Computationally Accelerated Discovery of High Entropy Pyrochlore Oxides

Pitike, Krishna Chaitanya; Macias, Antonio; Eisenbach, Markus; Bridges, Craig A.; Cooper, Valentino R.

doi:10.1021/acs.chemmater.1c02361

Computationally Accelerated Discovery of High Entropy Pyrochlore Oxides

Journal Article · Mon Feb 07 00:00:00 EST 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c02361· OSTI ID:1863317

^[1]; Macias, Antonio ^[2]; ^[3]; ^[1]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Berkeley, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). National Center for Computational Sciences

High entropy ceramics provide enhanced flexibility for tailoring a wide range of physical properties, emerging from the diverse chemical and configurational degrees of freedom. Expanding upon the endeavors of recently synthesized high entropy ceramics in rock salt, fluorite, spinel, and perovskite structures, we explore the relative feasibility of formation of high entropy pyrochlore oxides, A₂B₂O₇, with multication occupancy of the B-site, estimated from first-principles-based thermodynamic descriptors. Subsequently, we used Monte Carlo simulations to estimate the phase composition, oxygen vacancy concentration, and local ionic segregation as a function of temperature and oxygen partial pressure. In synergy with the theoretical calculations, we have investigated the synthesis of several multicomponent oxides with a pyrochlore composition, related to our computational investigations, resulting in four phase pure and one 97.4% pure high entropy pyrochlore oxides. Ultimately, our approach allows us to evaluate potential impurity phases, ionic disorder, and oxygen vacancy concentration in response to the experimental variables, thereby making realistic predictions that can direct and accelerate experimental synthesis of novel multicomponent ceramics.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1863317

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 4 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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