ABSTRACT
Poly(lactic acid) (PLA) is a readily available, compostable biobased polyester with high strength and toughness, and it is excellent for 3D printing applications. Polymer blending is an economic and easy way to improve its properties, such as its slow degradation and crystallization rates and its small elongation, and thus, make it more versatile. In this work, the effects of different 2,5-furan dicarboxylic acid (FDCA)-based polyesters on the physicochemical and mechanical properties of PLA were studied. Poly(butylene furan 2,5-dicarboxylate) (PBF) and its copolymers with poly(butylene adipate) (PBAd) were synthesized in various comonomer ratios and were blended with 70 wt% PLA using melt compounding. The thermal, morphological and mechanical properties of the blends are investigated. All blends were immiscible, and the presence of the dispersed phases improved the crystallization ability of PLA. Mechanical testing revealed the plasticization of PLA after blending, and a small but measurable mass loss after burying in soil for 7 months. Reactive blending was evaluated as a compatibilizer-free method to improve miscibility, and it was found that when the thermal stability of the blend components allowed it, some transesterification reactions occurred between the PLA matrix and the FDCA-based dispersed phase after 20 min at 250 °C.
ABSTRACT
Poly(ethylene 2,5-furandicarboxylate) (PEF) nanocomposites reinforced with various content of graphene nanoplatelets (GNPs) were synthesized in situ in this work. PEF is a widely known biobased polyester with promising physical properties and is considered as the sustainable counterpart of PET. Despite its exceptional gas barrier and mechanical properties, PEF presents with a low crystallization rate. In this context, a small number of GNPs were incorporated into the material to facilitate the nucleation and overall crystallization of the matrix. Kinetic analysis of both the cold and melt crystallization processes of the prepared materials was achieved by means of differential scanning calorimetry (DSC). The prepared materials' isothermal crystallization from the glass and melt states was studied using the Avrami and Hoffman-Lauritzen theories. The Dobreva method was applied for the non-isothermal DSC measurements to calculate the nucleation efficiency of the GNPs on the PEF matrix. Furthermore, Vyazovkin's isoconversional method was employed to estimate the effective activation energy values of the amorphous materials' glass transition. Finally, the nanomechanical properties of the amorphous and semicrystalline PEF materials were evaluated via nanoindentation measurements. It is shown that the GNPs facilitate the crystallization process through heterogeneous nucleation and, at the same time, improve the nanomechanical behavior of PEF, with the semicrystalline samples presenting with the larger enhancements.
ABSTRACT
This work aims to improve the properties of poly(lactic acid) (PLA) for future biomedical applications by investigating the effect of montmorillonite (MMT) nanoclay on physicochemical and mechanical behavior. PLA nanocomposite filaments were fabricated using different amounts of MMT (1.0, 2.0, and 4.0 wt.%) and 2 wt.% Joncryl chain extenders. The 3D-printed specimens were manufactured using Fused Filament Fabrication (FFF). The composites were characterized by Gel Permeation Chromatography (GPC), Melt Flow Index (MFI), X-ray Diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR). The thermal properties were studied by means of Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). Moreover, the hydrophilicity of the PLA/MMT nanocomposites was investigated by measuring the water contact angle. The mechanical behavior of the PLA/MMT nanocomposites was examined with nanoindentation, compression tests, and Dynamic Mechanical Analysis (DMA). The presence of Joncryl, as well as the pretreatment of MMT before filament fabrication, improved the MMT distribution in the nanocomposites. Furthermore, MMT enhanced the printability of PLA and improved the hydrophilicity of its surface. In addition, the results of nanoindentation testing coupled with Finite Element Analysis showed that as the MMT weight fraction increased, as well as an increased Young's modulus. According to the results of the mechanical analysis, the best mechanical behavior was achieved for PLA nanocomposite with 4 wt.% MMT.
ABSTRACT
Fused deposition modeling (FDM) is currently the most popular 3D printing method, where thermoplastic polymers are predominantly used. Among them, the biobased poly(lactic acid) (PLA) governs the FDM filament market, with demand higher than supply, since not all grades of PLA are suitable for FDM filament production. In this work, the effect of a food grade chain extender (Joncryl ADR® 4400) on the physicochemical properties and printability of PLA marketed for injection molding was examined. All samples were characterized in terms of their mechanical and thermal properties. The microstructure of the filaments and 3D-printed fractured surfaces following tensile testing were examined with optical and scanning electron microscopy, respectively. Molecular weight and complex viscosity increased, while the melt flow index decreased after the incorporation of Joncryl, which resulted in filaments of improved quality and 3D-printed constructs with enhanced mechanical properties. Dielectric spectroscopy revealed that the bulk properties of PLA with respect to molecular mobility, both local and segmental, were, interestingly, not affected by the modifier. Indirectly, this may suggest that the major effects of the extender are on chain length, without inducing chain branching, at least not to a significant extent.
