A Molecular-Scale Understanding of Misorientation Toughening in Corals and Seashells

Andrew J Lew^{1

2}, Cayla A Stifler³, Alexandra Tits⁴, Connor A Schmidt^{3

5}, Andreas Scholl⁶, Astrid Cantamessa⁴, Laura Müller⁴, Yann Delaunois⁷, Philippe Compère⁷, Davide Ruffoni⁴, Markus J Buehler¹, Pupa U P A Gilbert^{3

5

8

9}

Affiliations

¹ Laboratory for Atomistic and Molecular Mechanics (LAMM), Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, 02139, USA.
² Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, 02139, USA.
³ Department of Physics, University of Wisconsin, Madison, WI, 53706, USA.
⁴ Mechanics of Biological and Bioinspired Materials Laboratory, Department of Aerospace and Mechanical Engineering, University of Liège, Liège, B-4000, Belgium.
⁵ Department of Chemistry, University of Wisconsin, Madison, WI, 53706, USA.
⁶ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁷ Laboratory of Functional and Evolutionary Morphology (FOCUS Research Unit) and Center for Applied Research and Education in Microscopy (CAREM), University of Liège, Liège, B-4000, Belgium.
⁸ Departments of Materials Science and Engineering, Geoscience, University of Wisconsin, Madison, WI, 53706, USA.
⁹ Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.

PMID: 36864010
DOI: 10.1002/adma.202300373

Free article

A Molecular-Scale Understanding of Misorientation Toughening in Corals and Seashells

Andrew J Lew et al. Adv Mater. 2023 Jul.

Free article

. 2023 Jul;35(28):e2300373.

doi: 10.1002/adma.202300373. Epub 2023 Apr 25.

Authors

Affiliations

¹ Laboratory for Atomistic and Molecular Mechanics (LAMM), Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, 02139, USA.
² Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, 02139, USA.
³ Department of Physics, University of Wisconsin, Madison, WI, 53706, USA.
⁴ Mechanics of Biological and Bioinspired Materials Laboratory, Department of Aerospace and Mechanical Engineering, University of Liège, Liège, B-4000, Belgium.
⁵ Department of Chemistry, University of Wisconsin, Madison, WI, 53706, USA.
⁶ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁷ Laboratory of Functional and Evolutionary Morphology (FOCUS Research Unit) and Center for Applied Research and Education in Microscopy (CAREM), University of Liège, Liège, B-4000, Belgium.
⁸ Departments of Materials Science and Engineering, Geoscience, University of Wisconsin, Madison, WI, 53706, USA.
⁹ Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.

PMID: 36864010
DOI: 10.1002/adma.202300373

Abstract

Biominerals are organic-mineral composites formed by living organisms. They are the hardest and toughest tissues in those organisms, are often polycrystalline, and their mesostructure (which includes nano- and microscale crystallite size, shape, arrangement, and orientation) can vary dramatically. Marine biominerals may be aragonite, vaterite, or calcite, all calcium carbonate (CaCO₃ ) polymorphs, differing in crystal structure. Unexpectedly, diverse CaCO₃ biominerals such as coral skeletons and nacre share a similar characteristic: Adjacent crystals are slightly misoriented. This observation is documented quantitatively at the micro- and nanoscales, using polarization-dependent imaging contrast mapping (PIC mapping), and the slight misorientations are consistently between 1° and 40°. Nanoindentation shows that both polycrystalline biominerals and abiotic synthetic spherulites are tougher than single-crystalline geologic aragonite. Molecular dynamics (MD) simulations of bicrystals at the molecular scale reveal that aragonite, vaterite, and calcite exhibit toughness maxima when the bicrystals are misoriented by 10°, 20°, and 30°, respectively, demonstrating that slight misorientation alone can increase fracture toughness. Slight-misorientation-toughening can be harnessed for synthesis of bioinspired materials that only require one material, are not limited to specific top-down architecture, and are easily achieved by self-assembly of organic molecules (e.g., aspirin, chocolate), polymers, metals, and ceramics well beyond biominerals.

Keywords: crystal misorientation; nacre; nanoindentation; synthetic spherulites; toughening.

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References

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A Molecular-Scale Understanding of Misorientation Toughening in Corals and Seashells

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A Molecular-Scale Understanding of Misorientation Toughening in Corals and Seashells

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