Fluorite-pyrochlore transformation in Eu 2Zr 2O 7 - Direct calorimetric measurement of phase transition, formation and surface enthalpies

M. P. Saradhi, S. V. Ushakov, A. Navrotsky

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35 Scopus citations


The energetics of the order-disorder phase transformation in the binary oxide system, Eu 2O 3-ZrO 2, is studied by powder X-ray diffraction and high temperature drop solution calorimetry. The nanocrystalline defect fluorite phase of Eu 2Zr 2O 7 is synthesized on crystallization of an amorphous precursor from aqueous precipitation. The defect fluorite transforms to an ordered pyrochlore above 1200 °C. Aerodynamic levitation combined with laser heating is used to prepare coarse defect fluorite, which is otherwise impossible by conventional synthesis techniques. Formation enthalpies from oxides are -62.4 ± 2.6 and -24.6 ± 3.7 kJ mol -1 for the pyrochlore and defect fluorite phase, respectively. The transformation enthalpy from pyrochlore to defect flourite in the coarse sample is 37.8 ± 3.1 kJ mol -1 at 25 °C. The enthalpy of water vapor adsorption on the surface of the nanocrystalline defect fluorite Eu 2Zr 2O 7 is -75 ± 2.5 kJ mol -1 H 2O for coverage of 9.5 ± 0.8 H 2O/nm 2. The calculated surface enthalpies for the anhydrous and hydrous surfaces of defect fluorite Eu 2Zr 2O 7 are 1.47 ± 0.13 and 1.01 ± 0.15 J m -2, respectively.

Original languageEnglish (US)
Pages (from-to)3328-3334
Number of pages7
JournalRSC Advances
Issue number8
StatePublished - Apr 21 2012
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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