The manufacture of polyetheretherketone/hydroxyapatite (PEEK/HA) composites is seen as a viable approach to help enhance direct bone apposition in orthopaedic implants. A range of methods have been used to produce composites, including Selective Laser Sintering and injection moulding. Such techniques have drawbacks and lack flexibility to manufacture complex, custom-designed implants. 3D printing gets around many of the restraints and provides new opportunities for innovative solutions that are structurally suited to meet the needs of the patient. This work reports the direct 3D printing of extruded PEEK/HA composite filaments via a Fused Filament Fabrication (FFF) approach. In this work samples are 3D printed by a custom modified commercial printer Ultimaker 2+ (UM2+). SEM-EDX and µCT analyses show that HA particles are evenly distributed throughout the bulk and across the surface of the native 3D printed samples, with XRD highlighting up to 50% crystallinity and crystalline domains clearly observed in SEM and HR-TEM analyses. This highlights the favourable temperature conditions during 3D printing. The yield stress and ultimate tensile strength obtained for all the samples are comparable to human femoral cortical bone. The results show how FFF 3D printing of PEEK/HA composites up to 30 wt% HA can be achieved.

Poly(ether ether ketone) (PEEK) is a high‐performance thermoplastic with a distinctive combination of corrosion resistance, thermo‐oxidative stability and outstanding physical and mechanical properties at high temperatures. A pertinent step forward in the development of this thermoplastic has been the inclusion of electrically conductive fillers to expand its functionality. In this review an overview of the research on electrically conductive PEEK composites is provided. Conductive filler type, fabrication methods, characterization details and different properties are described. Carbon nanotubes, graphene nanoplatelets and other organic and inorganic conductive fillers such as expanded graphite and nickel have been incorporated into PEEK by techniques such as extrusion, injection moulding and cold and hot compression moulding and in some cases with pre‐processing steps including mechanochemical modifications in organic solvents. The influences of type, loading and compatibilization of fillers and processing conditions on the mechanical and electrical conductivity properties of the composites are analysed and compared. The incorporated fillers have been able to enhance the electrical conductivity of the PEEK composites to either the semiconducting or conductive regions. PEEK composites containing carbon nanotubes compatibilized by polysulfones and poly(ether imide) achieved electrical conductivity values in the semiconducting region at the lowest electrical percolation threshold of 0.1 wt%. Additionally, the inclusion of 10 wt% expanded graphite and 10 vol% inorganic macroparticles of nickel noticeably improved the electrical conductivity of PEEK into the conductive region. © 2021 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Hardness is a useful measure of a material’s resistance to permanent indentation; but for viscoelastic polymers, hardness data are highly dependent on the test type and the parameter set chosen. Vickers microhardness testing is used to leave small indents (<150 µm) and is shown to be applicable to polymers. A detailed investigation of the required steps for microhardness testing in isotactic polypropylene (iPP) is provided. Samples should be mounted in epoxy resin in order to maintain curing temperatures at room temperature. Mounted samples can be ground and polished in a semi-automatic polisher using graduated SiC paper (wet grinding) but progressing onto alumina suspension for polishing. Final polishing should be performed with 0.05-µm alumina suspension. The hardness measured was shown to be dependent on load and dwell time with a much greater dependency on dwell time. Strain recovery was shown to be completed after a time period equal to the dwell time. This study shows that indents can be measured thereafter, and it is recommended that they be measured within a 24 h period after the indent was created. After data fitting, the equation for hardness was shown to follow a power law with load and dwell time as the main variables. Fitting parameters were compared to those found in the literature, and it was found that parameters were significantly different to those reported elsewhere. Therefore, this study highlights the importance of calibrating on a case-by-case basis. Finally, to show the usefulness of the Vickers micro-hardness testing method, the calibrated test method was applied on iPP with additions of carbon black up to 3 wt.%. Comparisons were made with data from the literature, but the hardness data generated in our work were found to be at least twice that reported in the literature. The testing parameters were not cited in the literature: specifically, the dwell time was not provided, and this generated doubt on the usefulness of the cited data. Hence, this work is intended to serve as an exemplar of how to prepare and proceed with hardness testing of polymers.

Polyetheretherketone (PEEK) is a high-performance thermoplastic polymer which has found increasing application in orthopaedics and has shown a lot of promise for ‘made-to-measure’ implants via additive manufacturing approaches. However, PEEK is bioinert and needs to undergo surface modification to make it at least osteoconductive to ensure a more rapid, improved, and stable fixation that will last longer in vivo. One approach to solving this issue is to modify PEEK with bioactive agents such as hydroxyapatite (HA). The work reported in this study demonstrates the direct 3D printing of PEEK/HA composites of up to 30 weight percent (wt%) HA using a Fused Filament Fabrication (FFF) approach. The surface characteristics and in vitro properties of the composite materials were investigated. X-ray diffraction revealed the samples to be semi-crystalline in nature, with X-ray Photoelectron Spectroscopy and Time-of-Flight Secondary Ion Mass Spectrometry revealing HA materials were available in the uppermost surface of all the 3D printed samples. In vitro testing of the samples at 7 days demonstrated that the PEEK/HA composite surfaces supported the adherence and growth of viable U-2 OS osteoblast like cells. These results demonstrate that FFF can deliver bioactive HA on the surface of PEEK bio-composites in a one-step 3D printing process.