Fabrication of freeform bone-filling calcium phosphate ceramics by gypsum 3D printing method

Transformation of gypsum model fabricated by three-dimensional printing (3DP) into hydroxyapatite (HA) by treating in ammonium phosphate solution is possible. However, 3DP powder supplied by the manufacturer contains unknown additives which may be questionable for biomaterials. Accordingly, pure plaster of Paris (POP) powder was used for fabrication in the present study. For accurate fabrication, reduction of supplied binder ink to 80% of standard amount for 3DP powder supplied by the manufacturer was found to be the optimal condition for POP fabrication. Transformation from POP to HA was done by immersing into 1 mol/L ammonium phosphate solution. However, preheating of fabricated POP specimen at 200°C for 30 min to change from calcium sulfate dihydrate into calcium sulfate hemihydrate could accelerate the transformation into HA effectively. To increase compressive strength, HA transformed specimen was sintering at 1150°C for 3 h. The compressive strength increased four times comparing with as transformed HA specimen. However, crystal structure was transformed to β-TCP due to the chemical reaction between the transformed HA and remained phosphate from ammonium phosphate solution at the sintering temperature. A sophisticated application of the present 3DP method to fabricate the freeform bioceramic for osseous defect was attempted, and jaw bone defect filling biomaterial of β-TCP and scaffold with macroporous structures could be fabricated. Present 3DP method has possibility to fabricate freeform bioceramic for osseous defect or scaffold.