RESUMO
To enhance PLA gas barrier properties, multilayer designs with highly polar barrier layers, such as nanocelluloses, have shown promising results. However, the properties of these polar layers change with humidity. As a result, we investigated water transport phenomena in PLA films coated with nanometric layers of chitosan and nanocelluloses, utilizing a combination of techniques including dynamic vapor sorption (DVS) and long-term water vapor adsorption-diffusion experiments (back-face measurements) to understand the influence of each layer on the behavior of multilayer films. Surprisingly, nanometric coatings impacted PLA water vapor transport. Chitosan/nanocelluloses layers, representing less than 1 wt.% of the multilayer film, increased the water vapor uptake of the film by 14.6%. The nanometric chitosan coating appeared to have localized effects on PLA structure. Moreover, nanocelluloses coatings displayed varying impacts on sample properties depending on their interactions (hydrogen, ionic bonds) with chitosan. The negatively charged CNF TEMPO coating formed a dense network that demonstrated higher resistance to water sorption and diffusion compared to CNF and CNC coatings. This work also highlights the limitations of conventional water vapor permeability measurements, especially when dealing with materials containing ultrathin nanocelluloses layers. It shows the necessity of considering the synergistic effects between layers to accurately evaluate the transport properties.
RESUMO
Nanocelluloses are promising high gas barrier materials for biobased food packaging, but they must be protected from water to preserve high performance. The respective O2 barrier properties of different types of nanocelluloses were compared (nanofibers (CNF), oxidized nanofibers (CNF TEMPO) and nanocrystals (CNC)). The oxygen barrier performance for all types of nanocelluloses was similarly high. To protect the nanocellulose films from water, a multilayer material architecture was used with poly(lactide) (PLA) on the outside. To achieve this, a biobased tie layer was developed, using Corona treatment and chitosan. This allowed thin film coating with nanocellulose layers between 60 and 440 nm thickness. AFM images treated with Fast Fourier Transform showed the formation of locally-oriented CNC layers on the film. Coated PLA(CNC) films performed better (3.2 × 10-20 m3.m/m2.s.Pa) than PLA(CNF) and PLA(CNF TEMPO) (1.1 × 10-19 at best), because thicker layers could be obtained. The oxygen barrier properties were constant during successive measurements at 0 % RH, 80 % RH and again at 0 % RH. This shows that PLA is sufficiently shielding nanocelluloses from water uptake to keep high performance in an extended range of RH and opens the way to high oxygen barrier films which are biobased and biodegradable.
RESUMO
The aim of this study was to find alternative starch plasticizers to glycerol that yielded a less tacky material in high-moisture conditions without leading to starch crystallization. A range of glycerol films containing different potential plasticizers (linear alkane diols) were therefore produced, and it was shown that 1,3-propanediol, in combination with glycerol, was a possible solution to the problem. Several additional interesting features of the starch films were however also revealed. The larger diols, instead of showing plasticizing features, yielded a variety of unexpected structures and film properties. Films with 1,6-hexanediol and 1,7-heptanediol showed an ultraporous film surface and near-isoporous core. The most striking feature was that starch films with these two diols moved/rotated over the surface when placed on water, with no other stimulus than the interaction with water. Films with 1,8-octanediol and 1,10-decanediol did not show these features, but there was clear evidence of a structure with phase-separated crystallized diol in a starch matrix, as observed in high-resolution scanning electron microscopy (SEM) images.