Autonomic Self-Healing of Polymers: Mechanisms, Applications, and Challenges

Mechanical loads degrade polymers by enabling mechanochemical fragmentation of macromolecular backbones. In most polymers, this fragmentation is irreversible, and its accumulation leads to the appearance and propagation of cracks and, ultimately, fracture of the material. Self-healing describes a diverse and loosely defined collection of approaches that aim at reversing this damage. Most reported synthetic self-healing polymers are non-autonomic, i.e., they require the user to input free energy (in the form of heat, irradiation, or reagents) into the damaged material to initiate its repair. Here, we critically discuss emerging chemical approaches to autonomic self-healing that rely on regenerating the density of load-bearing, dissociatively-inert backbone bonds either after the load on a partially damaged material dissipated or continuously and in competition with the mechanochemically driven loss of backbones in the loaded material. We group the reported chemistries into three broad types whose analysis yields a set of criteria against which the potential of a prospective approach to yield practically relevant self-healing polymers can be assessed quantitatively. Our analysis suggests that the direct chain-to-chain addition in mechanically loaded unsaturated polyolefins is the most promising chemical strategy reported to date to achieve autonomic synchronous self-healing of practical significance.