With the rise and development of aerospace, communications, electronics, medical, transportation and other fields, magnesium (Mg) and its alloys have attracted much attention for their high specific strength and stiffness, good electromagnetic shielding properties, excellent damping properties and other advantages. However, magnesium has a high affinity for oxygen, producing magnesium oxide (MgO), and MgO’s Pilling–Bedworth ratio (PBR) of 0.81 is not protective. The occurrence of catastrophic oxidation is unavoidable with the increase of oxidation time and temperature. A promising approach is to perform an appropriate pretreatment in conjunction with alloying to obtain a dense and compact composite protective film. In this work, the effect of a preheating treatment on the oxidation resistance (OR) of Mg-xCa (x = 1, 3 and 5 wt. %) was investigated. The preheating was carried out in an Ar atmosphere at 400 °C for 8 h. Upon it, a dense and compact MgO/CaO composite protective film was formed on the surface, which is CaO-rich especially in the vicinity to the surface. The alloys’ oxidation resistance was strongly increased due to the composite protective film formed during the preheating treatment, in particular for Mg-3Ca. Relative to the Mg-hcp phase, the OR of the Mg2Ca phase was significantly raised.
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