Mechanical properties of nanocomposite biomaterials improved by extrusion during direct ink writing

In this study, single filaments of acrylated epoxidized soybean oil (AESO)/polyethylene glycol diacrylate (PEGDA)/nanohydroxyapatite (nHA)-based nanocomposites intended for bone defect repair have displayed significant improvement of their mechanical properties when extruded through smaller needle gauges before UV curing. These nanocomposite inks can be deposited layer-by-layer during direct ink writing (DIW) - a form of additive manufacturing. Single filaments were prepared by extruding the nanocomposite ink through needles with varying diameters from 0.21 mm to 0.84 mm and then UV cured. Filaments and cast specimens were tensile tested to determine elastic modulus, strength and toughness. The cured nanocomposite filaments were further characterized using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). SEM confirmed that the hydroxyapatite nanoparticles were well dispersed in the polymer matrices. The ultimate tensile strength and moduli increased as the diameter of the extrusion needle was decreased. These correlated with increased matrix crystallinity and fewer defects. For instance, filaments extruded through 0.84 mm diameter needles had ultimate tensile stress and modulus of 26.3 ± 2.8 MPa and 885 ± 100 MPa, respectively, whereas, filaments extruded through 0.21 mm needles had ultimate tensile stress and modulus of 48.9 ± 4.0 MPa and 1696 ± 172 MPa, respectively. This study has demonstrated enhanced mechanical properties resulting from extrusion-based direct ink writing of a new AESO-PEGDA-nHA nanocomposite biomaterial intended for biomedical applications. These enhanced properties are the result of fewer defects and increased crystallinity. A means of achieving mechanical properties suitable for repairing bone defects is apparent.