Energetics of cubic and monoclinic yttrium oxide polymorphs: Phase transitions, surface enthalpies, and stability at the nanoscale

Peng Zhang, Alexandra Navrotsky, Bing Guo, Ian Kennedy, Alisha N. Clark, Charles Lesher, Qingyuan Liu

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Abstract

The energetics of Y2O3 cubic (C-type) and monoclinic (B-type) polymorphs as a function of surface area have been studied by high-temperature oxide melt solution calorimetry and water adsorption calorimetry. The hydrated surface of the monoclinic phase has a lower surface enthalpy (0.64 ± 0.49 J/m2) than that of the cubic (1.25 ± 0.17 J/m2). However, the anhydrous surface of the monoclinic form is less stable (surface enthalpy = 2.78 ± 0.49 J/m2) than that of the cubic (1.66 ± 0.14 J/m2). The phase transformation enthalpy (monoclinic to cubic) for coarse Y2O3́ is -21.8 ± 3.2 kJ/mol. An energetic crossover is suggested between the polymorphs under ambient conditions, in which the surfaces are hydrated, at a size of 7 ± 6 nm; however, anhydrous monoclinic yttria of any particle size is thermodynamically metastable at atmosphere pressure. Surface hydration controls the energetic landscape of Y2O3 polymorphs. The phase transformation process of monoclinic nanocrystals to the cubic phase was also studied using measurements of surface area, X-ray diffraction, and differential scanning calorimetry.

Original languageEnglish
Pages (from-to)932-938
Number of pages7
JournalJournal of Physical Chemistry C
Volume112
Issue number4
DOIs
Publication statusPublished - 31 Jan 2008

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ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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