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Article Dans Une Revue Physics and Chemistry of Minerals Année : 2020

Synchrotron high-resolution XRD and thermal expansion of synthetic Mg calcites

Résumé

The structural parameters and the thermal behavior of a complete series of Ca–Mg carbonates synthesized at high pressure and temperature (1–1.5 GPa, 1273–1373 K) in the range 0–50 mol% MgCO3 have been investigated by in situ powder synchrotron high-resolution X-ray diffraction at ambient and up to 1073 K under self-controlled CO2 partial pressure. The crystal structures are disordered Mg calcite in the range 1–41 mol% MgCO3, and Ca dolomite at 49 mol% MgCO3. New calibration curves of the cell parameters for the Mg content and thermal expansion from ambient to 1073 K are given. Short-range structural effects of cation substitution and ordering and their thermal behavior as a function of Mg content were identified from three sets of data: the peak broadening, the cell parameter strains and the Raman band enlargements. Both intra- and inter-crystalline levels of compositional heterogeneity are identified and allow splitting the Mg calcites into two groups: low- and high-Mg calcites. The low-Mg calcites (up to 22 mol% MgCO3) are homogeneous in Mg content with short-range ordering. High-Mg calcite (up to 41 mol% MgCO3) displays domains with different local ordering configurations and similar or slightly different Mg contents, and to which is added a compositional variation between crystals, as determined by EMP, of the order of  ± 0.8 mol% MgCO3. The cation ordering in Ca-rich dolomites similarly occurs in high-Mg synthetic calcites. The role of (CO3)2− group ordering is shown to be an important factor in the formation of Ca–Mg carbonates.

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hal-02975828 , version 1 (23-10-2020)

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Nicole Floquet, Daniel Vielzeuf, Vasile Heresanu, Didier Laporte, Jonathan Perrin. Synchrotron high-resolution XRD and thermal expansion of synthetic Mg calcites. Physics and Chemistry of Minerals, 2020, 47 (48), ⟨10.1007/s00269-020-01115-5⟩. ⟨hal-02975828⟩
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