Multilayer coextrusion processing was applied to produce 2049-layer film of poly(butylene succinate-co-butylene adipate) (PBSA) confined against poly(lactic acid) (PLA) using forced assembly, where the PBSA layer thickness was about 60 nm. This unique technology allowed to process semicrystalline PBSA as confined polymer and amorphous PLA as confining polymer in a continuous manner. The continuity of PBSA layers within the 80/20 wt % PLA/PBSA layered films was clearly evidenced by atomic force microscopy (AFM). Similar thermal events to the reference films were revealed by thermal studies; indicating no diffusion of polymers during the melt-processing. Mechanical properties were measured for the multilayer film and the obtained results were those expected considering the fraction of each polymer, revealing the absence of delamination in the PLA/PBSA multinanolayer film. The confinement effect induced by PLA led to a slight orientation of the crystals, an increase of the rigid amorphous fraction (RAF) in PBSA with a densification of this fraction without changing film crystallinity. These structural changes allowed to strongly improve the water vapor and gas barrier properties of the PBSA layer into the multilayer film up to two decades in the case of CO gas. By confining the PBSA structure in very thin and continuous layers, it was then possible to improve the barrier performances of a biodegradable system and the resulting barrier properties were successfully correlated to the effect of confinement on the microstructure and the chain segment mobility of the amorphous phase. Such investigation on these multinanolayers of PLA/PBSA with the aim of evidencing relationships between microstructure implying RAF and barrier performances has never been performed yet. Besides, gas and water permeation results have shown that the barrier improvement obtained from the multilayer was mainly due to the reduction of solubility linked to the reduction of the free volume while the tortuosity effect, as usually expected, was not really observed. This work brings new insights in the field of physicochemical behaviors of new multilayer films made of biodegradable polyesters but also in interfacial processes due to the confinement effect induced in these multinanolayer structures obtained by the forced assembly coextrusion. This original coextrusion process was a very advantageous technique to produce eco-friendly materials with functional properties without the help of tie layer, additives, solvents, surface treatments, or inorganic fillers.

Polyester multilayer membranes with more than 2000 alternating layers of poly(lactic acid) (PLA) and poly (butylene succinate) (PBS) were successfully prepared via a nanolayer coextrusion process equipped with a multiplying-element device. This process allows to make films consisting of very thin layers of polymers and in which a confinement effect of the semicrystalline polymer can be induced at point to significantly improve its physical properties. In this work, a homogeneous multinanolayer film of PLA/PBS was obtained without defaults or delamination, while the two polymers are immiscible. Continuous and homogeneous ultrathin layers of PBS (~45 nm) were obtained and the resulting confined structure of PBS led to an improvement of its barrier performances until 30% for oxygen, 40% for water and 70% for carbon dioxide. This improvement was explained by a decrease of the solubility coefficient and surprisingly not by the diffusion coefficient. This result was attributed to a slight orientation of the crystals in the extrusion direction and to the probable presence of an interphase between the layers of PLA and PBS.

A B S T R A C TFilms of PC and MXD6 were prepared via multilayer coextrusion. Films presenting stretched nodules/lamellas of MXD6 in the PC matrix, and films with quasi-continuous thin MXD6 layers alternating with PC layers were obtained.The transport properties were specifically investigated from water and gas permeation kinetics, and the corresponding permeation parameters were determined. The confinement effect of MXD6 in the multilayer structure was highlighted by comparing the permeability predicted from the series model equation with the experimental data. Although the MXD6 layers were not homogeneous and continuous for all membranes, water and gas permeabilities of the PC/MXD6 multilayer film were largely reduced. Such improvement of barrier properties was related to the change of the MXD6 structure, considering that the confinement of the MXD6 layers induced by PC layers allowed to bring chain orientation and to reduce the chain segment mobility in the MXD6 amorphous constrained zones. In addition, in the case of a PC/MXD6 multilayer structure well defined with continuous layers and relatively homogeneous thicknesses, the degree of crystallinity was slightly increased.

A multilayer film composed of alternating layers of polycarbonate (PC) and poly(m-xylene adipamide) (MXD6) was elaborated by using an innovative multilayer coextrusion process. Quasi-continuous thin MXD6 layers (nanolayers) alternating with PC layers were successfully obtained. The PC/MXD6 multilayer film showed a confining effect of MXD6 exerted by PC layers leading to an improvement of barrier properties despite a low degree of crystallinity (X c < 10 wt%). In order to further improve the barrier performances, crystallization treatments induced by water and by heating were then applied on the multilayer film and allowed reaching around 30 wt% of crystallinity in MXD6 layers. To decouple crystallization and geometrical constraint effects on the barrier properties in the multilayer films, the two treatments were also applied on MXD6 films. Surprisingly, despite an increase of the degree of crystallinity from 6 to 26%, water crystallization did not permit to improve gas barrier performances of the MXD6 film nor into the PC/MXD6 multilayer film. On the other hand, thermal crystallization of MXD6 in the multilayer film seems to be a more efficient route to strongly decrease the gas and moisture permeability, up to 75% for nitrogen, 58% for oxygen, 84% for carbon dioxide and 43% for water.

Biodegradable PLA/PBSA multinanolayer nanocomposites were obtained from semi-crystalline poly(butylene succinate-co-butylene adipate) (PBSA) nanolayers filled with nanoclays and confined against amorphous poly(lactic acid) (PLA) nanolayers in a continuous manner by applying an innovative coextrusion technology. The cloisite 30B (C30B) filler incorporation in nanolayers was considered to be an improvement of barrier properties of the multilayer films additional to the confinement effect resulting to forced assembly during the multilayer coextrusion process. 2049-layer films of ~300 µm thick were processed containing loaded PBSA nanolayers of ~200 nm, which presented certain homogeneity and were mostly continuous for the 80/20 wt% PLA/PBSA composition. The nanocomposite PBSA films (monolayer) were also processed for comparison. The presence of exfoliated and intercalated clay structure and some aggregates were observed within the PBSA nanolayers depending on the C30B content. A greater reduction of macromolecular chain segment mobility was measured due to combined effects of confinement effect and clays constraints. The absence of both polymer and clays interdiffusions was highlighted since the PLA glass transition was unchanged. Besides, a larger increase in local chain rigidification was evidenced through RAF values due to geometrical constraints initiated by close nanoclay contact without changing the crystallinity of PBSA. Tortuosity effects into the filled PBSA layers adding to confinement effects induced by PLA layers have caused a significant improvement of water barrier properties through a reduction of water permeability, water vapor solubility and water vapor diffusivity. The obtaining barrier properties were successfully correlated to microstructure, thermal properties and mobility of PBSA amorphous phase.

Food packaging films must be reinvented in order to answer the new demanding ecological requirements. Biobased and/or biodegradable polymers appear as an interesting alternative to reduce petroleum dependence and carbon dioxide emissions. Poly(ethylene furanoate) (PEF) appears today as a new promising biopolymer thanks to its good gas barrier and mechanical properties, despite its high price that could limit its industrial applications. Its combination with other polymers is thus of great interest and for the first time, film coextrusion process is used to create PLA-PEF and PET-PEF multi-micro/nano layered films. A new PEF grade developed by AVA Biochem in the H2020 Mypack program, has been used and firstly analysed in terms of melt processability, mechanical, thermal and gas barrier properties. Our major results confirmed the good gas barrier as well as mechanical properties of amorphous PEF. Post-extrusion PEF bulk thermal crystallization led to very brittle material making gas barrier measurements impossible. Micro/nanolayered PLA-PEF and PET-PEF films with different PEF layer thicknesses have been processed and post-extrusion annealing treatment was carried out. The relationship between crystallinity, mechanical and gas barrier properties will be investigated.

No abstract