1500°时ZrO2-CeO2-Dy2O3体系的相关系研究С

O. Korniienko
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引用次数: 1

摘要

含有铈、镝和氧化锆的体系是节能技术解决方案和固体氧化物燃料电池(SOFC)发展的前景。基于zro2的陶瓷被用作SOFC的高温电解质。基于CeО 2的固溶体是最有前途的电解质,在中等温度下工作,因为它们的离子电导率和对氧分压变化的高灵敏度远高于y2o3 (YSZ)稳定的ZrO 2。本文首先利用x射线衍射研究了三元体系ZrО 2 -CeО 2 -Dy 2o3在空气中温度1500°С (150 h)时的相平衡和固溶体的物理化学性质。以氧化铈硝酸Ce(no3) 3∙6h2o和氧化锆硝酸ZrO(no3) 2 ×2Н 2 О为原料,品位为«ch»(98%以上,氧化镝为默克公司生产的99.99%)和分析级硝酸。样品以1-5 mol %的浓度步骤从硝酸盐溶液中制备,随后通过在1200°С下退火2小时将硝酸盐蒸发和分解成氧化物。粉末在10-30 mpa的压力下压成颗粒(直径5 mm,高度4 mm)。样品的XRD分析采用粉末法,在DRON-3仪器上进行,环境温度下CuКa辐射。扫描步长在2θ = 15-90°范围内为0.05-0.1°。采用最小二乘法计算晶格参数,计算误差不小于0.0001 nm。三元体系中的任何新相都在1500°С时显露出来。边界二元体系的结构决定了ZrО 2 -CeО 2 -Dy 2o3体系的相平衡。确定了基于四方(Т)改性ZrО 2、立方(С)改性Dy 2o3和萤石型结构立方(F)改性СеО 2 (ZrО 2)的固溶体。
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PHASE RELATION STUDIES IN THE ZrO2-CeO2-Dy2O3 SYSTEM AT 1500 °С
The systems containing ceria, dysprosium and zirconia are perspective for the development of energy saving technological solutions and solid oxide fuel cells (SOFC). Ceramics based on ZrO 2 is used as a high temperature electrolyte for SOFC. The solid solutions based on CeО 2 are the most perspective electrolytes, operating at moderate temperatures, because of their ionic conductivity and high sensitivity to changes of oxygen partial pressure is much higher than ones of ZrO 2 stabilized with Y 2 O 3 (YSZ). In the present work, first the phase equilibria and physicochemical properties for solid solutions in the ternary ZrО 2 -CeО 2 -Dy 2 O 3 system at temperature 1500 °С (150 h) in air were studied by X-ray diffraction in the overall concentration range of compositions. Cerium oxide nitrate Ce(NO 3 ) 3 ∙6H 2 O and zirconium oxide nitrate ZrO(NO 3 ) 2 ×2Н 2 О of grade «ch» (above 98%, dysprosium oxide (99.99 % produced by Merck Corp.) and analytical-grade nitric acid were used as the starting materials. Samples were prepared with a concentration step of 1-5 mol % from nitrate solutions with subsequent evaporation and decomposіtion of nitrates into oxides through annealing at 1200 °С for 2 h. Powders were pressed in pellets (diameter 5 mm, height 4 mm) under a pressure of 10-30 MPа. XRD analysis of samples was performed by powder procedure on a DRON-3 apparatus at ambient temperature under CuКa radiation. Scanning step was 0.05-0.1 degrees in the range 2θ = 15–90°. Lattice parameters were calculated by the least square method using the LATTIC computer code with an error of not lower than 0.0001 nm for the cubic phase. Any new phase in the ternary system was revealed at 1500 °С. The structure of the boundary binary systems defines the phase equilibria in the ZrО 2 -CeО 2 -Dy 2 O 3 system. Solid solutions based on tetragonal (Т) modification ZrО 2 , cubic (С) modification Dy 2 O 3 and cubic with fluorite-type structure (F) modifications СеО 2 (ZrО 2 ) were determined.
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