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True solutions of single-walled carbon nanotubes for assembly into macroscopic materials

Nature Nanotechnology volume 4, pages 830–834 (2009)Cite this article

Abstract

Translating the unique characteristics of individual single-walled carbon nanotubes into macroscopic materials such as fibres and sheets has been hindered by ineffective assembly. Fluid-phase assembly is particularly attractive, but the ability to dissolve nanotubes in solvents has eluded researchers for over a decade. Here, we show that single-walled nanotubes form true thermodynamic solutions in superacids, and report the full phase diagram, allowing the rational design of fluid-phase assembly processes. Single-walled nanotubes dissolve spontaneously in chlorosulphonic acid at weight concentrations of up to 0.5wt%, 1,000 times higher than previously reported in other acids. At higher concentrations, they form liquid-crystal phases that can be readily processed into fibres and sheets of controlled morphology. These results lay the foundation for bottom-up assembly of nanotubes and nanorods into functional materials.

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Figure 1: Phase diagram of SWNTs in superacids and cross-polarized light micrographs showing the effect of solvent quality and SWNT concentration on microstructure.
Figure 2: Cryo-TEM image of SWNTs (0.134 vol%) in chlorosulphonic acid.
Figure 3: Dispersions of SWNTs (10.8 vol%) in sulphuric acid processed using different coagulation conditions.
Figure 4: Fibre spun from 8.5 vol% SWNTs in pure chlorosulphonic acid and coagulated in 96% aqueous sulphuric acid.

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Acknowledgements

The authors acknowledge the help of R. Duggal, S. Ramesh, L. Ericson, C. Lupu, E. Whitsitt, R. Pinnick, C. Kittrell, W.-F. Hwang, H. Schmidt, B. Yakobson, J. Tour, K. Winey, K. Strong and B. Maruyama. Funding was provided by the Office of Naval Research under grant no. N00014-01-1-0789, AFOSR grant no. FA9550-06-1-0207, AFRL agreements FA8650-07-2-5061 and 07-S568-0042-01-C1, NSF CAREER, USA-Israel Binational Science Foundation, and the Evans-Attwell Welch Postdoctoral Fellowship. Cryo-TEM imaging was performed at the Hannah and George Krumholz Laboratory for Advanced Microscopy, part of the Technion Project on Complex Liquids, Nanostructure and Macromolecules.

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Author notes

  1. Virginia A. Davis & Micah J. Green

    Present address: Present address: Department of Chemical Engineering, Auburn University, Auburn, Alabama 36849, USA (V.A.D.); Department of Chemical Engineering, Texas Tech University, Lubbock, Texas 79409, USA (M.J.G.),

  2. A. Nicholas G. Parra-Vasquez, Micah J. Green and Pradeep K. Rai: These authors contributed equally to this work

  3. Richard E. Smalley: Deceased 28 October 2005

Authors and Affiliations

  1. Richard E. Smalley Institute for Nanoscale Science and Technology, Rice University, Houston, 77005, Texas, USA

    Virginia A. Davis, A. Nicholas G. Parra-Vasquez, Micah J. Green, Pradeep K. Rai, Natnael Behabtu, Valentin Prieto, Richard D. Booker, Hua Fan, W. Wade Adams, Robert H. Hauge, Richard E. Smalley & Matteo Pasquali

  2. Department of Chemical and Biomolecular Engineering, Rice University, Houston, 77005, Texas, USA

    Virginia A. Davis, A. Nicholas G. Parra-Vasquez, Micah J. Green, Pradeep K. Rai, Natnael Behabtu, Valentin Prieto & Matteo Pasquali

  3. Department of Chemistry, Rice University, Houston, 77005, Texas, USA

    Robert H. Hauge, Richard E. Smalley & Matteo Pasquali

  4. Department of Chemical Engineering, Technion–Israel Institute of Technology, Haifa, 32000, Israel

    Judith Schmidt, Ellina Kesselman, Yachin Cohen & Yeshayahu Talmon

  5. Department of Material Science and Engineering, University of Pennsylvania, Philadelphia, Pennsylvania, USA

    Wei Zhou & John E. Fischer

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Contributions

V.A.D., M.J.G., M.P., A.N.G.P.V. and N.B. analysed the data and co-wrote the paper. M.J.G. and M.P. performed theoretical analysis and modelling. V.A.D., A.N.G.P.V., M.J.G., P.K.R., N.B., V.P. and W.Z. performed phase boundary experiments and A.N.G.P.V., N.B., M.J.G., R.D.B. and H.F. performed fibre and film experiments, all with direction and analysis from W.W.A., R.H., J.F., R.E.S. and M.P. J.S., E.K. and A.N.G.P.V. performed cryo-TEM experiments with direction and analysis from Y.C., Y.T. and M.P. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Matteo Pasquali.

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Davis, V., Parra-Vasquez, A., Green, M. et al. True solutions of single-walled carbon nanotubes for assembly into macroscopic materials. Nature Nanotech 4, 830–834 (2009). https://doi.org/10.1038/nnano.2009.302

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