LAUSR

Soft silicone is an ideal flexible material for application, e.g., in soft robotics, flexible electronics, bionics, or implantable biomedical devices. However, gravity‐driven sagging, filament stretching, and deformation can cause inevitable defects during rapid manufacturing, making it hard to obtain complex, high‐resolution 3D silicone structures with direct ink writing (DIW) technology. Here, rapid DIW of soft silicone enabled by a phase‐change‐induced, reversible change of the ink's hierarchical microstructure is presented. During printing, the silicone‐based ink, containing silica nanoparticles and wax microparticles, is extruded from a heated nozzle into a cold environment under controlled stress. The wax phase change (solid–liquid–solid) during printing rapidly destroys and rebuilds the particle networks, realizing fast control of the ink flow behavior and printability. This high‐operating‐temperature DIW method is fast (maximum speed ≈3100 mm min−1) and extends the DIW scale range of soft silicone. The extruded filaments have small diameters (50 ± 5 µm), and allow for large spans (≈13‐fold filament diameter) and high aspect ratios (≈1), setting a new benchmark in the DIW of soft silicone. Printed silicone structures exhibit excellent performance as flexible sensors, superhydrophobic surfaces, and shape‐memory bionic devices, illustrating the potential of the new 3D printing strategy.