Thermal expansion and structural transformations of stuffed derivatives of quartz along the LiAlSiO4–SiO2 join: a variable-temperature powder synchrotron XRD study |
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| Authors: | H Xu P J Heaney A Navrotsky |
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| Institution: | (1) Department of Geosciences and Princeton Materials Institute, Princeton University, Princeton, New Jersey 08544, USA, US;(2) Department of Geosciences, The Pennsylvania State University, University Park, Pennsylvania 16802, USA, US;(3) Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, California 95616, USA, US |
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| Abstract: | The structural behavior of stuffed derivatives of quartz within the Li1−
x
Al1−
x
Si1+
x
O4 system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD).
Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about
the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz
dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in
spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe
a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5.
Received: 26 June 2000 / Accepted: 1 December 2000 |
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| Keywords: | Thermal expansion Phase transition β -Eucryptite Quartz X-ray diffraction |
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