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It was taken as typical steelmaking fluorine-containing slag systems with the remelting electroslag, continuous casting mould flux and refining slag. The volatilization behaviour of each slag system was analysed by thermogravimetric (TG) and mass spectrometry (MS) detection. The results showed that the remelting electroslag volatilized significantly above 1300°C and the volatiles were mainly CaF2, MgF2 with a small amount of SiF4 and AlF3; the continuous casting mould flux volatilization was divided into two stages, in the first stage (500