Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Superconductivity in W-containing diamond-like nanocomposite films

Superconductivity in a tungsten-containing carbon-oxide film was reported. The film with 500 nm thickness was deposited onto polycrystalline silicon oxides using chemical vapor deposition and the co-sputtering of a tungsten metal target. The bonding state of the carbon atoms and the macroscopic and microscopic crystal structure of the film were investigated by Raman spectroscopy, X-ray diffraction and transmission electron microscopy measurements. From the experimental results, we determined that this film essentially had an amorphous structure. The temperature dependence on resistivity was measured in the temperature range of 2–300 K. Resistive superconducting transition was observed at 3.8 K. The dc magnetizations were measured in the temperature range of 1.8–6.5 K. The diamagnetism resulting from a superconductive state was observed below 3.75 K, which is consistent with a resistive superconducting transition. It is thought that the finite sized clusters of the different superconductive transition temperatures cooperatively produce a macroscopic superconducting phenomenon.     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Highly hydrogenated dietary soybean oil modifies the responses to polychlorinated biphenyls in rats

The effects of dietary highly hydrogenated soybean oil (HSO) upon the changes caused by dietary polychlorinated biphenyls (PCBs) were examined in rats. Six groups of rats were fed the following diets for 30 d: a 20% soybean oil-containing diet (control diet), a diet in which a half of soybean oil was substituted with HSO (HSO-A diet), a diet in which cellulose powder was replaced with HSO (HSO-B diet) and these diets supplemented with 100 ppm PCBs (control+PCBs, HSO-A+PCBs and HSO-B+PCBs diets). Hepatic concentration of PCBs and relative liver weight were markedly decreased in rats fed with the HSO-A+PCBs diet compared with those fed with the other diets containing PCBs. Liver lipids and liver cholesterol were considerably decreased with a reciprocal increase in fecal sterol excretion by rats fed the HSO-A+PCBs and the HSO-B+PCBs diets compared with those fed with the control+PCBs diet. The fatty acid composition in hepatic phospholipids showed an independent increase of the saturated fatty acid content induced by dietary HSO and PCBs. Dietary PCBs also caused decreases in the amounts of monounsaturated and n-3 polyunsaturated fatty acids. These results suggest that dietary HSO prevents accumulation of PCBs in the liver and promotes the excretion of lipids stimulated by PCBs, accompanied by a change in fatty acid metabolism.     

Design of a high-temperature and high-pressure liquid flow cell for x-ray absorption fine structure measurements under catalytic reaction conditions

The design and performance of a new high-pressure and high-temperature cell for measurement of x-ray absorption fine structure (XAFS) spectra of solid catalysts working in a flowing liquid are presented. The cell has flat, high-purity sintered cubic boron nitride (c-BN) windows which can tolerate high temperature (900 K) and high pressure (10 MPa). The c-BN is a new material which has the highest tensile strength, second only to diamond, and is also chemically and thermally stable. The use of the cell is demonstrated for measurements of PtPdAl(2)O(3) and Ni(2)PSiO(2) hydrodesulfurization catalysts at reaction conditions. A technique called delta chi (Deltachi), involving determining the difference between XAFS spectra of the sample at reaction conditions and the bare sample, is introduced.     

汽车仪表盘冲击破坏的数值模拟研究

应用LS-DYNA的显式积分算法,对汽车副驾附气囊仪表盘的冲击破坏进行了仿真计算。计算中对附气囊仪表盘中FOAM材料分别采用了等效应力失效准则、最大主应力失效准则、有效应变失效准则和最大主应变失效准则四种不同的失效准则进行失效设置,将在这四种不同失效准则下的计算结果与试验结果进行了对比,分析了FOAM材料应用不同的的失效准则对计算结果产生的影响,确定了合适的失效准则,为以后的副驾附气囊仪表盘冲击破坏计算提供了有益的参考。     

Temperature dependence of cyclic creep behavior of a Cu–SiO2 bicrystal with a [0 1 1] 20° twist boundary

Temperature dependence of cyclic creep behavior has been studied using a Cu bicrystal containing dispersed SiO₂ particles and a [0 1 1] 20° twist boundary. Failure occurred at shorter times with increasing temperature and stress amplitude. The fracture-mode of the bicrystals changed sharply from transgranular to intergranular at a certain critical stress amplitude. The brittle intergranular fracture that occurred below the critical stress amplitude caused discontinuous life shortening. The observed fracture-mode change at the critical stress amplitude is discussed in relation to grain-boundary sliding and grain-boundary cracking.     

Anthropogenic lead inputs to the western Pacific during the 20th century

Unlike in the North Atlantic, no continuous record of anthropogenic lead (Pb) has been available in the western Pacific. We reconstructed historical changes in anthropogenic Pb on the basis of Pb isotope ratios recorded in annually-banded coral retrieved from Ogasawara Island, Japan. Whereas the predominant natural source of Pb to the surface of the western Pacific apparently is Chinese loess, anthropogenic Pb has affected the western Pacific at least since the late 19th century. From the late 19th to the early 20th century, Australian Pb used in Japan was an important source of anthropogenic Pb. During 1920-1940, Pb emitted from parts of the world other than Japan contributed somewhat to the western Pacific, and the amount of Pb imported from Australia declined. Alkyl Pb used in Japan became the main source from 1950 until the mid-1970s, when leaded gasoline began to be regulated in Japan. Since the mid-1980s, aerosols from China have been the predominant source of Pb in the western Pacific. During the 1990s, around 60% of Pb in the surface of the western Pacific was from Chinese aerosols. We also investigated the present spatial distribution and likely sources of Pb in the western Pacific by using coral samples. Enrichment in 208Pb, which is a characteristic of Pb from China, was found in all coral samples except that from Pohnpei, Micronesia, suggesting that at present anthropogenic Pb is transported to the western Pacific mainly from China via westerly winds.     

Allene as an alternative functional group for drug design: effect of C--C multiple bonds conjugated with quinazolines on the inhibition of EGFR tyrosine kinase

A series of allenic quinazolines were synthesized as receptor tyrosine kinase inhibitors by using a simple protocol for palladium-catalyzed allene transformation. Among the compounds synthesized, two allenic 4-anilinoquinazolines selectively suppressed epidermal growth factor receptor (EGFR) tyrosine kinase activity in vitro. According to immunoblot analysis, the allenic quinazolines inhibited the EGF-mediated phosphorylation of EGFR and its downstream kinases in A431 cells. Furthermore, one of these allenic quinazolines decreased the proliferation of A431 cells through the induction of cell-cycle arrest and apoptosis.     

Gas analysis of the CVD process for high yield growth of carbon nanotubes over metal-supported catalysts

Changes in the gas composition during the methane chemical vapor deposition growth of single- and double-walled carbon nanotubes over metal-supported MgO catalysts were investigated in an attempt to increase the nanotube yield. Monitoring the gas composition by gas chromatography as a function of the reaction time provides information on the activity and lifetime of the catalyst. The degree of methane decomposition, i.e., the C-H bond dissociation, was closely related to the nanotube yield, and the Fe-Mo binary catalyst exhibited a high activity. The effects of water vapor on the catalytic nanotube growth were also studied by introducing water vapor in the inlet gas. An appropriate amount of water prolonged the lifetime of the catalyst and increased the nanotube yield by 35%.