Search Results (315)

Driven by global carbon reduction targets, supersulfated cement has emerged as a promising low-carbon cementitious material. This study investigates the influence of a polycarboxylate superplasticizer (PCE) on the rheological behavior and early interfacial evolution of phosphogypsum-based supersulfated cement (PSSC). Rheological measurements, pore solution ion analysis, hydration heat analysis, X-ray diffraction (XRD), and scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM–EDS) are employed to correlate early hydration processes with structural development. The results indicate that the incorporation of PCE significantly reduces the initial yield stress and moderates the structural build-up rate. At a PCE dosage of 0.3 wt.%, the initial static yield stress decreases from 1313 Pa to approximately 125 Pa, while the structural build-up index I_s,s reaches 10.19, indicating improved particle dispersion while maintaining progressive structural reconstruction during hydration. Phosphogypsum (PG) functions not only as a sulfate source but also as an active interfacial substrate that promotes the preferential nucleation of AFt on its surface. In the absence of PCE, continuous Ca–P-enriched layers form on PG particles, accompanied by localized AFt accumulation. After the incorporation of PCE, the primary crystalline phases remain unchanged; however, gypsum dissolution and AFt formation are delayed. Meanwhile, Ca–P enrichment shifts from continuous coverage to a more dispersed distribution, promoting the spatially separated growth of AFt crystals rather than dense localized aggregation. Overall, PCE influences the evolution of the structure and properties of the system by regulating early interfacial reactions and the spatial organization of hydration products. Full article

The presence of impurities directly affects the properties of α-hemihydrate gypsum (α-HH) prepared from phosphogypsum (PG) as a raw material. However, the effect of soluble fluorine impurities on the properties of α-HH by autoclaving remains insufficiently understood. This study investigated the influence of sodium fluoride on the morphology, hydration, and hardening properties of α-HH, using XRD, XPS, SEM, MIP, and tests of setting time, evolution of hydration temperature increase, and strength. The results showed that during the preparation of α-HH, some F⁻ reacted with Ca²⁺ to form CaF₂, which adhered to the surface of the α-HH crystal, hindering the growth and development of the crystal and resulting in small crystals with rough surfaces. When α-HH hydrated, sodium fluoride caused the early, rapid nucleation of dihydrate gypsum (DH) crystals, accelerating the crystallization process of DH. The introduction of sodium fluoride inhibited the early hydration of α-HH and promoted its later hydration. The increase in sodium fluoride content caused the initial setting time of α-HH hydration to first increase and then decrease, while the final setting time continued to decrease. In the absence of sodium fluoride, the average pore diameter of the hardened paste was approximately 617.99 nm. When the NaF content was 0.2%, the DH crystals were prismatic and densely packed, which resulted in a decrease in the average pore diameter to 449.35 nm. When the NaF content was 0.6%, the DH crystals exhibited a plate-like morphology and were loosely interlocked, leading to an increase in the average pore diameter to 1169.58 nm. Based on these results, the sodium fluoride content in PG should be controlled below 0.2%. Full article

This study investigates the development and optimization of a multi-component modifying additive based on industrial waste for improving the mechanical and durability properties of concrete. The additive consists of microsilica (Ms), phosphogypsum (PhG), soapstock (Sp), and post-alcohol bard (PaB), and its performance was evaluated using a staged experimental approach. The results showed that the optimal content of microsilica is 20% of the cement mass; the optimal content of phosphogypsum is 15% of the combined mass of the cement and microsilica; the optimal content of soapstock is 10% of the total mass of the cement, microsilica, and phosphogypsum; and the optimal post-alcohol bard is 5% of the water mass. At these concentrations, the compressive strength increased by up to 28.3% compared to the reference sample. Soapstock significantly reduced water absorption (up to 36.8%) and improved freeze–thaw resistance due to the hydrophobization of the cement matrix. However, excessive soapstock content led to a reduction in strength. The addition of post-alcohol bard provided a plasticizing effect and reduced water absorption, with the optimal concentration for strength being 2.5%, while the highest freeze–thaw resistance was observed at 5%. The combined effect of the components resulted in the formation of a denser microstructure and improved durability of concrete. These findings demonstrate the effectiveness of industrial waste-based additives in enhancing concrete performance and durability, contributing to sustainable material development. Full article

This study investigates the mechanical properties and internal pore structure characteristics of raw phosphogypsum–basalt fiber (RPG-BF) cementitious materials with varying raw phosphogypsum (PG) replacement ratios. Specifically, six different PG addition levels (0%, 3%, 6%, 9%, 12%, and 15% by mass of cementitious materials) with a constant basalt fiber dosage of 0.1% (by volume of concrete) were adopted. The mechanical properties of RPG-BF cementitious materials were evaluated by testing the 7-day and 28-day compressive strengths, 28-day split tensile strength, and 28-day flexural strength. Meanwhile, the pore distribution characteristics of the RPG-BF cementitious materials were systematically analyzed using liquid nitrogen adsorption (LNA) tests and scanning electron microscopy (SEM) observations. The experimental results indicate the following: (a) With an increase in PG content, the mechanical properties of RPG-BF cementitious materials exhibit a significant downward trend: the 28-day compressive strength, split tensile strength, and flexural strength decrease by 49%, 44%, and 43%, respectively. (b) The internal pores of the RPG-BF cementitious materials possess excellent fractal characteristics, with fractal dimensions ranging from 2.52 to 2.62. As the PG content increases, the pore structure becomes more intricate and less homogeneous, which is a microstructural factor associated with the degradation of mechanical properties. (c) There exists a strong Pearson’s linear correlation (R > 0.82, with R² ranging from 0.67 to 0.94) between the pore fractal dimension of RPG-BF cementitious materials and their 7-day/28-day compressive strength, split tensile strength, and flexural strength. (d) SEM observations show that the quantity of micropores and microcracks in the RPG-BF cementitious materials increases with increasing PG content, further confirming deterioration of the material microstructure. Full article

The inefficient utilization of industrial by-product phosphogypsum, coupled with the increasing global demand for cooling, has spurred the development of sustainable radiative cooling materials. Compared with conventional cooling coatings that primarily rely on expensive synthetic materials or complex fabrication processes, this study provides a promising cost-effective and sustainable route for integrating industrial solid waste valorization with zero-energy cooling technologies. In this study, we fabricated a composite coating (β-HPG@CA/SiO₂@OTS) consisting of β-hemihydrate phosphogypsum (β-HPG), a derivative product of phosphogypsum, cellulose acetate (CA), SiO₂ particles and octadecyltrichlorosilane (OTS) by a facile combination of blade coating and spraying, which exhibited strong solar reflectivity (90.9%), high mid-infrared emissivity (98.7%) and satisfactory superhydrophobicity (157°). The as-prepared composite achieved an ambient temperature drop of 18.7 °C under direct sunlight during sunny weather, achieving a net cooling power of 92.23 W/m². Meanwhile, the composite coating exhibits excellent durability after prolonged immersion in strongly acidic and alkaline solutions, ultraviolet radiation and outdoor testing. Owing to its simple fabrication process and robust cooling performance, this coating shows promise for scalable production and practical outdoor applications, such as building envelopes and equipment enclosures. Full article

Accurate quantification of phosphogypsum (PG) filler in epoxy composites is essential for quality control and performance optimization. Conventional separation by muffle furnace calcination suffers from slow epoxy decomposition and risks thermal degradation of CaSO₄, leading to inaccurate PG quantification. This study introduces a microwave-assisted separation method that leverages molecular vibration heating to achieve faster heating rates and more uniform temperature distribution, enabling complete epoxy removal while minimizing CaSO₄ decomposition. Comprehensive characterization (X-ray diffraction, XRD; Fourier transform infrared spectroscopy, FT-IR; scanning electron microscopy-energy dispersive spectroscopy, SEM-EDS) confirms the structural integrity of the isolated PG filler. Among five quantification methods evaluated, inductively coupled plasma optical emission spectrometry (ICP-OES) based on sulfur content provides the highest accuracy (spike recovery: 91–99.8%, relative standard deviation, RSD ≤ 4.2%), while gravimetry suffices for single-filler systems. This work establishes a reliable analytical framework for PG characterization in epoxy composites, supporting quality control and resource valorization. Full article

As solid waste generated from shield tunnel construction, shield muck is characterized by its massive volume, high water content, and poor engineering properties. Large-scale stockpiling not only occupies precious land resources but also poses potential environmental risks. This has become one of the key bottlenecks hindering the green, low-carbon, and sustainable development of rail transit construction. Efficient dewatering is a key prerequisite for its subsequent disposal or reutilization. Lime, cement, phosphogypsum, nano-SiO₂, and ground granulated blast furnace slag were employed in this research as composite conditioning agents to dewater shield tunnel muck. A range of water content, pH, and total organic carbon analyses tests were conducted to explore the roles of lime, cement, phosphogypsum, nano-SiO₂, and ground granulated blast furnace slag on the dewatering effect of shield tunnel muck. Furthermore, microstructures and elemental distribution of typical mixes were analyzed by scanning electron microscopy and energy-dispersive X-ray spectroscopy tests. Results indicate that a composite agent consisting of 3.5% lime, 4% cement, 1% phosphogypsum, 0.2% nano-SiO₂, and 4% ground granulated blast furnace slag exhibits optimal performance, reducing water content from 50% to 29.8% within 24 h. Phosphogypsum significantly decreased pH and reduced TOC to below 1 g/kg after 15 days, effectively mitigating the environmental hazards associated with muck disposal. The formation of cementitious products, including calcium aluminate hydrate, calcium aluminosilicate hydrate gels, and calcium silicate hydrate, effectively bonds soil particles. Additionally, ettringite crystals produced by the reaction between phosphogypsum and calcium aluminate phases filled interparticle voids. These processes were identified as the primary mechanisms for water reduction. Although nano-SiO₂ exerted a limited direct influence on water content, it acted as a pozzolanic catalyst that accelerated hydration reactions of lime and cement, rapidly reducing muck fluidity. The synergistic effect of the composite dewatering agent components establishes a multi-mechanism dewatering system characterized by “hydration gel + AFt filling + nano-catalysis.” The dewatering system developed in this study achieves both high efficiency and environmental friendliness for shield tunnel muck. This provides technical support for subsequent resource utilization, such as subgrade filling, while promoting the recycling of industrial solid wastes like phosphogypsum and blast furnace slag, ultimately contributing to green, low-carbon, and sustainable development. Full article

Phosphogypsum (PG), a major by-product of the phosphate industry, has potential for improving acidic and nutrient-poor red soils, yet its agronomic benefits and heavy metal risks require systematic evaluation. A field experiment was conducted with five treatments, CK (soil only), GT (50% modified phosphogypsum, MPG), TT (40% MPG), ZT (50% phosphorite tailings), and DT (25% MPG + 25% lake sediment), to assess their effects on soil properties, enzyme activities, peanut growth, yield, quality, and heavy metal accumulation. All amendments improved soil structure, moisture retention, nutrient availability, and enzymatic activities. Peanut pod and kernel yields increased under all treatments, with DT achieving the greatest improvements (29.89% and 40.88%, respectively), whereas ZT showed the weakest response (1.91% and 6.26%). DT also achieved the highest soil quality index, and performed best in both yield improvement and root development. Although Cd accumulation increased under DT, heavy metal concentrations in peanut kernels remained below national food safety limits. Overall, DT was identified as the most effective amendment for enhancing red soil fertility and peanut productivity, while long-term monitoring of Cd bioavailability is recommended to ensure sustainable and safe application. Full article

This study investigates the effects of three solid waste powders—fly ash (FA), silica fume (SF), and phosphogypsum (P)—on the drying shrinkage behavior of metakaolin-based geopolymers. To systematically evaluate the performance and underlying mechanisms, a comprehensive experimental program was conducted, including compressive strength and elastic modulus testing, early-age and variable-humidity drying shrinkage monitoring, mercury intrusion porosimetry, and microcalorimetry analysis. Results demonstrate that all three materials effectively reduce drying shrinkage through distinct mechanisms. The incorporation of 30% FA optimized the capillary pore network and densified the matrix, achieving a peak compressive strength of 53.51 MPa and an elastic modulus of 9.23 GPa. SF exhibited a dose-dependent effect; at an optimal content of 7%, it enhanced compressive strength by 28.3% through its nucleation effect and micro-aggregate filling. However, excessive SF (9%) led to pore coarsening and increased shrinkage. Although P incorporation slightly reduced mechanical strength, it decreased cumulative porosity by up to 8% and formed needle-like Wairakite-Ca crystals that provided micro-structural support, resulting in a net shrinkage reduction of up to 137.83 µε. This study provides a scientific basis for designing low-shrinkage, low-carbon geopolymers by tailoring solid waste incorporation to engineer multiscale pore structures. Full article

Building 3D printing technology exhibits remarkable construction advantages, with solid waste-based 3D printing slurry emerging as a research hotspot in the field. Phosphogypsum is compatible with diverse solid wastes for the fabrication of geopolymer, whereas its feasibility as a 3D printing material merits further investigation. In this study, calcium carbide slag (CS), ground granulated blast-furnace slag (GGBS), recycled concrete powder (RCP), and phosphogypsum (PG) underwent co-activation. The mix proportion received optimization via response surface methodology (RSM), and printability assessment proceeded based on the optimized proportion. Key conclusions include the following: PG exerts a role in optimizing the internal structure within the geopolymer matrix. The 28-day compressive strength of the composite geopolymer exceeds 25 MPa. Application as a 3D printing material facilitates enhancement of slurry stability in the later stage. Excessive PG addition elevates the shear stress and viscosity of the 3D printing paste, shortens the paste open time, and impedes paste extrusion and molding. Based on a comprehensive analysis of printability and the performance of printed specimens, the optimal mix proportion of the phosphogypsum-based geopolymer 3D printing paste was determined as follows: CS: 22.5%; GGBS: 45%; RCP: 22.5%; PG: 10%; W/b: 0.4. Full article

As an extremely toxic heavy metal, lead is difficult to be degraded in the environment, and its curing and disposal is a key challenge in environmental pollution control. In this study, supersulfated cement (SSC) prepared from phosphogypsum, granulated blast furnace slag powder, and slaked lime as raw materials was used as curing cementitious material, and the curing effect and curing mechanism of SSC on lead ions were investigated by adopting testing methods such as compressive strength, electrical resistivity, X-ray diffraction (XRD), scanning electron microscopy (SEM), heavy metal ion leaching toxicity analysis, and ion concentration analysis of pore solutions. The results show that with an increase in Pb²⁺ concentration, the compressive strength of the SSC-cured paste gradually decreased, the electrical resistivity was obviously reduced, and the generation of hydration products was inhibited. The microanalysis results show that the microstructure of the cured paste became loose, and the concentration of lead ions in the SSC leach solution gradually increased, but it was much lower than the limit value stipulated in Chinese standards. Full article

The efficient recovery of rare earth elements from associated rare-earth-bearing phosphate ores is of paramount importance for expanding the supply of rare earth resources. In contrast to conventional studies that focus on extracting rare earths either from phosphate concentrates or from phosphogypsum generated during the sulfuric acid wet-process, this study takes as its subject the rare-earth-enriched residue—an intermediate product obtained after the selective leaching of phosphorus via the hydrochloric acid route—from a rare-earth-bearing phosphate ore in Zhijin, Guizhou Province. The occurrence states, leaching behavior, and kinetic mechanisms of rare earth elements within this residue were systematically elucidated. Analyses using scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM–EDS) and aberration-corrected scanning transmission electron microscopy (STEM) reveal that rare earth elements are hosted in residual fluorapatite and newly formed CaF₂ through isomorphic substitution. The substitution of REE³⁺ for Ca²⁺ induces lattice contraction in CaF₂, with the interplanar spacing decreasing from 0.27 nm to 0.26 nm. Through single-factor experiments and response surface methodology (RSM) optimization, the optimal leaching conditions were determined to be a temperature of 80 °C, a leaching time of 120 min, a hydrochloric acid dosage of 160% of the theoretical requirement, a solid–liquid ratio of 1:6, and a agitation speed of 500 r·min⁻¹. Under these conditions, the leaching efficiency of rare earth elements reached as high as 92.69%. Kinetic analysis indicates that the leaching process follows the shrinking-core model, with the rate controlled by diffusion through the solid product layer. The apparent activation energy was calculated to be 37.2 kJ·mol⁻¹, characteristic of a diffusion-controlled process. Furthermore, response surface analysis of variance confirms that leaching temperature and time are the most significant factors influencing rare earth leaching. This study elucidates, from multiple perspectives, the leaching mechanism of rare earth elements from enriched residues within a hydrochloric acid system, thereby providing important theoretical support for the efficient recovery and process optimization of rare earth resources from associated phosphate ores. Full article

Supersulfated cement (SSC) is an environmentally friendly cementitious material with a low clinker content, in which industrial byproduct gypsum serves as the sulfate source, thereby enabling the valorization of solid waste. The hydration process, pore structure, microstructure, and hydration products were investigated using paste samples by means of isothermal calorimetry, X-ray diffraction (XRD), thermogravimetric analysis (TG–DTG), Fourier transform–infrared spectroscopy (FT-IR), mercury intrusion porosimetry (MIP), and scanning electron microscopy (SEM), while compressive strength was evaluated using mortar specimens. Compared with ordinary Portland cement (OPC), SSC offers clear advantages in reducing energy consumption and greenhouse gas emissions. In this study, the effects of titanium gypsum (TG) and flue gas desulfurization gypsum (FGD) on the hydration behavior, fluidity, mechanical properties, and microstructural evolution of an anhydrite (AH)–phosphogypsum (PG)-based SSC were systematically investigated. The results indicate that the incorporation of 11% TG and FGD mitigates the strong sulfate environment caused by the rapid dissolution of soluble AH, thereby regulating the hydration process. As the proportion of TG and FGD increased, the cumulative heat release within 72 h gradually decreased. When AH was completely replaced, the cumulative heat release of TG4 and FG4 decreased by approximately 19.7% and 28.6%, respectively. TG and FGD exhibited opposite effects on the fluidity of SSC while both promoting strength development. Among all mixtures, TG2 and FG2 showed the best performance, with the highest 28-day compressive strengths of 50.15 MPa and 51.95 MPa, respectively. Microstructural analysis reveals that differences in particle size distribution and dissolution kinetics among gypsums governed the sulfate release characteristics and slag activation mechanisms, thus leading to distinct hydration pathways, pore structure evolution, and microstructural densification. This study provides a theoretical basis for the efficient utilization of various industrial byproduct gypsums and offers important guidance for the controllable design of SSC performance. Full article

The long-term accumulation of phosphogypsum (PG) stacks has caused combined pollution of total phosphorus (TP), fluoride (F⁻), metals and metalloids (MMs), posing a severe threat to regional ecological security. To clarify the migration characteristics of pollutants in PG stacks, water leaching experiments and environmental risk assessment were conducted in 21 typical PG stacks in Southwest China. The spatial differentiation and vertical migration characteristics of pollutants under various coverage measures (high-density polyethylene (HDPE) film covering, soil covering, a composite of film–soil covering, and open-air storage) at different pH conditions were systematically analyzed. Results indicated that under open-air stockpiling conditions, the surface accumulation of TP and F⁻ was the most significant among all covering measures, corresponding to the highest environmental risk. In contrast, the membrane–soil composite covering exhibited the optimal inhibitory effect on the surface diffusion of TP and F⁻, but was less effective for metal and metalloid enrichment. Under acidic conditions (pH < 6), the vertical migration capacity of TP, F⁻, and MMs (Cu, Cd, Cr, Pb, and Zn) increased, leading to enrichment in the deep layers of the stack. With the increase in pH, the calcium-mediated precipitation–adsorption effect created a “geochemical barrier”, facilitating the solid-phase fixation of pollutants. A significant positive correlation among pollutants indicates synergistic release and fixation behaviors. In addition, a pH-controlled P-F-MM source-to-sink conceptual model was established, outlining the dissolution, precipitation, adsorption, fixation and re-enrichment pathway from fresh stock to leachate. This work provides insights for optimizing cover designs and pollution control strategies. Full article

Phosphogypsum (PG) has the potential to elevate phosphorus levels in compost; however, it may also retard the composting maturation process, and its underlying mechanism for phosphorus activation remains unclear. In this study, sawdust was mixed with pig manure or chicken manure at a ratio of 1:4 (m:m, fresh weight) and added 10% PG as the treatment group, and added no PG as control treatment. The entire composting process lasts for 60 days. During the composting process, temperature was monitored daily, pH, electrical conductivity (EC), germination index (GI), phosphorus and its distribution were measured to monitor the composting process, and bacterial communities and predict phosphate-solubilizing genes and bacteria through the KEGG database. Pearson correlation analysis between phosphate-solubilizing bacteria and phosphorus components was conducted. The results demonstrated that (1) PG supplementation delayed the temperature rise and humification during composting, yet the final compost maturity was maintained (GI ≈ 90%). (2) PG addition increased the abundance of the ppx-gppa and phoR genes in pig manure compost, while enhancing the phnE and phoP genes in chicken manure compost. (3) In pig manure composting, Dietzia and Clostridium sensu stricto_1 were identified as key bacteria responsible for phosphorus activation, and promoting their growth favored phosphorus mobilization. (4) In chicken manure compost, Lactobacillus and Pseudomonas played crucial roles in phosphorus activation, though inhibiting their growth was found to enhance phosphorus availability. Overall, PG addition promoted phosphorus activation in compost, significantly increasing the NaHCO₃-P content in both pig manure and chicken manure composts (by 9.36 and 17.86 percentage points, respectively). Full article