Formulations with active functional additives for 3D printing of preceramic polymers, and methods of 3D-printing the formulations

A 3D-printing composition comprising:

• (a) from about 10 vol % to about 99 vol % of one or more preceramic, UV-curable monomers;
• (b) from about 1 vol % to about 70 vol % of solid-phase functional additives, wherein said functional additives have an average effective diameter from about 5 nanometers to about 1000 nanometers, wherein said functional additives actively improve a final ceramic structure through one or more changes induced by said functional additives during pyrolysis of a polymerized form of said one or more preceramic, UV-curable monomers, and wherein said functional additives are characterized by the property that at a temperature of 1300° C., said functional additives catalyze nucleation and/or crystallization associated with conversion of a polymerized form of said one or more said one or more preceramic, UV-curable monomers into a solid ceramic phase;
• (c) a photoinitiator or photoacid generator;
• and
• (d) a 3D-printing resolution agent,
• wherein said functional additives are selected from silicon carbide, silicon oxycarbide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, silicon carbonitride, silicon boronitride, silicon boron carbonitride, or combinations thereof;
• and
• wherein said functional additives contain a surface treatment that increases the compatibility, solubility, and/or bonding reactivity of said functional additives with said preceramic, UV-curable monomers.