1. Statistical modeling and optimization of the drawing process of bioderived polylactide/poly(dodecylene furanoate) wet-spun fibersDaniele Rigotti, Giulia Fredi, Davide Perin, Dimitrios Bikiaris, Alessandro Pegoretti, Andrea Dorigato, 2022, izvirni znanstveni članek Opis: 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. Ključne besede: fibers, poly(lactic acid), furanoate polyesters, drawing, response surface methodology, genetic algorithms Objavljeno v DKUM: 24.03.2025; Ogledov: 0; Prenosov: 2
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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. Improving the Thermomechanical Properties of Poly(lactic acid) via Reduced Graphene Oxide and Bioderived Poly(decamethylene 2,5-furandicarboxylate)Giulia Fredi, Mahdi Karimi Jafari, Andrea Dorigato, Dimitrios Bikiaris, Alessandro Pegoretti, 2022, izvirni znanstveni članek Opis: 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. Ključne besede: nanocomposites, reduced graphene oxide, poly(decamethylene 2, 5-furandicarboxylate), furanoate polyesters, polylactic acid, compatibilization Objavljeno v DKUM: 20.03.2025; Ogledov: 0; Prenosov: 1
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