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Surface-initiated self-healing of polymers in aqueous media

Abstract

Polymeric materials that intrinsically heal at damage sites under wet or moist conditions are urgently needed for biomedical and environmental applications1,2,3,4,5,6. Although hydrogels with self-mending properties have been engineered by means of mussel-inspired metal-chelating catechol-functionalized polymer networks7,8,9,10, biological self-healing in wet conditions, as occurs in self-assembled holdfast proteins in mussels and other marine organisms11,12, is generally thought to involve more than reversible metal chelates. Here we demonstrate self-mending in metal-free water of synthetic polyacrylate and polymethacrylate materials that are surface-functionalized with mussel-inspired catechols. Wet self-mending of scission in these polymers is initiated and accelerated by hydrogen bonding between interfacial catechol moieties, and consolidated by the recruitment of other non-covalent interactions contributed by subsurface moieties. The repaired and pristine samples show similar mechanical properties, suggesting that the triggering of complete self-healing is enabled underwater by the formation of extensive catechol-mediated interfacial hydrogen bonds.

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Figure 1: Schematic diagram of the steps entailed in polymer-rod healing studies.
Figure 2: NEXAFS spectra of catechol-functionalized polymer samples at incident radiation angles ranging from 30° to 120°.
Figure 3: Cohesive interactions between polymer films functionalized with exposed and blocked catechols as measured by the surface forces apparatus.
Figure 4: Adhesion force between various polymeric surfaces with a contact time of 5 s and 250 mN of applied load.

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Acknowledgements

The authors gratefully acknowledge financial support from the Office of Naval Research N000141310867, the United Soybean Board, the Institute for Collaborative Biotechnologies through grant W911NF-09-0001 from the US Army Research Office (the content of the information does not necessarily reflect the position or the policy of the Government, and no official endorsement should be inferred), the National Science Foundation MRSEC DMR-1121053, and the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences under Award DE-FG02-87ER-45331 (J.N.I. for the instrument modification of the Surface Forces Apparatus for the adhesion measurements and D.W.L. for the adhesion measurements). The authors also acknowledge assistance from T. Mates for XPS, Y. Li for XRR, and L. Perez for NEXAFS and GIWAXS.

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B.K.A. and D.W.L designed the research, performed the experiments, and wrote the paper. J.N.I. advised the experimental design of the modified SFA and experimental measurements, and the interpretation of results. J.H.W. supervised the overall experimental design and writing.

Corresponding authors

Correspondence to Jacob N. Israelachvili or J. Herbert Waite.

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The authors declare no competing financial interests.

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Ahn, B., Lee, D., Israelachvili, J. et al. Surface-initiated self-healing of polymers in aqueous media. Nature Mater 13, 867–872 (2014). https://doi.org/10.1038/nmat4037

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