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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.
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Queijo , Soro do Leite , Hidroxibutiratos , Ácidos Pentanoicos , PoliésteresRESUMO
Framing the Circular Bioeconomy, the use of reactive compatibilizers was applied in order to increase the interfacial adhesion and, hence, the physical properties and applications of green composites based on biopolymers and food waste derived lignocellulosic fillers. In this study, poly(butylene succinate) grafted with maleic anhydride (PBS-g-MAH) was successfully synthetized by a reactive melt-mixing process using poly(butylene succinate) (PBS) and maleic anhydride (MAH) that was induced with dicumyl peroxide (DCP) as a radical initiator and based on the formation of macroradicals derived from the hydrogen abstraction of the biopolymer backbone. Then, PBS-g-MAH was used as reactive compatibilizer for PBS filled with different contents of pistachio shell flour (PSF) during melt extrusion. As confirmed by Fourier transform infrared (FTIR), PBS-g-MAH acted as a bridge between the two composite phases since it was readily soluble in PBS and could successfully form new esters by reaction of its multiple MAH groups with the hydroxyl (-OH) groups present in cellulose or lignin of PSF and the end ones in PBS. The resultant compatibilized green composites were, thereafter, shaped by injection molding into 4-mm thick pieces with a wood-like color. Results showed significant increases in the mechanical and thermomechanical rigidity and hardness, meanwhile variations on the thermal stability were negligible. The enhancement observed was related to the good dispersion and the improved filler-matrix interfacial interactions achieved by PBS-g-MAH and also to the PSF nucleating effect that increased the PBS's crystallinity. Furthermore, water uptake of the pieces progressively increased as a function of the filler content, whereas the disintegration in controlled compost soil was limited due to their large thickness.
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Materiais Biocompatíveis/química , Butileno Glicóis/química , Farinha/análise , Anidridos Maleicos/química , Peróxidos/química , Pistacia/química , Polímeros/química , Temperatura , Resistência à TraçãoRESUMO
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.
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Filmes Comestíveis , Embalagem de Alimentos , Nanotubos/química , Poliésteres/química , Nanocompostos/química , Análise Espectral , Resistência à Tração , Termodinâmica , Ondas UltrassônicasRESUMO
This study presents the valorization of cotton waste from the textile industry for the development of sustainable and cost-competitive biopolymer composites. The as-received linter of recycled cotton was first chopped to obtain short fibers, called recycled cotton fibers (RCFs), which were thereafter melt-compounded in a twin-screw extruder with partially bio-based polyethylene terephthalate (bio-PET) and shaped into pieces by injection molding. It was observed that the incorporation of RCF, in the 1â»10 wt% range, successfully increased rigidity and hardness of bio-PET. However, particularly at the highest fiber contents, the ductility and toughness of the pieces were considerably impaired due to the poor interfacial adhesion of the fibers to the biopolyester matrix. Interestingly, RCF acted as an effective nucleating agent for the bio-PET crystallization and it also increased thermal resistance. In addition, the overall dimensional stability of the pieces was improved as a function of the fiber loading. Therefore, bio-PET pieces containing 3â»5 wt% RCF presented very balanced properties in terms of mechanical strength, toughness, and thermal resistance. The resultant biopolymer composite pieces can be of interest in rigid food packaging and related applications, contributing positively to the optimization of the integrated biorefinery system design and also to the valorization of textile wastes.
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Materiais Biocompatíveis/química , Materiais Biocompatíveis/economia , Custos e Análise de Custo , Fibra de Algodão/economia , Polietilenotereftalatos/química , Varredura Diferencial de Calorimetria , Módulo de Elasticidade , Fenômenos Mecânicos , Reciclagem , Temperatura , TermogravimetriaRESUMO
The present work evaluates the food packaging performance of previously developed films of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced with atomized microfibrillated cellulose (MFC) compatibilized by a reactive melt-mixing process. To this end, the novel green composite films were originally applied herein as lids in aluminum trays to preserve two dissimilar types of fatty foods, namely minced pork meat and sunflower oil. Results indicated that the PHBV/MFC films effectively preserved the physicochemical and microbiological quality of pork meat for one week of storage at 5 °C. In particular, the compatibilized green composite lid film yielded the lowest weight loss and highest oxidative stability, showing values of 0.935% and 0.78 malonaldehyde (MDA)/kg. Moreover, none of the packaged meat samples exceeded the acceptable Total Aerobial Count (TAC) level of 5 logs colony-forming units (CFU)/g due to the improved barrier properties of the lids. Furthermore, the green composite films successfully prevented sunflower oil oxidation in accelerated oxidative storage conditions for 21 days. Similarly, the compatibilized PHBV/MFC lid film led to the lowest peroxide value (PV) and conjugated diene and triene contents, with respective values of 19.5 meq O2/kg and 2.50 and 1.44 g/100 mL. Finally, the migration of the newly developed PHBV-based films was assessed using two food simulants, proving to be safe since their overall migration levels were in the 1-3 mg/dm2 range and, thus, below the maximum level established by legislation.
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The present study reports on the development by thermoforming of highly sustainable trays based on a bilayer structure composed of paper substrate and a film made of a blend of partially bio-based poly(butylene succinate) (PBS) and poly(butylene succinate-co-adipate) (PBSA). The incorporation of the renewable succinic acid derived biopolyester blend film slightly improved the thermal resistance and tensile strength of paper, whereas its flexural ductility and puncture resistance were notably enhanced. Furthermore, in terms of barrier properties, the incorporation of this biopolymer blend film reduced the water and aroma vapor permeances of paper by two orders of magnitude, while it endowed the paper structure with intermediate oxygen barrier properties. The resultant thermoformed bilayer trays were, thereafter, originally applied to preserve non-thermally treated Italian artisanal fresh pasta, "fusilli calabresi" type, which was stored under refrigeration conditions for 3 weeks. Shelf-life evaluation showed that the application of the PBS-PBSA film on the paper substrate delayed color changes and mold growth for 1 week, as well as reduced drying of fresh pasta, resulting in acceptable physicochemical quality parameters within 9 days of storage. Lastly, overall migration studies performed with two food simulants demonstrated that the newly developed paper/PBS-PBSA trays are safe since these successfully comply with current legislation on plastic materials and articles intended to come into contact with food.
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In this research, bio-based electrospun multilayered films for food packaging applications with good barrier properties and close to superhydrophobic behavior were developed. For this purpose, two different biopolymers, a low-melting point and fully bio-based synthetic aliphatic copolyamide 1010/1014 (PA1010/1014) and the microbially synthesized poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and food-contact-complying organomodified silica (SiO2) nanostructured microparticles, were processed by electrospinning. The production of the multilayer structure was finally obtained by means of a thermal post-treatment, with the aim to laminate all of the components by virtue of the so-called interfiber coalescence process. The so developed fully electrospun films were characterized according to their morphology, their permeance to water vapor and oxygen, the mechanical properties, and their water contact angle properties. Interestingly, the annealed electrospun copolyamide did not show the expected improved barrier behavior as a monolayer. However, when it was built into a multilayer form, the whole assembly exhibited a good barrier, an improved mechanical performance compared to pure PHBV, an apparent water contact angle of ca. 146°, and a sliding angle of 8°. Consequently, these new biopolymer-based multilayer films could be a bio-based alternative to be potentially considered in more environmentally friendly food packaging strategies.
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In the present study, the effectiveness of a multilayer film of polylactide (PLA), fully bio-based and compostable, was ascertained to develop a novel sustainable packaging solution for the preservation of fresh pork meat. To this end, the multilayer PLA films were first characterized in terms of their thermal characteristics, structure, mechanical performance, permeance to water and aroma vapors and oxygen, and optical properties and, for the first time, compared with two commercial high-barrier multilayer packaging films. Thereafter, the multilayers were thermosealed to package fillets of fresh pork meat and the physicochemical changes, lipid oxidation levels, and microbiological counts were monitored in the food samples during storage under refrigeration conditions. Results showed that the meat fillets packaged in PLA developed a redder color and showed certain indications of dehydration and oxidation, being more noticeably after 11 days of storage, due to the higher water vapor and oxygen permeance values of the biopolymer multilayer. However, the pH changes and bacterial growth in the cold-stored fresh pork meat samples were minimal and very similar in the three tested multilayer films, successfully accomplishing the requirements of the food quality and safety standards at the end of storage.
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The present work puts the Circular Bioeconomy's concept into action, originally valorizing residues of spent coffee grains from the beverage liquor coffee industry to develop green composite pieces of polylactide (PLA). The as-received spent coffee grains were first milled to obtain the so-called spent coffee grounds (SCGs) that were, thereafter, incorporated at 20 wt.% into PLA by extrusion. Finally, the resultant green composite pellets were shaped into pieces by injection molding. Moreover, two oligomers of lactic acid (OLAs), namely OLA2 and OLA2mal, the latter being functionalized with maleic anhydride (MAH), were added with SCGs during the extrusion process at 10 wt.%. The results show that, opposite to most claims published in the literature of green composites of PLA, the incorporation of the liquor waste derived SCGs increased the ductility of the pieces by approximately 280% mainly due to their high lipid content. Moreover, the simultaneous addition of OLA2 and OLA2mal further contributed to improve the tensile strength of the green composite pieces by nearly 36% and 60%, respectively. The higher performance of OLA2mal was ascribed to the chemical interaction achieved between the biopolyester and the lignocellulosic fillers by the MAH groups. The resultant green composite pieces are very promising as disposable food-serving utensils and tableware.
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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.
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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.
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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.
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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.
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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.
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Food quality and safety are key aspects to guarantee that foods reach consumers in optimal conditions from the point of view of freshness and microbiology. Nanotechnology offers significant potential to secure or even enhance these aspects. Novel technologies, such as nanofabrication and nanoencapsulation, can provide new added value solutions for the fortification of foods with bioactives and targeted controlled release in the gut. Nanomaterials can also support food preservation aspects by being added directly into a food matrix or into food contact materials such as packaging. Thus, nanomaterials can be leveraged in the form of nanocomposites in food packaging design by melt compounding, solvent casting, lamination or electrohydrodynamic processing (EHDP) to promote passive, active, and even bioactive properties such as barrier, antimicrobial, antioxidant, and oxygen scavenging roles and the controlled release of functional ingredients. These attributes can be exerted either by the intended or non-intended migration of the nanomaterials or by the active substances they may carry. Lastly, nanomaterials can be advantageously applied to provide unique opportunities in Circular Bioeconomy strategies in relation to the valorization of, for instance, agro-industrial wastes and food processing by-products.
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In the last decade, continuous research advances have been observed in the field of environmentally friendly polymers and polymer composites due to the dependence of polymers on fossil fuels and the sustainability issues related to plastic wastes. This research activity has become much more intense in the food packaging industry due to the high volume of waste it generates. Biopolymers are nowadays considered as among the most promising materials to solve these environmental problems. However, they still show inferior performance regarding both processability and end-use application. Blending currently represents a very cost-effective strategy to increase the ductility and impact resistance of biopolymers. Furthermore, different lignocellulosic materials are being explored to be used as reinforcing fillers in polymer matrices for improving the overall properties, lower the environmental impact, and also reduce cost. Moreover, the use of vegetable oils, waste derived liquids, and essential oils opens up novel opportunities as natural plasticizers, reactive compatibilizers or even active additives for the development of new polymer formulations with enhanced performance and improved sustainability profile.
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In the last few years, a remarkable growth in the use of functional polyesters has been observed.
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In this research, different contents of eugenol in the 2.5-25 wt.% range were first incorporated into ultrathin fibers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) by electrospinning and then subjected to annealing to obtain antimicrobial monolayers. The most optimal concentration of eugenol in the PHBV monolayer was 15 wt.% since it showed high electrospinnability and thermal stability and also yielded the highest bacterial reduction against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). This eugenol-containing monolayer was then selected to be applied as an interlayer between a structural layer made of a cast-extruded poly(3-hydroxybutyrate) (PHB) sheet and a commercial PHBV film as the food contact layer. The whole system was, thereafter, annealed at 160°C for 10 s to develop a novel multilayer active packaging material. The resultant multilayer showed high hydrophobicity, strong adhesion and mechanical resistance, and improved barrier properties against water vapor and limonene vapors. The antimicrobial activity of the multilayer structure was also evaluated in both open and closed systems for up to 15 days, showing significant reductions (R ≥ 1 and < 3) for the two strains of food-borne bacteria. Higher inhibition values were particularly attained against S. aureus due to the higher activity of eugenol against the cell membrane of Gram positive (G+) bacteria. The multilayer also provided the highest antimicrobial activity for the closed system, which better resembles the actual packaging and it was related to the headspace accumulation of the volatile compounds. Hence, the here-developed multilayer fully based on polyhydroxyalkanoates (PHAs) shows a great deal of potential for antimicrobial packaging applications using biodegradable materials to increase both quality and safety of food products.
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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 (Et) and flexural (Ef) 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.
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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.