Fabrication of ZrO₂ Armor Ceramics by 3D Printing Accompanied with Microwave Sintering

Ceramic armor protection with complex shapes is limited by the difficult molding or machining processing, and 3D printing technology provides a feasible method for complex-shaped ceramics. In this study, ZrO₂ ceramics were manufactured by 3D printing accompanied with microwave sintering. In 3D printing, the formula of photosensitive resin was optimized by controlling the content of polyurethane acrylic (PUA) as oligomer, and the photosensitive resin with 50% PUA showed excellent curing performance with a small volume shrinkage of 4.05%, media viscosity of 550 mPa·s, and low critical exposure of 20 mJ/cm². Compared to conventional sintering, microwave sintering was beneficial to dense microstructures with fine grain size, and microwave sintering at 1500 °C was confirmed as an optimized sintering process for the 3D-printed ZrO₂ ceramics, and the obtained ceramics showed a relative density of 98.2% and mean grain size of 2.1 μm. The PUA content further affected the microstructure and mechanical property of the ZrO₂ ceramics. The sample with 10%~40% PUA showed some pores due to the low viscosity and large volume shrinkage of photosensitive resins, and the sample with 60% PUA exhibited an inhomogeneous microstructure with agglomeration, attributed to the high viscosity of photosensitive resins. Finally, the ZrO₂ ceramics via 3D printing with 50% PUA showed superior mechanical properties, whose Vickers hardness was 3.4 GPa, fracture toughness was 7.4 MPa·m^1/2, flexure strength was 1038 MPa, and dynamic strength at 1200 s⁻¹ was 4.9 GPa, conducive to the material’s employment as armor protection ceramics.