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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.

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.

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.

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.

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.