Gel-mediated chemo-mechanical control of calcium carbonate crystal formation

Damian Palin*, Jennie A.M.R. Kunitake, Marina P. Chang, Stephan Sutter, Lara A. Estroff

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

1 Citation (Scopus)
14 Downloads (Pure)

Abstract

The production of synthetic crystals with controlled shapes and properties is an enticing prospect, yet, the production of such materials is an ongoing challenge. Here, we present a strategy for chemo-mechanically directing the growth of crystals with non-equilibrium structures using a custom-designed double-diffusion cell. We combine chemical additives (e.g., Mg2+ ions) and mechanical confinement (e.g., hydrogel networks) to modulate the growth of calcium carbonate crystals. Specifically, the combination of Mg2+ ions with a strong agarose gel results in calcitic structures, at the gel-glass slide interface, with distinct fried egg-like morphologies and radial or Maltese-cross extinction patterns. In contrast, precipitation with only Mg2+ or agarose results in aragonite spherulites or squished calcite rhombohedra, respectively. Raman spectroscopy and energy dispersive spectroscopy of the “fried eggs” reveals that they are composed of Mg-calcite, which becomes less disordered over time, and the “egg whites” make this transition before the “yolks”. We propose that the “fried eggs” form due to a spherulitic growth process molded by the crystallization-induced delamination of the gel away from the glass slide at the gel-glass interface. In support of the importance of the gel-glass interface, the “fried eggs” do not form when the glass slide is treated with a hydrophobic silane, suppressing heterogeneous nucleation and weakening the interfacial adhesion between the gel and glass, making it easier for the gel to delaminate, thus reducing the confinement effect. As such, this work highlights the important chemo-mechanical role that gel environments can play in crystal formation.

Original languageEnglish
Article number126943
JournalJournal of Crystal Growth
Volume602
DOIs
Publication statusPublished - 2023

Bibliographical note

Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.

Keywords

  • A1. Biocrystallization
  • A1. Crystal morphology
  • A1. Impurities
  • A2. Growth from solution
  • B1. Calcium compounds
  • B1. Minerals

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