Permeation and separation of organic liquid mixtures through liquid-crystalline polymer networks

A side-chain liquid-crystalline polymer (LCP) was synthesized by the addition of the mesogenic monomer to poly(methyl siloxane) in presence of a Pt-catalyst. When an aqueous solution of 10wt% ethanol was permeated through a LCP membrane by pervaporation at various temperatures, the permeation rate increased with increasing temperature and drastically changed at glass-nematic (Tg) and nematic-isotropic (TNI) transition temperatures of the LCP membrane. The LCP membrane exhibited the waterpermselectivity in the glassy and liquid-crystalline states. The ethanol concentration in the permeate increased with increasing permeation temperature and the LCP membrane changed from the waterpermselectivity to the ethanol-permselectivity around TNI. These results suggested that the permselectivity was influenced by the change of the LCP membrane structure, that is, its state transformation. It was found that a balance of the orientation of mesogenic groups and flexibility of siloxane chains is very important for the permeability and selectivity.     

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.     

Pulsed NMR study in nuclear ordered solid3He

The nuclear spin dynamics in nuclear spin ordered solid³He in low magnetic fields on the melting curve has been studied by pulsed NMR down to 0.6 mK. The free induction decay signals (FID) were measured in single crystals of solid³He at three operating frequencies of 920, 1380, and 1840 kHz. The FIDs were nonexponential and dependent on the rf pulse strength _p H ₁ t _w , where is the gyromagnetic ratio,H ₁ is the rf field strength, andt _w is the pulse width. At small _p they decayed almost linearly in time with a small exponential tail at the end. When _p was further increased they became shorter and neither exponential nor linear in time. At large _p they decayed very rapidly and sometimes could not be observed at all because of the dead time of the NMR detection system. Such behavior of the FID was observed in many different single crystals in the given temperature range at 920 kHz. Tsubota and Tsuneto have shown by solving the nonlinear equations of motion numerically that the motion of the nuclear spin becomes chaotic when the tipping angle exceeds a critical value. Comparing their result with our experimental results, we concluded that some of the results of the rapid decay of the FID at large _p might be attributed to the onset of the chaotic motion. At 1840 kHz it is expected that the nonlinear effects in the equations of motion become less effective than that at 920 kHz. In fact, at this operating frequency the FIDs even at large _p and the tipping angle-dependent frequency shift could be observed. These frequency shifts were in rather good agreement with Namaizawa's theory provided an effective tipping angle was taken into account.     

Possibility of superconductivity with highT c in La-Sr-Nb-O system

We prepared La-Sr-Nb-O system samples both in bulk form and as a film, with sharp resistive transitions at temperatures of 228–323 K, depending on the annealing conditions. The sharp resistive transitions might be attributable to superconductivity. Magnetic ordering was observed over a narrow temperature range around 40 K for some of the samples.     

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.     

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.     

Studies on syntheses and permeabilities of special polymer membranes

Summary The permeation and separation characteristics of methanol/n-pentanol systems and n-propanol/n-heptane systems through nylon 12 membranes were studied by changing the feed composition of the binary organic mixtures. These characteristics were discussed from the viewpoints of physical and chemical nature of the permeating molecules and the membrane.     

Kinetic study on the first stage during thermal degradation of polystyrene

The kinetic parameters of the first stage of polystyrene degradation have been investigated to elucidate the reaction mechanisms using the flow reactor system. The decrease in molecular weight of polystyrene was recorded at minute intervals over the temperature range 310°–390°C. Generally, the first and second stages were observed by thermogravimetric analysis (t.g.a.), however in the early stage of the degradation volatile yields of at least 5% occurred. Therefore, using t.g.a. analysis it is difficult to detect this earlier stage. It became evident that the first stage in the earlier part of the reaction could be detected by g.p.c. analysis. We have observed the hidden kinetic parameters of the nature of the first stage of the polystyrene degradation. The results indicate that the main chains were degraded randomly with the small quantitative volatile groups in the first stage and the rates of decrease in molecular weight in the first stage against reaction temperatures were evaluated as log k_s = 12.0 ? 41300/RT.