A comparative study of the barrier properties of cast film of polypropylene carbonate (PPC) and cast film of poly(lactic acid) (PLA) has been made in this paper. Dynamic transmission measurements were conducted to obtain the barrier properties for oxygen transmission and for water vapour transmission. A special algorithm fminsearch in Matlab was used to adapt an exponential expression to the measured values. In this way the time needed to reach a 95% level of steady state was made possible to identify. The oxygen permeability was lower for PPC compared to PLA and this could be explained by a much higher positive enthalpy of solution for oxygen in PPC. The enthalpy of diffusion was close to similar for both PPC and PLA and was higher than for enthalpy of solution. The enthalpy of water vapour permeability was higher for PPC compared to PLA and this resulted in substantially higher water vapour permeability for PLA. The uptake of water vapour was also higher for PLA compared to PPC as shown by dynamic vapour sorption measurements. Differential scanning calorimetry confirmed that PPC is an amorphous polymer and that the PLA used in this study had a minimum of crystallinity which made it comparable to PPC.

The mechanical properties of self-supporting films based on starch-plasticizer and starch-PVOH-plasticizer and the barrier properties of paperboard coated with solutions of these polymers have been studied. The plasticizers used were glycerol, polyethylene glycol and citric acid. It was shown that the addition of a plasticizer and PVOH to starch substantially increases the flexibility of starch films. It was seen that curing the self-supporting films led to a decrease in flexibility. After heat-treatment, a substantial increase in storage modulus was observed only in the starch-PVOH-citric-acid blend films. Tensile tests on the films indicate that citric acid did not cause any noticeable phase separation. Citric acid acted as a compatibilizer for starch-PVOH blends even though a similar enrichment of PVOH at the air-solid interface was observed with both citric acid and polyethylene glycol as plasticizer. The properties of barrier coatings greatly reflected the compatibility of starch-PVOH blends containing citric acid. The only plasticizer that resulted in a lower water vapour transmission rate through the starch and starch-PVOH coatings was citric acid, which suggests that cross-linking took place. With four layers, coatings based of starch-PVOH possessed the same oxygen- transmission rate with citric acid as without citric acid.

Noncrystalline cellulose-based gel beads were used as a model material to investigate the effect of osmotic stress on a cellulosic network. The gel beads were exposed to osmotic stress by immersion in solutions with different concentrations of high molecular mass dextran and the equilibrium dimensional change of the gel beads was studied using optical microscopy. The volume fraction of cellulose was calculated from the volume of the gel beads in dextran solutions and their dry content and the relation between the cellulose volume fraction and the total osmotic pressure was thus obtained. The results show that the contribution to the osmotic pressure from counterions increases the water-retaining capacity of the beads at high osmotic pressures but also that the main factor controlling the gel bead collapse at high osmotic strains is the resistance to the deformation of the polymer chain network within the beads. Furthermore, the osmotic pressure associated with the deformation of the polymer network, which counteracts the deswelling of the beads, could be fitted to the Wall model indicating that the response of the cellulose polymer networks was independent of the charge of the cellulose. The best fit to the Wall model was obtained when the Flory-Huggins interaction parameter (χ) of the cellulose-water system was set to 0.55-0.60, in agreement with the well-established insolubility of high molecular mass β-(1,4)-d-glucan polymers in water.

Sulfoethylated nanofibrillated cellulose (NFCSulf) was produced by an industrially relevant process. The properties of the NFCSulf were compared with those of carboxymethylated nanofibrillated cellulose (NFCCarb), which has been identified as an attractive NFC for several industrial applications. The investigations revealed that NFCSulf is characterized by a higher degree of fibrillation and has superior redispersion properties. Furthermore, NFCSulf displays higher stability in varying pH values as compared to NFCCarb. Hence, NFCSulf may be a more attractive alternative than NFCCarb in applications such as rheological modifiers or adsorbing components in personal care products, in which the performance of NFC must remain unaffected in varying ambient conditions. The superior properties of NFCSulf compared to NFCCarb were proposed to be due to the combination of the unique chemical characteristics of the sulfoethylated reagent, and the larger size of the sulfonate group compared to the carboxymethyl group.

Development of sustainable biobased fibers is required to displace their fossil-based counterparts, e.g., in textile, nonwoven, or composite applications. Regenerated protein fibers have a potential in this regard if their mechanical properties are improved. Herein, we study for the first time the use of nanocellulose as reinforcement in regenerated protein fibers produced using wet spinning. The influence of cellulose nanocrystals (CNC) incorporated into regenerated casein fibers is examined in terms of mechanical and morphological properties. The influence of different conditions for fiber chemical cross-linking is also investigated. Incorporation of CNC (up to 37.5 wt %) into spin dopes results in a continuous increase of fiber Young's modulus (up to twofold) in the dry state. Both maximum and breaking tenacity of dry fibers are enhanced by CNC, with a maximum at 7.0-10.5 wt % of CNC. When testing after being wetted, both breaking tenacity and Young's modulus of the composite fibers decrease, likely due to weakening of hydrogen bonds between CNC in the presence of water. We also demonstrate that the presence of salt during chemical cross-linking is crucial to produce intact and separated fibers in the yarn.

Commercial potato protein concentrate (PPC) was investigated as a source of thermoformed bio-based plastic film. Pressing temperatures of 100 to 190°C with 15 to 25% glycerol were used to form PPC films. The shape of the tensile stress-strain curve in thermoformed PPC was controlled by glycerol level and was independent of processing temperature. Tensile testing revealed that elongation at break increased with processing temperature while Young's modulus was unaffected by processing temperature, both in contrast to previous results in protein based systems. Also in contrast to previous studies, Young's modulus was found to be only sensitive to glycerol level. Maximum tensile stress increased with increasing processing temperature for PPC films. Maximum stress and strain at break correlated with the extractable high molecular weight protein content of the processed films measured with size exclusion chromatography. Infrared absorption indicated that the content of β-sheet structure increased from the commercial protein concentrate to that pressed at 100°C, but did not further develop with increasing press temperature. Changes in structural arrangements were observed by small angle X-ray scattering indicating the development of different correlation distances with processing temperature but with no clear long range order at the supramolecular level. The novel Young's modulus behaviour appears to be due to constant secondary structure or the effect of aggregated protein structure formed during protein production. Unique strain at break behaviour with processing temperature was demonstrated, likely due to new connections formed between those aggregates.

Polycondensations of cis-9,10-epoxy-18-hydroxyoctadecanoic acid, isolated from birch outer bark, were performed at 75°C in toluene as solvent and at 85°C In bulk using immobilized Candida antarctica lipase B as catalyst. The polycondensation performed in toluene in presence of molecular sieves gave a polyester with DP 50 after 24 h. The same DP was obtained at much shorter reaction time (3 h) by bulk polymerization in an open vial without any drying agent present.

A study was conducted that demonstrated that the blending of edible oils leads to changes in surface tension, thermal properties, viscosity, and oil penetration times through a barrier-coated paperboard. The results emphasize the significance of testing the oil and grease resistance (OGR) oil blends in order-to verify the suitability of the packaging material for real-life end-use applications. The results of the OGR determinations suggest that hydroxypropylated-starch-based composite coatings containing an oleophilic high aspect ratio mineral can be tailored for food shaving different fatty acid compositions by varying the pigmentation level. Compared to standard OGR tests, confocal laser scanning microscopy (CLSM)-based techniques make it possible to evaluate the oil penetration time and its diffusion behavior very accurately, both inside the coating layer and in the bulk matrix. It was found that, at room temperature, coconut oil tends to crystallize inside the substrate, inducing swelling of the coating layer, which probably has an influence on the physicomechanical properties of the packaging material.

Montmorillonite (MMT) was organically modified with tributyl citrate (TBC). Organoclays (OMMTs) were processed with diisononyl phthalate (DINP)-plasticized polyvinyl chloride (PVC) to form polymer nanocomposites. The produced composite materials showed a contradictory change in properties to that expected of a layered silicate nanocomposite, with a decreased E-modulus and increased gas permeability compared with a material without OMMT. It was experimentally shown that the TBC modifier was extracted from the OMMT and was dispersed in the PVC/DINP matrix, whereupon the OMMT collapsed and formed micrometer-sized agglomerates. Further investigation revealed that TBC has a significant effect on the gas permeability and the E-modulus, even at low additions to a DINP-plasticized PVC. A PVC nanocomposite with the TBC acting as both the OM for MMT and as the primary plasticizer was produced. This material showed a significantly increased E-modulus as well as a decrease in gas permeability, confirming that it is possible to develop a nanocomposite based on plasticized PVC, if both the organo-modification of the MMT and the formulation of the matrix are carefully selected.

Structural changes of fibrils and fibril aggregates in the fibre wall were studied after oxidation of the cellulose by 2,2,6,6-tetramethyl-1-piperidinyloxy to high charge densities (highest charge density: 1300 μeq/g). The increase in pore volume was measured by mini-WRV at two different pH levels, and the supramolecular structure in the fibre wall in terms of aggregate size, specific surface area and average pore size was measured by solid state NMR, DVS desorption and BET N2 gas adsorption. A structural change in the arrangement of the fibrils inside the fibril aggregates was observed although the oxidation did not lead to a complete liberation of individual fibrils, i.e. they still exist as an aggregated structure after oxidation. Theoretical estimates suggest that the electrostatic repulsion energy connected with the increase in surface charge of the fibrils can be sufficient to gradually separate the fibrils enough to expose all fibril surfaces to oxidation chemicals.

Xylan extracted from rapeseed straw was chemically modified to gain hydrophobic and thermoplastic properties via macroinitiator formation followed by a free radical grafting-from polymerization with octadecyl acrylate. Biocomposites were then prepared by incorporation of 5 or 20% (w/w) rapeseed straw xylan into a poly(ε-caprolactone) (PCL) matrix by melt extrusion. The grafted xylan was homogeneously distributed within the biocomposite and reinforced the PCL matrix while at the same time preserving the ability to elongate to tensile strains >500%. Analogous biocomposites made from unmodified xylan in a PCL matrix resulted in heterogeneous mixtures and brittle tensile properties.

This article describes nanocomposite films with separately grown protein nanofibrils (PNFs) in a nonfibrillar protein matrix from the same protein starting material (whey). Tensile tests on the glycerol-plasticized films indicate an increased elastic modulus and a decreased extensibility with increasing content of PNFs, although the films are still ductile at the maximum PNF content (15 wt %). Infrared spectroscopy confirms that the strongly hydrogen-bonded β-sheets in the PNFs are retained in the composites. The films appear with a PNF-induced undulated upper surface. It is shown that micrometer-scale spatial variations in the glycerol distribution are not the cause of these undulations. Instead, the undulations seem to be a feature of the PNF material itself. It was also shown that, apart from plasticizing the protein film, the presence of glycerol seemed to favor to some extent exfoliation of stacked β-sheets in the proteins, as revealed by X-ray diffraction.