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

Research output: Contribution to journalArticle

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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 (US)
Pages (from-to)932-938
Number of pages7
JournalJournal of Physical Chemistry C
Volume112
Issue number4
DOIs
StatePublished - Jan 31 2008

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yttrium oxides
Yttrium oxide
Polymorphism
Enthalpy
Phase transitions
enthalpy
heat measurement
Calorimetry
phase transformations
yttria
Hydration
Nanocrystals
Oxides
hydration
Differential scanning calorimetry
crossovers
nanocrystals
Particle size
Adsorption
atmospheres

ASJC Scopus subject areas

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

Cite this

Energetics of cubic and monoclinic yttrium oxide polymorphs : Phase transitions, surface enthalpies, and stability at the nanoscale. / Zhang, Peng; Navrotsky, Alexandra; Guo, Bing; Kennedy, Ian; Clark, Alisha N.; Lesher, Charles; Liu, Qingyuan.

In: Journal of Physical Chemistry C, Vol. 112, No. 4, 31.01.2008, p. 932-938.

Research output: Contribution to journalArticle

Zhang, Peng ; Navrotsky, Alexandra ; Guo, Bing ; Kennedy, Ian ; Clark, Alisha N. ; Lesher, Charles ; Liu, Qingyuan. / Energetics of cubic and monoclinic yttrium oxide polymorphs : Phase transitions, surface enthalpies, and stability at the nanoscale. In: Journal of Physical Chemistry C. 2008 ; Vol. 112, No. 4. pp. 932-938.
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