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Probing disorder in isometric pyrochlore and related complex oxides

Nature Materials volume 15, pages 507–511 (2016)Cite this article

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Abstract

There has been an increased focus on understanding the energetics of structures with unconventional ordering (for example, correlated disorder that is heterogeneous across different length scales1). In particular, compounds with the isometric pyrochlore structure2, A2B2O7, can adopt a disordered, isometric fluorite-type structure, (A, B)4O7, under extreme conditions3,4,5,6,7. Despite the importance of the disordering process there exists only a limited understanding of the role of local ordering on the energy landscape. We have used neutron total scattering to show that disordered fluorite (induced intrinsically by composition/stoichiometry or at far-from-equilibrium conditions produced by high-energy radiation) consists of a local orthorhombic structural unit that is repeated by a pseudo-translational symmetry, such that orthorhombic and isometric arrays coexist at different length scales. We also show that inversion in isometric spinel occurs by a similar process. This insight provides a new basis for understanding order-to-disorder transformations important for applications such as plutonium immobilization4, fast ion conduction8, and thermal barrier coatings9,10.

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Figure 1: Neutron PDFs and structural models for ordered (Ho2Ti2O7) and disordered (Ho2Zr2O7) pyrochlore.
Figure 2: Neutron powder diffraction pattern (open circles) of Ho2Zr2O7 refined with the isometric disordered fluorite structure (solid red line).
Figure 3: Comparison of neutron PDFs (open circles) for intrinsically and extrinsically disordered pyrochlores.
Figure 4: Neutron PDFs and structural models for normal (MgAl2O4) and inverse (NiAl2O4) spinel.

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Acknowledgements

We thank T. Egami, A. Fuentes and B. Haberl for discussions. This work was supported as part of the Materials Science of Actinides, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0001089. This research at ORNL’s Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy.

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Authors and Affiliations

  1. Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996, USA

    Jacob Shamblin & Maik Lang

  2. Department of Physics and Astronomy, University of Tennessee, Knoxville, Tennessee 37996, USA

    Jacob Shamblin & Haidong Zhou

  3. Chemical and Engineering Materials Division, Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    Mikhail Feygenson & Joerg Neuefeind

  4. Department of Geological Sciences, Stanford University, Stanford, California 94305-2115, USA

    Cameron L. Tracy & Rodney C. Ewing

  5. Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, Michigan 48109, USA

    Fuxiang Zhang

  6. Forschungszentrum Jülich, Institute of Energy and Climate Research, IEK-6: Nuclear Waste Management and Reactor Safety, 52425 Jülich, Germany

    Sarah Finkeldei & Dirk Bosbach

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Contributions

J.S., C.L.T., R.C.E. and M.L. conceived and designed the experiments. M.L. and C.L.T. designed and coordinated the irradiation procedure. J.S., F.Z., S.F., D.B. and H.Z. synthesized the samples. J.S., M.F., C.L.T., J.N. and M.L. collected and interpreted the neutron scattering data. J.S., C.L.T., R.C.E. and M.L. prepared the manuscript.

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Correspondence to Maik Lang.

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Shamblin, J., Feygenson, M., Neuefeind, J. et al. Probing disorder in isometric pyrochlore and related complex oxides. Nature Mater 15, 507–511 (2016). https://doi.org/10.1038/nmat4581

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