The surface wetting of five biopolymers, used as coating materials for a plastic film, was monitored over a span of 8 min by means of the optical contact angle technique. Because most of the total variation was observed to occur during the first 60 s, we decided to focus on this curtailed temporal window. Initial contact angle values (θ(0)) ranged from ∼91° for chitosan to ∼30° for pullulan. However, the water drop profile began to change immediately following drop deposition for all biocoatings, confirming that the concept of water contact angle equilibrium is not applicable to most biopolymers. First, a three-parameter decay equation [θ(t) = θ(0) exp(kt(n))] was fit to the experimental contact angle data to describe the kinetics of the contact angle change for each biocoating. Interestingly, the k constant correlated well with the contact angle evolution rate and the n exponent seemed to be somehow linked to the physicochemical phenomena underlying the overall kinetics process. Second, to achieve a reliable description of droplet evolution, the contact angle (CA) analysis was coupled with image analysis (IA) through a combined geometric/trigonometric approach. Absorption and spreading were the key factors governing the overall mechanism of surface wetting during the 60 s analysis, although the individual quantification of both phenomena demonstrated that spreading provided the largest contribution for all biopolymers, with the only exception of gelatin, which showed two quasi-equivalent and counterbalancing effects. The possible correlation between these two phenomena and the topography of the biopolymer surfaces are then discussed on the basis of atomic force microscopy analyses.

A new antifog coating made of pullulan is described in this work. The antifog properties are discussed in terms of wettability, surface chemistry/morphology, and by quantitative assessment of the optical properties (haze and transparency) before and after fog formation. The work also presents the results of antifog tests simulating the typical storage conditions of fresh foods. In these tests, the antifog efficiency of the pullulan coating was compared with that of two commercial antifog films, whereas an untreated low-density polyethylene (LDPE) film was used as a reference. The obtained results revealed that the pullulan coating behaved as a "wetting enhancer", mainly due to the low water contact angle (∼24°), which in turn can be ascribed to the inherent hydrophilic nature of this polysaccharide, as also suggested by the X-ray photoelectron spectroscopy experiments. Unlike the case of untreated LDPE and commercial antifog samples, no discrete water formations (i.e., droplets or stains) were observed on the antifog pullulan coating on refrigeration during testing. Rather, an invisible, continuous and thin layer of water occurred on the biopolymer surface, which was the reason for the unaltered haze and increased transparency, with the layer of water possibly behaving as an antireflection layer. As confirmed by atomic force microscopy analysis, the even deposition of the coating on the plastic substrate compared to the patchy surfacing of the antifog additives in the commercial films is another important factor dictating the best performance of the antifog pullulan coating.

In this paper, the preparation and characterization of oxygen barrier pullulan sodium montmorillonite (Na+-MMT) nanocomposite coatings are presented for the first time. Full exfoliation of platelets during preparation of the coating water dispersions was mediated by ultrasonic treatment, which turned out to be a pivotal factor in the oxygen barrier performance of the final material even at high relative humidity (RH) conditions [oxygen permeability coefficients ∼1.43 ± 0.39 and 258.05 ± 13.78 mL·μm·m–2·(24 h)−1·atm–1 at 23 °C and 0% RH and 70% RH, respectively]. At the micro- and nanoscale, the reasons are discussed. The final morphology of the coatings revealed that clay lamellae were stacked on top of one another, probably due to the forced confinement of the platelets within the coating thickness after solvent evaporation. This was also confirmed by modeling the experimental oxygen permeability data with the well-known Nielsen and Cussler permeation theoretical models, which suggested a reasonable aspect ratio (α) of ∼100. Electron microscopic analyses also disclosed a peculiar cell-like arrangement of the platelets. The stacking of the clay lamellae and the cell-like arrangement create the excellent oxygen barrier properties. Finally, we demonstrated that the slight haze increase in the bionanocomposite coating materials arising from the addition of the clays depends on the clay concentration but not so much on the sonication time, due to the balance of opposite effects after sonication (an increase in the number of scattering centers but a reduction in their size).

The scope of this study encompassed the evaluation of pullulan as a suitable biopolymer for the development of oxygen barrier coatings to be applied on poly(ethylene terephthalate) (PET), especially for food packaging applications. To enhance the oxygen barrier properties of the organic phase (pullulan) even at high relative humidity values, an inorganic phase (silica), obtained through in situ polymerization, was also utilized to obtain hybrid coatings via the sol-gel technique. Transmission electron microscopy (TEM) images and Fourier transform infrared (FT-IR) spectra showed that mixing the two phases yielded a three-dimensional hybrid network formed by self-assembly and mediated by the occurrence of new hydrogen-bond interactions at the intermolecular level, although the formation of new covalent bonds could not be excluded. The deposition of the hybrid coatings decreased the oxygen transmission rate (OTR) of the plastic substrate by up to 2 orders of magnitude under dry conditions. The best performance throughout the scanned humidity range (0%-80% relative humidity) was obtained for the formulation with the lowest amount of silica (that is, an organic/inorganic ratio equal to 3).

Societal and industrial demands for lower environmental impact, cost effectiveness, and high-performance goods and services are increasingly impacting the choice of technologies which are developed and deployed in consumer products. Like many other sectors, food packaging is moving to new technologies; the use of biopolymers is one of the most promising strategies toward an optimized use of traditional packaging materials (e.g., oil-based plastics) without impairing the goal of extending shelf life. Among other food packaging materials, pullulan is attracting much attention due to its unique features. The goal of this review is to provide an overview of current and emerging applications of pullulan within the food packaging sector. In particular, the functional properties of interest for the food packaging industry will be discussed in light of the physicochemical attributes of this exopolysaccharide. Future challenges that may dictate the successful penetration of pullulan in the food packaging market are also outlined.