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Layered nanocomposites by shear-flow-induced alignment of nanosheets

Nature volume 580, pages 210–215 (2020)Cite this article

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Abstract

Biological materials, such as bones, teeth and mollusc shells, are well known for their excellent strength, modulus and toughness1,2,3. Such properties are attributed to the elaborate layered microstructure of inorganic reinforcing nanofillers, especially two-dimensional nanosheets or nanoplatelets, within a ductile organic matrix4,5,6. Inspired by these biological structures, several assembly strategies—including layer-by-layer4,7,8, casting9,10, vacuum filtration11,12,13 and use of magnetic fields14,15—have been used to develop layered nanocomposites. However, how to produce ultrastrong layered nanocomposites in a universal, viable and scalable manner remains an open issue. Here we present a strategy to produce nanocomposites with highly ordered layered structures using shear-flow-induced alignment of two-dimensional nanosheets at an immiscible hydrogel/oil interface. For example, nanocomposites based on nanosheets of graphene oxide and clay exhibit a tensile strength of up to 1,215 ± 80 megapascals and a Young’s modulus of 198.8 ± 6.5 gigapascals, which are 9.0 and 2.8 times higher, respectively, than those of natural nacre (mother of pearl). When nanosheets of clay are used, the toughness of the resulting nanocomposite can reach 36.7 ± 3.0 megajoules per cubic metre, which is 20.4 times higher than that of natural nacre; meanwhile, the tensile strength is 1,195 ± 60 megapascals. Quantitative analysis indicates that the well aligned nanosheets form a critical interphase, and this results in the observed mechanical properties. We consider that our strategy, which could be readily extended to align a variety of two-dimensional nanofillers, could be applied to a wide range of structural composites and lead to the development of high-performance composites.

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Fig. 1: Fabrication and mechanism of the layered nanocomposite films featuring aligned nanosheets.
Fig. 2: Control over the uniformity and continuity of the layered nanocomposite films.
Fig. 3: Structural characterization of the layered nanocomposite films.
Fig. 4: Materials characterization of the layered nanocomposite films.

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Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.

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References

  1. Mayer, G. Rigid biological systems as models for synthetic composites. Science 310, 1144–1147 (2005).

    Article  CAS  ADS  Google Scholar 

  2. Meyers, M. A., McKittrick, J. & Chen, P. Structural biological materials: critical mechanics-materials connections. Science 339, 773–779 (2013).

    Article  CAS  ADS  Google Scholar 

  3. Wegst, U. G. K., Bai, H., Saiz, E., Tomsia, A. P. & Ritchie, R. O. Bioinspired structural materials. Nat. Mater. 14, 23–36 (2015).

    Article  CAS  ADS  Google Scholar 

  4. Podsiadlo, P. et al. Ultrastrong and stiff layered polymer nanocomposites. Science 318, 80–83 (2007).

    Article  CAS  ADS  Google Scholar 

  5. Munch, E. et al. Tough, bio-inspired hybrid materials. Science 322, 1516–1520 (2008).

    Article  CAS  ADS  Google Scholar 

  6. Mao, L. et al. Synthetic nacre by predesigned matrix-directed mineralization. Science 354, 107–110 (2016).

    Article  CAS  ADS  Google Scholar 

  7. Tang, Z., Kotov, N. A., Magonov, S. & Ozturk, B. Nanostructured artificial nacre. Nat. Mater. 2, 413–418 (2003).

    Article  CAS  ADS  Google Scholar 

  8. Richardson, J. J., Björnmalm, M. & Caruso, F. Technology-driven layer-by-layer assembly of nanofilms. Science 348, aaa2491 (2015).

    Article  Google Scholar 

  9. Zhang, M., Huang, L., Chen, J., Li, C. & Shi, G. Ultratough, ultrastrong, and highly conductive graphene films with arbitrary sizes. Adv. Mater. 26, 7588–7592 (2014).

    Article  CAS  Google Scholar 

  10. Das, P. et al. Nacre-mimetics with synthetic nanoclays up to ultrahigh aspect ratios. Nat. Commun. 6, 5967 (2015).

    Article  ADS  Google Scholar 

  11. Walther, A. et al. Large-area, lightweight and thick biomimetic composites with superior material properties via fast, economic, and green pathways. Nano Lett. 10, 2742–2748 (2010).

    Article  CAS  ADS  Google Scholar 

  12. Putz, K. W., Compton, O. C., Palmeri, M. J., Nguyen, S. T. & Brinson, L. C. High-nanofiller-content graphene oxide-polymer nanocomposites via vacuum-assisted self-assembly. Adv. Funct. Mater. 20, 3322–3329 (2010).

    Article  CAS  Google Scholar 

  13. Dikin, D. A. et al. Preparation and characterization of graphene oxide paper. Nature 448, 457–460 (2007).

    Article  CAS  ADS  Google Scholar 

  14. Erb, R. M., Libanori, R., Rothfuchs, N. & Studart, A. R. Composites reinforced in three dimensions by using low magnetic fields. Science 335, 199–204 (2012).

    Article  MathSciNet  CAS  ADS  Google Scholar 

  15. Liu, M. et al. An anisotropic hydrogel with electrostatic repulsion between cofacially aligned nanosheets. Nature 517, 68–72 (2015).

    Article  CAS  ADS  Google Scholar 

  16. Guell, D. & Bénard, A. Flow-Induced Alignment in Composite Materials (eds Papathanasiou, T. D. & Guell, D. C.) Ch. 1, 1–42 (Woodhead Publishing, 1997).

  17. Ding, F. et al. Biomimetic nanocoatings with exceptional mechanical, barrier, and flame-retardant properties from large-scale one-step coassembly. Sci. Adv. 3, e1701212 (2017).

    Article  ADS  Google Scholar 

  18. Yu, X., Prevot, M. S., Guijarro, N. & Sivula, K. Self-assembled 2D WSe2 thin films for photoelectrochemical hydrogen production. Nat. Commun. 6, 7596 (2015).

    Article  ADS  Google Scholar 

  19. Zhang, P. et al. Superspreading on immersed gel surfaces for the confined synthesis of thin polymer films. Angew. Chem. Int. Ed. 55, 3615–3619 (2016).

    Article  CAS  Google Scholar 

  20. Zhao, C. et al. Superspreading-based fabrication of asymmetric porous PAA-g-PVDF membranes for efficient water flow gating. Adv. Mater. Interfaces 3, 1600615 (2016).

    Article  Google Scholar 

  21. Hao, Q. et al. Confined synthesis of two-dimensional covalent organic framework thin films within superspreading water layer. J. Am. Chem. Soc. 140, 12152–12158 (2018).

    Article  CAS  Google Scholar 

  22. de Gennes, P.-G., Brochard-Wyart, F. & Quéré, D. Capillarity and Wetting Phenomena (Springer, 2004).

  23. Wu, L. et al. Magnetically induced anisotropic orientation of graphene oxide locked by in situ hydrogelation. ACS Nano 8, 4640–4649 (2014).

    Article  CAS  Google Scholar 

  24. Zerda, A. S. & Lesser, A. J. Intercalated clay nanocomposites: morphology, mechanics, and fracture behavior. J. Polym. Sci. B 39, 1137–1146 (2001).

    Article  CAS  Google Scholar 

  25. Pavlidou, S. & Papaspyrides, C. D. A review on polymer–layered silicate nanocomposites. Prog. Polym. Sci. 33, 1119–1198 (2008).

    Article  CAS  Google Scholar 

  26. Genix, A. C. et al. Understanding the static interfacial polymer layer by exploring the dispersion states of nanocomposites. ACS Appl. Mater. Interfaces 11, 17863–17872 (2019).

    Article  CAS  Google Scholar 

  27. An, Z., Compton, O. C., Putz, K. W., Brinson, L. C. & Nguyen, S. B. T. Bio-inspired borate cross-linking in ultra-stiff graphene oxide thin films. Adv. Mater. 23, 3842–3846 (2011).

    CAS  PubMed  Google Scholar 

  28. Zhu, J., Zhang, H. & Kotov, N. A. Thermodynamic and structural insights into nanocomposites engineering by comparing two materials assembly techniques for graphene. ACS Nano 7, 4818–4829 (2013).

    Article  CAS  Google Scholar 

  29. Kinloch, I. A., Suhr, J., Lou, J., Young, R. J. & Ajayan, P. M. Composites with carbon nanotubes and graphene: an outlook. Science 362, 547–553 (2018).

    Article  CAS  ADS  Google Scholar 

  30. Wen, Y., Wu, M., Zhang, M., Li, C. & Shi, G. Topological design of ultrastrong and highly conductive graphene films. Adv. Mater. 29, 1702831 (2017).

    Article  Google Scholar 

  31. Xiong, R. et al. Ultrarobust transparent cellulose nanocrystal-graphene membranes with high electrical conductivity. Adv. Mater. 28, 1501–1509 (2016).

    Article  CAS  Google Scholar 

  32. Hu, K., Gupta, M. K., Kulkarni, D. D. & Tsukruk, V. V. Ultra-robust graphene oxide-silk fibroin nanocomposite membranes. Adv. Mater. 25, 2301–2307 (2013).

    Article  Google Scholar 

  33. Ramanathan, T. et al. Functionalized graphene sheets for polymer nanocomposites. Nat. Nanotechnol. 3, 327–331 (2008).

    Article  CAS  ADS  Google Scholar 

  34. Bansal, A. et al. Quantitative equivalence between polymer nanocomposites and thin polymer films. Nat. Mater. 4, 693–698 (2005).

    Article  CAS  ADS  Google Scholar 

  35. Ritchie, R. O. The conflicts between strength and toughness. Nat. Mater. 10, 817–822 (2011).

    Article  CAS  ADS  Google Scholar 

  36. Fujisawa, T. et al. Small-angle X-ray scattering station at the SPring-8 RIKEN beamline. J. Appl. Crystallogr. 33, 797–800 (2000).

    Article  MathSciNet  CAS  Google Scholar 

  37. Feng, S. et al. Hierarchical structure in oriented fibers of a dendronized polymer. Macromolecules 42, 281–287 (2009).

    Article  CAS  ADS  Google Scholar 

  38. Nie, Y. et al. New insights into thermodynamic description of strain-induced crystallization of peroxide cross-linked natural rubber filled with clay by tube model. Polymer 52, 3234–3242 (2011).

    Article  CAS  Google Scholar 

  39. Doi, M. Soft Matter Physics (Oxford Univ. Press, 2013).

  40. Man, X. & Doi, M. Ring to mountain transition in deposition pattern of drying droplets. Phys. Rev. Lett. 116, 066101 (2016).

    Article  ADS  Google Scholar 

  41. Tanner, L. H. The spreading of silicone oil drops on horizontal surfaces. J. Phys. D 12, 1473–1484 (1979).

    Article  CAS  ADS  Google Scholar 

Download references

Acknowledgements

This research was supported by the National Key R&D Program of China (2017YFA0207800), the National Natural Science Funds for Distinguished Young Scholars (21725401), the National Natural Science Foundation (21988102, 21774004), the 111 project (B14009) and the Fundamental Research Funds for the Central Universities. The small-angle X-ray scattering measurements were performed at BL45XU in SPring-8 with the approval of the RIKEN SPring-8 Center (proposal 20180067).

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Author notes

  1. These authors contributed equally: Chuangqi Zhao, Pengchao Zhang, Jiajia Zhou

Authors and Affiliations

  1. Key Laboratory of Bioinspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry, Beihang University, Beijing, China

    Chuangqi Zhao, Jiajia Zhou, Shuanhu Qi, Ruirui Shi, Ruochen Fang, Antoni P. Tomsia, Mingjie Liu & Lei Jiang

  2. CAS Key Laboratory of Bio-Inspired Materials and Interfacial Science, CAS Center for Excellence in Nanoscience, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, China

    Pengchao Zhang, Shutao Wang & Lei Jiang

  3. International Research Institute for Multidisciplinary Science, Beihang University, Beijing, China

    Jiajia Zhou, Shuanhu Qi & Mingjie Liu

  4. RIKEN Center for Emergent Matter Science, Wako, Japan

    Yoshihiro Yamauchi & Yasuhiro Ishida

  5. Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing, China

    Antoni P. Tomsia, Mingjie Liu & Lei Jiang

  6. Research Institute of Frontier Science, Beihang University, Beijing, China

    Mingjie Liu & Lei Jiang

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Contributions

C.Z., P.Z. and J.Z. contributed equally to this work. L.J. and M.L. contributed to the initiating idea. C.Z. performed the experiments. R.S. contributed to the fabrication of nanocomposite films and mechanical tests. J.Z. contributed to the theoretical analysis of the spreading liquid. Y.I. and Y.Y. supported the X-ray diffraction measurements at SPring-8. S.Q., R.F., S.W., A.P.T. and L.J. contributed to the analysis of mechanical properties. C.Z., P.Z., J.Z. and M.L. analysed all the data and wrote the manuscript. All authors commented on the manuscript.

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Correspondence to Mingjie Liu.

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The authors declare no competing interests.

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Peer review information Nature thanks André Studart, Hongbin Lu and Karl W. Putz for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 Schematic pictures of a spreading droplet.

a, Coordinate system of the spreading process for a single droplet. b, Spreading on a solid wetting surface. c, Spreading on a soft gel surface. See Methods for nomenclature.

Extended Data Fig. 2 The spreading radius of reaction solutions with different concentrations as a function of time.

a, The spreading radius (R) of a single droplet as a function of time (t) for various spreading solutions with different concentrations. The time evolution of the radius shows a transition from t1 (red line) to t1/4 (blue line) scaling. b, The spreading radius R of various spreading solutions with different concentrations on a moving substrate as a function of time. The time evolution of the radius shows a transition from t1 (red line) to t1/3 (blue line) scaling. For a and b the compositions of the four kinds of reaction solutions are listed in Supplementary Table 5 (the reaction solutions for the resulting clay/CNT-based nanocomposite films).

Extended Data Fig. 3 Factors affecting the spreading diameter d.

a, The spreading diameter d as a function of the moving speed of the hydrogel substrate V for a given reaction solution with a viscosity of 6 mPa s. The flow rate Q was 70 ml h−1. The composition of the reaction solution is 0.03 wt% GO and 0.15 wt% NaAlg. b, The spreading diameter d as a function of the viscosity of the reaction solutions η. The moving speed of the hydrogel substrate V was 5 mm s−1 and the flow rate Q was 70 ml h−1. The viscosity of the aqueous solution was changed by altering the concentration of NaAlg and GO nanosheets. Red lines, fitting curves; error bars, ±1 s.d.

Extended Data Fig. 4 The influence of the concentration of the reaction solution on the orientation degree and on the mechanical properties of the GO/clay/CNT-based nanocomposite films.

a–c, Plots of azimuthal angle (φ; a), orientation order parameter (f) versus concentration (b), and stress–strain curves (c) of the prepared GO/clay/CNT-based nanocomposite films, using reaction solutions with different concentrations of nanofillers (in wt%, see key). The constitution of the four kinds of reaction solutions, the detailed orientation order parameter (f), and the detailed mechanical properties data are listed in Supplementary Tables 5 and 6.

Extended Data Fig. 5 Structural characterization of the layered nanocomposite films with various weight percentages of nanofillers (GO, clay and CNTs).

a, b, Plots of azimuthal angle φ (a) and the orientation order parameter (f) of the layered nanocomposite films with different weight percentages of nanofillers prepared by the superspreading strategy (see key). These results confirm that nanosheets were assembled into highly ordered structures in all these films. The constitution of the reaction solutions and the detailed orientation order parameter (f) are listed in Extended Data Table 1.

Extended Data Fig. 6 Fracture behaviour of the SS-GO/clay/CNT nanocomposite films.

a, A failure crack propagates almost in a straight line and perpendicular to the tensile stress direction. b, The morphology of the cross-section view of the fracture surface. CNTs were rarely pulled out from the relatively neat fracture surface, indicating the strong interactions between nanofillers and polymers. c, The energy dispersive X-ray spectroscopy (EDS) image of Si originating from clay in the SS-GO/clay/CNT nanocomposite films, revealing the even distribution of clay nanosheets. The scale bar in SEM image b applies also to SEM image a and EDS image c.

Extended Data Fig. 7 Fracture behaviour of the SS-clay/CNT nanocomposite films.

a, The morphology of the cross-section view of the fracture surface. b, The crack path shows a wavy line parallel to the crack propagation path and a damaged zone around the propagating crack tip (indicated by yellow arrows), indicating the efficient dissipation of fracture energy. c, At a higher magnification, the pull-out of CNTs further contributes to fracture energy dissipation. a–c are SEM images.

Extended Data Table 1 Summary of results
Full size table

Supplementary information

Supplementary Information

This file contains Materials, Supplementary Figures 1-22, Supplementary Tables 1-9 and References.

Video 1

The super spreading process of different reaction solutions on an immersed hydrogel surface. The detailed composition and viscosities of the reaction solution are listed in Supplementary Tables 1-2.

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Zhao, C., Zhang, P., Zhou, J. et al. Layered nanocomposites by shear-flow-induced alignment of nanosheets. Nature 580, 210–215 (2020). https://doi.org/10.1038/s41586-020-2161-8

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