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Structural mechanisms underlying near-zero thermal expansion in β-eucryptite: A combined synchrotron x-ray and neutron Rietveld analysis

Published online by Cambridge University Press:  31 January 2011

Hongwu Xu ,
Peter J. Heaney ,
Douglas M. Yates ,
Robert B. Von Dreele  and
Mark A. Bourke
Hongwu Xu
Affiliation:
Princeton Materials Institute and Department of Geosciences, Princeton University, Princeton, New Jersey 08544
Peter J. Heaney
Affiliation:
Princeton Materials Institute and Department of Geosciences, Princeton University, Princeton, New Jersey 08544
Douglas M. Yates
Affiliation:
Princeton Materials Institute and Department of Geosciences, Princeton University, Princeton, New Jersey 08544
Robert B. Von Dreele
Affiliation:
Manuel Lujan Neutron Scattering Center, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Mark A. Bourke
Affiliation:
Manuel Lujan Neutron Scattering Center, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
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Abstract

The structures of ordered and disordered β-eucryptite have been determined from Rietveld analysis of powder synchrotron x-ray and neutron diffraction data over a temperature range of 20 to 873 K. On heating, both materials show an expansion within the (001) plane and a contraction along the c axis. However, the anisotropic character of the thermal behavior of ordered β-eucryptite is much more pronounced than that of the disordered compound; the linear expansion coefficients of the ordered and disordered phases are αa = 7.26 × 10−6 K−1; αc = −16.35 × 10−6 K−1, and αa = 5.98 × 10−6 K−1; αc = −3.82 × 10−6 K−1, respectively. The thermal behavior of β-eucryptite can be attributed to three interdependent processes that all cause an increase in a but a decrease in c with increasing temperature: (i) Si/Al tetrahedral deformation, (ii) Li positional disordering, and (iii) tetrahedral tilting. Because disordered β-eucryptite does not exhibit tetrahedral tilting, the absolute values of its axial thermal coefficients are smaller than those for the ordered sample. At low temperatures, both ordered and disordered β-eucryptite exhibit a continuous expansion parallel to the c axis with decreasing temperature, whereas a remains approximately unchanged. Our difference Fourier synthesis reveals localization of Li ions below room temperature, and we suggest that repulsion between Li and Al/Si inhibits contraction along the a axes.

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Articles
Information
Journal of Materials Research , Volume 14 , Issue 7 , July 1999 , pp. 3138 - 3151
Copyright
Copyright © Materials Research Society 1999

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