Search

Abstract Poly(lactic acid)/poly(butylene succinate‐co‐adipate) (PLA/PBSA) blends are found promising for film packaging applications because of their flexibility, resistance, and compostability. Industrially extruded granules and films based on PLA and containing different amounts of PBSA are reprocessed through mini‐extrusion, to simulate recycling, and tested in terms of their melt flow rate as a function of PBSA content. Moreover, pure PLA commercial granules and the film produced extruding the PLA/PBSA 60/40 blend are reprocessed several times by injection molding and characterized in terms of melt flow rate, mechanical properties, thermal properties, and color as a function of injection molding cycles. The variation in melt fluidity and thermo‐mechanical properties is negligible up to 3 injection molding cycles for both pure PLA granules and PLA/PBSA blend. In the case of blend the change in color (yellowing and darkening) is more evident and slight local compositional change in injection molded items can be evidenced as well as a slight decrease in PBS crystallinity as a function of injection molding cycles. Nevertheless, in applications where these aspects are not critical, these materials can be recycled by extrusion or injection molding before being composted, thus prolonging their life cycle and storing carbon in them as longer as possible.

Bone defects are a significant health problem worldwide. Novel treatment approaches in the tissue engineering field rely on the use of biomaterial scaffolds to stimulate and guide the regeneration of damaged tissue that cannot repair or regrow spontaneously. This work aimed at developing and characterizing new piezoelectric scaffolds to provide electric bio-signals naturally present in bone and vascular tissues. Mixing and extrusion were used to obtain nanocomposites made of polyhydroxybutyrate (PHB) as a matrix and barium titanate (BaTiO3) nanoparticles as a filler, at BaTiO3/PHB compositions of 5/95, 10/90, 15/85 and 20/80 (w/w%). The morphological, thermal, mechanical and piezoelectric properties of the nanocomposites were studied. Scanning electron microscopy analysis showed good nanoparticle dispersion within the polymer matrix. Considerable increases in the Young’s modulus, compressive strength and the piezoelectric coefficient d31 were observed with increasing BaTiO3 content, with d31 = 37 pm/V in 20/80 (w/w%) BaTiO3/PHB. 3D printing was used to produce porous cubic-shaped scaffolds using a 90° lay-down pattern, with pore size ranging in 0.60–0.77 mm and good mechanical stability. Biodegradation tests conducted for 8 weeks in saline solution at 37 °C showed low mass loss (∼4%) for 3D printed scaffolds. The results obtained in terms of piezoelectric, mechanical and chemical properties of the nanocomposite provide a new promising strategy for vascularized bone tissue engineering.

In this study, four different plastic materials usually used in the agricultural sector (polystyrene film (PS), polyethylene terephthalate film (PET), low-density polyethylene film (LDPE) and linear low-density polyethylene film (LLDPE)) were subjected to different abiotic treatments, including photo-oxidation (ultraviolet and e-beam radiation) and thermochemical treatments, to enhance polymer degradation. The extensive use of these polymers leads to large amounts of plastic waste generation, including small plastic pieces, known as microplastics, which affect the quality of the agricultural environment, including soil fertility and quality. Therefore, polymer degradation strategies are needed to effectively reduce plastic waste to protect the agricultural sector. The degree of polymer degradation was assessed by the use of thermal and spectroscopic analyses, such as TGA and FTIR. In addition, efficiency, cost–benefits, and potential side-effects were also evaluated to propose the optimal degradation strategy to reduce plastic waste from the point of view of efficiency. The results obtained showed that the pre-treatments based on photo-oxidation (ultraviolet B and C and e-beam radiation) were more efficient and had a better cost–benefit for the degradation of the polymers studied in relation to the thermochemical treatments. Specifically, ultraviolet photo-oxidation worked well for PS and PET, requiring low energy and medium times. However, e-beam radiation was recommended for PE (LDPE and LLDPE) degradation, since high energy and long times were needed when ultraviolet energy was applied to this polymer. Furthermore, the overall efficiency of the plastic degradation of pre-treatments should be studied using a multicriteria approach, since FTIR assessments, in some cases, only consider oxidation processes on the plastic surface and do not show the potential integrity changes on the plastic probes.

When properly compatibilized, the blending of polyethylene (PE) and polyamide (PA) leads to materials that combine low prices, suitable processability, impact resistance, and attractive mechanical properties. Moreover, the possibility of using these polymers without prior separation may be a suitable opportunity for their recycling. In this work, the use of an epoxidized waste vegetable oil (EWVO) was investigated as a green compatibilizer precursor (CP) for the reactive blending of a high-density PE (HDPE) with a polyamide-6 (PA6). EWVO was synthesized from waste vegetable cooking oil (WVO) using ion-exchange resin (Amberlite) as a heterogeneous catalyst. HDPE/PA6 blends were produced with different weight ratios (25/75, 75/25, 85/15) and amounts of EWVO (1, 2, 5 phr). Samples with WVO or a commercial fossil-based CP were also prepared for comparison. All the blends were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), rheology, and mechanical tests. In the case of HDPE/PA6 75/25 and 85/15 blends, the addition of EWVO at 2 phr showed a satisfactory compatibilizing effect, thus yielding a material with improved mechanical properties with respect to the blend without compatibilizer. On the contrary, the HDPE/PA6 25/75 ratio yielded a material with a high degree of crosslinking that could not be further processed or characterized. In conclusion, the results showed that EWVO had a suitable compatibilizing effect in HDPE/PA6 blends with high HDPE content, while it resulted in unsuitable for blends with high content of PA6.

Chitin is a very abundant polysaccharide that can be obtained from well-known marine sources (crustaceans), but also from terrestrial sources (mushrooms and insects). In the case where animal sources are considered, the material can be obtained by much abundant food or feeding waste. The extraction methodologies were not developed with similar technical readiness levels considering the different sources and the further conversion to chitin nanofibrils and chitosan is also under study, enabling the production of products differentiated for their macromolecular structures and morphology.Chitin nanofibrils from sea food sources were used in sanitary, cosmetic and packaging applications, where their anti-microbial properties and good biocompatibility were very useful. Chitin from mushrooms and sea food was used as starting material in possible coatings for cellulosic and bioplastic substrates. Currently chitin from insects (Hermetia Illucens) is also under study as well as the methodologies for extracting derivatives from it. Infrared analysis is an interesting technique to compare chitins, chitin nanofibrils and chitosan from different sources as well as electron microscopy for studying their morphology. The derivatives of chitin, such as chitosan and chitin nanofibrils, show anti-microbial properties. Hence, their use in several applications, ranging from packaging to sanitary and cosmetics, can conjugate high performance novel products with a reduced environmental concern. The comparison between chitin derivatives from different sources is very useful to address the biopolymers to specific applications, including the agricultural sector. While more and more applications for chitin derivatives will be developed, differences between them should be clarified and correlated to the sources, the methodologies of their production and their physical-chemical properties.

Over the past few decades, microbial polysaccharides hydrogels have been used in the field of tissue regeneration due to their ability to mimic the physical-chemical and mechanical characteristics of the extracellular matrix. Gellan gum, an anionic heteropolysaccharide that can form hydrogel in presence of di or trivalent cations, has interesting properties in terms of biodegradability, biocompatibility and the ability to integrate with surrounding tissues. However, it also has some limitations such as the lack of specific sites within the polysaccharide chains for cell recognition and adhesion, high hygroscopicity and limited mechanical properties. Gellan gum has also been proposed for application in the field of controlled release of bioactive molecules; the bio-inert nature of gellan gum makes it suitable for the encapsulation of biomolecules, drugs, enzymes and nutraceutical formulations. Furthermore, the anionic nature of this polysaccharide makes it suitable as a pH sensitive drug delivery system. This work deals with the production and characterization of hydrogels based on gellan gum and polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) for the creation of matrices, containing curcumin as an antioxidant agent, having a micro-engineered surface obtained using micro-molded silicone molds. The properties of gellan hydrogels mixed with PVA or PVP containing curcumin, before and after crosslinking with Ca2+ ions, were investigated. The highest curcumin solubility was observed in PVP solution (0.0156 mg/mL) as compared to PVA solution (0.0074 mg/mL). The contribution of gellan hydrogels mixed with PVA or PVP to the antioxidant capacity of curcumin, expressed as % inhibition, was 22% and 25%, respectively.

Three-dimensional scaffold-based culture has been increasingly gaining influence in oncology as a therapeutic strategy for tumors with a high relapse percentage. This study aims to evaluate electrospun poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) scaffolds to create a 3D model of colorectal adenocarcinoma. Specifically, the physico-mechanical and morphological properties of PCL and PLA electrospun fiber meshes collected at different drum velocities, i.e., 500 rpm, 1000 rpm and 2500 rpm, were assessed. Fiber size, mesh porosity, pore size distribution, water contact angle and tensile mechanical properties were investigated. Caco-2 cells were cultured on the produced PCL and PLA scaffolds for 7 days, demonstrating good cell viability and metabolic activity in all the scaffolds. A cross-analysis of the cell–scaffold interactions with morphological, mechanical and surface characterizations of the different electrospun fiber meshes was carried out, showing an opposite trend of cell metabolic activity in PLA and PCL scaffolds regardless of the fiber alignment, which increased in PLA and decreased in PCL. The best samples for Caco-2 cell culture were PCL500 (randomly oriented fibers) and PLA2500 (aligned fibers). Caco-2 cells had the highest metabolic activity in these scaffolds, with Young’s moduli in the range of 8.6–21.9 MPa. PCL500 showed Young’s modulus and strain at break close to those of the large intestine. Advancements in 3D in vitro models of colorectal adenocarcinoma could move forward the development of therapies for this cancer.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is among the most attracting low environmental impact polymeric materials. Coffee Silverskin (CS), an agro-food residue, has been compounded in variable amounts into a PHBV matrix in the presence of acetyl tributyl citrate (ATBC) as plasticizer, and calcium carbonate (CaCO3) as filler, to produce biocomposites through a pre-industrial scale melt extrusion technique. Thermal, morphological and mechanical properties have been investigated in order to validate whether these PHBV/CS based biocomposites could be used to manufacture moulded items, e.g. coffee capsules body. The increasing concentration of CS in PHBV improves the stiffness and the heat deflection temperature properties of the biocomposites. Coffee capsules body have been produced by injection moulding starting from the optimized formulations, based on the PHBV/CS system, and were characterized in terms of migration properties in contact with simulants. Notably, the overall migration at 100 °C was below the limit (10 mg/dm2) required for plastic materials in food contact applications.

The present work focused on the development and characterization of biocomposites based on a fully bio-based polyester, poly(butylene succinate-co-butylene adipate) (PBSA), and wheat bran derived by flour milling. PBSA-bran composites containing 5, 10, 15, and 20 wt.% of wheat bran were produced via melt extrusion and processed by injection molding. Their thermal, rheological, morphological, and tensile properties were investigated. In addition, a biodegradation test in a natural marine environment was conducted on composite dog-bones to assess the capacity of the used filler to increase the PBSA biodegradation rate. The composites maintained similar melt processability and mechanical properties to virgin PBSA with up to 15 wt.% bran content. This result was also supported by morphological investigation, which showed good filler dispersion within the polymer matrix at low-mid bran content, whereas poor polymer-filler dispersion occurred at higher concentrations. Furthermore, the biodegradation tests showed bran’s capacity to improve the PBSA biodegradation rate, probably due to the hygroscopic bran swelling, which induced the fragmentation of the dog-bone with a consequent increase in the polymeric matrix–seawater interfacial area, accelerating the degradation mechanisms. These results encourage the use of wheat bran, an abundant and low-cost agri-food by-product, as a filler in PBSA-based composites to develop products with good processability, mechanical properties, and controlled biodegradability in marine environments.

Type-1 diabetes is one of the most prevalent metabolic disorders worldwide. It results in a significant lack of insulin production by the pancreas and the ensuing hyperglycemia, which needs to be regulated through a tailored administration of insulin throughout the day. Recent studies have shown great advancements in developing an implantable artificial pancreas. However, some improvements are still required, including the optimal biomaterials and technologies to produce the implantable insulin reservoir. Here, we discuss the employment of two types of cyclic olefin copolymers (Topas 5013L-10 and Topas 8007S-04) for an insulin reservoir fabrication. After a preliminary thermomechanical analysis, Topas 8007S-04 was selected as the best material to fabricate a 3D-printed insulin reservoir due to its higher strength and lower glass transition temperature (Tg). Fiber deposition modeling was used to manufacture a reservoir-like structure, which was employed to assess the ability of the material to prevent insulin aggregation. Although the surface texture presents a localized roughness, the ultraviolet analysis did not detect any significant insulin aggregation over a timeframe of 14 days. These interesting results make Topas 8007S-04 cyclic olefin copolymer a potential candidate biomaterial for fabricating structural components in an implantable artificial pancreas.

The depletion of fossil resources and the growing demand for plastic waste reduction has put industries and academic researchers under pressure to develop increasingly sustainable packaging solutions that are both functional and circularly designed. In this review, we provide an overview of the fundamentals and recent advances in biobased packaging materials, including new materials and techniques for their modification as well as their end-of-life scenarios. We also discuss the composition and modification of biobased films and multilayer structures, with particular attention to readily available drop-in solutions, as well as coating techniques. Moreover, we discuss end-of-life factors, including sorting systems, detection methods, composting options, and recycling and upcycling possibilities. Finally, regulatory aspects are pointed out for each application scenario and end-of-life option. Moreover, we discuss the human factor in terms of consumer perception and acceptance of upcycling.

This study focused on the development of a novel biocomposite material formed by a thermoplastic biodegradable polyester, poly(butylene succinate-co-adipate) (PBSA), and a carbonaceous filler as biochar (BC) derived by the pyrolysis of woody biomass waste. Composites with various BC contents (5, 10, 15, and 20 wt.%) were obtained by melt extrusion and investigated in terms of their processability, thermal, rheological, and mechanical properties. In all the composites, BC lowered melt viscosity, behaving as a lubricant, and enhancing composite extrudability and injection moulding at high temperatures up to 20 wt.% of biochar. While the use of biochar did not significantly change composite thermal stability, it increased its stiffness (Young modulus). Differential scanning calorimeter (DSC) revealed the presence of a second crystal phase induced by the filler addition. Furthermore, results suggest that biochar may form a particle network that hinders polymer chain disentanglement, reducing polymer flexibility. A biochar content of 10 wt.% was selected as the best trade-off concentration to improve the composite processability and cost competitiveness without compromising excessively the tensile properties. The findings support the use of biochar as a sustainable renewable filler and pigment for PBSA. Biochar is a suitable candidate to replace more traditional carbon black pigments for the production of biodegradable and inexpensive innovative PBSA composites with potential fertilizing properties to be used in agricultural applications.

Polylactic acid (PLA) is a compostable and sustainable polymer, derived from renewable resources, with high elastic modulus and high transparency. By the way PLA has even some limitations such as low glass transition temperature, low thermal stability, high brittleness, and low crystallization rate. To increase flexibility of PLA based materials it is possible to add low molecular weight plasticizers or prepare blends with another flexible polymer, such as poly(butylene adipate-co-terephthalate) (PBAT). Even the use of a compatibilizer may allow a modulation of mechanical properties thanks to the achievement of a phase morphology characterized by a lower dimension of the dispersed PBAT phase and an increased adhesion. In the present study, blends of PLA and PBAT were prepared by adding different plasticizers combinations based on an oligomer of lactic acid, a polyester of adipic acid and 1,2-propane diol, and an epoxy functionalised resin. All the plasticizers were effective in providing flexibility to the blends, with higher efficiency from the epoxy functionalised plasticizer, and the polyester of adipic acid. Fox’s equation showed that all plasticizers have the tendency to disperse more in the amorphous PBAT matrix than in the PLA one.

Chitin nanofibrils (CN) can be obtained from crustaceans and fungal sources and can be used for preparing coatings for bioplastic films, that are fundamental for developing a safe and sustainable biodegradable food packaging. Coatings with different concentrations of CN from shrimps were applied on different bioplastic substrates, like Poly (butylene succinate-co-adipate)/Poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PBSA/PHBV) blend, Polybutylene succinate (PBS), and Polybutylene adipate terephthalate/Poly(lactic acid) (PBAT/PLA) blend, but the adhesion to the substrates was scarce. On the contrary, the fungal-based CN showed a better adhesion. Additionally, it was found that the use of an additive based on oligomeric lactic acid was useful to prepare a coating with an improved adhesion to bioplastics. The gas barrier properties to oxygen and water vapour of coated and un-coated films were measured, revealing an improvement of these properties thanks to applied coatings, especially towards the oxygen. Antimicrobial properties and biodegradation capacity were also evaluated revealing an antibacterial effect of the coatings that did not significantly interfere with their biodegradability. The results are discussed and interpreted considering the correlation between composition and macromolecular structures with the observed functional properties.

The present work aims to enhance the use of agricultural byproducts for the production of bio-composites by melt extrusion. It is well known that in the production of such bio-composites, the weak point is the filler-matrix interface, for this reason the adhesion between a polylactic acid (PLA)/poly(butylene succinate)(PBSA) blend and rice and wheat bran platelets was enhanced by a treatment method applied on the fillers using a suitable beeswax. Moreover, the coupling action of beeswax and inorganic fillers (such as talc and calcium carbonate) were investigated to improve the thermo-mechanical properties of the final composites. Through rheological (MFI), morphological (SEM), thermal (TGA, DSC), mechanical (Tensile, Impact), thermomechanical (HDT) characterizations and the application of analytical models, the optimum among the tested formulations was then selected.

Low-cost composites with high water absorption capacity were prepared by free radical copolymerization of acrylic acid (AA), acrylamide (AM) and gelatin in aqueous media using N,N' methylene bis-acrylamide (MBA) as crosslinker, potassium persulfate (KPS) as initiator and rice husk (RH) as a filler. The composites were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The effects of different parameters such as the alkaline treatment on the rice husk, the media pH and salinity and the composition of the composites on their water absorption capacity were investigated. The water retention and biodegradation tests in soil were also carried out. The optimized composite containing treated RH showed a maximum water uptake value of 825 g∙g−1 in distilled water and good resistance in saline solutions and in the pH range of 6–10. Positive effects on the soil water retention were obtained after 30 days samples of soil containing 1 wt% of superabsorbent composites still contained about 7% of the initial absorbed water. Growth attributes, photosynthetic pigments and nodulation traits of droughted peanut were improved by 60 kg∙ha−1 dosage of SAC. On the basis of the good results of water retention and controlled biodegradability in the soil, the developed composites have the potential to be used in agriculture for better water management, with relevant environmental benefits.

Background and Objective: The use of biopolyesters and natural fibres or fillers for production of biobased composites has attracted interest of various application sectors ranging from packaging to automotive components and other high value applications in agreement with a bioeconomy approach. In the present paper biobased composites were produced by using compostable polymers degradable even in soil and marine water such as polyhydroxyalkanoates with natural fibres or fillers derived by food wastes (legumes by-products) and by wood industry. Material and Methods: Polyhydroxyalkanoates were processed with a biobased, biodegradable plasticizer such as acetyltributylcitrate and calcium carbonate as inorganic filler. The selected polymeric matrix was used for the production of composites with variable amounts of natural fibres. Green composites were manufactured by extrusion and injection moulding. Thermal, rheological, mechanical and morphological characterizations of the developed composites were performed. Results and Conclusion: The bio composites properties match the requirements for production of rigid food packaging or other single use items where the market is looking for more sustainable solutions versus the products actually used and hardly recyclable, opening a route for valorization of food residue. Pukanzsky’s model predicts with good accuracy the tensile behavior of the composites showing a medium intensity adhesion between fibres and polymer matrix in both cases analyzed. Conflict of interest: The authors declare no conflict of interest.

The paper tissue industry is a constantly evolving sector that supplies markets that require products with different specific properties. In order to meet the demand of functional properties, ensuring a green approach at the same time, research on bio-coatings has been very active in recent decades. The attention dedicated to research on functional properties has not been given to the study of the morphological and mechanical properties of the final products. This paper studied the effect of two representative bio-based coatings on paper tissue. Coatings based on chitin nanofibrils or polyphenols were sprayed on paper tissues to provide them, respectively, with antibacterial and antioxidant activity. The chemical structure of the obtained samples was preliminarily compared by ATR-FTIR before and after their application. Coatings were applied on paper tissues and, after drying, their homogeneity was investigated by ATR-FTIR on different surface areas. Antimicrobial and antioxidant properties were found for chitin nanofibrils- and polyphenols-treated paper tissues, respectively. The mechanical properties of treated and untreated paper tissues were studied, considering as a reference the same tissue paper sample treated only with water. Different mechanical tests were performed on tissues, including penetration, tensile, and tearing tests in two perpendicular directions, to consider the anisotropy of the produced tissues for industrial applications. The morphology of uncoated and coated paper tissues was analysed by field emission scanning electron microscopy. Results from mechanical properties evidenced a correlation between morphological and mechanical changes. The addition of polyphenols resulted in a reduction in mechanical resistance, while the addition of chitin enhanced this property. This study evidenced the different effects produced by two novel coatings on paper tissues for personal care in terms of properties and structure.

In this work biocomposites based on plasticized poly(lactic acid) (PLA)–poly(butylene succinate-co-adipate) (PBSA) matrix containing wheat bran fiber (a low value by-product of food industry) were investigated. The effect of the bran addition on the mechanical properties is strictly correlated to the fiber-matrix adhesion and several analytical models, based on static and dynamic tests, were applied in order to estimate the interfacial shear strength of the biocomposites. Finally, the essential work of fracture approach was carried out to investigate the effect of the bran addition on composite fracture toughness.

PBS, an acronym for poly (butylene succinate), is an aliphatic polyester that is attracting increasing attention due to the possibility of bio-based production, as well as its balanced properties, enhanced processability, and excellent biodegradability. This brief review has the aim to provide the status concerning the synthesis, production, thermal, morphological and mechanical properties underlying biodegradation ability, and major applications of PBS and its principal copolymers.

Three different commercial nucleating agents (LAK, talc, and calcium carbonate) were added at different weight percentages into poly (lactic acid) (PLA) in order to investigate the mechanical and thermo-mechanical behavior of blends in correlation to injection molding parameters. After as-sessing the best content of each nucleating agent, analyzing isothermal and non-isothermal crys-tallization, two cycle times that can be industrially adopted were selected. Crystallinity highly impacts the flexural modulus, while it improves the heat deflection temperature only when the crystallinity percentage is above 50%; nevertheless, an excessive crystallinity content leads to a decrement of impact resistance. LAK does not appear to be sensitive to cycle time while talc and calcium carbonate proved to be effective if a cycle time of 60 s is adopted. Since the choice of nu-cleating agent is not univocal, the identification of the best nucleating agents is subject to the technical specifications required by the application, accotuing for the most important commercial requirements (productivity, temperature, and impact resistance).

In the present study, for the first time the evolution of tensile mechanical properties of different poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymers (PHBV8 and PHBV12, with 8 mol% and 12 mol% of HV co-units, respectively) as a function of the storage time at room temperature has been investigated in parallel with the quantification of the crystalline, mobile amorphous, and rigid amorphous fractions. A comparison with the evolution of the crystalline and amorphous fractions in the homopolymer poly(3-hydroxybutyrate) (PHB) was also performed. For all the samples, the crystallinity was found to slightly increase during storage. In parallel, the mobile amorphous fraction (MAF) decreased markedly, with the result that a relevant increase in the rigid amorphous fraction (RAF) was detected. The RAF content in the copolymers was lower than that of PHB. For all the samples, the RAF formation during aging was ascribed to the growth of secondary crystals in geometrically restricted areas. It was demonstrated that the storage at Troom leads in PHB, PHBV8, and PHBV12 to a progressive increase in the total solid fraction (crystal phase + rigid amorphous fraction) and to a simultaneous physical aging of the rigid amorphous fraction. The two different processes cannot be separated and distinguished, so that only the resulting effect on the mechanical properties was considered. The experimental elastic modulus of both PHBV8 and PHBV12 was found to increase regularly with the total solid fraction, as well as the tensile strength. Conversely, the elongation at break turned out to be an increasing function of the mobile amorphous fraction. The elastic moduli of the crystalline, mobile amorphous, and rigid amorphous fractions of PHBV8 and PHBV12 were estimated by means of a three-phase modified Takayanagi's model, to take into account also the contribution of the rigid amorphous fraction. The calculated values were found in agreement with theoretical expectations.

In this study, non-chlorinated solvents such as cyclohexanone (CYC) and three ionic liquids, (ILs) (1-ethyl-3-methylimidazolium dimethylphosphate, [EMIM][DMP], 1-ethyl-3-methylimidazolium diethylphosphate, [EMIM][DEP] and 1-ethyl-3-methylimidazolium methylphosphite, [EMIM][MP]) were tested to extract polyhydroxyalkanoates (PHAs) from the purple non-sulfur photosynthetic bacterium (PNSB) Rhodovulumsulfidophilum DSM-1374. The photosynthetic bacterium was cultured in a new generation photobioreactor with 4 L of working volume using a lactate-rich medium. The extracted PHAs were characterized using a thermogravimetric analysis, differential scanning calorimetry, infrared spectroscopy, proton nuclear magnetic resonance and gel permeation chromatography. The most promising results were obtained with CYC at 125 °C with an extraction time of above 10 min, obtaining extraction yields higher than 95% and a highly pure poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-HV) with around 2.7 mol% of hydroxylvalerate (HV). A similar yield and purity were obtained with chloroform (CHL) at 10 °C for 24 h, which was used as the referent solvent Although the three investigated ILs at 60 °C for 4 and 24 h with biomass/IL up to 1/30 (w/w) obtained PHAs strongly contaminated by cellular membrane residues, they were not completely solubilized by the investigated ILs.

The development of new bio-based coating materials to be applied on cellulosic and plastic based substrates, with improved performances compared to currently available products and at the same time with improved sustainable end of life options, is a challenge of our times. Enabling cellulose or bioplastics with proper functional coatings, based on biopolymer and functional materials deriving from agro-food waste streams, will improve their performance, allowing them to effectively replace fossil products in the personal care, tableware and food packaging sectors. To achieve these challenging objectives some molecules can be used in wet or solid coating formulations, e.g., cutin as a hydrophobic water- and grease-repellent coating, polysaccharides such as chitosan-chitin as an antimicrobial coating, and proteins as a gas barrier. This review collects the available knowledge on functional coatings with a focus on the raw materials used and methods of dispersion/application. It considers, in addition, the correlation with the desired final properties of the applied coatings, thus discussing their potential.

Cosmetics has recently focused on biobased skin-compatible materials. Materials from natural sources can be used to produce more sustainable skin contact products with enhanced bioactivity. Surface functionalization using natural-based nano/microparticles is thus a subject of study, aimed at better understanding the skin compatibility of many biopolymers also deriving from biowaste. This research investigated electrospray as a method for surface modification of cellulose tissues with chitin nanofibrils (CNs) using two different sources—namely, vegetable (i.e., from fungi), and animal (from crustaceans)—and different solvent systems to obtain a biobased and skin-compatible product. The surface of cellulose tissues was uniformly decorated with electrosprayed CNs. Biological analysis revealed that all treated samples were suitable for skin applications since human dermal keratinocytes (i.e., HaCaT cells) successfully adhered to the processed tissues and were viable after being in contact with released substances in culture media. These results indicate that the use of solvents did not affect the final cytocompatibility due to their effective evaporation during the electrospray process. Such treatments did not also affect the characteristics of cellulose; in addition, they showed promising anti-inflammatory and indirect antimicrobial activity toward dermal keratinocytes in vitro. Specifically, cellulosic substrates decorated with nanochitins from shrimp showed strong immunomodulatory activity by first upregulating then downregulating the pro-inflammatory cytokines, whereas nanochitins from mushrooms displayed an overall anti-inflammatory activity via a slight decrement of the pro-inflammatory cytokines and increment of the anti-inflammatory marker. Electrospray could represent a green method for surface modification of sustainable and biofunctional skincare products.

Poly(lactic acid) (PLA) is the most widely produced biobased, biodegradable and biocompatible polyester. Despite many of its properties are similar to those of common petroleum-based polymers, some drawbacks limit its utilization, especially high brittleness and low toughness. To overcome these problems and improve the ductility and the impact resistance, PLA is often blended with other biobased and biodegradable polymers. For this purpose, poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene succinate-co-butylene adipate) (PBSA) are very advantageous copolymers, because their toughness and elongation at break are complementary to those of PLA. Similar to PLA, both these copolymers are biodegradable and can be produced from annual renewable resources. This literature review aims to collect results on the mechanical, thermal and morphological properties of PLA/PBAT and PLA/PBSA blends, as binary blends with and without addition of coupling agents. The effect of different compatibilizers on the PLA/PBAT and PLA/PBSA blends properties is here elucidated, to highlight how the PLA toughness and ductility can be improved and tuned by using appropriate additives. In addition, the incorporation of solid nanoparticles to the PLA/PBAT and PLA/PBSA blends is discussed in detail, to demonstrate how the nanofillers can act as morphology stabilizers, and so improve the properties of these PLA-based formulations, especially mechanical performance, thermal stability and gas/vapor barrier properties. Key points about the biodegradation of the blends and the nanocomposites are presented, together with current applications of these novel green materials.

The potential use of paper sludge (PS) as filler in the production of bio-composites based on poly lactic acid (PLA) and polybutylene adipate terephthalate (PBAT) was investigated. PS/PLA/PBAT composites, with addition of acetyl tributyl citrate (ATBC) as biobased plasticizer, were produced with PS loadings up to 30 wt.% by twin-screw extrusion followed by injection moulding. The composites were characterized by rheological measurements, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and mechanical tests (tensile and impact resistance) to study the effect of PS on the processability, thermal stability, crystallinity and mechanical performance of polymeric matrix. The optimized composites at higher PS content were successfully processed to produce pots for horticulture and, in view of this application, preliminary phytotoxicity tests were conducted using the germination test on Lepidium sativum L. seeds. Results revealed that developed composites up to 30 wt.% PS had good processability by extrusion and injection moulding showing that PS is a potential substitute of calcium carbonate as filler in the production of bio-composites, and the absence of phytotoxic effects showed the possibility of their use in the production of pots/items for applications in floriculture and/or horticulture.

In this work poly(lactic) acid (PLA)/poly(butylene succinate-co-adipate) (PBSA) biobased binary blends were investigated. PLA/PBSA mixtures with different compositions of PBSA (from 15 up to 40 wt.%) were produced by twin screw-extrusion. A first screening study was performed on these blends that were characterized from the melt fluidity, morphological and thermo-mechanical point of view. Starting from the obtained results, the effect of an epoxy oligomer (EO) (added at 2 wt.%) was further investigated. In this case a novel approach was introduced studying the micromechanical deformation processes by dilatometric uniaxial tensile tests, carried out with a videoextensometer. The characterization was then completed adopting the elasto-plastic fracture approach, by the measurement of the capability of the selected blends to absorb energy at a slow rate. The obtained results showed that EO acts as a good compatibilizer, improving the compatibility of the rubber phase into the PLA matrix. Dilatometric results showed different micromechanical responses for the 80–20 and 60–40 blends (probably linked to the different morphology). The 80–20 showed a cavitational behavior while the 60–40 a deviatoric one. It has been observed that while the addition of EO does not alter the micromechanical response of the 60–40 blend, it profoundly changes the response of the 80–20, that passed to a deviatoric behavior with the EO addition.

In this work, processability and mechanical performances of bio-composites based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) containing 5, 10, and 15 wt % of bran fibers, untreated and treated with natural carnauba and bee waxes were evaluated. Wheat bran, the main byproduct of flour milling, was used as filler to reduce the final cost of the PHBV-based composites and, in the same time, to find a potential valorization to this agro-food by-product, widely available at low cost. The results showed that the wheat bran powder did not act as reinforcement, but as filler for PHBV, due to an unfavorable aspect ratio of the particles and poor adhesion with the polymeric matrix, with consequent moderate loss in mechanical properties (tensile strength and elongation at break). The surface treatment of the wheat bran particles with waxes, and in particular with beeswax, was found to improve the mechanical performance in terms of tensile properties and impact resistance of the composites, enhancing the adhesion between the PHBV-based polymeric matrix and the bran fibers, as confirmed by predictive analytic models and dynamic mechanical analysis results.

In this paper, the production and the characterization of poly (lactic) acid (PLA)-based composites containing different amounts (from 10 wt.% to 25 wt.%) of ultra-short cellulose fibers (Arbocel 600 BE/PU) have been investigated. On the basis of a previous study, it was observed that the addition of the cellulose fibers led to an embrittlement of the composite. Consequently, in order to obtain a composite with enhanced impact resistance and elongation at break, the effect of the Einar 101 addition (a bio-based dispersing aid additive) was analyzed. The role of the adhesion between the fiber and the matrix, coupled with a better fiber dispersion, was thus evaluated. Also, the consequences on the final mechanical properties (tensile and impact test) caused by the Einar addition were investigated. Analytical models were also applied in order to obtain an evaluation of the variation of the interfacial shear stress (IFSS) (strictly correlated to the fiber-matrix adhesion) caused by the Einar introduction. Furthermore, due to the very low aspect ratio of the Arbocel fibers, a suitable Bader and Boyer model variation was adopted in order to have a better quantitative estimation of the IFSS value.

Polyhydroxyalkanoates (PHAs) are a family of bio-based polyesters that have found different biomedical applications. Chitin and lignin, byproducts of fishery and plant biomass, show antimicrobial and anti-inflammatory activity on the nanoscale. Due to their polarities, chitin nanofibril (CN) and nanolignin (NL) can be assembled into micro-complexes, which can be loaded with bioactive factors, such as the glycyrrhetinic acid (GA) and CN-NL/GA (CLA) complexes, and can be used to decorate polymer surfaces. This study aims to develop completely bio-based and bioactive meshes intended for wound healing. Poly(3-hydroxybutyrate)/Poly(3-hydroxyoctanoate-co-3-hydroxydecanoate), P(3HB)/P(3HO-co-3HD) was used to produce films and fiber meshes, to be surface-modified via electrospraying of CN or CLA to reach a uniform distribution. P(3HB)/P(3HO-co-3HD) fibers with desirable size and morphology were successfully prepared and functionalized with CN and CLA using electrospinning and tested in vitro with human keratinocytes. The presence of CN and CLA improved the indirect antimicrobial and anti-inflammatory activity of the electrospun fiber meshes by downregulating the expression of the most important pro-inflammatory cytokines and upregulating human defensin 2 expression. This natural and eco-sustainable mesh is promising in wound healing applications.

In this paper the production of biopolymeric blends of poly(butylene succinate) PBS and plasticized whey protein (PWP), obtained from a natural by-product from cheese manufacturing, has been investigated for the production of films and/or sheets. In order to add the highest possible whey protein content, different formulations (from 30 to 50 wt.%) were studied. It was found that by increasing the amount of PWP added to PBS, the mechanical properties were worsened accordingly. This trend was attributed to the low compatibility between PWP and PBS. Consequently, the effect of the addition of soy lecithin and glycerol monostearate (GMS) as compatibilizers was investigated and compared to the use of whey protein modified with oleate and laurate groups obtained by Schotten-Baumann reaction. Soy lecithin and the Schotten-Baumann modified whey were effective in compatibilizing the PWP/PBS blend. In fact, a significant increase in elastic modulus, tensile strength and elongation at break with respect to the not compatibilized blend was observed and the length of aliphatic chains as well as the degree of modification of the Schotten–Baumann proteins affected the results. Moreover, thanks to DSC investigations, these compatibilizers were also found effective in increasing the PBS crystallinity.

The use of biopolyesters, as polymeric matrices, and natural fillers derived from wastes or by-products of food production to achieve biocomposites is nowadays a reality. The present paper aims to valorize mussel shells, 95% made of calcium carbonate (CaCO3), converting them into high-value added products. The objective of this work was to verify if CaCO3, obtained from Mediterranean Sea mussel shells, can be used as filler for a compostable matrix made of Polylactic acid (PLA) and Poly(butylene adipate-co-terephthalate) (PBAT). Thermal, mechanical, morphological and physical properties of these biocomposites were evaluated, and the micromechanical mechanism controlling stiffness and strength was investigated by analytical predictive models. The performances of these biocomposites were comparable with those of biocomposites produced with standard calcium carbonate. Thus, the present study has proved that the utilization of a waste, such as mussel shell, can become a resource for biocomposites production, and can be an effective option for further industrial scale-up.

Environmental impacts and consumer concerns have necessitated the study of bio-based materials as alternatives to petrochemicals for packaging applications. The purpose of this review is to summarize synthetic and non-synthetic materials feasible for packaging and textile applications, routes of upscaling, (industrial) applications, evaluation of sustainability, and end-of-life options. The outlined bio-based materials include polylactic acid, polyethylene furanoate, polybutylene succinate, and non-synthetically produced polymers such as polyhydrodyalkanoate, cellulose, starch, proteins, lipids, and waxes. Further emphasis is placed on modification techniques (coating and surface modification), biocomposites, multilayers, and additives used to adjust properties especially for barriers to gas and moisture and to tune their biodegradability. Overall, this review provides a holistic view of bio-based packaging material including processing, and an evaluation of the sustainability of and options for recycling. Thus, this review contributes to increasing the knowledge of available sustainable bio-based packaging material and enhancing the transfer of scientific results into applications.

The world is confronted with the depletion of natural resources due to their unsustainable use and the increasing size of populations. In this context, the efficient use of by-products, residues and wastes generated from agro-industrial and food processing opens the perspective for a wide range of benefits. In particular, legume residues are produced yearly in very large amounts and may represent an interesting source of plant proteins that contribute to satisfying the steadily increasing global protein demand. Innovative biorefinery extraction cascades may also enable the recovery of further bioactive molecules and fibers from these insufficiently tapped biomass streams. This review article gives a summary of the potential for the valorization of legume residual streams resulting from agro-industrial processing and more particularly for pea, green bean and chickpea by-products/wastes. Valuable information on the annual production volumes, geographical origin and state-of-the-art technologies for the extraction of proteins, fibers and other bioactive molecules from this source of biomass, is exhaustively listed and discussed. Finally, promising applications, already using the recovered fractions from pea, bean and chickpea residues for the formulation of feed, food, cosmetic and packaging products, are listed and discussed.

The objective of this study was the preparation and physico-chemical, mechanical, biological, and functional characterization of a multifunctional coating for an innovative, fully implantable device. The multifunctional coating was designed to have three fundamental properties: adhesion to device, close mechanical resemblance to human soft tissues, and control of the inflammatory response and tissue repair process. This aim was fulfilled by preparing a multilayered coating based on three components: a hydrophilic primer to allow device adhesion, a poly(vinyl alcohol) hydrogel layer to provide good mechanical compliance with the human tissue, and a layer of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) fibers. The use of biopolymer fibers offered the potential for a long-term interface able to modulate the release of an anti-inflammatory drug (dexamethasone), thus contrasting acute and chronic inflammation response following device implantation. Two copolymers, poly(vinyl acetate-acrylic acid) and poly(vinyl alcohol-acrylic acid), were synthetized and characterized using thermal analysis (DSC, TGA), Fourier transform infrared spectroscopy (FT-IR chemical imaging), in vitro cell viability, and an adhesion test. The resulting hydrogels were biocompatible, biostable, mechanically compatible with soft tissues, and able to incorporate and release the drug. Finally, the multifunctional coating showed a good adhesion to titanium substrate, no in vitro cytotoxicity, and a prolonged and controlled drug release.

A device (prototype) with a working volume of 200 L was used to deplete olive mill wastewater (OMW) of polyphenols. The OMW transformed into feedstock by means of the device was then used for feeding a lab-scale photobioreactor, just for testing the production of bioH2. The main novelty of this prototype consists in the combination of several adsorbent matrices and the exploitation of their synergic action. In this investigation, three matrices have been used: active carbon, Azolla and zeolite. The device was operated at an olive oil company located in the heart of the Chianti zone (Province of Florence, Italy). The efficiency of polyphenol removal obtained using the device was ≥96%. The multi-matrix effluent (MMeff) generated was then used to obtain three different culture broths containing 25%, 50% and 100% of MMeff, respectively. The diluted (with water) culture broths were suitable for hydrogen generation, with the highest hydrogen production rate (12.7 mL H2/Lculture/h) being obtained using 50% MMeff. The hydrogen yields were: 334 mL H2/L of MMeff, when feeding the photofermenter with pure effluent (100%); 1308 mL H2/L of MMeff, with the half-diluted effluent (50%, v/v); and 432 mL H2/L of MMeff, with the highest-diluted effluent (25%, v/v).

In this work, biocomposites based on poly(lactic acid) (PLA) and short flax fibers (10−40 wt.%) were produced by extrusion and characterized in terms of thermal, mechanical, morphological, and thermo-mechanical properties. Analytical models were adopted to predict the tensile properties (stress at break and elastic modulus) of the composites, and to assess the matrix/fiber interface adhesion. The resulting composites were easily processable by extrusion and injection molding up to 40 wt.% of flax fibers. It was observed that despite any superficial treatment of fibers, the matrix/fiber adhesion was found to be sufficiently strong to ensure an efficient load transfer between the two components obtaining composites with good mechanical properties. The best mechanical performance, in terms of break stress (66 MPa), was obtained with 20 wt.% of flax fibers. The flax fiber acted also as nucleating agent for PLA, leading to an increment of the composite stiffness and, at 40 wt.% of flax fibers, improving the elastic modulus decay near the PLA glass transition temperature.

Consumer awareness about the damages that plastic packaging waste cause to the environment, coupled with bio-economy and circular economy policies, are pushing plastic packaging versus the use of bio-based and biodegradable materials. In this contest, even cosmetic packaging is looking for sustainable solutions, and research is focusing on modifying bio-based and biodegradable polymers to meet the challenging requirements for cosmetic preservation, while maintaining sustainability and biodegradability. Several bio-based and biodegradable polymers such as poly(lactic acid), polyhydroxyalkanoates, polysaccharides, etc., are available, and some first solutions for both rigid and flexible packaging are already present on the market, while many others are under study and optimization. A fruitful cooperation among researchers and industries will drive the cosmetic sector toward being more ecological and contributing to save our environment.

The thermal, mechanical and viscoelastic properties of biocomposites of poly(lactic acid) (PLA) with 20 wt.% of potato pulp powder were investigated. The potato pulp powder utilized is a byproduct from the production and extraction of starch. The results showed that the potato pulp powder does not act as reinforcement, but as filler for PLA, due to an unfavorable aspect ratio and the irregular shape of the particles. In order to improve the mechanical response of the PLA/potato pulp powder biocomposites, surface treatment of the potato pulp particles with bio-based and petroleum-based waxes was investigated. This treatment was found to improve the properties of the biocomposites, enhancing the adhesion between the PLA based polymeric matrix and the potato pulp fibers. The best result is obtained with a petroleum-based wax, but also the bio-based waxes lead to good mechanical properties of the biocomposite. Thus, the addition to PLA of potato pulp powder, treated with waxes, appears a method able to (i) utilize and valorize an abundant agro-food biomass such as potato pulp, according to the principles of circular economy, (ii) favor the production of articles with properties valuable for practical applications, and (iii) reduce the cost of the final products, considering the relatively high cost of PLA.

The circular economy policy and the interest for sustainable material are inducing a constant expansion of the bio-composites market. The opportunity of using natural fibers in bio-based and biodegradable polymeric matrices, derived from industrial and/or agricultural waste, represents a stimulating challenge in the replacement of traditional composites based on fossil sources. The coupling of bioplastics with natural fibers in order to lower costs and promote degradability is one of the primary objectives of research, above all in the packaging and agricultural sectors where large amounts of non-recyclable plastics are generated, inducing a serious problem for plastic disposal and potential accumulation in the environment. Among biopolymers, poly(lactic acid) (PLA) is one of the most used compostable, bio-based polymeric matrices, since it exhibits process ability and mechanical properties compatible with a wide range of applications. In this study, two types of cellulosic fibers were processed with PLA in order to obtain bio-composites with different percentages of microfibers (5%, 10%, 20%). The mechanical properties were evaluated (tensile and impact test), and analytical models were applied in order to estimate the adhesion between matrix and fibers and to predict the material’s stiffness. Understanding these properties is of particular importance in order to be able to tune and project the final characteristics of bio-composites.

The thermal and mechanical properties of biocomposites of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) containing 5 wt % of valerate units, with 20 wt % of potato pulp powder were investigated in order (i) to obtain information on possible miscibility/compatibility between the biopolymers and the potato pulp, and (ii) to quantify how the addition of this filler modifies the properties of the polymeric material. The potato pulp powder utilized is a residue of processing for the production and extraction of starch. The final aim of this study is the preparation of PHBV based materials with reduced cost, thanks to biomass valorization, in agreement with the circular economy policy, as result of the incorporation of agricultural organic waste. The results showed that the potato pulp powder does not act as reinforcement, but rather as filler for the PHBV polymeric matrix. A moderate loss in mechanical properties is detected (decrease in elastic modulus, tensile strength and elongation at break), which regardless still meets the technical requirements indicated for rigid packaging production. In order to improve the mechanical response of the PHBV/potato pulp powder biocomposites, surface treatment of the potato pulp powder with bio-based and petroleum-based waxes was investigated. Good enhancement of the mechanical properties was achieved with the natural carnauba and bee waxes.

The thermal, mechanical, and rheological properties of biocomposites of poly(lactic acid) (PLA) with potato pulp powder were investigated in order to (1) quantify how the addition of this filler modifies the structure of the polymeric material and (2) to obtain information on the possible miscibility and compatibility between PLA and the potato pulp. The potato pulp powder utilized is a residue of the processing for the production and extraction of starch. The study was conducted by analyzing the effect of the potato pulp concentration on the thermal, mechanical, and rheological properties of the biocomposites. The results showed that the potato pulp powder does not act as reinforcement but as filler for the PLA polymeric matrix. A progressive decrease in elastic modulus, tensile strength, and elongation at break was observed with increasing the potato pulp percentage. This moderate loss of mechanical properties, however, still meets the technical requirements indicated for the production of rigid packaging items. The incorporation of potato pulp powder to PLA offers the possibility to reduce the cost of the final products and promotes a circular economy approach for the valorization of agro-food waste biomass.

Chitin-nanofibrils are obtained in water suspension at low concentration, as nanoparticles normally are, to avoid their aggregation. The addition of the fibrils in molten PLA during extrusion is thus difficult and disadvantageous. In the present paper, the use of poly(ethylene glycol) (PEG) is proposed to prepare a solid pre-composite by water evaporation. The pre-composite is then added to PLA in the extruder to obtain transparent nanocomposites. The amount of PEG and chitin nanofibrils was varied in the nanocomposites to compare the reinforcement due to nanofibrils and plasticization due to the presence of PEG, as well as for extrapolating, where possible, the properties of reinforcement due to chitin nanofibrils exclusively. Thermal and morphological properties of nanocomposites were also investigated. This study concluded that chitin nanofibrils, added as reinforcing filler up to 12% by weight, do not alter the properties of the PLA based material; hence, this additive can be used in bioplastic items mainly exploiting its intrinsic anti-microbial and skin regenerating properties.

In this work, composites based on poly(3-hydroxybutyrate-3-hydroxyvalerate) (PHB-HV) and waste wood sawdust (SD) fibers, a byproduct of the wood industry, were produced by melt extrusion and characterized in terms of processability, thermal stability, morphology, and mechanical properties in order to discriminate the formulations suitable for injection molding. Given their application in agriculture and/or plant nursery, the biodegradability of the optimized composites was investigated under controlled composting conditions in accordance with standard methods (ASTM D5338-98 and ISO 20200-2004). The optimized PHB-HV/SD composites were used for the production of pots by injection molding and their performance was qualitatively monitored in a plant nursery and underground for 14 months. This study presents a sustainable option of valuation of wood factory residues and lowering the production cost of PHB-HV-based compounds without affecting their mechanical properties, improving their impact resistance and biodegradability rates in terrestrial environments.

Poly(lactic acid)/triacetine plasticized cellulose acetate (PLA/pCA) blends were prepared by extrusion at two different temperatures and tetrabutylammonium tetraphenyl borate (TBATPB) was added as a transesterification catalyst to reactively promote the formation of PLA-CA copolymer during the reactive extrusion. The occurrence of chain scission in the PLA phase and branching/crosslinking in the CA phase in the presence of TBATPB, resulting also in a darkening of the material, were demonstrated by studying torque measurements and by performing proper thermogravimetric tests on CA with the different additives. Tensile and impact tests onto the blends prepared at the lower temperature showed better properties than the ones obtained at a higher temperature. Then, the mechanical properties of PLA/plasticized cellulose acetate (pCA) blends prepared at the lower temperature were investigated as a function of the content of plasticized CA in the blend. A range of compositions was observed where blends exhibited improved impact properties with respect to pure PLA without a significant decrease in their elastic modulus. The study of the phase morphology of the blends revealed that the occurrence of reactive compatibilization did not significantly affect the phase distribution. In general, fibrillar CA particles were formed in the PLA matrix during extrusion, thus allowing the preparation of CA fibre reinforced composites. The trend of morphology as a function of the composition and processing conditions was then discussed by considering the evolution of phase morphology in immiscible polymer blends.

In order to produce sustainable, bio-based and highly biodegradable materials, composites based on poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) and fibers of Posidonia oceanica (PO), a dominant Mediterranean seagrass, were produced by simple melt mixing and characterized in terms of thermal stability, morphology and rheological/mechanical properties. In view of their potential application in marine environments, degradation of the developed composites was evaluated under simulated and real marine environmental conditions for 1 year. Using 10 wt % of acetyl tributyl citrate (ATBC) as a plasticizer, smooth processing was achieved for up to 30 wt % of PO fibers, despite the reduction of the melt fluidity observed with increasing fiber loading. The tensile modulus slightly increased (from 2 to 2.4 GPa) while the tensile strength and the elongation decreased (from 23.6 to 21.5 MPa and from 3.2 to 1.9%, respectively) by increasing the PO fiber content from 0 to 30 wt %. Interestingly, the impact resistance of the composites increased with the increasing of the PO content: the Charpy’s impact energy increased from 3.6 (without fiber) to 4.4 kJ/m2 for the composite with 30 wt %. The results of the aerobic biodegradation under simulated marine conditions showed that the presence of PO fibers favored the physical disintegration of the composite increasing the biodegradation rate of the polymeric matrix: after 216 days, the composite with 20 wt % PO fibers showed a biodegradability of about 30% compared to 20% of the composite without fibers. Under real marine conditions, the specimens containing PO fibers showed higher weight losses and deterioration of tensile properties compared to those without fibers. Presumably, biodegradation occurred after colonization of the specimen, and the specimens with 20 wt % PO fibers showed well-developed biofilm consisting of bacteria and fungi on the surface after only 3 months of incubation in marine sediments, unlike the no-fiber specimens. Consequently, the persistence of an adequate mechanical performance for a relatively long period (1 year), due to a moderate rate of biodegradation in the marine environment, make the developed PHBV/PO composites particularly suitable for the production of relatively low-cost and biodegradable items which are usable in the sea and/or sand dunes, increasing the market opportunities for biopolymers such as PHBV and, at the same time, finding an eco-sustainable valorization for the PO fibrous residues accumulated in large quantities on Mediterranean beaches, which represents a problem for coastal municipalities.

Poly(lactic acid) (PLA) was melt mixed in a laboratory extruder with poly(butylene adipate-co-terephthalate) (PBAT) and poly(butylene succinate) (PBS) in the presence of polypropylene glycol di glycidyl ether (EJ400) that acted as both plasticizer and compatibilizer. The process was then scaled up in a semi-industrial extruder preparing pellets having different content of a nucleating agent (LAK). All of the formulations could be processed by blowing extrusion and the obtained films showed mechanical properties dependent on the LAK content. In particular the tearing strength showed a maximum like trend in the investigated composition range. The films prepared with both kinds of blends showed a tensile strength in the range 12–24 MPa, an elongation at break in the range 150–260% and a significant crystallinity.

Multilayer plastic films provide a range of properties, which cannot be obtained from monolayer films but, at present, their recyclability is an open issue and should be improved. Research to date has shown the possibility of using whey protein as a layer material with the property of acting as an excellent barrier against oxygen and moisture, replacing petrochemical non-recyclable materials. The innovative approach of the present research was to achieve the recyclability of the substrate films by separating them, with a simple process compatible with industrial procedures, in order to promote recycling processes leading to obtain high value products that will beneficially impact the packaging and food industries. Hence, polyethyleneterephthalate (PET)/polyethylene (PE) multi-layer film was prepared based on PET coated with a whey protein layer, and then the previous structure was laminated with PE. Whey proteins, constituting the coating, can be degraded by enzymes so that the coating films can be washed off from the plastic substrate layer. Enzyme types, dosage, time, and temperature optima, which are compatible with procedures adopted in industrial waste recycling, were determined for a highly-efficient process. The washing of samples based on PET/whey and PET/whey/PE were efficient when performed with enzymatic detergent containing protease enzymes, as an alternative to conventional detergents used in recycling facilities. Different types of enzymatic detergents tested presented positive results in removing the protein layer from the PET substrate and from the PET/whey/PE multilayer films at room temperature. These results attested to the possibility of organizing the pre-treatment of the whey-based multilayer film by washing with different available commercial enzymatic detergents in order to separate PET and PE, thus allowing a better recycling of the two different polymers. Mechanical properties of the plastic substrate, such as stress at yield, stress and elongation at break, evaluated by tensile testing on films before and after cleaning, were are not significantly affected by washing with enzymatic detergents.