Phase transformation in CaCO₃ polymorphs

A spectroscopic, microscopic and diffraction study

verfasst von

Moritz Schmidt, Thorsten Stumpf, Clemens Walther, Horst Geckeis, Thomas Fanghänel

Abstract

This study presents results of the phase transformation from Cm(III) and Eu(III) doped vaterite to calcite. This transformation of one solid solution (An/Ln:vaterite) to another (An/Ln:calcite) was observed by powder X-ray diffraction and scanning electron microscopy. These observations were combined with site-selective time-resolved laser fluorescence spectroscopy (TRLFS), using Eu³⁺ and Cm³⁺ as atomic probes, which give an internal view of the structure. The transition from vaterite to the thermodynamically stable CaCO₃ polymorph calcite lasts several days. It could be shown that the transformation is taking place in four steps: initial precipitation of low crystalline vaterite, followed by transformation into the crystalline phase, upon suspending the vaterite in CaCO₃ solution the phase transformation to calcite starts. As third step a transition state with again partly hydrated Eu³⁺ can be observed before the transformation is completed after 72h. No transition is observed in vaterite kept in vacuum, demonstrating that the transition follows a dissolution/precipitation mechanism. Comparison with Eu³⁺-doped calcite directly synthesized under near-equilibrium conditions shows that identical solid solutions are formed, independent of the reaction path. Moreover the trivalent guest cations are fully transferred to the newly formed phase. This is strong evidence for a thermodynamic driving force for the solid solution formation in these systems.

Externe Organisation(en)

Karlsruher Institut für Technologie (KIT)
Ruprecht-Karls-Universität Heidelberg
Gemeinsame Forschungsstelle (GFS)

Typ

Artikel

Journal

Journal of Colloid and Interface Science

Band

351

Seiten

50-56

Anzahl der Seiten

7

ISSN

0021-9797

Publikationsdatum

11.2010

Publikationsstatus

Veröffentlicht

Peer-reviewed

Ja

ASJC Scopus Sachgebiete

Elektronische, optische und magnetische Materialien, Biomaterialien, Oberflächen, Beschichtungen und Folien, Kolloid- und Oberflächenchemie

Elektronische Version(en)

https://doi.org/10.1016/j.jcis.2010.07.026 (Zugang: Unbekannt)