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Title: Surface Wetting Controls Calcium Carbonate Crystallization Kinetics

Abstract

Because of the widespread presence of foreign substrates in natural settings, mineral precipitation usually occurs via heterogeneous nucleation. This process is controlled by the interplay between the fluid supersaturation and interfacial energies present between the fluid, nucleus, and substrate. Among a number of physicochemical parameters, the surface wetting properties have been shown to be a key parameter controlling heterogeneous nucleation. The present study aims at elucidating the pathway and kinetics of CaCO 3 heterogeneous nucleation on a set of phlogopite micas with and without fluorine/hydroxyl substitutions, yielding substrates with contrasting hydrophilicity. Our results show that, irrespective of surface wetting properties, amorphous calcium carbonate (ACC) is formed during the early stages. The surface wetting properties have a strong effect on the crystallization kinetics: ACC precipitates persist longer on the hydrophilic (hydroxylated) surface than on the less hydrophilic (fluorinated) one. We show that this stabilization could have a thermodynamic origin because of the lower interfacial free energy between the hydrated amorphous precursor and the hydrophilic substrate. Furthermore, these results are highly relevant for biomineralization studies, where differences in wetting properties of organic moieties present in calcifying organisms could be used to accelerate or decelerate the crystallization of the initially formed amorphous precursormore » phase.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [4];  [4]; ORCiD logo [5];  [2]
  1. Univ. Grenoble Alpes, Grenoble (France); Princeton Univ., Princeton, NJ (United States)
  2. Univ. Grenoble Alpes, Grenoble (France)
  3. CNRS−Sorbonne Univ.−UPMC UMR 8234, Paris (France)
  4. Univ. Complutense de Madrid, Madrid (Spain); Instituto de Geociencias (UCM-CSIC), Madrid (Spain)
  5. Advanced Photon Source, Argonne National Laboratory, Argonne, 60439 Illinois, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Centre National de la Recherche Scientifique (CNRS); USDOE
OSTI Identifier:
1526694
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 9; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Koishi, Ayumi, Fernandez-Martinez, Alejandro, Van Driessche, Alexander E. S., Michot, Laurent J., Pina, Carlos M., Pimentel, Carlos, Lee, Byeongdu, and Montes-Hernandez, German. Surface Wetting Controls Calcium Carbonate Crystallization Kinetics. United States: N. p., 2019. Web. doi:10.1021/acs.chemmater.9b00417.
Koishi, Ayumi, Fernandez-Martinez, Alejandro, Van Driessche, Alexander E. S., Michot, Laurent J., Pina, Carlos M., Pimentel, Carlos, Lee, Byeongdu, & Montes-Hernandez, German. Surface Wetting Controls Calcium Carbonate Crystallization Kinetics. United States. doi:10.1021/acs.chemmater.9b00417.
Koishi, Ayumi, Fernandez-Martinez, Alejandro, Van Driessche, Alexander E. S., Michot, Laurent J., Pina, Carlos M., Pimentel, Carlos, Lee, Byeongdu, and Montes-Hernandez, German. Wed . "Surface Wetting Controls Calcium Carbonate Crystallization Kinetics". United States. doi:10.1021/acs.chemmater.9b00417.
@article{osti_1526694,
title = {Surface Wetting Controls Calcium Carbonate Crystallization Kinetics},
author = {Koishi, Ayumi and Fernandez-Martinez, Alejandro and Van Driessche, Alexander E. S. and Michot, Laurent J. and Pina, Carlos M. and Pimentel, Carlos and Lee, Byeongdu and Montes-Hernandez, German},
abstractNote = {Because of the widespread presence of foreign substrates in natural settings, mineral precipitation usually occurs via heterogeneous nucleation. This process is controlled by the interplay between the fluid supersaturation and interfacial energies present between the fluid, nucleus, and substrate. Among a number of physicochemical parameters, the surface wetting properties have been shown to be a key parameter controlling heterogeneous nucleation. The present study aims at elucidating the pathway and kinetics of CaCO3 heterogeneous nucleation on a set of phlogopite micas with and without fluorine/hydroxyl substitutions, yielding substrates with contrasting hydrophilicity. Our results show that, irrespective of surface wetting properties, amorphous calcium carbonate (ACC) is formed during the early stages. The surface wetting properties have a strong effect on the crystallization kinetics: ACC precipitates persist longer on the hydrophilic (hydroxylated) surface than on the less hydrophilic (fluorinated) one. We show that this stabilization could have a thermodynamic origin because of the lower interfacial free energy between the hydrated amorphous precursor and the hydrophilic substrate. Furthermore, these results are highly relevant for biomineralization studies, where differences in wetting properties of organic moieties present in calcifying organisms could be used to accelerate or decelerate the crystallization of the initially formed amorphous precursor phase.},
doi = {10.1021/acs.chemmater.9b00417},
journal = {Chemistry of Materials},
number = 9,
volume = 31,
place = {United States},
year = {2019},
month = {4}
}

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This content will become publicly available on April 24, 2020
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