Recycling of Plastics from E-Waste via Photodegradation in a Low-Pressure Reactor: The Case of Decabromodiphenyl Ether Dispersed in Poly(acrylonitrile-butadiene-styrene) and Poly(carbonate).

Recycling of plastic waste from electrical and electronic equipment (EEE), containing brominated flame retardants (BFR) remains difficult due to the increasingly stringent regulations on their handling and recovery. This report deals with photodegradation in a low-pressure reactor applying UV-visible light on Decabromodiphenyl ether (DBDE or BDE-209) randomly dispersed in commercially available Poly(acrylonitrile-butadiene-styrene) (ABS) and Poly(carbonate) (PC). The aim of this study is to investigate the possibility of decomposing a BFR in plastic waste from EEE while maintaining the specifications of the polymeric materials in order to allow for their recycling. The photodegradation of the extracted BFR was monitored using infrared spectroscopy and gas chromatography coupled with mass spectroscopy. DBDE underwent rapid photodegradation during the first minutes of exposure to UV-visible light and reached degradation yields superior to 90% after 15 min of irradiation. The evaluation of polymer properties (ABS and PC) after irradiation revealed superficial crosslinking effects, which were slightly accelerated in the presence of DBDE. However, the use of a low-pressure reactor avoids large photooxidation and allowed to maintain the thermal and structural properties of the virgin polymers.

Electron Beam Processing as a Promising Tool to Decontaminate Polymers Containing Brominated Flame Retardants.

Electron Beam (EB) irradiation was utilized to decontaminate model systems of industrial polymers that contain a brominated flame retardant (BFR). Acrylonitrile-butadiene-styrene (ABS) and Polycarbonate (PC) are two types of polymers commonly found in Waste Electrical and Electronic Equipment (WEEE). In this study, these polymers were exposed to EB irradiation to degrade DecaBromoDiphenylEther (DBDE), one of the most toxic BFRs. Fourier-transform infrared spectroscopy analysis demonstrated an 87% degradation rate of DBDE for the ABS-DBDE system and 91% for the PC-DBDE system following an 1800 kGy irradiation dose. Thermal analysis using Differential Scanning Calorimetry revealed the presence of crosslinking in ABS and a minor reduction in the glass transition temperature of PC after EB processing. Polymers exhibited thermal stability after photolysis, as indicated by thermogravimetric analysis. In summary, EB irradiation had no impact on the overall thermal properties of both polymers. High-resolution mass spectrometry analysis has confirmed the debromination of both ABS-DBDE and PC-DBDE systems. Therefore, the results obtained are promising and could offer an alternative approach for removing bromine and other additives from plastic E-waste.

A simple and reliable method for separation of mineral oil/polychlorobiphenyl mixtures.

Polychlorinated biphenyls (PCBs) were broadly applied worldwide as electrical insulators in transformers and power capacitors, due to their high dielectric constant and non-flammability. They were often added to mineral oils (MOs) and used as dielectric fluids, which are nowadays classified as hazardous waste. Indeed, the Stockholm Convention aims to eliminate the use of equipment with PCB content greater than 0.005 wt-% (=50 ppm) by 2025. Accurate identification and quantification of small traces of PCBs contained in MO thus represent a great analytical challenge. To achieve this goal, a simple, cost-effective and fast chromatographic process was developed to separate PCBs from MO, allowing to obtain reliable data to determine the concentration of PCBs, reduced to 2-3 ppm. Experimental and analytical methods, such as thin layer chromatography, column chromatography as well as gas chromatography coupled with mass spectroscopy, were applied to acquire a high level of qualitative and quantitative determination of PCBs in transformer MOs.

Degradation processes of brominated flame retardants dispersed in high impact polystyrene under UV-visible radiation.

In order to protect human health and the environment, several regulations have been introduced in recent years to reduce or even eliminate the use of some brominated flame retardants (BFRs) due to their toxicity, persistence and bioaccumulation. Dispersions of these BFRs in polymers are widely used for various applications. In this report, four different brominated molecules, decabromodiphenyl ether (DBDE), hexabromocyclododecane (HBCDD), decabromodiphenyl ethane (DBDPE) and tris(tribromophenoxy)triazine (TTBPT), were dispersed in the solid matrix of an industrial polymer, high impact polystyrene (HIPS). The possibility of degradation of these BFRs within HIPS under UV-visible irradiation in ambient air was investigated. The degradation kinetics of DBDE and HBCDD were followed by Fourier transform infrared spectroscopy (FTIR) and high-resolution two-step laser mass spectrometry (L2MS). The thermal properties of the pristine and irradiated polymer matrix were monitored by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), which showed that these properties were globally preserved. Volatile photoproducts from the degradation of DBDE, DBDPE and TTBPT were identified by headspace gas chromatography/mass spectrometry analysis. Under the chosen experimental conditions, BFRs underwent rapid degradation after a few seconds of irradiation, with conversions exceeding 50% for HIPS/DBDE and HIPS/HBCDD systems.

Effect of Plasticization/Annealing on Thermal, Dynamic Mechanical, and Rheological Properties of Poly(Lactic Acid).

This study investigates the use of low molecular weight poly(ethylene glycol) (PEG) as a plasticizer for poly(lactic acid) (PLA). PLA/PEG blend films were prepared using the solvent casting method with varying mixing ratios. The films were analyzed using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and dynamic rheological analysis. The results indicate that the addition of PEG as a plasticizer affects the thermal and mechanical properties of the PLA/PEG blend films. The study found that the glass transition and cold crystallization temperatures decreased with increasing PEG content up to 20 wt%, while the crystallinity and crystallization rate increased. The blends with up to 20 wt% PEG were miscible, but phase separation occurred when the plasticizer content was increased to 30 wt%. Subsequently, amorphous samples of neat PLA and PLA plasticized with 10 wt% of PEG underwent annealing at various temperatures (Ta = 80-120 °C) for durations ta of 1 and 24 h. The samples were then analyzed using DSC and DMA. The addition of PEG to PLA altered the content of α' and α crystalline forms compared to neat PLA at a given (Ta; ta) and favored the formation of a mixture of α' and α crystals. The crystallinity achieved upon annealing increased with increasing Ta or ta and with the incorporation of PEG.

Removal of Malachite Green by Poly(acrylamide-co-acrylic acid) Hydrogels: Analysis of Coulombic and Hydrogen Bond Donor-Acceptor Interactions.

Water pollution caused by dyes poses a significant threat to life on earth. Poly(acrylamide-co-acrylic acid) hydrogels are widely used to treat wastewater from various pollutants. This study aims to examine the removal of malachite green (MG), a harmful and persistent dye that could cause extensive environmental damage, from an aqueous solution by adjusting the initial concentration of acrylamide (AM) and the degree of copolymer crosslinking. The copolymer hydrogels efficiently eliminate MG in a brief timeframe. The most successful hydrogel accomplished a removal rate exceeding 96%. The copolymer of 4 wt % 1,6-hexanediol diacrylate and a concentration of 100 mg/mL AM was effective. The degree of swelling was affected by crosslinking density as expected, with low crosslinking ratios resulting in significant swelling and high ratios resulting in less swelling. To evaluate the results, a docking approach was used which presented three crosslinked models: low, medium, and high. The copolymer-dye hydrogel system displayed robust hydrogen bonding interactions, as confirmed by the high quantities of both donors and acceptors. It was determined that MG contains six rotatable bonds, enabling it to adapt and interact with the copolymer chains. The dye and copolymer enhance H-bond formation by providing two hydrogen bond donors and 16 hydrogen bond acceptors, respectively. Through capitalizing on cationic and anionic effects, the ionic MG/copolymer hydrogel system improves retention efficiency by enhancing attraction between opposing charges. It is interesting to note that the synthesized copolymer is able to remove 96.4% of MG from aqueous media within one hour of contact time.

Decoloration of orange G (OG) using electrochemical reduction.

The electrocatalytic hydrogenation of Orange G is investigated using spectrophotometric experiments in laboratory cells. The working electrode consists of a thin grid coated with a layer of nickel in which fine particles of Raney nickel are dispersed. The optimal conditions of decoloration are as follows: basic pH, 0.05 g/L of dye concentration and 0.05 A of current density. Under these conditions, the OG decoloration efficiency reached 100% after only 1800 s of reaction. The observed values of the maximum absorbance in the spectra of the reaction mixture fitted well the polynomials of the fifth degree with respect to reaction time. The initial degradation rate of the dye is obtained easily as the differential coefficient of the functions at initial time. The degradation rate of the dye in the initial stage of the reaction is given by the first-order rate equation. The instantaneous current efficiency was calculated and the results indicated that cathodic reduction was the main contributor to the decoloration of OG. Direct cathodic reduction ofazo dyes allows decolorization of intensively coloured textile wastewater without addition of chemicals or formation of sludge. The technique is of particular interest for the treatment of concentrated dye baths. The effect of current density, dye concentration, and concentration and nature of the supporting electrolyte on the reduction of the Orange G are reported.

Cleaning of Wastewater Using Crosslinked Poly(Acrylamide-co-Acrylic Acid) Hydrogels: Analysis of Rotatable Bonds, Binding Energy and Hydrogen Bonding.

The discharge of untreated wastewater, often contaminated by harmful substances, such as industrially used dyes, can provoke environmental and health risks. Among various techniques, the adsorption of dyes, using three-dimensional (3D) networks consisting of hydrophilic polymers (hydrogels), represents a low-cost, clean, and efficient remediation method. Three industrially used dyes, Methylene Blue, Eosin, and Rose Bengal, were selected as models of pollutants. Poly(acrylamide) (poly(AM)) and poly(acrylamide-co-acrylic acid) (poly(AM-co-AA)) networks were chosen as adsorbent materials (hydrogels). These polymers were synthesized by crosslinking the photopolymerization of their respective monomer(s) in an aqueous medium under exposure to UV light. Experimental adsorption measurements revealed substantially higher dye uptakes for poly(AM-co-AA) compared to poly(AM) hydrogels. In this report, a theoretical model based on docking simulations was applied to analyze the conformation of polymers and pollutants in order to investigate some aspects of the adsorption process. In particular, hydrogen and halogen interactions were studied. The presence of strong hydrogen bonding plays a crucial role in the retention of dyes, whereas halogen bonding has a small or negligible effect on adsorption. An evaluation of binding energies allowed us to obtain information about the degree of affinity between polymers and dyes. The number of rotatable bonds in the copolymer exceeds those of poly(AM),meaning that poly(AM-co-AA) is revealed to be more suitable for obtaining a high retention rate for pollutants.

Temperature Controlled Mechanical Reinforcement of Polyacrylate Films Containing Nematic Liquid Crystals.

This investigation reports on the thermomechanical properties of Poly-tripropyleneglycoldiacrylate (Poly-TPGDA)/liquid crystal (LC) blends, developed via free radical polymerization processes, which are induced by Electron Beam (EB) and Ultraviolet (UV) radiation. The EB-cured Poly-TPGDA network exhibits a higher glass transition temperature (Tg), a higher tensile storage, and Young moduli than the corresponding UV-cured sample, indicating a lower elasticity and a shorter distance between the two adjacent crosslinking points. Above Tg of Poly-TPGDA/LC blends, the LC behaves as a plasticizing agent, whereas, for EB-cured networks, at temperatures below Tg, the LC shows a strong temperature dependence on the storage tensile modulus: the LC reinforces the polymer due to the presence of nano-sized phase separated glassy LC domains, confirmed by electron microscopy observations. In the case of the UV-cured TPGDA/LC system, the plasticizing effect of the LC remains dominant in both the whole composition and the temperature ranges explored. The rubber elasticity and Tg of Poly-TPGDA/LC films were investigated using mechanical measurements.

Development of a TiO2/Sepiolite Photocatalyst for the Degradation of a Persistent Organic Pollutant in Aqueous Solution.

A clay-based TiO2 nanocomposite material was synthesized by a facile method, to investigate its structure and photocatalytic efficiency. The supported TiO2 nanoparticles were generated using a sol-gel method, and subsequently, mixed with a suspension of sepiolite. The material was recovered in powder form (Mc-80) and then calcined to properly arrange the crystal lattice of the TiO2 particles for use in heterogeneous photocatalysis (Mc-80-500). A powder X-ray diffractogram of Mc-80-500 revealed a dispersion of anatase and rutile phase TiO2 particles on the clay surface, exhibiting a size in the order of 4-8 nm. TEM images of Mc-80-500 confirmed the presence of isolated TiO2 beads on the surface of the fibrous sepiolite. The specific surface area of Mc-80-500 was larger than that of raw sepiolite and that of free TiO2 nanoparticles. Mc-80-500 was found to be more efficient in heterogeneous photocatalysis compared to other TiO2 materials based on sepiolite. Total depollution of a reactive dye (Orange G) was achieved after 1 h irradiation time, which is relatively quick compared to previous reports. The photocatalyst material can be washed with distilled water without chemical additives or calcination, and can be reused several times for photocatalysis, without loss of efficiency.