Special features of phase transformations in the system SiO2-Al2O3-CaF2 are considered regarding the synthesis of metal-protective coatings for graphite-containing crucibles. It is shown that the compound CaAl2Si2O8 obtained in the oxide-fluoride mixture Al2Si2O7 + SiO2 + CaF2 is stable toward aluminum alloys. The use of metal-protective coatings increases the stability of graphite-containing crucibles more than 4-fold.