Structure and Properties of Nanocomposites Formed by the Occlusion of Block Copolymer Worms and Vesicles Within Calcite Crystals |
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Authors: | Yi‐Yeoun Kim Mona Semsarilar Joseph D. Carloni Kang Rae Cho Alexander N. Kulak Iryna Polishchuk Coit T. Hendley IV Paul J. M. Smeets Boaz Pokroy Chiu C. Tang Lara A. Estroff Shefford P. Baker Steven P. Armes Fiona C. Meldrum |
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Affiliation: | 1. School of Chemistry, University of Leeds, Leeds, UK;2. Department of Chemistry, The University Of Sheffield, Sheffield, UK;3. Department of Materials Science and Engineering, Cornell University, Ithaca, NY, USA;4. Kavli Institute for Nanoscale Science, Physical Sciences Building, Cornell University, Ithaca, NY, USA;5. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA;6. Department of Materials Science and Engineering and the Russell Berrie Nanotechnology Institute Technion, Israel Institute of Technology, Haifa, Israel;7. Diamond Light Source, Harwell Science and Innovation Campus, Didcot, UK |
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Abstract: | This article describes an experimentally versatile strategy for producing inorganic/organic nanocomposites, with control over the microstructure at the nano‐ and mesoscales. Taking inspiration from biominerals, CaCO3 is coprecipitated with anionic diblock copolymer worms or vesicles to produce single crystals of calcite occluding a high density of the organic component. This approach can also be extended to generate complex structures in which the crystals are internally patterned with nano‐objects of differing morphologies. Extensive characterization of the nanocomposite crystals using high resolution synchrotron powder X‐ray diffraction and vibrational spectroscopy demonstrates how the occlusions affect the short and long‐range order of the crystal lattice. By comparison with nanocomposite crystals containing latex particles and copolymer micelles, it is shown that the effect of these occlusions on the crystal lattice is dominated by the interface between the inorganic crystal and the organic nano‐objects, rather than the occlusion size. This is supported by in situ atomic force microscopy studies of worm occlusion in calcite, which reveal flattening of the copolymer worms on the crystal surface, followed by burial and void formation. Finally, the mechanical properties of the nanocomposite crystals are determined using nanoindentation techniques, which reveal that they have hardnesses approaching those of biogenic calcites. |
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Keywords: | bioinspired block‐copolymers calcium carbonate crystallization nanocomposites, biominerals, calcite |
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