Polyethylene terephthalate (PET) was depolymerized to monomer bis(2-hydroxyethyl) terephthalate (BHET) using excess ethylene glycol (EG) in the presence of metal oxides that were impregnated on different forms of silica support [silica nanoparticles (SNPs) or silica microparticles (SMPs)] as glycolysis catalysts. The reactions were carried out at 300 degrees C and 1.1 MPa at an EG-to-PET molar ratio of 11:1 and a catalyst-to-PET-weight ratio of 1.0% for 40-80 min. Among the four prepared catalysts (Mn3O4/SNPs, ZnO/SNPs, Mn3O4/SMPs, and ZnO/SMPs), the Mn3O4/SNPs nanocomposite had the highest monomer yield (> 90%). This high yield may be explained by the high surface area, amorphous and porous structure, and existence of numerous active sites on the nanocomposite catalyst. The BHET yield increased with time and reached the highest level where equilibrium was established between BHET and its dimer. The catalysts were characterized by their SEM, TEM, and BET surface areas, and via XRD, whereas the monomer BHET was characterized by HPLC and FT-IR. The glycolysis with the Mn3O4/SNPs nanocomposite as the glycolysis catalyst produced a maximum BHET in a short reaction time.
Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.
A series of plastic materials from recycled polyethylene (PE) and oyster-shell powder were prepared to test their fire-retardant properties with an aim of finding a practical way of waste recycling. Oyster-shell powder was found to be mainly composed of calcium carbonate and it decomposed to calcium oxide and carbon dioxide at temperature higher than ϳ800°C, thus preventing fire from access of oxygen by the produced carbon dioxide. This fireretardation mechanism is environmental-friendly, since another available method, the inclusion of halogen-containing compounds, normally generates toxic chemicals like dioxine during incineration. To improve mechanical properties of this composite material, surface of oyster-shell powder was coated with cetyltrimethylammonium bromide (CTAB). Flame retardation and the mechanical properties of these composite resins were analyzed.
We added surface-modified silica nanoparticles to poly(ethylene 2,6-naphthalate) (PEN) to investigate their effect on the mechanical properties on the PEN nanocomposite material. The torque and total torque values of the composites decreased in the silica nanoparticle composites. The tensile modulus of the composites reinforced with unmodified silica nanoparticles increased upon increasing the silica content, while the tensile strength and elongation decreased accordingly. In contrast, stearic acid-modified, silica nanoparticle reinforced PEN composites exhibited an increase in elongation and a decrease in tensile modulus upon addition of the silica nanoparticles because the stearic acid that had adsorbed onto the surface of the silica nanoparticle in multilayers could act as a plasticizer during melt compounding. Stearic acid modification had a small effect on the crystallization behavior of the composites. We calculated theoretical values of the tensile modulus using the Einstein, Kerner, and Nielsen equations and compared these values with the experimental data obtained from the composites. The parameters calculated using the Nielsen equation and the Nicolais Narkis model revealed that the interfacial adhesion between silica nanoparticles and the PEN matrix could be improved.
A large amount of silicon debris particles are generated during the slicing of silicon ingots into thin wafers for the fabrication of integrated-circuit chips and solar cells. This results in a significant loss of valuable materials at about 40% of the mass of ingots. In addition, a hazardous silicon sludge waste is produced containing largely debris of silicon, and silicon carbide, which is a common cutting material on the slicing saw. Efforts in material recovery from the sludge and recycling have been largely directed towards converting silicon or silicon carbide into other chemicals. Here, we report an aerosol-assisted method to extract silicon nanoparticles from such sludge wastes and their use in lithium ion battery applications. Using an ultrasonic spray-drying method, silicon nanoparticles can be directly recovered from the mixture with high efficiency and high purity for making lithium ion battery anode. The work here demonstrated a relatively low cost approach to turn wafer slicing wastes into much higher value-added materials for energy applications, which also helps to increase the sustainability of semiconductor material and device manufacturing.
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