Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Anisotropic structure of alkali metaphosphate glasses

Orientation anisotropy, which is well known in organic polymers with appropriate network structures, is less common in oxide glasses. We present the intermediate-range order in anisotropic alkali metaphosphate glass which consists of oriented PO₄ tetrahedral chains and intervening alkali cations along the elongation direction. The X-ray total structure factor S(Q) indicates that the inter-chain spacing depends on the size of alkali cations and varies from 5.03 to 6.28 Å. The mixed alkali effect is primarily related to an increase of the separation. The total correlation function T(r) provides the first definite evidence that the anisotropic structure is composed of phosphorus-bridging oxygen bonds (P–O_B) lying along the elongation direction and phosphorus-non-bridging oxygen bonds (P–O_T) oriented perpendicular to the elongation direction. The present result unveils fundamental aspects of the anisotropic structure of an oxide glass and provides essential information for the development of oxide glasses to control structural anisotropy.     

Hydrothermal flames in supercritical water oxidation: investigation in a pilot scale continuous reactor

Hydrothermal flames at 25 MPa supercritical water environment were investigated using a 4800 ml reaction tower, in which the sapphire windows were fitted for optical access. Down flowing hydrothermal flames were observed for oxidation of 2-propanol when the reactor was fed with inlet organic concentration higher than 2 vol% and air ratio higher than 1.8. Flame temperature, as high as 1100 °C, was measured by means of a thermocouple and the temperature was found to be strongly influenced by air ratio. Effective and stable oxidation of organics with TOC removal rate of 99.9% was achieved. Dioxins were also decomposed with a ratio higher than 99.9%, within 1 min reaction time in this reactor configuration.     

Synthesis and surface properties of novel fluoroalkyl end-capped amphiphilic fullerene cooligomers

New fluoroalkyl end-capped fullerene cooligomers were prepared by the reactions of fluoroalkanoyl peroxides with fullerene and comonomers such as acryloylmorpholine, N,N-dimethylacrylamide and acrylic acid. These fluorinated fullerene cooligomers were easily soluble in water and common organic solvents, and were able to reduce the surface tensions of both water and benzene, quite effectively. Additionally, these fullerene cooligomers were found to form a stable monomolecular film at the air-water interface, and the modified polystyrene surface treated with these cooligomers was shown to have a strong hydrophilicity with good oil repellency.     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Porous Glass-Ceramics with a Skeleton of the Fast-Lithium-Conducting Crystal Li1+xTi2−xAlx(PO4)3

Porous glass-ceramics with a skeleton of the fast-lithium-conducting crystal Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ (where x = 0.3–0.5) were prepared by crystallization of glasses in the Li₂O─CaO─TiO₂─Al₂O₃–P₂O₅ system and subsequent acid leaching of the resulting dense glass-ceramics composed of the interlocking of Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ and β-Ca₃(PO₄)₂ phases. The median pore diameter and surface area of the resulting porous Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ glass-ceramics were approximately 0.2 μm and 50 m²/g, respectively. The electrical conductivity of the porous glass-ceramics after heating in LiNO₃ aqueous solution was 8 × 10⁻⁵ S/cm at 300 K or 2 × 10⁻² S/cm at 600 K.     

混合制冷工质核态沸腾的传热研究

Heat transfer coefficients in nucleate pool boiling were measured on a horizontal copper surface for refrigerants, HFC-134a, HFC-32, and HFC-125, their binary and ternary mixtures under saturated conditions at 0.9MPa. Compared to pure components, both binary and ternary mixtures showed lower heat transfer coefficients.This deterioration was more pronounced as heat flux was increased. Experimental data were compared with some empirical and semi-empirical correlations available in literature. For binary mixture, the accuracy of the correlations varied considerably with mixtures and the heat flux. Experimental data for HFC-32/134a/125 were also compared with available correlated equation obtained by Thome. For ternary mixture, the boiling range of binary mixture composed by the pure fluids with the lowest and the medium boiling points, and their concentration difference had important effects on boiling heat transfer coefficients.     

Built-in Nanostructures in Transparent Oxides for Novel Photonic and Electronic Functions Materials

We review distinct photonic/electronic properties originating from built-in nanostructures in transparent oxide-based materials, emphasizing potential of nanostructures hidden in crystal structure. Materials focused on are oxychalcogenides LaCuOCh (Ch = chalcogen ion) and homologous oxides InGaO₃(ZnO)_m(m = integer) having naturally formed multi-quantum well structures and 12CaO· 7Al₂O₃ (C12A7) with a unique nanoporous structure. Novel functions and devices arising from the built-in nanostructure are: (1) modulation doping of positive holes and room-temperature stable exciton in LaCuOCh, (2) high-performance transparent field-effect transistor fabricated in InGaO₃(ZnO)₅ epitaxial thin films, and (3) conversion of insulator to persistent electronic conductor by carrier doping in 12CaO·7Al₂O₃ (C12A7).     

Impact fracture behavior of ethylene ionomer and structural change after stretching

We carried out tensile impact test and very low speed tensile test on ethylene‐based Ionomers (E/15wt %MAA) to clarify the relation between impact toughness and high‐ordered structure. We also studied the changes in high‐ordered structure under deformation by observing Differential Scanning Calorimetory (DSC) and Small‐Angle X‐ray Scattering (SAXS) of fractured surface. Na Ionomers showed ductile fracture in both high speed tensile impact (3 m/s) and very low speed tensile (2 mm/min). The disappearance of secondary melting point (Ti) in Na Ionomers was due to the destruction of ordered structure surrounding the ionic aggregate. Similar behavior was observed in 60% (or less) neutralized Zn Ionomers. However, 80% neutralized Zn Ionomer showed brittle failure in high‐speed tensile impact, and Ti did not disappear. SAXS studies of Na and Zn Ionomers after fracture, show no change both after molding (no aging) and after aging. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1712–1720, 2001