Healable dual organic-inorganic crosslinked sol-gel based polymers: Crosslinking density and tetrasulfide content effect

ABSTRACT In this article, the first generation of healable sol–gel based polymers is reported. A dual organic–inorganic crosslinked network is developed containing non‐reversible crosslinks and reversible (tetrasulfide) groups. The designed polymer architecture allows thermally induced mesoscale flow leading to damage closure followed by interfacial strength restoration due to reformation of the reversible groups. While the reversible bonds are responsible for the flow and the interface restoration, the irreversible crosslinks control the required mechanical integrity during the healing process. The temperature dependent gap closure kinetics is strongly affected by the crosslinking density and tetrasulfide content. Raman spectroscopy is used to explain the gap closure kinetics in air and dry nitrogen. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1953–1961 Novel organic–inorganic sol–gel based polymers restore their integrity by selective breaking of tetrasulfide groups upon moderate thermo‐mechanical stimulus. The hybrid sol–gel architecture offers an attractive combination of a tuneable mesoscopic flow due to the presence of thermo‐responsive reversible bonds while preserving relatively high mechanical properties during the healing stage as a result of the stable crosslinked network.