Abstract
Structural characterization at the nanometric scale of the Nautilus sp shell was carried out by high-resolution transmission electron microscopy and high-angle annular dark field to understand how the organic and inorganic components are related. The inorganic phase that built the shell is made of calcium carbonate (CaCO3), with the orthorhombic unit cell of the aragonite, in a texturized arrangement in such a way that the c-axis is always perpendicular to the shell surface. The organic material forms films through the plates. We observed for a very first time some aragonite nanocrystals embedded in the organic matrix. This observation supports the hypothesis that the proteins and other organic compounds guide the crystal growth because the organic matrixes are the places where the nanocrystals grow.
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J. Wang, Y. Xu, Y. Zhao, Y. Huang, D. Wang, L. Jiang, J. Wu, D. Xu: Morphology and crystalline characterization of abalone shell and mimetic mineralization. J. Cryst. Growth 252, 367 (2003).
A. Lin, M. Andre: Growth and structure in abalone shell. Mater. Sci. Eng. A 390, 27 (2005).
H. Tsuno, H. Kagi, T. Akagi: Effects of trace lanthanum ion on the stability of vaterite and transformation from vaterite to calcite in an aquatic system. Bull. Chem. Soc. Jpn. 74, 479 (2001).
C.M. Zaremba, A.M. Belcher, M. Fritz, Y. Li, S. Mann, P.K. Hansma, D.E. Morse, J.S. Speck, G.D. Stucky: Critical transitions in the biofabrication of abalone shell and flat pearls. Chem. Mater. 8, 679 (1996).
K. Wada: Nucleation and growth of aragonite crystals in the nacre of some bivalve molluscs. Biomineralization 6, 141 (1972).
S.W. Wise: Microarchitecture and mode of formation of nacre (mother of pearl) in Pelecypods. Gastropods Cephalopods Eclogae Geol Helv. 63, 775 (1970).
M. Rousseau, E. Lopez, P. Stempflé, M. Brendlé, L. Franke, A. Guette, R. Naslai, X. Bourrat: Multiscale structure of sheet nacre. Biomaterials 26, 6254 (2005).
A.G. Checa, Rodriguez-A.B. Navarro: Self organization of nacre in the shell of Pterioida (Bivalvia: Mollusca). Biomaterials 26, 1071 (2005).
L. Addadi, S. Weiner: Biomineralization: Chemical and Biochemical Perspectives (VCH, New York, 1989).
E.M. Greenfield, M.A. Chrenshaw: Origin, Evolution and Modern Aspects of Biomineralization in Plants and Animals (Plenum Press, New York, 1989) pp. 303–308.
M. Fritz, A.M. Belcher, M. Radmacher, D.A. Walters, P.K. Hansma, G.D. Stucky, D.E. Morse, S. Mann: Flat pearls from biofabrication of organized composites on inorganic substrates. Nature 371, 49 (1994).
A.M. Belcher, X.H. Wu, R.J. Christensen, P.K. Hansma, G.D. Stucky, D.E. Morse: Control of crystal phase switching and orientation by soluble mollusc-shell proteins. Nature 381, 56 (1996).
L. Addadi, S. Weiner: A pavement of pearl. Nature 389, 912 (1997).
D.J. Bevan, E. Rossmanith, D.K. Mylrea, S.E. Ness, M.R. Tylor, C. Cuff: On the structure of aragonite: Lawrence Bragg revisited. Acta Cryst. B 58, 448 (2002).
F. Song, X.H. Zhang, Y.L. Bai: Microstructure and characterization in the organic matrix layers of nacre. J. Mater. Res. 17, 1567 (2002).
Z. Zhu, H. Tong, Y. Ren, J. Hu: Meretrix lusoria: A natural biocomposite: In situ analysis of hierarchical fabrication and micro-hardness. J. Mater. Res. 37, 35 (2006).
J. Aizenberg, S. Albeck, S. Weiner, L. Addadi: Crystal-protein interactions studied by overgrowth of calcite on biogenic skeletal elements. J. Cryst. Growth 142, 156 (1994).
K. Gunnison, M. Sarikaya, J. Liu, and I.A. Aksay: Structure-mechanical property relationships in a biological ceramic-polymer composite: Nacre, in Hierarchically Structured Materials edited by I.A. Aksay, E. Baer, M. Sarikaya, and D.A. Tirrell (Mater. Res. Soc. Symp. Proc. 255, Pittsburgh, PA, 1992) pp. 171–183.
K.M. Towe, G.H. Hamilton: Ultrastructure and inferred calcification of the mature and developing nacre in bivalve mollusk. Calcif. Tissue Res. 1, 306 (1968).
L. Wang, R. Tang, T. Bonstein, C.A. Orme, P.J. Bush, G.H. Nancollas: A new model for nanoscale enamel dissolution. J. Phys. Chem. B 109, 999 (2005).
C. Liu, R.D. Twesten, M. Gibson: High-angle annular dark-field imaging of self-assembled Ge islands on Si (001). Ultramicroscopy 87, 79 (2001).
A. Howie, L.D. Marks, S.J. Pennycook: New imaging methods for catalyst particles. Ultramicroscopy 8, 163 (1992).
N.D. Browning, D.J. Wallis, P.D. Nellist, S.J. Pennycook: EELS in the STEM: Determination of materials properties on the atomic scale. Micron 28, 333 (1997).
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Velázquez-Castillo, R., Reyes-Gasga, J., García-Gutierrez, D.I. et al. Nanoscale characterization of nautilus shell structure: An example of natural self-assembly. Journal of Materials Research 21, 1484–1489 (2006). https://doi.org/10.1557/jmr.2006.0190
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DOI: https://doi.org/10.1557/jmr.2006.0190