Co 3O 4-Co 2ZnO 4 spinels: The case for a solid solution

Nicola H. Perry; Thomas O. Mason; Chengcheng Ma; Alexandra Navrotsky; Yezhou Shi; Joanna S. Bettinger; Michael F. Toney; Tula R. Paudel; Stephan Lany; Alex Zunger

doi:10.1016/j.jssc.2012.02.022

Co ₃O ₄-Co ₂ZnO ₄ spinels: The case for a solid solution

Nicola H. Perry, Thomas O. Mason^*, Chengcheng Ma, Alexandra Navrotsky, Yezhou Shi, Joanna S. Bettinger, Michael F. Toney, Tula R. Paudel, Stephan Lany, Alex Zunger

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

In prior first-principles theoretical work we predicted a complete solid solution in the Co ₃O ₄-Co ₂ZnO ₄ system, with a negligibly small mixing enthalpy. In this work we tested this prediction on bulk, large-grained specimens across the Co ₃O ₄-Co ₂ZnO ₄ join, combining oxide melt solution calorimetry, differential scanning calorimetry, precise lattice parameter measurements, anomalous X-ray and neutron diffraction, and in situ electrical measurements. The calorimetric results confirm the presence of a solid solution at high temperatures, but with a large enthalpy of mixing that exceeds the predicted value. Because Co ₃O ₄ and Co ₂ZnO ₄ have essentially identical lattice parameters, this energetic destabilization must arise from factors other than the strain energy resulting from size mismatch. Changes in Co ³ spin states vs. temperature and zinc content are proposed to account for the positive excess enthalpy, and may also provide additional entropy to stabilize the solid solution at high temperature.

Original language	English (US)
Pages (from-to)	143-149
Number of pages	7
Journal	Journal of Solid State Chemistry
Volume	190
DOIs	https://doi.org/10.1016/j.jssc.2012.02.022
State	Published - Jun 2012

Funding

This work was supported by the ''Center for Inverse Design,'' an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, U.S. Department of Energy, under Grant No. DE-AC36-08GO28308. CM and AN acknowledge funding from DOE Basic Energy Sciences grant DE-FG02-05ER15667 . The X-ray diffraction work was conducted in the J. B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (Grant No. DMR-0520513 ) at the Materials Research Center of Northwestern University. The anomalous X-ray diffraction work was carried out at the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. We acknowledge the support of the National Institute of Standards and Technology, U. S. Department of Commerce, in providing the neutron research facilities used in this work. YS, JSB, and MFT are grateful to Dr. Mark Green for his help with data collection and discussion about data refinement.

Keywords

Calorimetry
Co O
Diffraction
Electrical conductivity
Mixing thermodynamics
ZnCo O

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.jssc.2012.02.022

Cite this

@article{46d50a21ebc3468e8c78629abad6d012,

title = "Co 3O 4-Co 2ZnO 4 spinels: The case for a solid solution",

abstract = "In prior first-principles theoretical work we predicted a complete solid solution in the Co 3O 4-Co 2ZnO 4 system, with a negligibly small mixing enthalpy. In this work we tested this prediction on bulk, large-grained specimens across the Co 3O 4-Co 2ZnO 4 join, combining oxide melt solution calorimetry, differential scanning calorimetry, precise lattice parameter measurements, anomalous X-ray and neutron diffraction, and in situ electrical measurements. The calorimetric results confirm the presence of a solid solution at high temperatures, but with a large enthalpy of mixing that exceeds the predicted value. Because Co 3O 4 and Co 2ZnO 4 have essentially identical lattice parameters, this energetic destabilization must arise from factors other than the strain energy resulting from size mismatch. Changes in Co 3 spin states vs. temperature and zinc content are proposed to account for the positive excess enthalpy, and may also provide additional entropy to stabilize the solid solution at high temperature.",

keywords = "Calorimetry, Co O, Diffraction, Electrical conductivity, Mixing thermodynamics, ZnCo O",

author = "Perry, {Nicola H.} and Mason, {Thomas O.} and Chengcheng Ma and Alexandra Navrotsky and Yezhou Shi and Bettinger, {Joanna S.} and Toney, {Michael F.} and Paudel, {Tula R.} and Stephan Lany and Alex Zunger",

note = "Funding Information: This work was supported by the ''Center for Inverse Design,'' an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, U.S. Department of Energy, under Grant No. DE-AC36-08GO28308. CM and AN acknowledge funding from DOE Basic Energy Sciences grant DE-FG02-05ER15667 . The X-ray diffraction work was conducted in the J. B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (Grant No. DMR-0520513 ) at the Materials Research Center of Northwestern University. The anomalous X-ray diffraction work was carried out at the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. We acknowledge the support of the National Institute of Standards and Technology, U. S. Department of Commerce, in providing the neutron research facilities used in this work. YS, JSB, and MFT are grateful to Dr. Mark Green for his help with data collection and discussion about data refinement. ",

year = "2012",

month = jun,

doi = "10.1016/j.jssc.2012.02.022",

language = "English (US)",

volume = "190",

pages = "143--149",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Co 3O 4-Co 2ZnO 4 spinels

T2 - The case for a solid solution

AU - Perry, Nicola H.

AU - Mason, Thomas O.

AU - Ma, Chengcheng

AU - Navrotsky, Alexandra

AU - Shi, Yezhou

AU - Bettinger, Joanna S.

AU - Toney, Michael F.

AU - Paudel, Tula R.

AU - Lany, Stephan

AU - Zunger, Alex

N1 - Funding Information: This work was supported by the ''Center for Inverse Design,'' an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, U.S. Department of Energy, under Grant No. DE-AC36-08GO28308. CM and AN acknowledge funding from DOE Basic Energy Sciences grant DE-FG02-05ER15667 . The X-ray diffraction work was conducted in the J. B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (Grant No. DMR-0520513 ) at the Materials Research Center of Northwestern University. The anomalous X-ray diffraction work was carried out at the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. We acknowledge the support of the National Institute of Standards and Technology, U. S. Department of Commerce, in providing the neutron research facilities used in this work. YS, JSB, and MFT are grateful to Dr. Mark Green for his help with data collection and discussion about data refinement.

PY - 2012/6

Y1 - 2012/6

N2 - In prior first-principles theoretical work we predicted a complete solid solution in the Co 3O 4-Co 2ZnO 4 system, with a negligibly small mixing enthalpy. In this work we tested this prediction on bulk, large-grained specimens across the Co 3O 4-Co 2ZnO 4 join, combining oxide melt solution calorimetry, differential scanning calorimetry, precise lattice parameter measurements, anomalous X-ray and neutron diffraction, and in situ electrical measurements. The calorimetric results confirm the presence of a solid solution at high temperatures, but with a large enthalpy of mixing that exceeds the predicted value. Because Co 3O 4 and Co 2ZnO 4 have essentially identical lattice parameters, this energetic destabilization must arise from factors other than the strain energy resulting from size mismatch. Changes in Co 3 spin states vs. temperature and zinc content are proposed to account for the positive excess enthalpy, and may also provide additional entropy to stabilize the solid solution at high temperature.

AB - In prior first-principles theoretical work we predicted a complete solid solution in the Co 3O 4-Co 2ZnO 4 system, with a negligibly small mixing enthalpy. In this work we tested this prediction on bulk, large-grained specimens across the Co 3O 4-Co 2ZnO 4 join, combining oxide melt solution calorimetry, differential scanning calorimetry, precise lattice parameter measurements, anomalous X-ray and neutron diffraction, and in situ electrical measurements. The calorimetric results confirm the presence of a solid solution at high temperatures, but with a large enthalpy of mixing that exceeds the predicted value. Because Co 3O 4 and Co 2ZnO 4 have essentially identical lattice parameters, this energetic destabilization must arise from factors other than the strain energy resulting from size mismatch. Changes in Co 3 spin states vs. temperature and zinc content are proposed to account for the positive excess enthalpy, and may also provide additional entropy to stabilize the solid solution at high temperature.

KW - Calorimetry

KW - Co O

KW - Diffraction

KW - Electrical conductivity

KW - Mixing thermodynamics

KW - ZnCo O

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SN - 0022-4596

VL - 190

SP - 143

EP - 149

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

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