Polyetheretherketone (PEEK)/β‐tricalcium phosphate (β‐TCP) scaffolds are expected to be able to combine the excellent mechanical strength of PEEK and the good bioactivity and biodegradability of β‐TCP. While PEEK acts as a closed membrane in which β‐TCP is completely wrapped after the melting/solidifying processing, the PEEK membrane degrades very little, hence the scaffolds cannot display bioactivity and biodegradability. The strategy reported here is to blend a biodegradable polymer with PEEK and β‐TCP to fabricate multi‐material scaffolds via selective laser sintering (SLS). The biodegradable polymer first degrades and leaves caverns on the closed membrane, and then the wrapped β‐TCP is exposed to body fluid. In this study, poly(l‐lactide) (PLLA) is adopted as the biodegradable polymer. The results show that large numbers of caverns form on the membrane with the degradation of PLLA, enabling direct contact between β‐TCP and body fluid, and allowing for their ion‐exchange. As a consequence, the scaffolds display the bioactivity, biodegradability and cytocompatibility. Moreover, bone defect repair studies reveal that new bone tissues grow from the margin towards the center of the scaffolds from the histological analysis. The bone defect region is completely connected to the host bone end after 8 weeks of implantation.

The poor bonding strength between biopolymer and bioceramic has remained an unsolved issue. In this study, graphene oxide (GO) was introduced as an interface phase to improve the interfacial bonding between polyetheretherketone (PEEK) and hydroxyapatite (HAP) for tissue engineering scaffolds. On the one hand, the conjugated structure of GO could form strong π-π stacking interaction with the benzene rings in PEEK. On the other hand, GO with a negatively charge resulting from oxygen functional groups could adsorb the positively charged calcium atoms (C sites) of HAP. Consequently, the dispersibility and compatibility of HAP in the PEEK matrix increased with increasing GO content up to 1 wt%. At this time, the compressive strength and modulus of scaffolds increased by 79.45% and 42.07%, respectively. Furthermore, the PEEK-HAP with GO (PEEK-HAP/GO) scaffolds possessed the ability to induce formation of bone-like apatite. And they could support cellular adhesion, proliferation as well as osteogenic differentiation. More importantly,in vivobone defect repair experiments showed that new bone formed throughout the scaffolds at 60 days after implantation. All these results suggested that the PEEK-HAP/GO scaffolds have a promising potential for bone tissue engineering application.