scale analysis of the impact of polylactide morphology on gas barrier properties. Polymer, Elsevier, 2017, 108, pp.163-172. 10.1016/j.polymer.2016 Multi-scale analysis of the impact of polylactide morphology on gas barrier properties Samira Fernandes Nassar
t r a c tSemicrystalline polylactide (PLA) films with controlled morphology were produced by thermal crystallization to optimize the oxygen barrier properties. The crystalline morphology of PLA at the scales of the lamella and the spherulite was investigated and the mobile amorphous phase dynamics were studied. The crystalline morphology had a negligible impact on the oxygen diffusion coefficient. The occurrence of a rigid amorphous fraction (RAF) in the amorphous phase due to its insufficient decoupling from the crystalline phase provided an accelerated pathway for diffusion, though. As a conclusion, for reaching optimal barrier properties, semicrystalline PLA should be pre-nucleated and rapidly crystallized from the glass in the a-polymorph in the aim to reach a high crystallinity degree and decoupling of the amorphous and the crystalline phase. These recommendations can benefit to industry for the optimization of PLA annealing treatments.
Multi-nanolayered Polystyrene/Poly(L,L-lactide) (PS/PLLA) films were obtained by the layermultiplying co-extrusion process, with an individual PLLA layer thickness as thin as 20 nm. The confinement of the amorphous PLLA induced a change in the molecular mobility, evidenced by a drop of the Cooperative Rearranging Region (CRR) size at the glass transition. The annealing of confined PLLA layers revealed slower crystallization kinetics and two-dimensional crystalline growth geometry. Furthermore, the annealing of PLLA in confined layers allowed a decoupling between the amorphous and crystalline phase, evidenced by the absence of a Rigid Amorphous Fraction (RAF). As a consequence, the dynamic heterogeneity at the glass transition remained unaffected by the annealing procedure. In bulk polymers, where the level of coupling between amorphous and crystals is high, the glass transition temperature increased significantly whereas the CRR size fell. It is deduced that the glass transition dynamics in semi-crystalline polymers is strongly related to the mobility landscape at the interface with crystals.
The physical aging behavior of amorphous polylactide constrained against polystyrene in layers of 300 nm, thanks to the layeremultiplying coeextrusion process, was investigated by fastescanning calorimetry (FSC). By cooling down the sample from the liquid state to the glassy one at very fast scanning rates, it was possible to investigate the structural relaxation of the polymer glass at high temperatures for which the time needed to reach the equilibrium was shortened. Therefore it was possible to perform the study of physical aging in experimental conditions providing an expanded view of the structural relaxation for short aging times. Taking benefit of this property, it was highlighted that the aging kinetics of polylactide occurred significantly slower in the multilayer film, in comparison with a bulk amorphous film. The process of recovery in the multilayer system was found to occur at similar rates, or even slower, than in a threeelayer film in which polylactide reached its maximum extent of crystallinity. This was attributed to mobility hindrance that might be inherent to the extrusion conditions or associated with the presence of capped interfaces with polystyrene.
The barrier properties of poly(L-lactide) (PLLA) were investigated in multinanolayer systems, probing the effect of confinement, the compatibility between the confining and the confined polymer, crystal orientation, and amorphous phase properties. The multilayer coextrusion process was used to confine PLLA between two amorphous polymers (polystyrene, PS; and polycarbonate, PC), which have different chemical affinities with PLLA. Confined PLLA layers of approximately 20 nm thickness were obtained. The multinanolayer materials were annealed at different temperatures to obtain PLLA crystallites with distinct polymorphs. PLLA annealed in PC/PLLA films at 120°C afforded a crystallinity degree up to 65%, and PLLA annealed in PC/PLLA or PS/PLLA films at 85°C had a crystallinity degree of 45%. WAXS measurements evidenced that the PLLA lamellas between PS layers had a mixed in-plane and on-edge orientation. PLLA lamellas between PC layers were uniquely oriented in-plane. DMA results evidenced a shift of the PC glass transition toward lower temperature, suggesting the possible presence of an interphase. The development of the rigid amorphous fraction (RAF) in the amorphous phase during annealing was impacted by the confiner polymer. The RAF content of semicrystalline PLLA was about 15% in PC/ PLLA, whereas it was neglectable in PS/PLLA. The oxygen barrier properties appeared to be governed by RAF content, and no impact of the PLLA polymorph or the crystalline orientation was observed. This study shows that the confinement of PLLA on itself does not impact barrier properties but that the proper choice of the confiner polymer can lead to decrease the phase coupling which creates the RAF. It is the prevention of RAF that decreases permeability.
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