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Title: Tunable magnetic ordering through cation selection in entropic spinel oxides

Abstract

Twelve multicomponent spinels, comprised of (Mg, Cr, Mn, Co, Fe, Ni, Cu, and/or Zn)(Cr,Fe,orAl)2O4, were prepared using solid state synthesis methods, resulting in nine homogenous, single phase samples with a Fm-3m structure, and three samples with multiple phases. Using dc magnetometry in conjunction with x-ray diffraction, scanning electron microscopy with energy dispersive x-ray spectroscopy, and x-ray absorption spectroscopy, the effects of multicomponent material design on the structural, magnetic, and chemical properties are explored. The ferritic spinel high-entropy oxide (HEO) samples show high-temperature ferrimagnetic transitions and both ferritic and chromium-based HEO spinel samples show evidence of low-temperature antiferromagnetic ordering. Blocking temperatures are evident in some samples and magnetic transition temperatures are reported. Constituent valence states and temperature dependent valence is described for the example case of (Mg0.2Fe0.2Co0.2Ni0.2Cu0.2)Cr2O4, including the unexpected presence of Cr4+, indicating a 2–4 type spinel configuration. Valence trends for two ferritic HEO spinels are also discussed. Some of these compositions are synthesized for the first time and this work provides an investigation into the magnetic properties of the novel class of cubic spinel multicomponent oxides showing interesting behavior that warrants further investigation.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [3];  [4];  [1];  [1];  [1]
  1. Univ. of Tennessee, Knoxville, TN (United States). Joint Inst. of Neutron Science
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1606826
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 10; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Magnetic phase transitions; Magnetism; Polycrystalline materials; Spinel; Magnetization measurements; X-ray absorption spectroscopy; X-ray magnetic linear dichroism

Citation Formats

Musico, Brianna L., Wright, Quinton, Ward, Zac, Grutter, Alexander, Arenholz, Elke, Gilbert, Dustin, Mandrus, David, and Keppens, Veerle. Tunable magnetic ordering through cation selection in entropic spinel oxides. United States: N. p., 2019. Web. https://doi.org/10.1103/PhysRevMaterials.3.104416.
Musico, Brianna L., Wright, Quinton, Ward, Zac, Grutter, Alexander, Arenholz, Elke, Gilbert, Dustin, Mandrus, David, & Keppens, Veerle. Tunable magnetic ordering through cation selection in entropic spinel oxides. United States. https://doi.org/10.1103/PhysRevMaterials.3.104416
Musico, Brianna L., Wright, Quinton, Ward, Zac, Grutter, Alexander, Arenholz, Elke, Gilbert, Dustin, Mandrus, David, and Keppens, Veerle. Mon . "Tunable magnetic ordering through cation selection in entropic spinel oxides". United States. https://doi.org/10.1103/PhysRevMaterials.3.104416. https://www.osti.gov/servlets/purl/1606826.
@article{osti_1606826,
title = {Tunable magnetic ordering through cation selection in entropic spinel oxides},
author = {Musico, Brianna L. and Wright, Quinton and Ward, Zac and Grutter, Alexander and Arenholz, Elke and Gilbert, Dustin and Mandrus, David and Keppens, Veerle},
abstractNote = {Twelve multicomponent spinels, comprised of (Mg, Cr, Mn, Co, Fe, Ni, Cu, and/or Zn)(Cr,Fe,orAl)2O4, were prepared using solid state synthesis methods, resulting in nine homogenous, single phase samples with a Fm-3m structure, and three samples with multiple phases. Using dc magnetometry in conjunction with x-ray diffraction, scanning electron microscopy with energy dispersive x-ray spectroscopy, and x-ray absorption spectroscopy, the effects of multicomponent material design on the structural, magnetic, and chemical properties are explored. The ferritic spinel high-entropy oxide (HEO) samples show high-temperature ferrimagnetic transitions and both ferritic and chromium-based HEO spinel samples show evidence of low-temperature antiferromagnetic ordering. Blocking temperatures are evident in some samples and magnetic transition temperatures are reported. Constituent valence states and temperature dependent valence is described for the example case of (Mg0.2Fe0.2Co0.2Ni0.2Cu0.2)Cr2O4, including the unexpected presence of Cr4+, indicating a 2–4 type spinel configuration. Valence trends for two ferritic HEO spinels are also discussed. Some of these compositions are synthesized for the first time and this work provides an investigation into the magnetic properties of the novel class of cubic spinel multicomponent oxides showing interesting behavior that warrants further investigation.},
doi = {10.1103/PhysRevMaterials.3.104416},
journal = {Physical Review Materials},
number = 10,
volume = 3,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: X-ray diffraction for single phase HEO spinel compositions that are a) chromium based, b) iron based and c) aluminum based compared with ICSD reference patterns showing single phase spinel $Fd$-$3m$ structure.

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