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Biomimetic Water-Responsive Self-Healing Epoxy with Tunable Properties

  • Dian Yuan
    Dian Yuan
    Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106, United States
    More by Dian Yuan
  • Sébastien Delpierre
    Sébastien Delpierre
    Laboratory of Polymeric and Composite Materials (LPCM), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons, Place du Parc 23, 7000 Mons, Belgium
  • Kai Ke*
    Kai Ke
    Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106, United States
    *E-mail: [email protected] (K.K.).
    More by Kai Ke
  • Jean-Marie Raquez*
    Jean-Marie Raquez
    Laboratory of Polymeric and Composite Materials (LPCM), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons, Place du Parc 23, 7000 Mons, Belgium
    *E-mail: [email protected] (J.-M.R.).
  • Philippe Dubois
    Philippe Dubois
    Laboratory of Polymeric and Composite Materials (LPCM), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons, Place du Parc 23, 7000 Mons, Belgium
  • , and 
  • Ica Manas-Zloczower*
    Ica Manas-Zloczower
    Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106, United States
    *E-mail: [email protected] (I.M.-Z.).
Cite this: ACS Appl. Mater. Interfaces 2019, 11, 19, 17853–17862
Publication Date (Web):April 18, 2019
Copyright © 2019 American Chemical Society

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    Abstract Image

    As dynamic cross-linking networks are intrinsically weaker than permanent covalent networks, it is a big challenge to obtain a stiff self-healing polymer using reversible networks. Inspired by the self-healable and mechanically adaptive nature of sea cucumber, we design a water-responsive self-healing polymer system with reversible and permanent covalent networks by cross-linking poly(propylene glycol) with boroxine and epoxy. This double cross-linked structure is self-healing due to the boroxine reversible network as well as showing a room-temperature tensile modulus of 1059 MPa and a tensile stress of 37 MPa, on a par with classic thermosets. The dynamic boroxine bonds provide the self-healing response and enable up to 80% recovery in modulus and tensile strength upon water contact. The system shows superior adhesion to metal substrates by comparison with the commercial epoxy-based structural adhesive. Besides, this system can change modulus from a stiff thermoset to soft rubber (by a factor of 150) upon water stimulus, enabling potential applications of either direct or transform printing for micro/nanofabrication. Moreover, by incorporating conductive nanofillers, it becomes feasible to fabricate self-healing and versatile strain/stress sensors based on a single thermoset, with potential applications in wearable electronics for human healthcare.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b04249.

    • FTIR, DMA of epoxy-boroxine system, and DSC curves of epoxy and epoxy-boroxine; TGA of cured epoxy-boroxine; tensile properties of original and healed epoxy-boroxine; swelling test of epoxy and epoxy-boroxine in DMF and water; FTIR and tensile properties of epoxy-boroxine under two wet-dry cycles; representative stress–strain curve of original epoxy-boroxine and epoxy-boroxine exposed to different humidity conditions for two weeks; tensile properties of original epoxy-boroxine and epoxy-boroxine exposed to ambient humidity for two weeks; TEM of CNS; OPM of epoxy-boroxine with CNS; and linear fitting of relative resistance change (ΔR/R0) versus strain for CNS-epoxy-boroxine samples (PDF)

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