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Thermodynamics of ZnxMn3−xO4 and Mg1−zCuzCr2O4 spinel solid solutions

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  • Thermodynamics of Complex Solids
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Abstract

The thermodynamic properties of ZnxMn3−xO4 and Mg1−zCuzCr2O4 spinel solid solutions have been studied using high-temperature oxide melt solution calorimetry. Except for MgCr2O4 spinel, which possesses cubic structure, the other three end-members are tetragonal. The enthalpies of mixing are small endothermic and fit subregular solution behavior. The main contribution to the energetics of mixing of both spinel systems comes from the difference in the crystal structure between the end-members: a change in the tetragonal distortion for ZnxMn3−xO4 solid solutions and a transition from cubic to tetragonal for the Mg1−zCuzCr2O4 system. If all Mg1−zCuzCr2O4 spinels possessed the same structure, the mixing enthalpies would be close to zero. Because both series have normal cation distributions, the entropies of mixing are equal to the configurational entropies of mixing of Zn2+ and Mn2+ and of Mg2+ and Cu2+ on tetrahedral sites, and the activities would follow Raoult’s law. The calculated Gibbs energy of mixing confirms the absence of solvus at any temperature for both systems.

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Acknowledgments

Financial support from DOE Grant DE-FG02-97ER1 is gratefully acknowledged. The authors thank Dr. Ram Seshadri (University of California, Santa Barbara) for his valuable contribution and support.

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Author notes

  1. Daniel P. Shoemaker

    Present address: Materials Science and Engineering Department, University of Illinois, Urbana, Illinois, 61801, USA

Authors and Affiliations

  1. Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California Davis, Davis, California, 95616, USA

    Kristina Lilova, Geetu Sharma, Shmuel Hayun & Alexandra Navrotsky

  2. Department of Materials Engineering, Ben Gurion University of the Negev, Beer-Sheva, 84105, Israel

    Shmuel Hayun

  3. Materials Department and Materials Research Laboratory, University of California, Santa Barbara, California, 93106, USA

    Daniel P. Shoemaker

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Correspondence to Alexandra Navrotsky.

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This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/editor-manuscripts/.

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Lilova, K., Sharma, G., Hayun, S. et al. Thermodynamics of ZnxMn3−xO4 and Mg1−zCuzCr2O4 spinel solid solutions. Journal of Materials Research 34, 3305–3311 (2019). https://doi.org/10.1557/jmr.2019.196

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  • DOI: https://doi.org/10.1557/jmr.2019.196

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