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991.
Enn Lust Gunnar Nurk Silvar Kallip Indrek Kivi Priit Möller 《Journal of Solid State Electrochemistry》2005,9(10):674-683
The analysis of the medium temperature half-cell Ce0.8Gd0.2O1.9|70 wt% La0.6Sr0.4CoO3- (LSCO) + 30 wt % Ce0.8Gd0.2O1.9 (CGO) has been made by electrochemical impedance, cyclic voltammetry and chronoamperometry. The shape of complex impedance plots depends on temperature and cathodic polarisation of the electrode. Nyquist (Z, Z-) plots were fitted by equivalent circuit taking into account the electrolyte properties (at very high frequencies), charge transfer process at grain boundaries (at high frequencies), and medium and low frequency O2 reduction process at the cathode surface and inside the porous cathode material. Two different time constants have been obtained for the cathode process, i.e. for electroreduction of oxygen. It was found that the addition of CGO into the cathode material (LSCO) only somewhat decreases the surface catalytic activity but the noticeably higher low-frequency resistance (i.e. mainly diffusion-like mass transfer resistance RD) values at lower temperatures have been calculated. It was found that the mainly bulk diffusion-limited process at T773 K deviates toward the kinetically mixed process (diffusion + charge transfer) with increasing temperature. 相似文献
992.
993.
A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS 总被引:1,自引:0,他引:1
XiaoXuanLIU XingHongZHANG GuangGuoWU JianWenYANG ZhaoHuaZENG YongLieCHEN 《中国化学快报》2003,14(10):1085-1088
The photoinduced bulk polymerization of a reactive-hindered amine fight stabilizers(r-HALS), 4-acryloyl-2, 2, 6, 6-tetramethylpiperidinyl (ATMP), was performed at 80℃ by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen.It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d =1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism. 相似文献
994.
PTC特性的复合导电体系中炭粒子分布的逾渗模型与电阻率的计算 总被引:17,自引:0,他引:17
综述了炭黑填充型导电高分子复合体系的几种导电理论;讨论了导电载流子分布的各种假说及模型;比较了不同模型的理论预测与实验结果的差异性。 相似文献
995.
Jian-bin Zhang De-zhu Ma Hua Zhong Xiao-lie Luo Department of Polymer Science Engineering University of Science Technology of China Hefei China 《高分子科学》2000,(6):569-572
The surface morphology of free-surface PCL ringed spherulites was investigated by using atomic forcemicroscopy. The spherulites were obtained by crystallization of PCL/PVC blends of different compositions. It was found thatthe ringed spherulite exhibited regularly fluctuating rings on its surface. Compared with the bright-dark ring pattern of thespherulite under a polarizing microscope, it was proved that the optical characteristics of the ringed spherulite underpolarizing microscope coincided with its surface characteristics. The bright rings in polarizing micrographs of the spherulite coincided with the convex rings on its surface, while the dark rings coincided with the concave rings. 相似文献
996.
本文通过对锌(Ⅱ)—硫氰酸盐—孔雀绿体系溶剂浮选过程的考察,提出了待测Zn~(2+)离子从水相被输送到有机相,可以用吸附机理和粘附机理来解释;同时还对影响锌溶剂浮选的主要因素:溶液的pH,气泡的大小和气体流速等进行了讨论。 相似文献
997.
Gunter Zwilling 《Monatshefte für Chemie / Chemical Monthly》1981,112(2):157-165
The anodic overvoltage on carbon and platinum electrodes in the electrochemical production of high purity gadolinium from molten 75 LiF-25 mol% GdF3 solutions is discussed. At the cell temperature of 840°C calciumimpregnated anodes led to the reduction of inert electrode films and to a current yield of nearly 100%.The deposited gadolinium contained 75, 22, 54 and less than 100 ppm of the interstitial elements H, N, O and C respectively; the concentrations of the highest other analysed impurities were: Si (89), Fe (15), Y (5), Zr (3), Nd (3), Tb (71), Ta (49), W (23) and Re (<3 ppm).Partly performed at the Ames Laboratory—U.S. Department of Energy. 相似文献
998.
999.
Treatment of (thd)H (thd=2,2,6,6-tetramethyl-3,5-heptandionate) with excess Os3(CO)12 in an autoclave at 180°C gives the formation of a brown metal chain complex [Os2(CO)5(thd)2]2 (1) and a yellow CO2 cluster complex [Os4(-H)(-CO2)(thd)(CO)13] (2) in low yields. Complex 2 was fully identified by a combination of spectroscopic methods and X-ray diffraction study, showing a unique CO2 ligand bridging a triosmium metal fragment, Os3(-H)(CO)10 and a monometallic osmium fragment, Os(CO)3(thd). Upon treatment of 1 with Me3NO at an elevated temperature, oxidation of the CO ligand occurred at the position trans to the unique CO2 ligand on the Os(CO)3(thd) fragment, giving the formation of a second CO2 cluster [Os4(-H)(-CO2)(thd)(CO)12(NCMe)] (3), which is stabilized by a weakly coordinated acetonitrile molecule. 相似文献
1000.
A novel type of heterogenized CuCl2 catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl– while keeping the catalytic activity of the homogeneous CuCl2 catalyst, we adopted, as supports (or ligands) of CuCl2, four polymers, bearing a 2,2-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2-bipyridine-5,5-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N-bisphenylene-2,2-bipyridine-4,4-dicarboxylic amide) (Bpya), and poly(4-methyl-4-vinyl-2,2-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl2 and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl2 and Ppy-CuCl2 catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl2 catalyst. This high activity appears to be associated with the presence of the -conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl2 catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl2 leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system. 相似文献