Recent advances in the relationships between biofilms and microplastics in natural environments.

Plastic pollution in the form of microplastics (MPs), poses a significant threat to natural ecosystems, with detrimental ecological, social, and economic impacts. This review paper aims to provide an overview of the existing research on the interaction between microbial biofilms and MPs in natural environments. The review begins by outlining the sources and types of MPs, emphasizing their widespread presence in marine, freshwater, and terrestrial ecosystems. It then discusses the formation and characteristics of microbial biofilms on MPs surfaces, highlighting their role in altering the physicochemical properties of MPs and facilitating processes such as vertical transport, biodegradation, dispersion of microorganisms, and gene transfer. Different methods used to assess these interactions are discussed, including microbiological and physicochemical characterization. Current gaps and challenges in understanding the complex relationships between biofilms and MPs are identified, highlighting the need for further research to elucidate the mechanisms underlying these complex interactions and to develop effective mitigation strategies. Innovative solutions, including bioremediation techniques and their combination with other strategies, such as nanotechnology, advanced filtration technologies, and public awareness campaigns, are proposed as promising approaches to address the issue of MPs pollution. Overall, this review underscores the urgent need for a multidisciplinary approach to combating MPs pollution, combining scientific research, technological innovation, and public engagement to safeguard the health and integrity of natural ecosystems.

Microbiological Characterization of the Biofilms Colonizing Bioplastics in Natural Marine Conditions: A Comparison between PHBV and PLA.

Biodegradable polymers offer a potential solution to marine pollution caused by plastic waste. The marine biofilms that formed on the surfaces of poly(lactide acid) (PLA) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were studied. Bioplastics were exposed for 6 months to marine conditions in the Mediterranean Sea, and the biofilms that formed on their surfaces were assessed. The presence of specific PLA and PHBV degraders was also studied. PHBV showed extensive areas with microbial accumulations and this led to higher microbial surface densities than PLA (4.75 vs. 5.16 log CFU/cm2). Both polymers' surfaces showed a wide variety of microbial structures, including bacteria, fungi, unicellular algae and choanoflagellates. A high bacterial diversity was observed, with differences between the two polymers, particularly at the phylum level, with over 70% of bacteria affiliated to three phyla. Differences in metagenome functions were also detected, revealing a higher presence of proteins involved in PHBV biodegradation in PHBV biofilms. Four bacterial isolates belonging to the Proteobacteria class were identified as PHBV degraders, demonstrating the presence of species involved in the biodegradation of this polymer in seawater. No PLA degraders were detected, confirming its low biodegradability in marine environments. This was a pilot study to establish a baseline for further studies aimed at comprehending the marine biodegradation of biopolymers.

Effect of the Presence of Lignin from Woodflour on the Compostability of PHA-Based Biocomposites: Disintegration, Biodegradation and Microbial Dynamics.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) has gained attention as a possible substitute for conventional polymers that could be integrated into the organic recycling system. Biocomposites with 15% of pure cellulose (TC) and woodflour (WF) were prepared to analyze the role of lignin on their compostability (58 °C) by tracking the mass loss, CO2 evolution, and the microbial population. Realistic dimensions for typical plastic products (400 µm films), as well as their service performance (thermal stability, rheology), were taken into account in this hybrid study. WF showed lower adhesion with the polymer than TC and favored PHBV thermal degradation during processing, also affecting its rheological behavior. Although all materials disintegrated in 45 days and mineralized in less than 60 days, lignin from woodflour was found to slow down the bioassimilation of PHBV/WF by limiting the access of enzymes and water to easier degradable cellulose and polymer matrix. According to the highest and the lowest weight loss rates, TC incorporation allowed for higher mesophilic bacterial and fungal counts, while WF seemed to hinder fungal growth. At the initial steps, fungi and yeasts seem to be key factors in facilitating the later metabolization of the materials by bacteria.

Biodegradable blends from bacterial biopolyester PHBV and bio-based PBSA: Study of the effect of chain extender on the thermal, mechanical and morphological properties.

Being aware of the global problem of plastic pollution, our society is claiming new bioplastics to replace conventional polymers. Balancing their mechanical performance is required to increase their presence in the market. Brittleness of bacterial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was attempted to be decreased by melt blending with flexible starch-based poly(butylene succinate-co-butylene adipate) (PBSA). An epoxy-functionalized chain extender was used to enhance interaction between both immiscible biopolyesters. Mechanical performance, morphology, rheology, and crystallization behavior of injection-molded PHBV-PBSA blends (70-30, 50-50, and 30-70 wt%) were assessed in the presence and absence of the chain extender. Crystallization of PHBV was hindered, which was reflected in the improvement of mechanical properties. When PBSA >50 %, the homogeneity of results increased within the same sample while for PHBV-PBSA 70-30 wt% the elongation was 45 % higher. During the flexural test, it changed from brittle to non-breakable. The additive did not change the type of morphology developed by each blend nor the toughening mechanisms, so impact strength was barely affected. However, it reduced the size of dispersed phase domains due to a viscosity change, improving their processability. The higher the PHBV in the blend, the higher the effect of the chain extender.

Valorization of Agricultural Waste Lignocellulosic Fibers for Poly(3-Hydroxybutyrate-Co-Valerate)-Based Composites in Short Shelf-Life Applications.

Biocircularity could play a key role in the circular economy, particularly in applications where organic recycling (composting) has the potential to become a preferred waste management option, such as food packaging. The development of fully biobased and biodegradable composites could help reduce plastic waste and valorize agro-based residues. In this study, extruded films made of composites of polyhydroxybutyrate-co-valerate (PHBV) and lignocellulosic fibers, namely almond shell (AS) and Oryzite® (OR), a polymer hybrid composite precursor, have been investigated. Scanning electron microscopy (SEM) analysis revealed a weak fiber-matrix interfacial interaction, although OR composites present a better distribution of the fiber and a virtually lower presence of "pull-out". Thermogravimetric analysis showed that the presence of fibers reduced the onset and maximum degradation temperatures of PHBV, with a greater reduction observed with higher fiber content. The addition of fibers also affected the melting behavior and crystallinity of PHBV, particularly with OR addition, showing a decrease in crystallinity, melting, and crystallization temperatures as fiber content increased. The mechanical behavior of composites varied with fiber type and concentration. While the incorporation of AS results in a reduction in all mechanical parameters, the addition of OR leads to a slight improvement in elongation at break. The addition of fibers improved the thermoformability of PHBV. In the case of AS, the improvement in the processing window was achieved at lower fiber contents, while in the case of OR, the improvement was observed at a fiber content of 20%. Biodisintegration tests showed that the presence of fibers promoted the degradation of the composites, with higher fiber concentrations leading to faster degradation. Indeed, the time of complete biodisintegration was reduced by approximately 30% in the composites with 20% and 30% AS.

Electric Conductivity Study of Porous Polyvinyl Alcohol/Graphene/Clay Aerogels: Effect of Compression.

In this work, poly(vinyl alcohol) (PVOH)/graphene (GN) oxide/clay aerogels were prepared using montmorillonite (MMT) and kaolinite (KLT) as fillers. This work paves the way for the development of aerogels filled with MMT or KLT with high conductivity. The mechanical properties of the polymer/clay aerogels are enhanced by incorporating GN into these systems. These composite materials have an enhanced thermal stability, and the combination of PVOH and GN leads to interconnected channels which favored the conductivity when a clay (MMT or KLT) is added to the mixed PVOH/GN matrix. However, after compressing the samples, the conductivities drastically decreased. These results show that the design of solid MMT/GN and KLT/GN composites as aerogels allows maximizing the space utilization of the electrode volume to achieve unhindered ion transport, which seems contrary to the general design principle of electrode materials where a suitable porous structure is desired, such as in our uncompressed samples. These findings also demonstrate the potential of these materials in electrodes, sensors, batteries, pressure-sensing applications, and supercapacitors.

Development and Characterization of Fully Renewable and Biodegradable Polyhydroxyalkanoate Blends with Improved Thermoformability.

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

In Service Performance of Toughened PHBV/TPU Blends Obtained by Reactive Extrusion for Injected Parts.

Moving toward a more sustainable production model based on a circular economy, biopolymers are considered as one of the most promising alternatives to reduce the dependence on oil-based plastics. Polyhydroxybutyrate-co-valerate (PHBV), a bacterial biopolyester from the polyhydroxialkanoates (PHAs) family, seems to be an attractive candidate to replace commodities in many applications such as rigid packaging, among others, due to its excellent overall physicochemical and mechanical properties. However, it presents a relatively poor thermal stability, low toughness and ductility, thus limiting its applicability with respect to other polymers such as polypropylene (PP). To improve the performance of PHBV, reactive blending with an elastomer seems to be a proper cost-effective strategy that would lead to increased ductility and toughness by rubber toughening mechanisms. Hence, the objective of this work was the development and characterization of toughness-improved blends of PHBV with thermoplastic polyurethane (TPU) using hexamethylene diisocyanate (HMDI) as a reactive extrusion agent. To better understand the role of the elastomer and the compatibilizer, the morphological, rheological, thermal, and mechanical behavior of the blends were investigated. To explore the in-service performance of the blends, mechanical and long-term creep characterization were conducted at three different temperatures (-20, 23, 50 °C). Furthermore, the biodegradability in composting conditions has also been tested. The results showed that HMDI proved its efficiency as a compatibilizer in this system, reducing the average particle size of the TPU disperse phase and enhancing the adhesion between the PHBV matrix and TPU elastomer. Although the sole incorporation of the TPU leads to slight improvements in toughness, the compatibilizer plays a key role in improving the overall performance of the blends, leading to a clear improvement in toughness and long-term behavior.

Role of Plasticizers on PHB/bio-TPE Blends Compatibilized by Reactive Extrusion.

Poly(hydroxybutyrate) (PHB) is a biopolymer biologically synthesized by controlled bacterial fermentation from a wide variety of microorganisms. PHB is proposed as a potential green alternative to commonly used plastics in packaging, due to its biodegradability and biocompatibility. However, if PHB is to replace commodities, it has some limitations regarding its thermo-mechanical performance to overcome. Among them are its critically the low toughness values at room temperature and poor thermoforming ability. With the aim of overcoming these weaknesses, in this work, blends of PHB with the addition of a biodegradable thermoplastic elastomer (bio-TPE) were prepared and evaluated. Films of such compounds were made by cast extrusion. In order to enhance the compatibility of both polymers during the extrusion process, three different reactive agents (poly-hexametylene diisocianate, triglycidyl isocyanurate, and Joncryl® ADR-4368) were assessed. The morphology and mechanical- and thermal properties of the films obtained were analyzed. In addition, the thermoforming ability of the produced films was evaluated. The results show that the plasticizers present in the bio-TPE interacted with the reactive agents, making them chemical competitors and altering the outcome of the blends.

Study of the Compatibilization Effect of Different Reactive Agents in PHB/Natural Fiber-Based Composites.

Fiber-matrix interfacial adhesion is one of the key factors governing the final properties of natural fiber-based polymer composites. In this work, four extrusion reactive agents were tested as potential compatibilizers in polyhydroxylbutyrate (PHB)/cellulose composites: dicumyl peroxide (DCP), hexamethylene diisocyanate (HMDI), resorcinol diglycidyl ether (RDGE), and triglycidyl isocyanurate (TGIC). The influence of the fibers and the different reactive agents on the mechanical properties, physical aging, and crystallization behavior were assessed. To evaluate the compatibilization effectiveness of each reactive agent, highly purified commercial cellulose fibers (TC90) were used as reference filler. Then, the influence of fiber purity on the compatibilization effect of the reactive agent HMDI was evaluated using untreated (U_RH) and chemically purified (T_RH) rice husk fibers, comparing the results with the ones using TC90 fibers. The results show that reactive agents interact with the polymer matrix at different levels, but all compositions showed a drastic embrittlement due to the aging of PHB. No clear compatibilization effect was found using DCP, RDGE, or TGIC reactive agents. On the other hand, the fiber-polymer interfacial adhesion was enhanced with HMDI. The purity of the fiber played an important role in the effectiveness of HMDI as a compatibilizer, since composites with highly purified fibers showed the greatest improvements in tensile strength and the most favorable morphology. None of the reactive agents negatively affected the compostability of PHB. Finally, thermoformed trays with good mold reproducibility were successfully obtained for PHB/T_RH/HMDI composition.

Toughness Enhancement of PHBV/TPU/Cellulose Compounds with Reactive Additives for Compostable Injected Parts in Industrial Applications.

Poly(3-hydroxybutyrate-co-3-valerate), PHBV, is a bacterial thermoplastic biopolyester that possesses interesting thermal and mechanical properties. As it is fully biodegradable, it could be an alternative to the use of commodities in single-use applications or in those intended for composting at their end of life. Two big drawbacks of PHBV are its low impact toughness and its high cost, which limit its potential applications. In this work, we proposed the use of a PHBV-based compound with purified α-cellulose fibres and a thermoplastic polyurethane (TPU), with the purpose of improving the performance of PHBV in terms of balanced heat resistance, stiffness, and toughness. Three reactive agents with different functionalities have been tested in these compounds: hexametylene diisocianate (HMDI), a commercial multi-epoxy-functionalized styrene-co-glycidyl methacrylate oligomer (Joncryl® ADR-4368), and triglycidyl isocyanurate (TGIC). The results indicate that the reactive agents play a main role of compatibilizers among the phases of the PHBV/TPU/cellulose compounds. HMDI showed the highest ability to compatibilize the cellulose and the PHBV in the compounds, with the topmost values of deformation at break, static toughness, and impact strength. Joncryl® and TGIC, on the other hand, seemed to enhance the compatibility between the fibres and the polymer matrix as well as the TPU within the PHBV.