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Optically healable supramolecular polymers

Nature volume 472, pages 334–337 (2011)Cite this article

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Abstract

Polymers with the ability to repair themselves after sustaining damage could extend the lifetimes of materials used in many applications1. Most approaches to healable materials require heating the damaged area2,3,4. Here we present metallosupramolecular polymers that can be mended through exposure to light. They consist of telechelic, rubbery, low-molecular-mass polymers with ligand end groups that are non-covalently linked through metal-ion binding. On exposure to ultraviolet light, the metal–ligand motifs are electronically excited and the absorbed energy is converted into heat. This causes temporary disengagement of the metal–ligand motifs and a concomitant reversible decrease in the polymers’ molecular mass and viscosity5, thereby allowing quick and efficient defect healing. Light can be applied locally to a damage site, so objects can in principle be healed under load. We anticipate that this approach to healable materials, based on supramolecular polymers and a light–heat conversion step, can be applied to a wide range of supramolecular materials that use different chemistries.

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Figure 1: Mechanism and synthesis of photohealable metallosupramolecular polymers.
Figure 2: Characterization of Zn-based metallosupramolecular polymers.
Figure 3: Mechanical properties and healing of the metallosupramolecular polymers.
Figure 4: Characterization of La-based metallosupramolecular polymers.

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Acknowledgements

This material is based on work supported by the US Army Research Office (W911NF-09-1-0288 and W911NF-06-1-0414); the National Science Foundation under grant numbers CHE-0704026, DMR-0602869 and MRI-0821515; the Adolphe Merkle Foundation; and the Postgraduate Research Participation Program at the US Army Research Laboratory, administered by the Oak Ridge Institute of Science and Education through an interagency agreement between the US Department of Energy and Army Research Laboratory (contract number ORISE-1120-1120-99). We thank S. Dellinger for the design and the fabrication of a device to introduce well-defined defects and Kraton Performance Polymers Inc for the donation of the hydroxyl-terminated poly(ethylene-co-butylene).

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Authors and Affiliations

  1. Department of Macromolecular Science and Engineering, Case Western Reserve University, 2100 Adelbert Road, Cleveland, 44106-7202, Ohio, USA

    Mark Burnworth, Liming Tang, Justin R. Kumpfer, Stuart J. Rowan & Christoph Weder

  2. US Army Research Laboratory, Aberdeen Proving Ground, 21005-5069, Maryland, USA

    Andrew J. Duncan & Frederick L. Beyer

  3. Adolphe Merkle Institute and Fribourg Center for Nanomaterials, University of Fribourg, CH-1700 Fribourg, Switzerland

    Gina L. Fiore & Christoph Weder

Authors
  1. Mark Burnworth
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  2. Liming Tang
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  3. Justin R. Kumpfer
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  6. Gina L. Fiore
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  7. Stuart J. Rowan
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  8. Christoph Weder
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Contributions

M.B., L.T. and J.R.K. developed the procedures for synthesis and characterization of 3. M.B. prepared and processed all supramolecular polymers. M.B. and G.L.F. did the MDSC experiments. A.J.D. and F.L.B. carried out the TEM and SAXS experiments. M.B. did the mechanical testing. G.L.F. carried out the light–heat conversion experiments. M.B. conducted the photohealing experiments. S.J.R. and C.W. designed the study. All authors discussed results and contributed to the interpretation of data. M.B., S.J.R. and C.W. wrote the paper. All authors contributed to editing the manuscript.

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Correspondence to Stuart J. Rowan or Christoph Weder.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Figures 1-12 with legends, a Supplementary Discussion and Supplementary Tables 1-3 with legends. (PDF 2229 kb)

Supplementary Movie 1

The movie shows optical healing of Zn-based metallo-supramolecular polymer. Shown is a damaged film of 3•[Zn(NTf2)2]0.7 before, during, and after exposure to light in the wavelength range from 320-390 nm at an intensity of 950 mW/cm2, focused on the center of the film, demonstrating the localized healing of metallo-supramolecular. (MPG 5686 kb)

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Burnworth, M., Tang, L., Kumpfer, J. et al. Optically healable supramolecular polymers. Nature 472, 334–337 (2011). https://doi.org/10.1038/nature09963

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