Effect of Steel Slag Content on the Performance and Hydration Mechanism of Phosphogypsum–Steel Slag–Fly Ash All-Solid-Waste Binders

To promote the synergistic utilization of phosphogypsum (PG), steel slag (SS), and fly ash (FA), a ternary all-solid-waste binder, namely PG-SS-FA cementitious material (PSA), was prepared. The effects of SS content on workability, setting behavior, mechanical properties, hydration products, pore structure, and microstructure were systematically investigated. The results showed that increasing SS content continuously reduced the fluidity of PSA, while the setting time first shortened and then increased. The fastest setting was observed at 40% SS, with initial and final setting times of 126 and 321 min, respectively. Increasing SS from 20% to 40% enhanced the hydration reaction, promoted the formation of AFt and C-(A)-S-H gel, reduced residual unreacted phases, and refined the pore structure, resulting in the highest compressive and flexural strengths for M40. However, further increasing SS to 60% and 80% reduced the fly ash proportion and limited the sustained supply of reactive Si/Al species, despite increasing Ca2+ availability and alkalinity, thereby restricting later-age gel accumulation and pore refinement and ultimately weakening mechanical performance. Overall, the performance evolution of PSA is governed by the coupled effects of alkali/Ca supply from SS, sulfate supply from PG, and reactive Si/Al supply from FA. The optimal performance at 40% SS is attributed to the synergistic construction of an AFt framework and continuous pore filling by C-(A)-S-H gel.