Near-Net Shaping and Additive Manufacturing of Ultra-High Temperature Ceramics via Colloidal Processing

Abstract

Ceramic colloidal processing routes such as slip casting, gelcasting and direct ink writing provide valuable insight into the role of interaction forces between particles, solvents, and polymeric additives in the rheology, particle packing, and strength of a ceramic green body. For difficult-to-densify ceramics such as the UHTCs, which find their place in extreme environment applications, precise control of each step of the manufacturing process is key. In this work, a fundamental study on the interaction between particles in non-aqueous slip casting is performed comparing the rheological behavior and consolidation with current models for interaction potential within a suspension. The advantages and drawbacks of such a model are discussed in relation to formulating a colloidal process for advanced ceramics such as ZrB2, and a case for a cyclohexane slip casting system resulting in low viscosity, shear-thinning behavior and green density of 64%, is made. The focus on non-aqueous colloidal processing is extended to gelcasting, involving three different sets of chemically curable polymer systems: HEMA+MBAM, TMPTA, and PEGDA. Merits of the gelcasting process including homogeneity, green strength, and processing time reduction are discussed, with the HEMA+MBAM system resulting in nearly an order of magnitude increase in green density from slip casting. Gelcast samples were also sintered to a density of 88% and capable of being processed in a variety of complex shapes with fine feature size on the mm scale. The properties examined in slip casting and gelcasting, as well as others pertaining to the setup of an extrusion-based additive manufacturing system, are carefully considered to design an ink that has been used to print ZrB2. The role of each additive as well as the solvent in creating an ink that is not only within the correct viscosity range for extrusion and shape retention, but also produces a strong and densely packed green body, is discussed. Finally, adjustment of printing parameters, and the method of using a low-cost rheology match to tune the settings of a pneumatic screw-extrusion printing setup, are explained. Each of these processes points to new and practical methods of complex shaping ZrB2 that can provide insight into processing of these challenging materials and create new avenues for their use in extreme environment applications, such as thermal protection systems in atmospheric re-entry vehicles.