Microphase separation 3D printing of binary inorganic polymer precursors to prepare nanostructured carbon-ceramic multimaterials

Traditionally, combining carbon and ceramic materials has been challenging due to their different chemical and physical properties. Despite the development of numerous methodologies for their synthesis, these techniques frequently necessitate intricate, multi-stage protocols and specialized equipment. This study introduces a novel approach for fabricating nanostructured carbon-ceramic multimaterials through polymerization-induced microphase separation 3D printing. By combining inorganic precursors, polycarbosilane, and acrylonitrile (AN) within a photocurable resin, heterogeneous nanostructured materials composed of PAN-preceramic and sacrificial polymer phases are 3D printed. Upon pyrolysis, PAN-preceramic domains transformed into a carbon-ceramic matrix while sacrificial polymer domains thermally decomposed to yield nanoscale voids. The utilization of synchrotron X-ray spectroscopy and microscopy techniques revealed that the phase compositions and microstructure of the resulting multi-materials are significantly influenced by the initial composition of the resins. The co-existence of ceramic and carbon phases within a single 3D printed material brought together a combination of properties from both phases, such as the low thermal conductivity of ceramics and the relatively high electrical conductivity of carbon, along with the exceptional chemical resistance. The insights into the microstructure, atomic configuration, and property relationships of the resulting materials have broad implications for the development of multi-phase nanostructured hybrid materials.