To achieve the large-scale, high-value utilization of vanadium–titanium slag (VTS) in the metallurgical industry, this study replaces blast furnace slag (BFS) with VTS to construct a quaternary all-solid-waste cementitious system composed of VTS, BFS, steel slag (SS), and desulfurization gypsum (DG). It systematically investigates the effects of VTS content (0–60%) on the mechanical properties, leaching toxicity, and hydration heat behavior of the system. XRD, TG–DSC, and SEM–EDS techniques are employed to explore the influence of VTS on hydration behavior and microstructural evolution. The results show that when VTS replaces 30% of the BFS (A3, VTS:BFS:SS:DG = 3:3:3:1), the 28-day compressive strength reaches 31.33 MPa. The leaching concentrations of heavy metals in all specimens are far below the standards for drinking water quality. Hydration heat analysis reveals that the incorporation of VTS advances the acceleration period of hydration. The A3 specimen maintains a relatively high heat release rate in the middle and later stages (after 72 h), and its cumulative heat release is significantly higher than that of the system without VTS, revealing the “slow hydration” mechanism of VTS at later stages. The SiO4–AlO4 bonds in VTS undergo a depolymerization–repolymerization process. In addition, an appropriate amount of VTS promotes the deposition of hydration products such as ettringite (AFt), C–S–H, and C–A–S–H gels through micro-filling effects and heterogeneous nucleation, thereby improving the microstructure of the system. However, excessive VTS (≥45%) significantly inhibits the hydration reaction and reduces gel formation due to the decrease in highly reactive BFS components and the increased TiO2 content. This study provides new insights into the resource utilization of VTS in multi-solid-waste cementitious materials. In addition, VTS-based cementitious materials are suitable for practical scenarios with low early strength requirements, such as goaf backfilling. Therefore, future studies should further investigate the long-term sulfate resistance and carbonation resistance of these materials under real application conditions.
Su et al. (Sat,) studied this question.