Turning Vulcanized Natural Rubber into a Self-Healing Polymer: Effect of the Disulfide/Polysulfide Ratio

Marianella Hernandez Santana, Antonio Grande, W. Dierkes, Johan Bijleveld

Research output: Contribution to journalArticleScientificpeer-review

122 Citations (Scopus)


A self-healing sulfur vulcanized natural rubber (NR) is here reported using the common ingredients in a traditional NR formulation. The dynamic character of the di- and polysulfide bonds naturally present in covalently cross-linked rubbers was found to be responsible for the healing ability and the full recovery of mechanical properties at moderate temperatures provided the material was employed in a nonfully cured starting state. Results show that a compromise between mechanical performance and healing capability can be reached by tailoring the amount of sulfur, the cross-linking density, and the disulfide/polysulfide ratio. The healing efficiency was found to depend on the postcuring storage time, the time between damage creation and re-establishment of mechanical contact, and the actual healing time. Furthermore, a dedicated electron spin resonance (ESR) test allowed establishing the underlying healing principle based on temperature-induced free sulfur radicals. The main observations presented here can serve as the basis for the design and preparation of other self-healing polymers with long-term durability based on di-/ polysulfide bridges and other reversible moieties
Original languageEnglish
Pages (from-to)5776−5784
JournalACS Sustainable Chemistry and Engineering
Publication statusPublished - 2016


  • Vulcanized natural rubber
  • Degree of curing
  • Self-healing
  • Disulfides, Polysulfides
  • Elastomer
  • Time dependence
  • Electron spin resonance


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