Currently, one of the most important problems of environmental protection is the deep and complex processing of mineral raw materials. This problem is especially relevant when processing substandard ores and production waste, one of which is phosphogypsum. This study examines the process of CaSO4/CaS composite material formation during the reduction of phosphogypsum with citric acid. The composite structure formation mechanism is proposed. The resulting materials are characterized using various methods, including X-ray diffraction (XRD), transmission electron microscopy, the Scherrer method, thermogravimetric analysis (TGA), and FT-IR spectroscopy. The reduced sample emits orange radiation in the range of 500–750 nm with a quantum yield of 0.17. Experimental results showed that the sample decomposition process in the solid state consisted of two components with a predominant contribution from the long-lived component (~46 ns). The optimal conditions for producing luminescent materials by reducing phosphogypsum with citric acid were determined: a heat treatment temperature of 1073 K, a holding time of 60 min, and a reducing agent mole fraction of 37%. It was found that an increase in temperature with a simultaneous decrease in heat treatment time, as well as a decrease in temperature with a simultaneous increase in heat treatment time, led to a decrease in the luminescent properties of the synthesized material compared to optimal values. The results can be used to develop technology for recycling large-tonnage waste from the chemical industry into luminescent materials.
One of the priority goals of sustainable socio-economic development for the period up to 2030 is providing food for the planet’s population. This entails an increase in the output of mineral fertilizers and, consequently, an increase in the quantities of solid industrial waste. Phosphogypsum, a by-product of phosphate fertilizer production from apatite ore, is one example of such waste. The problem of solid industrial waste recycling is urgent. The present study examines the process of converting calcium sulfate, in the form of a reagent, and phosphogypsum into a composite material of calcium sulfate/sulfide. An environmentally friendly material, sucrose, is used as a reducing agent. Reduced phosphogypsum (as well as calcium sulfate) luminescence is suggested to be associated with the formation of a CaS/CaSO4 composite material. The synthesized materials are characterized by X-ray phase analysis, X-ray photoelectron spectroscopy, elemental analysis, and calcium sulfide qualitative and quantitative content in the samples. It is shown that in the reduction process at the phase contact point, crystal grids are formed with a significant number of defects, which contributes to the convergence of some of the energy levels of the calcium cation and sulfide anion, facilitating the transitions of electrons from the valence zone to the core zone and the formation of luminescence centers (cross-luminescence). Both samples of reduced phosphogypsum and alkaline earth metal sulfates are found to exhibit luminescence properties under ultraviolet radiation. The data obtained open up broad prospects for the use of solid industrial waste for the synthesis of new materials.
This paper explores the feasibility of producing manganese- and lead-doped luminescent materials from phosphogypsum. For the first time, orange- and red-emitting ultraviolet pigments were obtained using a sulfide matrix reduced from phosphogypsum. The resulting materials were characterized using X-ray diffraction (XRD), transmission electron microscopy, Fourier transform infrared spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy (XPS). Doping with manganese or lead cations is shown to produce luminophores whose luminescence shifts from orange to red–orange under UV radiation as lead cations replace manganese cations in the CaS:Mn1-xPbx solid solution. A sharp increase in red luminescence intensity was observed for CaS: Mn luminophores when they were irradiated with short-wavelength ultraviolet radiation. These results open up broad possibilities for using phosphogypsum, a high production volume (HPV) chemical waste product, to produce highly innovative products.