Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Probing disorder in isometric pyrochlore and related complex oxides

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

Subjects

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

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.

Similar content being viewed by others

References

  1. Keen, D. A. & Goodwin, A. L. The crystallography of correlated disorder. Nature 521, 303–309 (2015).

    Article  CAS  Google Scholar 

  2. Subramanian, M. A., Aravamudan, G. & Rao, G. V. S. Oxide pyrochlores—a review. Prog. Solid State Chem. 15, 55–143 (1983).

    Article  CAS  Google Scholar 

  3. Sickafus, K. E. et al. Radiation tolerance of complex oxides. Science 289, 748–751 (2000).

    Article  CAS  Google Scholar 

  4. Ewing, R. C., Weber, W. J. & Lian, J. Nuclear waste disposal-pyrochlore (A2B2O7): nuclear waste form for the immobilization of plutonium and “minor” actinides. J. Appl. Phys. 95, 5949–5971 (2004).

    Article  CAS  Google Scholar 

  5. Sickafus, K. E. et al. Radiation-induced amorphization resistance and radiation tolerance in structurally related oxides. Nature Mater. 6, 217–223 (2007).

    Article  CAS  Google Scholar 

  6. Zhang, F. X. et al. Phase stability and pressure dependence of defect formation in Gd2Ti2O7 and Gd2Zr2O7 pyrochlores. Phys. Rev. Lett. 100, 045503 (2008).

    Article  CAS  Google Scholar 

  7. Zhang, F. X., Lang, M., Liu, Z. & Ewing, R. C. Pressure-induced disordering and anomalous lattice expansion in La2Zr2O7 pyrochlore. Phys. Rev. Lett. 105, 015503 (2010).

    Article  CAS  Google Scholar 

  8. Wuensch, B. J. et al. Connection between oxygen-ion conductivity of pyrochlore fuel-cell materials and structural change with composition and temperature. Solid State Ion. 129, 111–133 (2000).

    Article  CAS  Google Scholar 

  9. Padture, N. P., Gell, M. & Jordan, E. H. Thermal barrier coatings for gas-turbine engine applications. Science 296, 280–284 (2002).

    Article  CAS  Google Scholar 

  10. Wu, J. et al. Low-thermal-conductivity rare-earth zirconates for potential thermal-barrier-coating applications. J. Am. Ceram. Soc. 85, 3031–3035 (2002).

    Article  CAS  Google Scholar 

  11. Castro Neto, A. H., Guinea, F., Peres, N. M. R., Novoselov, K. S. & Geim, A. K. The electronic properties of graphene. Rev. Mod. Phys. 81, 109–162 (2009).

    Article  CAS  Google Scholar 

  12. Hsieh, P. et al. Photon transport enhanced by transverse Anderson localization in disordered superlattices. Nature Phys. 11, 268–274 (2015).

    Article  CAS  Google Scholar 

  13. Civale, L. et al. Vortex confinement by columnar defects in YBa2Cu3O7 crystals—enhanced pinning at high fields and temperatures. Phys. Rev. Lett. 67, 648–651 (1991).

    Article  CAS  Google Scholar 

  14. Biswas, K. et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature 489, 414–418 (2012).

    Article  CAS  Google Scholar 

  15. Oh, S. H., Black, R., Pomerantseva, E., Lee, J.-H. & Nazar, L. F. Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium-O2 batteries. Nature Chem. 4, 1004–1010 (2012).

    Article  CAS  Google Scholar 

  16. Rooksby, H. P. & White, E. A. D. Rare-earth niobates and tantalates of defect fluorite-type and weberite-type structures. J. Am. Ceram. Soc. 47, 94–96 (1964).

    Article  CAS  Google Scholar 

  17. Li, Y. et al. Defect formation energies in A2B2O7 pyrochlores. Scr. Mater. 107, 18–21 (2015).

    Article  CAS  Google Scholar 

  18. Lian, J. et al. Effect of structure and thermodynamic stability on the response of lanthanide stannate-pyrochlores to ion beam irradiation. J. Phys. Chem. B 110, 2343–2350 (2006).

    Article  CAS  Google Scholar 

  19. Norberg, S. T. et al. Pyrochlore to fluorite transition: the Y2(Ti1−xZrx)2O7 (0.0 ≤ x ≤ 1.0) system. Chem. Mater. 24, 4294–4300 (2012).

    Article  CAS  Google Scholar 

  20. Blanchard, P. E. R. et al. Does local disorder occur in the pyrochlore zirconates? Inorg. Chem. 51, 13237–13244 (2012).

    Article  CAS  Google Scholar 

  21. Sanjuan, M. L. et al. Raman and X-ray absorption spectroscopy study of the phase evolution induced by mechanical milling and thermal treatments in R2Ti2O7 pyrochlores. Phys. Rev. B 84, 104207 (2011).

    Article  Google Scholar 

  22. King, G., Thompson, C. M., Greedan, J. E. & Llobet, A. Local structure of the vacancy disordered fluorite Yb3TaO7 from neutron total scattering. J. Mater. Chem. A 1, 10487–10494 (2013).

    Article  CAS  Google Scholar 

  23. Walker, J. D. S., Hayes, J. R., Gaultois, M. W., Aluri, E. R. & Grosvenor, A. P. A case for oxygen deficiency in Gd2Ti2−xZrxO7 pyrochlore-type oxides. J. Alloys Compd. 565, 44–49 (2013).

    Article  CAS  Google Scholar 

  24. Jiang, C., Stanek, C. R., Sickafus, K. E. & Uberuaga, B. P. First-principles prediction of disordering tendencies in pyrochlore oxides. Phys. Rev. B 79, 104203 (2009).

    Article  Google Scholar 

  25. Verwey, E. J. W. & Heilmann, E. L. Physical properties and cation arrangement of oxides with spinel structures I. Cation arrangement in spinels. J. Chem. Phys. 15, 174–180 (1947).

    Article  CAS  Google Scholar 

  26. Sickafus, K. E. et al. Cation disorder in high-dose, neutron-irradiated spinel. J. Nucl. Mater. 219, 128–134 (1995).

    Article  CAS  Google Scholar 

  27. Redfern, S. A. T., Harrison, R. J., O’Neill, H. S. C. & Wood, D. R. R. Thermodynamics and kinetics of cation ordering in MgAl2O4 spinel up to 1600 degrees C from in situ neutron diffraction. Am. Mineral. 84, 299–310 (1999).

    Article  CAS  Google Scholar 

  28. Asbrink, S., Waskowska, A., Olsen, J. S. & Gerward, L. High-pressure phase of the cubic spinel NiMn2O4 . Phys. Rev. B 57, 4972–4974 (1998).

    Article  CAS  Google Scholar 

  29. Ivanov, V. G. et al. Short-range B-site ordering in the inverse spinel ferrite NiFe2O4 . Phys. Rev. B 82, 024104 (2010).

    Article  Google Scholar 

  30. Jiang, C., Sickafus, K. E., Stanek, C. R., Rudin, S. P. & Uberuaga, B. P. Cation disorder in MgX2O4 (X = Al, Ga, In) spinels from first principles. Phys. Rev. B 86, 024203 (2012).

    Article  Google Scholar 

  31. Finkeldei, S. et al. Dissolution of ZrO2 based pyrochlores in the acid pH range: a macroscopic and electron microscopy study. Appl. Geochem. 49, 31–41 (2014).

    Article  CAS  Google Scholar 

  32. Ziegler, J. F., Ziegler, M. D. & Biersack, J. P. SRIM—The stopping and range of ions in matter (2010). Nucl. Instrum. Methods Phys. Res. B 268, 1818–1823 (2010).

    Article  CAS  Google Scholar 

  33. Farrow, C. L. et al. PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals. J. Phys. Condens. Matter 19, 335219 (2007).

    Article  CAS  Google Scholar 

Download references

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.

Author information

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

Authors
  1. Jacob Shamblin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mikhail Feygenson
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Joerg Neuefeind
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Cameron L. Tracy
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Fuxiang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sarah Finkeldei
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Dirk Bosbach
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Haidong Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Rodney C. Ewing
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Maik Lang
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Corresponding author

Correspondence to Maik Lang.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 5247 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat4581

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing