1. Effect of micro- and nano-lignin on the thermal, mechanical, and antioxidant properties of biobased PLA–lignin composite filmsSofia P. Makri, Eleftheria Xanthopoulou, Panagiotis A. Klonos, Alexios Grigoropoulos, Apostolos Kyritsis, Konstantinos Tsachouridis, Antonios Anastasiou, Ioanna Deligkiozi, Nikolaos P. Nikolaidis, Dimitrios Bikiaris, 2022, izvirni znanstveni članek Opis: 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. Ključne besede: poly(lactic acid), PLA, lignin, nanolignin, composite films, nucleation, mechanical properties, antioxidant activity, food packaging Objavljeno v DKUM: 26.03.2025; Ogledov: 0; Prenosov: 1
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2. Compatibilization of polylactide/poly(ethylene 2,5-furanoate) (PLA/PEF) blends for sustainable and bioderived packagingGiulia Fredi, Andrea Dorigato, Alessandro Dussin, Eleftheria Xanthopoulou, Dimitrios Bikiaris, Luigi Botta, Vincenzo Fiore, Alessandro Pegoretti, 2022, izvirni znanstveni članek Opis: Despite the advantages of polylactide (PLA), its inadequate UV-shielding and gas-barrier
properties undermine its wide application as a flexible packaging film for perishable items. These
issues are addressed in this work by investigating the properties of melt-mixed, fully bioderived
blends of polylactide (PLA) and poly(ethylene furanoate) (PEF), as a function of the PEF weight
fraction (1–30 wt %) and the amount of the commercial compatibilizer/chain extender Joncryl ADR
4468 (J, 0.25–1 phr). J mitigates the immiscibility of the two polymer phases by decreasing and
homogenizing the PEF domain size; for the blend containing 10 wt % of PEF, the PEF domain size
drops from 0.67 ± 0.46 µm of the uncompatibilized blend to 0.26 ± 0.14 with 1 phr of J. Moreover,
the increase in the complex viscosity of PLA and PLA/PEF blends with the J content evidences
the effectiveness of J as a chain extender. This dual positive contribution of J is reflected in the
mechanical properties of PLA/PEF blends. Whereas the uncompatibilized blend with 10 wt % of
PEF shows lower mechanical performance than neat PLA, all the compatibilized blends show higher
tensile strength and strain at break, while retaining their high elastic moduli. The effects of PEF
on the UV- and oxygen-barrier properties of PLA are also remarkable. Adding only 1 wt % of PEF
makes the blend an excellent barrier for UV rays, with the transmittance at 320 nm dropping from
52.8% of neat PLA to 0.4% of the sample with 1 wt % PEF, while keeping good transparency in the
visible region. PEF is also responsible for a sensible decrease in the oxygen transmission rate, which
decreases from 189 cc/m2
·day for neat PLA to 144 cc/m2
·day with only 1 wt % of PEF. This work
emphasizes the synergistic effects of PEF and J in enhancing the thermal, mechanical, UV-shielding,
and gas-barrier properties of PLA, which results in bioderived blends that are very promising for
packaging applications. Ključne besede: polylactide, furanoates, poly(ethylene furanoate), blends, compatibilization, gas-permeability, UV-shielding Objavljeno v DKUM: 24.03.2025; Ogledov: 0; Prenosov: 3
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3. Study on impact of monomers towards high molecular weight bio-based poly(ethylene furanoate) via solid state polymerization techniqueJohan Stanley, Eleftheria Xanthopoulou, Margaritis Kostoglou, Lidija Fras Zemljič, Dimitra A. Lambropoulou, Dimitrios Bikiaris, 2024, izvirni znanstveni članek Opis: 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. Ključne besede: 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 Objavljeno v DKUM: 10.03.2025; Ogledov: 0; Prenosov: 6
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4. Effect of monomer type on the synthesis and properties of poly(ethylene furanoate)Johan Stanley, Zoi Terzopoulou, Panagiotis A. Klonos, Alexandra Zamboulis, Eleftheria Xanthopoulou, Savvas Koltsakidis, Dimitrios Tzetzis, Lidija Fras Zemljič, Dimitra A. Lambropoulou, Apostolos Kyritsis, George Z. Papageorgiou, Dimitrios Bikiaris, 2023, izvirni znanstveni članek Opis: This work aimed to produce bio-based poly(ethylene furanoate) (PEF) with a high molecular weight using 2,5-furan dicarboxylic acid (FDCA) or its derivative dimethyl 2,5-furan dicarboxylate (DMFD), targeting food packaging applications. The effect of monomer type, molar ratios, catalyst, polycondensation time, and temperature on synthesized samples’ intrinsic viscosities and color intensity was evaluated. It was found that FDCA is more effective than DMFD in producing PEF with higher molecular weight. A sum of complementary techniques was employed to study the structure– properties relationships of the prepared PEF samples, both in amorphous and semicrystalline states. The amorphous samples exhibited an increase in glass transition temperature of 82–87 ◦C, and annealed samples displayed a decrease in crystallinity with increasing intrinsic viscosity, as analyzed by differential scanning calorimetry and X-ray diffraction. Dielectric spectroscopy showed moderate local and segmental dynamics and high ionic conductivity for the 2,5-FDCA-based samples. The spherulite size and nuclei density of samples improved with increased melt crystallization and viscosity, respectively. The hydrophilicity and oxygen permeability of the samples were reduced with increased rigidity and molecular weight. The nanoindentation test showed that the hardness and elastic modulus of amorphous and annealed samples is higher at low viscosities due to high intermolecular interactions and degree of crystallinity. Ključne besede: bio-based polymers, poly(ethylene furanoate), polycondensation, thermal properties, mechanical properties, oxygen transmission rates Objavljeno v DKUM: 13.02.2025; Ogledov: 0; Prenosov: 3
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5. Synthesis of poly(ethylene furanoate) based nanocomposites by in situ polymerization with enhanced antibacterial properties for food packaging applicationsJohan Stanley, Eleftheria Xanthopoulou, Matjaž Finšgar, Lidija Fras Zemljič, Panagiotis A. Klonos, Apostolos Kyritsis, Savvas Koltsakidis, Dimitrios Tzetzis, Dimitra A. Lambropoulou, Diana Baciu, Theodore Steriotis, Georgia Charalambopoulou, Dimitrios Bikiaris, 2023, izvirni znanstveni članek Ključne besede: biobased polymers, poly(ethylene furanoate), nanoparticles, nanocomposites, antimicrobial properties Objavljeno v DKUM: 10.04.2024; Ogledov: 160; Prenosov: 19
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6. Fabrication of poly(ethylene furanoate)/silver and titanium dioxide nanocomposites with improved thermal and antimicrobial propertiesJohan Stanley, Eleftheria Xanthopoulou, Lidija Fras Zemljič, Panagiotis A. Klonos, Apostolos Kyritsis, Dimitra A. Lambropoulou, Dimitrios Bikiaris, 2024, izvirni znanstveni članek Opis: Poly(ethylene furanoate) (PEF)-based nanocomposites were fabricated with silver (Ag) and titanium dioxide (TiO2) nanoparticles by the in-situ polymerization method. The importance of this research work is to extend the usage of PEF-based nanocomposites with improved material properties. The PEF-Ag and PEF-TiO2 nanocomposites showed a significant improvement in color concentration, as determined by the color colorimeter. Scanning electron microscopy (SEM) photographs revealed the appearance of small aggregates on the surface of nanocomposites. According to crystallinity investigations, neat PEF and nanocomposites exhibit crystalline fraction between 0–6%, whereas annealed samples showed a degree of crystallinity value above 25%. Combining the structural and molecular dynamics observations from broadband dielectric spectroscopy (BDS) measurements found strong interactions between polymer chains and nanoparticles. Contact angle results exhibited a decrease in the wetting angle of nanocomposites compared to neat PEF. Finally, antimicrobial studies have been conducted, reporting a significant rise in inhibition of over 15% for both nanocomposite films against gram-positive and gram-negative bacteria. From the overall results, the synthesized PEF-based nanocomposites with enhanced thermal and antimicrobial properties may be optimized and utilized for the secondary packaging (unintended food-contact) materials. Ključne besede: active agents, antimicrobial studies, biobased polymers, crystallinity, poly(ethylene 2, 5-furandicarboxylate) Objavljeno v DKUM: 03.04.2024; Ogledov: 214; Prenosov: 12
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