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Title: A classical view on nonclassical nucleation

Abstract

Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO 3 ) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO 3 nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the so-called nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid–liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO 3 in dilute aqueous solutions. We propose that a dense liquid phase (containing 4–7 H 2 O per CaCO 3 unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO 3 in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca 2+ + z CO 3 2− → z CaCO 3 . The results show that all steps in thismore » process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1378782
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 38; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Smeets, Paul J. M., Finney, Aaron R., Habraken, Wouter J. E. M., Nudelman, Fabio, Friedrich, Heiner, Laven, Jozua, De Yoreo, James J., Rodger, P. Mark, and Sommerdijk, Nico A. J. M. A classical view on nonclassical nucleation. United States: N. p., 2017. Web. doi:10.1073/pnas.1700342114.
Smeets, Paul J. M., Finney, Aaron R., Habraken, Wouter J. E. M., Nudelman, Fabio, Friedrich, Heiner, Laven, Jozua, De Yoreo, James J., Rodger, P. Mark, & Sommerdijk, Nico A. J. M. A classical view on nonclassical nucleation. United States. doi:10.1073/pnas.1700342114.
Smeets, Paul J. M., Finney, Aaron R., Habraken, Wouter J. E. M., Nudelman, Fabio, Friedrich, Heiner, Laven, Jozua, De Yoreo, James J., Rodger, P. Mark, and Sommerdijk, Nico A. J. M. Tue . "A classical view on nonclassical nucleation". United States. doi:10.1073/pnas.1700342114.
@article{osti_1378782,
title = {A classical view on nonclassical nucleation},
author = {Smeets, Paul J. M. and Finney, Aaron R. and Habraken, Wouter J. E. M. and Nudelman, Fabio and Friedrich, Heiner and Laven, Jozua and De Yoreo, James J. and Rodger, P. Mark and Sommerdijk, Nico A. J. M.},
abstractNote = {Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO 3 ) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO 3 nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the so-called nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid–liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO 3 in dilute aqueous solutions. We propose that a dense liquid phase (containing 4–7 H 2 O per CaCO 3 unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO 3 in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca 2+ + z CO 3 2− → z CaCO 3 . The results show that all steps in this process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms.},
doi = {10.1073/pnas.1700342114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 38,
volume = 114,
place = {United States},
year = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1073/pnas.1700342114

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Cited by: 18 works
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