Natural load-bearing materials such as tendons have a high water content of about 70 per cent but are still strong and tough, even when used for over one million cycles per year, owing to the hierarchical assembly of anisotropic structures across multiple length scales1. Synthetic hydrogels have been created using methods such as electro-spinning2, extrusion3, compositing4,5, freeze-casting6,7, self-assembly8 and mechanical stretching9,10 for improved mechanical performance. However, in contrast to tendons, many hydrogels with the same high water content do not show high strength, toughness or fatigue resistance. Here we present a strategy to produce a multi-length-scale hierarchical hydrogel architecture using a freezing-assisted salting-out treatment. The produced poly(vinyl alcohol) hydrogels are highly anisotropic, comprising micrometre-scale honeycomb-like pore walls, which in turn comprise interconnected nanofibril meshes. These hydrogels have a water content of 70–95 per cent and properties that compare favourably to those of other tough hydrogels and even natural tendons; for example, an ultimate stress of 23.5 ± 2.7 megapascals, strain levels of 2,900 ± 450 per cent, toughness of 210 ± 13 megajoules per cubic metre, fracture energy of 170 ± 8 kilojoules per square metre and a fatigue threshold of 10.5 ± 1.3 kilojoules per square metre. The presented strategy is generalizable to other polymers, and could expand the applicability of structural hydrogels to conditions involving more demanding mechanical loading.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
NPG Asia Materials Open Access 05 August 2022
Nature Communications Open Access 29 July 2022
Nature Communications Open Access 21 July 2022
Subscribe to Nature+
Get immediate online access to the entire Nature family of 50+ journals
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the findings of this study are available from the corresponding author on reasonable request.
Maganaris, C. N. & Paul, J. P. In vivo human tendon mechanical properties. J. Physiol. (Lond.) 521, 307–313 (1999).
Gu, L., Jiang, Y. & Hu, J. Scalable spider-silk-like supertough fibers using a pseudoprotein polymer. Adv. Mater. 31, 1904311 (2019).
Hong, S. et al. 3D printing of highly stretchable and tough hydrogels into complex, cellularized structures. Adv. Mater. 27, 4034–4040 (2015).
Xiang, C. et al. Stretchable and fatigue-resistant materials. Mater. Today 34, 7–16 (2020).
Huang, Y. et al. Energy-dissipative matrices enable synergistic toughening in fiber reinforced soft composites. Adv. Funct. Mater. 27, 1605350 (2017).
Zhang, H. et al. Aligned two- and three-dimensional structures by directional freezing of polymers and nanoparticles. Nat. Mater. 4, 787–793 (2005).
Zhang, H. Ice Templating and Freeze-Drying for Porous Materials and their Applications (Wiley-VCH, 2018).
Qin, H., Zhang, T., Li, N., Cong, H. P. & Yu, S. H. Anisotropic and self-healing hydrogels with multi-responsive actuating capability. Nat. Commun. 10, 2202 (2019).
Mredha, M. T. I. et al. Anisotropic tough multilayer hydrogels with programmable orientation. Mater. Horiz. 6, 1504–1511 (2019).
Mredha, M. T. I. et al. A facile method to fabricate anisotropic hydrogels with perfectly aligned hierarchical fibrous structures. Adv. Mater. 30, 1704937 (2018).
Wegst, U. G. K., Bai, H., Saiz, E., Tomsia, A. P. & Ritchie, R. O. Bioinspired structural materials. Nat. Mater. 14, 23–36 (2015).
Sun, J.-Y. et al. Highly stretchable and tough hydrogels. Nature 489, 133–136 (2012).
Gong, J. P., Katsuyama, Y., Kurokawa, T. & Osada, Y. Double-network hydrogels with extremely high mechanical strength. Adv. Mater. 15, 1155–1158 (2003).
Hu, X., Vatankhah-Varnoosfaderani, M., Zhou, J., Li, Q. & Sheiko, S. S. Weak hydrogen bonding enables hard, strong, tough, and elastic hydrogels. Adv. Mater. 27, 6899–6905 (2015).
Lin, P., Ma, S., Wang, X. & Zhou, F. Molecularly engineered dual-crosslinked hydrogel with ultrahigh mechanical strength, toughness, and good self-recovery. Adv. Mater. 27, 2054–2059 (2015).
He, Q., Huang, Y. & Wang, S. Hofmeister effect-assisted one step fabrication of ductile and strong gelatin hydrogels. Adv. Funct. Mater. 28, 1705069 (2018).
Lin, S. et al. Anti-fatigue-fracture hydrogels. Sci. Adv. 5, eaau8528 (2019).
Bai, R., Yang, J., Morelle, X. P. & Suo, Z. Flaw-insensitive hydrogels under static and cyclic loads. Macromol. Rapid Commun. 40, 1800883 (2019).
Lin, S., Liu, J., Liu, X. & Zhao, X. Muscle-like fatigue-resistant hydrogels by mechanical training. Proc. Natl Acad. Sci. USA 116, 10244–10249 (2019).
Illeperuma, W. R. K., Sun, J. Y., Suo, Z. & Vlassak, J. J. Fiber-reinforced tough hydrogels. Extreme Mech. Lett. 1, 90–96 (2014).
Lin, S. et al. Design of stiff, tough and stretchy hydrogel composites via nanoscale hybrid crosslinking and macroscale fiber reinforcement. Soft Matter 10, 7519–7527 (2014).
King, D. R., Okumura, T., Takahashi, R., Kurokawa, T. & Gong, J. P. Macroscale double networks: design criteria for optimizing strength and toughness. ACS Appl. Mater. Interfaces 11, 35343–35353 (2019).
Fan, H. & Gong, J. P. Fabrication of bioinspired hydrogels: challenges and opportunities. Macromolecules 53, 2769–2782 (2020).
Zhao, X. Multi-scale multi-mechanism design of tough hydrogels: building dissipation into stretchy networks. Soft Matter 10, 672–687 (2014).
Wang, Z. et al. Stretchable materials of high toughness and low hysteresis. Proc. Natl Acad. Sci. USA 116, 5967–5972 (2019).
Iwaseya, M., Watanabe, M., Yamaura, K., Dai, L. X. & Noguchi, H. High performance films obtained from PVA/Na2SO4/H2O and PVA/CH3COONa/H2O systems. J. Mater. Sci. 40, 5695–5698 (2005).
Zhang, Y. & Cremer, P. S. Interactions between macromolecules and ions: the Hofmeister series. Curr. Opin. Chem. Biol. 10, 658–663 (2006).
van de Witte, P., Dijkstra, P. J., Van Den Berg, J. W. A. & Feijen, J. Phase separation processes in polymer solutions in relation to membrane formation. J. Membr. Sci. 117, 1–31 (1996).
Lake, G. J. & Thomas, A.G. The strength of highly elastic materials. Proc. R. Soc. A 300, 108–119 (1967).
Kinloch, A. J. & Young, R. J. (eds) Fracture Behaviour of Polymers (Springer Science & Business Media, 1984).
Johnston, I. D., McCluskey, D. K., Tan, C. K. L. & Tracey, M. C. Mechanical characterization of bulk Sylgard 184 for microfluidics and microengineering. J. Micromech. Microeng. 24, 035017 (2014).
Wood, L. A. Uniaxial extension and compression in stress-strain relations of rubber. Rubber Chem. Technol. 51, 840–851 (1978).
Ebrahimi, D. et al. Silk – its mysteries, how it is made, and how it is used. ACS Biomater. Sci. Eng. 1, 864–876 (2015).
Long, R. & Hui, C. Y. Fracture toughness of hydrogels: measurement and interpretation. Soft Matter 12, 8069–8086 (2016).
Jiang, Z. GIXSGUI: a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films. J. Appl. Cryst. 48, 917–926 (2015).
Peppas, N. A. & Merrill, E. W. Differential scanning calorimetry of crystallized PVA hydrogels. J. Appl. Polym. Sci. 20, 1457–1465 (1976).
This research was supported by NSF CAREER award 1724526, AFOSR awards FA9550-17-1-0311, FA9550-18-1-0449 and FA9550-20-1-0344, and ONR awards N000141712117 and N00014-18-1-2314. X.Z. acknowledges Shanghai Municipal Government 18JC1410800 and National Natural Science Foundation of China 51690151. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357.
The authors declare no competing interests.
Peer review information Nature thanks Jiaxi Cui, Sylvain Deville and the other, anonymous, reviewer(s) 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 Micro- and nanostructures and stress–strain curves of PVA hydrogels fabricated by different methods and their corresponding fracture energies and critical strains.
a, ‘DF + Salting out’ denotes a hydrogel prepared by directional freezing of a 5% PVA solution and salting out in 1.5 M sodium citrate solution for 24 h. b, ‘F + Salting out’ represents a hydrogel prepared by non-directional freezing of a 5% PVA solution in the fridge and salting out in 1.5 M sodium citrate solution for 24 h. c, ‘DFT-3 cycle’ denotes a hydrogel prepared by directional freezing and thawing of a 5% PVA solution for three cycles. d, ‘FT-3 cycle’ indicates a hydrogel prepared by non-directional freezing in the fridge and thawing of a 5% PVA solution for three cycles. e, ‘Chemical Crosslinking’ represents a hydrogel prepared by mixing 0.5% glutaraldehyde and 0.5% hydrochloric acid into a 5% PVA solution for gelation. f, Salting out resulted in non-gelation. Only weak globules of loose and random nanofibrils were made by directly adding a 1.5 M sodium citrate solution into a 5% PVA solution. Panels a–c are the same as Fig. 3a–c.
a, Fatigue threshold of HA-20PVA. When loading above the threshold energy release rate (ε = 400%), the crack propagates slowly. N, number of cycles. b, Validation of fatigue threshold with an energy release rate slightly lower than the fatigue threshold. No crack propagation or failure was observed for 30,000 loading cycles.
a, Water content of HA-xPVA hydrogels for x = 2, 5, 10 and 20. The error bars (1 s.d. from five measured samples) were obtained from five measured samples with standard deviations of 1.72%, 2.29%, 2.69% and 2.43% for x = 2, 5, 10 and 20, respectively. b, Fracture energy of HA-xPVA hydrogels, x = 2, 5, 10 and 20, measured by pure shear tests. The error bars (1 s.d. from five measured samples) were obtained from five measured samples with standard deviations of 0.16, 4.83, 5.44 and 5.62 kJ m−2 for x = 2, 5, 10 and 20, respectively.
a, Photograph of HA-5alginate hydrogel. b, Tensile stress–strain curve of a HA-5alginate hydrogel compared to that of a regular calcium-alginate hydrogel. Scale bar, 5 mm.
This file includes a list of materials, Supplementary Text, Supplementary References, Supplementary Figs. 1–13, Supplementary Tables 1–3 and full captions for Videos 1 to 4.
Tensile loading of HA-5PVA dog-bone shaped hydrogel specimen.
Tensile loading of HA-5PVA hydrogel with pre-made crack.
Tensile loading of HA-20PVA hydrogel with pre-made crack.
Tensile loading of 5PVA hydrogel prepared by non-directional freezing and salting out with pre-made crack.
About this article
Cite this article
Hua, M., Wu, S., Ma, Y. et al. Strong tough hydrogels via the synergy of freeze-casting and salting out. Nature 590, 594–599 (2021). https://doi.org/10.1038/s41586-021-03212-z
NPG Asia Materials (2022)
Macromolecule conformational shaping for extreme mechanical programming of polymorphic hydrogel fibers
Nature Communications (2022)
Approaching intrinsic dynamics of MXenes hybrid hydrogel for 3D printed multimodal intelligent devices with ultrahigh superelasticity and temperature sensitivity
Nature Communications (2022)
Nature Nanotechnology (2022)
Nature Communications (2022)