Dynamic Covalent Chemistry at Interfaces: Development of Tougher, Healable Composites through Stress Relaxation at the Resin–Silica Nanoparticles Interface

Abstract The interfacial region in composites that incorporate filler materials of dramatically different modulus relative to the resin phase acts as a stress concentrator and becomes a primary locus for composite failure. A novel adaptive interface (AI) platform formed by coupling moieties capable of dynamic covalent chemistry (DCC) is introduced to the resin–filler interface to promote stress relaxation. Specifically, silica nanoparticles (SNP) are functionalized with a silane capable of addition fragmentation chain transfer (AFT), a process by which DCC‐active bonds are reversibly exchanged upon light exposure and concomitant radical generation, and copolymerized with a thiol‐ene resin. At a fixed SNP loading of 25 wt%, the toughness (2.3 MJ m−3) is more than doubled and polymerization shrinkage stress (0.4 MPa) is cut in half in the AI composite relative to otherwise identical composites that possess a passive interface (PI) with similar silane structure, but without the AFT moiety. In situ activation of the AI during mechanical loading results in 70% stress relaxation and three times higher fracture toughness than the PI control. When interfacial DCC was combined with resin‐based DCC, the toughness was improved by 10 times relative to the composite without DCC in either the resin or at the resin–filler interface.