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The generation of long-chain branches (LCB) in biobased and biodegradable polylactide (PLA) by adding different amounts of a chain extender is studied. The rheological and calorimetric behavior have been used to determine the effect of LCB presence and their topology on PLA melt strength and crystallization behavior. Rheological modeling of linear and non-linear viscoelastic shear and extensional properties identified several possible branched structures. Moreover, remarkable differences were observed for the different topologies regarding the intrinsic non-linear parameters and the intra-cycle elastic and viscous non-linearities. Differential scanning calorimetry and polarized light optical microscopy measurements revealed a significant increase in the nucleation density and rate of PLA with increasing the amount of LCB, albeit they provoke a decrease in the growth rate due to a reduction in chain diffusion. Nevertheless, overall crystallization rate values revealed a predominant effect of nucleation over crystal growth. The introduction of LCB within the chains is highly beneficial as they increase nucleation, crystallinity, and elongational viscosity, thus improving the properties of biodegradable PLA., Competing Interests: Declaration of competing interest We are confirming that there are no known conflicts of interest associated with this publication, and there has been no significant financial support for this work that could have influenced its outcome., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

This work presents, for the first time, a detailed report on how the nucleation and crystallization of polylactide (PLLA) are affected by biobased aliphatic polyesters plasticizers. Three biobased polyesters were synthesized via solvent-free two-stage melt polycondensation of adipic acid (AdA) with three different biobased aliphatic diols and used as plasticizers for poly (L-lactic acid) (PLLA). The molecular structure of the synthesized polyesters was proved using 1 H NMR, 13 C NMR and Fourier transform infrared (FTIR) spectroscopy. PLLA/AdA-based blends containing 10 wt% of the polyester plasticizers were studied by tensile tests, dynamic mechanical analysis (DMA), wide-angle x-ray scattering (WAXS), differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM). Adding the plasticizers to PLLA decreased T g by up to 11 °C and significantly increased the elongation at break by about 8 times compared with neat PLLA. The addition of 10 wt% of any AdA-based plasticizer to PLLA increases the nucleation rate from the glassy state by around 50-110 % depending on the plasticizer. The overall crystallization rate from the glassy state was 2-3 times faster for the plasticized PLLAs than neat PLLA. These results are a consequence of the lower energy barrier for both nucleation and growth processes. The incorporation of AdA-based linear polyesters had an incremental impact on the crystal growth rate (or secondary nucleation) of PLLA spherulites from the melt and glassy states. In conclusion, the AdA-based aliphatic polyesters allowed to enhance PLLA crystallization rates and showed interesting potential for the formulation of fully biobased PLLA blends., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Polylactide is one of the most versatile biopolymers, but its slow crystallization limits its temperature usage range. Hence finding ways to enhance it is crucial to widen its applications. Linear and cyclic poly (L-lactide) (l-PLLA and c-PLLA) of similarly low molecular weights (MW) were synthesized by ring-opening polymerization of L-lactide, and ring-expansion methodology, respectively. Two types of blends were prepared by solution mixing: (a) l-PLLA/c-PLLA, at extreme compositions (rich in linear or in cyclic chains), and (b) blends of each of these low MW materials with a commercial high MW linear PLA. The crystallization of the different blends was evaluated by polarized light optical microscopy and differential scanning calorimetry. It was found, for the first time, that in the l-PLLA rich blends, small amounts of c-PLLA (i.e., 5 and 10 wt%) increase the nucleation density, nucleation rate (1/τ 0 ), spherulitic growth rate (G), and overall crystallization rate (1/τ 50% ), when compared to neat l-PLLA, due to a synergistic effect (i.e., nucleation plus plasticization). In contrast, the opposite effect was found in the c-PLLA rich blends. The addition of small amounts of l-PLLA to a matrix of c-PLLA chains causes a decrease in the nucleation density, 1/τ 0 , G, and 1/τ 50% values, due to threading effects between cyclic and linear chains. Small amounts of l-PLLA and c-PLLA enhance the crystallization ability of a commercial high MW linear PLA without affecting its melting temperature. The l-PLLA only acts as a plasticizer for the PLA matrix, whereas c-PLLA has a synergistic effect in accelerating the crystallization of PLA that goes beyond simple plasticization. The addition of small amounts of c-PLLA affects not only PLA crystal growth but also its nucleation due to the unique cyclic chains topology., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Poly(hydroxyalkanoates) are biodegradable and biocompatible polymers suitable for tissue engineering. Fused deposition modeling (FDM) belongs to modern rapid prototyping techniques for the fabrication of scaffolds. In this work, poly(3-hydroxybutyrate (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) were tested for FDM. Thermal and rheological properties of industrial PHAs were compared with poly(lactic acid) (PLA), which is a biodegradable polymer commonly used for FDM. The massive decrease in viscosity and loss of molecular weight of PHB and PHBV precluded their use for FDM. On the other hand, the thermal stability of PHBH was comparable to that of PLA. PHBH scaffolds prepared by FDM exhibited excellent mechanical properties, no cytotoxicity and large proliferation of mouse embryonic fibroblast cells within 96 h. The hydrolytic degradation of PHBH and PLA scaffolds tested in synthetic gastric juice for 52 days confirmed a faster degradation of PHBH than PLA. The decrease in molecular weight confirmed the first-order kinetics with a slightly higher (0.0169 day -1 ) degradation rate constant for PHBH as compared to the value (0.0107 day -1 ) obtained for PLA. These results indicate that PHBH could be used to produce scaffolds by FDM with application in tissue engineering., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)