Structure and properties of nanocomposites formed by the occlusion of block copolymer worms and vesicles within calcite crystals

DOI: 10.1002/adfm.201504292

Authors: Yi-Yeoun Kim (University of Leeds) , Mona Semsarilar (The University Of Sheffield) , Joseph D. Carloni (Cornell University) , Kang Rae Cho (Lawrence Berkeley National Laboratory) , Alexander N. Kulak (University of Leeds) , Iryna Polishchuk (Israel Institute of Technology) , Coit T. Hendley (Cornell University) , Paul J. M. Smeets (Lawrence Berkeley National Laboratory) , Lee Fielding (University of Sheffield) , Boaz Pokroy (Israel Institute of Technology) , Chiu C. Tang (Israel Institute of Technology) , Lara A. Estroff (Cornell University) , Shefford P. Baker (Cornell University) , Steven P. Armes (The University Of Sheffield) , Fiona Meldrum (University of Leeds)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Advanced Functional Materials , VOL 26 (9) , PAGES 1382 - 1392

State: Published (Approved)
Published: March 2016

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.

Subject Areas: Materials


Instruments: I11-High Resolution Powder Diffraction

Added On: 02/03/2016 12:17

Discipline Tags:

Materials Science Nanoscience/Nanotechnology Polymer Science

Technical Tags:

Diffraction X-ray Powder Diffraction