Crystallization of potassium titanate from the amorphous phase

By using amorphous potassium titanates as the starting materials, a sintered body of K₂Ti₄O₉ or K₂Ti₆O₁₃ with porous and fibrous textures was prepared. K₂Ti₂O₅ and a new phase, K₆Ti₄O₁₁ were synthesized by the thermal reaction of KNO₃ with TiO₂ at 1000° C for 10 to 20 h. On leaching in water to expel excess of potassium ions, both phases became amorphous. After mixing and moulding these amorphous materials in the desired proportion, a sintered body containing fibrous crystals of K₂Ti₄O₉ was readily fabricated by heating at 1000° C for 12 h. When 5 wt % B₂O₃ was added to the amorphous phases, single phase K₂Ti₆O₁₃, with a fibrous texture grew well on heating at 1000° C for 12 h. Addition of PVA polymer to the amorphous phases was responsible for controlling the porosity of the sintered body, e.g. about 52% theoretical density at 20 wt% PVA polymer. The optimum conditions for preparing the amorphous phases were systematically examined and the effect of the chemical reaction environments, such as different crucible materials on the calcination of KNO₃ and TiO₂ were also discussed.     

Formation of monodispersed Ta2O5 powders

The Ta₂O₅ powders synthesized by the hydrolysis of tantalum pentaethoxide, Ta(OC₂H₅)₅ in alcoholic solution were monodispersed fine oxide particles, which were a uniform, spherical shape, non-agglomerate, and had a narrow size distribution. They grew to 1.2m after ageing for 1 h after hydrolysis. Powder X-ray diffraction and differential thermal analysisthermogravimetric analysis showed the particles were amorphous and hydrated. These particles lost the water at 290° C and gave well-crystalline Ta₂O at 740° C. Throughout these thermal processes, the particle morphology was kept almost the same.     

Studies on syntheses and permeabilities of special polymer membranes. XVI. Permeation and separation characteristics of aqueous polymer solutions for acrylonitrile-styrene copolymer membranes

The permeation and separation characteristics of aqueous polymer solutions using acrylonitrile-styrene copolymer membranes were investigated under various conditions. The membranes obtained from dimethyl sulfoxide solution of acrylonitrile-styrene copolymer have not a sufficient reproducibility and stability of permeation. These lacks were improved by adding ethylene glycol or glycerol to the casting solution and treating the membranes with pressure. The permeation and separation characteristics were influenced significantly by the additional amount of above additives, the heat treatment temperature, and the operating pressure. It was found that the concentration polarization of poly(vinyl alcohol) molecules onto the surface of the acrylonitrile-styrene copolymer membranes is smaller than that onto hydrophilic polymer membranes such as membranes of cellulose acetate, cellulose nitrate, and nylon 12, etc. Moreover, the acrylonitrile-styrene copolymer membranes show better performance for separation and concentrating of aqueous polymer solutions than hydrophilic membranes.     

Effects of support and additive on oxidation state and activity of Pt catalyst in propane combustion

The effects of support and additive on the oxidation state and catalytic activity of Pt catalyst in the low temperature propane combustion were systematically investigated on Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂–Al₂O₃. The catalytic activity varied much with both support materials and additives. The catalyst on the more acidic support showed higher activity, and the catalytic activity on every support materials increased as the electronegativity of additives increased, while some additives decreased the activity. The oxidation state of platinum, estimated by white line intensity of Pt L_III-edge XANES spectrum, also varied with the support and additives, and additives with higher electronegativity greatly prevented the platinum from its oxidation under oxidising atmosphere. Among almost all the catalysts with various supports and various additives, a clear relationship was observed between the oxidation state of platinum and the catalytic activity; the more metallic platinum showed higher activity. Thus, it was concluded that the total electrophilic/electrophobic property derived from those of the support and additive controls the oxidation state of platinum, which intensively affects the catalytic activity; i.e. higher electrophilic property provides less oxidised platinum, resulting in high catalytic activity. The mechanism of this effect was also discussed on the basis of thermochemical data, and it was proposed that the electrophobic materials promote the noble metal oxidation since the noble metal oxo-anion such as PtO^δ− is more stabilised with electrophobic cation.     

Fibrous support for immobilization of enzymes

A poly(vinyl alcohol) (PVA) fiber support incorporating various aminoacetal functional groups has been developed for immobilizing enzymes. The aminated PVA fiber seems to adsorb enzymes with electrostatic force of attraction; thus the immobilization procedure is simple. By the use of this fiber having immobilized enzymes, the reaction between enzymes and substrates is nearly independent of the size of subtstrates. This newly developed type of fiber, which is formed by a mass superfine fibers (SFF), each measuring 1 μm or less in diameter, permits much more increased surface area than the conventional enzyme immobilization supports. Our studies of the properties of the fiber for immobilization of enzymes show the following results: (1) SFF has a greater ability for the immobilization of invertase than ordinary fibers; (2) dimethyl-aminated SFF has the best performance for the immobilization of invertase. From these results, it is concluded that the dimethyl-aminated SFF is an excellent support for the immobilization of invertase.     

Bonelike Hydroxyapatite Induction by a Gel-Derived Titania on a Titanium Substrate

Gel-derived titania coating on commercial pure (c.p.) titanium induces hydroxyapatite formation onto its surface from a simulated body fluid (SBF, a metastable calcium phosphate solution). The induced apatite is similar to bone apatite in that it is poorly crystallized, calcium-deficient, and carbonate-containing. Furthermore, the carbonate (CO^2–3) groups go into the apatite lattice and lie at the positions of PO^3–4 and OH^– to replace these ionic groups, resembling the (CO^2–3) groups of bone apatite. Therefore, the apatite induced by the gel-derived titania is said to be bonelike. A chemical stimulation, stemming from abundant hydroxyl groups and negative charges at the surface of the titania gel, is believed to be responsible for the bonelike apatite induction. The potential of bone-bonding is predicted for the gel-derived titania, for it is an efficient bonelike apatite inducer in the SBF.     

Anodic Dissolution of Uranium Mononitride in Lithium Chloride-Potassium Chloride Eutectic Melt

Uranium-plutonium nitride is a candidate fuel for fast reactors, but its major drawback is ¹⁴C formation from natural nitrogen. One would probably have to use highly ¹⁵N-enriched nitrogen. A pyrochemical process with molten-salt electroreflning has been proposed as a means to increase the nuclear proliferation resistance of the fuel cycle. Molten-salt electroreflning could also be applied to nitride fuels to make possible the recycling of ¹⁵N. The anodic dissolution behavior of UN in LiCI-KCI melt was studied to provide the basis for a feasibility study of electroreflning of irradiated nitride fuels.     

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.     

Studies on syntheses and permeabilities of special polymer membranes

Summary The permeabilities of various cellulose ester membranes and cellulose membranes were investigated using pure water and aqueous solution of glycerol as feed. In all membranes, the permeation rate for aqueous solution of glycerol was greater than for pure water. The permeation rates of cellulose ester membranes increased with an increase in number of carbon atoms of the substituent group in cellulose ester.     

Internal fracture of notched epoxy resins

The brittle fracture of round-notched epoxy resin bars subjected to plane strain bending has been studied at varying strain rates. Observations of fracture processes and surface morphologies revealed that the internal crack was nucleated at the plastic-elastic boundary when the plastic deformation zone at the notch root reached a certain size. A slip-line field theory allows calculation of the stress components at the plastic-elastic boundary from a knowledge of the location of the internal crack. An analysis of the data concluded that the triaxial stress level ahead of the plastic zone was raised by plastic constraints to an ideal fracture stress which is considerably larger than that of glassy thermoplastics.