Immediate implant placement (IIP) has garnered significant attention due to its minimally invasive approach and ability to facilitate immediate crown replacement. Nevertheless, challenges persist in processing complex geometries and selecting suitable materials. This study successfully fabricated high-performance, complex-structured (Ce, Y)-TZP-based composite ceramics using vat photopolymerization (VPP) technology, combining second-phase strengthening and grain boundary segregation effects. The incorporation of α-Al2O3 as a secondary phase led to a progressive refinement of (Ce, Y)-TZP grains, with the most favorable grain size achieved at 20 wt% α-Al2O3, reducing the average grain size to 0.75 μm. However, excessive α-Al2O3 content resulted in micropore formation, compromising the material's mechanical performance. At an optimal concentration of 15 wt% α-Al2O3, the composite exhibited superior mechanical properties, including a Vickers hardness of 11.53 ± 0.27 GPa and a flexural strength of 525.5 ± 21.3 MPa. Despite these improvements, some coarse (Ce, Y)-TZP grains persisted within the ceramic matrix. To further enhance grain refinement at lower α-Al2O3 content, a minimal addition of La3+ (0.1 wt%) was introduced, promoting grain boundary segregation and additional grain refinement. This modification reduced the (Ce, Y)-TZP grain size to 0.74 μm, increased hardness to 13.03 ± 0.31 GPa, and elevated flexural strength to 550.4 ± 39.8 MPa, while maintaining excellent material stability.
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