A new compositional microscopic degree of freedom at grain boundaries in complex compounds: a case study in spinel

Hatton, Peter; Uberuaga, Blas Pedro

doi:10.1039/d4cp01070a

Title: A new compositional microscopic degree of freedom at grain boundaries in complex compounds: a case study in spinel

Journal Article · Thu May 16 00:00:00 UTC 2024 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/d4cp01070a · OSTI ID:2356999

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Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

The accurate computational treatment of polycrystalline materials requires the rigorous generation of grain boundary (GB) structures as many quantities of interest depend strongly on the specifics of the macroscopic and microscopic degrees of freedom (DoFs) used in their creation. In complex materials, containing multiple sublattices and where atomic composition can vary spatially through the system, we introduce a new microscopic DoF based on this compositional variation which we find governs observable properties. In spinel – a wide class of complex oxides where this compositional variation manifests as cation inversion – we exploit this DoF to generate and analyze low-energy microstates of two GBs with three spinel chemistries (FeCr₂O₄, NiCr₂O₄ and MgAl₂O₄). This treatment is found to allow for the co-redistribution of cations at the GBs which acts to modify the spatial charge distribution, defect segregation energy and defect transport through these regions. Additionally, we generate low-energy metastable microstates of the GB system with an induced cation disorder, simulating those which may develop as a result of damage events. These are then analyzed to discover their composition and defect transport properties which depend strongly on the amount of induced damage. We conclude that considering this new DoF is important in describing the properties of GBs in complex materials.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Fundamental Understanding of Transport Under Reactor Extremes (FUTURE); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC). Office of Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2356999

Report Number(s):: LA-UR--24-21131

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 22 Vol. 26; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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