Probing disorder in pyrochlore oxides using in situ synchrotron diffraction from levitated solids–A thermodynamic perspective

Maram, Pardha S.; Ushakov, Sergey V.; Weber, Richard J. K.; Benmore, Chris J.; Navrotsky, Alexandra

doi:10.1038/s41598-018-28877-x

Title: Probing disorder in pyrochlore oxides using in situ synchrotron diffraction from levitated solids–A thermodynamic perspective

Journal Article · Fri Jul 13 00:00:00 EDT 2018 · Scientific Reports

DOI:https://doi.org/10.1038/s41598-018-28877-x· OSTI ID:1459466

;

; Weber, Richard J. K.; Benmore, Chris J.;

Abstract Pyrochlore, an ordered derivative of the defect fluorite structure, shows complex disordering behavior as a function of composition, temperature, pressure, and radiation damage. We propose a thermodynamic model to calculate the disordering enthalpies for several RE ₂ Zr ₂ O ₇ (RE = Sm, Eu, Gd) pyrochlores from experimental site distribution data obtained by in situ high temperature synchrotron X-ray diffraction. Site occupancies show a gradual increase in disorder on both cation and anion sublattices with increasing temperature and even greater disorder is achieved close to the phase transition to defect fluorite. The enthalpy associated with cation disorder depends on the radius of the rare earth ion, while the enthalpy of oxygen disordering is relatively constant for different compositions. The experimental data support trends predicted by ab initio calculations, but the obtained enthalpies of disordering are less endothermic than the predicted values. Thermal expansion coefficients are in the range (8.6–10.8) × 10 ⁻⁶ K ⁻¹ . These new experimental determinations of defect formation energies are important for understanding the stability of pyrochlore oxides and their disordering mechanisms, which are essential in the context of their potential applications in nuclear waste management and other technologies.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1459466

Alternate ID(s):: OSTI ID: 1480857

Journal Information:: Scientific Reports, Journal Name: Scientific Reports Vol. 8 Journal Issue: 1; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 22 works

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