The Final Frontier of Sustainable Materials: Current Developments in Self-Healing Elastomers.

It is impossible to describe the recent progress of our society without considering the role of polymers; however, for a broad audience, "polymer" is usually related to environmental pollution. The poor disposal and management of polymeric waste has led to an important environmental crisis, and, within polymers, plastics have attracted bad press despite being easily reprocessable. Nonetheless, there is a group of polymeric materials that is particularly more complex to reprocess, rubbers. These macromolecules are formed by irreversible crosslinked networks that give them their characteristic elastic behavior, but at the same time avoid their reprocessing. Conferring them a self-healing capacity stands out as a decisive approach for overcoming this limitation. By this mean, rubbers would be able to repair or restore their damage automatically, autonomously, or by applying an external stimulus, increasing their lifetime, and making them compatible with the circular economy model. Spain is a reference country in the implementation of this strategy in rubbery materials, achieving successful self-healable elastomers with high healing efficiency and outstanding mechanical performance. This article presents an exhaustive summary of the developments reported in the previous 10 years, which demonstrates that this property is the last frontier in search of truly sustainable materials.

Development of Sustainable, Mechanically Strong, and Self-Healing Bio-Thermoplastic Elastomers Reinforced with Alginates.

New bio-thermoplastic elastomer composites with self-healing capacities based on epoxidized natural rubber and polycaprolactone blends reinforced with alginates were developed. This group of salts act as natural reinforcing fillers, increasing the tensile strength of the unfilled rubber from 5.6 MPa to 11.5 MPa without affecting the elongation at break (~1000% strain). In addition, the presence of ionic interactions and hydrogen bonds between the components provides the material with a thermally assisted self-healing capacity, as it is able to restore its catastrophic damages and recover diverse mechanical properties up to ~100%. With the results of this research, an important and definitive step is planned toward the circularity of elastomeric materials.

Understanding the Molecular Dynamics of Dual Crosslinked Networks by Dielectric Spectroscopy.

The combination of vulcanizing agents is an adequate strategy to develop multiple networks that consolidate the best of different systems. In this research, sulfur (S), and zinc oxide ( ZnO) were combined as vulcanizing agents in a matrix of carboxylated nitrile rubber (XNBR). The resulting dual network improved the abrasion resistance of up to ~15% compared to a pure ionically crosslinked network, and up to ~115% compared to a pure sulfur-based covalent network. Additionally, the already good chemical resistance of XNBR in non-polar fluids, such as toluene and gasoline, was further improved with a reduction of up to ~26% of the solvent uptake. A comprehensive study of the molecular dynamics was performed by means of broadband dielectric spectroscopy (BDS) to complete the existing knowledge on dual networks in XNBR. Such analysis showed that the synergistic behavior that prevails over purely ionic vulcanization networks is related to the restricted motions of rubber chain segments, as well as of the trapped chains within the ionic clusters that converts the vulcanizate into a stiffer and less solvent-penetrable material, improving abrasion resistance and chemical resistance, respectively. This combined network strategy will enable the production of elastomeric materials with improved performance and properties on demand.

Design of Rubber Composites with Autonomous Self-Healing Capability.

The development of self-healing rubbers is currently under investigation as a strategy to promote their reuse and, hence, reduce their waste. However, autonomous, multicycle self-healing rubbers with good mechanical properties have so far proven difficult to achieve. Here, mechanically robust composites based on epoxidized natural rubber (ENR) and thermally reduced graphene oxide (TRGO) were successfully designed and prepared with a high healing efficiency of up to 85% at room temperature without applying external stimuli. The incorporation of TRGO not only improves the mechanical performance in more than 100% in relation to pristine ENR but also promotes the hydrogen bonding interactions with the rubber. This leads to a homogenous dispersion of TRGO within the ENR matrix, which further increases its self-healing capability.