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[Display omitted] • Passive film composition changes during long-term passivation of Ni-Cr-X alloys. • Cr enriches in film and Ni enriches at the metal/film interface with time. • Aliovalent Mo and W enrichment in passive films occurs during Cr(III) enrichment. • Corundum forms early, while spinel forms over time by phase transformation. • The applied passivation potential and time influence spinel protectiveness. The passivation of Ni-22Cr, Ni-22Cr-6Mo, and Ni-22Cr-6Mo-3W (wt%) was characterized from 100 s to 10 days in 0.1 M NaCl in pH 4 at various potentials in the passive range. The influence of aqueous solution exposure time in NaCl (exposure aging), passivation potential, as well as Ni-Cr-X alloy composition (Mo or W) on passive film growth, composition, oxidation state, molecular identity, and inner versus outer film layering were investigated. Initial passive film formation was dominated by Ni(II). Cr(III) oxides and hydroxides tended to enrich upon formation and exposure aging. Corundum and rock salt are speculated to undergo a solid-state phase transformation to form NiCr 2 O 4 at long times under certain conditions. The concept of the time-potential-transformation diagrams to describe the evolution of passive film phases and protectiveness is introduced. Factors limiting Cr(III) enrichment were discussed. Aliovalent Mo and W ions were detected in passive films, particularly after aging. The roles of Cr enrichment, Ni depletion, and Mo and/or W aliovalent cations after oxide aging towards protectiveness to passive and localized corrosion in chloride (Cl-) solutions were discussed. [ABSTRACT FROM AUTHOR]