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An in situ study of the phase transitions among CaCO3 high-pressure polymorphs

Published online by Cambridge University Press:  02 July 2018

Xueyin Yuan*
Affiliation:
MNR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China;
Chao Gao
Affiliation:
MNR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China;
Jing Gao
Affiliation:
Key Laboratory of Orogenic Belts and Crustal Evolution, Ministry of Education, Peking University, Beijing 100871, China
*
*Author for correspondence: Xueyin Yuan, Email: [email protected]

Abstract

The phase transitions involving calcite (CaCO3-I), CaCO3-II, CaCO3-III and CaCO3-IIIb were investigated using a diamond anvil cell and micro-Raman spectroscopy. Based on the results obtained from in situ observations and Raman measurements made with six natural calcite crystals, the phase transition from calcite to CaCO3-II took place between 1.56 and 1.67 GPa under ambient temperature. Under a precise pressure of 1.97 ± 0.03 GPa, three CaCO3 samples were observed to transform from CaCO3-II directly to CaCO3-III, while in the other three samples both CaCO3-III and CaCO3-IIIb crystal structures were detected. Transformation from CaCO3-IIIb to CaCO3-III was completed in a short period in one sample, whereas in the other two samples coexistence of CaCO3-III and CaCO3-IIIb was observed over a wide pressure range from 1.97 to 3.38 GPa, with sluggish transformation from CaCO3-IIIb to CaCO3-III being observed after the samples were preserved under 3.38 GPa for 72 h. Hence, it can be concluded that CaCO3-IIIb is a metastable intermediate phase occurring during the reconstructive transformation from CaCO3-II to CaCO3-III. Splitting of the C–O in-plane bending (ν4) and symmetric stretching (ν1) vibrations and appearance of new lattice vibrations in the Raman spectra of CaCO3-III and CaCO3-IIIb suggest a lowering in crystal symmetry during the transformation from CaCO3-II through CaCO3-IIIb to CaCO3-III, which is in good agreement with the observed sequence of phase symmetries.

Type
Article
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2018 

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Footnotes

Associate Editor: Koichi Momma

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