Thermodynamics-Inspired High-Entropy Oxide Synthesis

Fuente: arXiv
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Autori principali: Almishal, Saeed S. I., Furst, Matthew, Tan, Yueze, Sivak, Jacob T., Bejger, Gerald, Srikanth, Dhiya, Petruska, Joseph, Rost, Christina M., Sinnott, Susan B., Chen, Long-Qing, Maria, Jon-Paul
Natura: Preprint
Pubblicazione: 2025
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author Almishal, Saeed S. I.
Furst, Matthew
Tan, Yueze
Sivak, Jacob T.
Bejger, Gerald
Srikanth, Dhiya
Petruska, Joseph
Rost, Christina M.
Sinnott, Susan B.
Chen, Long-Qing
Maria, Jon-Paul
author_facet Almishal, Saeed S. I.
Furst, Matthew
Tan, Yueze
Sivak, Jacob T.
Bejger, Gerald
Srikanth, Dhiya
Petruska, Joseph
Rost, Christina M.
Sinnott, Susan B.
Chen, Long-Qing
Maria, Jon-Paul
contents High-entropy oxide (HEO) thermodynamics transcend temperature-centric approaches, spanning a multidimensional landscape where oxygen chemical potential plays a decisive role. Here, we experimentally demonstrate how controlling the oxygen chemical potential coerces multivalent cations into divalent states in rock salt HEOs. We construct a preferred valence phase diagram based on thermodynamic stability and equilibrium analysis, alongside a high throughput enthalpic stability map derived from atomistic calculations leveraging machine learning interatomic potentials. We identify and synthesize seven equimolar single-phase rock salt compositions that accommodate multivalent Mn, Fe, or both, as confirmed by X-ray diffraction and fluorescence. X-ray absorption fine structure spectra reveal predominantly divalent cations. Ultimately, we introduce oxygen chemical potential overlap as a key complementary descriptor predicting HEO stability and synthesizability. Although we focus on rock salt HEOs, our methods are chemically and structurally agnostic, providing a broadly adaptable framework for navigating HEOs thermodynamics and enabling a broader compositional range with contemporary property interest.
format Preprint
id arxiv_https___arxiv_org_abs_2503_07865
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Thermodynamics-Inspired High-Entropy Oxide Synthesis
Almishal, Saeed S. I.
Furst, Matthew
Tan, Yueze
Sivak, Jacob T.
Bejger, Gerald
Srikanth, Dhiya
Petruska, Joseph
Rost, Christina M.
Sinnott, Susan B.
Chen, Long-Qing
Maria, Jon-Paul
Materials Science
High-entropy oxide (HEO) thermodynamics transcend temperature-centric approaches, spanning a multidimensional landscape where oxygen chemical potential plays a decisive role. Here, we experimentally demonstrate how controlling the oxygen chemical potential coerces multivalent cations into divalent states in rock salt HEOs. We construct a preferred valence phase diagram based on thermodynamic stability and equilibrium analysis, alongside a high throughput enthalpic stability map derived from atomistic calculations leveraging machine learning interatomic potentials. We identify and synthesize seven equimolar single-phase rock salt compositions that accommodate multivalent Mn, Fe, or both, as confirmed by X-ray diffraction and fluorescence. X-ray absorption fine structure spectra reveal predominantly divalent cations. Ultimately, we introduce oxygen chemical potential overlap as a key complementary descriptor predicting HEO stability and synthesizability. Although we focus on rock salt HEOs, our methods are chemically and structurally agnostic, providing a broadly adaptable framework for navigating HEOs thermodynamics and enabling a broader compositional range with contemporary property interest.
title Thermodynamics-Inspired High-Entropy Oxide Synthesis
topic Materials Science
url https://arxiv.org/abs/2503.07865