Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate

Calcium carbonate is a ubiquitous mineral that represents one of the most significant biominerals,a major contributor to carbon sequestration through geological deposits, and a technological hindrance as a result of scale formation. Amorphous calcium carbonate is intimately involved in the nucleatio...

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Main Authors: Raiteri, Paolo, Gale, Julian
Format: Journal Article
Published: The American Chemical Society 2010
Online Access:http://hdl.handle.net/20.500.11937/46049
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author Raiteri, Paolo
Gale, Julian
author_facet Raiteri, Paolo
Gale, Julian
author_sort Raiteri, Paolo
building Curtin Institutional Repository
collection Online Access
description Calcium carbonate is a ubiquitous mineral that represents one of the most significant biominerals,a major contributor to carbon sequestration through geological deposits, and a technological hindrance as a result of scale formation. Amorphous calcium carbonate is intimately involved in the nucleation and growth of this material, yet much remains undiscovered regarding the atomic detail. Through dynamical simulation we demonstrate that nucleation of amorphous calcium carbonate follows a nonclassical pathway. This arises from the addition of ion pairs to clusters exhibiting a consistently exothermic free energy that persists with increasing particle size. Furthermore, the disruption of the surrounding water of solvation by the atomically rough surface reduces the barrier to growth to the order of ambient thermal energy, thereby allowing the amorphous phase to grow faster than crystalline polymorphs. Amorphous calcium carbonate nanoparticles are also found to exploit size-dependent water content to render itself more stable than the favored bulk phase, calcite, below a critical diameter of close to 4 nm.
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spelling curtin-20.500.11937-460492017-09-13T15:51:04Z Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate Raiteri, Paolo Gale, Julian Calcium carbonate is a ubiquitous mineral that represents one of the most significant biominerals,a major contributor to carbon sequestration through geological deposits, and a technological hindrance as a result of scale formation. Amorphous calcium carbonate is intimately involved in the nucleation and growth of this material, yet much remains undiscovered regarding the atomic detail. Through dynamical simulation we demonstrate that nucleation of amorphous calcium carbonate follows a nonclassical pathway. This arises from the addition of ion pairs to clusters exhibiting a consistently exothermic free energy that persists with increasing particle size. Furthermore, the disruption of the surrounding water of solvation by the atomically rough surface reduces the barrier to growth to the order of ambient thermal energy, thereby allowing the amorphous phase to grow faster than crystalline polymorphs. Amorphous calcium carbonate nanoparticles are also found to exploit size-dependent water content to render itself more stable than the favored bulk phase, calcite, below a critical diameter of close to 4 nm. 2010 Journal Article http://hdl.handle.net/20.500.11937/46049 10.1021/ja108508k The American Chemical Society restricted
spellingShingle Raiteri, Paolo
Gale, Julian
Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate
title Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate
title_full Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate
title_fullStr Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate
title_full_unstemmed Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate
title_short Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate
title_sort water is the key to nonclassical nucleation of amorphous calcium carbonate
url http://hdl.handle.net/20.500.11937/46049