Water sorption behaviour of two series of PHA/montmorillonite films and determination of the mean water cluster size.

Biodegradable polyester-based films constituted of poly(hydroxyalkanoates) (PHA) were successfully extruded with various Cloisite 30B contents. The morphology was highly dependent on the matrix, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(3-hydroxybutyrate-co-4-hydroxybutyrate), the polymer crystalline phase fraction, the matrix/nanoclay interfacial regions as well as the nanoclay content. Water vapour resistance was investigated through sorption kinetics, isotherms, modelling aspect, and diffusivity. A typical sigmoid-shaped isotherm was obtained in every case. It emerges that the nanoclay highly contributed to the increase of water solubility of matrices. The dependence of polymer crystallinity on the affinity of the nanocomposite films for water was highlighted. Thermodynamic and kinetic contributions of the sorption process were also correlated with the film morphology. According to the matrix used, water diffusivity in films was differently impacted by the sorbed water amount. The access of sorbed water molecules within films was examined through a mathematical modelling approach and the deduced mean cluster size of water vs. its activity was corroborated by sorption kinetics.

Structure-barrier property relationship of biodegradable poly(butylene succinate) and poly[(butylene succinate)-co-(butylene adipate)] nanocomposites: influence of the rigid amorphous fraction.

Composites composed of polyesters, poly(butylene succinate) (PBS) or poly[(butylene succinate)-co-(butylene adipate)] (PBSA), and 5 wt% of montmorillonite (CNa) or organo-modified montmorillonite (C30B) were melt-processed and transformed into films by either compression-molding or extrusion-calendering. XRD, rheological measurements and TEM images clearly indicated that films containing CNa are microcomposites, while nanocomposites were observed for those containing C30B. Using Flash DSC, it was possible, for the first time, not only to measure the heat capacity step at the glass transition of these two materials in their amorphous state, but also to investigate whether the preparation technique influenced the Rigid Amorphous Fraction (RAF) in our PBS- and PBSA-based nanocomposites. In this work, we have successfully shown the correlation between the microstructure of the films and their barrier properties, and especially the role played by the RAF. Indeed, the lowest permeabilities to gases and to water were determined in the films containing the highest RAF in both PBS- and PBSA-based materials.

Tunable water barrier properties of EVA by clay insertion?

Organo-modified Cloisite clays at varying contents were incorporated into poly(ethylene-co-vinyl acetate) (EVA) by melt blending. Nanoclay dispersion in films was first evaluated. The water transport properties were investigated by pervaporation and sorption measurements. A decrease of the water permeation flux was obtained when incorporating nanoparticles. This barrier effect is usually attributed to the increase of the diffusion pathways due to nanoclay-induced tortuosity effects. However, the diffusion coefficient was found to be dependent on water concentration, which generally reflects a plasticization effect of water. Besides, at 7 wt% of loading, an unexpected increase of water diffusivity was measured with a time-scale shift of the permeation flux. This was correlated with the formation of preferential diffusion pathways along interfacial regions due to free volumes existing between the EVA matrix and nanoclays as well as the water affinity of microfillers. As a consequence, water mass gain was found to be increased. The water-induced plasticization of sorbed water molecules was also highlighted through sorption kinetics. Eventually, some applications to these films in which water barrier behaviour is required were discussed.

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) based nanocomposites: influence of the microstructure on the barrier properties.

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-co-4HB) films containing various contents of organo-modified montmorillonite C30B nanoclays were prepared by melt intercalation. Wide angle X-ray diffraction measurements and transmission electron microscopy observations evidenced aggregated and intercalated structures with individual nanoclay platelets in the nanocomposites and an orientation of nanoclays. Differential scanning calorimetry measurements showed that the nanoclay did not influence the crystalline structure of the matrix because it is mainly located in the polymer amorphous phase. The influence of the filler on the barrier properties of the film was evaluated by water diffusion, gas permeation (CO2, N2, O2) and liquid water sorption measurements. A decrease of the N2 permeability was measured due to the tortuosity effect of the filler associated with a decrease of the solubility within the matrix. The influence of the filler was more marked for O2 due to the larger decrease of O2 solubility. In contrast, the CO2 permeability increased whatever the filler content because of a facilitated transport mechanism due induced by the presence of quaternary ammonium cations on the C30B surface. The decrease of the water permeability with the filler was explained by a competition between the kinetic (diffusivity) and thermodynamic (solubility) contributions defining the permeability process.