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The widespread and increasing use of plastic-based goods in the present-day world has been raising many concerns about the formation of microplastics, their release, their impacts on the environment and, ultimately, on living organisms. These concerns are even greater regarding nanoplastics, i.e., nanosized microplastics, which may have even greater impacts. In this brief review, although without any claim or intention to exhaustively cover all the aspects of such a complex and many-sided issue, the very topical problem of the formation of microplastics, and the even more worrisome nanoplastics, from polymer-based products was considered. The approach is focused on a terse, straightforward, and easily accessible analysis oriented to the main technological engineering aspects regarding the sources of microplastics and nanoplastics released into the environment, their nature, some of the consequences arising from the release, the different polymers involved, their technological form (i.e., products or processes, with particular attention towards unintentional release), the formation mechanisms, and some possible mitigation pathways.

Versatility of the anionic algal polysaccharide carrageenan has long been discussed and explored, especially for their affinity towards water molecules. While this feature is advantageous in certain applications such as water remediation, wound healing, etc., the usefulness of this biopolymer is extremely limited when it comes to applications such as food packaging. Scientists around the globe are carrying out research works on venturing diverse methods to integrate hydrophobic nature into these polysaccharides without compromising their other functionalities. Considering these foregoing studies, this review is designed to have an in-depth understanding of diverse methods and techniques adopted for tuning the hydrophobic nature of carrageenan-based bionanocomposites, both via surface alterations or by changes made to their chemical structure and attached functional groups. This review article mainly focuses on how the hydrophobicity of carrageenan bionanocomposites varies as a function of the type and refinement of carrageenan, and with the incorporation of additives including plasticisers, nanofillers, bioactive agents, etc. Incorporation of nanofillers such as polysaccharide-based nanoparticles, nanoclays, bioceramic and mineral based nanoparticles, carbon dots and nanotubes, metal oxide nanoparticles, etc., along with their synergistic effects in hybrid bionanocomposites are also dealt with in this comprehensive review article.

Biodegradable polymers have recently become popular; in particular, blends of poly(lactic acid) (PLA) and poly(butylene adipate terephthalate) (PBAT) have recently attracted significant attention due to their potential application in the packaging field. However, there is little information about the thermomechanical properties of these blends and especially the effect induced by the addition of PBAT on the shape memory properties of PLA. This work, therefore, aims at producing and investigating the microstructural, thermomechanical and shape memory properties of PLA/PBAT blends prepared by melt compounding. More specifically, PLA and PBAT were melt-blended in a wide range of relative concentrations (from 85/15 to 25/75 wt%). A microstructural investigation was carried out, evidencing the immiscibility and the low interfacial adhesion between the PLA and PBAT phases. The immiscibility was also confirmed by differential scanning calorimetry (DSC). A thermogravimetric analysis (TGA) revealed that the addition of PBAT slightly improved the thermal stability of PLA. The stiffness and strength of the blends decreased with the PBAT amount, while the elongation at break remained comparable to that of neat PLA up to a PBAT content of 45 wt%, while a significant increment in ductility was observed only for higher PBAT concentrations. The shape memory performance of PLA was impaired by the addition of PBAT, probably due to the low interfacial adhesion observed in the blends. These results constitute a basis for future research on these innovative biodegradable polymer blends, and their physical properties might be further enhanced by adding suitable compatibilizers.

3D printability of green composites is currently experiencing a boost in importance and interest, envisaging a way to valorise agricultural waste, in order to obtain affordable fillers for the preparation of biodegradable polymer-based composites with reduced cost and environmental impact, without undermining processability and mechanical performance. In this work, an innovative green composite was prepared by combining a starch-based biodegradable polymer (Mater-Bi ® , MB) and a filler obtained from the lignocellulosic waste coming from Solanum lycopersicum (i.e., tomato plant) harvesting. Different processing parameters and different filler amounts were investigated, and the obtained samples were subjected to rheological, morphological, and mechanical characterizations. Regarding the adopted filler amounts, processability was found to be good, with adequate dispersion of the filler in the matrix. Mechanical performance was satisfactory, and it was found that this is significantly affected by specific process parameters such as the raster angle. The mechanical properties were compared to those predictable from the Halpin-Tsai model, finding that the prepared systems exceed the expected values., Competing Interests: The authors declare no conflict of interest.

In this work, an innovative green composite was produced by adding Hedysarum coronarium (HC) flour to a starch-based biodegradable polymer (Mater-Bi ® , MB). The flour was obtained by grinding together stems, leaves and flowers and subsequently sieving it, selecting a fraction from 75 μm to 300 μm. Four formulations have been produced by compression molding (CM) and fused deposition modeling (FDM) by adding 5%, 10%, 15% and 20% of HC to MB. The influence of filler content on the processability was tested, and rheological, morphological and mechanical properties of composites were also assessed. Through CM, it was possible to obtain easily homogeneous samples with all filler amounts. Concerning FDM, 5% and 10% HC-filled composites proved also easily printable. Mechanical results showed filler effectively acted as reinforcement: Young's modulus and tensile strengths of the composites increased from 74.3 MPa to 236 MPa and from 18.6 MPa to 33.4 MPa, respectively, when 20% of HC was added to the pure matrix. FDM samples, moreover, showed higher mechanical properties if compared with CM ones due to rectilinear infill and fibers orientation. In fact, regarding the 10% HC composites, Young's modulus of the CM and FDM ones displayed a relative increment of 176% and 224%, respectively.

Three dimensional-printability of green composites is recently growing in importance and interest, especially in the view of feasibility to valorize agricultural and marine waste to attain green fillers capable of reducing bioplastic costs, without compromising their processability and performance from an environmental and mechanical standpoint. In this work, two lignocellulosic fillers, obtained from Opuntia ficus indica and Posidonia oceanica , were added to PLA and processed by FDM. Among the 3D printed biocomposites investigated, slight differences could be found in terms of PLA molecular weight and filler aspect ratio. It was shown that it is possible to replace up to 20% of bioplastic with low cost and ecofriendly natural fillers, without significantly modifying the processability and the mechanical performance of the neat matrix; at the same time, an increase of surface hydrophilicity was found, with possible positive influence on the biodegradability of such materials after disposal.

The research on cellulose fiber-reinforced nanocomposites has increased by an unprecedented magnitude over the past few years due to its wide application range and low production cost. However, the incompatibility between cellulose and most thermoplastics has raised significant challenges in composite fabrication. This paper addresses the behavior of plasma-modified polyethylene (PE) reinforced with cellulose nanofibers extracted from isora plants (i.e., isora nanofibrils (INFs)). The crystallization kinetics of PE-INF composites were explained using the Avrami model. The effect of cellulose nanofillers on tuning the physiochemical properties of the nanocomposite was also explored in this work. The increase in mechanical properties was due to the uniform dispersion of fillers in the PE. The investigation on viscoelastic properties confirmed good filler-matrix interactions, facilitating the stress transfer.

It is well known that the need for more environmentally friendly materials concerns, among other fields, the food packaging industry. This regards also, for instance, nets used for agricultural product (e.g., citrus fruits, potatoes) packaging. These nets are typically manufactured by film blowing technique, with subsequent slicing of the films and cold drawing of the obtained strips, made from traditional, non-biodegradable polymer systems. In this work, two biodegradable polymer systems were characterized from rheological, processability, and mechanical points of view, in order to evaluate their suitability to replace polyethylene-based polymer systems typically used for agricultural product net manufacturing. Furthermore, laboratory simulation of the above-mentioned processing operation paths was performed. The results indicated a good potential for biodegradable polymer systems to replace polyethylene-based systems for agricultural product packaging.

In this paper, gas permeability studies were performed on materials based on natural rubber/acrylonitrile butadiene rubber blends and nanoclay incorporated blend systems. The properties of natural rubber (NR)/nitrile rubber (NBR)/nanoclay nanocomposites, with a particular focus on gas permeability, are presented. The measurements of the barrier properties were assessed using two different gases-O 2 and CO 2 -by taking in account the blend composition, the filler loading and the nature of the gas molecules. The obtained data showed that the permeability of gas transport was strongly affected by: (i) the blend composition-it was observed that the increase in acrylonitrile butadiene rubber component considerably decreased the permeability; (ii) the nature of the gas-the permeation of CO 2 was higher than O 2 ; (iii) the nanoclay loading-it was found that the permeability decreased with the incorporation of nanoclay. The localization of nanoclay in the blend system also played a major role in determining the gas permeability. The permeability of the systems was correlated with blend morphology and dispersion of the nanoclay platelets in the polymer blend.

The formulation of polymeric films endowed with the abilities of controlled release of antimicrobials and biodegradability is the latest trend of food packaging. Biodegradable polymer (Bio-Flex ® )-based nanocomposites containing carvacrol as an antimicrobial agent, and a nanoclay as a filler, were processed into blown films. The presence of such hybrid loading, while not affecting the overall filmability of the neat matrix, led to enhanced mechanical properties, with relative increments up to +70% and +200% in terms of elastic modulus and elongation at break. FTIR/ATR analysis and release tests pointed out that the presence of nanoclay allowed higher carvacrol loading efficiency, reasonably hindering its volatilization during processing. Furthermore, it also mitigated the burst delivery, thereby enabling a more controlled release of the antimicrobial agent. The results of mass loss tests indicated that all the formulations showed a rather fast degradation with mass losses ranging from 37.5% to 57.5% after 876 h. The presence of clay and carvacrol accelerated the mass loss rate of Bio-Flex ® , especially when added simultaneously, thus indicating an increased biodegradability. Such ternary systems could be, therefore, particularly suitable as green materials for food packaging applications, and for antimicrobial wrapping applications.

The environmental performance of biodegradable materials has attracted attention from the academic and the industrial research over the recent years. Currently, degradation behavior and possible recyclability features, as well as actual recycling paths of such systems, are crucial to give them both durability and eco-sustainability. This paper presents a review of the degradation behaviour of biodegradable polymers and related composites, with particular concern for multi-layer films. The processing of biodegradable polymeric films and the manufacturing and properties of multilayer films based on biodegradable polymers will be discussed. The results and data collected show that: poly-lactic acid (PLA), poly-butylene adipate-co-terephthalate (PBAT) and poly-caprolactone (PCL) are the most used biodegradable polymers, but are prone to hydrolytic degradation during processing; environmental degradation is favored by enzymes, and can take place within weeks, while in water it can take from months to years; thermal degradation during recycling basically follows a hydrolytic path, due to moisture and high temperatures (β-scissions and transesterification) which may compromise processing and recycling; ultraviolet (UV) and thermal stabilization can be adequately performed using suitable stabilizers., Competing Interests: The authors declare no conflict of interest.

The use of polyamide/polyolefin blends has gained importance and concern for years, but they also show some issues to be adequately addressed, such as the incompatibility between the two components. This is usually overcome by using suitable compatibilizers, typically based on functionalized polyolefins. However, there is only little information about the use of a degraded polyolefins to induce compatibilization. This is even truer, as far as polyamide 6/polypropylene (PA6/PP) blends are concerned. In this work, compatibilization of PA6/PP blends by using small amounts of photo-oxidized PP was investigated; furthermore, the effects due to the presence of the photo-oxidized PP were studied also in relationship to the spinning operation, where the existence of the non-isothermal elongational flow can lead to significant, further morphological changes. It was found that isotropic samples showed significant enhancements of the tensile properties upon adding the photo-oxidized PP. Under non-isothermal elongational flow conditions, the presence of the photo-oxidized PP was particularly effective in improving the mechanical properties in comparison to the uncompatibilized blend fibers. Furthermore, an important result was found: The elongational-flow processing allowed obtaining anisotropic samples where the improvements of the properties, in comparison to the isotropic samples, were similar to those achieved by using a compatibilizer.

Polyamide/polyolefin blends have gained attention from the academia and the industry for several years. However, in order to optimize their properties, some drawbacks such as chemical incompatibility must be adequately overcome. This can be done by adding suitable compatibilizers. On the other hand, it is less known that suitable processing techniques may also lead to significant results. In a previous work on a low-density polyethylene/polyamide 6 (LDPE/PA6) blend, we found that the orientation due to elongational flow processing conditions could lead to an unexpected brittle⁻ductile transition. In this work, this phenomenon was further investigated and the attention was mainly focused on the effects that processing can have on the morphology and, as a consequence, on the final properties of a polymer blends. With regard to LDPE/PA6 blend, an important result was found, i.e., the effects on the ductility induced by the elongational flow orientation are similar to those obtained by using an ethylene-glycidyl methacrylate compatibilizer.

The use of biodegradable/bio-based polymers is of great importance in addressing several issues related to environmental protection, public health, and new, stricter legislation. Yet some applications require improved properties (such as barrier or mechanical properties), suggesting the use of nanosized fillers in order to obtain bio-based polymer nanocomposites. In this work, bionanocomposites based on two different biodegradable polymers (coming from the Bioflex and MaterBi families) and two different nanosized fillers (organo-modified clay and hydrophobic-coated precipitated calcium carbonate) were prepared and compared with traditional nanocomposites with high-density polyethylene (HDPE) as matrix. In particular, the injection molding processability, as well as the mechanical and rheological properties of the so-obtained bionanocomposites were investigated. It was found that the processability of the two biodegradable polymers and the related nanocomposites can be compared to that of the HDPE-based systems and that, in general, the bio-based systems can be taken into account as suitable alternatives.

Creep behavior of polymer nanocomposites has not been extensively investigated so far, especially when its effects are combined with those due to photooxidation, which are usually studied in completely independent ways. In this work, the photooxidation behavior of a low density polyethylene/organomodified clay nanocomposite system was monitored by measuring the creep curves obtained while subjecting the sample to the combined action of temperature, tensile stress, and UV radiation. The creep curves of the irradiated samples were found to be lower than those of the non-irradiated ones and progressively diverging, because of the formation of branching and cross-linking due to photooxidation. This was further proved by the decrease of the melt index and the increase of the intrinsic viscosity; at the same time, the formation of carbonyl groups was observed. This behavior was more observable in the nanocomposite sample, because of its faster photooxidation kinetics., Competing Interests: The authors declare no conflict of interest.

Polymer composites containing natural fibers are receiving growing attention as possible alternatives for composites containing synthetic fibers. The use of biodegradable matrices obtained from renewable sources in replacement for synthetic ones is also increasing. However, only limited information is available about the creep behavior of the obtained composites. In this work, the tensile creep behavior of PLA based composites, containing flax and jute twill weave woven fabrics, produced through compression molding, was investigated. Tensile creep tests were performed at different temperatures (i.e., 40 and 60 °C). The results showed that the creep behavior of the composites is strongly influenced by the temperature and the woven fabrics used. As preliminary characterization, quasi-static tensile tests and dynamic mechanical tests were carried out on the composites. Furthermore, fabrics (both flax and jute) were tested as received by means of quasi-static tests and creep tests to evaluate the influence of fabrics mechanical behavior on the mechanical response of the resulting composites. The morphological analysis of the fracture surface of the tensile samples showed the better fiber-matrix adhesion between PLA and jute fabric.

The rising concerns in terms of environmental protection and the search for more versatile polymer-based materials have led to an increasing interest in the use of polymer composites filled with natural organic fillers (biodegradable and/or coming from renewable resources) as a replacement for traditional mineral inorganic fillers. At the same time, the recycling of polymers is still of fundamental importance in order to optimize the utilization of available resources, reducing the environmental impact related to the life cycle of polymer-based items. Green composites from biopolymer matrix and wood flour were prepared and the investigation focused on several issues, such as the effect of reprocessing on the matrix properties, wood flour loading effects on virgin and reprocessed biopolymer, and wood flour effects on material reprocessability. Tensile, Dynamic-mechanical thermal (DMTA), differential scanning calorimetry (DSC) and creep tests were performed, pointing out that wood flour leads to an improvement of rigidity and creep resistance in comparison to the pristine polymer, without compromising other properties such as the tensile strength. The biopolymer also showed a good resistance to multiple reprocessing; the latter even allowed for improving some properties of the obtained green composites.