In order to promote the high-quality utilization of solid waste—steel slag—this study prepared ground steel slag powder with specific surface areas of 400 m²/kg, 500 m²/kg and 600 m²/kg respectively. Different fineness levels of steel slag powder were used to replace cement to prepare ultra-high performance concrete (UHPC), with replacement rates of 20%, 30% and 40% respectively. The effects of fineness and dosage of steel slag powder on the workability, mechanical properties and microstructure of UHPC were further investigated. The results show that the incorporation of steel slag powder can significantly reduce the yield stress and plastic viscosity of UHPC, thereby increasing its fluidity, but also decreasing its thixotropy. The tensile properties of UHPC mixed with steel slag powder were all superior to those of the reference group. The compressive strength of UHPC prepared by using steel slag powder with a specific surface area of 400 m²/kg or 600 m²/kg instead of 20% cement was higher than that of the reference group. The compressive strength of UHPC mixed with 600 m²/kg specific surface area steel slag powder was generally stronger at the same dosage. At the same fineness, the mechanical properties of UHPC decreased gradually with the increase in steel slag powder content. The recommended dosage for the steel slag powder with a specific surface area of 400 m²/kg is 20%, which results in the best comprehensive properties in UHPC. At this time, compared with the reference group, the compressive strength increased by 3.35%, and the tensile strength increased by 20.73%. Moreover, adequate fineness of the steel slag powder can be achieved without excessive grinding energy, which contributes to sustainability.

Calcium leaching increases the hydraulic concrete material’s porosity and the diffusion coefficient, thereby jeopardizing engineering safety. Fly ash and silica fume are commonly used mineral admixtures in hydraulic concrete, and their effects on the material’s leaching characteristics, especially its microstructural and transport properties, require further investigation. In this study, calcium leaching tests were conducted on cement paste (CP), silica fume–cement paste (SF), and fly ash–cement paste (FA) using a 6 mol/L ammonium chloride solution to accelerate the leaching process. Subsequently, a series of quantitative and qualitative analyses was performed on the deteriorated specimens, including phenolphthalein indicator spraying, X-ray diffraction (XRD), nuclear magnetic resonance (NMR), and scanning electron microscopy (SEM). Additionally, the diffusion coefficients of the material at different locations were calculated and analyzed. The results show that partially replacing cement with silica fume or fly ash increases the initial porosity, gel pore content, and initial diffusion coefficients. After 28 days of leaching, compared to the initial values, the porosity increases in the 0–4 mm layer from the leached surface were 83.6% for CP, 11.0% for SF, and 39.0% for FA. The diffusion coefficients increased by factors of 14.3 (CP), 6.1 (SF), and 13.6 (FA), indicating enhanced resistance to leaching. The primary reason for this is that the reactive silica in the admixtures undergoes a pozzolanic reaction with the calcium hydroxide generated by cement hydration, producing additional calcium silicate hydrate (C-S-H) gel, which reduces the capillary pores that would otherwise result from calcium hydroxide decomposition.