435 resultados para Ce-Zr oxides

em Chinese Academy of Sciences Institutional Repositories Grid Portal


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A series of La2O3-ZrO2-CeO2 composite oxides were synthesized by solid-state reaction. The final product keeps fluorite structure when the molar ratio Ce/Zr >= 0.7/0.3, and below this ratio only mixtures of La2Zr2O7 (pyrochlore) and La2O3-CeO2 (fluorite) exist. Averagely speaking, the increase of CeO2 content gives rise to the increase of thermal expansion coefficient and the reduction of thermal conductivity, but La-2(Zr0.7Ce0.3)(2)O-7 has the lowest sintering ability and the lowest thermal conductivity which could be explained by the theory of phonon scattering. Based on the large thermal expansion coefficient of La2Ce3.25O9.5, the low thermal conductivities and low sintering abilities of La2Zr2O7 and La-2(Zr0.7Ce0.3)(2)O-7, double-ceramic-layer thermal barrier coatings were prepared. The thermal cycling tests indicate that such a design can largely improve the thermal cycling lives of the coatings. Since no single material that has been studied so far satisfies all the requirements for high temperature thermal barrier coatings, double-ceramic-layer coating may be an important development direction of thermal barrier coatings.

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Autothermal reforming of methanol for hydrogen production was investigated over ZnO-ZnCr2O4 supported on a series of metal oxides (Al2O3, CeO2, ZrO2 and CeO2-ZrO2)CeO2-ZrO2 mixed oxides with Ce /Zr molar ratio of 4/1 was found to be the optimal support which showed significant effect on the catalytic activity and selectivity. The ZnO-ZnCr2O4/CeO2-ZrO2 and ZnO-ZnCr2O4 catalysts were characterized by XRD, TEM, H-2-TPR and XPS. The results show that CeO2-ZrO2 mixed oxides have significant effect on the catalytic performance and the supported catalyst shows more uniform temperature distribution in the catalyst bed which was mainly due to its reasonable redox properties.

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Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

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Mg-8Gd-0.6Zr-1RE (RE = La or Ce, wt.%) alloys were prepared by casting. The microstructures, age hardening behavior and mechanical properties were investigated. The results show that the addition of 1 wt.% La or Ce to a Mg-8Gd-0.6Zr alloy reduces the dendrite arm spacing and slightly improves the mechanical properties and age hardening response.

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The larger chemical shift of cerium compounds was discoveried. The chemical states of the cerium compounds were identified by the chemical shifts of Auger energy. The changes in Anger energy and parameters are principally due to the changes in extra-atomic relaxation or polarization energy. The increase of the polarizable properties in anions of cerium compounds corresponds to the increase of Auger energy and parameter. The Auger parameter can be measured more accurately. Ce(CF3COO)(x)Cl-3-x was also studied by ESCA. It is shown that the electron density at cerium atom increases with the increase of x, while the electron density at oxygen atom decreases.

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Photoluminescence spectrum of Ce:YAG single crystal was studied employing vacuum ultraviolet (VUV) synchrotron radiation. Intrinsic absorption edge at about 52,000 cm(-1) was observed in the absorption spectrum. From the VUV excitation spectrum, the energy of the highest d-component of 53,191 cm(-1) (188 nm) for the Ce3+ ions in YAG was obtained at 300 K. The disappearance of the third 5d level at 37,735 cm(-1) (265 nm) in absorption and excitation spectra in our samples may be due to the impurity Fe3+ ions absorption. (C) 2006 Elsevier Ltd. All rights reserved.

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在综合文献报导的基础上,我们选择了LnMsbO_6和Ln_2M_2O_7 (M = Zr, Ti)做为研究体系,对其合成、组成、结构以及稀土离子在其中的发光性质进行了较为系统的研究。用氢氧化物共沉淀的方法,在等摩尔阳离子原料配比条件下,我们制备了LnMsbO_6和Ln_2M_2O_7(M = Zr, Ti, Ln = La - Yb, Y除Ce和Pm)。根据对组成的分析结果并与文献对比,我们认为得到的化合物组成与给出的分子式是一致的。由热分析并结合x-ray衍射分析对LnZrsbO_6的形成反应进行了研究,其结果表明化合物的形成过程是一个较慢的固相反应过程。通过x-ray粉沫衍射物相分析并结合掺杂Eu~(3+)的发光光谱,我们确定了在不同条件下合成的LnMsbO_6和Ln_2M_2O_7化合物的结构类型,并计算了所有化合物的晶胞参数。在对上述结构特性及其变化规律进行研究后,我们认为Ln_2M_2O_7结构变化规律与ΔZ/(d~2) (Z为阳离子电荷,d为阳离子与阴离距离)有关,随ΔZ/(d~2)值由小到大,Ln_2M_2O_7(M = Zr, Ti)先是形成具有荧石结构的阳离子无序固溶体,然后逐渐过渡到荧石结构的变型——有序的立方烧绿石结构,最后变型到单斜晶系结构。LnMsbO_6(M = Zr, Ti)低温相结构与Ln_2M_2O_7(M = Zr, Ti)是有联系的,即基本保持了其立方晶系结构。然后锑的加入使这种结构变得很不稳定,因此在高温灼烧下上述立方相将不可逆地变为更稳定的高温结构相。利用磁天平对LnMsbO_6和Ln_2M_2O_7进行了室温条件下的磁学性质测量,其玻尔磁子数的实验值与Van Vleck理论值符合较好。由此也可说以说明化合物的组成与给出的分子式是一致的。用荧光光谱仪对Eu~(3+)在不同基质中做发光光谱,其结果表明Eu~(3+)在烧绿石结构的Ln_2M_2O_7中,Ln~(3+)是处于具有反演中心的D_(3d)格位,这时~5D_0 → ~7F_2的电体极跃迁(~610nm)是被禁阻的,因此Eu~(3+)主要的发光为~5D_0 → ~7F_1磁体极跃迁(~590nm),并劈裂为两条谱线。在其它不具有反演中心的格位中Eu~(3+)的~5D_0 → ~7F_2跃迁则是较强的。在La~(3+)有着多个较低对称性格位的La_2Ti_2O_7:Eu中,无论是Eu~(3+)的激发光谱,还是发射光谱,其~5D_0与~7F_0之间的跃迁谱线都不只一条,这与La~(3+)多对称性格位特性是一致的。在立方荧石结构的LnZrsbO_6:Eu中,用Eu~(3+)电荷迁移带激发的发光光谱与用其它激发带激发的很不相同,其~5D_1能级的跃迁谱线非常强,我们认为这可能是由于电荷迁移激发态,将大部分能量传递给3~5D_1能级的结果。另外,我们比较了在Ln_2Zr_2O_7和LnZrsbO_6中Eu~(3+)的发光强度,发现前者要比后者强许多。在研究Bi~(3+)对Eu~(3+)的敏化作用时,我们发现在Y_2M_2O_7:Bi, Bu中Bi~(3+)对Eu~(3+)有较好的敏化作用,而在YMsbO_6:Bi, Eu中则没有。同时我们注意到对于Eu~(3+)取代六配位La~(3+)格位时,其电荷还移带位置和符合Hoefdraad认为是不变的规律,而是随着基质晶格的不同发生变化的。对Dy~(3+)在LnMsbO_6和Ln_2M_2O_7基质中发光性质研究中,我们看到Dy~(3+)的发光主要为兰色的~4F_(9/2) → ~6H_(15/2)跃迁(~480nm)和黄色的~4F_(9/2) → ~6H_(13/2)跃迁(~580nm)。其黄光与兰光的强度比值(R)随基质晶格的不同可以有很大的变化。一般情况下R值总是要大小1,且不随湿度和Dy~(3+)掺杂浓度变化。同时我们比较了在Ln_2Zr_2O_7和LnZrsbO_6 (Ln = Y, Gd, La)基质体系中Dy~(3+)的发光强度,发现同Eu~(3+)类似前者较后者强许多。在论文中我们给出了在Y_2M_2O_7和YMsbO_6 (M = Zr, Ti)中Sm~(3+)的激发光谱与发射光谱,从中可以看到当Sm~(3+)在Y_2Ti_2O_7中取代占据D_(3d)格位的Y~(3+)时,其~4G_(5/2) → ~6H_(9/2) (~650nm)电体极跃迁是被禁阻的。同时还给出了在YZrsbO_6中H_0~(3+)和Er~(3+)的激发光谱与发射光谱。此外,我们研究了Eu~(3+)和Dy~(3+)在一些基质体系中发光强度随温度的变化规律。发现Y_2Zr_2O_7:Eu的临界猝来温度要比La_2Zr_2O_7:Eu的高,Ln_2Zr_2O_7:Dy (Ln = La, Y)的温度猝来曲线则大致相同,且随温度和猝来要比Ln_2Zr_2O_7:Eu缓慢,对于上述现象我们利用位形坐标给出了一定的解释。然而所有的样品发光强度从室温开始,随温度的升高都是单调下降的。

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通过气体保护制备了Mg-RE-Zn-Zr[RE=Ce-40La(wt%)的富铈稀土]合金,并对合金进行了热处理,测试了不同状态下合金的硬度、抗拉强度及伸长率等力学性能,采用光学显微镜、X射线衍射仪及扫描电镜对合金显微组织、拉伸断口进行了分析。结果发现,采用T6热处理工艺后,合金的晶粒尺寸明显细化,硬度、抗拉强度、屈服强度和伸长率显著提高,分别提高了11%,24%,7.3%和102%

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Microstructure and some dynamic performances of Ti0.17Zr0.08V0.34RE0.01Cr0.1Ni0.3 (RE=Ce, Dy) hydrogen storage electrode alloys have been investigated using XRD, FESEM-EDS, ICP-MS and EIS measurements. The alloy is composed of V-based solid solution phase with a dendritic shape and a continuous C14 Laves phase with a network shape surrounding the dendrite. Pressure-composition isotherm curves indicate that the alloy with Dy addition has a lower equilibrium hydrogen pressure and a wider plateau region. The alloy electrode with Dy addition has higher discharge capacity, while the alloy electrode with Ce addition has better activation and higher cycle stability. The alloy electrode with Ce addition has better electrochemical activity with higher exchange current density (127.5 mA g(-1)), lower charge transfer resistance (1.37 Omega) and lower apparent activation energy (30.5 kJ mol(-1)). The capacity degradation behavior for the alloy electrode is attributed to two main factors: one is the dissolutions of V and Zr element to KOH solution, and another is the larger charge transfer resistance which increases with increasing cycle number.

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Ce and MgO were added simultaneously to La-Sr-Ni-O catalyst and a substantial enhancement of activity for NO decomposition was observed, which may be attributed to the formation of a new highly active site caused by the addition of Ce and MgO.

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A new compound Ce(6-x)Ln(x)MoO(15-delta) has been synthesized by wet-chemistry method. Their crystal structure and oxide ionic conductivity were characterized by powder X-ray diffraction, Raman, IR spectrum and A.C. impedance technique. The XRD results showed that Ce6MO15-delta, Ce(5)LnMoO(15-delta) have cubic symmetry with Fm3m space group. The refined lattice parameters showed that their lattice constants decrease with the decrease of the ionic radius of Ln(3+). The electrochemical measurements showed that the ionic conductivity of resulting oxides Ce(6-x)Ln(x)MoO(15-delta) have an enhance, which may be a kind of promising material for SOFCs.

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By using metal nitrates and oxides as the starting materials, Y2Al5O12 (YAG) and YAG:Re3+ (Re = Ce, Sm, Th) powder phosphors were prepared by solid-state (SS), coprecipitation (CP) and citrate gel (CG) methods. The resulting YAG and YAG-based phosphors were characterized by XRD, FT-IR, SEM and photoluminescent excitation and emission spectra. The purified crystalline phases of YAG were obtained at 800 degreesC (CG) and 900 degreesC (CP, SS). At an identical annealing temperature and doping concentration, the doped rare-earth ions showed the stronger emission intensity in the CP- and SS-derived phosphors than the CG-derived YAG phosphors. The poor emission intensity for the CG-derived phosphors is mainly caused by the contamination of carbon impurities from citric acid in the starting materials.

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Phorsphors of BaY2F8 : Ce3+, BaY2F8: EU2+ and BaY2F8 : Ce, Eu were prepared by higher temperature solid reaction and their excitation, emission and diffuse reflection spectra were made. We firstly found that the competition of energy transfer from Ce3+ to Eu2+ and electron transfer from Ce3+ to EU3+ existed in CeF3 and EuF3-co-doped BaY2F8 systems. The f-f transition emission of EU2+ was increased with increasing x in systems BaY2F8 : 0. 03Ce, xEU. Ce4+ ions coexist,with Ce3+ ions and substitute Y3+ for Ce4+ in the systems BaY2F8 : Eu, Cc.