Formation of Bromate Ion Through a Radical Pathway in a Continuous Flow Reactor

The contribution of ozone and hydroxyl radical to the formation of bromate ion was investigated in a continuous flow reactor. Experiments were conducted under a wide range of ozone dose (0.7 ～ 3.8 mgL), pH (6.5 ～ 8.5), and t-butanol concentration (0 ～ 0.5 mM). The formation of bromate ion was found to depend on radical reaction pathway, because the amount of bromate ion formed increased with pH and decreased with t-butanol, a radical scavenger, even when dissolved ozone concentrations were almost the same. In fact, the amount of bromate ion formed was reduced by 90% in the presence of t-butanol. Furthermore, the formation of bromate ion occurred even when dissolved ozone was not significantly detected in the presence of organic matter (TOC of 1 mgCL). The second-order reaction rate constant of hydroxyl radical with bromide ion, k _HO,Br^? of 1.7 × 10⁹ (M^?1s^?1), was obtained on the assumption that the reactions of bromide ion and t-butanol with hydroxyl radical were competitive with each other in the presence of t-butanol and that the formation of bromate ion depended on the reaction of bromide ion with hydroxyl radical. Therefore, it is concluded that the reaction of bromide ion with hydroxyl radical dominated in the overall reaction from bromide ion to bromate ion in the continuous flow reactor.     

Kinetics of Enthalpy Relaxation at the Glass Transition in Ternary Tellurite Glasses

The kinetics of enthalpy relaxation (recovery) at the glass transition in x K₂O·(20− x )MgO·80TeO₂ glasses has been examined from heat capacity measurements using differential scanning calorimetry to clarify the features of the structural relaxation in ternary TeO₂-based glasses. Ternary glasses such as 10K₂O·10MgO·80TeO₂ show high thermal resistance against crystallization compared with binary glasses. The degree of fragility m estimated from the activation energy for viscous flow E _η and the glass transition temperature T _g is m = 55–62, indicating a fragile character in TeO₂-based glasses. Large heat capacity changes of 43.1–48.2 J·mol⁻¹·K⁻¹ are also observed at the glass transition. The activation energy for enthalpy relaxation Δ H is evaluated from the cooling rate dependence of the limiting fictive temperature, and values of Δ H = 897–1268 kJ·mol⁻¹ are obtained. Negative deviation from additivity in Δ H is also observed. Values of the Kovacs–Aklonis–Huchinson–Ramos (KAHR) parameter θ estimated from Δ H and T _g are 0.33–0.42 K⁻¹. It has been proposed that ternary glasses have more homogeneous and constrained glass structure compared with binary glasses.     

Polymorphic behavior of gondoic acid and phase behavior of its binary mixtures with asclepic acid and oleic acid

Molecular properties of polymorphic forms of gondoic acid [cis-C_20:1Δ11ω9 (GOA)] have been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), optical microscopy, and Raman scattering, in comparison to those of six principal unsaturated fatty acids: oleic acid [cis-C_18:1Δ9ω9 (OA)], erucic acid [cis-C_22:1Δ13ω9 (ERA)], petroselinic acid [cis-C_18:1Δ6ω12 (PSA)], asclepic acid [cis-C_18:1Δ11ω7 (APA)], palmitoleic acid [cis-C_16:1Δ9ω7 (POA)], and elaidic acid [trans-C_18:1Δ9ω9 (ELA)]. In addition, phase behavior of binary mixtures of GOA and APA and OA was examined by XRD and DSC. The polymorphic structures of GOA are quite similar to those of APA, ERA, POA, and partly to OA. In particular, DSC and Raman scattering studies have shown that gondoic acid exhibits conformational disordering on heating at the ω-chain, a chain segment between the double bond and CH₃ group, as a transition from all-trans (γ form) to gauche-rich (α form) conformations. A miscible mixing phase was observed in the mixture of GOA and APA, yet eutectic phases were observed in the GOA and OA mixtures. This is a remarkable contrast because the binary mixture systems of varying combinations of cis-unsaturated fatty acids examined so far exhibited either eutectic nature or molecular compound formation. It is expected that specific molecular interactions between GOA and APA that originate from the equivalence of the length of the Δ-chain, the chain segment between the cis-double bond and COOH group, and also from the presence of the γ-α order-disorder transformation would be operating to form the miscible mixing phase.     

Multilayered thermal barrier coating for land-based gas turbines

Multilayered thermal barrier coatings (TBC) with different functions were proposed for the hot section components of land-based gas turbines. This article describes a multilayered TBC with an oxidation resistant layer. A conventional duplex TBC and a triplex TBC, in which an aluminized layer was added to the conventional duplex TBC to increase oxidation resistance, were prepared. It was confirmed by a burner rig test that the triplex TBC with the aluminized layer is resistant to oxidation and shows high durability in a thermal cycle test, compared with the conventional duplex TBC. The spalling in the thermal cycle test of each TBC specimen occurred at the same position, when the thickness of the oxidation layer was 11 to 13 μm. The mechanism of spalling of the coating in the thermal cycle test was discussed in terms of stress in the coating. Stress in the direction of spalling occurred by an uneven interface between the bond and top coat and increased with growth of the oxidation layer. It is thought that the high durability of the triplex TBC in the thermal cycle test is derived from suppressing the growth of the oxidation layer and decreasing the stress due to the addition of the aluminized layer.     

Effect of SiC on Interfacial Reaction and Sintering Mechanism of TiB2

Compacts of TiB₂ with densities approaching 100% are difficult to obtain using pressureless sintering. The addition of SiC was very effective in improving the sinterability of TiB₂. The oxygen content of the raw TiB₂ powder used in this research was 1.5 wt%. X-ray photoelectron spectroscopy showed that the powder surface consisted mainly of TiO₂ and B₂O₃. Using vacuum sintering at 1700°C under 13–0.013 Pa, TiB₂ samples containing 2.5 wt% SiC achieved 96% of their theoretical density, and a density of 99% was achieved by HIPing. TEM observations revealed that SiC reacts to form an amorphous phase. TEM-EELS analysis indicated that the amorphous phase includes Si, O, and Ti, and X-ray diffraction showed the reaction to be TiO₂+ SiC → SiO₂+ TiC. Therefore, the improved sinterability of TiB₂ resulted from the SiO₂ liquid phase that was formed during sintering when the raw TiB₂ powder had 1.5 wt% oxygen.     

Mercury oxidation by hydrochloric acid over TiO2 supported metal oxide catalysts in coal combustion flue gas

Mercury oxidation by hydrochloric acid over the metal oxides supported by anatase type TiO₂ catalysts, 1 wt.% MO_x/TiO₂ where M = V, Cr, Mn, Fe, Ni, Cu, and Mo, was investigated by the Hg⁰ oxidation and the NO reduction measurements both in the presence and absence of NH₃. The catalysts were characterized by BET surface area measurement and Raman spectroscopy. The metal oxides added to the catalyst were observed to disperse well on the TiO₂ surface. For all catalysts studied, the Hg⁰ oxidation by hydrochloric acid was confirmed to proceed. The activity of the catalysts was found to follow the trend MoO₃ ~ V₂O₅ > Cr₂O₃ > Mn₂O₃ > Fe₂O₃ > CuO > NiO. The Hg⁰ oxidation activity of all catalysts was depressed considerably by adding NH₃ to the reactant stream. This suggests that the metal oxide catalysts undergo the inhibition effect by NH₃. The activity trend of the Hg⁰ oxidation in the presence of NH₃ was different from that observed in its absence. A good correlation was found between the NO reduction and the Hg⁰ oxidation activities in the NH₃ present condition. The catalyst having high NO reduction activity such as V₂O₅/TiO₂ showed high Hg⁰ oxidation activity. The result obtained in this study suggests that the oxidation of Hg⁰ proceeds through the reaction mechanism, in which HCl competes for the active catalyst sites against NH₃. NH₃ adsorption may predominate over the adsorption of HCl in the presence of NH₃.     

Impurity Effects on Energy Gap in Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CaCu<Subscript>2</Subscript>O<Subscript>8+<Emphasis Type="Italic">y</Emphasis></Subscript> Investigated by Electronic Raman Scattering

The Raman scattering experiments were carried out in Zn-doped and Zn-free Bi₂Sr₂CaCu₂O_8+y with optimal hole concentration below and above T _c . The energy of pair-breaking peak in the B _1g Raman spectrum, corresponding to the magnitude of superconducting gap 2Δ ₀, is suppressed by 1% Zn-doping. In the normal state, the B _1g Raman spectrum for Zn-doped sample shows no pseudogap behaviour, suggesting that the pseudogap is strongly smeared by Zn-doping.     

Anisotropy of structural response of single crystal austenitic stainless steel to friction stir welding

The structural response of an austenitic stainless steel single crystal to friction stir welding (FSW) was examined. The microstructural changes induced by FSW were found to essentially vary around the rotating tool. This effect was attributed to variable orientation of the shear plane and shear direction inherent to the FSW process, which significantly influenced slip activity of the single crystal.     

Inhibition of DNA polymerase λ by glucosyl compounds from soybean (Glycine max L.) and their associated inflammatory activity

During the screening of selective DNA polymerase (pol) inhibitors, we isolated two glucosyl compounds, a cerebroside (glucosyl ceramide, AS-1-4, compound 1) and a steroidal glycoside (eleutheroside A, compound 2) from soybean (Glycine max L.). Compounds 1 and 2 selectively inhibited the activity of eukaryotic pol λ in vitro, with IC₅₀ values of 12.2 and 9.1 μM, respectively. These compounds did not influence the activities of other eukaryotic pols including those from the A-family (pol γ), B-family (pols α, δ and ε), and Y-family (pols η, ι and κ), and also showed no effect on the activity of pol β which is of the same family (X) as pol λ. The tendency for in vitro pol λ inhibition by these compounds showed a positive correlation with the in vivo suppression of TPA (12-O-tetradecanoylphorbol-13-acetate)-induced inflammation in mouse ear. These results suggest that these glucosyl compounds from soybean may be useful for their anti-inflammatory properties.