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Concept
Zirconium dioxide
Summary
Zirconium dioxide (ZrO2) (sometimes known as zirconia, not to be confused with zircon) is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabilized cubic structured zirconia, cubic zirconia, is synthesized in various colours for use as a gemstone and a diamond simulant.
Zirconia is produced by calcining zirconium compounds, exploiting its high thermostability.
Three phases are known: monoclinic below 1170 °C, tetragonal between 1170 °C and 2370 °C, and cubic above 2370 °C. The trend is for higher symmetry at higher temperatures, as is usually the case. A small percentage of the oxides of calcium or yttrium stabilize in the cubic phase. The very rare mineral tazheranite, , is cubic. Unlike , which features six-coordinated titanium in all phases, monoclinic zirconia consists of seven-coordinated zirconium centres. This difference is attributed to the larger size of the zirconium atom relative to the titanium atom.
Zirconia is chemically unreactive. It is slowly attacked by concentrated hydrofluoric acid and sulfuric acid. When heated with carbon, it converts to zirconium carbide. When heated with carbon in the presence of chlorine, it converts to zirconium(IV) chloride. This conversion is the basis for the purification of zirconium metal and is analogous to the Kroll process.
Zirconium dioxide is one of the most studied ceramic materials. adopts a monoclinic crystal structure at room temperature and transitions to tetragonal and cubic at higher temperatures. The change of volume caused by the structure transitions from tetragonal to monoclinic to cubic induces large stresses, causing it to crack upon cooling from high temperatures. When the zirconia is blended with some other oxides, the tetragonal and/or cubic phases are stabilized. Effective dopants include magnesium oxide (MgO), yttrium oxide (, yttria), calcium oxide (), and cerium(III) oxide ().
Zirconia is often more useful in its phase 'stabilized' state.
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