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.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
White, S. R. et al. Autonomic healing of polymer composites. Nature 409, 794–797 (2001).
Trau, M., Saville, D. A. & Aksay, I. A. Assembly of colloidal crystals at electrode interfaces. Langmuir 13, 6375–6381 (1997).
Chen, X. X. et al. A thermally re-mendable cross-linked polymeric material. Science 295, 1698–1702 (2002).
Chiu, J. J., Kim, B. J., Kramer, E. J. & Pine, D. J. Control of nanoparticle location in block copolymers. J. Am. Chem. Soc. 127, 5036–5037 (2005).
Bockstaller, M. R. & Thomas, E. L. Proximity effects in self-organized binary particle-block copolymer blends. Phys. Rev. Lett. 93, 166106 (2004).
Buxton, G. A., Lee, J. Y. & Balazs, A. C. Computer simulation of morphologies and optical properties of filled diblock copolymers. Macromolecules 36, 9631–9637 (2003).
Thompson, R. B., Ginzburg, V. V., Matsen, M. W. & Balazs, A. C. Predicting the mesophases of copolymer-nanoparticle composites. Science 292, 2469–2472 (2001).
Lin, Y. et al. Self-directed self-assembly of nanoparticle/copolymer mixtures. Nature 434, 55–59 (2005).
Lee, J. Y., Shou, Z. & Balazs, A. C. Modeling the self-assembly of copolymer/nanoparticle mixtures confined between solid surfaces. Phys. Rev. Lett. 91, 136103–136107 (2003).
Lee, J. Y., Buxton, G. A. & Balazs, A. C. Using nanoparticles to create self-healing composites. J. Chem. Phys. 121, 5531–5540 (2004).
Tyagi, S., Lee, J. Y., Buxton, G. A. & Balazs, A. C. Using nanocomposite coatings to heal surface defects. Macromolecules 37, 9160–9168 (2004).
McGuigan, A. P., Briggs, G. A. D., Burlakov, V., Yanaka, M. & Tsukahara, Y. An elastic-plastic shear lag model for fracture of layered coatings. Thin Solid Films 424, 219–223 (2003).
Suo, Z., Prevost, J. H. & Liang, J. Kinetics of crack initiation and growth in organic-containing integrated structures. J. Mech. Phys. Solids 51, 2169–2190 (2003).
Ito, H., Russell, T. P. & Wignall, G. D. Interactions in mixtures of poly(ethylene oxide) and poly(methyl methacrylate). Macromolecules 20, 2213–2220 (1987).
Kim, J. U. & O’Shaughnessy, B. Morphology selection of nanoparticle dispersions by polymer media. Phys. Rev. Lett. 89, 238301 (2002).
Krausch, G. Dewetting at the interface between two immiscible polymers. J. Phys. Condens. Matter 9, 7741–7752 (1997).
Lin, Y. et al. Nanoparticle assembly at fluid interfaces: structure and dynamics. Langmuir 21, 191–194 (2005).
Chen, Y. F., Ji, T. H. & Rosenzweig, Z. Synthesis of glyconanospheres containing luminescent CdSe-ZnS quantum dots. Nano Lett. 3, 581–584 (2003).
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).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Rights and permissions
About this article
Cite this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nmat1582
This article is cited by
-
Hybrid inorganic-organic fluorescent silica nanoparticles—influence of dye binding modes on dye leaching
Journal of Sol-Gel Science and Technology (2023)
-
Balancing the film strain of organic semiconductors for ultrastable organic transistors with a five-year lifetime
Nature Communications (2022)
-
Evaluation of Self-Healing Performance and Mechanism Analysis of Nano-Montmorillonite-Modified Asphalt
International Journal of Pavement Research and Technology (2022)
-
Self-healing of electrical damage in polymers using superparamagnetic nanoparticles
Nature Nanotechnology (2019)
-
An unexpected N-dependence in the viscosity reduction in all-polymer nanocomposite
Nature Communications (2019)