The viscosity of the CaO–SiO
2–MnO(–CaF
2) slags (CaO/SiO
2 = 1.0, MnO = 10, 40 mass%) was measured to clarify the effect of CaF
2 on the viscous flow of molten slags at high temperatures. Furthermore, the Raman spectra of the quenched glass samples were quantitatively analyzed to investigate the structural role of CaF
2 in a depolymerization of silicate networks. The critical temperature of the slags abruptly increased at 15 mass% CaF
2, which was confirmed to originate from a crystallization of cuspidine using XRD analysis. The viscosity of the slags continuously decreased by CaF
2 addition in the 10 mass% MnO system, whereas the viscosity of the 40 mass% MnO system was not significantly affected by CaF
2 addition. The activation energy for the viscous flow of silicate melts decreased by CaF
2 addition and its tendency became less significant in the more basic composition,
i.e. in the 40 mass% MnO system. The effect of CaF
2 on the viscosity of the slags was quantitatively analyzed using micro-Raman spectra of quenched glass samples accompanying with a concept of silicate polymerization index, Q
3/Q
2 ratio. A polymerization index continuously decreased with increasing content of CaF
2 in the 10 mass% MnO system, whereas it was not affected by CaF
2 in the 40 mass% MnO system. Consequently, the bulk thermophysical property of the CaO–SiO
2–MnO–CaF
2 slags was quantitatively correlated to the structural information.
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