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Poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV) is a very promising biodegradable copolyester of high interest in food packaging. Its inherent brittleness and narrow processing window make it necessary to blend it with flexible biopolyesters, such as poly(butylene succinate- co -adipate) (PBSA). However, the resultant biopolyester blends are thermodynamically immiscible, which impairs their performance and limits their applications. This study is the first to explore the use of poly(butylene succinate- co -adipate) grafted with maleic anhydride (PBS- g -MAH) as a novel reactive additive to compatibilize PHBV/PBSA blends. The compatibilizer was prepared by a reactive melt-mixing process of PBSA and maleic anhydride (MAH) using dicumyl peroxide (DCP) as an organic radical initiator, achieving a grafting degree (G d ) of 5.4%. Biopolyester blend films were thereafter prepared via cast extrusion and their morphological, thermal, mechanical, and barrier properties were characterized. Compatibilization by PBSA- g -MAH was confirmed by observing an improved phase interaction and lower dispersed domain sizes in the blends with 15 wt% PBSA. These compatibilized PHBV/PBSA blends were thermally stable up to 285 °C, showed enhanced ductility and toughness, as well as providing an improved barrier against water and limonene vapors and oxygen. These findings suggest that the use of MAH-grafted biopolyesters can represent an effective strategy to improve the properties of biopolyester blends and open up new opportunities for the application of PHBV-based formulations for food packaging.

The forest industry produces several low-value by-products, such as bark, sawdust, limbs, and leaves, that are not ultimately disposed of and remain in the forests and sawmill facilities. Among these by-products are leaves, which contain not only cellulose fibers and lignin but also essential oils such as terpenes. These are biosynthesized in a similar way as cis-1,4-polyisoprene. In this context, this work evaluates the use of screened and unscreened dried Eucalyptus nitens leaves in natural rubber. Among the most relevant results of this work is a significant increase in mechanical properties, such as tensile strength and elongation at break, reaching values of 9.45 MPa and 649% of tensile strength and elongation at break, respectively, for a sample of natural rubber containing sieved dried leaves of Eucalyptus nitens. In addition, it is observed that the content of this vegetable filler allows for inhibiting the antibacterial effect of vulcanized rubber against several bacteria, such as Bacillus subtilis, Staphylococcus aureus, Escherichia coli K 12, Escherichia coli FT 17 and Pseudomonas fluorescens. These results are promising because they not only add value to a by-product of the forestry industry, improving the mechanical properties of natural rubber from a sustainable approach but also increase the affinity of rubber with bacterial microorganisms that may play a role in certain ecosystems.

Poly(3-hydroxybutyrate- co -3-valerate) (PHBV), being one of the most studied and commercially available polyhydroxyalkanoates (PHAs), presents an intrinsic brittleness and narrow processing window that currently hinders its use in several plastic applications. The aim of this study was to develop a biodegradable PHA-based blend by combining PHBV with poly(3-hydroxybutyrate- co -3-hydroxyhexanoate) (PHBH), another copolyester of the PHA family that shows a more ductile behavior. Blends of PHBV with 20% wt., 30% wt., and 40% wt. of PHBH were obtained by melt mixing, processed by cast extrusion in the form of films, and characterized in terms of their morphology, crystallization behavior, thermal stability, mechanical properties, and thermoformability. Full miscibility of both biopolymers was observed in the amorphous phase due to the presence of a single delta peak, ranging from 4.5 °C to 13.7 °C. Moreover, the incorporation of PHBH hindered the crystallization process of PHBV by decreasing the spherulite growth rate from 1.0 µm/min to 0.3 µm/min. However, for the entire composition range studied, the high brittleness of the resulting materials remained since the presence of PHBH did not prevent the PHBV crystalline phase from governing the mechanical behavior of the blend. Interestingly, the addition of PHBH greatly improved the thermoformability by widening the processing window of PHBV by 7 s, as a result of the increase in the melt strength of the blends even for the lowest PHBH content.

In the present study, poly(ethylene- co -vinyl alcohol) with 44 mol % ethylene content (EVOH 44 ) 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 EVOH 44 melting point, leading to continuous transparent fiber-based films. The morphological analysis revealed the successful distribution of CNCs into EVOH 44 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 (T C and T m ) 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 m 3 ·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.

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.

This study focuses on the potential uses in textiles of fibers of soy protein (SP) and chitin, which are naturally occurring polymers that can be obtained from agricultural and food processing by-products and wastes. The as-received natural fibers were first subjected to a three-step manufacturing process to develop yarns that were, thereafter, converted into fabrics by weft knitting. Different characterizations in terms of physical properties and comfort parameters were carried out on the natural fibers and compared to waste derived fibers of coir and also conventional cotton and cotton-based fibers, which are widely used in the textile industry. The evaluation of the geometry and mechanical properties revealed that both SP and chitin fibers showed similar fineness and tenacity values than cotton, whereas coir did not achieve the expected properties to develop fabrics. In relation to the moisture content, it was found that the SP fibers outperformed the other natural fibers, which could successfully avoid variations in the mechanical performance of their fabrics as well as impair the growth of microorganisms. In addition, the antimicrobial activity of the natural fibers was assessed against different bacteria and fungi that are typically found on the skin. The obtained results indicated that the fibers of chitin and also SP, being the latter functionalized with biocides during the fiber-formation process, showed a high antimicrobial activity. In particular, reductions of up to 100% and 60% were attained for the bacteria and fungi strains, respectively. Finally, textile comfort was evaluated on the weft-knitted fabrics of the chitin and SP fibers by means of thermal and tactile tests. The comfort analysis indicated that the thermal resistance of both fabrics was similar to that of cotton, whereas their air permeability was higher, particularly for chitin due to its higher fineness, which makes these natural fibers very promising for summer clothes. Both the SP and chitin fabrics also presented relatively similar values of fullness and softness than the pure cotton fabric in terms of body feeling and richness. However, the cotton/polyester fabric was the only one that achieved a good range for uses in winter-autumn cloths. Therefore, the results of this work demonstrate that non-conventional chitin and SP fibers can be considered as potential candidates to replace cotton fibers in fabrics for the textile industry due to their high comfort and improved sustainability. Furthermore, these natural fibers can also serve to develop novel functional textiles with antimicrobial properties.

Copper(II) sulfate-loaded chitosan microparticles were herein prepared using ionic cross-linking with sodium tripolyphosphate (STPP) followed by spray drying. The microencapsulation process was optimal using an inlet temperature of 180 °C, a liquid flow-rate of 290 mL/h, an aspiration rate of 90%, and an atomizing gas flow-rate of 667 nL/h. Chitosan particles containing copper(II) sulfate of approximately 4 µm with a shrunken-type morphology were efficiently attained and, thereafter, fixated on a paper substrate either via cross-linking with STPP or using a chitosan hydrogel. The latter method led to the most promising system since it was performed at milder conditions and the original paper quality was preserved. The developed cellulose substrates were reduced and then exposed to different humidity conditions and characterized using colorimetric measurements in order to ascertain their potential as irreversible indicators for moisture detection. The results showed that the papers coated with the copper(II) sulfate-containing chitosan microparticles were successfully able to detect ambient moisture shown by the color changes of the coatings from dark brown to blue, which can be easily seen with the naked eye. Furthermore, the chitosan microparticles yielded no cytotoxicity in an in vitro cell culture experiment. Therefore, the cellulose substrates herein developed hold great promise in paper packaging as on-package colorimetric indicators for monitoring moisture in real time.

In the present study, poly(3-hydroxybutyrate- co -3-hydroxyhexanoate) [P(3HB- co -3HHx)] was reinforced with hydroxyapatite nanoparticles (nHA) to produce novel nanocomposites for potential uses in bone reconstruction. Contents of nHA in the 2.5-20 wt % range were incorporated into P(3HB- co -3HHx) by melt compounding and the resulting pellets were shaped into parts by injection molding. The addition of nHA improved the mechanical strength and the thermomechanical resistance of the microbial copolyester parts. In particular, the addition of 20 wt % of nHA increased the tensile (E t ) and flexural (E f ) moduli by approximately 64% and 61%, respectively. At the highest contents, however, the nanoparticles tended to agglomerate, and the ductility, toughness, and thermal stability of the parts also declined. The P(3HB- co -3HHx) parts filled with nHA contents of up to 10 wt % matched more closely the mechanical properties of the native bone in terms of strength and ductility when compared with metal alloys and other biopolymers used in bone tissue engineering. This fact, in combination with their biocompatibility, enables the development of nanocomposite parts to be applied as low-stress implantable devices that can promote bone reconstruction and be reabsorbed into the human body.

Green composites made of polylactide (PLA) and short flaxseed fibers (FFs) at 20 wt % were successfully compounded by twin-screw extrusion (TSE) and subsequently shaped into pieces by injection molding. The linen waste derived FFs were subjected to an alkalization pretreatment to remove impurities, improve the fiber surface quality, and make the fibers more hydrophobic. The alkali-pretreated FFs successfully reinforced PLA, leading to green composite pieces with higher mechanical strength. However, the pieces also showed lower ductility and toughness and the lignocellulosic fibers easily detached during fracture due to the absence or low interfacial adhesion with the biopolyester matrix. Therefore, four different compatibilization strategies were carried out to enhance the fiber-matrix interfacial adhesion. These routes consisted on the silanization of the alkalized FFs with a glycidyl silane, namely (3-glycidyloxypropyl) trimethoxysilane (GPTMS), and the reactive extrusion (REX) with three compatibilizers, namely a multi-functional epoxy-based styrene-acrylic oligomer (ESAO), a random copolymer of poly(styrene- co -glycidyl methacrylate) (PS- co -GMA), and maleinized linseed oil (MLO). The results showed that all the here-tested compatibilizers improved mechanical strength, ductility, and toughness as well as the thermal stability and thermomechanical properties of the green composite pieces. The highest interfacial adhesion was observed in the green composite pieces containing the silanized fibers. Interestingly, PS- co -GMA and, more intensely, ESAO yielded the pieces with the highest mechanical performance due to the higher reactivity of these additives with both composite components and their chain-extension action, whereas MLO led to the most ductile pieces due to its secondary role as plasticizer for PLA.

In the present study, partially bio-based polyethylene terephthalate (bio-PET) was melt-mixed at 15-45 wt% with recycled polyethylene terephthalate (r-PET) obtained from remnants of the injection blowing process of contaminant-free food-use bottles. The resultant compounded materials were thereafter shaped into pieces by injection molding for characterization. Poly(styrene- co -glycidyl methacrylate) (PS- co -GMA) was added at 1-5 parts per hundred resin (phr) of polyester blend during the extrusion process to counteract the ductility and toughness reduction that occurred in the bio-PET pieces after the incorporation of r-PET. This random copolymer effectively acted as a chain extender in the polyester blend, resulting in injection-molded pieces with slightly higher mechanical resistance properties and nearly the same ductility and toughness than those of neat bio-PET. In particular, for the polyester blend containing 45 wt% of r-PET, elongation at break (ε b ) increased from 10.8% to 378.8% after the addition of 5 phr of PS- co -GMA, while impact strength also improved from 1.84 kJ·m -2 to 2.52 kJ·m -2 . The mechanical enhancement attained was related to the formation of branched and larger macromolecules by a mechanism of chain extension based on the reaction of the multiple glycidyl methacrylate (GMA) groups present in PS- co -GMA with the hydroxyl (-OH) and carboxyl (-COOH) terminal groups of both bio-PET and r-PET. Furthermore, all the polyester blend pieces showed thermal and dimensional stabilities similar to those of neat bio-PET, remaining stable up to more than 400 °C. Therefore, the use low contents of the tested multi-functional copolymer can successfully restore the properties of bio-based but non-biodegradable polyesters during melt reprocessing with their recycled petrochemical counterparts and an effective mechanical recycling is achieved.

This study originally explores the use of gallic acid (GA) as a natural additive in bio-based high-density polyethylene (bio-HDPE) formulations. Thus, bio-HDPE was first melt-compounded with two different loadings of GA, namely 0.3 and 0.8 parts per hundred resin (phr) of biopolymer, by twin-screw extrusion and thereafter shaped into films using a cast-roll machine. The resultant bio-HDPE films containing GA were characterized in terms of their mechanical, morphological, and thermal performance as well as ultraviolet (UV) light stability to evaluate their potential application in food packaging. The incorporation of 0.3 and 0.8 phr of GA reduced the mechanical ductility and crystallinity of bio-HDPE, but it positively contributed to delaying the onset oxidation temperature (OOT) by 36.5 °C and nearly 44 °C, respectively. Moreover, the oxidation induction time (OIT) of bio-HDPE, measured at 210 °C, was delayed for up to approximately 56 and 240 min, respectively. Furthermore, the UV light stability of the bio-HDPE films was remarkably improved, remaining stable for an exposure time of 10 h even at the lowest GA content. The addition of the natural antioxidant slightly induced a yellow color in the bio-HDPE films and it also reduced their transparency, although a high contact transparency level was maintained. This property can be desirable in some packaging materials for light protection, especially UV radiation, which causes lipid oxidation in food products. Therefore, GA can successfully improve the thermal resistance and UV light stability of green polyolefins and will potentially promote the use of natural additives for sustainable food packaging applications.

This work reports the effect of the addition of an oligomer of lactic acid (OLA), in the 5-20 wt% range, on the processing and properties of polylactide (PLA) pieces prepared by injection molding. The obtained results suggested that the here-tested OLA mainly performs as an impact modifier for PLA, showing a percentage increase in the impact strength of approximately 171% for the injection-molded pieces containing 15 wt% OLA. A slight plasticization was observed by the decrease of the glass transition temperature (T g ) of PLA of up to 12.5 °C. The OLA addition also promoted a reduction of the cold crystallization temperature (T cc ) of more than 10 °C due to an increased motion of the biopolymer chains and the potential nucleating effect of the short oligomer chains. Moreover, the shape memory behavior of the PLA samples was characterized by flexural tests with different deformation angles, that is, 15°, 30°, 60°, and 90°. The obtained results confirmed the extraordinary effect of OLA on the shape memory recovery (R r ) of PLA, which increased linearly as the OLA loading increased. In particular, the OLA-containing PLA samples were able to successfully recover over 95% of their original shape for low deformation angles, while they still reached nearly 70% of recovery for the highest angles. Therefore, the present OLA can be successfully used as a novel additive to improve the toughness and shape memory behavior of compostable packaging articles based on PLA in the new frame of the Circular Economy.

This research work aims to study the influence of the reprocessing cycles on the mechanical, thermal, and thermomechanical properties of polylactide (PLA). To this end, PLA was subjected to as many as six extrusion cycles and the resultant pellets were shaped into pieces by injection molding. Mechanical characterization revealed that the PLA pieces presented relatively similar properties up to the third reprocessing cycle, whereas further cycles induced an intense reduction in ductility and toughness. The effect of the reprocessing cycles was also studied by the changes in the melt fluidity, which showed a significant increase after four reprocessing cycles. An increase in the bio-polyester chain mobility was also attained with the number of the reprocessing cycles that subsequently favored an increase in crystallinity of PLA. A visual inspection indicated that PLA developed certain yellowing and the pieces also became less transparent with the increasing number of reprocessing cycles. Therefore, the obtained results showed that PLA suffers a slight degradation after one or two reprocessing cycles whereas performance impairment becomes more evident above the fourth reprocessing cycle. This finding suggests that the mechanical recycling of PLA for up to three cycles of extrusion and subsequent injection molding is technically feasible., Competing Interests: The authors declare no conflict of interest.

This research deals with the influence of different curing and post-curing temperatures on the mechanical and thermomechanical properties as well as the gel time of an epoxy resin prepared by the reaction of diglycidyl ether of bisphenol A (DGEBA) with an amine hardener and a reactive diluent derived from plants at 31 wt %. The highest performance was obtained for the resins cured at moderate-to-high temperatures, that is, 80 ° C and 90 ° C , which additionally showed a significant reduction in the gel time. This effect was ascribed to the formation of a stronger polymer network by an extended cross-linking process of the polymer chains during the resin manufacturing. Furthermore, post-curing at either 125 ° C   or 150 ° C yielded thermosets with higher mechanical strength and, more interestingly, improved toughness, particularly for the samples previously cured at moderate temperatures. In particular, the partially bio-based epoxy resin cured at 80 ° C and post-cured at 150 ° C for 1 h and 30 min, respectively, showed the most balanced performance due to the formation of a more homogeneous cross-linked structure.

Novel green composites were prepared by melt compounding a binary blend of polylactide (PLA) and poly(ε-caprolactone) (PCL) at 4/1 (wt/wt) with particles of walnut shell flour (WSF) in the 10-40 wt % range, which were obtained as a waste from the agro-food industry. Maleinized linseed oil (MLO) was added at 5 parts per hundred resin (phr) of composite to counteract the intrinsically low compatibility between the biopolymer blend matrix and the lignocellulosic fillers. Although the incorporation of WSF tended to reduce the mechanical strength and thermal stability of PLA/PCL, the MLO-containing composites filled with up to 20 wt % WSF showed superior ductility and a more balanced thermomechanical response. The morphological analysis revealed that the performance improvement attained was related to a plasticization phenomenon of the biopolymer blend and, more interestingly, to an enhancement of the interfacial adhesion of the green composites achieved by extrusion with the multi-functionalized vegetable oil.

This work presents an in-depth kinetic study of the thermal degradation of recycled acrylonitrile-butadiene-styrene (ABS) polymer. Non-isothermal thermogravimetric analysis (TGA) data in nitrogen atmosphere at different heating rates comprised between 2 and 30 K min -1 were used to obtain the apparent activation energy ( E a ) of the thermal degradation process of ABS by isoconversional (differential and integral) model-free methods. Among others, the differential Friedman method was used. Regarding integral methods, several methods with different approximations of the temperature integral were used, which gave different accuracies in E a . In particular, the Flynn-Wall-Ozawa (FWO), the Kissinger-Akahira-Sunose (KAS), and the Starink methods were used. The results obtained by these methods were compared to the Kissinger method based on peak temperature ( T m ) measurements at the maximum degradation rate. Combined Kinetic Analysis (CKA) was also carried out by using a modified expression derived from the general Sestak-Berggren equation with excellent results compared with the previous methods. Isoconversional methods revealed negligible variation of E a with the conversion. Furthermore, the reaction model was assessed by calculating the characteristic y ( α ) and z ( α ) functions and comparing them with some master plots, resulting in a n th order reaction model with n = 1.4950, which allowed calculating the pre-exponential factor ( A ) of the Arrhenius constant. The results showed that E a of the thermal degradation of ABS was 163.3 kJ mol -1 , while ln A was 27.5410 ( A in min -1 ). The predicted values obtained by integration of the general kinetic expression with the calculated kinetic triplet were in full agreement with the experimental data, thus giving evidence of the accuracy of the obtained kinetic parameters.