The Impact of Post-Printing Hydration in NaCl Solution on the Properties of Binder Jet 3D-Printed Calcium Sulfate and Its Converted Hydroxyapatite

Binder jet 3D printing of calcium sulfate-based materials combined with phase transformation offers a versatile route for fabricating customized bone grafts; however, controlling the transformation process remains a key challenge. This study investigates the effect of post-printing hydration in sodium chloride (NaCl) solutions on the phase transformation, dimension, and compressive properties of binder jet-printed calcium sulfate (3DPCaS) toward hydroxyapatite (3DPHA) formation. The as-printed 3DPCaS primarily consisted of bassanite with minor gypsum, which progressively transformed into gypsum upon immersion in NaCl solutions of varying concentrations (1-5 M) and durations (2-30 min). Increased immersion time and moderate NaCl concentrations (2-4 M) promoted gypsum formation without inducing dimensional instability. Subsequent transformation in phosphate solution produced 3DPHA with high hydroxyapatite (HA) purity, reaching 100% conversion. Microstructural analysis revealed recrystallized, plate-like gypsum crystals that served as favorable templates for HA nucleation. The resulting 3DPHA exhibited enhanced specific modulus (up to 274.9 MPa.m³/kg) and specific strength (up to 7.5 MPa.m³/kg). The optimal condition, immersion in 4 M NaCl solution for 30 min, achieved a balance between complete HA transformation, mechanical enhancement, and dimensional stability. Controlled ionic hydration thus represents a simple, low-cost, and effective strategy for improving properties of 3DPHA bone grafts.