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Review article

Factors Influencing the Stability of Low Temperature Tetragonal ZrO2

Goran Štefanić ; Division of Materials Chemistry, Ruđer Bošković Institute, P O. Box 180, 10002 Zagreb, Croatia
Svetozar Musić ; Division of Materials Chemistry, Ruđer Bošković Institute, P O. Box 180, 10002 Zagreb, Croatia

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Various factors that influence the appearance of a tetragonal (t-) ZrO2 polymorph at room temperature have been extensively investigated. Several proposed models emphasize the role of anionic impurities (SO42-, OH-), crystallite size (surface energy), structural similarities between the starting material and t-ZrO2, lattice strains, water vapor, lattice defects (oxygen vacancies), etc. Our investigations, focused on the stability of low temperature t-ZrO2, showed that, regardless of the structural differences in the starting zirconium materials, their thermal decomposition products crystallized into a metastable t-ZrO2. The t-ZrO2 -> m-ZrO2 transforma-tion occurred during the cooling or further calcination in the pres-ence of air at atmospheric pressure. On the other hand, if these processes are performed in vacuum, the metastable phase is pre-served. These observations indicate that a metastable t-ZrO2 appears at room temperature as a result of stabilization caused by introduction of oxygen vacancies, similarly as in the solid Solutions with aliovalent cations. A decrease in the specific surface area of ZrO2 grains or the presence of the substances that enter into strong surface interactions with ZrO2 (SO42-, Cr2O3) prevents the diffusion of oxygen from the atmosphere into the ZrO2 lattice and due to this fact the metastable t-ZrO2 is stabilized. On the other hand, lattice strain and grain size of metastable t-ZrO2 could not be clearly related to its stability.


t-ZrO<sub>2</sub>, m-ZrO<sub>2</sub>, hydrous zirconia, oxygen vacancies, lattice strain, XRD, DSC

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