The effects of physiologically relevant environmental conditions on the mechanical properties of 3D-printed biopolymer nanocomposites.

The demand for synthetic bone graft biomaterials has grown in recent years to alleviate the dependence on natural bone grafts and metal prostheses which are associated with significant practical and clinical issues. Biopolymer nanocomposites are a class of materials that display strong potential for these synthetic materials, especially when processed using additive manufacturing technologies. Novel nanocomposite biomaterials capable of masked stereolithography printing have been developed from functionalized plant-based monomers and hydroxyapatite (HA) with mechanical properties exceeding those of commercial bone cements. However, these biomaterials have not been evaluated under relevant physiological conditions. The effects of temperature (room temperature vs. 37 °C) and water absorption on the physical, surface, and mechanical properties of HA-containing biopolymer nanocomposites were investigated. Exposure to relevant conditions led to substantial impacts on material performance, such as significantly reduced mechanical strength and stiffness. For instance, a composite containing 10 vol% HA and functionalized monomers had 26 and 21% reductions in compressive yield strength and elastic modulus, respectively. After 14 days incubation in phosphate buffered saline, the same composition displayed a 62% decrease in compressive yield strength to 28 MPa. This manuscript demonstrates the relevance and importance of evaluating biomaterials under appropriate physiological conditions throughout their development and provides direction for future material development of HA-containing biopolymer nanocomposites.

The effect of triglycerol diacrylate on the printability and properties of UV curable, bio-based nanohydroxyapatite composites.

3D printable biopolymer nanocomposites composed of hydroxyapatite nanoparticles and functionalized plant-based monomers demonstrate potential as sustainable and structural biomaterials. To increase this potential, their printability and performance must be improved. For extrusion-based 3D printing, such as Direct Ink Writing (DIW), printability is important for print fidelity. In this work, triglycerol diacrylate (TGDA) was added to an acrylated epoxidized soybean oil:polyethylene glycol diacrylate resin to increase hydrogen bonding. Greater hydrogen bonding was hypothesized to improve printability by increasing the ink's shear yield strength, and therefore shape holding after deposition. The effects of this additive on material and mechanical properties were quantified. Increased hydrogen bonding due to TGDA content increased the ink's shear yield stress and viscosity by 916% and 27.6%, respectively. This resulted in improved printability, with best performance at 3 vol% TGDA. This composition achieved an ultimate tensile strength (UTS) of 32.4 ± 2.1 MPa and elastic modulus of 1.15 ± 0.21 GPa. These were increased from the 0 vol% TGDA composite, which had an UTS of 24.8 ± 1.8 MPa and a modulus of 0.88 ± 0.06 GPa. This study demonstrates the development of bio-based additive manufacturing feedstocks for potential uses in sustainable manufacturing, rapid prototyping, and biomaterial applications.

Extrusion Based 3D Printing of Sustainable Biocomposites from Biocarbon and Poly(trimethylene terephthalate).

Three-dimensional (3D) printing manufactures intricate computer aided designs without time and resource spent for mold creation. The rapid growth of this industry has led to its extensive use in the automotive, biomedical, and electrical industries. In this work, biobased poly(trimethylene terephthalate) (PTT) blends were combined with pyrolyzed biomass to create sustainable and novel printing materials. The Miscanthus biocarbon (BC), generated from pyrolysis at 650 °C, was combined with an optimized PTT blend at 5 and 10 wt % to generate filaments for extrusion 3D printing. Samples were printed and analyzed according to their thermal, mechanical, and morphological properties. Although there were no significant differences seen in the mechanical properties between the two BC composites, the optimal quantity of BC was 5 wt % based upon dimensional stability, ease of printing, and surface finish. These printable materials show great promise for implementation into customizable, non-structural components in the electrical and automotive industries.

Strategy To Improve Printability of Renewable Resource-Based Engineering Plastic Tailored for FDM Applications.

This work features the first-time use of poly(trimethylene terephthalate) (PTT), a biobased engineering thermoplastic, for fused deposition modeling (FDM) applications. Additives such as chain extenders (CEs) and impact modifiers are traditionally used to improve the processability of polymers for injection molding; as a proof of concept for their use in FDM, the same strategies were applied to PTT to improve its printability. The filament processing conditions and printing parameters were optimized to generate complete, warpage-free samples. The blends were characterized through physical, thermal, viscoelastic, and morphological analyses. In the optimal blend (90 wt % PTT, 10 wt % impact modifier, and 0.5 phr CE), the filament diameter was improved by ∼150%, the size of the spherulites significantly decreased to 5% of the ∼26 µm spherulite size found in neat PTT, and the melt flow index decreased to ∼4.7 g/10 min. From this blend, FDM samples with a high impact performance of ∼61 J/m were obtained, which are comparable to other conventional FDM thermoplastics. The ability to print complete and warpage-free samples from this blend suggests a new filament feedstock material for industrial and home-use FDM applications. This paper discusses methods to improve hard-to-print polymers and presents the improved printability of PTT as proof of these methods' effectiveness.