Abstract
Finding a synthetic pathway to artificial analogs of nacre and bones represents a fundamental milestone in the development of composite materials. The ordered brick-and-mortar arrangement of organic and inorganic layers is believed to be the most essential strength- and toughness-determining structural feature of nacre. It has also been found that the ionic crosslinking of tightly folded macromolecules is equally important. Here, we demonstrate that both structural features can be reproduced by sequential deposition of polyelectrolytes and clays. This simple process results in a nanoscale version of nacre with alternating organic and inorganic layers. The macromolecular folding effect reveals itself in the unique saw-tooth pattern of differential stretching curves attributed to the gradual breakage of ionic crosslinks in polyelectrolyte chains. The tensile strength of the prepared multilayers approached that of nacre, whereas their ultimate Young modulus was similar to that of lamellar bones. Structural and functional resemblance makes clay– polyelectrolyte multilayers a close replica of natural biocomposites. Their nanoscale nature enables elucidation of molecular processes occurring under stress.
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Acknowledgements
N.A.K. thanks the financial support of this project from the National Science Foundation (NSF) CAREER, NSF-Biophotonics, Air Force Office of Scientific Research (AFOSR), Oklahoma Center for Advancement of Science and Technology (OCAST) and Nomadics. The authors are grateful to Arif Mamedov (Nomadics) for LBL consultations, R. Ruoff, F. Fisher, and P. Messersmith (Northwestern University) for helpful critical suggestions and to Phoebe Doss (Oklahoma State University) for assistance with TEM and SEM.
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Figure S1 Effect of delaminating agent on the structure of the multilayers.
Figure S2 Optical microphotograph of the broken edge in (P/C)100 film. (PDF 1811 kb)
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Tang, Z., Kotov, N., Magonov, S. et al. Nanostructured artificial nacre. Nature Mater 2, 413–418 (2003). https://doi.org/10.1038/nmat906
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DOI: https://doi.org/10.1038/nmat906
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