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Determination of Crystal Structures01:29

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Phase transformation in CaCO3 polymorphs: a spectroscopic, microscopic and diffraction study.

Moritz Schmidt1, Thorsten Stumpf, Clemens Walther

  • 1Institut für Nukleare Entsorgung, Forschungszentrum Karlsruhe, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany.

Journal of Colloid and Interface Science
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Summary

This study reveals how lanthanide-doped vaterite transforms into calcite over several days. The process involves dissolution and reprecipitation, forming stable solid solutions regardless of the reaction path.

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Area of Science:

  • Geochemistry
  • Materials Science
  • Crystallography

Background:

  • Vaterite is a metastable polymorph of calcium carbonate.
  • Lanthanide doping can stabilize vaterite but its transformation to calcite is complex.
  • Understanding solid solution formation is crucial for geochemistry and materials science.

Purpose of the Study:

  • To investigate the phase transformation of lanthanide-doped vaterite to calcite.
  • To elucidate the mechanism and kinetics of this transformation.
  • To analyze the resulting solid solution formation.

Main Methods:

  • Powder X-ray diffraction (PXRD) for structural analysis.
  • Scanning electron microscopy (SEM) for morphological observation.
  • Site-selective time-resolved laser fluorescence spectroscopy (TRLFS) using Eu(3+) and Cm(3+) as probes.

Main Results:

  • The transformation from vaterite to calcite occurs in four steps over several days.
  • The process follows a dissolution/precipitation mechanism, confirmed by the absence of transformation in vacuum.
  • Identical solid solutions (An/Ln:calcite) are formed irrespective of the reaction path, with complete transfer of guest cations.

Conclusions:

  • The phase transformation is thermodynamically driven, favoring the formation of stable solid solutions.
  • Lanthanide ions are fully incorporated into the calcite lattice during transformation.
  • This study provides insights into the formation of doped carbonate minerals and solid solutions.