Glass–ceramic samples were prepared from a mixture that was composed of blast furnace slag, tailing and coal fly ash. FactSage software was used to calculate the batch viscosity and plot of the CaO–Al2O3–SiO2–6 wt-%MgO system phase diagram. The main mechanical properties, crystal morphology and crystalline phase transition of glass–ceramics were investigated as functions of batch viscosity, binary basicity (CaO/SiO2) and Al2O3 content by differential thermal analysis, X-ray diffraction, SEM-EDX and Fourier transform infrared spectroscopy techniques. Research results indicate that Al3+ cations play different roles in samples with various binary basicity values and Al2O3 contents for the formation of [AlO4] tetrahedral or [AlO6] octahedral structure, which is different from the role of Ca2+ ones. With the increase in binary basicity, the formula of high performance has a trend toward higher Al2O3 content region.
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