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

The structures of ordered and disordered beta-eucryptite have been determin ed from Rietveld analysis of powder synchrotron x-ray and neutron diffracti on 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 axi s. However, the anisotropic character of the thermal behavior of ordered be ta-eucryptite is much more pronounced than that of the disordered compound; the linear expansion coefficients of the ordered and disordered phases are alpha(a), = 7.26 x 10(-6) K-1; ex, = -16.35 x 10(-6) K-1, and cr, -3.82 x 10-6 K-1, respectively. The thermal behavior of 5.98 x 10-6 K-1: beta-eucry ptite 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 t etrahedral deformation, (ii) Li positional disordering, and (iii) tetrahedr al tilting. Because disordered beta-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 d isordered beta-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 ro om temperature, and we suggest that repulsion between Li and Al/Si inhibits contraction along the a axes.