Polylactide (PLA) was blended by conventional and reactive extrusion with limonene (LM) or myrcene (My) as bio-based plasticizers. As-processed blends were carefully analyzed by a multiscale and multidisciplinary approach to tentatively determine their chemical structure, microstructure, thermal properties, tensile and impact behaviors, and hydrothermal stability. The main results indicated that LM and My were efficient plasticizers for PLA, since compared to neat PLA, the glass transition temperature was reduced, the ultimate tensile strain was increased, and the impact strength was increased, independently of the type of extrusion. The addition of a free radical initiator during the extrusion of PLA/LM was beneficial for the mechanical properties. Indeed, the probable formation of local branched/crosslinked regions in the PLA matrix enhanced the matrix crystallinity, the tensile yield stress, and the tensile ultimate stress compared to the non-reactive blend PLA/LM, while the other properties were retained. For PLA/My blends, reactive extrusion was detrimental for the mechanical properties since My polymerization was accelerated resulting in a drop of the tensile ultimate strain and impact strength, and an increase of the glass transition temperature. Indeed, large inclusions of polymerized My were formed, decreasing the available content of My for the plasticization and enhancing cavitation from inclusion-matrix debonding.

ABSTRACT This work aims at identifying defects called deformation heterogeneities developing in polylactide (PLA)‐based materials upon drawing at room temperature. The influence of the initial crystallinity and of the plasticization methodology (physical blending vs. reactive blending) on the type of defect is also investigated. Defects are characterized in situ by (a) calculating the volume strain from digital image correlation (DIC), (b) measuring their surface density from optical microscopy, and (c) assessing their scattering invariant from small‐angle X‐ray scattering. Complementary structural analyses are done by microcomputed X‐ray tomography and atomic force microscopy. Drawing is accompanied by crazing in the case of low‐crystalline PLA, cracking in the case of annealed PLA, no defect in the case of plasticized PLA by physical blending, and shear bands and cracking in the case of plasticized PLA by reactive blending. These observations are discussed based on the initial structural features of the materials. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56 , 1452–1468

This work focused on the determination of crystallization kinetics of neat polylactide (PLA) and a plasticized grade of PLA obtained by reactive extrusion (pPLA), as a function of thermomechanical recycling. In particular, the materials were submitted to repeated extrusion and injection procedures to simulate recycling. Prior reprocessing, spherulitic growth rate determined by polarized light optical microscopy indicated that pPLA crystallized into much smaller spherulites as compared to PLA. This finding was explained by a lower nucleation energy barrier promoted by the plasticization of pPLA. Isothermal overall crystallization kinetics were determined by differential scanning calorimetry measurements. It was found that pPLA crystallized much faster than neat PLA due to the plasticization effect. With increasing the number of processing cycles up to 5, PLA crystallization rate gradually increased, while at the same time that of pPLA remained constant. This result was explained by more important degradation mechanisms in PLA as compared to pPLA that enhanced chain mobility, as shown by molecular weight measurements. Moreover, pPLA had a very high initial chain mobility that is maintained regardless of the number of processing cycles. However, the final crystallinity degree was lower in reprocessed pPLAs, as grafting and cross-linking reactions produced during reactive extrusion interrupt crystallizable linear crystallizable sequences and reduced the amount of crystals formed.

A multiscale characterization approach is developed to resolve the structure of inclusions in polylactide (PLA) plasticized with acrylated poly(ethylene glycol) (acrylPEG) by reactive extrusion. Scanning transmission X-ray microscopy (STXM) coupled with near-edge X-ray absorption fine structure (NEXAFS) nanospectroscopy demonstrates that these inclusions have a core–shell morphology. This technique also proves that the inclusions consist of polymerized acrylPEG (poly(acrylPEG)), which is also confirmed by elastic modulus measurement using an atomic force microscope. The shell consists of poly(acrylPEG)-rich domains, while the core is less rich in the polymerized plasticizer. Upon drawing, the density of the inclusion's core and shell markedly decreases as shown by microcomputed X-ray tomography measurements, and no inclusion–matrix debonding is observed. At the same time, sub-micrometer cracks are noted between inclusions by STXM/NEXAFS imaging, which may result from the presence of crosslinking points restricting the local chain mobility. Novel knowledge about the reactive extrusion-induced PLA structure is released.

The thermo-mechanical recycling of poly(lactide) (PLA) by reprocessing was recently considered as a new end-of-life scenario for this biosourced and biodegradable polymer. With this regard, the degradation mechanisms of plasticized PLA (pPLA) engendered by multiple reprocessing were little investigated to date, and hence, the relevancy of its reprocessing was not assessed. They were identified in this paper by a multiscale approach in the case of a lab-developed grade of pPLA obtained by the reactive extrusion of PLA with acrylated poly(ethylene glycol) (acryl-PEG) as reactive plasticizer. pPLA structure consisted of a semi-crystalline PLA matrix in which grafted poly(acryl-PEG) micro-inclusions were dispersed. Up to 5 successive processing cycles including extrusion and compression-molding, the tensile and impact properties drastically dropped indicating an embrittlement of pPLA. Structural analyses revealed that reprocessing caused these mechanisms: chain scission of PLA, crystallization of PLA, damaging of the inclusions, decrease of the size of poly(acryl-PEG) phases within the inclusions, and cracking of PLA. At the same time, the amount of grafted poly(acryl-PEG) was not influenced by the reprocessing. Inclusion damaging and matrix cracking are believed to be responsible for the embrittlement of pPLA after multiple reprocessing, which makes it not suitable for being reused for its initial application.

This work aimed at identifying the tensile deformation mechanisms of an original grade of plasticized polylactide (pPLA) obtained by reactive extrusion. This material had a glass transition temperature of 32.6 °C and consisted of a polylactide (PLA) matrix grafted with poly(acryl-poly(ethylene glycol)) (poly(Acryl-PEG)) inclusions. pPLA behaved like a rubber-toughened amorphous polymer at 20 °C, and its tensile behavior evolved toward a rubbery semicrystalline polymer with increasing temperature. The drawing of pPLA involved orientation of amorphous and crystalline chains, crystallization, and destruction of crystals. It was found that crystal formation and crystal destruction were in competition below 50 °C, resulting in a constant or slightly decreasing crystallinity with strain. Increasing temperature enhanced crystal formation and limited crystal destruction, resulting in an increased crystallinity with the strain level. Drawing yielded a transformation of the initial spherical poly(Acryl-PEG) inclusions into ellipsoids oriented in the tensile direction. This mechanism may engender the formation of nanovoids within the inclusions due to a decreased density, assumed to be responsible for the whitening of the specimen. © 2015 Society of Chemical Industry