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Self-healing and thermoreversible rubber from supramolecular assembly


Rubbers exhibit enormous extensibility up to several hundred per cent, compared with a few per cent for ordinary solids, and have the ability to recover their original shape and dimensions on release of stress1,2. Rubber elasticity is a property of macromolecules that are either covalently cross-linked1,2 or connected in a network by physical associations such as small glassy or crystalline domains3,4,5, ionic aggregates6 or multiple hydrogen bonds7,8,9,10,11,12,13,14,15,16. Covalent cross-links or strong physical associations prevent flow and creep. Here we design and synthesize molecules that associate together to form both chains and cross-links via hydrogen bonds. The system shows recoverable extensibility up to several hundred per cent and little creep under load. In striking contrast to conventional cross-linked or thermoreversible rubbers made of macromolecules, these systems, when broken or cut, can be simply repaired by bringing together fractured surfaces to self-heal at room temperature. Repaired samples recuperate their enormous extensibility. The process of breaking and healing can be repeated many times. These materials can be easily processed, re-used and recycled. Their unique self-repairing properties, the simplicity of their synthesis, their availability from renewable resources and the low cost of raw ingredients (fatty acids and urea) bode well for future applications.

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Figure 1: Supramolecular network.
Figure 2: Synthesis pathway.
Figure 3: Rheological and mechanical properties.
Figure 4: Self-mending at room temperature.

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We thank P.-G. de Gennes for interest and support. We thank M. Cloître, J.-M. Lehn, K. Matyjaszewski and S. Stupp for discussions. We also thank M. Milléquant and S. Girault for their help with chromatography and X-ray scattering experiments, respectively. We are indebted to Arkema and in particular to M. Hidalgo for enlarging our views on some industrial aspects of this project. CNRS, ESPCI, Arkema and DGA are thanked for financial support.

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Correspondence to Ludwik Leibler.

Supplementary information

Supplementary Figures

The file contains Supplementary Figures 1-6 with Legends. (PDF 230 kb)

Supplementary Movie 1

The file contains Supplementary Movie 1 demonstrating self healing of supramolecular rubber. Small movie showing the tensile test of a mended sample (compound B). Originally the sample was cut and the cut parts were brought together and healed at room temperature. At the beginning of the movie, the scar is not visible. It appears during the stretching and finally a fracture propagates and the sample breaks. We inked a rectangular area so that the deformation can be appreciated. Please note the elastic recovery after the sample is broken. (MP4 3780 kb)

Supplementary Movie 2

The file contains Supplementary Movie 2 demonstrating extensibility of supramolecular rubber. Small movie showing the extensibility of the supramolecular rubber plasticized by water. (MPG 335 kb)

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Cordier, P., Tournilhac, F., Soulié-Ziakovic, C. et al. Self-healing and thermoreversible rubber from supramolecular assembly. Nature 451, 977–980 (2008).

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