--d-glucopyranoside and 1-(6-chloro-5-hydroxy-5-stigmast-3-yl)--d-glu-copyranoside, denoted as blattellastanoside-A and blattellastanoside-B, respectively. They represented arrestant activity as median effective doses (ED₅₀) at 0.044 (A) and 3.2 (B) nmol on 1.0 cm² of Whatman No. 1 filter paper.