Effect of Dopants on Zirconia Stabilization—An X-Ray Absorption
Effect of Dopants on Zirconia Stabilization-An X-ray Absorption Study: II, Tetravalent Dopants Ping Li* and I-Wei Chen* Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109-2136 James E. Penner-Hahn Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109- 1055 X-ray absorption spectra at Zr-K, Ce-L,,,, and Ge-K edges approach the cubic The phase diagrams of these sys- in Zr0,-CeO, and Zr0,-GeO, solid solutions have been tems are also dependent on dopant sizes. The tetragonal solid measured at 10 K. Both Ce and Ge substitute for Zr in the solution region in ZrO,-Ce0,5 is much wider than those in cation network, but CeO, and GeO, polyhedra are main- Zr0,-MO and Zr0,-M,O, systems." Similar observations hold tained around the dopants. The yversized CeO, is com- in the Zr0,-UO, and Zr0,-Tho, systems.12 " With undersized pressed t2 a Ce-0 distance of 2.30 A, which is smaller than dopants, a series of AB0,-type ordered compounds is found.4 the 2.35 A seen in fluorite-type CeO,. Meanwhile, the distor- These include ZrTiO,, an a-Pb0,-like structure with a fairly tion of the Zr-cation network is increased and the tetrago- narrow composition range; ZrGeO,, a scheelite structure with a nalityoisreduced. The undersized Ge has a Ge-0 distance of broader composition range; and Zr3Ge0,, also a scheelite-like 1.80 4, which is much shorter than the Zr-0, distance of structure with a similarly broad composition range.9 In addition, 2.10 A.
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