Photosensitive Composite Inks for Digital Light Processing Four-Dimensional Printing of Shape Memory Capture Devices.

High-performance shape memory thermosetting polymers and their composites for four-dimensional (4D) printing are essential in practical applications. To date, most printable thermosets suffer from complicated processes, poor thermodynamic performances, and low printing speed. Here, photosensitive composite inks for fast photocuring printing are developed. The inks consist of epoxy acrylate (EPAc), polyethylene glycol dimethacrylate (PEGDMA), and carbon fillers, which form a firm network structure when exposed to UV light. EPAc is synthesized via addition esterification of epoxy resin and acrylic acid under mild conditions. It is worth noting that raw materials for the reaction are diverse, including not only various epoxy resins but also molecules with epoxy groups. The 4D printing speed of up to 180 mm/h is mainly attributed to the exothermic reaction initiated by free radicals, which accelerates the polymerization of EPAc and PEGDMA. Most importantly, by increasing the exposure time of each layer from 1 s to 3 s during the printing process, the epoxy composite-infilled carbon nanotubes and carbon fibers are printed to ensure the integrity of the microlayer structure. Furthermore, we design a claw-like catcher device based on the above printable composite inks to demonstrate its potential applications in aerospace, such as grasping end-of-service spacecraft or explosive debris. Undoubtedly, 4D printing technology opens up a new portal for the manufacturing of thermoset epoxy composites and complex structures, which make the shape memory thermosetting epoxy resins and their composites possess excellent properties and good engineering application prospects.