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Entropy-driven segregation of nanoparticles to cracks in multilayered composite polymer structures

Abstract

Multilayer composites, which combine ductile polymers with brittle films, constitute vital components for optical communications, microelectronics and bio-engineering applications. However, crack formation is a critical problem in these materials; thus, designing layered systems that can respond to environmental changes and undergo self-healing is particularly important for a range of technologies. Here, nanoparticles dispersed in a polymer matrix were found to migrate to a crack generated at the interface between the polymer and a glassy layer. Segregation of the nanoparticles to the crack depended on both the enthalpic and entropic interactions between the polymer and nanoparticles. In particular, poly(ethylene oxide)-covered 5.2-nm spherical nanoparticles in a poly(methyl methacrylate) matrix diffused to cracks in the adjoining silicon oxide layer, whereas tri-n-octylphosphine oxide-covered nanoparticles did not. These results point to a simple means of fabricating systems that can self-heal, improving the durability of multilayered systems, or form the basis for auto-responsive materials.

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Figure 1
Figure 2: Cracks in 500-nm-thick SiOx layer on PMMA/TOPO-covered 3.8-nm CdSe/ZnS nanoparticles.
Figure 3: TEM images of the cross-section of nanoparticle/PMMA composite films.
Figure 4: Fluorescence microscope image of a crack in a 60 nm SiOx layer on a mixture of PMMA with PEO-covered 3.8-nm-diameter CdSe/ZnS nanoparticles.
Figure 5: Plot of the fluorescence intensity in cracks as a function of time for 3 nm (circle) and 5.2 nm diameter (square) PEO-covered CdSe nanoparticles at 140  C.

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Acknowledgements

This work was supported by the DOE (DE-FG-02-96ER45), the NSF supported MRSEC at the University of Massachusetts Amherst (DMR 9400488), the Army Research Laboratory through the MURI program, and the Army Research Office (W911NF041 0233).

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Correspondence to Todd Emrick or Thomas P. Russell.

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Gupta, S., Zhang, Q., Emrick, T. et al. Entropy-driven segregation of nanoparticles to cracks in multilayered composite polymer structures. Nature Mater 5, 229–233 (2006). https://doi.org/10.1038/nmat1582

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