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Title: Disordered amorphous calcium carbonate from direct precipitation

Abstract

Amorphous calcium carbonate (ACC) is known to play a prominent role in biomineralization. Different studies on the structure of biogenic ACCs have illustrated that they can have distinct short-range orders. However, the origin of so-called proto-structures in synthetic and additive-free ACCs is not well understood. In the current work, ACC has been synthesised in iso-propanolic media by direct precipitation from ionic precursors, and analysed utilising a range of different techniques. The data suggest that this additive-free type of ACC does not resemble clear proto-structural motifs relating to any crystalline polymorph. This can be explained by the undefined pH value in iso-propanolic media, and the virtually instantaneous precipitation. Altogether, this work suggests that aqueous systems and pathways involving pre-nucleation clusters are required for the generation of clear proto-structural features in ACC. Experiments on the ACC-to-crystalline transformation in solution with and without ethanol highlight that polymorph selection is under kinetic control, while the presence of ethanol can control dissolution re-crystallisation pathways.

Authors:
 [1];  [2];  [1];  [1];  [2];  [3];  [1]
  1. Univ. of Konstanz (Germany)
  2. Dalhousie Univ. (Canada)
  3. Stockholm Univ. (Sweden)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1214327
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
CrystEngComm (Online)
Additional Journal Information:
Journal Name: CrystEngComm (Online); Journal Volume: 17; Journal Issue: 26; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Farhadi Khouzani, Masoud, Chevrier, Daniel M., Güttlein, Patricia, Hauser, Karin, Zhang, Peng, Hedin, Niklas, and Gebauer, Denis. Disordered amorphous calcium carbonate from direct precipitation. United States: N. p., 2015. Web. doi:10.1039/C5CE00720H.
Farhadi Khouzani, Masoud, Chevrier, Daniel M., Güttlein, Patricia, Hauser, Karin, Zhang, Peng, Hedin, Niklas, & Gebauer, Denis. Disordered amorphous calcium carbonate from direct precipitation. United States. doi:10.1039/C5CE00720H.
Farhadi Khouzani, Masoud, Chevrier, Daniel M., Güttlein, Patricia, Hauser, Karin, Zhang, Peng, Hedin, Niklas, and Gebauer, Denis. Mon . "Disordered amorphous calcium carbonate from direct precipitation". United States. doi:10.1039/C5CE00720H. https://www.osti.gov/servlets/purl/1214327.
@article{osti_1214327,
title = {Disordered amorphous calcium carbonate from direct precipitation},
author = {Farhadi Khouzani, Masoud and Chevrier, Daniel M. and Güttlein, Patricia and Hauser, Karin and Zhang, Peng and Hedin, Niklas and Gebauer, Denis},
abstractNote = {Amorphous calcium carbonate (ACC) is known to play a prominent role in biomineralization. Different studies on the structure of biogenic ACCs have illustrated that they can have distinct short-range orders. However, the origin of so-called proto-structures in synthetic and additive-free ACCs is not well understood. In the current work, ACC has been synthesised in iso-propanolic media by direct precipitation from ionic precursors, and analysed utilising a range of different techniques. The data suggest that this additive-free type of ACC does not resemble clear proto-structural motifs relating to any crystalline polymorph. This can be explained by the undefined pH value in iso-propanolic media, and the virtually instantaneous precipitation. Altogether, this work suggests that aqueous systems and pathways involving pre-nucleation clusters are required for the generation of clear proto-structural features in ACC. Experiments on the ACC-to-crystalline transformation in solution with and without ethanol highlight that polymorph selection is under kinetic control, while the presence of ethanol can control dissolution re-crystallisation pathways.},
doi = {10.1039/C5CE00720H},
journal = {CrystEngComm (Online)},
number = 26,
volume = 17,
place = {United States},
year = {2015},
month = {6}
}

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