Multilayer Film Comprising Polybutylene Adipate Terephthalate and Cellulose Nanocrystals with High Barrier and Compostable Properties.

In the present study, a multilayer, high-barrier, thin blown film based on a polybutylene adipate terephthalate (PBAT) blend with polyhydroxyalkanoate (PHA), and composed of four layers including a cellulose nanocrystal (CNC) barrier layer and an electrospun poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) hot-tack layer, was characterized in terms of the surface roughness, surface tension, migration, mechanical and peel performance, barrier properties, and disintegration rate. The results showed that the film exhibited a smooth surface. The overall migration tests showed that the material is suitable to be used as a food contact layer. The addition of the CNC interlayer had a significant effect on the mechanical properties of the system, drastically reducing the elongation at break and, thus, the flexibility of the material. The film containing CNCs and electrospun PHBV hot-tack interlayers exhibited firm but not strong adhesion. However, the multilayer was a good barrier to water vapor (2.4 ± 0.1 × 10-12 kg·m-2·s-1·Pa-1), and especially to oxygen (0.5 ± 0.3 × 10-15 m3·m-2·s-1·Pa-1), the permeance of which was reduced by up to 90% when the CNC layer was added. The multilayer system disintegrated completely in 60 days. All in all, the multilayer system developed resulted in a fully compostable structure with significant potential for use in high-barrier food packaging applications.

NMR Analyses and Statistical Modeling of Biobased Polymer Microstructures-A Selected Review.

NMR analysis combined with statistical modeling offers a useful approach to investigate the microstructures of polymers. This article provides a selective review of the developments in both the NMR analysis of biobased polymers and the statistical models that can be used to characterize these materials. The information obtained from NMR and statistical models can provide insights into the microstructure and stereochemistry of appropriate biobased polymers and establish a systematic approach to their analysis. In suitable cases, the analysis can help optimize the synthetic procedures and facilitate the development of new or modified polymeric materials for various applications. Examples are given of the studies of poly(hydroxyalkanoates), poly(lactic acid), and selected polysaccharides, e.g., alginate, pectin, and chitosan. This article may serve as both a reference and a guide for future workers interested in the NMR sequence analysis of biobased materials.

Development and Characterization of Electrospun Fiber-Based Poly(ethylene-co-vinyl Alcohol) Films of Application Interest as High-Gas-Barrier Interlayers in Food Packaging.

In the present study, poly(ethylene-co-vinyl alcohol) with 44 mol % ethylene content (EVOH44) was managed to be processed, for the first time, by electrospinning assisted by the coaxial technology of solvent jacket. In addition to this, different suspensions of cellulose nanocrystals (CNCs), with contents ranging from 0.1 to 1.0 wt %, were also electrospun to obtain hybrid bio-/non-bio nanocomposites. The resultant fiber mats were thereafter optimally annealed to promote interfiber coalescence at 145 °C, below the EVOH44 melting point, leading to continuous transparent fiber-based films. The morphological analysis revealed the successful distribution of CNCs into EVOH44 up to contents of 0.5 wt %. The incorporation of CNCs into the ethylene-vinyl alcohol copolymer caused a decrease in the crystallization and melting temperatures (TC and Tm) of about 12 and 7 °C, respectively, and also crystallinity. However, the incorporation of CNCs led to enhanced thermal stability of the copolymer matrix for a nanofiller content of 1.0 wt %. Furthermore, the incorporation of 0.1 and 0.5 wt % CNCs produced increases in the tensile modulus (E) of ca. 38% and 28%, respectively, but also yielded a reduction in the elongation at break and toughness. The oxygen barrier of the hybrid nanocomposite fiber-based films decreased with increasing the CNCs content, but they were seen to remain high barrier, especially in the low relative humidity (RH) regime, i.e., at 20% RH, showing permeability values lower than 0.6 × 10-20 m3·m·m-2·Pa-1·s-1. In general terms, an optimal balance in physical properties was found for the hybrid copolymer composite with a CNC loading of 0.1 wt %. On the overall, the present study demonstrates the potential of annealed electrospun fiber-based high-barrier polymers, with or without CNCs, to develop novel barrier interlayers to be used as food packaging constituents.

Development and Characterization of Electrospun Biopapers of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Derived from Cheese Whey with Varying 3-Hydroxyvalerate Contents.

In the present study, three different newly developed copolymers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with 20, 40, and 60 mol % contents in 3-hydroxyvalerate (3HV) were produced by the biotechnological process of mixed microbial cultures (MMCs) using cheese whey (CW), a by-product from the dairy industry, as feedstock. The CW-derived PHBV copolyesters were first purified and then processed by solution electrospinning, yielding fibers of approximately 2 µm in cross-section in all cases. The resultant electrospun PHBV mats were, thereafter, post-processed by annealing at different temperatures, below their maximum of melting, selected according to their 3HV content in order to obtain continuous films based on coalesced fibers, so-called biopapers. The resultant PHBV films were characterized in terms of their morphology, crystallinity, and mechanical and barrier properties to assess their potential application in food packaging. The CW-derived PHBV biopapers showed high contact transparency but a slightly yellow color. The fibers of the 20 mol % 3HV copolymer were seen to contain mostly poly(3-hydroxybutyrate) (PHB) crystals, the fibers of the 40 mol % 3HV copolymer a mixture of PHB and poly(3-hydroxyvalerate) (PHV) crystals and lowest crystallinity, and the fibers of the 60 mol % 3HV sample were mostly made of PHV crystals. To understand the interfiber coalesce process undergone by the materials during annealing, the crystalline morphology was also assessed by variable-temperature both combined small-angle and wide-angle X-ray scattering synchrotron and Fourier transform infrared experiments. From these experiments and, different from previously reported biopapers with lower 3HV contents, all samples were inferred to have a surface energy reduction mechanism for interfiber coalescence during annealing, which is thought to be activated by a temperature-induced decrease in molecular order. Due to their reduced crystallinity and molecular order, the CW-derived PHBV biopapers, especially the 40 mol % 3HV sample, were found to be more ductile and tougher. In terms of barrier properties, the three copolymers performed similarly to water and limonene, but to oxygen, the 40 mol % sample showed the highest relative permeability. Overall, the materials developed, which are compatible with the Circular Bioeconomy organic recycling strategy, can have an excellent potential as barrier interlayers or coatings of application interest in food packaging.

High-Oxygen-Barrier Multilayer Films Based on Polyhydroxyalkanoates and Cellulose Nanocrystals.

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.

Blends of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate) with Fruit Pulp Biowaste Derived Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate-co-3-Hydroxyhexanoate) for Organic Recycling Food Packaging.

In the present study, a new poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) [P(3HB-co-3HV-co-3HHx)] terpolyester with approximately 68 mol% of 3-hydroxybutyrate (3HB), 17 mol% of 3-hydroxyvalerate (3HV), and 15 mol% of 3-hydroxyhexanoate (3HHx) was obtained via the mixed microbial culture (MMC) technology using fruit pulps as feedstock, a processing by-product of the juice industry. After extraction and purification performed in a single step, the P(3HB-co-3HV-co-3HHx) powder was melt-mixed, for the first time, in contents of 10, 25, and 50 wt% with commercial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Thereafter, the resultant doughs were thermo-compressed to obtain highly miscible films with good optical properties, which can be of interest in rigid and semirigid organic recyclable food packaging applications. The results showed that the developed blends exhibited a progressively lower melting enthalpy with increasing the incorporation of P(3HB-co-3HV-co-3HHx), but retained the PHB crystalline morphology, albeit with an inferred lower crystalline density. Moreover, all the melt-mixed blends were thermally stable up to nearly 240 °C. As the content of terpolymer increased in the blends, the mechanical response of their films showed a brittle-to-ductile transition. On the other hand, the permeabilities to water vapor, oxygen, and, more notably, limonene were seen to increase. On the overall, this study demonstrates the value of using industrial biowaste derived P(3HB-co-3HV-co-3HHx) terpolyesters as potentially cost-effective and sustainable plasticizing additives to balance the physical properties of organic recyclable polyhydroxyalkanoate (PHA)-based food packaging materials.

Tailoring the Properties of Thermo-Compressed Polylactide Films for Food Packaging Applications by Individual and Combined Additions of Lactic Acid Oligomer and Halloysite Nanotubes.

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 (Tg) 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.

Valorization of Municipal Biowaste into Electrospun Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Biopapers for Food Packaging Applications.

The present study reports on the production and characterization of a new biopackaging material made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from municipal biowaste (MBW) and produced by the mixed bacterial culture technology. After purification and extraction, the MBW-derived PHBV was processed by electrospinning to yield defect-free ultrathin fibers, which were thermally post-treated. Annealing at 130 °C, well below the biopolymer's melting temperature (Tm), successfully yielded a continuous film resulting from coalescence of the electrospun fibrillar morphology, the so-called biopaper, exhibiting enhanced optical and color properties compared to traditional melt compounding routes. The crystallinity and crystalline morphology were comprehensively studied as a function of temperature by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and combined time-resolved synchrotron small- and wide-angle X-ray scattering (SAXS and WAXS) experiments, which clearly indicated that the molecular order within the copolyester was improved up to a maximum at 130 °C, and then it decreased at the biopolymer's Tm. It was hypothesized that by annealing at the temperature at which the thermally induced molecular order is maximized, the fibers generated sufficient mobility to align alongside, hence reducing surface energy and porosity. The data suggest that this material shows a good balance between enhanced mechanical and improved barrier properties to vapors and gases in comparison to traditional paper and other currently used petroleum-derived polymers, thus presenting significant potential to be part of innovative food biopackaging designs for the protection and preservation of foods in a circular bioeconomy scenario.

Reactive Melt Mixing of Poly(3-Hydroxybutyrate)/Rice Husk Flour Composites with Purified Biosustainably Produced Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate).

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.

Electrospun Antimicrobial Films of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Containing Eugenol Essential Oil Encapsulated in Mesoporous Silica Nanoparticles.

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.

Nanoencapsulation of Aloe vera in Synthetic and Naturally Occurring Polymers by Electrohydrodynamic Processing of Interest in Food Technology and Bioactive Packaging.

This work originally reports on the use of electrohydrodynamic processing (EHDP) to encapsulate Aloe vera (AV, Aloe barbadensis Miller) using both synthetic polymers, i.e., polyvinylpyrrolidone (PVP) and poly(vinyl alcohol) (PVOH), and naturally occurring polymers, i.e., barley starch (BS), whey protein concentrate (WPC), and maltodextrin. The AV leaf juice was used as the water-based solvent for EHDP, and the resultant biopolymer solution properties were evaluated to determine their effect on the process. Morphological analysis revealed that, at the optimal processing conditions, synthetic polymers mainly produced fiber-like structures, while naturally occurring polymers generated capsules. Average sizes ranged from 100 nm to above 3 µm. As a result of their different and optimal morphology and, hence, higher AV content, PVP, in the form of nanofibers, and WPC, of nanocapsules, were further selected to study the AV stability against ultraviolet (UV) light exposure. Fourier transform infrared (FTIR) spectroscopy confirmed the successful encapsulation of AV in the biopolymer matrices, presenting both encapsulants a high chemical interaction with the bioactive components. Ultraviolet-visible (UV-vis) spectroscopy showed that, while PVP nanofibers offered a poor effect on the AV degradation during UV light exposure (∼10% of stability after 5 h), WPC nanobeads delivered excellent protection (stability of >95% after 6 h). This was ascribed to positive interactions between WPC and the hydrophilic components of AV and the inherent UV-blocking and oxygen barrier properties provided by the protein. Therefore, electrospraying of food hydrocolloids interestingly appears as a novel potential nanotechnology tool toward the formulation of more stable functional foods and nutraceuticals.