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Microfluidics-enabled orientation and microstructure control of macroscopic graphene fibres

Nature Nanotechnology volume 14, pages 168–175 (2019)Cite this article

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Abstract

Macroscopic graphene structures such as graphene papers and fibres can be manufactured from individual two-dimensional graphene oxide sheets by a fluidics-enabled assembling process. However, achieving high thermal-mechanical and electrical properties is still challenging due to non-optimized microstructures and morphology. Here, we report graphene structures with tunable graphene sheet alignment and orientation, obtained via microfluidic design, enabling strong size and geometry confinements and control over flow patterns. Thin flat channels can be used to fabricate macroscopic graphene structures with perfectly stacked sheets that exhibit superior thermal and electrical conductivities and improved mechanical strength. We attribute the observed shape and size confinements to the flat distribution of shear stress from the anisotropic microchannel walls and the enhanced shear thinning degree of large graphene oxide sheets in solution. Elongational and step expansion flows are created to produce large-scale graphene tubes and rods with horizontally and perpendicularly aligned graphene sheets by tuning the elongational and extensional shear rates, respectively.

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Fig. 1: Size and shape confinements controlling sheet orientation in solution and thus the microstructure and mechanical properties of the annealed graphene structures.
Fig. 2: Contraction and step expansion flow patterns for horizontally and vertically aligned graphene structures.
Fig. 3: Shape and size confinements of microchannels on GO sheet alignment, shear stress/distribution and rheological properties of the fluidic flow.
Fig. 4: Influences of elongational and expansion flow patterns on GO sheet orientation degree and alignment.
Fig. 5: Super strong and highly thermally/electrically conductive graphene belts fabricated from flat microchannels.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

References

  1. Xu, Z. & Gao, C. Graphene chiral liquid crystals and macroscopic assembled fibres. Nat. Commun. 2, 571 (2011).

    Article  Google Scholar 

  2. Xu, Z. & Gao, C. Graphene in macroscopic order: liquid crystals and wet-spun fibers. Acc. Chem. Res. 47, 1267–1276 (2014).

    Article  CAS  Google Scholar 

  3. Dong, Z. et al. Facile fabrication of light, flexible and multifunctional graphene fibers. Adv. Mater. 24, 1856–1861 (2012).

    Article  CAS  Google Scholar 

  4. Xiang, C. et al. Graphene nanoribbons as an advanced precursor for making carbon fiber. ACS Nano 7, 1628–1637 (2013).

    Article  CAS  Google Scholar 

  5. Huang, G. et al. Highly strong and elastic graphene fibres prepared from universal graphene oxide precursors. Sci. Rep. 4 (2014).

  6. Xin, G. et al. Highly thermally conductive and mechanically strong graphene fibers. Science 349, 1083–1087 (2015).

    Article  CAS  Google Scholar 

  7. Hu, X., Xu, Z., Liu, Z. & Gao, C. Liquid crystal self-templating approach to ultrastrong and tough biomimic composites. Sci. Rep. 3 (2013).

  8. Zhao, X., Xu, Z., Zheng, B. & Gao, C. Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide. Sci. Rep. 3 (2013).

  9. Xu, Z. et al. Ultrastiff and strong graphene fibers via full-scale synergetic defect engineering. Adv. Mater. 28, 6449–6456 (2016).

    Article  CAS  Google Scholar 

  10. Xu, Z., Sun, H., Zhao, X. & Gao, C. Ultrastrong fibers assembled from giant graphene oxide sheets. Adv. Mater. 25, 188–193 (2013).

    Article  CAS  Google Scholar 

  11. Qin, X., Lu, Y., Xiao, H., Wen, Y. & Yu, T. A comparison of the effect of graphitization on microstructures and properties of polyacrylonitrile and mesophase pitch-based carbon fibers. Carbon. N. Y. 50, 4459–4469 (2012).

    Article  CAS  Google Scholar 

  12. Emmerich, F. G. Young’s modulus, thermal conductivity, electrical resistivity and coefficient of thermal expansion of mesophase pitch-based carbon fibers. Carbon 79, 274–293 (2014).

    Article  CAS  Google Scholar 

  13. Xin, G. et al. Large-area free standing graphene paper for superior thermal management. Adv. Mater. 26, 4521–4526 (2014).

    Article  CAS  Google Scholar 

  14. Erik, F., Frank, H. & R, B. M. Carbon fibers: precursors, manufacturing, and properties. Macromol. Mater. Eng. 297, 493–501 (2012).

    Article  Google Scholar 

  15. Huang, X. Fabrication and properties of carbon fibers. Materials 2, 2369 (2009).

    Article  CAS  Google Scholar 

  16. Liu, Y. & Kumar, S. Recent progress in fabrication, structure and properties of carbon fibers. Polym. Rev. 52, 234–258 (2012).

    Article  CAS  Google Scholar 

  17. Gârlea, I. C. et al. Finite particle size drives defect-mediated domain structures in strongly confined colloidal liquid crystals. Nat. Commun. 7, 12112 (2016).

    Article  Google Scholar 

  18. Shen, T.-Z., Hong, S.-H. & Song, J.-K. Electro-optical switching of graphene oxide liquid crystals with an extremely large Kerr coefficient. Nat. Mater. 13, 394–399 (2014).

    Article  CAS  Google Scholar 

  19. Maiti, U. N., Lim, J., Lee, K. E., Lee, W. J. & Kim, S. O. Three-dimensional shape engineered, interfacial gelation of reduced graphene oxide for high rate, large capacity supercapacitors. Adv. Mater. 26, 615–619 (2014).

    Article  CAS  Google Scholar 

  20. Wang, G. et al. Flexible pillared graphene-paper electrodes for high-performance electrochemical supercapacitors. Small. 8, 452–459 (2012).

    Article  CAS  Google Scholar 

  21. Seo, D. H., Han, Z. J., Kumar, S. & Ostrikov, K. Structure-controlled, vertical graphene-based, binder-free electrodes from plasma-reformed butter enhance supercapacitor performance. Adv. Energy Mater. 3, 1316–1323 (2013).

    Article  CAS  Google Scholar 

  22. Li, G., Zhang, X., Wang, J. & Fang, J. From anisotropic graphene aerogels to electron- and photo-driven phase change composites. J. Mater. Chem. A 4, 17042–17049 (2016).

    Article  CAS  Google Scholar 

  23. Håkansson, K. M. O. et al. Hydrodynamic alignment and assembly of nanofibrils resulting in strong cellulose filaments. Nat. Commun. 5, 4018 (2014).

    Article  Google Scholar 

  24. Qiu, L., Zheng, X. H., Zhu, J., Su, G. P. & Tang, D. W. The effect of grain size on the lattice thermal conductivity of an individual polyacrylonitrile-based carbon fiber. Carbon 51, 265–273 (2013).

    Article  CAS  Google Scholar 

  25. Yuan, G. et al. The structure and properties of ribbon-shaped carbon fibers with high orientation. Carbon 68, 426–439 (2014).

    Article  CAS  Google Scholar 

  26. Gallego, N. C. et al. The thermal conductivity of ribbon-shaped carbon fibers. Carbon 38, 1003–1010 (2000).

    Article  CAS  Google Scholar 

  27. Trebbin, M. et al. Anisotropic particles align perpendicular to the flow direction in narrow microchannels. Proc. Natl Acad. Sci. USA 110, 6706–6711 (2013).

    Article  CAS  Google Scholar 

  28. Vincent, M. & Agassant, J. F. Experimental and theoretical study of short fiber orientation in diverging flows. Rheol. Acta 24, 603–610 (1985).

    Article  CAS  Google Scholar 

  29. Kiriya, D., Kawano, R., Onoe, H. & Takeuchi, S. Microfluidic control of the internal morphology in nanofiber-based macroscopic cables. Angew. Chem. Int. Ed. 51, 7942–7947 (2012).

    Article  CAS  Google Scholar 

  30. Cançado, L. G. et al. General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy. Appl. Phys. Lett. 88, 163106 (2006).

    Article  Google Scholar 

  31. Gspann, T. S. et al. High thermal conductivities of carbon nanotube films and micro-fibres and their dependence on morphology. Carbon 114, 160–168 (2017).

    Article  CAS  Google Scholar 

  32. Adams, P. M., Katzman, H. A., Rellick, G. S. & Stupian, G. W. Characterization of high thermal conductivity carbon fibers and a self-reinforced graphite panel. Carbon 36, 233–245 (1998).

    Article  CAS  Google Scholar 

  33. Wu, Z., Chen, Y., Wang, M. & Chung, A. J. Continuous inertial microparticle and blood cell separation in straight channels with local microstructures. Lab Chip 16, 532–542 (2016).

    Article  CAS  Google Scholar 

  34. Endo, M. et al. Structural analysis of the B-doped mesophase pitch-based graphite fibers by Raman spectroscopy. Phys. Rev. B 58, 8991–8996 (1998).

    Article  CAS  Google Scholar 

  35. Zhang, L., Zhang, G., Liu, C. & Fan, S. High-density carbon nanotube buckypapers with superior transport and mechanical properties. Nano Lett. 12, 4848–4852 (2012).

    Article  CAS  Google Scholar 

  36. Son, Y. Determination of shear viscosity and shear rate from pressure drop and flow rate relationship in a rectangular channel. Polymer 48, 632–637 (2007).

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported financially by the US National Science Foundation under the award no. DMR 1742806. Thermal conductivity measurement of the macroscopic graphene structures was supported by the US National Science Foundation under the award CMMI 1463083.

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Authors and Affiliations

  1. Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY, USA

    Guoqing Xin, Weiguang Zhu, Yanxiang Deng, Jie Cheng, Lucy T. Zhang, Aram J. Chung, Suvranu De & Jie Lian

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  1. Guoqing Xin
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  4. Jie Cheng
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  8. Jie Lian
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Contributions

G.X. and J.L. designed the research. G.X. and Y.D. designed the microfluidic channels. G.X and W.Z. collected and analysed thermal, mechanical and microstructure data. G.X., Y.D., J.C. and L.T.Z. performed computational fluid dynamics simulations. G.X., A.J.C., S.D. and J.L. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Jie Lian.

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Xin, G., Zhu, W., Deng, Y. et al. Microfluidics-enabled orientation and microstructure control of macroscopic graphene fibres. Nature Nanotech 14, 168–175 (2019). https://doi.org/10.1038/s41565-018-0330-9

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