Biobased free-standing films and coatings with low oxygen permeability were designed from a wood hydrolysate according to a recovery and formulation procedure that provides added value to wood converting industrial processes. Wood components released to the wastewater in the hydrothermal treatment of spruce wood were recovered and converted to an oligo- and polysaccharide-rich, noncellulosic fraction that was utilized in film formulations in a range of concentrations and compositions. Free-standing smooth and transparent films as well as coatings on thin PET were prepared and characterized with respect to oxygen permeability, tensile properties, structure, and water vapor transmission. With oxygen permeabilities as low as below 1 cm(3) μm m(-2) day(-1) kPa(-1) and with adequate mechanical properties, the films and coatings show promising property profiles for renewable packaging applications.
Biomass is converted to oxygen barriers through a conceptually unconventional approach involving the preservation of the biomass native interactions and macromolecular components and enhancing the effect by created interactions with a co-component. A combined calculation/assessment model is elaborated to understand, quantify, and predict which compositions that provide an intermolecular affinity high enough to mediate the molecular packing needed to create a functioning barrier. The biomass used is a wood hydrolysate, a polysaccharide-rich but not highly refined mixture where a fair amount of the native intermolecular and intramolecular hemicelluloses-lignin interactions are purposely preserved, resulting in barriers with very low oxygen permeabilities (OP) both at 50 and 80% relative humidity and considerably lower OPs than coatings based on the corresponding highly purified spruce hemicellulose, O-acetyl galactoglucomannan (AcGGM). The component interactions and mutual affinities effectively mediate an immobilization of the chain segments in a dense disordered structure, modeled through the Hansen's solubility parameter concept and quantified on the nanolength scale by positron annihilation lifetime spectrum (PALS).
Barrier performance and retrostructural modeling of the macromolecular components demonstrate new design principles for film formulations based on renewable wood hydrolysates. Hardwood hydrolysates, which contain a fair share of lignin coexisting with poly- and oligosaccharides, offer excellent oxygen-barrier performance. A Hansen solubility parameter (HSP) model has been developed to convert the complex hydrolysate structural compositions into relevant matrix oxygen-permeability data allowing a systematic prediction of how the biomass should be formulated to generate an efficient barrier. HSP modeling suggests that the molecular packing ability plays a key role in the barrier performance. The actual size and distribution of free volume holes in the matrices were quantified in the subnanometer scale with Positron annihilation lifetime spectroscopy (PALS) verifying the affinity-driven assembly of macromolecular segments in a densely packed morphology and regulating the diffusion of small permeants through the matrix. The model is general and can be adapted to determine the macromolecular affinities of any hydrolysate biomass based on chemical composition.
Positron annihilation lifetime spectroscopy (PALS) was used to quantify the free volume and molecular packing in hydrolysate and hemicellulose-based barriers films, derived from process streams during wood processing operations. These hydrolysate films, comprising a fair share of lignin coexisting with poly- and oligo-saccharides, have very low but variable oxygen permeability but differ among themselves with respect to barrier performance as well as molecular weight, degree of branching, and monosaccharide residue main chain composition. From PALS measurements on hydrolysates, the free volume hole radius (r(h)), radius distributions (n(r(h))), volume-weighted hole sizes (
An advanced approach for the efficient and controllable production of softwood hydrolysate-based coatings with excellent oxygen-barrier performance is presented. An innovative conversion of the spray-drying technique into a coating applicator process allowed for a fast and efficient coating process requiring solely aqueous solutions of softwood hydrolysate, even without additives. Compared to analogous coatings prepared by manual application, the spray-drying produced coatings were more homogeneous and smooth, and they adhered more strongly to the substrate. The addition of glyoxal to the aqueous softwood hydrolysate solutions prior to coating formation allowed for hemicellulose cross-linking, which improved both the mechanical integrity and the oxygen-barrier performance of the coatings. A real-time scanning electron microscopy imaging assessment of the tensile deformation of the coatings allowed for a deeper understanding of the ability of the coating layer itself to withstand stress as well as the coating-to-substrate adhesion.
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