This paper reports on the development and characterization of oxygen scavenging films made of poly(3-hydroxybutyrate) (PHB) containing palladium nanoparticles (PdNPs) prepared by electrospinning followed by annealing treatment at 160 °C. The PdNPs were modified with the intention to optimize their dispersion and distribution in PHB by means of two different surfactants permitted for food contact applications, i.e., hexadecyltrimethylammonium bromide (CTAB) and tetraethyl orthosilicate (TEOS). Analysis of the morphology and characterization of the chemical, thermal, mechanical, and water and limonene vapor barrier properties and the oxygen scavenging capacity of the various PHB materials were carried out. From the results, it was seen that a better dispersion and distribution was obtained using CTAB as the dispersing aid. As a result, the PHB/PdNP nanocomposites containing CTAB provided also the best oxygen scavenging performance. These films offer a significant potential as new active coating or interlayer systems for application in the design of novel active food packaging structures.

The main goal of this study was to obtain, for the first time, highly efficient water barrier and oxygen-scavenging multilayered electrospun biopaper coatings of biodegradable polymers over conventional cellulose paper, using the electrospinning coating technique. In order to do so, poly(3-hydroxybutyrate) (PHB) and polycaprolactone (PCL) polymer-containing palladium nanoparticles (PdNPs) were electrospun over paper, and the morphology, thermal properties, water vapor barrier, and oxygen absorption properties of nanocomposites and multilayers were investigated. In order to reduce the porosity, and to enhance the barrier properties and interlayer adhesion, the biopapers were annealed after electrospinning. A previous study showed that electrospun PHB-containing PdNP did show significant oxygen scavenging capacity, but this was strongly reduced after annealing, a process that is necessary to form a continuous film with the water barrier. The results in the current work indicate that the PdNP were better dispersed and distributed in the PCL matrix, as suggested by focus ion beam-scanning electron microscopy (FIB-SEM) experiments, and that the Pd enhanced, to some extent, the onset of PCL degradation. More importantly, the PCL/PdNP nanobiopaper exhibited much higher oxygen scavenging capacity than the homologous PHB/PdNP, due to most likely, the higher oxygen permeability of the PCL polymer and the somewhat higher dispersion of the Pd. The passive and active multilayered biopapers developed here may be of significant relevance to put forward the next generation of fully biodegradable barrier papers of interest in, for instance, food packaging.