Strain-induced ordering of microdomain structures in polystyrene-block-polybutadiene-block-polystyrene triblock copolymers cross-linked in the disordered state

Strain-induced ordering of microdomain structures in cross-linked polystyrene-block-polybutadiene-block-polystyrene (SBS) triblock copolymers was examined by the small-angle X-ray scattering technique. To stretch the SBS samples at elevated temperature above the glass transition temperature of polystyrene, polybutadiene blocks were chemically cross-linked in the disordered state. The initial morphology was disorder-like or bicontinuous due to incompletion of microphase separation in the presence of the chemical cross-links. When the cross-linked SBS samples were mechanically stretched at 130 °C and were further annealed for 24 h under a stretched state, the random domain structures ordered gradually and lamellar-like regularity was finally attained. It was found that the ordering proceeded more for the case of the higher strain.     

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.     

Influence of ash composition on heavy metal emissions in ash melting process

Two kinds of fly ash, discharged in the combustion of either refused derived fuel (RDF) or car shredder dust (SD), were examined for the emission of heavy metals in melting process under oxidizing and reducing conditions. The residual fractions of heavy metal in slag were experimentally estimated. As a result, it was confirmed that several volatile heavy metals were readily emitted during melting process. The type of atmosphere provided for the melting process was found to affect the emission of some volatile metals in RDF ash, but not in SD ash. The emission of volatile heavy metals in RDF ash under oxidizing conditions was lower than under any other conditions in this study. The emission behavior of iron and heavy metals in RDF ash under reducing conditions was similar to that in SD ash. These facts indicated that phosphorous in RDF ash had the property of fixing the volatile metals in the slag only under oxidizing conditions. Then the mixture of SD ash with phosphorous oxide powder was also tested in a melting process, and the result was consistent with the above inference of the effect of phosphorous.     

Iodine reaction of vinyl acetate/vinyl propionate copolymers. III. Iodine affinities of the radically polymerized copolymers and the copolymers derived from partially saponified polyvinyl acetate

The minimum sequence lengths (n_c) of vinyl acetate (VAc) units necessary to form a colored iodine complex were determined to be 4 and 17 for radically polymerized VAc/vinyl propionate (VPr) and VAc/isopropenyl acetate (IPAc) copolymers, respectively. The iodine affinities (I/VAc) of VAc/VPr copolymers (SP-series) obtained by propionylation of partially saponified polyvinyl acetate (PVAc) were remarkably affected by the saponification conditions. An increase of the water content in acetone/water mixture as saponification solvent brought about a decrease of the iodine affinities of the SP-series. The dependence of the iodine affinity on the saponification of monomer units in the SP-series was compared with that in the radically polymerized VAc/VPr copolymers by taking the sequence probability as the measure of monomer unit distribution. The results strongly supported an occurence of the slide fastener reaction at high degrees of saponification, which was well-known in the saponification of PVAc. Furthermore, it was found that the saponification mode of PVAc at low degrees of saponification was influenced uniquely by the water content in saponification solvents and the saponification temperature.     

Preparation of superacid of iron-supported zirconia for reaction of butane to isobutane

A highly active superacid of 2 wt% Fe-supported ZrO₂ for the skeletal isomerization of butane to isobutane was obtained by sfexposing Fe₂O₃/ZrO₂ to 1 N H₂SO₄ followed by calcining in air at 700°C for more than 24 h; the Fe₂O₃/ZrO₂ was prepared by impregnating zirconia gel with a solution of Fe(NO₃)₃ followed by drying at 300°C (2 wt% Fe). A much lower activity was observed with the opposite procedure, where the first impregnation was sulfation of the gel, followed by a second impregnation with the iron compound. It was proved from analysis of the sulfur content in the catalysts that residual sulfur species were not related with generation of the superacidic sites. XPS showed the catalyst to be Fe₂O₃ supported on ZrO₂.Superacids by metal oxides, VIII. For previous publications VI and VII in this series see refs. [10,11].     

Chaos in parametric resonance flow at water-mercury interface

In the electrochemical system with liquid-liquid interface, intense local convections by the resonance with potential pulses take place. Therefore, with laser beam scattering, temporal movement of the water-mercury interface was observed. As a result, the scattering efficiency showed non-linear oscillation.

Such non-linear response could be controlled by potential pulse height. As the potential height was increased, new scattering peaks in the oscillation emerged, which was expected of a kind of bifurcation phenomenon. From these results, phase portrait, Poincarè section, correlation dimension of the strange attractor and the largest Lyapunov exponent of the trajectories were obtained. Consequently, it was concluded that all the parameters indicate chaotic behavior of the resonance flow.     

Synthesis and electrode performance of layered nickel dioxide containing alkaline ions

Several polymorphs of layered nickel dioxide were prepared by using the chemical insertion of alkaline ions into Li_0.10NiO₂. We used aqueous AOH (A = Li, Na, K) solutions as reducing agents. Sodium and potassium insertion resulted in hydrated layered compounds that can be classified as γ-NiOOH with high crystallinity, while lithium insertion occurred without hydration. We discuss the coordination environment around the A⁺ ions for these inserted compounds. The thermal behavior, analyzed using high temperature (HT) X-ray diffraction (XRD) and thermogravimetric (TG) measurements, indicated that heating the hydrate at 150 °C yielded its dehydrate. The electrode performance of the nickelate was studied in lithium cells. We discuss the effect of interlayer water on cell rechargeability and the similarity between these nickelate and hydrated manganese dioxide (birnessite).     

Cationic copolymerization behavior of a bicyclic orthoester having hydroxy group with glycidyl phenyl ether and volume change on their copolymerization

This article describes cationic ring‐opening copolymerization of a bicyclic orthoester having hydroxy group (BOE‐OH) and glycidyl phenyl ether (GPE), and the volume shrinkage behavior during the copolymerization. THF soluble polyethers [poly(BOE‐OH‐co‐GPE)] were obtained by the copolymerizations at 80–180°C, while crosslinked poly(BOE‐OH‐co‐GPE) was obtained by the copolymerizations at 220–250°C. This crosslinking reaction may originate from the dehydration of methylol groups in the side chain of poly(BOE‐OH‐co‐GPE). The volume shrinkage during the cationic copolymerization reduced as the increase of the BOE‐OH feed ratio. By contrast, the volume shrinkage on the crosslinking polymerization was almost independent on the BOE‐OH feed ratio. Poly(BOE‐OH‐co‐GPE)s with higher BOE‐OH composition showed lower thermal weight loss temperature owing to the release of H₂O by dehydration of methylol groups. The BOE‐OH component in the THF soluble poly(BOE‐OH‐co‐GPE)s lowered the glass transition temperature (T_g), while that in the crosslinked poly(BOE‐OH‐co‐GPE) increased the T_g probably because of the higher crosslinking density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1356–1361, 2006