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Formation and structure of calcium carbonate thin films and nanofibers precipitated in the presence of poly(allylamine hydrochloride) and magnesium ions

Paunov, Vesselin N.; Cantaert, Bram; Kim, Yi Yeoun; Kröger, Roland; Ludwig, Henning; Meldrum, Fiona C.; Verch, Andreas

Authors

Bram Cantaert

Yi Yeoun Kim

Roland Kröger

Henning Ludwig

Fiona C. Meldrum

Andreas Verch

Abstract

That the cationic polyelectrolyte poly(allylamine hydrochloride) (PAH) exerts a significant influence on CaCO₃ precipitation challenges the idea that only anionic additives have this effect. Here, we show that in common with anionic polyelectrolytes such as poly(aspartic acid), PAH supports the growth of calcite thin films and abundant nanofibers. While investigating the formation of these structures, we also perform the first detailed structural analysis of the nanofibers by transmission electron microscopy (TEM) and selected area electron diffraction. The nanofibers are shown to be principally single crystal, with isolated domains of polycrystallinity, and the single crystal structure is even preserved in regions where the nanofibers dramatically change direction. The formation mechanism of the fibers, which are often hundreds of micrometers long, has been the subject of intense speculation. Our results suggest that they form by aggregation of amorphous particles, which are incorporated into the fibers uniquely at their tips, before crystallizing. Extrusion of polymer during crystallization may inhibit particle addition at the fiber walls and result in local variations in the fiber nanostructure. Finally, we investigate the influence of Mg²+ on CaCO₃ precipitation in the presence of PAH, which gives thinner and smoother films, together with fibers with more polycrystalline, granular structures.

Journal Article Type Article
Publication Date Dec 23, 2013
Journal Chemistry of materials
Print ISSN 0897-4756
Electronic ISSN 1520-5002
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 25
Issue 24
Pages 4994-5003
Institution Citation Paunov, V. N., Cantaert, B., Kim, Y. Y., Kröger, R., Ludwig, H., Meldrum, F. C., & Verch, A. (2013). Formation and structure of calcium carbonate thin films and nanofibers precipitated in the presence of poly(allylamine hydrochloride) and magnesium ions. Chemistry of materials : a publication of the American Chemical Society, 25(24), 4994-5003. https://doi.org/10.1021/cm403497g
DOI https://doi.org/10.1021/cm403497g
Keywords Calcite, Crystallization, Nanowire, PILP, Bioinspired, TEM
Publisher URL http://pubs.acs.org/doi/abs/10.1021/cm403497g
Copyright Statement Creative Commons Attribution 4.0 International Public License
Additional Information Copy of article first published in: Chemistry of materials, 2013, v.25, issue 24

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Copyright Statement
Creative Commons Attribution 4.0 International Public License



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