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.

In this study, Strontium (Sr) and Zinc (Zn) doped-HA nanoparticles were synthesized and incorporated into polyetheretherketone (PEEK) up to 30 wt.% and processed by a novel approach i.e., fused deposition modelling (FDM) 3D printing for the production of patient specific cranial implants with improved bioactivity and the required mechanical performance. Filaments were produced via extrusion and subsequently 3D-printed using FDM. To further improve the bioactivity of the 3D-printed parts, the samples were dip-coated in polyethylene glycol-DOPA (PEG-DOPA) solution. The printing quality was influenced by filler loading, but was not significantly influenced by the nature of doped-HA. Hence, the printing conditions were optimized for each sample. Micro-CT and Scanning Electron Microscopy (SEM) showed a uniform distribution of bioceramic particles in PEEK. Although agglomeration of particles increased with increase in filler loadings. Differential Scanning Calorimetry (DSC) showed that the melting point and crystallinity of PEEK increased with an increase in doped-HA loading from 343 °C to 355 °C and 27.7% to 34.6%, respectively. Apatite formation was confirmed on the 3D-printed samples after immersion in simulated body fluid (SBF) for 7, 14 and 28 days via SEM, X-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). The tensile strength and impact strength decreased from 75 MPa to 51 MPa and 14 kJ/m² to 4 kJ/m², respectively, while Young’s modulus increased with increasing doped-HA content from 2.8 GPa to 4.2 GPa. However, the tensile strengths of composites remained in the range of human cortical bone i.e., ≥50 MPa. In addition, there was a slight increase in mechanical strength after 28 days immersion which was attributed to apatite formation. Water contact angle showed that the hydrophilicity of the samples improved after coating the 3D-printed samples with PEG-DOPA. Hence, based on the results, the 3D-printed PEEK nanocomposites with 20 wt.% doped-HA is selected as the best candidate for the 3D-printing of craniomaxillofacial implants.

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.

Semi-crystalline polymers develop higher amounts of residual stress and part distortion (warpage) compared to amorphous polymers due to their crystalline nature. Additionally, the FDM processing parameters such as ambient temperature play an important role in the resulting residual stresses and part distortion of the printed part. Hence, in this study, the effect of ambient temperature on the in-built residual stresses and warpage of amorphous acrylonitrile-butadiene-styrene (ABS) and semi-crystalline polypropylene (PP) polymers was investigated. From the results, it was observed that increasing the ambient temperature from 50 °C to 75 °C and further to 120 °C resulted in 0.22-KPa and 0.37-KPa decreases in residual stress of ABS, but no significant change in the amount of warpage. For PP, increasing ambient temperature from 50 °C to 75 °C led to a more considerable decrease in residual stress (0.5 MPa) and about 3% increase in warpage. Further increasing to 120 °C resulted in a noticeable 2 MPa decrease in residual stress and a 3.4% increase in warpage. Reduction in residual stress in both ABS and PP as a result of increasing ambient temperature was due to the reduced thermal gradients. The enhanced warpage in PP with increase in ambient temperature, despite the reduction in residual stress, was ascribed to crystallization and shrinkage.

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.

In fused deposition modelling (FDM) based on the selected raster pattern, the developed internal thermal residual stresses can vary considerably affecting the mechanical properties and leading to distinct part distortions. This phenomenon is more pronounced in semi-crystalline than amorphous polymers due to crystallisation. Hence, this study focuses on the simulation of the FDM process of a semi-crystalline polymer (polypropylene) with raster patterns such as line (90°/90°), line (0°/90°), zigzag (45°/45°), zigzag (45°/−45°), and concentric from Cura (slicing software). The simulation provides visualisation and prediction of the internally developed thermal residual stresses and resulting warpage with printing time and temperature. The sample with a line (90°/90°) raster pattern is considered as the reference sample in order to compare the relative levels of residual stress and warpage in the other printed/simulated samples. Among the considered raster patterns, the concentric pattern displays the lowest amount of warpage (5.5% decrease) along with a significant drop in residual stress of 21%. While the sample with a zigzag (45°/−45°) pattern showed the highest increase of 37% in warpage along with a decrease of 9.8% in residual stresses. The sample with a zigzag (45°/45°) pattern, exhibited a considerable increase of 16.2% in warpage with a significant increase of 31% in residual stresses. Finally, the sample with a line (0°/90°) raster pattern displayed an increase of 24% increase in warpage with an increase of 6.6% in residual stresses.