3D‐Printed Architectured Silicones with Autonomic Self‐Healing and Creep‐Resistant Behavior

Self-healing silicones that are able to restore functionalities and extend the lifetime of soft devices hold great potential in many applications. However, currently available silicones need to be triggered to self-heal or suffer from creep-induced irreversible deformation during use. Here, a platform is proposed to design and print silicone objects that are programmed at the molecular and architecture levels to achieve self-healing at room temperature while simultaneously resisting creep. At the molecular scale, dioxaborolanes moieties are incorporated into silicones to synthesize self-healing vitrimers, whereas conventional covalent bonds are exploited to make creep-resistant elastomers. When combined into architectured printed parts at a coarser length scale, the layered materials exhibit fast healing at room temperature without compromising the elastic recovery obtained from covalent polymer networks. A patient-specific vascular phantom and fluidic chambers are printed to demonstrate the potential of architectured silicones in creating damage-resilient functional devices using molecularly designed elastomer materials.