Three-Dimensional Printing of Ceramics through "Carving" a Gel and "Filling in" the Precursor Polymer

Achieving a viable process for three-dimensional (3D) printing of ceramics is a sought-after goal in a wide range of fields including electronics and sensors for harsh environments, microelectromechanical devices, energy storage materials, and structural materials, among others. Low laser absorption of ceramic powders renders available additive manufacturing (AM) technologies for metals not suitable for ceramics. Polymer solutions that can be converted to ceramics (preceramic polymers) offer a unique opportunity to 3D-print ceramics; however, due to the low viscosity of these polymers, so far, their 3D printing has only been possible by combining them with specialized light-sensitive agents and subsequently cross-linking them layer by layer by rastering an optical beam. The slow rate, lack of scalability to large specimens, and specialized chemistry requirements of this optical process are fundamental limitations. Here, we demonstrate 3D printing of ceramics enabled by dispensing the preceramic polymer at the tip of a moving nozzle into a gel that can reversibly switch between fluid and solid states, and subsequently thermally cross-linking the entire printed part "at-once" while still inside the same gel. The solid gel, which is composed of mineral oil and silica nanoparticles, converts to fluid at the tip of the moving nozzle, allows the polymer solution to be dispensed, and quickly returns to a solid state to maintain the geometry of the printed polymer both during printing and the subsequent high-temperature (160 °C) cross-linking. We retrieve the cross-linked part from the gel and convert it to ceramic by high-temperature pyrolysis. This scalable process opens up new opportunities for low-cost and high-speed production of complex three-dimensional ceramic parts and will be widely used for high temperature and corrosive environment applications, including electronics and sensors, microelectromechanical systems, energy and structural applications.