Oxidative coupling of methane over some titanates based perovskite oxides

A series of perovskites of the formula Ca_1–xSr_xTi_1–yM_yO_3– (M = Fe or Co,x = 0–1,y = 0–0.6 for Fe,y = 0–0.5 for Co) were prepared and tested as the catalyst for the oxidative coupling of methane. The catalysts were stable under the reaction conditions. The catalysts of high p-type and oxide ionic conductivity afforded the high selectivity. Some catalysts containing Co on B-sites are thermally unstable and decomposed to metal oxide components at high temperature, giving rise to synthesis gas production.     

Selective catalytic reduction of NOx with propylene in the presence of oxygen over Co–Pt promoted H-MFI and HY

Kinetic and in situ spectroscopic studies of Co–Pt/MFI and Co–Pt/HY catalysts for the selective reduction of NO_x with propylene in the presence of oxygen were carried out. The results of catalytic tests of Co–Pt/MFI showed that the addition of Pt to Co based catalyst improved the activity, but a small increase in selectivity to N₂O (15–20%) was observed. In the case of Co–Pt/HY catalyst, the addition of Pt improved the activity more significantly and however, a larger increase in selectivity to N₂O (6–72%) was obtained. It was also found from the results of FT-IR studies of Co–Pt/MFI that the reduction of NO to N₂ was as follows: firstly the oxidation of NO to NO₂ occurred over metallic Pt and NO₂ forms Co–NO₂, Co–ONO, and/or Co–ONO₂; secondly, the partial oxidation of C₃H₆ was happened over Brønsted acid sites and the reaction of NO₂ formed on Co sites with partial oxidized C₃H₆ produced organo-nitro species. These species were dehydrated and isomerized to form isocyanate. Finally, [NCO] type intermediates react with NO from gas phase to selectively yield N₂.     

B含量对Fe90-xPt10Bx液态急冷合金组织结构和磁性能的影响

本工作研究了低Pt含量的Fe_90-xPt₁₀B_x (x=15~40,原子分数,%)系液态急冷合金热处理前后的组织结构和磁性能。结果表明,x由15增加至25~30可提高合金的非晶形成能力,急冷合金由非晶+fcc-FePt复相组织转变为单一非晶态结构;当x进一步增加至35和40时,合金分别由fcc-FePt+Fe₂B+FeB和L1₀-FePt+FeB纳米复相组织构成。经适当热处理后,x=15~20的合金具有fcc-FePt+Fe₂B复相组织而呈软磁性;x=25~40的合金形成了由有序面心四方结构的永磁L1₀-FePt相和软磁Fe₂B/FeB组成的纳米复相组织,显示出永磁特性,其中x=30的合金经823 K热处理900 s后具有最佳的永磁性能,矫顽力、剩磁和最大磁能积分别为173.2 kA/m,1.20 T和88.3 kJ/m^₃,其优异的永磁性能源于分布均匀、平均晶粒尺寸约为15 nm的永磁L1₀-FePt相和软磁Fe₂B相间的交换耦合作用。     

Mechanochemical block copolymerization of poly(vinyl chloride) with methyl methacrylate by ultrasonic irradiation

Summary Mechanical degradation and mechanochemical block copolymerization in systems of poly(vinyl chloride)-methyl methacrylate-solvents have been studied by ultrasonic irradiation at 60°C. The effect of the concentrations of poly(vinyl chloride) on mechanical degradation was investigated. In addition, the effects of poly(vinyl chloride) and methyl methacrylate concentrations on mechanochemical block copolymerization were investigated. The rate equation for mechanochemical block copolymerization has been deduced, and the experimental results were in fairly good agreement with the equation. The changes in the composition of the block copolymer and homopolymers in the reaction products were followed by turbidimetric titration.     

Microstructures and luminescent properties of Ce-doped transparent mica glass-ceramics

Transparent mica glass-ceramics were prepared by heating parent glasses that had been doped with 0.5–15 mol% CeO₂. During the melting and heat treatment, Ce⁴⁺ ions in the specimens were reduced to Ce³⁺ ions, and one or both of these ion species were then replaced with Li⁺ ions in the interlayers of the separated mica crystals. However, scanning transmission electron microscope (STEM) and Z-contrast imaging revealed that the mica crystals did not contain the same amount of Ce. On excitation at 254 nm, the parent glasses and glass-ceramics emitted blue light, which originated from the 5d to 4f transition of the Ce³⁺ ions. The emission of the glass-ceramic containing a smaller amount of Ce was attributed to the Ce³⁺ ions in both the glass phase and the mica crystals, whereas that of the glass-ceramics containing a larger amount of Ce was caused mainly by Ce³⁺ ions in the mica crystals. The dependence of the emission band of the parent glasses on the amount of Ce was a unique feature of the Ce-doped transparent mica glass-ceramics and was not observed in previous studies of Eu-doped parent glasses and mica glass-ceramics.     

Surface modification of titanium by hydrothermal treatment in Mg-containing solution and early osteoblast responses

Surface modification on titanium was carried out in order to improve its bioactivity. Pure titanium was hydrothermally treated in distilled water and 0.1 M MgCl₂ solutions at 200°C for 24 h. Surface morphology, roughness, wettability and chemical composition were characterized before and after treatment. Bovine serum albumin was used as model to study protein adsorption. MC3T3-E1 cells were cultured and initial cell attachment, morphology, proliferation were evaluated. After hydrothermal treatment, nano-sized precipitations were observed and samples showed superhydrophilicity. Magnesium (Mg) was immobilized into titanium surface by hydrothermal treatment. Protein adsorption was significantly increased on Mg-containing samples. Cell attachment was improved and cell spreading was enhanced on Mg-containing samples compared with untreated or those treated in distilled water. Increased early cellular attachment on the MgTi surface resulted in subsequent increase of number of proliferated cells. Hydrothermal treatment in MgCl₂ solution was expected to be an effective method to fabricate titanium implant with good bioactivity.     

Fabrication of Mg alloy tubes for biodegradable stent application

Though Mg alloys are promising candidates for biodegradable stents, it is very difficult to fabricate stent tubes with high dimensional accuracy using Mg alloys because of their low deformability. This study aimed to develop thin-walled, high-quality Mg alloy tubes with good performance in stent applications. Cold drawing with a fixed mandrel was carried out for extruded Mg-0.8%Ca and AZ61 alloy tubes using optimized drawing parameters and lubrication, and stent tubes with 1.5–1.8 mm outer diameter and 150 μm thickness were fabricated. A dimensional evaluation showed that the tube dimensional errors were within 0.02–2.5%. Also, an immersion test of pure Mg with different crystal orientations showed that the crystal orientation affected the corrosion properties, results that are the same with other Mg alloys. The crystal orientation of the stent tube could be controlled by changing the deformation amount and direction in the drawing, showing that it is possible to further improve the biodegradability of stents by approaching their fabrication from a processing aspect.     

Induction of DNA DSB and its rejoining in clamped and non-clamped tumours after exposure to carbon ion beams in comparison to X rays

We studied double-strand breaks (DSB) induction and rejoining in clamped and non-clamped transplanted tumours in mice leg after exposure to 80 keV μm(-1) carbon ions and X rays. The yields of DSB in the tumours were analysed by a static-field gel electrophoresis. The OER of DSB after X rays was 1.68±0.31, and this value was not changed after 1 h rejoining time (1.40±0.26). These damages in oxygenated conditions were rejoined 60-70% within 1 h in situ. No difference was found between the exposure to X rays and carbon ions for the induction and rejoining of DSB. Thus, the values of OER and rejoined fraction after exposure to carbon ions were similar to those after X rays, and the calculated relative biological effectivenesses of carbon ion were around 1 under both oxygen conditions. The yields of DSB in vivo depend on exposure doses, oxygen conditions and rejoining time, but not on the types of radiation quality.     

Characterization of macroporous carbonate-substituted hydroxyapatite bodies prepared in different phosphate solutions

Bone mineral of human is different in composition from the stoichiometric hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) in that it contains additional ions, of which CO₃²⁻ is the most abundant species. Carbonate-substituted hydroxyapatite (CHA) bodies were prepared by the hydrothermal treatment of highly porous calcium carbonate (CaCO₃) body at 120 °C in 1 M M₂HPO₄ and M₃PO₄ solutions (M = NH₄ or K). It was found that CaCO₃ body was almost transformed into CHA body after hydrothermal treatment for 24 h irrespective of type of phosphate solution. However, a small amount of CaCO₃ still remained after the treatment in K₃PO₄ for 48 h. Crystal shape of CHA bodies prepared in those solutions except for K₂HPO₄ was flake-like, which was different from that (stick-like) of original CaCO₃ body used for the preparation of CHA body. CHA prepared in the K₂HPO₄ showed globule-like crystal. Average pore size and hole size of the CHA bodies were 150, 70 μm and their porosities were about 89% irrespective of the solution. Carbonate content was slightly higher in the CHA bodies obtained from potassium phosphate solutions than in those obtained from ammonium phosphate solutions. Mostly B-type CHA was obtained after the hydrothermal treatment in the potassium phosphate solutions. On the other hand, mixed A- and B-type CHA (ca. 1–2 in molar ratio) was obtained in the ammonium phosphate solutions. The content of CO₃²⁻ in the CHA body depended on the type of phosphate solution and was slightly larger in the potassium phosphate solutions.