Zirconia toughened hydroxyapatite biocomposite formed by a DLP 3D printing process for potential bone tissue engineering.

The construction of ceramic components with UV curing is a developing trend by an additive manufacturing (AM) technology, due to the excellent advantages of high precision selective fixation and rapid prototyping, the application of this technology to bone defect repair had become one of the hotspots of research. Hydroxyapatite (HAP) is one of the most popular calcium phosphate biomaterials, which is very close to the main ingredient of human bones. Thus, hydroxyapatite biomaterials are popular as bone graft materials. In summary, the preparation of HAP bioceramics by a 3D printing of digital light processing (DLP) is a promising work. However, the preparation of HAP hybrid suspensions with high solid loading and good fluidity that can be printed by DLP encountered some challenges. Therefore, the purpose of this work is to improve and develop a novel UV-curing suspension with a high solids loading, which the suspension with the hydrodynamic properties and stability are suitable for DLP printer, in order to compensate for the brittleness of HAP ceramics itself to a certain extent, a low amount of zirconia was added in the suspension as an additive to fabricate a zirconia toughened HAP bioceramic composite by a DLP of 3D printing. In this work, the HAP powder was pre-modified by two organic modifiers to improve the compatibility in the acrylic resin system, and the addition of the castor oil phosphate further reduced the shear stress of the suspension to ensure strong liquidity. The UV suspension with 60 wt% powder particle loading had a minimum viscosity of 7495 mPa·s at 30 rpm, which was vacuum sintered at 1100 °C, 1200 °C, and 1250 °C, respectively. The composite ceramics (with 6 wt% ZrO) at 1200 °C had a relative density of 90.7%, while the sintered samples at 1250 °C had stronger tensile strength and bending strength. The toughening effect of zirconia incorporation on HAP ceramics was also confirmed by the change of tensile modulus and bending modulus, whereas the corresponding mechanical properties were also significantly enhanced.