One severe weakness of most biopolymers, in terms of their use as packaging materials, is their relatively high solubility in water. The addition of kraft lignin to starch coating formulations has been shown to reduce the water solubility of starch in dry coatings. However, lignin may also migrate into aqueous solutions. For this paper, kraft lignin isolated using the LignoBoost process was used in order to examine the effect of pH level on the solubility of lignin with and without ammonium zirconium carbonate (AZC). Machine-glazed (MG) paper was coated in a pilot coating machine, with the moving substrate at high speed, and laboratory-coated samples were used as a reference when measuring defects (number of pinholes). Kraft lignin became soluble in water at lower pH levels when starch was added to the solution, due to the interactions between starch and lignin. This made it possible to lower the pH of the coating solutions, resulting in increased water stability of the dry samples; that is, the migration of lignin to the model liquids decreased when the pH of the coating solutions was reduced. No significant difference was observed in the water vapor transmission rate (WVTR) between high and low pH for the pilot-coated samples. The addition of AZC to the formulation reduced the migration of lignin from the coatings to the model liquids and led to an increase in the water contact angle, but also increased the number of pinholes in the pilot-coated samples.

The presence of the crystalline regions in poly(vinyl alcohol) coating films acts as barrier clusters forcing the gas molecules to diffuse in a longer pathway in the amorphous region of the polymer, where diffusivity and solubility are promoted in comparison. Evaluating the influence of crystalline regions on the oxygen barrier property of a semi-crystalline polymer is thus essential to prepare better coating films. Poly(vinyl alcohol) coating films with varying induced crystallinity were prepared on a polyethylene terephthalate (PET) substrate by drying at different annealing temperatures for 10 min. The coating films were first delaminated from the PET substrate and then characterized using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and X-ray diffraction (XRD) techniques to determine and confirm the induced percentage of crystallinity. The barrier performance of the coating films, i.e., the oxygen transmission rate (OTR), was measured at room temperature. Results showed a decrease in the OTR values of poly(vinyl alcohol) film with an increase in the degree of crystallinity of the polymer matrix. Tortuosity-based models, i.e., modified Nielsen models, were adopted to predict the barrier property of the semi-crystalline PVOH film with uniform or randomly distributed crystallites. A modified Nielsen model for orderly distributed crystallites with an aspect ratio of 3.4 and for randomly distributed crystallites with an aspect ratio of 10.4 resulted in a good correlation with the experimental observation. For the randomly distributed crystallites, lower absolute average relative errors of 4.66, 4.45, and 5.79% were observed as compared to orderly distributed crystallites when the degree of crystallinity was obtained using FTIR, DSC, and XRD data, respectively.

Barrier coatings based on starch and starch-PVOH plasticized with glycerol and without plasticizer were applied to two different paperboard substrates, a triple coated board and duplex board, in order to investigate the tendency for cracks to develop in the barrier coating layers during creasing and folding. Tensile properties of films based on the starch and starch-PVOH blend were determined to investigate the relationship between the flexibility of the films and the cracking in the barrier coating layers. Furthermore, the oxygen transmission rate through the barrier-coated paperboard was measured before and after creasing and folding. The oxygen transmission rate through the barrier-coated samples was over the measurable range i. e. OTR>10000cm³/m²day after creasing and folding, which indicated failure in the barrier coating layers. Optical microscopy revealed small cracks in the barrier coating layers, probably related to an increase in flexibility of the barrier coating layers. It was observed in scanning electron micrographs that cracks in the barrier coating layers seemed to follow the fibers when the barrier coating was applied on the rear side of the duplex board. Scanning electron micrographs and surface profiler images revealed that cracks in the barrier coating layers might have originated from the mineral coating layer when the starch and starch/PVOH coating layers were applied on the mineral-coated side of the triple coated board. An increase in the thickness of the barrier coating layer did not seem to increase the resistance to failure.

A barrier material is usually needed on a fiber-based food package to protect the packed food from gases and moisture and thus maintain its quality. Barrier materials presently used in food packaging applications are mostly petroleum-based polymers. Over the last few decades, efforts have been made to replace petroleum-based materials with bio-based materials. The present work has focused on the possibility of using a natural barrier material on a fiber-based food package and the  effects of plasticizing and cross-linking on the mechanical and barrier properties, and the stability in water of coatings based on starch-poly(vinyl alcohol) (PVOH) and starch-lignin blends.

The flexibility of the starch films was increased by adding PVOH further by adding a plasticizer. It was shown that citric acid can act as a compatibilizer and cross-linker for starch and PVOH, and the use of citric acid may slow down the diffusion of both oxygen and water vapor if a multilayer coating strategy is used. The addition of polyethylene glycol to the pre-coating recipe resulted in a lower oxygen transmission rate through polyethylene-extruded board than when citric acid was added to the pre-coating. The flexibility of the barrier coatings and the properties of the base substrate affect the cracking tendency of the barrier coatings during the creasing and folding of a barrier-coated board.

The addition of lignin to the starch reduced the migration of starch from the starch-lignin films and the addition of ammonium zirconium carbonate as a cross-linker reduced the migration of both starch and lignin from the films. The addition of starch to the lignin solution increased the solubility of lignin at low pH, and the pilot-coated board showed a significant decrease in migration of lignin from the coatings containing ammonium zirconium carbonate when the pH of the coating solution was decreased.

A barrier material is usually needed on a fiber-based food package to maintain quality by protecting packed food from gases and moisture. Over the last few decades, efforts have been made to replace petroleum-based materials with bio-based materials. The present work has focused on the possibility of using a natural barrier material on fiber-based food packaging materials, and the effects of plasticizing and cross-linking on the mechanical and barrier properties and on the stability in water of coatings based on starch-PVOH and starch-lignin blends have been evaluated.

Citric acid can act as a compatibilizer and cross-linker for starch and PVOH, and the use of citric acid may retard the diffusion of both oxygen and water vapor if a multilayer coating strategy is used. A polyethylene extrusion coating on a board pre-coated with a recipe containing polyethylene glycol resulted in a greater reduction in the rate of oxygen transmission than through a board pre-coated with a recipe containing citric acid. The addition of lignin to the starch solution decreased the migration of starch from the starch-lignin films, and the addition of ammonium zirconium carbonate as a cross-linker decreased the migration of both starch and lignin from the films. 

The mechanical properties and chemical stability in water of self-supporting films made from aqueous solutions of starch and lignin, and the barrier properties of paperboard coated with solutions of these polymers have been studied. The dissolution of starch from the starch-lignin films in contact with the model liquids was decreased significantly when lignin was added to the starch films. The addition of ammonium zirconium carbonate (AZC) to the formulations as a crosslinking agent substantially increased the storage modulus of the starch-lignin films, which indicated that crosslinking had occurred. The addition of AZC to the formulations also led to a decrease in dissolution of both starch and lignin from the starch-lignin films in contact with model liquids. The effect of AZC on the water stability of the films was greater when the pH of the starch-lignin-AZC solution was adjusted with ammonia rather than NaOH. The addition of NH4Cl solution as a presumed catalyst to the recipe when the pH adjustment was performed with NaOH did not improve the effect of AZC on the water stability of the films. The water vapour transmission rate of the coated paperboard decreased slightly when AZC was added to the coating formulation.

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.

In the last decades, intensive research has been carried out in order to replace oil-based polymers with bio-based polymers due to growing environmental concerns. So far, most of the barrier materials used in food packaging are petroleum-based materials. The purpose of the barrier is to protect the packaged food from oxygen, water vapour, water and fat. The mechanical and barrier properties of coatings based on starch-plasticizer and starch-poly(vinyl alcohol) (PVOH)-plasticizer blends have been studied in the work described in this thesis. The plasticizers used were glycerol, polyethylene glycol and citric acid. In a second step, polyethylene coatings were extruded onto paperboard pre-coated with a starch-PVOH-plasticizer blend. The addition of PVOH to the starch increased the flexibility of the film. Curing of the film led to a decrease in flexibility and an increase in tensile strength. The flexibility of the starch-PVOH films was increased more when glycerol or polyethylene glycol was added than citric acid. The storage modulus of the starch-PVOH films containing citric acid increased substantially at high temperature.

It was seen that the addition of polyethylene glycol or citric acid to the starch-PVOH blend resulted in an enrichment of PVOH at the surface of the films. Tensile tests on the films indicated that citric acid acted as a compatibilizer and increased the compatibility of the starch and PVOH in the blend. The addition of citric acid to the coating recipe substantially decreased the water vapour transmission rate through the starch-PVOH coated paperboard, which indicated that citric acid acts as a cross-linker for starch and/or PVOH. The starch-PVOH coatings containing citric acid showed oxygen-barrier properties similar to those of pure PVOH or of a starch-PVOH blend without plasticizer when four coating layers were applied on a paperboard. The oxygen-barrier properties of coatings based on a starch-PVOH blend containing citric acid indicated a cross-linking and increase in compatibility of the starch-PVOH blends.

Polyethylene extrusion coating on a pre-coated paperboard resulted in a clear reduction in the oxygen transmission rate for all the pre-coating formulations containing plasticizers. The addition of a plasticizer to the pre-coating reduced the adhesion of polyethylene to pre-coated board. Polyethylene extrusion coating gave a board with a lower oxygen transmission rate when the paperboard was pre-coated with a polyethylene-glycol-containing formulation than with a citric-acid-containing formulation. The addition of polyethylene glycol to pre-coatings indicated an increase in wetting of the pre-coated paperboard by the polyethylene melt, and this may have sealed the small defects in the pre-coating leading to low oxygen transmission rate. The increase in brittleness of starch-PVOH films containing citric acid at a high temperature seemed to have a dominating effect on the barrier properties developed by the extrusion coating process. 

Over the last few decades, industry and academia have made joint efforts to generate knowledge about renewable barrier materials in order to replace the oil-based barrier materials currently used in food packaging. This work has focused on the possibility of producing a material with high oxygen barrier properties including polyethylene as a moisture protection.

The flexibility of starch films was increased by adding poly(vinyl alcohol) (PVOH) to the starch and the addition of a plasticizer to the starch-PVOH blend films further increase the flexibility of the films. The plasticizers used were glycerol, polyethylene glycol and citric acid. Curing of the films reduce their flexibility. The addition of citric acid to a starch-PVOH blend increased the compatibility of the starch-PVOH blend and affected the barrier properties of the coating layers containing citric acid. When a sufficient number of coating layers was applied, the starch-PVOH-citric-acid coatings showed oxygen-transmission-rate-values similar to those of the pure PVOH and of the starch-PVOH blend without plasticizers. Polyethylene extrusion coating on pre-coated paperboard resulted in a clear reduction in the oxygen transmission rate of all the pre-coating recipes based on starch-PVOH blends. The polyethylene extrusion coating showed a higher oxygen transmission rate for a board pre-coated with citric-acid-containing recipes than for a board pre-coated with polyethylene-glycol-containing recipes.