Dual ionically cross-linked hydrogels with ultra-tough, stable, and self-healing properties

  • Bo Xu
  • Xiong Zhang
  • Shuchun Gan
  • Jianhao Zhao
  • Jianhua RongEmail author
Polymers & biopolymers


Excellent mechanical and self-healing features could make hydrogels an ideal candidate for the application of load-bearing soft tissue replacements such as cartilage. In this study, a dual ionically cross-linked 2-hydroxypropyltrimethyl ammonium chloride chitosan (HACC)/poly(acrylic acid) (PAAc)-Fe3+ hydrogel was constructed using a one-pot method (in situ polymerization of AAc in the presence of HACC and Fe3+). Both macromolecular positively charged HACC and Fe3+ metal ions acted as cross-linkers to form ionic bonds with negatively charged PAAc. The HACC/PAAc-Fe3+ hydrogels demonstrated ultra-high mechanical strengths (tensile strength of ca. 9.86 MPa and compressive stresses greater than 95 MPa at 99% strain), excellent self-recoverability (ca. over 90% toughness recovery within 5 h without any external stimuli), outstanding self-healing properties (ca. 74% self-healing efficiency at 70 °C for 48 h), transparency, and high stabilities in aqueous environments. The mechanical properties of the hydrogels could be adjusted by varying the concentration of HACC and Fe3+. This work provides a new approach for the construction of novel tough and transparent hydrogels with a fully ionically cross-linked network.



Mouse embryo fibroblasts


Acroleic acid


Ammonium persulfate


Attenuated total reflectance Fourier-transform infrared


Cell counting kit-8


Dulbecco’s modified eagle’s medium


Fetal bovine serum


2-Hydroxypropyltrimethyl ammonium chloride chitosan


Polyacrylic acid




Scanning electron microscope




Xanthan gum



This work was supported by the National Natural Science Foundation of China (No. 51173070), National Natural Science Foundation of Guangdong, China (No. 2016A030313097), and the Science and Technology Program of Guangzhou, China (No. 201707010264).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2019_3773_MOESM1_ESM.docx (2.5 mb)
Supplementary material 1 (DOCX 2509 kb)


  1. 1.
    Gong JP (2010) Why are double network hydrogels so tough? Soft Matter 6:2583–2590CrossRefGoogle Scholar
  2. 2.
    Crompton KE, Goud JD, Bellamkonda RV, Gengenbach TR, Finkelstein DI, Horne MK, Forsythe JS (2007) Polylysine-functionalised thermoresponsive chitosan hydrogel for neural tissue engineering. Biomaterials 28:441–449CrossRefGoogle Scholar
  3. 3.
    Deng JN, Liang WL, Fang JY (2016) Liquid crystal droplet-embedded biopolymer hydrogel sheets for biosensor applications. ACS Appl Mater Interfaces 8:3928–3932CrossRefGoogle Scholar
  4. 4.
    Higa K, Kitamura N, Goto K, Kurokawa T, Gong JP, Kanaya F, Yasuda K (2017) Effects of osteochondral defect size on cartilage regeneration using a double-network hydrogel. BMC Musculoskelet Disord 18:210CrossRefGoogle Scholar
  5. 5.
    Lei ZY, Wang QK, Sun ST, Zhu WC, Wu PY (2017) A bioinspired mineral hydrogel as a self-healable, mechanically adaptable ionic skin for highly sensitive pressure sensing. Adv Mater 29:1700321CrossRefGoogle Scholar
  6. 6.
    Liu JY, Pang Y, Zhang SY et al (2017) Triggerable tough hydrogels for gastric resident dosage forms. Nat Commun 8:124CrossRefGoogle Scholar
  7. 7.
    Murakami K, Aoki H, Nakamura S et al (2010) Hydrogel blends of chitin/chitosan, fucoidan and alginate as healing-impaired wound dressings. Biomaterials 31:83–90CrossRefGoogle Scholar
  8. 8.
    Ding CX, Zhao LL, Liu FY et al (2010) Dually responsive injectable hydrogel prepared by in situ cross-linking of glycol chitosan and benzaldehyde-capped PEO-PPO-PEO. Biomacromol 11:1043–1051CrossRefGoogle Scholar
  9. 9.
    Chen Q, Yan XQ, Zhu L et al (2016) Improvement of mechanical strength and fatigue resistance of double network hydrogels by ionic coordination interactions. Chem Mater 28:5710–5720CrossRefGoogle Scholar
  10. 10.
    Gong JP, Katsuyama Y, Kurokawa T, Osada Y (2003) Double-network hydrogels with extremely high mechanical strength. Adv Mater 15:1155–1158CrossRefGoogle Scholar
  11. 11.
    Yang YY, Wang X, Yang F, Shen H, Wu DC (2016) A universal soaking strategy to convert composite hydrogels into extremely tough and rapidly recoverable double-network hydrogels. Adv Mater 28:7178–7184CrossRefGoogle Scholar
  12. 12.
    Yuan NX, Xu L, Wang HL et al (2016) Dual physically cross-linked double network hydrogels with high mechanical strength, fatigue resistance, notch-insensitivity, and self-healing properties. ACS Appl Mater Interface 8:34034–34044CrossRefGoogle Scholar
  13. 13.
    Haraguchi K, Takehisa T (2002) Nanocomposite hydrogels: a unique organic–inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties. Adv Mater 14:1120–1124CrossRefGoogle Scholar
  14. 14.
    Jiang HB, Wang ZF, Geng HY, Song XF, Zeng HB, Zhi CY (2017) Highly flexible and self-healable thermal interface material based on boron nitride nanosheets and a dual cross-linked hydrogel. ACS Appl Mater Inter 9:10078–10084CrossRefGoogle Scholar
  15. 15.
    Sakai T, Matsunaga T, Yamamoto Y et al (2008) Design and fabrication of a high-strength hydrogel with ideally homogeneous network structure from tetrahedron-like macromonomers. Macromolecules 41:5379–5384CrossRefGoogle Scholar
  16. 16.
    Huang T, Xu HG, Jiao KX, Zhu LP, Brown HR, Wang HL (2007) A novel hydrogel with high mechanical strength: a macromolecular microsphere composite hydrogel. Adv Mater 19:1622–1626CrossRefGoogle Scholar
  17. 17.
    Gu S, Duan LJ, Ren XY, Gao GH (2017) Robust, tough and anti-fatigue cationic latex composite hydrogels based on dual physically cross-linked networks. J Colloid Interface Sci 492:119–126CrossRefGoogle Scholar
  18. 18.
    Dai XY, Zhang YY, Gao LN, Bai T, Wang W, Cui YL, Liu WG (2015) A mechanically strong, highly stable, thermoplastic, and self-healable supramolecular polymer hydrogel. Adv Mater 27:3566–3571CrossRefGoogle Scholar
  19. 19.
    Li WB, An HY, Tan Y, Lu CG, Liu C, Li PC, Xu K, Wang PX (2012) Hydrophobically associated hydrogels based on acrylamide and anionic surface active monomer with high mechanical strength. Soft Matter 8:5078–5086CrossRefGoogle Scholar
  20. 20.
    Luo F, Sun TL, Nakajima T et al (2016) Strong and tough polyion-complex hydrogels from oppositely charged polyelectrolytes: a comparative study with polyampholyte hydrogels. Macromolecules 49:2750–2760CrossRefGoogle Scholar
  21. 21.
    Luo F, Sun TL, Nakajima T et al (2015) Oppositely charged polyelectrolytes form tough, self-healing, and rebuildable hydrogels. Adv Mater 27:2722–2727CrossRefGoogle Scholar
  22. 22.
    Sun TL, Kurokawa T, Kuroda S et al (2013) Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity. Nat Mater 12:932–937CrossRefGoogle Scholar
  23. 23.
    Gong ZY, Zhang GP, Zeng XL, Li JH, Li G, Huang WP, Sun R, Wong CP (2016) High-strength, tough, fatigue resistant, and self-healing hydrogel based on dual physically cross-linked network. ACS Appl Mater Interfaces 8:24030–24037CrossRefGoogle Scholar
  24. 24.
    Feng ZB, Zuo HL, Gao WS, Ning NY, Tian M, Zhang LQ (2018) A robust, self-healable, and shape memory supramolecular hydrogel by multiple hydrogen bonding interactions. Macromol Rapid Commun 39:e1800138CrossRefGoogle Scholar
  25. 25.
    Wang YX, Wang ZC, Wu KL, Wu JN, Meng GH, Liu ZY, Guo XH (2017) Synthesis of cellulose-based double-network hydrogels demonstrating high strength, self-healing, and antibacterial properties. Carbohydr Polym 168:112–120CrossRefGoogle Scholar
  26. 26.
    Hu Y, Du ZS, Deng XL, Wang T, Yang ZH, Zhou WY, Wang CY (2016) Dual physically cross-linked hydrogels with high stretchability, toughness, and good self-recoverability. Macromolecules 49:5660–5668CrossRefGoogle Scholar
  27. 27.
    Cai TT, Huo SJ, Wang T, Sun WX, Tong Z (2018) Self-healable tough supramolecular hydrogels crosslinked by poly-cyclodextrin through host-guest interaction. Carbohydr Polym 193:54–61CrossRefGoogle Scholar
  28. 28.
    Han L, Yan LW, Wang KF et al (2017) Tough, self-healable and tissue-adhesive hydrogel with tunable multifunctionality. NPG Asia Mater 9:e372CrossRefGoogle Scholar
  29. 29.
    Burattini S, Colquhoun HM, Fox JD et al (2009) A self-repairing, supramolecular polymer system: healability as a consequence of donor-acceptor π–π stacking interactions. Chem Commun 44:6717–6719CrossRefGoogle Scholar
  30. 30.
    Wang X-H, Song F, Qian D, He Y-D, Nie W-C, Wang X-L, Wang Y-Z (2018) Strong and tough fully physically crosslinked double network hydrogels with tunable mechanics and high self-healing performance. Chem Eng J 349:588–594CrossRefGoogle Scholar
  31. 31.
    He QY, Huang Y, Wang SY (2018) Hofmeister effect-assisted one step fabrication of ductile and strong gelatin hydrogels. Adv Funct Mater 28:1705069CrossRefGoogle Scholar
  32. 32.
    Ren Y, Lou RY, Liu XC et al (2016) A self-healing hydrogel formation strategy via exploiting endothermic interactions between polyelectrolytes. Chem Commun 52:6273–6276CrossRefGoogle Scholar
  33. 33.
    Zhao YR, Li MN, Liu BC et al (2018) Ultra-tough injectable cytocompatible hydrogel for 3D cell culture and cartilage repair. J Mater Chem B 6:1351–1358CrossRefGoogle Scholar
  34. 34.
    Yuan NX, Xu L, Xu B, Zhao JH, Rong JH (2018) Chitosan derivative-based self-healable hydrogels with enhanced mechanical properties by high-density dynamic ionic interactions. Carbohydr Polym 193:259–267CrossRefGoogle Scholar
  35. 35.
    Duan JJ, Liang XC, Cao Y, Wang S, Zhang LN (2015) High strength chitosan hydrogels with biocompatibility via new avenue based on constructing nanofibrous architecture. Macromolecules 48:2706–2714CrossRefGoogle Scholar
  36. 36.
    Zheng SY, Ding HY, Qian J, Yin J, Wu ZL, Song YH, Zheng Q (2016) Metal-coordination complexes mediated physical hydrogels with high toughness, stick-slip tearing behavior, and good processability. Macromolecules 49:9637–9646CrossRefGoogle Scholar
  37. 37.
    Song YB, Zhou JP, Li Q, Guo Y, Zhang LN (2009) Preparation and characterization of novel quaternized cellulose nanoparticles as protein carriers. Macromol Biosci 9:857–863CrossRefGoogle Scholar
  38. 38.
    You J, Xie SY, Cao JF, Ge H, Xu M, Zhang LN, Zhou JP (2016) Quaternized chitosan/poly(acrylic acid) polyelectrolyte complex hydrogels with tough, self-recovery, and tunable mechanical properties. Macromolecules 49:1049–1059CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Materials Science and Engineering, College of Chemistry and Materials ScienceJinan UniversityGuangzhouChina

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