Dewetting Dynamics of Sheared Thin Polymer Films: An Experimental Study.

An experimental investigation is reported on the effect of shear on the bursting of molten ultrathin polymer films embedded in an immiscible matrix. By use of an optical microscope coupled with a shearing hot stage, the dewetting dynamics, i.e., the growth of dewetting holes, is monitored over time at various shear rates. It is observed that their circularity is modified by shear and that for all temperatures and thicknesses studied the growth speed of the formed holes rapidly increases with increasing shear rate. A model balancing capillary forces and viscous dissipation while taking into account shear thinning is then proposed and captures the main features of the experimental data, such as the ellipsoid shape of the holes and the faster dynamics in the direction parallel to the shear. This research will help to understand the instabilities occurring during processing of layered polymeric structures, such as multilayer coextrusion.

Dual Transient Networks of Polymer and Micellar Chains: Structure and Viscoelastic Synergy.

Dual transient networks were prepared by mixing highly charged long wormlike micelles of surfactants with polysaccharide chains of hydroxypropyl guar above the entanglement concentration for each of the components. The wormlike micelles were composed of two oppositely charged surfactants potassium oleate and n-octyltrimethylammonium bromide with a large excess of anionic surfactant. The system is macroscopically homogeneous over a wide range of polymer and surfactant concentrations, which is attributed to a stabilizing effect of surfactants counterions that try to occupy as much volume as possible in order to gain in translational entropy. At the same time, by small-angle neutron scattering (SANS) combined with ultrasmall-angle neutron scattering (USANS), a microphase separation with the formation of polymer-rich and surfactant-rich domains was detected. Rheological studies in the linear viscoelastic regime revealed a synergistic 180-fold enhancement of viscosity and 65-fold increase of the longest relaxation time in comparison with the individual components. This effect was attributed to the local increase in concentration of both components trying to avoid contact with each other, which makes the micelles longer and increases the number of intermicellar and interpolymer entanglements. The enhanced rheological properties of this novel system based on industrially important polymer hold great potential for applications in personal care products, oil recovery and many other fields.

Structural and Barrier Properties of Compatibilized PE/PA6 Multinanolayer Films.

The barrier performance and structural lightening of organic materials are increasingly desired and constitute a major challenge for manufacturers, particularly for transport and packaging. A promising technique which tends to emerge in recent years is that of multinanolayer coextrusion. The advantage is that it can produce multilayers made of thousands of very thin layers, leading to new properties due to crystalline morphology changes induced by confinement. This paper is focusing on the study of multinanolayered films with alternated polyethylene (PE), compatibilizer (PEgMA) and polyamide 6 (PA6) layers and made by a forced assembly coextrusion process equipped with layer multiplying elements (LME). PE/PA6 multilayer films consisting of 5 to 2049 layers (respectively 0 to 9 LME) were successfully obtained with well-organized multilayered structure. The evolution of the morphology and the microstructure of these two semi-crystalline polymers, when the thickness of each polymer layer decreases from micro-scale to nano-scale, was correlated to the water and gas transport properties of the PE/PA multilayers. The expected improvement of barrier properties was limited due to the on-edge orientation of crystals in very thin PE and PA6 layers. Despite this change of crystalline morphology, a slight improvement of the gas barrier properties was shown by comparing experimental results with permeabilities predicted on the basis of a serial model developed by considering a PE/PA6 interphase. This interphase observed by TEM images and the on-edge crystal orientation in multilayers were evidenced from mechanical properties showing an increase of the stiffness and the strength.

Impact of Nanoconfinement on Polylactide Crystallization and Gas Barrier Properties.

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.

Biodegradable PLA/PBSA Multinanolayer Nanocomposites: Effect of Nanoclays Incorporation in Multinanolayered Structure on Mechanical and Water Barrier Properties.

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.

Nanorheology with a Conventional Rheometer: Probing the Interfacial Properties in Compatibilized Multinanolayer Polymer Films.

Measuring the viscoelastic behavior of polymers in the vicinity of a surface or under confinement is an experimental challenge. Simple rheological tests of nanolayered films of polyethylene/polyamide 6 compatibilized in situ during the coextrusion process enabled the probing of these interfacial properties. Taking advantage of the different melting points and of the multiplication of the number of interfaces, a drastic increase of dynamic moduli was reported when increasing the interphase volume fraction in the films. A solid-like behavior for the interphase was identified. The complex viscosity of nanolayered films as a function of angular frequency was quantitatively captured for all samples using a weighted mixing law of bulk and interphase viscosities, without additional adjusting parameters, highlighting the interfacial synergy developed in nanolayered polymer films.

Structure and Barrier Properties of Multinanolayered Biodegradable PLA/PBSA Films: Confinement Effect via Forced Assembly Coextrusion.

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 CO2 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.