Process Development for Fabricating 3D-Printed Polycaprolactone-Infiltrated Hydroxyapatite Bone Graft Granules: Effects of Infiltrated Solution Concentration and Agitating Liquid

Bone grafts are commonly used in orthopedic and dental surgeries to facilitate bone repair and regeneration. A new type of bone graft, polycaprolactone-infiltrated three dimensionally printed hydroxyapatite (3DP HA/PCL), was previously developed by infiltrating polycaprolactone (PCL) into preformed three-dimensional-printed hydroxyapatite (3DP HA) that was fabricated using binder jetting technology combined with a low-temperature phase transformation process. However, when producing small granules, which are often used for bone grafting, issues of granule agglomeration emerged, complicating the application of this method. This study aimed to develop a fabrication process for 3DP HA/PCL bone graft granules using solution infiltration and liquid agitation. The effects of varying PCL solution concentrations (40% and 50% <i>w</i>/<i>w</i>) and different agitating liquids (deionized water or DI, N-Methyl-2-Pyrrolidone or NMP, and an NMP-DI mixture) on the properties of the resulting composites were investigated. XRD and FTIR analysis confirmed the coexistence of HA and PCL within the composites. The final PCL content was comparable across all conditions. The contact angles of 3DP HA/PCL were 26.3 and 69.8 degree for 40% and 50% PCL solution, respectively, when using DI, but were zero when using NMP and NMP-DI. The highest compression load resistance and diametral tensile strength were achieved using the 50% PCL solution with DI or the NMP-DI mixture. DI resulted in a dense PCL coating, while NMP and the NMP-DI mixture produced a porous and irregular surface morphology. All samples exhibited a porous internal microstructure due to PCL infiltration into the initial pores of the 3D-printed HA. Biocompatibility tests showed that all samples supported the proliferation of MC3T3-E1 cells, with the greatest OD values observed for the 50% PCL solution with DI or the NMP-DI mixture at each cultured period. Considering the microstructural, mechanical, and biological properties, the 50% PCL solution with the NMP-DI mixture demonstrated overall desirable properties.