Recycling of Thermoset Materials and Thermoset-Based Composites: Challenge and Opportunity

Thermoset materials and their composites are characterized by a long life cycle with their main applications in aircrafts, wind turbines and constructions as insulating materials. Considering the importance of recovery and valorization of these materials at their end-of-life, avoiding landfilling, the interest concerning their recycling grows continuously. The thermoset materials and their composites, to be successfully recovered and valorized, must degrade their three-dimensional structures and recover the mono-oligomers and/or fillers. The thermoset materials could successfully degrade through thermal treatment at different temperatures (for example, above 1000 degrees C for incineration, ca. 500 degrees C for oxidation/combustion of organic constituents, etc.), chemical degradation by catalyst, irradiation with or without the presence of water, alcohol, etc., and mechanical recycling, obtaining fine particles that are useful as filler and/or reinforcement additives. Among these recycling methods, this mini-review focuses on the formulation and recovery method of innovative thermoset with in-build recyclability, i.e., materials having chemical links that could be degraded on-demand or containing dynamic covalent bonds to have re-processable and/or recyclable thermoset. This issue could be considered the future perspective in developing novel thermoset materials. The aim of this review is to get an overview of the state of the art in thermoset recycling and of the most commonly used thermoset composites, recovering valuable reinforcing fibers. Additionally, in this work, we also report not only known recycling routes for thermoset and thermoset-based composites, but also new and novel formulating strategies for producing thermosets with built-in recyclability, i.e., containing chemical-triggered on-demand links. This mini-review is also a valuable guide for educational purposes for students and specialized technicians in polymer production and recycling

Sustainable Materials Containing Biochar Particles: A Review

The conversion of polymer waste, food waste, and biomasses through thermochemical decomposition to fuels, syngas, and solid phase, named char/biochar particles, gives a second life to these waste materials, and this process has been widely investigated in the last two decades. The main thermochemical decomposition processes that have been explored are slow, fast, and flash pyrolysis, torrefaction, gasification, and hydrothermal liquefaction, which produce char/biochar particles that differ in their chemical and physical properties, i.e., their carbon-content, CHNOS compositions, porosity, and adsorption ability. Currently, the main proposed applications of the char/biochar particles are in the agricultural sector as fertilizers for soil retirement and water treatment, as well as use as high adsorption particles. Therefore, according to recently published papers, char/biochar particles could be successfully considered for the formulation of sustainable polymer and biopolymer-based composites. Additionally, in the last decade, these particles have also been proposed as suitable fillers for asphalts. Based on these findings, the current review gives a critical overview that highlights the advantages in using these novel particles as suitable additives and fillers, and at the same time, it shows some drawbacks in their use. Adding char/biochar particles in polymers and biopolymers significantly increases their elastic modulus, tensile strength, and flame and oxygen resistance, although composite ductility is significantly penalized. Unfortunately, due to the dark color of the char/biochar particles, all composites show brown-black coloration, and this issue limits the applications

A review of bioplastics and their adoption in the circular economy

The European Union is working towards the 2050 net-zero emissions goal and tackling the ever-growing environmental and sustainability crisis by implementing the European Green Deal. The shift towards a more sustainable society is intertwined with the production, use, and disposal of plastic in the European economy. Emissions generated by plastic production, plastic waste, littering and leakage in nature, insufficient recycling, are some of the issues addressed by the European Commission. Adoption of bioplastics–plastics that are biodegradable, bio-based, or both–is under assessment as one way to decouple society from the use of fossil resources, and to mitigate specific environmental risks related to plastic waste. In this work, we aim at reviewing the field of bioplastics, including standards and life cycle assessment studies, and discuss some of the challenges that can be currently identified with the adoption of these materials

Polar Wax as Adhesion Promoter in Polymeric Blend Films for Durable Photovoltaic Encapsulants

Technological developments in the solar photovoltaic field must guarantee the high performance and low deterioration of solar cells in order for solar power plants to be more efficient and competitive. The solar cell needs comprehensive protection offered by a polymeric encapsulant, which improves UV stability, reduces water and moisture absorption, reduces oxygen and vapor permeability and enhances mechanical resistance. Moreover, high transparency and adhesion yields improved the solar panel performance. The current work analyzes polymeric films based on poly(ethylene-co-vinyl acetate) (EVA) and polyolefin (PO) for photovoltaic encapsulant use (the high temperature resistance is improved by adding PO to EVA, as investigated and documented before). To enhance the mechanical resistance and optical properties of the investigated matrices, a crosslinking agent, an adhesion promoter and stabilizing agents have been incorporated in both EVA and EVA/PO systems. The adhesion promoter is a polar wax–silane-free agent; the absence of the silane function allows the integrity of the module to be maintained over time. All samples were characterized through mechanical and rheological analysis, and their long-term UV stability was investigated by accelerated ageing and by FTIR and UV–vis spectroscopy. The obtained results suggest that the presence of a crosslinking agent, an adhesion promoter and stabilizers in EVA/PO-based films allows for the achievement of the required features for the encapsulants, showing mechanical and rheological behavior similar to those of EVA containing the same additives

Slow pyrolysis as a method for biochar production from carob waste: Process investigation and products’ characterization

The zero-waste city challenge of the modern society is inevitably addressed to the development of model’s waste-to-energy. In this work, carob waste, largely used in the agro-industrial sector for sugar extraction or locust beangum (LBG) production, is considered as feedstock for the slow pyrolysis process. According to the Food and Agriculture Organization of the United Nations (FAO), in 2012, the world production of carobs was ca. 160,000 tons, mainly concentrated in the Mediterranean area (Spain, Italy, Morocco, Portugal, and Greece). To evaluate the biomass composition, at first, the carob waste was subjected to thermo-gravimetric analysis. The high content of fixed carbon suggests that carobs are a plausible candidate for pyrolysis conversion to biochar particles. The thermal degradation of the carob waste proceeds by four different steps related to the water and volatile substances’ removal, degradation of hemicellulose, lignin and cellulose degradation, and lignin decomposition. Considering this, the slow pyrolysis was carried out at three different temperatures, specifically, at 280, 340, and 400◦C, and the obtained products were characterized. Varying the processing temperature, the proportion of individual products’ changes with a reduction in the solid phase and an increase in liquid and gas phases, with an increase in the pyrolysis temperature. The obtained results suggest that carob waste can be considered a suitable feedstock for biochar production, rather than for fuels’ recovery

Control of end-of-life oxygen-containing groups accumulation in biopolyesters through introduction of crosslinked polysaccharide particles

The formulation of bio-based materials with good performance in service and controlled end-of-life is imperative for an effective circular economy. In this work, an innovative approach to induce and control the end-of-life of biodegradable polyesters through introduction of crosslinked polysaccharide particles is proposed. Chitosan (Ch) has been subjected to ionotropically crosslinking and then added to polylactic acid (PLA) at different amounts (1.0–4.0%w) by melt mixing. All obtained results suggest that the addition of crosslinked Ch (cCh) particles does not modify significantly the investigated biopolyester properties. Specifically, the thermal analysis of the composites reveals that the addition of unmodified Ch alters the PLA thermal behavior, while the addition of cCh particles does not change the PLA glass transition, cold crystallization and fusion phenomena. The infrared and UV–visible spectroscopic analyses suggest no significant changes in PLA structure. PLA/cCh films show a good optical transparency, which is a desirable property for food packaging applications. In addition, thin PLA-based films have been subjected to UVB exposure and the accumulation of oxygen-containing groups has been monitored in time through spectroscopic analysis. Interestingly, at low exposure time, the presence of chitosan slows down the accumulation of these groups, while at long exposure time, chitosan induces accelerated oxygen-groups formation, supporting its beneficial effect as end-of-life accelerant

Green composites of organic materials and recycled post-consumer polyethylene

International audienceAddition of organic fillers to post‐consumer recycled plastics can give rise to several advantages. First of all, the cost of these fillers is usually very low, the organic fillers are biodegradable contributing to an improved environmental impact and, last but not least, some mechanical and thermomechanical properties can be enhanced. Organic fillers are not widely used in the plastic industry although their use is increasing. Bad dispersion into the polymer matrix at high‐level content and poor adhesion with the matrix are the more important obstacles to this approach. In this work various organic fillers have been used with a post‐consumer plastic material originating from films for greenhouses. The properties of these green composites have been compared with those of materials filled with a conventional inorganic filler. The organic fillers cause slightly worse processability, due to an increase of viscosity, an enhancement of the rigidity and of the thermomechanical resistance similar to that measured for the inorganic filler, while a reduction of the impact strength is observed. Copyright © 2004 Society of Chemical Industry

Sonication-induced modification of carbon nanotubes: Effect on the rheological and thermo-oxidative behaviour of polymer-based nanocomposites

The aim of this work is the investigation of the effect of ultrasound treatment on the structural characteristics of carbon nanotubes (CNTs) and the consequent influence that the shortening induced by sonication exerts on the morphology, rheological behaviour and thermo-oxidative resistance of ultra-high molecular weight polyethylene (UHMWPE)-based nanocomposites. First, CNTs have been subjected to sonication for different time intervals and the performed spectroscopic and morphological analyses reveal that a dramatic decrease of the CNT's original length occurs with increased sonication time. The reduction of the initial length of CNTs strongly affects the nanocomposite rheological behaviour, which progressively changes from solid-like to liquid-like as the CNT sonication time increases. The study of the thermo-oxidative behaviour of the investigated nanocomposites reveals that the CNT sonication has a detrimental effect on the thermo-oxidative stability of nanocomposites, especially for long exposure times. The worsening of the thermo-oxidative resistance of sonicated CNT-containing nanocomposites could be attributed to the lower thermal conductivity of low-aspect-ratio CNTs, which causes the increase of the local temperature at the polymer/nanofillers interphase, with the consequent acceleration of the degradative phenomena

Biochar from Digestate Pyrolysis as a Filler for Biopolymer Blends: Effect of Blend Composition

This study investigates the effect of biochar (BC) as a filler for biopolymer blends, with a focus on the effect of the biopolymer weight ratio on the final BC-added blends. The blends studied in this work were obtained by varying the weight ratio of poly-butylene adipate-co-terephthalate (PBAT) and polylactic acid (PLA) due to their great importance in packaging and agricultural fields. BC has been produced in our laboratories by the slow pyrolysis of the digestate obtained from the anaerobic digestion of the organic fraction of municipal solid waste (OFMSW). After pyrolysis, digestate-derived biochar has been milled and sieved to produce a powdery form with diameter of less than 45 μm. In order to better investigate the filler/polymer interactions, biochar particles were dimensionally, morphologically and chemically characterised. The inhomogeneity of the feedstock is responsible for content and high diversity of inorganics in biochar surface. The effect of BC on PBAT and PLA biopolymer matrices is different, and for the blend compositions the relative weight ratio between PBAT and PLA plays an important role. Furthermore, the biocomposite blend has been fully characterised: rheological, morphological, mechanical and dynamic-mechanical characterisations have been carried out, highlighting how the properties results strongly influenced by the presence of BC in the blend. In addition, a study of the viscous molar mass of the two polymer matrices when processed in the presence or absence of BC particless highlighting that a strong chemical interaction occurs between PLA and BC particles, unlike PBAT and BC

Structure-properties relationships of polyhedral oligomeric silsesquioxane (POSS) filled PS nanocomposites

The polyhedral oligomeric silsesquioxane (POSS) additivated polystyrene (PS) based nanocomposites were prepared by melt processing and the structure-properties relationships of the POSS-PS systems were compared to those of the neat PS. In order to investigate the effect of these structural parameters on the final properties of the polymer nanocomposites, five different kinds of POSS samples were used, in particular, POSS with different inorganic cage and with different organic pendent groups. The rheological investigation suggests clearly that the POSS acts as a plasticizer and that the processability of the PS was positively modified. The affinity between the POSS samples and the PS matrix was estimated by the calculated theoretical solubility parameters, considering the Hoy’s method and by morphology analysis. Minor difference between the solubility parameter of POSS and the matrix means better compatibility and no aggregation tendency. Furthermore, the POSS loading leads to a decrease of the rigidity, of the glass transition temperature and of the damping factor of the nanocomposite systems. The loading of different POSS molecules with open cage leads to a more pronounced effect on all the investigated properties that the loading of the POSS molecules with closed cage. Moreover, the melt properties are significantly influenced by the type of inorganic framework, by the type of the pendent organic groups and by the interaction between the POSS organic groups and the host matrix, while, the solid state properties appears to be influenced more by the kind of cage