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.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The data that support the findings of this study are available from the corresponding author on reasonable request.
Change history
23 May 2020
A Correction to this paper has been published: https://doi.org/10.1038/s41586-020-2372-z
References
Mayer, G. Rigid biological systems as models for synthetic composites. Science 310, 1144–1147 (2005).
Meyers, M. A., McKittrick, J. & Chen, P. Structural biological materials: critical mechanics-materials connections. Science 339, 773–779 (2013).
Wegst, U. G. K., Bai, H., Saiz, E., Tomsia, A. P. & Ritchie, R. O. Bioinspired structural materials. Nat. Mater. 14, 23–36 (2015).
Podsiadlo, P. et al. Ultrastrong and stiff layered polymer nanocomposites. Science 318, 80–83 (2007).
Munch, E. et al. Tough, bio-inspired hybrid materials. Science 322, 1516–1520 (2008).
Mao, L. et al. Synthetic nacre by predesigned matrix-directed mineralization. Science 354, 107–110 (2016).
Tang, Z., Kotov, N. A., Magonov, S. & Ozturk, B. Nanostructured artificial nacre. Nat. Mater. 2, 413–418 (2003).
Richardson, J. J., Björnmalm, M. & Caruso, F. Technology-driven layer-by-layer assembly of nanofilms. Science 348, aaa2491 (2015).
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).
Das, P. et al. Nacre-mimetics with synthetic nanoclays up to ultrahigh aspect ratios. Nat. Commun. 6, 5967 (2015).
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).
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).
Dikin, D. A. et al. Preparation and characterization of graphene oxide paper. Nature 448, 457–460 (2007).
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).
Liu, M. et al. An anisotropic hydrogel with electrostatic repulsion between cofacially aligned nanosheets. Nature 517, 68–72 (2015).
Guell, D. & Bénard, A. Flow-Induced Alignment in Composite Materials (eds Papathanasiou, T. D. & Guell, D. C.) Ch. 1, 1–42 (Woodhead Publishing, 1997).
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).
Yu, X., Prevot, M. S., Guijarro, N. & Sivula, K. Self-assembled 2D WSe2 thin films for photoelectrochemical hydrogen production. Nat. Commun. 6, 7596 (2015).
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).
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).
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).
de Gennes, P.-G., Brochard-Wyart, F. & Quéré, D. Capillarity and Wetting Phenomena (Springer, 2004).
Wu, L. et al. Magnetically induced anisotropic orientation of graphene oxide locked by in situ hydrogelation. ACS Nano 8, 4640–4649 (2014).
Zerda, A. S. & Lesser, A. J. Intercalated clay nanocomposites: morphology, mechanics, and fracture behavior. J. Polym. Sci. B 39, 1137–1146 (2001).
Pavlidou, S. & Papaspyrides, C. D. A review on polymer–layered silicate nanocomposites. Prog. Polym. Sci. 33, 1119–1198 (2008).
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).
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).
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).
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).
Wen, Y., Wu, M., Zhang, M., Li, C. & Shi, G. Topological design of ultrastrong and highly conductive graphene films. Adv. Mater. 29, 1702831 (2017).
Xiong, R. et al. Ultrarobust transparent cellulose nanocrystal-graphene membranes with high electrical conductivity. Adv. Mater. 28, 1501–1509 (2016).
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).
Ramanathan, T. et al. Functionalized graphene sheets for polymer nanocomposites. Nat. Nanotechnol. 3, 327–331 (2008).
Bansal, A. et al. Quantitative equivalence between polymer nanocomposites and thin polymer films. Nat. Mater. 4, 693–698 (2005).
Ritchie, R. O. The conflicts between strength and toughness. Nat. Mater. 10, 817–822 (2011).
Fujisawa, T. et al. Small-angle X-ray scattering station at the SPring-8 RIKEN beamline. J. Appl. Crystallogr. 33, 797–800 (2000).
Feng, S. et al. Hierarchical structure in oriented fibers of a dendronized polymer. Macromolecules 42, 281–287 (2009).
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).
Doi, M. Soft Matter Physics (Oxford Univ. Press, 2013).
Man, X. & Doi, M. Ring to mountain transition in deposition pattern of drying droplets. Phys. Rev. Lett. 116, 066101 (2016).
Tanner, L. H. The spreading of silicone oil drops on horizontal surfaces. J. Phys. D 12, 1473–1484 (1979).
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).
Author information
Authors and Affiliations
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.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review information Nature thanks André Studart, Hongbin Lu and Karl W. Putz for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
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.
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.
Rights and permissions
About this article
Cite this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-020-2161-8
This article is cited by
-
Bidirectionally promoting assembly order for ultrastiff and highly thermally conductive graphene fibres
Nature Communications (2024)
-
Scalable production of structurally colored composite films by shearing supramolecular composites of polymers and colloids
Nature Communications (2024)
-
Animating hydrogel knotbots with topology-invoked self-regulation
Nature Communications (2024)
-
Bioinspired structural hydrogels with highly ordered hierarchical orientations by flow-induced alignment of nanofibrils
Nature Communications (2024)
-
Large-area ultrastrong and stiff aramid nanofiber based layered nanocomposite films
Nano Research (2024)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.