Plasticized Mechanical Recycled PLA Films Reinforced with Microbial Cellulose Particles Obtained from Kombucha Fermented in Yerba Mate Waste.

In this study, yerba mate waste (YMW) was used to produce a kombucha beverage, and the obtained microbial cellulose produced as a byproduct (KMW) was used to reinforce a mechanically recycled poly(lactic acid) (r-PLA) matrix. Microbial cellulosic particles were also produced in pristine yerba mate for comparison (KMN). To simulate the revalorization of the industrial PLA products rejected during the production line, PLA was subjected to three extrusion cycles, and the resultant pellets (r3-PLA) were then plasticized with 15 wt.% of acetyl tributyl citrate ester (ATBC) to obtain optically transparent and flexible films by the solvent casting method. The plasticized r3-PLA-ATBC matrix was then loaded with KMW and KMN in 1 and 3 wt.%. The use of plasticizer allowed a good dispersion of microbial cellulose particles into the r3-PLA matrix, allowing us to obtain flexible and transparent films which showed good structural and mechanical performance. Additionally, the obtained films showed antioxidant properties, as was proven by release analyses conducted in direct contact with a fatty food simulant. The results suggest the potential interest of these recycled and biobased materials, which are obtained from the revalorization of food waste, for their industrial application in food packaging and agricultural films.

Effects of Steam Heat and Dry Heat Sterilization Processes on 3D Printed Commercial Polymers Printed by Fused Deposition Modeling.

Fused deposition modeling (FDM), the most widely used additive manufacturing (AM) technology, is gaining considerable interest in the surgical sector for the production of single-use surgical devices that can be tailor-made according to specific requirements (e.g., type of patient surgery, specific shapes, etc.) due to its low cost, ease of access to materials (3D-printing filament), and the relatively low complexity. However, surgical 3D-printing parts should resist sterilization treatments without losing structural, mechanical, and dimensional accuracy. Thus, in this work, 3D-filaments based on poly(lactic acid) (PLA), poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate) (PETG), and a modified PETG material (CPE) were used to produce 3D-printed parts and further subjected to moist heat (MH) and dry heat (DH) sterilization processes as affordable and widely used sterilization processes in the medical field. The effect of MH and DH was evaluated by performing a complete mechanical, structural, thermal, and morphological characterization before and after both treatments. In general, the moist heat treatment produced a higher degradation of the polymeric matrix of PETG and CPE due to hydrolytic and thermal degradation, particularly affecting the tensile test and flexural properties. For instance, the linear coefficient of thermal expansion (LCTE) before glass transition temperature (Tg) increased 47% and 31% in PETG samples due to the MH and DH, respectively, while it increased 31% in CPE due to MH and was mainly maintained after the DH process. Nevertheless, in PLA, the MH produced an increase of 20% in LCTE value and the DH showed an increase of 33%. Dry heat treatment resulted in being more suitable for medical applications in which dimensional accuracy is not a key factor and there are no great mechanical demands (e.g., surgical guides).

Films Based on Thermoplastic Starch Blended with Pine Resin Derivatives for Food Packaging.

Completely biobased and biodegradable thermoplastic starch (TPS) based materials with a tunable performance were prepared for food packaging applications. Five blends were prepared by blending TPS with 10 wt%. of different pine resins derivatives: gum rosin (GR), disproportionated gum rosin (RD), maleic anhydride-modified gum rosin (CM), pentaerythritol ester of gum rosin (LF), and glycerol ester of gum rosin (UG). The materials were characterized in terms of thermo-mechanical behavior, surface wettability, color performance, water absorption, X-ray diffraction pattern, and disintegration under composting conditions. It was determined that pine resin derivatives increase the hydrophobicity of TPS and also increase the elastic component of TPS which stiffen the TPS structure. The water uptake study revealed that GR and LF were able to decrease the water absorption of TPS, while the rest of the resins kept the water uptake ability. X-ray diffraction analyses revealed that GR, CM, and RD restrain the aging of TPS after 24 months of aging. Finally, all TPS-resin blends were disintegrated under composting conditions during the thermophilic incubation period (90 days). Because of the TPS-resin blend's performance, the prepared materials are suitable for biodegradable rigid food packaging applications.

Films Based on Mater-Bi® Compatibilized with Pine Resin Derivatives: Optical, Barrier, and Disintegration Properties.

Mater-Bi® NF866 (MB) was blended with gum rosin and two pentaerythritol esters of gum rosin (labeled as LF and UT), as additives, to produce biobased and compostable films for food packaging or agricultural mulch films. The films were prepared by blending MB with 5, 10, and 15 wt.% of each additive. The obtained films were characterized by optical, colorimetric, wettability, and oxygen barrier properties. Moreover, the additives and the MB-based films were disintegrated under composting conditions and the effect of each additive on the biodegradation rate was studied. All films were homogeneous and optically transparent. The color of the films tended to yellow tones due to the addition of pine resin derivatives. All the formulated films presented a complete UV-transmittance blocking effect in the UVA and UVB region, and those with 5 wt.% of pine resin derivatives increased the MB hydrophobicity. Low amounts of resins tend to maintain the oxygen transmission rate (OTR) values of the neat MB, due to its good solubilizing and compatibilizing effects. The disintegration under composting conditions test revealed that gum rosin completely disintegrates in about 90 days, while UT degrades 80% and LF degrades 5%, over 180 days of incubation. As expected, the same tendency was obtained for the disintegration of the studied films, although Mater-Bi® reach 28% of disintegrability over the 180 days of the composting test.

Gum Rosin as a Size Control Agent of Poly(Butylene Adipate-Co-Terephthalate) (PBAT) Domains to Increase the Toughness of Packaging Formulations Based on Polylactic Acid (PLA).

Gum rosin (GR) was used as a natural additive to improve the compatibility between polylactic acid, PLA, and poly(butylene adipate-co-terephthalate, PBAT, blended with 20 wt.% of PBAT (PLA/PBAT). The PBAT was used as a soft component to increase the ductility of PLA and its fracture toughness. The coalescence of the PBAT domains was possible due to the plasticization effect of the GR component. These domains contributed to increasing the toughness of the final material due to the variation and control of the PBAT domains' size and consequently, reducing the stress concentration points. The GR was used in contents of 5, 10, 15, and 20 phr. Consequently, the flexural properties were improved and the impact resistance increased up to 80% in PLA/PBAT_15GR with respect to the PLA/PBAT formulation. Field emission scanning electron microscope (FESEM) images allowed observing that the size of PBAT domains of 2-3 µm was optimal to reduce the impact stress. Differential scanning calorimetry (DSC) analysis showed a reduction of up to 8 °C on the PLA melting temperature and up to 5.3 °C of the PLA glass transition temperature in the PLA/PBAT_20GR formulation, which indicates an improvement in the processability of PLA. Finally, transparent films with improved oxygen barrier performance and increased hydrophobicity were obtained suggesting the potential interest of these blends for the food packaging industry.

Silane-Functionalized Sheep Wool Fibers from Dairy Industry Waste for the Development of Plasticized PLA Composites with Maleinized Linseed Oil for Injection-Molded Parts.

Poly(lactic acid) (PLA) was plasticized with maleinized linseed oil (MLO) and further reinforced with sheep wool fibers recovered from the dairy industry. The wool fibers were firstly functionalized with 1 and 2.5 phr of tris(2-methoxyethoxy)(vinyl) (TVS) silane coupling agent and were further used in 1, 5, and 10 phr to reinforce the PLA/MLO matrix. Then, the composite materials were processed by extrusion, followed by injection-molding processes. The mechanical, thermal, microstructural, and surface properties were assessed. While the addition of untreated wool fibers to the plasticized PLA/MLO matrix caused a general decrease in the mechanical properties, the TVS treatment was able to slightly compensate for such mechanical losses. Additionally, a shift in cold crystallization and a decrease in the degree of crystallization were observed due to the fiber silane modification. The microstructural analysis confirmed enhanced interaction between silane-modified fibers and the polymeric matrix. The inclusion of the fiber into the PLA/MLO matrix made the obtained material more hydrophobic, while the yellowish color of the material increased with the fiber content.

Organic and Inorganic PCL-Based Electrospun Fibers.

In this work, different nanocomposite electrospun fiber mats were obtained based on poly(e-caprolactone) (PCL) and reinforced with both organic and inorganic nanoparticles. In particular, on one side, cellulose nanocrystals (CNC) were synthesized and functionalized by "grafting from" reaction, using their superficial OH- group to graft PCL chains. On the other side, commercial chitosan, graphene as organic, while silver, hydroxyapatite, and fumed silica nanoparticles were used as inorganic reinforcements. All the nanoparticles were added at 1 wt% with respect to the PCL polymeric matrix in order to compare the different behavior of the woven no-woven nanocomposite electrospun fibers with a fixed amount of both organic and inorganic nanoparticles. From the thermal point of view, no difference was found between the effect of the addition of organic or inorganic nanoparticles, with no significant variation in the Tg (glass transition temperature), Tm (melting temperature), and the degree of crystallinity, leading in all cases to high crystallinity electrospun mats. From the mechanical point of view, the highest values of Young modulus were obtained when graphene, CNC, and silver nanoparticles were added to the PCL electrospun fibers. Moreover, all the nanoparticles used, both organic and inorganic, increased the flexibility of the electrospun mats, increasing their elongation at break.

Cucumis metuliferus Fruit Extract Loaded Acetate Cellulose Coatings for Antioxidant Active Packaging.

A new active coating was developed by using Cucumis metuliferus fruit extract as antioxidant additive with the aim of obtaining an easy way to functionalize low-density polyethylene (LDPE) films for food packaging applications. Thus, an extraction protocol was first optimized to determine the total phenolic compounds and the antioxidant activity of CM. The aqueous CM antioxidant extract was then incorporated into cellulose acetate (CA) film-forming solution in different concentrations (1, 3 and 5 wt.%) to be further coated in corona-treated LDPE to obtain LDPE/CA-CM bilayer systems. CA and CA-CM film-forming solutions were successfully coated onto the surface of LDPE, showing good adhesion in the final bilayer structure. The optical, microstructural, thermal, mechanical and oxygen barrier performance, as well as the antioxidant activity, were evaluated. The active coating casted onto the LDPE film did not affect the high transparency of LDPE and improved the oxygen barrier performance. The antioxidant effectiveness of bilayer packaging was confirmed by release studies of Cucumis metuliferus from the cellulose acetate layer to a fatty food simulant. Finally, the LDPE/CA-CM active materials were also tested for their application in minimally processed fruits, and they demonstrated their ability to reduce the oxidation process of fresh cut apples. Thus, the obtained results suggest that CA-CM-based coating can be used to easily introduce active functionality to typically used LDPE at industrial level and enhance its oxygen barrier, without affecting the high transparency, revealing their potential application in the active food packaging sector to extend the shelf-life of packaged food by prevention of lipid oxidation of fatty food or by prevention fruit browning.

Interference of Biodegradable Plastics in the Polypropylene Recycling Process.

Recycling polymers is common due to the need to reduce the environmental impact of these materials. Polypropylene (PP) is one of the polymers called 'commodities polymers' and it is commonly used in a wide variety of short-term applications such as food packaging and agricultural products. That is why a large amount of PP residues that can be recycled are generated every year. However, the current increasing introduction of biodegradable polymers in the food packaging industry can negatively affect the properties of recycled PP if those kinds of plastics are disposed with traditional plastics. For this reason, the influence that generates small amounts of biodegradable polymers such as polylactic acid (PLA), polyhydroxybutyrate (PHB) and thermoplastic starch (TPS) in the recycled PP were analyzed in this work. Thus, recycled PP was blended with biodegradables polymers by melt extrusion followed by injection moulding process to simulate the industrial conditions. Then, the obtained materials were evaluated by studding the changes on the thermal and mechanical performance. The results revealed that the vicat softening temperature is negatively affected by the presence of biodegradable polymers in recycled PP. Meanwhile, the melt flow index was negatively affected for PLA and PHB added blends. The mechanical properties were affected when more than 5 wt.% of biodegradable polymers were present. Moreover, structural changes were detected when biodegradable polymers were added to the recycled PP by means of FTIR, because of the characteristic bands of the carbonyl group (between the band 1700⁻1800 cm-1) appeared due to the presence of PLA, PHB or TPS. Thus, low amounts (lower than 5 wt.%) of biodegradable polymers can be introduced in the recycled PP process without affecting the overall performance of the final material intended for several applications, such as food packaging, agricultural films for farming and crop protection.

On the Use of PLA-PHB Blends for Sustainable Food Packaging Applications.

Poly(lactic acid) (PLA) is the most used biopolymer for food packaging applications. Several strategies have been made to improve PLA properties for extending its applications in the packaging field. Melt blending approaches are gaining considerable interest since they are easy, cost-effective and readily available processing technologies at the industrial level. With a similar melting temperature and high crystallinity, poly(hydroxybutyrate) (PHB) represents a good candidate to blend with PLA. The ability of PHB to act as a nucleating agent for PLA improves its mechanical resistance and barrier performance. With the dual objective to improve PLAPHB processing performance and to obtain stretchable materials, plasticizers are frequently added. Current trends to enhance PLA-PHB miscibility are focused on the development of composite and nanocomposites. PLA-PHB blends are also interesting for the controlled release of active compounds in the development of active packaging systems. This review explains the most relevant processing aspects of PLA-PHB based blends such as the influence of polymers molecular weight, the PLA-PHB composition as well as the thermal stability. It also summarizes the recent developments in PLA-PHB formulations with an emphasis on their performance with interest in the sustainable food packaging field. PLA-PHB blends shows highly promising perspectives for the replacement of traditional petrochemical based polymers currently used for food packaging.

Plasticized poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB) blends incorporated with catechin intended for active food-packaging applications.

Active biobased packaging materials based on poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB) blends were prepared by melt blending and fully characterized. Catechin incorporation, as antioxidant compound, enhanced the thermal stability, whereas its release was improved by the addition of acetyl(tributyl citrate) (ATBC) as plasticizer. Whereas the incorporation of ATBC resulted in a reduction of elastic modulus and hardness, catechin addition produced more rigid materials due to hydrogen-bonding interactions between catechin hydroxyl groups and carbonyl groups of PLA and PHB. The quantification of catechin released into a fatty food simulant and the antioxidant effectiveness after the release process were demonstrated. The effect of the materials' exposure to a food simulant was also investigated. PHB-added materials maintained their structural and mechanical properties after 10 days in a test medium that represents the worst foreseeable conditions of the intended use. Thus, plasticized PLA-PHB blends with catechin show their potential as biobased active packaging for fatty food.

Free amino acids and biogenic amines in Alicante Monastrell wines.

The simultaneous determination of 17 free amino acids and 8 biogenic amines in Alicante Monastrell wines was investigated for the first time. The quantification was carried out by using a RP-HPLC method, based on a pre-column derivatization with o-phthaldialdehyde (OPA) and fluorescence detection. From the results obtained it may be concluded that the most abundant free amino acids were Glu, Arg, Ala Asp, and Lys. None of the wine samples analysed had histamine (HIM) or Tyramine (TYM) levels above the limits considered as a possible toxic risk for healthy individuals. No measurable amounts of cadaverine (CAD) or methylamine (MEA) were found, showing no spoilage symptoms of sensory properties of the wines. Tryptamine (TRM) content was significantly higher in aged wines compared to young wines. However ethanolamine (ETA) content was lower. These data were used to make a preliminary classification of the samples using cluster analysis.