This review summarizes recent development of functional materials to improve the barrier properties of paperboard with emphasis on bio-based polymers. Focus is directed to novel application techniques and water-borne, renewable coating materials. Some aspects on substrate properties and the requirements on food packaging are discussed as are the processability, convertability, recyclability and biodegradability of packaging materials. The functionality, advantages and disadvantages of several bio-based polymers are presented in detail. Among these are starch and cellulose derivatives, chitosan, alginate, wheat gluten, whey proteins, polycaprolactone, poly(lactic acid) and polyhydroxyalkanoates. Also discussed is the enhancement of barrier properties by incorporation of nanosized materials, by application of thin protective top coatings and local reinforcement by self-healing agents.

Plate-like ®llers are often added to improve barrier properties and to prevent blocking of dispersion coatings on paper and board. We have studied the effects of clay addition, neutralizing agent and drying conditions on water vapour permeability, water absorption, oxygen permeability and heat sealability of carboxylated styrene/butyl acrylate dispersion coatings on a pilot scale. The barrier dispersions were applied on a pre-coated side of a three-ply board, using a pre-metering roll coater. Coated strips were sealed under speci®ed conditions of temperature, time and pressure and the sealability was assessed by measuring the peak load necessary to break the joints. The surface composition of the barriercoated board was analysed and the mode of failure was characterized by ESCA. The occurrence of pinholes in the barrier coatings was assessed by both staining tests and ESEM/EDX analysis of the surface topography. The resulting barrier properties were satisfactory as far as resistance to water transport in both liquid and vapour form is concerned. The oxygen permeability was similar to that of similar amorphous polymers. Heat-sealing tests showed that the mode of failure was mainly cohesive in nature, as ®bre tear occurred when sealed strips were separated. Neutralization with sodium hydroxide gave poor adhesion and had a negative effect on the seal strength. Barrier measurements and ESEM/EDX analysis both showed that the pinholes present extended only through the barrier coating.

The effect on mechanical and barrier properties upon addition of glycerol to temperature-responsive hydrophobically modified (HM) potato starch was studied on free films. The addition of glycerol lowered the glass transition temperature, the storage modulus, and the water vapor permeability (WVP) for the HM starch films. The HM starch phase separates upon cooling below an upper critical temperature into a solid and a liquid phase. Adding glycerol to the warm starch solution had an inhibiting effect on the particulate precipitation. Substrates surface sized with HM starch with various amounts of glycerol were investigated with respect to barrier properties; WVP, contact angle and Cobb values. Hydroxypropylated starch was used as a reference. Cobb values and WVP results on surface-sized substrates indicated that the film formation properties of the starches were of great importance for the final surface properties. Good film formation properties were essential for the gas barrier and water resistance while they were less important for high contact angles. The WVP decreased as the glycerol content of the sizes increased, but no sufficient water vapor barrier could be obtained. The HM starches investigated in this work provided good oxygen barrier and the contact angles indicated a hydrophobic character of the surface. The role of the precipitate was investigated, and surface sizing with the precipitate gave low WVP and high contact angles despite its poor film-forming properties under the experimental conditions. Cobb 60 values were slightly improved for HM starch with increasing glycerol content over glycerol-free sizing.

The replacement of fl exible polyolefi n barrier layers with novel, thin, functional polymer coatings in the production of paperboard packaging involves the risk of deteriorated barrier and mechanical properties during the converting process. Local defects or cracks in the protective barrier layer can arise because of the stress induced in creasing and folding operations. In this study, the incorporation of microencapsulated self-healing agents in coating formulations applied both by spot-and uniform-coating techniques was studied. The preparation process of microcapsules with a hydrophobic core surrounded by a hydrophobically modifi ed polysaccharide membrane in aqueous suspension was developed to obtain capsules fulfi lling both the criteria of small capsule size and reasonably high solids content to match the requirements set on surface treatment of paperboard for enhancement of packaging functionality. The survival of the microcapsules during application and their effectiveness as self-healing agents were investigated. The results showed a reduced tendency for deteriorated barrier properties and local termination of cracks formed upon creasing. The self-healing mechanism involves the rupture of microcapsules local to the applied stress, with subsequent release of the core material. Crack propagation is hindered by plasticization of the underlying coating layer, while the increased hydrophobicity helps to maintain the barrier properties.

The film-forming properties of hydrophobically modified potato starch were studied to optimize coating and surface sizing formulations for improvement of barrier properties of paper and paperboard. The spontaneous fractionation of a potato starch hydrophobically modified with a quaternary dodecylammonium chloride resulted in an amylose-rich precipitate with properties differing from those of the original starch. Film formation was investigated in the presence of glycerol and poly(vinyl alcohol) plasticizers. Anti-plasticization was found to occur at low and intermediate plasticizer levels but highly flexible, continuous films were obtained when 30 parts of plasticizer were added to 100 parts of dry starch. The highest transparency and greatest flexibility were obtained with glycerol, while the hydrophobic film properties were maintained with poly(vinyl alcohol). A study of the glass transition temperatures and melting behavior of starch-plasticizer films by differential scanning calorimetry gave useful information about the crystallinity of the films.