Toward strong self-healing polyisoprene elastomers with dynamic ionic crosslinks.

To compromise high mechanical strength and efficient self-healing capability in an elastomer with dynamic crosslinks, optimization of the molecular structure is crucial in addition to the tuning of the dynamic properties of the crosslinks. Herein, we studied the effects of molecular weight, content of carboxy groups, and neutralization level of ionically crosslinked polyisoprene (PI) elastomers on their morphology, network rearrangement behavior, and self-healing and mechanical properties. In this PI elastomer, nanosized sphere-shaped ionic aggregates are formed by both neutralized and non-neutralized carboxy groups that act as stickers. The number density of the ionic aggregates that act as physical crosslinks increased with increase in the stickers' concentration, although the size of the ionic aggregates was independent of the molecular weight and the stickers' concentration. The ionic network was dynamically rearranged by the stickers' hopping between the ionic aggregates, and the rearrangement was accelerated by decreasing the neutralization level. We found that the 2Rg of the PI must be significantly larger than the average distance between the ionic aggregates to obtain a mechanically strong PI elastomer. We also found that further increase in the molecular weight is effective to enhance the dimensional stability of the elastomer. However, this approach reduced the elastomer's self-healing rate at the same time because the diffusion and randomization of the polymer chains between the damaged faces were reduced. In this work, we clearly demonstrated the principle in the optimization of the molecular structure for the ionically crosslinked PI elastomers to tune the mechanical and autonomous self-healing properties.

A gas-plastic elastomer that quickly self-heals damage with the aid of CO2 gas.

Self-healing materials are highly desirable because they allow products to maintain their performance. Typical stimuli used for self-healing are heat and light, despite being unsuitable for materials used in certain products as heat can damage other components, and light cannot reach materials located within a product or device. To address these issues, here we show a gas-plastic elastomer with an ionically crosslinked silicone network that quickly self-heals damage in the presence of CO2 gas at normal pressures and room temperature. While a strong elastomer generally exhibits slow self-healing properties, CO2 effectively softened ionic crosslinks in the proposed elastomer, and network rearrangement was promoted. Consequently, self-healing was dramatically accelerated by ~10-fold. Moreover, self-healing was achieved even at -20 °C in the presence of CO2 and the original mechanical strength was quickly re-established during the exchange of CO2 with air.