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.
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.
The combination of plant-derived polymer resins and mineral-based nanoparticles into three dimensional (3D) printable, high-performance nanocomposites suggests a means to improve the sustainability profile of rapid prototyping and additive manufacturing. In this work, our previously published nanocomposite biomaterial system of acrylated epoxidized soybean oil (AESO) and polyethylene glycol (PEGDA) diluent composited with calcium-deficient hydroxyapatite (nHA) nanorods was improved by the substitution of AESO with methacrylated AESO (mAESO) and the partial substitution of PEGDA with isosorbide methacrylate (IM). mAESO was used to increase the degree of crosslinking and reduce the ink viscosity. IM was synthesized by reacting the hydroxyl groups on isosorbide with methacrylic anhydride. The effects of partially replacing PEGDA with IM on the rheology and printability of the nanocomposite inks and the mechanical properties of the resulting nanocomposite materials were quantified. These masked stereolithography (mSLA) printed nanocomposites have greatly improved mechanical properties (tensile strength, Young’s modulus, and Mode-I fracture toughness) due to the shift to mAESO and IM. IM greatly improved the tensile fracture strength and Young’s modulus of the nanocomposites by acting as a reactive diluent and as a stiff segment in the polymer system. Dynamic mechanical analysis revealed that the glass transition temperature of the nanocomposite increased due to the addition of IM. However, IM decreased the strain-at–fracture, making the nanocomposites more brittle. This study demonstrates the development of high-performance mAESO-IM-nHA-based novel nanocomposites that can be easily 3D printed using desktop mSLA, suggesting a facile path forward to improved sustainability in rapid prototyping and additive manufacturing using nanocomposites for a broad range of applications.
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