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Plasma immersion ion implantation (PIII) is used here to improve the surface bioactivity of polyether ether ketone (PEEK) by modifying the chemical and mechanical properties and by introducing radicals. Modifications to the chemical and mechanical properties are characterised as a function of ion fluence (proportional to treatment time) to determine the suitability of the treated surfaces for biological applications. Radical generation increases with treatment time, where treatments greater than 400 seconds result in a high concentration of long-lived radicals. Radical reactions are responsible for oxidation of the surface, resulting in a permanent increase in the polar surface energy. The nano-scale reduced modulus was found to increase with treatment time at the surface from 4.4 to 5.2 GPa. The macromolecular Young’s modulus was also found to increase, but by an amount corresponding to the volume fraction of the ion implanted region. The treated surface layer exhibited cracking under cyclical loads, associated with an increased modulus due to dehydrogenation and crosslinking, however it did not show any sign of delamination, indicating that the modified layer is well integrated with the substrate – a critical factor for bioactive surface coatings to be used in-vivo. Protein immobilisation on the PIII treated surfaces was found to saturate after 240 seconds of treatment, indicating that there is room to tune surface mechanical properties for specific applications without affecting the protein coverage. Our findings indicate that the modification of the chemical and mechanical properties by PIII treatments as well as the introduction of radicals render PEEK well suited for use in orthopaedic implantable devices.
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