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Abstract The rocksalt structured (Co,Cu,Mg,Ni,Zn)O entropy-stabilized oxide (ESO) exhibits a reversible phase transformation that leads to the formation of Cu-rich tenorite and Co-rich spinel secondary phases. Using atom probe tomography, kinetic analysis, and thermodynamic modeling, we uncover the nucleation and growth mechanisms governing the formation of these two secondary phases. We find that these phases do not nucleate directly, but rather they first form Cu-rich and Co-rich precursor phases, which nucleate in regions rich in Cu and cation vacancies, respectively. These precursor phases then grow through cation diffusion and exhibit a rocksalt-like crystal structure. The Cu-rich precursor phase subsequently transforms into the Cu-rich tenorite phase through a structural distortion-based transformation, while the Co-rich precursor phase transforms into the Co-rich spinel phase through a defect-mediated transformation. Further growth of the secondary phases is controlled by cation diffusion within the primary rocksalt phase, whose diffusion behavior resembles other common rocksalt oxides. Graphical abstract
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High temperature stability of entropy-stabilized oxide (MgCoNiCuZn)0.2O in air
Entropy-stabilized oxides are single-phase, multicomponent oxides that are stabilized by a large entropy of mixing, ΔS, overcoming a positive enthalpy. Due to the −TΔS term in the Gibbs' free energy, G, it can be hypothesized that entropy-stabilized oxides demonstrate a robust thermal stability. Here, we investigate the high temperature stability (1300–1700 °C) of the prototypical entropy-stabilized rocksalt oxide (MgCoNiCuZn)0.2O in air. We find that at temperatures >1300 °C, the material gradually loses Cu and Zn with increasing temperature. Cu is lost through a selective melting as a Cu-rich liquid phase is formed. Zn is sublimed from the rocksalt phase at approximately similar temperatures to those corresponding to the Cu loss, significantly below both the melting temperature of ZnO and its solubility limit in a rocksalt phase. The elemental loss progressively reduces the entropy of mixing and results in a multiphase solid upon quenching to room temperature. We posit that the high-temperature solubility of Cu and Zn is correlated providing further evidence for entropic stabilization over general solubility arguments.
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- PAR ID:
- 10595147
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- Applied Physics Letters
- Volume:
- 124
- Issue:
- 15
- ISSN:
- 0003-6951
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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