Forming Anisotropic Crystal Composites: Assessing the Mechanical Translation of Gel Network Anisotropy to Calcite Crystal Form

Palin, D.; Style, Robert W.; Zlopasa, J.; Petrozzini, Jonathan J.; Pfeifer, Mark A.; Jonkers, H.M.; Dufresne, Eric R.; Estroff, Lara A.

doi:10.1021/jacs.0c12326

Forming Anisotropic Crystal Composites: Assessing the Mechanical Translation of Gel Network Anisotropy to Calcite Crystal Form

Title

Forming Anisotropic Crystal Composites: Assessing the Mechanical Translation of Gel Network Anisotropy to Calcite Crystal Form

Author

Palin, D. (TU Delft Materials and Environment; Cornell University)
Style, Robert W. (ETH Zürich)
Zlopasa, J. (TU Delft BT/Environmental Biotechnology)
Petrozzini, Jonathan J. (Cornell University)
Pfeifer, Mark A. (Cornell University)
Jonkers, H.M. (TU Delft Materials and Environment)
Dufresne, Eric R. (ETH Zürich)
Estroff, Lara A. (Cornell University; Kavli Institute at Cornell University)

Date

2021

Abstract

The promise of crystal composites with direction-specific properties is an attractive prospect for diverse applications; however, synthetic strategies for realizing such composites remain elusive. Here, we demonstrate that anisotropic agarose gel networks can mechanically "mold" calcite crystal growth, yielding anisotropically structured, single-crystal composites. Drying and rehydration of agarose gel films result in the affine deformation of their fibrous networks to yield fiber alignment parallel to the drying plane. Precipitation of calcium carbonate within these anisotropic networks results in the formation of calcite crystal composite disks oriented parallel to the fibers. The morphology of the disks, revealed by nanocomputed tomography imaging, evolves with time and can be described by linear-elastic fracture mechanics theory, which depends on the ratio between the length of the crystal and the elastoadhesive length of the gel. Precipitation of calcite in uniaxially deformed agarose gel cylinders results in the formation of rice-grain-shaped crystals, suggesting the broad applicability of the approach. These results demonstrate how the anisotropy of compliant networks can translate into the desired crystal composite morphologies. This work highlights the important role organic matrices can play in mechanically "molding" biominerals and provides an exciting platform for fabricating crystal composites with direction-specific and emergent functional properties.

Subject

Crystals
Crystallization
Composites
Deformation
Calcite

To reference this document use:

http://resolver.tudelft.nl/uuid:1a170bbb-ff55-4d08-abfa-e9000a11a3c4

DOI

https://doi.org/10.1021/jacs.0c12326

Embargo date

2022-03-01

ISSN

0002-7863

Source

Journal of the American Chemical Society, 143 (9), 3439-3447