Hierarchically porous ceramics via direct writing of preceramic polymer-triblock copolymer inks

Hierarchically porous ceramics possess tailored porosity across multiple length scales, giving rise to materials with low density, high specific properties, and multifunctionality. Here, we report a method that combines self-assembly and 3D printing to create ceramic architectures with hierarchical porosity spanning from the nano- to microscale. To programmably define their microscale porosity, an additive manufacturing method, known as direct ink writing, is used to create 3D lattices composed of cylindrical struts. Nanoscale porosity is generated within each strut by block copolymer templating followed by photopolymerization and pyrolysis in a non-oxidative environment, which transforms the preceramic polymer, polycarbosilane, into silicon oxycarbide with a “nanocoral” morphology. The resulting hierarchically porous ceramic lattices exhibit excellent mechanical energy absorption (0.31 MJ/m³), comparable to metal alloy foams. They also possess an order of magnitude lower thermal conductivity (0.087–0.16 W/m⋅K) compared to bulk preceramic polymer-derived ceramics. Prior to pyrolysis, the printed architectures can be manipulated to produce more complex shapes, including lattices with twisted, helical, and overhang features as well as repeated folding to create an origami airplane. By combining self- and directed assembly, our approach opens new avenues for creating hierarchically porous ceramics.