3D printed PEEK/HA composites for bone tissue engineering applications: effect of material formulation on mechanical performance and bioactive potential

Polyetheretherketone (PEEK) is a biocompatible polymer widely used for biomedical applications. Because it is biologically inert, bioactive phases, such as nano-hydroxyapatite (HA), have been added to PEEK in order to improve its bioactivity. 3D printing (3DP) technologies are being increasingly used today to manufacture patient specific devices and implants. However, processing of PEEK is challenging due to its high melting point which is above 340 °C. In this study, PEEK-based filaments containing 10 wt% of pure nano-HA, strontium (Sr)- doped nano-HA and Zinc (Zn)-doped nano-HA were produced via hot-melt extrusion and subsequently 3D printed via fused deposition modelling (FDM), following an initial optimization process. The raw materials, extruded filaments and 3D printed samples were characterized in terms of physicochemical, thermal and morphological analysis. Moreover, the mechanical performance of 3D printed specimens was assessed via tensile tensing. Although an increase in the melting point and a reduction in crystallization temperature was observed with the addition of HA and doped HA to pure PEEK, there was no noticeable increase in the degree of crystallinity. Regarding the mechanical behavior, no significant differences were detected following the addition of the inorganic phases to the polymeric matrix, although a small reduction in the ultimate tensile strength (~14%) and Young's modulus (~5%) in PEEK/HA was observed in comparison to pure PEEK. Moreover, in vitro bioactivity of 3D printed samples was evaluated via a simulated body fluid immersion test for up to 28 days; the formation of apatite was observed on the surfaces of sample surfaces containing HA, SrHA and ZnHA. These results indicate the potential to produce bioactive, 3DP PEEK composites for challenging applications such as in craniofacial bone repair.