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1.
Toxics ; 12(2)2024 Jan 26.
Article in English | MEDLINE | ID: mdl-38393198

ABSTRACT

The recovery and recycling of metals that generate toxic ions in the environment is of particular importance, especially when these are tungsten and, in particular, thorium. The radioactive element thorium has unexpectedly accessible domestic applications (filaments of light bulbs and electronic tubes, welding electrodes, and working alloys containing aluminum and magnesium), which lead to its appearance in electrical and electronic waste from municipal waste management platforms. The current paper proposes the simultaneous recovery of waste containing tungsten and thorium from welding electrodes. Simultaneous recovery is achieved by applying a hybrid membrane electrolysis technology coupled with nanofiltration. An electrolysis cell with sulphonated polyether-ether-ketone membranes (sPEEK) and a nanofiltration module with chitosan-polypropylene membranes (C-PHF-M) are used to carry out the hybrid process. The analysis of welding electrodes led to a composition of W (tungsten) 89.4%; Th 7.1%; O2 2.5%; and Al 1.1%. Thus, the parameters of the electrolysis process were chosen according to the speciation of the three metals suggested by the superimposed Pourbaix diagrams. At a constant potential of 20.0 V and an electrolysis current of 1.0 A, the pH is varied and the possible composition of the solution in the anodic workspace is analyzed. Favorable conditions for both electrolysis and nanofiltration were obtained at pH from 6 to 9, when the soluble tungstate ion, the aluminum hydroxide, and solid thorium dioxide were formed. Through the first nanofiltration, the tungstate ion is obtained in the permeate, and thorium dioxide and aluminum hydroxide in the concentrate. By adding a pH 13 solution over the two precipitates, the aluminum is solubilized as sodium aluminate, which will be found after the second nanofiltration in the permeate, with the thorium dioxide remaining integrally (within an error of ±0.1 ppm) on the C-PHF-M membrane.

2.
Polymers (Basel) ; 15(3)2023 Jan 30.
Article in English | MEDLINE | ID: mdl-36771997

ABSTRACT

Ultra-high-molecular-weight polyethylene (UHMWPE) matrices containing low-density polyethylene (LDPE), hydroxyapatite (HAp) as filler, and rosemary extract (RM) as stabilizer were investigated for their qualification for long-term applications. The significant contributions of the blend components were analyzed, and variations in mechanical properties, oxidation strength, thermal behavior, crystallinity, and wettability were discussed. SEM images of microstructural peculiarities completed the introspective survey. The stability improvement due to the presence of both additives was an increase in the total degradation period of 67% in comparison with an unmodified HDPE/UHMWPE blend when the materials were subjected to a 50 kGy γ-dose. There was growth in activation energies from 121 kJ mol-1 to 139 kJ mol-1 when HAp and rosemary extract delayed oxidation. The exposure of samples to the action of γ-rays was found to be a proper procedure for accomplishing accelerated oxidative degradation. The presence of rosemary extract and HAp powder significantly increased the thermal and oxidation resistances. The calculation of material lifetimes at various temperatures provided meaningful information on the wearability and integrity of the inspected composites.

3.
Materials (Basel) ; 15(14)2022 Jul 21.
Article in English | MEDLINE | ID: mdl-35888545

ABSTRACT

In this paper, the stability improvement of poly(lactic acid) (PLA)/styrene-isoprene block copolymer (SIS) loaded with silica nanoparticles is characterized. The protection efficiency in the material of thermal stability is mainly studied by means of high accurate isothermal and nonisothermal chemiluminescence procedures. The oxidation induction times obtained in the isothermal CL determinations increase from 45 min to 312 min as the polymer is free of silica or the filler loading is about 10%, respectively. The nonisothermal measurements reveal the values of onset oxidation temperatures with about 15% when the concentration of SiO2 particles is enhanced from none to 10%. The curing assay and Charlesby-Pinner representation as well as the modifications that occurred in the FTIR carbonyl band at 1745 cm-1 are appropriate proofs for the delay of oxidation in hybrid samples. The improved efficiency of silica during the accelerated degradation of PLA/SIS 30/n-SiO2 composites is demonstrated by means of the increased values of activation energy in correlation with the augmentation of silica loading. While the pristine material is modified by the addition of 10% silica nanoparticles, the activation energy grows from 55 kJ mol-1 to 74 kJ mol-1 for nonirradiated samples and from 47 kJ mol-1 to 76 kJ mol-1 for γ-processed material at 25 kGy. The stabilizer features are associated with silica nanoparticles due to the protection of fragments generated by the scission of hydrocarbon structure of SIS, the minor component, whose degradation fragments are early converted into hydroperoxides rather than influencing depolymerization in the PLA phase. The reduction of the transmission values concerning the growing reinforcement is evidence of the capacity of SiO2 to minimize the changes in polymers subjected to high energy sterilization. The silica loading of 10 wt% may be considered a proper solution for attaining an extended lifespan under the accelerated degradation caused by the intense transfer of energy, such as radiation processing on the polymer hybrid.

4.
Materials (Basel) ; 16(1)2022 Dec 24.
Article in English | MEDLINE | ID: mdl-36614495

ABSTRACT

A novel conductive composite material with homogeneous binary polymer matrix of HDPE (HD) and LLDPE (LLD), mixed with conductive filler consisting of carbon black (CB) and graphite (Gr), was tested against a HDPE composite with a similar conductive filler. Even the concentration of the conductive filler was deliberately lower for (CB + Gr)/(LLD + HD), and the properties of this composite are comparable or better to those of (CB + Gr)/HD. The kinetic parameters of the ρ-T curves and from the DSC curves indicate that the resistivity peak is obtained when the polymer matrix is fully melted. When subjected to repeated thermal cycles, the composite (CB + Gr)/(LLD + HD) presented a better electrical behavior than composite CB + Gr)/HD, with an increase in resistivity (ρmax) values with the number of cycles, as well as less intense NTC (Negative Temperature Coefficient) effects, both for the crosslinked and thermoplastic samples. Radiation crosslinking led to increased ρmax values, as well as to inhibition of NTC effects in both cases, thus having a clear beneficial effect. Limitation effects of surface temperature and current intensity through the sample were observed at different voltages, enabling the use of these materials as self-regulating heating elements at various temperatures below the melting temperature. The procedure based on physical mixing of the components appears more efficient in imparting lower resistivity in solid state and high PTC (Positive Temperature Coefficient) effects to the composites. This effect is probably due to the concentration of the conductive particles at the surface of the polymer domains, which would facilitate the formation of the conductive paths. Further work is still necessary to optimize both the procedure of composite preparation and the properties of such materials.

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