Water vapor transport properties of bio-based multilayer materials determined by original and complementary methods.

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.

Resilient high oxygen barrier multilayer films of nanocellulose and polylactide.

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.

A macroscopic Washburn approach of liquid imbibition in wood derived from X-ray tomography observations.

Imbibition of water and silicone oil in poplar and spruce is investigated at the anatomical level by X-ray tomography observations and at the macroscopic level by imbibition kinetics. Imbibition mechanisms depend on both liquid and species. In poplar, oil penetrates vessels with a small contact angle, consistent with the value measured on solid wood (ca. [Formula: see text]). Surprisingly, no direct penetration of water was observed in vessels. The large contact angle for water blocks the capillary rise at the scars between vessel cells. In spruce, oil and water penetrate primarily in latewood, where bordered pits remain open. Subsequently, water slowly invades the rest of the growth ring, while transversal migration is quasi-absent for oil. These 3D observations were quantified to feed a simple imbibition model that satisfactorily simulates macroscopic imbibition kinetics. A 1D approach is sufficient for oil imbibition while a 2D approach is required for water, revealing dual scale effects.

A validated Distributed Activation Energy Model (DAEM) to predict the chemical degradation of biomass as a function of hydrothermal treatment conditions.

This study proposes a DAEM (Distributed Activation Energy Model) approach to predict the chemical alterations of lignocellulosic biomass as a function of hydrothermal treatment conditions. The model is first tuned by an original device allowing the sample shrinkage to be continuously assessed during hydrothermal treatment in saturated water vapor up to 190 °C. The shrinkage dynamic is supplied in the DAEM model as an indicator of the degree of biomass conversion. A set of chemical analyses was performed at selected residence times and treatment temperatures to correlate this degree of conversion with the resulting chemical molecules. A set of functions was then derived from this database to correlate the degree of conversion with the components concentrations. Finally, a validation database was built with different combinations of temperature levels and residence times. The model was proved to be predictive on this new dataset.

Multiscale investigation on the chemical and anatomical changes of lignocellulosic biomass for different severities of hydrothermal treatment.

The chemical changes sustained by lignocellulosic biomass during hydrothermal treatment are reflected at multiple scales. This study proposes to benefit from this multiscale nature in order to provide a global understanding of biomass alterations during hydrothermal treatment. For this purpose, complementary imaging techniques-confocal Raman microscopy and X-ray nano-tomography-analysed by image processing and coupled to chemical measurements were used. This unique combination of analyses provided valuable information on topochemical and morphological changes of poplar samples, without the artefacts of sample preparation. At the cell wall level, holocellulose hydrolysis and lignin modifications were observed, which corresponded to anatomical modifications observed at higher scales. Overall, after treatment, samples shrank and had thinner cell walls. When subjected to more severe pre-treatments, cells were disrupted and detached from adjacent cells. Anatomical changes were then used to obtain quantitative indicators of the treatment severity. The effects of treatment at different scales can thus be quantitatively connected in both directions, from micro to macro and from macro to micro.

In situ measurements of viscoelastic properties of biomass during hydrothermal treatment to assess the kinetics of chemical alterations.

This work aimed to use continuous measurements of viscoelastic properties to evaluate the effect of hydrothermal treatment on poplar samples. Different conditions (temperature and pre-soaking liquid: acidic, neutral and alkaline) were tested on wood in both tangential and radial directions. Two viscoelastic properties were determined: the modulus of elasticity and the stress relaxation. The applicability of these properties as indicators of the kinetics of biomass deconstruction was also evaluated, thanks to the chemical analyses performed on the treated solid and the recovered liquid phase. The ultimate goal is to build a macroscopic indicator capable of establishing rules to optimize the hydrothermal treatment before the explosion stage. The joint use of the two parameters succeeded in revealing the effects of chemical degradation, including the coexistence of cleavage and re-condensation and the impact of process conditions (temperature, residence time, and pre-soaking liquid). The monotonous behavior of stress relaxation is a major asset as a possible macroscopic indicator of biomass deconstruction.

Designed cellulose nanocrystal surface properties for improving barrier properties in polylactide nanocomposites.

Nanocomposites are an opportunity to increase the performance of polymer membranes by fine-tuning their morphology. In particular, the understanding of the contribution of the polymer matrix/nanofiller interface to the overall transport properties is key to design membranes with tailored selective and adsorptive properties. In that aim, cellulose nanocrystals (CNC)/polylactide (PLA) nanocomposites were fabricated with chemically designed interfaces, which were ensuring the compatibility between the constituents and impacting the mass transport mechanism. A detailed analysis of the mass transport behaviour of different permeants in CNC/PLA nanocomposites was carried out as a function of their chemical affinity to grafted CNC surfaces. Penetrants (O2 and cyclohexane), which were found to slightly interact with the constituents of the nanocomposites, provided information on the small tortuosity effect of CNC on diffusive mass transport. The mass transport of water (highly interacting with CNC) and anisole (interacting only with designed CNC surfaces) exhibited non-Fickian, Case II behaviour. The water vapour caused significant swelling of the CNC, which created a preferential pathway for mass transport. CNC surface grafting could attenuate this phenomenon and decrease the water transport rate. Anisole, an aromatic organic vapour, became reversibly trapped at the specifically designed CNC/PLA interface, but without any swelling or creation of an accelerated pathway. This caused the decrease of the overall mass transport rate. The latter finding could open a way to the creation of materials with specifically designed barrier properties by designing nanocomposites interfaces with specific interactions towards permeants.