Skip to main content
SpringerLink
Log in

Phonon density of states and negative thermal expansion in ZrW2O8

  • Letter
  • Published:

From Nature

View current issue Submit your manuscript

Abstract

Thermal expansion of solids arises from anharmonic lattice dynamics. The contrasting phenomenon of negative thermal expansion (NTE)—where expansion occurs on cooling rather than heating—was discovered1 in ZrW2O8 in 1968. Recently, this material has attracted interest in the context of NTE for several reasons: the magnitude of the effect is relatively large (−9 p.p.m. K−1); the temperature range over which NTE occurs is also large (from close to absolute zero up to the decomposition temperature of about 1,050 K); and the NTE effect is isotropic2, evidenced by the fact that ZrW2O8 remains cubic at all temperatures. These characteristics make ZrW2O8 an important system in which to study unusual lattice dynamics of this type, and potentially well suited for application in composite materials with an engineered thermal expansion coefficient3. Here we report neutron-scattering measurements of ZrW2O8 that allow us to investigate its phonon spectrum, and hence determine the energy scale for the lattice motions governing NTE. We find that NTE can be modelled by several low-energy phonon modes, suggesting that the effect arises from the unusual crystal structure of ZrW2O8, which supports highly anharmonic vibrational modes.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1: Generalized phonon density of states g (ω) of ZrW2O8 at T = 300 K.
Figure 2: Lattice parameter a (open circles) and Grüneisen parameter γ (crosses) of ZrW2O8 as a function of temperature.
Figure 3: Low-energy generalized density of states for T = 50 K, 100 K and 300 K as determined from inelastic neutron scattering.

Similar content being viewed by others

References

  1. Martinek, C. & Hummel, F. A. Linear thermal expansion of three tungstates. J. Am. Ceram. Soc. 51, 227–228 (1968).

    Article  CAS  Google Scholar 

  2. Mary, T. A., Evans, J. S. O., Vogt, T. & Sleight, A. W. Negative thermal expansion from 0.3 to 1050 Kelvin in ZrW2O8. Science 272, 90–92 (1996).

    Article  ADS  CAS  Google Scholar 

  3. Fleming, D. A., Johnson, D. W. & Lemaire, P. J. US Patent No. 5694503 (1997).

  4. Blackman, M. On the thermal expansion of solids. Proc. Phys. Soc. B 70, 827–832 (1957).

    Article  ADS  Google Scholar 

  5. Giddy, A. P., Dove, M. T., Pawley, G. S. & Heine, V. The determination of rigid unit modes as potential soft modes for displacive phase transitions in framework crystal structures. Acta Crystallogr. A 49, 697–703 (1993).

    Article  Google Scholar 

  6. Pryde, A. K. A. et al. Origin of the negative thermal expansion in ZrW2O8and ZrV2O7. J. Phys. Condens. Matter 8, 10973–10982 (1996).

    Article  ADS  CAS  Google Scholar 

  7. Barron, T. H. K., Collins, J. G. & White, G. K. Thermal expansion of solids at low temperatures. Adv. Phys. 29, 609–730 (1980).

    Article  ADS  CAS  Google Scholar 

  8. Ramirez, A. P. & Kowach, G. R. Large low temperature specific heat in the negative thermal expansion compound ZrW2O8. Phys. Rev. Lett. 80, 4903–4906 (1998).

    Article  ADS  CAS  Google Scholar 

  9. Lovesey, S. W. Theory of Neutron Scattering from Condensed Matter Vol. 1 (Clarendon, Oxford, (1984).

    Google Scholar 

  10. Squires, G. L. Introduction to the Theory of Thermal Neutron Scattering (Cambridge Univ. Press, (1978).

    Google Scholar 

  11. Evans, J. S. O., Mary, T. A., Vogt, T., Subramanian, M. A. & Sleight, A. W. Negative thermal expansion in ZrW2O8and HfW2O8. Chem. Mater. 8, 2809–2823 (1996).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank W. Kamitakahara, P. Littlewood, D. Neuman, A. Pinczuk, T. Siegrist, C.Varma, T. Yildrim and in particular S. Simon for discussions. Work at JHU was supported by the NSF; this work used neutron research facilities supported by NIST and the NSF.

Author information

Authors and Affiliations

  1. Bell Laboratories, Lucent Technologies, Murray Hill, 07974-0636, New Jersey, USA

    G. Ernst, G. R. Kowach & A. P. Ramirez

  2. Department of Physics and Astronomy, Johns Hopkins University, Baltimore, 21218, Maryland, USA

    C. Broholm

  3. Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, 20899, Maryland, USA

    C. Broholm

Authors
  1. G. Ernst
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. C. Broholm
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. R. Kowach
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. P. Ramirez
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. P. Ramirez.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ernst, G., Broholm, C., Kowach, G. et al. Phonon density of states and negative thermal expansion in ZrW2O8. Nature 396, 147–149 (1998). https://doi.org/10.1038/24115

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/24115

  • Springer Nature Limited

This article is cited by

Search

Navigation