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Abstract: Bio-based poly(lactic acid) (PLA) composite films were produced using unmodified soda micro- or nano-lignin as a green filler at four different contents, between 0.5 wt% and 5 wt%. The PLA– lignin composite polymers were synthesized by solvent casting to prepare a masterbatch, followed by melt mixing. The composites were then converted into films, to evaluate the effect of lignin content and size on their physicochemical and mechanical properties. Differential scanning calorimetry (DSC), supported by polarized light microscopy (PLM), infrared spectroscopy (FTIR-ATR), X-ray diffraction (XRD), and transmission electron microscopy (TEM) were employed to investigate the PLA crystallization and the interactions with Lignin (L) and Nanolignin (NL). The presence of both fillers (L and NL) had a negligible effect on the glass transition temperature (chain diffusion). However, it resulted in suppression of the corresponding change in heat capacity. This was indicative of a partial immobilization of the PLA chains on the lignin entities, due to interfacial interactions, which was slightly stronger in the case of NL. Lignin was also found to facilitate crystallization, in terms of nucleation; whereas, this was not clear in the crystalline fraction. The addition of L and NL led to systematically larger crystallites compared with neat PLA, which, combined with the higher melting temperature, provided indications of a denser crystal structure in the composites. The mechanical, optical, antioxidant, and surface properties of the composite films were also investigated. The tensile strength and Young’s modulus were improved by the addition of L and especially NL. The UV-blocking and antioxidant properties of the composite films were also enhanced, especially at higher filler contents. Importantly, the PLA–NL composite films constantly outperformed their PLA–L counterparts, due to the finer dispersion of NL in the PLA matrix, as verified by the TEM micrographs. These results suggest that bio-based and biodegradable PLA films filled with L, and particularly NL, can be employed as competitive and green alternatives in the food packaging industry.
Keywords: poly(lactic acid), PLA, lignin, nanolignin, composite films, nucleation, mechanical properties, antioxidant activity, food packaging
Published in DKUM: 26.03.2025; Views: 0; Downloads: 1
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Abstract: Drawing is a well-established method to improve the mechanical properties of wet-spun fibers, as it orients the polymer chains, increases the chain density, and homogenizes the microstructure. This work aims to investigate how drawing variables, such as the draw ratio, drawing speed, and temperature affect the elastic modulus (E) and the strain at break (εB) of biobased wet-spun fibers constituted by neat polylactic acid (PLA) and a PLA/poly(dodecamethylene 2,5-furandicarboxylate) (PDoF) (80/20 wt/wt) blend. Drawing experiments were conducted with a design of experiment (DOE) approach following a 24 full factorial design. The results of the quasi-static tensile tests on the drawn fibers, analyzed by the analysis of variance (ANOVA) and modeled through the response surface methodology (RSM), highlight that the presence of PDoF significantly lowers E, which instead is maximized if the temperature and draw ratio are both low. On the other hand, εB is enhanced when the drawing is performed at a high temperature. Finally, a genetic algorithm was implemented to find the optimal combination of drawing parameters that maximize both E and εB. The resulting Pareto curve highlights that the temperature influences the mechanical results only for neat PLA fibers, as the stiffness increases by drawing at lower temperatures, while optimal Pareto points for PLA/PDoF fibers are mainly determined by the draw ratio and the draw rate.
Keywords: fibers, poly(lactic acid), furanoate polyesters, drawing, response surface methodology, genetic algorithms
Published in DKUM: 24.03.2025; Views: 0; Downloads: 2
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Abstract: Polylactide (PLA) is the most widely used biopolymer, but its poor ductility and scarce gas barrier properties limit its applications in the packaging field. In this work, for the first time, the properties of PLA solvent-cast films are improved by the addition of a second biopolymer, i.e., poly(decamethylene 2,5-furandicarboxylate) (PDeF), added in a weight fraction of 10 wt%, and a carbon-based nanofiller, i.e., reduced graphene oxide (rGO), added in concentrations of 0.25–2 phr. PLA and PDeF are immiscible, as evidenced by scanning electron microscopy (SEM) and Fouriertransform infrared (FTIR) spectroscopy, with PDeF spheroidal domains showing poor adhesion to PLA. The addition of 0.25 phr of rGO, which preferentially segregates in the PDeF domains, makes them smaller and considerably rougher and improves the interfacial interaction. Differential scanning calorimetry (DSC) confirms the immiscibility of the two polymer phases and highlights that rGO enhances the crystallinity of both polymer phases (especially of PDeF). Thermogravimetric analysis (TGA) highlights the positive impact of rGO and PDeF on the thermal degradation resistance of PLA. Quasi-static tensile tests evidence that adding 10 wt% of PDeF and a small fraction of rGO (0.25 phr) to PLA considerably enhances the strain at break, which raises from 5.3% of neat PLA to 10.0% by adding 10 wt% of PDeF, up to 75.8% by adding also 0.25 phr of rGO, thereby highlighting the compatibilizing role of rGO on this blend. On the other hand, a further increase in rGO concentration decreases the strain at break due to agglomeration but enhances the mechanical stiffness and strength up to an rGO concentration of 1 phr. Overall, these results highlight the positive and synergistic contribution of PDeF and rGO in enhancing the thermomechanical properties of PLA, and the resulting nanocomposites are promising for packaging applications.
Keywords: nanocomposites, reduced graphene oxide, poly(decamethylene 2, 5-furandicarboxylate), furanoate polyesters, polylactic acid, compatibilization
Published in DKUM: 20.03.2025; Views: 0; Downloads: 1
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Abstract: This study presents the synthesis and characterization of a series of multiblock copolymers, poly(ethylene 2,5-furandicarboxylate)-poly(ε-caprolactone) (PEF-PCL), created through a combination of the two-step melt polycondensation method and ring opening polymerization, as sustainable alternatives to fossil-based plastics. The structural confirmation of these block copolymers was achieved through Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), ensuring the successful integration of PEF and PCL segments. X-ray Photoelectron Spectroscopy (XPS) was employed for chemical bonding and quantitative analysis, providing insights into the distribution and compatibility of the copolymer components. Differential Scanning Calorimetry (DSC) analysis revealed a single glass transition temperature (Tg), indicating the effective plasticizing effect of PCL on PEF, which enhances the flexibility of the copolymers. X-ray Diffraction (XRD) studies highlight the complex relationship between PCL content and crystallization in PEF-PCL block copolymers, emphasizing the need to balance crystallinity and mechanical properties for optimal material performance. Broadband Dielectric Spectroscopy (BDS) confirmed excellent distribution of PEF-PCL without phase separation, which is vital for maintaining consistent material properties. Mechanical properties were evaluated using Nanoindentation testing, demonstrating the potential of these copolymers as flexible packaging materials due to their enhanced mechanical strength and flexibility. The study concludes that PEF-PCL block copolymers are promising candidates for sustainable packaging solutions, combining environmental benefits with desirable material properties.
Keywords: poly(ethylene furanoate), poly(ε-caprolactone), block copolymers, thermal properties, molecular dynamics, crystallinity, mechanical properties, flexible packaging
Published in DKUM: 13.03.2025; Views: 0; Downloads: 5
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Abstract: In recent years, bio-based poly(ethylene furanoate) has gained the attention of packaging industries owing to its remarkable properties as a promising alternative to fossil-based polymers. It is necessary to synthesize high-molecular-weight polymers using effective and straightforward techniques for their commercialization. In this present work, poly(ethylene 2,5-furan dicarboxylate) (PEF) was produced with a high molecular weight of 0.43 dL/g using 2,5-furan dicarboxylic acid (FDCA) or its derivative Dimethyl-2,5-Furan dicarboxylate (DMFD), followed by solid-state polymerization (SSP) conducted at different temperatures and reaction times. The intrinsic viscosity ([η]), carboxyl end-group concentration (–COOH), and thermal properties of the produced polyesters were evaluated using differential scanning calorimetry (DSC). The results indicated that the SSP process improved the melting temperature and crystallinity of both the PEF samples as the reaction times and temperatures increased, as corroborated by DSC and X-ray diffraction (XRD) analyses. Additionally, both intrinsic viscosity and number-average molecular weight saw an increase with longer SSP durations and higher temperatures, while the concentration of carboxyl end groups decreased, aligning with expectations. The overall results indicate that PEF (DMFD) samples exhibited a significant increase in crystallization and molecular weight, attributed to their lower degree of crystallinity and their monomer’s high purity.
Keywords: bio-based polymers, 2, 5-furan dicarboxylic acid, dimethyl 2, 5-furan dicarboxylate, poly(ethylene 2, 5-furan dicarboxylate), poly(ethylene furanoate), solid state polymerization, thermal properties
Published in DKUM: 10.03.2025; Views: 0; Downloads: 6
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