Effect of Fluoride Content in Synthetic Phosphogypsum on the Hydration Behavior and Mechanical Properties of Cemented Paste Backfill

Phosphogypsum-based cemented paste backfill (PCPB) represents an effective solution for managing substantial accumulations of PG. However, its practical application is limited by excessive fluoride content and insufficient strength. To systematically investigate the influence of initial fluoride content on the hydration behavior, microstructures, and strength development of PCPB specimens, synthetic phosphogypsum was prepared using CaSO4·2H2O and NaF to eliminate impurity interference in this study. A series of specimens was designed with varying initial fluoride content (5–70 mg/L), sand-to-cement ratios (1:6, 1:8, 1:10), and concentrations (63 wt%, 65 wt%). Setting time, unconfined compressive strength, isothermal calorimetry, X-ray diffraction, and scanning electron microscopy were employed to elucidate the effects and underlying mechanisms of fluoride on PCPB performance. The results indicate that higher initial fluoride content markedly delayed setting and reduced early strength. Calorimetric analysis confirmed that fluoride postponed the exothermic peak and extended the induction period, primarily due to the formation of the CaF2 layer on clinker particle surfaces, which hindered nucleation and hydration. The microscopic results further revealed that high fluoride content suppressed the formation of ettringite and C-S-H gels, resulting in more porous and loosely bonded microstructures. Leaching tests indicated that fluoride immobilization in PCPB specimens occurred mainly through CaF2 precipitation, physical encapsulation, and ion exchange. These findings provide theoretical support for the fluoride thresholds in PG below which the adverse effects on cement hydration and strength development can be minimized, contributing to the sustainable goals of waste reduction, harmless disposal, and resource recovery in the phosphate industry.