Development and Characterisation of Composites Prepared from PHBV Compounded with Organic Waste Reinforcements, and Their Soil Biodegradation.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a biobased and biodegradable polymer. This polymer is considered promising, but it is also rather expensive. The objective of this study was to compound PHBV with three different organic fillers considered waste: human hair waste (HHW), sawdust (SD) and chitin from shrimp shells. Thus, the cost of the biopolymer is reduced, and, at the same time, waste materials are valorised into something useful. The composites prepared were characterised by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile strength and scanning electron micrograph (SEM). Tests showed that chitin and HHW did not have a reinforcing effect on tensile strength while the SD increased the tensile strength at break to a certain degree. The biodegradation of the different composites was evaluated by a soil burial test for five months. The gravimetric test showed that neat PHBV was moderately degraded (about 5% weight loss) while reinforcing the polymer with organic waste clearly improved the biodegradation. The strongest biodegradation was achieved when the biopolymer was compounded with HHW (35% weight loss). The strong biodegradation of HHW was further demonstrated by characterisation by Fourier-transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (NMR). Characterisation by SEM showed that the surfaces of the biodegraded samples were eroded.

Application of Immersed Membrane Bioreactor for Semi-Continuous Production of Polyhydroxyalkanoates from Organic Waste-Based Volatile Fatty Acids.

Volatile fatty acids (VFAs) appear to be an economical carbon feedstock for the cost-effective production of polyhydroxyalkanoates (PHAs). The use of VFAs, however, could impose a drawback of substrate inhibition at high concentrations, resulting in low microbial PHA productivity in batch cultivations. In this regard, retaining high cell density using immersed membrane bioreactor (iMBR) in a (semi-) continuous process could enhance production yields. In this study, an iMBR with a flat-sheet membrane was applied for semi-continuous cultivation and recovery of Cupriavidus necator in a bench-scale bioreactor using VFAs as the sole carbon source. The cultivation was prolonged up to 128 h under an interval feed of 5 g/L VFAs at a dilution rate of 0.15 (d-1), yielding a maximum biomass and PHA production of 6.6 and 2.8 g/L, respectively. Potato liquor and apple pomace-based VFAs with a total concentration of 8.8 g/L were also successfully used in the iMBR, rendering the highest PHA content of 1.3 g/L after 128 h of cultivation. The PHAs obtained from both synthetic and real VFA effluents were affirmed to be poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a crystallinity degree of 23.8 and 9.6%, respectively. The application of iMBR could open an opportunity for semi-continuous production of PHA, increasing the feasibility of upscaling PHA production using waste-based VFAs.

Application of Fungal Biomass for the Development of New Polylactic Acid-Based Biocomposites.

Fungal biomass (FB), a by-product of the fermentation processes produced in large volumes, is a promising biomaterial that can be incorporated into poly(lactic acid) (PLA) to develop enhanced biocomposites that fully comply with the biobased circular economy concept. The PLA/FB composites, with the addition of triethyl citrate (TEC) as a biobased plasticizer, were fabricated by a microcompounder at 150 °C followed by injection molding. The effects of FB (10 and 20 wt %) and TEC (5, 10, and 15 wt %) contents on the mechanical, thermal and surface properties of the biocomposites were analyzed by several techniques. The PLA/FB/TEC composites showed a rough surface in their fracture section. A progressive decrease in tensile strength and Young's modulus was observed with increasing FB and TEC, while elongation at break and impact strength started to increase. The neat PLA and biocomposite containing 10% FB and 15% TEC exhibited the lowest (3.84%) and highest (224%) elongation at break, respectively. For all blends containing FB, the glass transition, crystallization and melting temperatures were shifted toward lower values compared to the neat PLA. The incorporation of FB to PLA thus offers the possibility to overcome one of the main drawbacks of PLA, which is brittleness.

Production of polyhydroxyalkanoates (PHAs) by Bacillus megaterium using food waste acidogenic fermentation-derived volatile fatty acids.

High production costs still hamper fast expansion of commercial production of polyhydroxyalkanoates (PHAs). This problem is greatly related to the cultivation medium which accounts for up to 50% of the whole process costs. The aim of this research work was to evaluate the potential of using volatile fatty acids (VFAs), derived from acidogenic fermentation of food waste, as inexpensive carbon sources for the production of PHAs through bacterial cultivation. Bacillus megaterium could assimilate glucose, acetic acid, butyric acid, and caproic acid as single carbon sources in synthetic medium with maximum PHAs production yields of 9-11%, on a cell dry weight basis. Single carbon sources were then replaced by a mixture of synthetic VFAs and by a VFAs-rich stream from the acidogenic fermentation of food waste. After 72 h of cultivation, the VFAs were almost fully consumed by the bacterium in both media and PHAs production yields of 9-10%, on cell dry weight basis, were obtained. The usage of VFAs mixture was found to be beneficial for the bacterial growth that tackled the inhibition of propionic acid, iso-butyric acid, and valeric acid when these volatile fatty acids were used as single carbon sources. The extracted PHAs were revealed to be polyhydroxybutyrate (PHB) by characterization methods of Fourier-transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The obtained results proved the possibility of using VFAs from acidogenic fermentation of food waste as a cheap substrate to reduce the cost of PHAs production.

Synthesis of Lactic Acid-Based Thermosetting Resins and Their Ageing and Biodegradability.

The present work is focused on the synthesis of bio-based thermoset polymers and their thermo-oxidative ageing and biodegradability. Toward this aim, bio-based thermoset resins with different chemical architectures were synthesized from lactic acid by direct condensation with ethylene glycol, glycerol and pentaerythritol. The resulting branched molecules with chain lengths (n) of three were then end-functionalized with methacrylic anhydride. The chemical structures of the synthesized lactic acid derivatives were confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR) and Fourier transform infrared spectroscopy (FT-IR) before curing. To evaluate the effects of structure on their properties, the samples were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and the tensile testing. The samples went through thermo-oxidative ageing and biodegradation; and their effects were investigated. FT-IR and 1H-NMR results showed that three different bio-based resins were synthesized using polycondensation and end-functionalization. Lactic acid derivatives showed great potential to be used as matrixes in polymer composites. The glass transition temperature of the cured resins ranged between 44 and 52 °C. Pentaerythritol/lactic acid cured resin had the highest tensile modulus and it was the most thermally stable among all three resins. Degradative processes during ageing of the samples lead to the changes in chemical structures and the variations in Young's modulus. Microscopic images showed the macro-scale surface degradation on a soil burial test.

Hydrophobic Shape-Memory Biocomposites from Tung-Oil-Based Bioresin and Onion-Skin-Derived Nanocellulose Networks.

The fabrication of smart biocomposites from sustainable resources that could replace today's petroleum-derived polymer materials is a growing field of research. Here, we report preparation of novel biocomposites using nanocellulose networks extracted from food residue (onion skin) and a vegetable oil-based bioresin. The resin was synthesized via the Diels-Alder reaction between furfuryl methacrylate and tung oil at various ratios of the components. The onion-skin-extracted cellulose nanofiber and cellulose nanocrystal networks were then impregnated with the resins yielding biocomposites that exhibited improved mechanical strength and higher storage modulus values. The properties of the resins, as well as biocomposites, were affected by the resin compositions. A 190-240-fold increase in mechanical strength was observed in the cellulose nanofiber (CNF) and cellulose nanocrystal (CNC)-reinforced biocomposites with low furfuryl methacrylate content. The biocomposites exhibited interesting shape-memory behavior with 80-96% shape recovery being observed after 7 creep cycles.

Synthesis and Properties of Thermosets from Tung Oil and Furfuryl Methacrylate.

This work focuses on the development of cross-linked polymer from a highly unsaturated vegetable oil, tung oil (TO) and a bio-based acrylate, furfuryl methacrylate (FMA). The presence of a high degree of unsaturated carbon-carbon bonding in TO makes it a suitable precursor for polymer synthesis. Using this advantage of TO, in this work, we have synthesised a cross-linked polymer from TO and FMA through free radical polymerisation followed by Diels-Alder (DA) reaction. Successful incorporation of both of the raw materials and the two chemical reactions was shown using Fourier-transform infrared (FTIR) and Raman spectroscopy. The development of cross-linked structure was analysed through thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA).

Recycling strategies for polyhydroxyalkanoate-based waste materials: An overview.

The plastics market is dominated by fossil-based polymers, but their gradual replacement by bioplastics (e.g., polyhydroxyalkanoates) is occurring. However, recycling strategies need to be developed to truly unveil the impact of bioplastics on waste accumulation. This review provides a state of the art of recycling strategies investigated for polyhydroxyalkanoate-based polymers and proposes future research avenues. Research on mechanical and chemical recycling is dominated by the use of extrusion and pyrolysis, respectively, while that on biodegradation of polyhydroxyalkanoates is related to soil and aquatic samples, and to anaerobic digestion towards biogas production. Research gaps exist in the relationships between polymer composition and ease of use of all recycling strategies investigated. This is of utmost importance since it will influence the need for separation at the source. Therefore, research emphasis needs to be given to the area to follow the continuous improvement of the process economics towards widespread commercial production of polyhydroxyalkanoates.

Development of Bio-Based Films and 3D Objects from Apple Pomace.

Extensive quantities of apple pomace are generated annually but its disposal is still challenging. This study addresses this issue by introducing a new, environmentally-friendly approach for the production of sustainable biomaterials from apple pomace, containing 55.47% free sugars and a water insoluble fraction, containing 29.42 ± 0.44% hemicelluloses, 38.99 ± 0.42% cellulose, and 22.94 ± 0.12% lignin. Solution casting and compression molding were applied to form bio-based films and 3D objects (i.e., fiberboards), respectively. Using glycerol as plasticizer resulted in highly compact films with high tensile strength and low elongation (16.49 ± 2.54 MPa and 10.78 ± 3.19%, respectively). In contrast, naturally occurring sugars in the apple pomace showed stronger plasticizing effect in the films and resulted in a fluffier and connected structure with significantly higher elongation (37.39 ± 10.38% and 55.41 ± 5.38%, respectively). Benefiting from the self-binding capacity of polysaccharides, fiberboards were prepared by compression molding at 100 °C using glycerol or naturally occurring sugars, such as plasticizer. The obtained fiberboards exhibited tensile strength of 3.02⁻5.79 MPa and elongation of 0.93%⁻1.56%. Possible applications for apple pomace biomaterials are edible/disposable tableware or food packaging.

The Effect of Glycerol, Sugar, and Maleic Anhydride on Pectin-Cellulose Thin Films Prepared from Orange Waste.

This study was conducted to improve the properties of thin films prepared from orange waste by the solution casting method. The main focus was the elimination of holes in the film structure by establishing better cohesion between the major cellulosic and pectin fractions. For this, a previously developed method was improved first by the addition of sugar to promote pectin gelling, then by the addition of maleic anhydride. Principally, maleic anhydride was introduced to the films to induce cross-linking within the film structure. The effects of concentrations of sugar and glycerol as plasticizers and maleic anhydride as a cross-linking agent on the film characteristics were studied. Maleic anhydride improved the structure, resulting in a uniform film, and morphology studies showed better adhesion between components. However, it did not act as a cross-linking agent, but rather as a compatibilizer. The middle level (0.78%) of maleic anhydride content resulted in the highest tensile strength (26.65 ± 3.20 MPa) at low (7%) glycerol and high (14%) sugar levels and the highest elongation (28.48% ± 4.34%) at high sugar and glycerol levels. To achieve a uniform film surface with no holes present, only the lowest (0.39%) level of maleic anhydride was necessary.

Anaerobic degradation of bioplastics: A review.

Anaerobic digestion (AD) of the organic fraction of municipal solid waste (OFMSW), leading to renewable energy production in the form of methane, is a preferable method for dealing with the increasing amount of waste. Food waste is separated at the source in many countries for anaerobic digestion. However, the presence of plastic bags is a major challenge for such processes. This study investigated the anaerobic degradability of different bioplastics, aiming at potential use as collecting bags for the OFMSW. The chemical composition of the bioplastics and the microbial community structure in the AD process affected the biodegradation of the bioplastics. Some biopolymers can be degraded at hydraulic retention times usually applied at the biogas plants, such as poly(hydroxyalkanoate)s, starch, cellulose and pectin, so no possible contamination would occur. In the future, updated standardization of collecting bags for the OFMSW will be required to meet the requirements of effective operation of a biogas plant.