The role of (bio)degradability on the management of petrochemical and bio-based plastic waste.

In order to mitigate the social and ecological impacts of post-consumer plastic made of conventional petrochemical polymers, the market of (bio)degradable plastics have recently become more widespread. Although (bio)degradable plastics could be an environmentally friendly substitute of petrochemical ones, the consequences of their presence in the waste management system and in the environment (if not correctly disposed) are not always positive and plastic pollution is not automatically solved. Consequently, this work aims to review how plastic (bio)degradability affects the municipal solid waste management cycle. To this end, the state-of-the-art of the intrinsic (bio)degradability of conventional and unconventional petrochemical and bio-based polymers has been discussed, focusing on the environment related to the waste management system. Then, the focus was on strategies to improve polymer (bio)degradability: different types of eco-design and pre-treatment approach for plastics has been investigated, differently from other works that focused only on specific topics. The information gathered was used to discuss three typical disposal/treatment routes for plastic waste. Despite many of the proposed materials in eco-design have increased the plastics (bio)degradability and pre-treatments have showed interesting results, these achievements are not always positive in the current MSW management system. The effect on mechanical recycling is negative in several cases but the enhanced (bio)degradability can help the treatment with organic waste. On the other hand, the current waste treatment facility is not capable to manage this waste, leading to the incineration the most promising options. In this way, the consumption of raw materials will persist even by using (bio)degradable plastics, which strength the doubt if the solution of plastic pollution leads really on these materials. The review also highlighted the need for further research on this topic that is currently limited by the still scarce amount of (bio)degradable plastics in input to full-scale waste treatment plants.

Current Concerns about Microplastics and Nanoplastics: A Brief Overview.

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.

Recycling of Heterogeneous Mixed Waste Polymers through Reactive Mixing.

Anything that is not recycled and/or recovered from waste represents a loss of raw materials. Recycling plastics can help to reduce this loss and to reduce greenhouse gases, improving the goal of the decarbonization of plastic. While the recycling of single polymers is well assessed, the recycling of mixed plastics is very difficult because of the strong incompatibility among the different polymers usually present in urban waste. In this work, heterogeneous mixed polymers, i.e., polyethylene (PE), polypropylene (PP), polystyrene (PS) and polyethylenetherephthalate (PET) were processed using a laboratory mixer under different conditions of temperature, rotational speed and time to evaluate the effect of the above parameters on morphology, viscosity and mechanical properties of the final blends. Morphological analysis shows a strong incompatibility between the polyethylene matrix and the other dispersed polymers. The blends show, of course, a brittle behavior, but this behavior slightly improves with decreasing temperature and increasing rotational speed. A brittle-ductile transition was observed only at a high level of mechanical stress obtained by increasing rotational speed and decreasing temperature and processing time. This behavior has been attributed to both a decrease in the dimensions of the particles of the dispersed phase and to the formation of a small amount of copolymers that act as adhesion promoters between matrix and dispersed phases.

A Green Approach for Recycling Compact Discs.

Compact discs (CDs) and digital versatile discs (DVDs) are mainly made by polycarbonate disc, a thin layer of aluminum or silver, a thin layer of a coating and a thin layer of a label of paper or PET. The recycling of these discs is difficult due to the removal of these non-polymeric layers and to our best knowledge, no industrial plants have been resent for their recycling. In this work, we propose a facile way to remove the non-polymeric layers and investigate the effect of the repetitive extrusion process on the processability and on the mechanical properties of the recycled polycarbonate. A few works have been published dealing with both the removal of the non-polymeric layers and the mechanical recycling of the disk of polycarbonate. In our approach, the removal of the non-polymeric layers is easily obtained through a thermo-mechanical treatment in a basic solution by ammonia. This process can be considered green because is made at a low temperature with a small amount of water and a very small amount of ammonia, saving energy and water. The properties of the polycarbonate remain good if the mechanical recycling is made after drying the post-consumer polycarbonate.

Comparison of the Recycling Behavior of a Polypropylene Sample Aged in Air and in Marine Water.

During the processing and during their lifetime, polymers are subjected to several environmental stresses-thermomechanical, photo-oxidative, etc.-that can strongly modify their chemical and molecular structure and, consequently, their morphology. Reduction of the molecular weight and formation of double bonds and oxygenated groups are the main changes observed as a consequence of the degradation. As a result of these changes, the macroscopic properties are dramatically modified. These changes can have a relevant effect if the post-consumer plastic manufacts are recycled. In this work, a sample of polypropylene subjected to two different degradation histories-photo-oxidation in air and in marine water-is reprocessed two times in a mini twin-screw extruder in the same processing conditions. The effect of the thermomechanical degradation during the reprocessing is different. Indeed, the less severe degraded sample shows a higher degradation level during reprocessing because the shear stress is larger. This means that the thermomechanical degradation kinetics is larger in the less degraded samples. Nevertheless, the final properties of the recycled polymers are different because the properties of the photo-oxidized samples before reprocessing were very different.

Toward the Decarbonization of Plastic: Monopolymer Blend of Virgin and Recycled Bio-Based, Biodegradable Polymer.

Decarbonization of plastics is based on two main pillars: bio-based polymers and recycling. Mechanical recycling of biodegradable polymers could improve the social, economic and environmental impact of the use of these materials. In this regard, the aim of this study was to investigate whether concentrations of the same recycled biopolymer could significantly affect the rheological and mechanical properties of biodegradable monopolymer blends. Monopolymer blends are blends made of the same polymers, virgin and recycled. A sample of commercially available biodegradable blend was reprocessed in a single-screw extruder until two extrusion cycles were completed. These samples were exposed to grinding and melt reprocessed with 75% and 90% of the same virgin polymer. The blends were characterized by tensile tests and rheological tests. The results obtained showed that while multiple extrusions affected the mechanical and rheological properties of the polymer, the concentration of the reprocessed material present in the blends only very slightly affected the properties of the virgin material. In addition, the experimentally observed trends were accurately predicted by the additive model adopted.

The Use of Waste Hazelnut Shells as a Reinforcement in the Development of Green Biocomposites.

Biodegradable Mater-Bi (MB) composites reinforced with hazelnut shell (HS) powder were prepared in a co-rotating twin-screw extruder followed by compression molding and injection molding. The effects of reinforcement on the morphology, static and dynamic mechanical properties, and thermal and rheological properties of MB/HS biocomposites were studied. Rheological tests showed that the incorporation of HS significantly increased the viscosity of composites with non-Newtonian behavior at low frequencies. On the other hand, a scanning electron microscope (SEM) examination revealed poor interfacial adhesion between the matrix and the filler. The thermal property results indicated that HS could act as a nucleating agent to promote the crystallization properties of biocomposites. Furthermore, the experimental results indicated that the addition of HS led to a significant improvement in the thermomechanical stability of the composites. This paper demonstrates that the incorporation of a low-cost waste product, such as hazelnut shells, is a practical way to produce low-cost biocomposites with good properties. With a content of HS of 10%, a remarkable improvement in the elastic modulus and impact strength was observed in both compression and injection-molded samples. With a higher content of HS, however, the processability in injection molding was strongly worsened.

Influence of Different Environments and Temperatures on the Photo-Oxidation Behaviour of the Polypropylene.

The photo-oxidation of polypropylene at two different temperatures and in three different environments-air, distilled water and sea water-has been followed as a function of the irradiation time. The photo-oxidation kinetic is dramatically dependent on the amount of oxygen available for the oxidation reactions and on the temperature. While the photo-oxidation is very fast in air, the degradation is much slower in the two aqueous media. The degradation in sea water is slightly slower than in distilled water. In all cases, the degradation kinetic increases remarkably with the temperature. This behavior has been attributed to the lower oxygen availability for the oxidation reactions of the polymers. The light difference of the degradation kinetic between the two aqueous media depends on the small difference of the oxygen concentration at the test temperatures of 40 and 70 °C. At the latter temperature, the difference between the degradation kinetic in distilled water and sea water is still less important because increasing the temperature decreases the solubility of the oxygen, and it tends to became very similar in both samples of water.

Influence of Calcium Carbonate Nanoparticles on the Soil Burial Degradation of Polybutyleneadipate-Co-Butylenetherephthalate Films.

A polybutyleneadipate-co-butylenetherephthalate (PBAT) sample, commercially known as Ecoflex®, was processed via melt extrusion with CaCO3 nanoparticles coated with a hydrophobic coating. Blown films of PBAT and two composites with nanofiller (2% and 5%wt) were prepared and degradation tests in soil at 30 °C up to 180 days were carried out with weight loss measurements. Furthermore, biodegradation test according to ISO 14851 was carried out at 30 °C. The effect of CaCO3 on soil burial degradation was assessed by surface wettability and SEM. ATR-FTIR and XPS analyses highlighted chemical modifications induced by soil degradation. CaCO3 nanoparticles decreased surface wettability and discouraged the disintegration in soil. Interestingly, SEM images after soil degradation highlighted in the nanocomposite films selective zones of disintegration. XPS showed an increasing peak area C 1s ratio of C-O to C=O with degradation time. Moreover, after the soil burial test, carbonyl index determined by ATR-FTIR increased in both nanocomposites. In fact, the addition of CaCO3 leads to a rise in the carbonyl zone due to the presence of the carbonate group. Remarkably, FTIR data after soil degradation showed an enrichment of the aromatic content, a preferential cleavage and erosion of the aliphatic moiety in PBAT films, amplified by the presence of the CaCO3 nanofiller.

Biocomposite PBAT/lignin blown films with enhanced photo-stability.

Lignin can be obtained as a byproduct during cellulose-rich pulp fibers production and it is habitually treated as waste or intended for low-value destinations. However, due to UV absorption and mechanical properties, lignin can contribute to the fabrication of biodegradable blown films with superior performances. In this study, it was established the suitability of lignin for manufacturing biocomposite PBAT blown films with higher stiffness and photo-oxidation resistance. The effect of the filler concentration on the melt rheological behavior in non-isothermal elongational flow was investigated. The results allowed us to choose the correct filler concentration for producing films through a film blowing operation. The PBAT/lignin blown film composites displayed an increase of the elastic modulus if compared to neat PBAT films without affecting their elongation at break. Furthermore, the filler delayed the photo-oxidative degradation of PBAT hence potentially allowing open-air applications.

Effect of Moisture Content on the Processing and Mechanical Properties of a Biodegradable Polyester.

This work is focused on the influence of moisture content on the processing and mechanical properties of a biodegradable polyester used for applications in injection molding. The pellets of the biodegradable polyester were exposed under different relative humidity conditions at a constant temperature before being compression molded. The compression-molded specimens were again placed under the above conditions before the mechanical testing. With all these samples, it is possible to determine the effect of moisture content on the processing and mechanical properties separately, as well as the combined effect of moisture content on the mechanical properties. The results obtained showed that the amount of absorbed water-both before processing and before mechanical testing-causes an increase in elongation at break and a slight reduction of the elastic modulus and tensile strength. These changes have been associated with possible hydrolytic degradation during the compression molding process and, in particular, with the plasticizing action of the moisture absorbed by the specimens.

Biodegradable Polymers for the Production of Nets for Agricultural Product Packaging.

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.

Bionanocomposite Blown Films: Insights on the Rheological and Mechanical Behavior.

In this work, bionanocomposites based on two different types of biopolymers belonging to the MaterBi® family and containing two kinds of modified nanoclays were compounded in a twin-screw extruder and then subjected to a film blowing process, aiming at obtaining sustainable films potentially suitable for packaging applications. The preliminary characterization of the extruded bionanocomposites allowed establishing some correlations between the obtained morphology and the material rheological and mechanical behavior. More specifically, the morphological analysis showed that, regardless of the type of biopolymeric matrix, a homogeneous nanofiller dispersion was achieved; furthermore, the established biopolymer/nanofiller interactions caused a restrain of the dynamics of the biopolymer chains, thus inducing a significant modification of the material rheological response, which involves the appearance of an apparent yield stress and the amplification of the elastic feature of the viscoelastic behavior. Besides, the rheological characterization under non-isothermal elongational flow revealed a marginal effect of the embedded nanofillers on the biopolymers behavior, thus indicating their suitability for film blowing processing. Additionally, the processing behavior of the bionanocomposites was evaluated and compared to that of similar systems based on a low-density polyethylene matrix: this way, it was possible to identify the most suitable materials for film blowing operations. Finally, the assessment of the mechanical properties of the produced blown films documented the potential exploitation of the selected materials for packaging applications, also at an industrial level.

Structure-Property Relationships in Bionanocomposites for Pipe Extrusion Applications.

In this work, bionanocomposites based on different biodegradable polymers and two types of nanofillers, namely a nanosized calcium carbonate and an organomodified nanoclay, were produced through melt extrusion, with the aim to evaluate the possible applications of these materials as a potential alternative to traditional fossil fuel-derived polyolefins, for the production of irrigation pipes. The rheological behavior of the formulated systems was thoroughly evaluated by exploiting different flow regimes, and the obtained results indicated a remarkable effect of the introduced nanofillers on the low-frequency rheological response, especially in nanoclay-based bionanocomposites. Conversely, the shear viscosity at a high shear rate was almost unaffected by the presence of both types of nanofillers, as well as the rheological response under nonisothermal elongational flow. In addition, the analysis of the mechanical properties of the formulated materials indicated that the embedded nanofillers increased the elastic modulus when compared to the unfilled counterparts, notwithstanding a slight decrease of the material ductility. Finally, the processing behavior of unfilled biopolymers and bionanocomposites was evaluated, allowing for selecting the most suitable material and thus fulfilling the processability requirements for pipe extrusion applications.

Use of Biochar as Filler for Biocomposite Blown Films: Structure-Processing-Properties Relationships.

In this work, biocomposite blown films based on poly(butylene adipate-co-terephthalate) (PBAT) as biopolymeric matrix and biochar (BC) as filler were successfully fabricated. The materials were subjected to a film-blowing process after being compounded in a twin-screw extruder. The preliminary investigations conducted on melt-mixed PBAT/BC composites allowed PBAT/BC 5% and PBAT/BC 10% to be identified as the most appropriate formulations to be processed via film blowing. The blown films exhibited mechanical performances adequate for possible application as film for packaging, agricultural, and compost bags. The addition of BC led to an improvement of the elastic modulus, still maintaining high values of deformation. Water contact angle measurements revealed an increase in the hydrophobic behavior of the biocomposite films compared to PBAT. Additionally, accelerated degradative tests monitored by tensile tests and spectroscopic analysis revealed that the filler induced a photo-oxidative resistance on PBAT by delaying the degradation phenomena.

PBAT Based Composites Reinforced with Microcrystalline Cellulose Obtained from Softwood Almond Shells.

This study explores the processability, mechanical, and thermal properties of biocompostable composites based on poly (butylene adipate-co-terephthalate) (PBAT) as polymer matrix and microcrystalline cellulose (MCC) derived from softwood almond (Prunus dulcis) shells (as-MCC) as filler at two different weight concentration, i.e., 10 wt% and 20 wt%. The materials were processed by melt mixing and a commercial MCC (c-MCC) was used as filler comparison. The fibrillar shape of as-MCC particles was found to change the rheological behavior of PBAT, particularly at the highest concentration. The melt mixing processing allowed obtaining a uniform dispersion of both kinds of fillers, slightly reducing the L/D ratio of as-MCC fibers. The as-MCC particles led to a higher increase of the elastic modulus of PBAT if compared to the c-MCC counterparts. Both the MCC fillers caused a drastic reduction of the elongation at break, although it was higher than 120% also at the highest filler concentrations. DSC analysis revealed that both MCC fillers poorly affected the matrix crystallinity, although as-MCC induced a slight PBAT crystallinity increase from 8.8% up to 10.9% for PBAT/as-MCC 20%. Therefore, this work demonstrates the great potential of MCC particles derived from almond shells as filler for biocompostable composites fabrication.

Thermomechanical Analysis of Isora Nanofibril Incorporated Polyethylene Nanocomposites.

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.

Polymer Processing and Performance: 2018-2019.

The section "Polymer Processing and Performance" of Polymers has published, in the last two years, 175 high quality papers investigating the processing and properties of several polymer based systems [...].

Recycling of a Biodegradable Polymer Blend.

Mechanical recycling is one of the possible ways to enhance the value of postconsumer plastic materials. However, the final performance of the recycled material will strongly depend on the quality of the selection made on the recycled product and on the degradation of the properties. In this context, the present study examines the effect of reprocessing for five successive extrusion cycles on the rheological, mechanical and thermal properties of a poly(butylene adipate-co-terephthalate) (PBAT)-based blend on samples reprocessed in both dry and wet conditions. The results showed that when the sample was processed after drying, degradation of the material was less than when it was processed in wet conditions. However, the experimental results showed that the decrease of rheological and mechanical properties was not so dramatic, and therefore the material could be reused in both cases.

Influence of Short-Term Aging on Mechanical Properties and Morphology of Polymer-Modified Bitumen with Recycled Plastics from Waste Materials.

Polymer-modified bitumen (PMB) is bitumen that has been specifically engineered with polymer for providing enhanced performance in service. The aging of bitumen is a main aspect that is able to affect its final performance: during the production phase in a hot mix plant, all the binders experience short-term aging due to the high processing temperature. The same is true during the production of the modified binder, when the polymer is dispersed at high temperature in the bitumen mass. This paper aims at studying the effect of short-term aging when using different types of modifiers such as recycled polymers obtained from waste materials. A 50/70 penetration-grade bitumen has been modified, and bitumen characterization has been carried out before and after short-term aging; conventional tests, viscosity measurements, and dynamical mechanical analysis have been used to investigate the properties. Different aging indices have been determined for predicting the effect of short-term aging based on the type of modifier. Furthermore, the morphology of the modified bitumen has been investigated via fluorescent microscopy, before and after aging, in order to highlight morphological changes due to aging. The results confirm that aging affects all the modified binders, due to the thermal stress imposed during PMBs production. Nevertheless, polymer modification is proved to reduce the aging effect in terms of an increase in the elastic modulus as experienced by the original binder.