Recovery of Rose Flower Waste to Formulate Eco-Friendly Biopolymer Packaging Films.

Considering the circular principles of materials and investigating the possibility to use waste materials before their final disposal, in this work, dry rose flower (DRF) and rose flower waste (RFW), after oil extraction, have been considered as suitable materials for the formulation of biopolymer packaging films. Both DRF and RFW particles have been characterized by spectroscopy analysis, and their radical scavenger ability has been investigated. Moreover, DRF and RFW particles have been added by melt mixing to PolyLactic Acid (PLA), and formulated PLA-based films have been studied through rheology analysis, mechanical test, differential scanning calorimetry, and microscopy observations. Finally, the influence of both DRF and RFW particles on the photo-oxidation behavior of PLA has been evaluated by subjecting thin films to UVB exposure, and the progress of degradation has been monitored following the accumulations of oxygen-containing groups in time. Obtained results suggest that both DRF and RFW have a beneficial effect on the photo-oxidation behavior of PLA, and they can slow down PLA degradation upon UVB exposure. Therefore, PLA-based composite materials could be considered a good candidate for applications as packaging films.

Understanding the Effects of Adding Metal Oxides to Polylactic Acid and Polylactic Acid Blends on Mechanical and Rheological Behaviour, Wettability, and Photo-Oxidation Resistance.

Biopolymers are of growing interest, but to improve some of their poor properties and performance, the formulation of bio-based blends and/or adding of nanoparticles is required. For this purpose, in this work, two different metal oxides, namely zinc oxide (ZnO) and titanium dioxide (TiO2), at different concentrations (0.5, 1, and 2%wt.) were added in polylactic acid (PLA) and polylactic acid/polyamide 11 (PLA/PA11) blends to establish their effects on solid-state properties, morphology, melt behaviour, and photo-oxidation resistance. It seems that the addition of ZnO in PLA leads to a significant reduction in its rigidity, probably due to an inefficient dispersion in the melt state, while the addition of TiO2 does not penalize PLA rigidity. Interestingly, the addition of both ZnO and TiO2 in the PLA/PA11 blend has a positive effect on the rigidity because of blend morphology refinement and leads to a slight increase in film hydrophobicity. The photo-oxidation resistance of the neat PLA and PLA/PA11 blend is significantly reduced due to the presence of both metal oxides, and this must be considered when designing potential applications. The last results suggest that both metal oxides could be considered photo-sensitive degradant agents for biopolymer and biopolymer blends.

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 °C for incineration, ca. 500 °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.

Ecofriendly Biopolymer-Based Nanocomposite Films with Improved Photo-Oxidative Resistance.

The interest towards high performance biopolymer-based materials increases continuously and, to guarantee appropriately industrial applications, the photo-oxidative resistance and stability of these materials must be adequately addressed. In this study, innovative biopolymer-based nanocomposites, i.e., Polyamide 11 (PA11), containing ad-hoc modified Layered Double Hydroxides (LDH), were successfully formulated and characterized. Particularly, LDH were considered carriers for hindered amine light stabilizing molecules, so two different hindered amine moieties (HALS1 and HALS2) were anchored on LDH layered internal structures and/or outer surfaces. The presence of HALS1 and HALS2 in LDH were confirmed by X-ray diffraction, spectroscopy, and thermogravimetric analysis. Then, the novel LDH-HALS nanofillers (here named LDH-HALS1 and LDH-HALS2) were introduced into a PA11 matrix by melt mixing at 5 wt.%; the produced nanocomposites were characterized by differential scanning calorimetry, rheological, and morphological analysis. All obtained results suggest that the LDH-HALS1/HALS2 nanofillers were very well dispersed into the PA11 matrix. Additionally, the photo-oxidative resistance of the PA11-based nanocomposite films was evaluated by subjecting thin films to UVB exposure and the degradation process was monitored by spectroscopic analysis over time. The photo-oxidative resistance of the PA11/LDH-HALS1/HALS2 was compared to that of PA11-based nanocomposites containing unmodified LDH and the commercial hindered amine UV-stabilizer (Cyasorb® UV-3853). It was established that by anchoring the hindered amine moieties to the LDH, the PA11 nanocomposites were successfully protected against UVB exposure. This was because the hindered amine light stabilizing molecules were available to act at the critical zone where the degradation phenomena occur, which is at the interface between the matrix and the inorganic particles.

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.

Recycled (Bio)Plastics and (Bio)Plastic Composites: A Trade Opportunity in a Green Future.

Today's world is at the point where almost everyone realizes the usefulness of going green. Due to so-called global warming, there is an urgent need to find solutions to help the Earth and move towards a green future. Many worldwide events are focusing on the global technologies in plastics, bioplastic production, the recycling industry, and waste management where the goal is to turn plastic waste into a trade opportunity among the industrialists and manufacturers. The present work aims to review the recycling process via analyzing the recycling of thermoplastic, thermoset polymers, biopolymers, and their complex composite systems, such as fiber-reinforced polymers and nanocomposites. Moreover, it will be highlighted how the frame of the waste management, increasing the materials specificity, cleanliness, and a low level of collected material contamination will increase the potential recycling of plastics and bioplastics-based materials. At the same time, to have a real and approachable trade opportunity in recycling, it needs to implement an integrated single market for secondary raw materials.

Biochar Particles Obtained from Agricultural Carob Waste as a Suitable Filler for Sustainable Biocomposite Formulations.

In the context of sustainable and circular economy, the recovery of biowaste for sustainable biocomposites formulation is a challenging issue. The aim of this work is to give a new life to agricultural carob waste after glucose extraction carried out by a local factory for carob candy production. A pyrolysis process was carried out on bio-waste to produce biofuel and, later, the solid residual fraction of pyrolysis process was used as interesting filler for biocomposites production. In this work, biochar particles (BC) as a pyrolysis product, after fuels recovery of organic biowaste, specifically, pyrolyzed carobs after glucose extraction, were added on poly(butylene-adipate-co-terephthalate), (PBAT), at two different concentrations, i.e., 10 and 20 wt%. The BC have been produced using three pyrolysis processing temperatures (i.e., 280, 340 and 400 °C) to optimize the compositions of produced solid fractions and biofuels. The resulting particles from the pyrolysis process (BC280, BC340 and BC400) were considered as suitable fillers for PBAT. Firstly, the BC particles properties were characterized by elemental composition and spectroscopy analysis, particle size measurements and evaluation of radical scavenging activity and efficiency. Moreover, PBAT/BC composites were subjected to analysis of their rheological and thermal behavior, morphologies and mechanical properties. In addition, accelerated weathering, monitored by both tensile test and spectroscopic analysis, was carried out, and obtained results show that the biochar particles can exert a beneficial effect on photo-oxidation delay of PBAT matrix.

Flexible Perfluoropolyethers-Functionalized CNTs-Based UHMWPE Composites: A Study on Hydrogen Evolution, Conductivity and Thermal Stability.

Flexible conductive composites based on ultra-high molecular weight polyethylene (UHMWPE) filled with multi-walled carbon nanotubes (CNTs) modified by perfluoropolyethers (PFPEs) were produced. The bonding of PFPE chains, added in 1:1 and 2:1 weight ratios, on CNTs influences the dispersion of nanotubes in the UHMWPE matrix due to the non-polar nature of the polymer, facilitating the formation of nanofillers-rich conductive pathways and improving composites' electrical conductivity (two to five orders of magnitude more) in comparison to UHMWPE-based nanocomposites obtained with pristine CNTs. Electrochemical atomic force microscopy (EC-AFM) was used to evaluate the morphological changes during cyclic voltammetry (CV). The decrease of the overpotential for hydrogen oxidation peaks in samples containing PFPE-functionalized CNTs and hydrogen production (approximately -1.0 V vs. SHE) suggests that these samples could find application in fuel cell technology as well as in hydrogen storage devices. Carbon black-containing composites were prepared for comparative study with CNTs containing nanocomposites.

Biopolyester-based systems containing naturally occurring compounds with enhanced thermo-oxidative stability.

BACKGROUND: This work presents a sustainable approach for the stabilization of polylactic acid (PLA) against thermo-oxidative aging. METHODS: Naturally occurring phenolic and polyphenolic compounds, such as ferulic acid (FerAc), vanillic acid (VanAc), quercetin (Querc) and vitamin E (VitE), were introduced into PLA. RESULTS: The preliminary characterization of the systems formulated containing different amounts of natural stabilizers showed that all compounds used acted as plasticizers, leading to a decrease in rheological functions with respect to neat PLA, without significantly modifying the crystallinity of the raw material. The study of the thermo-oxidative behavior of neat PLA and PLA/natural compound systems, performed by spectrometric and thermal analyses, indicated that all stabilizers considered were able to exert a remarkable antioxidant action against thermo-oxidative phenomena. CONCLUSIONS: All natural compounds considered are thus proposed as ecofriendly stabilizers, to get fully bio-based polymer systems with enhanced thermo-oxidative stability, suitable for biomedical applications.