skip to main content

Title: A theoretical study of the stability of anionic defects in cubic ZrO 2 at extreme conditions

Using first principles density functional theory calculations, we present a study of the structure, mobility, and the thermodynamic stability of anionic defects in the high-temperature cubic phase of ZrO 2. Our results suggest that the local structure of an oxygen interstitial depends on the charge state and the cubic symmetry of the anionic sublattice is unstable at 0 K. In addition, the oxygen interstitials and the vacancies exhibit symmetry breaking transitions to low-energy structures with tetragonal distortion of the oxygen sublattice at 0 K. However, the vibrational entropy stabilizes the defect structures with cubic symmetry at 2600–2980 K. The formation free energies of the anionic defects and Gibbs free energy changes associated with different defect reactions are calculated by including the vibrational free energy contributions and the effect of pressure on these defect structures. By analyzing the defect chemistry, we obtain the defect concentrations at finite temperature and pressure conditions using the zero temperature ab initio results as input and find that at low oxygen partial pressures, neutral oxygen vacancies are most dominant and at high oxygen partial pressures, doubly charged anionic defects are dominant. As a result, the relevance of the results to the thermal protective coating capabilities ofmore » zirconium-based ceramic composites is elucidated.« less
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0022-2461
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Materials Science
Additional Journal Information:
Journal Volume: 51; Journal Issue: 10; Journal ID: ISSN 0022-2461
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
Country of Publication:
United States