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

Research output: Contribution to journalArticle

9 Citations (Scopus)

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 languageEnglish
Pages (from-to)143-149
Number of pages7
JournalJournal of Solid State Chemistry
Volume190
DOIs
Publication statusPublished - Jun 2012

Fingerprint

Enthalpy
Solid solutions
solid solutions
enthalpy
Lattice constants
lattice parameters
heat measurement
destabilization
Calorimetry
Neutron diffraction
Strain energy
Temperature
Oxides
electrical measurement
neutron diffraction
Zinc
Differential scanning calorimetry
Entropy
zinc
entropy

Keywords

  • Calorimetry
  • Co O
  • Diffraction
  • Electrical conductivity
  • Mixing thermodynamics
  • ZnCo O

ASJC Scopus subject areas

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

Cite this

Perry, N. H., Mason, T. O., Ma, C., Navrotsky, A., Shi, Y., Bettinger, J. S., ... Zunger, A. (2012). Co 3O 4-Co 2ZnO 4 spinels: The case for a solid solution. Journal of Solid State Chemistry, 190, 143-149. https://doi.org/10.1016/j.jssc.2012.02.022

Co 3O 4-Co 2ZnO 4 spinels : The case for a solid solution. / Perry, Nicola H.; Mason, Thomas O; Ma, Chengcheng; Navrotsky, Alexandra; Shi, Yezhou; Bettinger, Joanna S.; Toney, Michael F.; Paudel, Tula R.; Lany, Stephan; Zunger, Alex.

In: Journal of Solid State Chemistry, Vol. 190, 06.2012, p. 143-149.

Research output: Contribution to journalArticle

Perry, NH, Mason, TO, Ma, C, Navrotsky, A, Shi, Y, Bettinger, JS, Toney, MF, Paudel, TR, Lany, S & Zunger, A 2012, 'Co 3O 4-Co 2ZnO 4 spinels: The case for a solid solution', Journal of Solid State Chemistry, vol. 190, pp. 143-149. https://doi.org/10.1016/j.jssc.2012.02.022
Perry, Nicola H. ; Mason, Thomas O ; Ma, Chengcheng ; Navrotsky, Alexandra ; Shi, Yezhou ; Bettinger, Joanna S. ; Toney, Michael F. ; Paudel, Tula R. ; Lany, Stephan ; Zunger, Alex. / Co 3O 4-Co 2ZnO 4 spinels : The case for a solid solution. In: Journal of Solid State Chemistry. 2012 ; Vol. 190. pp. 143-149.
@article{b2653889302740319418c04705ad2eba,
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",
year = "2012",
month = "6",
doi = "10.1016/j.jssc.2012.02.022",
language = "English",
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

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

UR - http://www.scopus.com/inward/record.url?scp=84860723607&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84860723607&partnerID=8YFLogxK

U2 - 10.1016/j.jssc.2012.02.022

DO - 10.1016/j.jssc.2012.02.022

M3 - Article

AN - SCOPUS:84860723607

VL - 190

SP - 143

EP - 149

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

ER -