Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications1. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content2,3,4,5,6,7,8,9,10,11. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer–particle interactions. An unprecedented shift in glass transition temperature of over 40 °C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 °C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet– poly(methyl methacrylate) rivaling those for single-walled carbon nanotube–poly(methyl methacrylate) composites.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Keller, T. Recent all-composite and hybrid fiber reinforced polymer bridges and buildings. Prog. Struct. Eng. Mater. 3, 132–140 (2001).
Ajayan, P. M., Schadler, L. S., Giannaris, C. & Rubio, A. Single-walled carbon nanotube–polymer composites: Strength and weakness. Adv. Mater. 12, 750–753 (2000).
Thostenson, E. T., Ren, Z. F. & Chou, T. W. Advances in the science and technology of carbon nanotubes and their composites: a review. Comp. Sci. Tech. 61, 1899–1912 (2001).
Zheng, W. & Wong, S. C. Electrical conductivity and dielectric properties of PMMA/expanded graphite composites. Comp. Sci. Tech. 63, 225–235 (2003).
Zheng, W., Lu, X. H. & Wong, S. C. Electrical and mechanical properties of expanded graphite-reinforced high-density polyethylene. J. Appl. Polym. Sci. 91, 2781–2788 (2004).
Ramanathan, T., Liu, H., and Brinson, L. C. Functionalized SWNT/polymer nanocomposites for dramatic property improvement. J. Polym. Sci. B: Polym. Phys. 43, 2269–2279 (2005).
Ray, S. S. & Okamoto, M. Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog. Polym. Sci. 28, 1539–1641 (2003).
Zhu, J. et al. Improving the dispersion and integration of single-walled carbon nanotubes in epoxy composites through functionalization. Nano Lett. 3, 1107–1113 (2003).
Kim, B., Lee, J. & Yu, I. S. Electrical properties of single-wall carbon nanotube and epoxy composites. J. Appl. Phys. 94, 6724–6728 (2003).
Cho, D., Lee, S., Yang, G. M., Fukushima, H. & Drzal, L. T. Dynamic mechanical and thermal properties of phenylethynyl-terminated polyimide composites reinforced with expanded graphite nanoplatelets. Macromol. Mater. Eng. 290, 179–187 (2005).
Usuki, A., Hasegawa, N. & Kato, M. Polymer–clay nanocomposites. Adv. Polym. Sci. 179, 135–195 (2005).
Ramanathan, T. et al. Graphitic nanofillers in PMMA nanocomposites—an investigation of particle size and dispersion and their influence on nanocomposite properties. J. Polym. Sci. B: Polym. Phys. 45, 2097–2112 (2007).
Harmandaris, V. A., Daoulas, K. C. & Mavrantzas, V. G. Molecular dynamics simulation of a polymer melt/solid interface: Local dynamics and chain mobility in a thin film of polyethylene melt adsorbed on graphite. Macromolecules 38, 5796–5809 (2005).
Lin, E. K., Wu, W. I. & Satija, S. K. Polymer interdiffusion near an attractive solid substrate. Macromolecules 30, 7224–7231 (1997).
Starr, F. W., Schroder, T. B. & Glotzer, S. C. Molecular dynamics simulation of a polymer melt with a nanoscopic particle. Macromolecules 35, 4481–4492 (2002).
Desai, T., Keblinski, P. & Kumar, S. K., Molecular dynamics simulations of polymer transport in nanocomposites. J. Chem. Phys. 122, 134910 (2005).
Bansal, A. et al. Quantitative equivalence between polymer nanocomposites and thin polymer films. Nature Mater. 4, 693–698 (2005).
Moniruzzaman, M. & Winey, K. I. Polymer nanocomposites containing carbon nanotubes. Macromolecules 39, 5194–5205 (2006).
Fiedler, B., Gojny, F. H., Wichmann, M. H. G., Nolte, M. C. M. & Schulte, K., Fundamental aspects of nano-reinforced composites. Comp. Sci. Tech. 66, 3115–3125 (2006).
Kelly, B. T. Physics of Graphite (Applied Science, London, 1981).
Stankovich, S. et al. Graphene-based composite materials. Nature 442, 282–286 (2006).
Kotov, N. A. Materials science: Carbon sheet solutions. Nature 442, 254–255 (2006).
Schniepp, H. C. et al. Functionalized single graphene sheets derived from splitting graphite oxide. J. Phys. Chem. B 110, 8535–8539 (2006).
McAllister, M. J. et al. Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chem. Mater. 19, 4396–4404 (2007).
Duplock, E. J., Scheffler, M. & Lindan, P. J. D. Hallmark of perfect graphene. Phys. Rev. Lett. 92, 225502 (2004).
Smith, G. D., Bedrov, D., Li, L. W. & Byutner, O. A molecular dynamics simulation study of the viscoelastic properties of polymer nanocomposites. J. Chem. Phys. 117, 9478–9489 (2002).
Rittigstein, P., Priestley, R. D., Broadbelt, L. J. & Torkelson J. M. Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites. Nature Mater. 6, 278–282 (2007).
Celik, C. & Warner, S. B. Analysis of the structure and properties of expanded graphite-filled poly(phenylene ether)/atactic polystyrene nanocomposite fibers. J. Appl. Polym. Sci. 103, 645–652 (2007).
Uhl, F. M., Yao, Q. & Wilkie, C. A. Formation of nanocomposites of styrene and its copolymers using graphite as the nanomaterial. Polym. Adv. Tech. 16, 533–540 (2005).
Xiao, M., Sun, L. Y., Liu, J. J., Li, Y. & Gong, K. C. Synthesis and properties of polystyrene/graphite nanocomposites. Polymer 43, 2245–2248 (2002).
Yasmin, A. & Daniel, I. M. Mechanical and thermal properties of graphite platelet/epoxy composites. Polymer 45, 8211–8219 (2004).
Yuen, S. M. et al. Preparation and thermal, electrical, and morphological properties of multiwalled carbon nanotube and epoxy composites. J. Appl. Polym. Sci. 103, 1272–1278 (2007).
Putz, K. W., Mitchell, C. A., Krishnamoorti, R. & Green, P. F. Elastic modulus of single-walled carbon nanotube/poly(methyl methacrylate) nanocomposites. J. Polym. Sci. B: Polym. Phys. 42, 2286–2293 (2004).
We thank M. J. McAllister and D.L. Milius for technical assistance and helpful discussions, and A. Tamashausky of Asbury Carbons for providing the graphite used. Financial support from the NASA University Research, Engineering, and Technology Institute on BioInspired Materials (BIMat) under Award No. NCC-1-02037 is greatly appreciated; additional support from the NSF was provided to I.A.A., R.S.R. and to L.C.B. and S.T.N. through the NSF-MRSEC and NIRT program.
I.A.A. and R.K.P. are stockholders of Vorbeck Materials Corporation, which is now producing functionalized graphene sheets under the trade name Vor-x. However, all materials used in this study were prepared in our laboratories.
About this article
Cite this article
Ramanathan, T., Abdala, A., Stankovich, S. et al. Functionalized graphene sheets for polymer nanocomposites. Nature Nanotech 3, 327–331 (2008). https://doi.org/10.1038/nnano.2008.96
Materials & Design (2021)
Interpenetrating polymer network/functionalized‐reduced graphene oxide nanocomposite: As an advanced functional material
Journal of Applied Polymer Science (2021)
Two-dimensional materials modified layered double hydroxides: A series of fillers for improving gas barrier and permselectivity of poly(vinyl alcohol)
Composites Part B: Engineering (2021)
Understanding the mechanical and viscoelastic properties of graphene reinforced polycarbonate nanocomposites using coarse-grained molecular dynamics simulations
Computational Materials Science (2021)