Most research on the corrosive CoCrFeNi high-entropy alloy (HEA) has mainly modulated element species and atomic concentration recently. However, the corrosive resistance of the passive film in the elevated temperatures environment inevitably need to be extensively explored for application. In this work, the microstructure and corrosion behavior in the elevated temperatures of face-centered cubic (FCC) CoCrFeNiWx (x = 0 and 0.2) HEAs are investigated. The mechanism of passivation layers on the corrosion behavior of HEAs is further discussed for comparison to the alloy of addition tungsten. Through potentiodynamic polarization curves in 3.5 wt% NaCl solution from 25 °C to 70 °C, the addition of tungsten can raise the critical pitting temperature, while maintaining a lower passivation current density and a larger passivation range at the same time. The high resolution X-ray photoelectron spectrometer (HRXPS), electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) are all conducted to analyze the passivation composition and chemical reaction of the present alloys detailly. The CoCrFeNiW0.2 HEA exhibits the uniform Cr2O3 layer on the FCC matrix; the proportion of dispersive WO3 layer on the μ phase precipitates form a double-layer passive film under elevated temperature in 3.5 wt% NaCl. It shows that the synergistic effect of the double-layer passive film significantly enhances the pitting and corrosive resistance in this HEA.
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