Effect of surfactants on phenol removal by the method of polymerization and precipitation catalysed by Coprinus cinereus peroxidase

The removal of phenol by peroxidase‐catalysed polymerization was examined using Coprinus cinereus peroxidase in the presence of surfactants. The non‐ionic surfactants with poly(oxyethene) residues, Triton X‐100, Triton X‐405 and Tween 20, enhanced the phenol removal efficiency at a level similar to high relative molecular mass poly(ethylene glycol) (relative molecular mass 3000). Although the improvement in the removal efficiency was less than that of Triton X‐100, Span 20, sodium lauryl sulfate (SDS) and lauryl trimethylammonium bromide (DTAB) also enhanced the removal efficiency. The requirement of the enzyme for almost 100% removal of 100 mg dm^?3 phenol decreased to one‐fourth by the addition of 30 mg dm^?3 Triton X‐100. Triton X‐100, Triton X‐405, Tween 20 and DTAB could reactivate the enzyme precipitated with the phenol polymer, leading to the restarting of the phenol removal reaction. Copyright © 2003 Society of Chemical Industry     

Effect of polyurethane surface chemistry on its lipid sorption behavior

The relationships among surface, bulk properties and lipid sorption behaviors of segmented polyurethanes (SPUs) with various polyol soft segments were investigated. The polyols used in this study were poly(ethylene oxide) (PEO), poly(tetramethylene oxide) (PTMO), and poly(dimethylsiloxane) (PDMS). The hard segment of these segmented polyurethanes was composed of 4,4'-diphenylmethane diisocyanate and 1,4-butanediol, present at 50 wt%. X-ray photoelectron spectroscopic (XPS) and dynamic contact angle measurements were carried out in order to analyze the surface chemical structure in the air- and water-equilibrated states. XPS revealed that in the air-equilibrated state, lower surface free energy components were enriched at the air-solid interface, whereas in the water-equilibrated state, higher surface free energy components were enriched at the water-solid interface. The change in environment from air to water induced the surface reorganization in order to minimize interfacial free energy. Lipid sorption behaviors of SPUs were investigated by means of infrared spectroscopy. Even after extensive rinsing of the surface, the amount of lipid present on the SPU surface was more than that calculated on the assumption that a monolayer covers the SPU surface. Therefore, the lipid was not only adsorbed on the surface of SPU but absorbed into SPU. The SPU with hydrophilic PEO sorbed larger amount of phospholipid compared with that with hydrophobic polyol such as PTMO and PDMS. Also, the competitive sorption behaviors of phospholipid and cholesterol from their mixed liposome solution were studied. The ratio of sorbed cholesterol to phospholipid increased with an increase in surface hydrophobicity owing to the hydrophobic nature of cholesterol.     

Effects of nondensifying inclusions on the densification and microstructure of zinc oxide matrix composites

The densification and microstructure development of ZnO containing Zn₇Sb₂O₁₂, ZrO₂, and aggregated ZnO were investigated to elucidate the effect of nondensifying inclusions on the sintering of ceramic/ceramic composites. The inclusion retarded the densification, and the degree of retardation was found to depend on the chemical species of inclusion; Zn₇Sb₂O₁₂ had the largest effect, followed by ZrO₂ and then aggregated ZnO last. The experimental results for aggregated ZnO was explained by the theory which predicts the generation of backstresses. The backstresses give a less significant effect on the densification. For Zn₇Sb₂O₁₂ and ZrO₂, the microstructure of the matrix varied with distance from an inclusion particle; much porosity was observed in the region surrounding the inclusion. Circumferential voids, which are responsible for the suppression of densification, form during the initial stage of sintering. Inclusion particles generate an anchoring effect which retards the densification of the matrix immediately surrounding the inclusion particle during the intermediate stage.Supported by the Inamori Foundation.     

An important factor affecting synergism on coprocessing of Taiheiyo coal with Athabasca oil sand bitumen

A series of mixtures of Japanese subbituminous Taiheiyo coal and Athabasca oil sand bitumen (AOB) with various coal concentrations (0–100 wt%) was coprocessed in a 70 ml autoclave at 420°C for 1 h in the presence of H₂ (50 kg/cm² at room temperature) and sulfided Ni---Mo/Al₂O₂ catalyst. The mixture containing 2 wt% coal produced the largest amount of hexane soluble fraction (HS) and the smallest amount of benzene insoluble fraction (BI). Thus, a synergistic liquid production occurred for this mixture with 2 wt% coal by suppressing the retrogressive reactions which proceeded for pure AOB. The HS obtained from mixtures with 2–30 wt% showed higher H/C ratios and lower heteroatom contents than those obtained from pure AOB and the mixtures with more than 30 wt% coal. The amounts of transferable hydrogen contained in the mixtures were estimated using anthracene as a hydrogen acceptor. The mixtures with 2–10 wt% coal contained higher amounts of donor hydrogen than pure AOB. The HS yield from the various mixtures was correlated with the amount of donor hydrogens contained in the mixtures, except for the mixture with 10 wt% coal. Thus, the important factor which results in synergism is suggested to be the amount of donor hydrogens contained in the feed mixtures.     

Direct Spectroscopic Determination of Europium(Ⅱ) Concentration During Europium(Ⅲ) Electro-Reduction in Hydrochloric Acid Medium

UV-Vis spectroscopy was used to directly determine the concentration of Eu(Ⅱ) during electroreduction of Eu(Ⅲ) in hydrochloric acid medium. Electroreduction was carried out in a flow type electrolyzer with glassy carbon cathode at the constant potential of -800 mV vs. Ag/AgCl. The effects of oxygen and concentration of hydrochloric acid on the system were investigated. For 0.01 mol·L-1 hydrochloric acid, calibration curves for Eu(Ⅱ) absorption bands at 248 and 320 nm were constructed. Molar absorption coefficients were estimated to be 2016 and 648 L·mol-1·cm-1, respectively. The absorbance strongly decreased with decrease in pH of the solution, whereas concentration of chloride had only a negligible effect.     

Comparison of coal hydroliquefaction catalysed by ZnCl2-MCln (CuCl,CrCl3 and MoCl5) and ZnCl2 melts

Hydrogenation of four bituminous coals impregnated with 5 wt% of either mixtures of ZnCl₂-MCl_n (CuCl, CrCl₃ and MoCl₅) systems or ZnCl₂ was carried out using a batch autoclave system at 400° for 3 h at 9.8 MPa of initial hydrogen pressure. The ZnCl₂-MoCl₅ system showed the highest yield of the hexane-soluble (HS) fraction compared with the other systems irrespective of the coal used. The difference between the yields of HS fractions using the ZnCl₂-MoCl₅ and other systems was most marked for coals of fairly low volatile matter content, though the conversion was relatively low (47–66%), whilst for coals of high volatile matter content HS yields with the binary melt systems were high (86–91% conversion). Elemental analyses of the HS fractions indicated that the ZnCl₂-MoCl₅ system is most favourable in decreasing the average molecular weight and the heteroatom content of HS, this characteristic trend being confirmed also with five HS fractions separated by Chromatographic techniques. Both elemental analyses and molecular weights of asphaltene (benzene-soluble materials, BS) indicated that the ZnCl₂-MoCl₅ system is also most effective in cracking coal structure.     

Electron-microscopic procedure for acrylic rubber

The electron-microscopic visualization of acrylic rubber dispersed in a heterogeneous structural resin composition consisting of a rubber-modified two-phase plastic comprising essentially a butyl acrylate rubber phase and an acrylonitrile–styrene copolymer phase, respectively, has been accomplished. This procedure consists of the following: The molded resin specimen is treated with hydrazine hydrate solution to produce the acrylic acid hydrazides. Allow the treated specimen to soak in osmium tetroxide solution. The acrylic rubber may be indirectly fixed and stained. Some micrographs of ultrathin sections of two or three resin compositions, cut by an ultramicrotome, are presented.     

Dispersion of SiC in Aqueous Media with Al2O3 and Y2O3 as Sintering Additives

It has been well accepted that polyethylene imine (PEI) is an effective dispersant for silicon carbide (SiC) in aqueous media. However, after the addition of sintering additives (Al₂O₃ and Y₂O₃), this dispersing effect is reduced significantly. In this work, a second dispersant, citric acid, was used to resolve this problem. It was found that citric acid could decrease the slurry viscosity (without sintering additives) and enhance the PEI adsorption on SiC particle surface. The optimal amount of citric acid required to achieve a minimum viscosity for 55 vol% SiC suspensions was equal to ∼0.87 wt% (at pH ∼6.8). With the aid of citric acid, well-stabilized SiC suspensions (containing sintering additives) were realized, which exhibited slight shear thinning rheologies. After tape casting and SPS sintering, dense SiC samples were obtained with a homogeneous fine-crystalline microstructure. Results showed that citric acid was an effective dispersant for improving the dispersion of SiC particles containing sintering additives.     

Effect of pressure on phase transition and morphology of bulk poly(trans-1,4-butadiene)

The effect of pressure on the melting, solid-solid transition, and crystallization of poly(trans-1,4-butadiene) (PTBD) was investigated using the pressure range of 1–3000 kg/cm². D.t.a. measurements showed that, the melting and transition temperatures increase with increasing pressure, whose pressure coefficients are 38°C per 1000 kg/cm² and 22°C per 1000 kg/cm², respectively. These values were in fairly close agreement with those calculated from the Clausius-Clapeyron equation. Morphological studies using electron microscope and small-angle X-ray scattering method revealed that, the samples crystallized with relatively small supercoolings under normal or high pressure, are formed of distinct lamellae 400–800 Å thick. The lamellar thickness was inappreciably dependent on crystallization pressure. The significant effect of pressure on crystallization was recognized in a tendency of the crystallinity to increase, with increasing crystallization pressure. This pressure effect was explained by the mechanism that, the increased pressure might make the packing of molecular chains in liquid, more dense and that the secondary crystallization might be accelerated, to increase the lateral dimensions of lamellae.     

Preparation of soluble TiCl3 catalysts by reduction of TiCl4 with Grignard reagents and their use for copolymerization of ethylene with propylene

Summary Preparations of soluble TiCl₃ catalysts by reduction of TiCl₄ with some types of Grignard reagents were carried out in halogenated hydrocarbon solvents by using appropriate ethers as donor. The soluble TiCl₃·MgX₂·ether complex catalysts and triisobutylaluminum as co-catalyst showed high activities for the copolymerization of ethylene with propylene. It was first found that the soluble TiCl₃·MgX₂·ether complex catalysts enhance the activities for the copolymerizations in the same manner as solid titanium catalysts supported on MgCl₂ which show high activities for homopolymerizations of olefin monomers. The copolymers obtained possessed low crystallinities. Also, the copolymers seem to contain microblock sequences and have outstandingly high tensile strength and elongation at break compared to copolymers by the conventional VOCl₃/Al(Et)_1.5Cl_1.5 catalyst system.