Stereolithography-based additive manufacturing (AM) is a versatile and a technology of choice for small series or single unit production. It also allows the material-by-design fabrication, prime concern for most material chemists. State-of-the-art of three-dimensional (3D) structured organic-inorganic hybrid materials will be described and focus onto combined 3D printing technology.
Although the spectrum of available 3D-printed materials has been widened in recent years, there is still a lack of ceramic-based materials which can be processed with stereolithography on a routine basis. The extremely high melting point of many ceramics adds challenges to additive manufacturing as compared with metals and polymers. Because ceramics cannot be cast or machined easily, three-dimensional (3D) printing enables a big leap in geometrical flexibility and microstructured architecture.  
We report work on synthesis new ceramics from nanopowder and micropowder highly loaded resins that are cured with ultraviolet light in a stereolithography 3D printer. After a thermal debinding and sintering step the part turns into a dense ceramic open structure and gains its final properties, with uniform shrinkage and porosity control.
Currently it is therefore possible to print 3D-structures with a spatial resolution down to 50 µm, with complex shape and cellular architecture. The developed photosensitive resin formulation is a key parameter to control the printing resolution, so the geometry of the final ceramic. Highly complex three-dimensional open microstructures have been first digitally designed to lead to the best agreement between thermal insulation properties and mechanical toughness then 3D-printed, cured and characterized. The paper is focusing on the critical parameters that influence the uniformity and 3D-structure quality of the final ceramic part, including the understanding of thermal debinding and sintering step with in situ microstructural characterizations.
Experimental characterization and performances of the AM ceramic parts will be discussed with regard to high temperature super insulation material application, exhibiting simultaneously high-stiff properties. Those experimental results permit to validate calculated properties for open microstructures.