The main goal of this study was to develop poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) films with long-term antimicrobial capacity of interest in food packaging applications. To this end, eugenol was first highly efficiently encapsulated at 50 wt.-% in the pores of mesoporous silica nanoparticles by vapor adsorption. The eugenol-containing nanoparticles were then loaded in the 2.5–20 wt.-% range into PHBV by electrospinning and the resultant electrospun composite fibers were annealed at 155 °C to produce continuous films. The characterization showed that the PHBV films filled with mesoporous silica nanoparticles containing eugenol present sufficient thermal resistance and enhanced mechanical strength and barrier performance to water vapor and limonene. The antimicrobial activity of the films was also evaluated against foodborne bacteria for 15 days in open vs. closed conditions in order to simulate real packaging conditions. The electrospun PHBV films with loadings above 10 wt.-% of mesoporous silica nanoparticles containing eugenol successfully inhibited the bacterial growth, whereas the active films stored in hermetically closed systems increased their antimicrobial activity after 15 days due to the volatile portion accumulated in the system’s headspace and the sustained release capacity of the films. The resultant biopolymer films are, therefore, potential candidates to be applied in active food packaging applications to provide shelf life extension and food safety.

In the present study, circular economy based and potentially low-cost poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was produced by mixed microbial cultures derived from fruit pulp, an industrial by-product of the juice industry. Three different chemical routes, namely non-extraction, extraction with sodium hypochlorite (NaClO), and extraction with chloroform, in combination with filtering and centrifugation, were explored to purify the biopolymer and find the most optimal solution for its processing via electrospinning. The resultant ultrathin fiber mats of the different extracted PHBV materials were thermally post-processed at different temperatures in order to obtain continuous films adequate for food packaging applications. The resultant films were characterized in terms of morphology, crystallinity as well as thermal, mechanical, and barrier properties. The results showed that extraction with both chloroform and NaClO with a post-treatment of filtering and centrifugation of the PHBV-containing biomass were necessary refining steps to allow its processing by electrospinning. In particular, the PHBV extracted with chloroform presented the highest degree of purity, resulting in more transparent films with lower wettability and higher flexibility. The here-formulated electrospun films made of biomass derived from biowaste exhibit great potential as interlayers or coatings for food biopackaging applications.

Novel green composites based on commercial poly(3-hydroxybutyrate) (PHB) filled with 10 wt % rice husk flour (RHF) were melt-compounded in a mini-mixer unit using triglycidyl isocyanurate (TGIC) as compatibilizer and dicumyl peroxide (DCP) as initiator. Purified poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) produced by mixed bacterial cultures derived from fruit pulp waste was then incorporated into the green composite in contents in the 5–50 wt % range. Films for testing were obtained thereafter by thermo-compression and characterized. Results showed that the incorporation of up to 20 wt % of biowaste derived PHBV yielded green composite films with a high contact transparency, relatively low crystallinity, high thermal stability, improved mechanical ductility, and medium barrier performance to water vapor and aroma. This study puts forth the potential use of purified biosustainably produced PHBV as a cost-effective additive to develop more affordable and waste valorized food packaging articles.

In this work, films of polylactide (PLA) prepared by extrusion and thermo-compression were plasticized with oligomer of lactic acid (OLA) at contents of 5, 10, and 20 wt%. The PLA sample containing 20 wt% of OLA was also reinforced with 3, 6, and 9 parts per hundred resin (phr) of halloysite nanotubes (HNTs) to increase the mechanical strength and thermal stability of the films. Prior to melt mixing, ultrasound-assisted dispersion of the nanoclays in OLA was carried out at 100 °C to promote the HNTs dispersion in PLA and the resultant films were characterized with the aim to ascertain their potential in food packaging. It was observed that either the individual addition of OLA or combined with 3 phr of HNTs did not significantly affect the optical properties of the PLA films, whereas higher nanoclay contents reduced lightness and induced certain green and blue tonalities. The addition of 20 wt% of OLA increased ductility of the PLA film by nearly 75% and also decreased the glass transition temperature (T_g) by over 18 °C. The incorporation of 3 phr of HNTs into the OLA-containing PLA films delayed thermal degradation by 7 °C and additionally reduced the permeabilities to water and limonene vapors by approximately 8% and 47%, respectively. Interestingly, the highest barrier performance was attained for the unfilled PLA film plasticized with 10 wt% of OLA, which was attributed to a crystallinity increase and an effect of “antiplasticization”. However, loadings of 6 and 9 phr of HNTs resulted in the formation of small aggregates that impaired the performance of the blend films. The here-attained results demonstrates that the properties of ternary systems of PLA/OLA/HNTs can be tuned when the plasticizer and nanofiller contents are carefully chosen and the resultant nanocomposite films can be proposed as a bio-sourced alternative for compostable packaging applications.

This study reports on the development and characterization of organic recyclable high-oxygen-barrier multilayer films based on different commercial polyhydroxyalkanoate (PHA) materials, including a blend with commercial poly(butylene adipate-co-terephthalate) (PBAT), which contained an inner layer of cellulose nanocrystals (CNCs) and an electrospun hot-tack adhesive layer of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from cheese whey (CW). As a result, the full multilayer structures were made from bio-based and/or compostable materials. A characterization of the produced films was carried out in terms of morphological, optical, mechanical, and barrier properties with respect to water vapor, limonene, and oxygen. Results indicate that the multilayer films exhibited a good interlayer adhesion and contact transparency. The stiffness of the multilayers was generally improved upon incorporation of the CNC interlayer, whereas the enhanced elasticity of the blend was reduced to some extent in the multilayer with CNCs, but this was still much higher than for the neat PHAs. In terms of barrier properties, it was found that 1 µm of the CNC interlayer was able to reduce the oxygen permeance between 71% and 86%, while retaining the moisture and aroma barrier of the control materials.