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T-induced displacive phase transition of end-member Pb-lawsonite

  • Martin Ende (a1), Bernd Wunder (a2), Monika Koch-Müller (a2), Thoma. Pippinger (a1), Gernot Buth (a3), Gerald Giester (a1), Christian L. Lengauer (a1) and Eugen Libowitzky (a1)...
Abstract

Pb-lawsonite, PbAl2[(OH)2|Si2O7]·H2O, space group Pbnm, was synthesized as crystals up to 15 μm × 5 μm × 5 μm in size by a piston cylinder technique at a pressure of ∼4 GPa and a temperature of 873 ± 10 K. Temperature-dependent powder and single-crystal X-ray diffraction (XRD) analyses partly using synchrotron radiation as well as Raman spectroscopic investigations reveal a phase transition around 445 K resulting in the Cmcm high-temperature structure. The transformation temperature is considerably higher than that of lawsonite around 273 K, which is characterized predominantly by proton order/disorder. The transition is confirmed using principal component analysis and subsequent hierarchical cluster analysis on both the powder XRD patterns and the Raman spectra. Furthermore, a non-uniform change is observed around 355 K, which is not as pronounced as the 445 K transition and apparently comes from enhanced hydrogen bonding, which stops the atom shifts in Pb-lawsonite. These are the same bonds that mainly characterize the phase transition in lawsonite around 273 K. In contrast, the structural transition of Pblawsonite at 445 K seems to originate from the interaction of the SiO4 tetrahedra and AlO6 octahedra framework with the Pb2+ cation. The structural environment of Pb2+ can be described by a 12-fold coordination above 445 K, which changes towards irregular ten-fold coordination below this temperature. An assignment of the O–H stretching Raman bands confirms moderately strong H bonds in Pb-lawsonite, whereas both strong and weak H bonds exist in lawsonite. Therefore, a further phase transition of Pblawsonite, similar to that of lawsonite around 273 K, is not expected.

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Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016 This is an Open Access article, distributed under the terms of the Creative Commons Attribution license. (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted re-use, distribution, and reproduction in any medium, provided the original work is properly cited.
Corresponding author
*E-mail: martin.ende@univie.ac.at
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