Steel slag (SS) exhibits low hydration activities and expansive phases, which should be pretreated prior to using as binding materials. Thus, these properties of SS were improved through a combined treatment of alkali and then wet carbonation (A_C) in this study. Effect of sodium silicate modulus (M = 1.0–2.5) and carbonation temperature (50–200 °C) on cementitious property of SS was investigated. Results showed that the optimum modulus and temperature were 2.0 and 150 °C under single alkali and single carbonation treatment of SS, respectively. In case of combined treatment, the optimal modulus was 2.0 with an optimum temperature of 100 °C (A2.0_C100°C-SS). The 28 d compressive strength increased by 27.1% and expansion rate decreased by 17.7% of A2.0_C100°C-SS-PC compared to untreated SS-PC. This was attribute to the fact that the newly formed CaCO3 with micro-nano size and high activity existed in A_C-SS can react with Al-containing minerals in OPC to form monocarboaluminate, and Si-gels produced during carbonation can react with CH to form C-S-H phases. The early hydration activity of OPC was more obviously improved by adding A_C-SS compared to adding A_SS or C_SS. This was due to the micro-nano size effect of CaCO3 and Si-gels can provide nucleation sites for C-S-H formation. Alkali pretreatment can improve the SS carbonation, reaching the maximum carbonation degree of 53% at 100 °C compared to carbonation alone (47% at 150 °C). The embodied CO2 index of A2.0_C100-SS-OPC system decreased to 9.843 compared to OPC (10.511), indicating that the A_C treatment for SS was a more sustainable and environmentally friendly method.
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