Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Nanoconfined polymerization limits crack propagation in hysteresis-free gels

Nature Materials volume 23, pages 131–138 (2024)Cite this article

Subjects

Abstract

Consecutive mechanical loading cycles cause irreversible fatigue damage and residual strain in gels, affecting their service life and application scope. Hysteresis-free hydrogels within a limited deformation range have been created by various strategies. However, large deformation and high elasticity are inherently contradictory attributes. Here we present a nanoconfined polymerization strategy for producing tough and near-zero-hysteresis gels under a large range of deformations. Gels are prepared through in situ polymerization within nanochannels of covalent organic frameworks or molecular sieves. The nanochannel confinement and strong hydrogen bonding interactions with polymer segments are crucial for achieving rapid self-reinforcement. The rigid nanostructures relieve the stress concentration at the crack tips and prevent crack propagation, enhancing the ultimate fracture strain (17,580 ± 308%), toughness (87.7 ± 2.3 MJ m−3) and crack propagation strain (5,800%) of the gels. This approach provides a general strategy for synthesizing gels that overcome the traditional trade-offs of large deformation and high elasticity.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic illustration of the hysteresis-free and crack-propagation-insensitive hydrogels, ionogels and organogels prepared by the NCP strategy.
Fig. 2: Mechanical properties and rapid self-reinforcement of the hydrogels.
Fig. 3: Crack propagation insensitivity and fatigue resistance under uniaxial tension.
Fig. 4: Universality of NCP strategy.
Fig. 5: Structural transformation of hydrogels and strong hydrogen bond interaction between monomer and nanochannels.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available within the article and its Supplementary Information. The other relevant data are available at https://doi.org/10.5281/zenodo.8347583. Source data are provided with this paper.

References

  1. Dobashi, Y. et al. Piezoionic mechanoreceptors: force-induced current generation in hydrogels. Science 376, 502–507 (2022).

    Article  CAS  Google Scholar 

  2. Na, H. et al. Hydrogel-based strong and fast actuators by electroosmotic turgor pressure. Science 376, 301–307 (2022).

    Article  CAS  Google Scholar 

  3. Kirtane, A. R. et al. Development of oil-based gels as versatile drug delivery systems for pediatric applications. Sci. Adv. 8, eabm8478 (2022).

    Article  CAS  Google Scholar 

  4. Griffin, D. R. et al. Activating an adaptive immune response from a hydrogel scaffold imparts regenerative wound healing. Nat. Mater. 20, 560–569 (2021).

    Article  CAS  Google Scholar 

  5. Guo, J. L. et al. Modular, tissue-specific, and biodegradable hydrogel cross-linkers for tissue engineering. Sci. Adv. 5, eaaw7396 (2019).

    Article  CAS  Google Scholar 

  6. Christianson, C., Goldberg, N. N., Deheyn, D. D., Cai, S. & Tolley, M. T. Translucent soft robots driven by frameless fluid electrode dielectric elastomer actuators. Sci. Robot. 3, eaat1893 (2018).

    Article  Google Scholar 

  7. Liu, C. et al. Tough hydrogels with rapid self-reinforcement. Science 372, 1078–1081 (2021).

    Article  CAS  Google Scholar 

  8. Kim, J., Zhang, G., Shi, M. & Suo, Z. Fracture, fatigue, and friction of polymers in which entanglements greatly outnumber cross-links. Science 374, 212–216 (2021).

    Article  CAS  Google Scholar 

  9. Wang, Z. et al. Toughening hydrogels through force-triggered chemical reactions that lengthen polymer strands. Science 374, 193–196 (2021).

    Article  CAS  Google Scholar 

  10. Gong, J. P., Katsuyama, Y., Kurokawa, T. & Osada, Y. Double-network hydrogels with extremely high mechanical strength. Adv. Mater. 15, 1155–1158 (2003).

    Article  CAS  Google Scholar 

  11. Jiang, Z. et al. Strong, self-healable, and recyclable visible-light-responsive hydrogel actuators. Angew. Chem. Int. Ed. 59, 7049–7056 (2020).

    Article  CAS  Google Scholar 

  12. Haraguchi, K. & Takehisa, T. Nanocomposite hydrogels: a unique organic–inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties. Adv. Mater. 14, 1120–1124 (2002).

    Article  CAS  Google Scholar 

  13. Li, J., Suo, Z. & Vlassak, J. J. Stiff, strong, and tough hydrogels with good chemical stability. J. Mater. Chem. B 2, 6708–6713 (2014).

    Article  Google Scholar 

  14. Meng, X. et al. Hysteresis-free nanoparticle-reinforced hydrogels. Adv. Mater. 34, 2108243 (2022).

    Article  CAS  Google Scholar 

  15. Chen, Q. et al. A novel design strategy for fully physically linked double network hydrogels with tough, fatigue resistant, and self-healing properties. Adv. Funct. Mater. 25, 1598–1607 (2015).

    Article  CAS  Google Scholar 

  16. Zhang, H. J. et al. Tough physical double-network hydrogels based on amphiphilic triblock copolymers. Adv. Mater. 28, 4884–4890 (2016).

    Article  CAS  Google Scholar 

  17. Xia, L.-W. et al. Nano-structured smart hydrogels with rapid response and high elasticity. Nat. Commun. 4, 2226 (2013).

    Article  Google Scholar 

  18. Hu, J. et al. Microgel-reinforced hydrogel films with high mechanical strength and their visible mesoscale fracture structure. Macromolecules 44, 7775–7781 (2011).

    Article  CAS  Google Scholar 

  19. Lei, H. et al. Stretchable hydrogels with low hysteresis and anti-fatigue fracture based on polyprotein cross-linkers. Nat. Commun. 11, 4032 (2020).

    Article  CAS  Google Scholar 

  20. Fujiyabu, T. et al. Tri-branched gels: rubbery materials with the lowest branching factor approach the ideal elastic limit. Sci. Adv. 8, eabk0010 (2022).

    Article  CAS  Google Scholar 

  21. Hua, M. et al. Strong tough hydrogels via the synergy of freeze-casting and salting out. Nature 590, 594–599 (2021).

    Article  CAS  Google Scholar 

  22. Li, W. et al. Supramolecular ionogels tougher than metals. Adv. Mater. 35, 2301383 (2023).

    Article  CAS  Google Scholar 

  23. Zhuo, Y. et al. Simultaneously toughening and stiffening elastomers with octuple hydrogen bonding. Adv. Mater. 33, 2008523 (2021).

    Article  CAS  Google Scholar 

  24. Liang, X. et al. Anisotropically fatigue-resistant hydrogels. Adv. Mater. 33, 2102011 (2021).

    Article  CAS  Google Scholar 

  25. Xiang, C. et al. Stretchable and fatigue-resistant materials. Mater. Today 34, 7–16 (2020).

    Article  CAS  Google Scholar 

  26. Liang, X. et al. Bioinspired 2D isotropically fatigue-resistant hydrogels. Adv. Mater. 34, 2107106 (2022).

    Article  CAS  Google Scholar 

  27. Biswal, B. P. et al. Mechanochemical synthesis of chemically stable isoreticular covalent organic frameworks. J. Am. Chem. Soc. 135, 5328–5331 (2013).

    Article  CAS  Google Scholar 

  28. Chandra, S. et al. Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination. J. Am. Chem. Soc. 135, 17853–17861 (2013).

    Article  CAS  Google Scholar 

  29. Lu, Y. et al. Self-recovery, fatigue-resistant, and multifunctional sensor assembled by a nanocellulose/carbon nanotube nanocomplex-mediated hydrogel. ACS Appl. Mater. Interfaces 13, 50281–50297 (2021).

    Article  CAS  Google Scholar 

  30. Sun, X. et al. Carbon nanotubes reinforced hydrogel as flexible strain sensor with high stretchability and mechanically toughness. Chem. Eng. J. 382, 122832 (2020).

    Article  CAS  Google Scholar 

  31. Hu, Y. et al. Graphene oxide encapsulating liquid metal to toughen hydrogel. Adv. Funct. Mater. 31, 2106761 (2021).

    Article  CAS  Google Scholar 

  32. Xia, Q. et al. Metal–organic framework (MOF) facilitated highly stretchable and fatigue-resistant ionogels for recyclable sensors. Mater. Horizons 9, 2881–2892 (2022).

    Article  CAS  Google Scholar 

  33. Huang, Y. et al. A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte. Nat. Commun. 6, 10310 (2015).

    Article  CAS  Google Scholar 

  34. Li, Y., Yan, J., Liu, Y. & Xie, X.-M. Super tough and intelligent multibond network physical hydrogels facilitated by Ti3C2Tx MXene nanosheets. ACS Nano 16, 1567–1577 (2022).

  35. Norioka, C., Inamoto, Y., Hajime, C., Kawamura, A. & Miyata, T. A universal method to easily design tough and stretchable hydrogels. NPG Asia Mater. 13, 34 (2021).

    Article  CAS  Google Scholar 

  36. Li, W. et al. Recyclable, healable, and tough ionogels insensitive to crack propagation. Adv. Mater. 34, 2203049 (2022).

    Article  CAS  Google Scholar 

  37. Zheng, Y. et al. Nanophase separation in immiscible double network elastomers induces synergetic strengthening, toughening, and fatigue resistance. Chem. Mater. 33, 3321–3334 (2021).

    Article  Google Scholar 

  38. Yang, Y., Wang, X., Yang, F., Shen, H. & Wu, D. A universal soaking strategy to convert composite hydrogels into extremely tough and rapidly recoverable double-network hydrogels. Adv. Mater. 28, 7178–7184 (2016).

    Article  CAS  Google Scholar 

  39. Wang, Y. J. et al. Ultrastiff and tough supramolecular hydrogels with a dense and robust hydrogen bond network. Chem. Mater. 31, 1430–1440 (2019).

    Article  CAS  Google Scholar 

  40. Li, W. et al. Tough hydrogels with isotropic and unprecedented crack propagation resistance. Adv. Funct. Mater. 32, 2207348 (2022).

    Article  CAS  Google Scholar 

  41. Zhao, X. et al. Soft materials by design: unconventional polymer networks give extreme properties. Chem. Rev. 121, 4309–4372 (2021).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (21835005, F.Y.; 52333002, F.Y.), Jiangsu Province Science Foundation for Carbon Emissions Peak and Carbon Neutrality Science and Technology Innovation (BK20220007, F.Y.), Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX22_3202, W.L.), Collaborative Innovation Center of Suzhou Nano Science and Technology and Priority Academic Program Development of Jiangsu Higher Education Institutions. We are grateful to Q. Zhang for the technical support with the SAXS measurement with the Vacuum Interconnected Nanotech Workstation (Nano-X) from Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences.

Author information

Authors and Affiliations

  1. Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Negative Carbon Technologies College of Chemistry, Suzhou Key Laboratory of Soft Material and New Energy, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, China

    Weizheng Li, Ziyang Liu, Xiuyang Zou, Lingling Li, Yu Guo & Feng Yan

  2. School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Xiaoliang Wang

  3. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Zhihao Shen & Dong Liu

  4. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, China

    Feng Yan

Authors
  1. Weizheng Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaoliang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ziyang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiuyang Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhihao Shen
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dong Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Lingling Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yu Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Feng Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

W.L. and F.Y. conceived the concept. F.Y. supervised the project. W.L. conducted the experiments. W.L. and F.Y. wrote the manuscript. X.W., Z.L., Z.S., D.L., L.L., Y.G. and X.Z. participated in optimizing the figures and assisted with material fabrication and characterization. All the authors contributed to the analysis and discussion of the data.

Corresponding author

Correspondence to Feng Yan.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Materials thanks Michael Dickey and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–34 and Discussion.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 3

Unprocessed gels.

Source Data Fig. 4

Statistical source data.

Source Data Fig. 5

Statistical source data.

Source Data Fig. 5

Unprocessed two-dimensional SAXS image and unprocessed molecular dynamics simulation snapshots.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, W., Wang, X., Liu, Z. et al. Nanoconfined polymerization limits crack propagation in hysteresis-free gels. Nat. Mater. 23, 131–138 (2024). https://doi.org/10.1038/s41563-023-01697-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-023-01697-9

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing