[en] 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.
Disciplines :
Engineering, computing & technology: Multidisciplinary, general & others
Author, co-author :
Lew, Andrew J; Laboratory for Atomistic and Molecular Mechanics (LAMM), Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, 02139, USA ; Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, 02139, USA
Stifler, Cayla A; Department of Physics, University of Wisconsin, Madison, WI, 53706, USA
Tits, Alexandra ; Université de Liège - ULiège > Aérospatiale et Mécanique (A&M)
Schmidt, Connor A; Department of Physics, University of Wisconsin, Madison, WI, 53706, USA ; Department of Chemistry, University of Wisconsin, Madison, WI, 53706, USA
Scholl, Andreas; Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA
Cantamessa, Astrid ; Université de Liège - ULiège > Aérospatiale et Mécanique (A&M)
Müller, Laura ; Université de Liège - ULiège > Aérospatiale et Mécanique (A&M)
Delaunois, Yann ; Université de Liège - ULiège > Freshwater and OCeanic science Unit of reSearch (FOCUS)
Compère, Philippe ; Université de Liège - ULiège > Département de Biologie, Ecologie et Evolution
Ruffoni, Davide ; Université de Liège - ULiège > Département d'aérospatiale et mécanique > Mécanique des matériaux biologiques et bioinspirés
Buehler, Markus J; Laboratory for Atomistic and Molecular Mechanics (LAMM), Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, 02139, USA
Gilbert, Pupa U P A ; Department of Physics, University of Wisconsin, Madison, WI, 53706, USA ; Department of Chemistry, University of Wisconsin, Madison, WI, 53706, USA ; Departments of Materials Science and Engineering, Geoscience, University of Wisconsin, Madison, WI, 53706, USA ; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA
Language :
English
Title :
A Molecular-Scale Understanding of Misorientation Toughening in Corals and Seashells.
ONR - Office of Naval Research ARO - Army Research Office NSF - National Science Foundation
Funding text :
The authors thank Andrew H. Knoll for discussions, Tali Mass for providing the coral skeleton, Noa Shenkar for providing the tunicate ascidians from the Steinhardt Museum of Natural History, Tel‐Aviv, Israel, Corinne Myers, Neil Landman, and Bushra M. Hussaini for providing the fossil shell from the American Museum of Natural History, New York, NY, USA. The authors are grateful to Shahrouz Amini for his expert advice on how to do toughness measurements and for his critical reading of the manuscript. The authors thank Nobumichi Tamura for providing precise xyz coordinates of atoms, unit cell dimensions, and angles for aragonite, vaterite, and calcite for the MD simulations, and Rajesh V. Chopdekar and Roland Koch for technical assistance during beamtime on PEEM‐3 at ALS. The authors would like to thank U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, under Awards DE‐FG02‐07ER15899 and FWP‐FP00011135 under Contract no. DE‐AC02‐05CH11231 (40% and 40%), NSF grants DMR‐1603192 and 2220274 (10% and 10%) (P.U.P.A.G.), Office of Naval Research grants N000141612333 and N000141912375, AFOSR‐MURI grant FA9550‐15‐1‐0514, Army Research Office grant W911NF1920098 (M.J.B. and A.J.L.), FNRS – FRIA (Fund for Scientific Research) (D.R., A.T., A.C., Y.D., and L.M.), NSF GRFP under Grant No. 1122374 (A.J.L.). PEEM experiments were done at the Advanced Light Source (ALS), which is supported by the Director, Office of Science, Office of Basic Energy Sciences, US Department of Energy under Contract No. DE‐AC02‐05CH11231. Stylophora pistillata Herdmania momus
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