Linking the Cu(II/I) and the Ni(IV/II) Potentials to Subsequent Passive Film Breakdown for a Cu−Ni Alloy in Aqueous 0.5 M NaCl

Abstract

Copper and copper–nickel alloys are known to form partially passive films in marine conditions, both naturally and under positive potential bias. Here, the anodic passivation behaviour of copper and of constantan (Cu54Ni45Mn1) as a model for a copper‐nickel alloy are investigated and compared at high positive overpotentials and in 0.5 M NaCl(aq). Abrupt potential‐dependent passive film breakdown is observed for both Cu and Cu−Ni alloys during voltammetry and during chronoamperometry experiments. For Cu, a single transitions occurs at 0.2 V vs. SCE consistent with a Cu(II/I) process, leading to interfacial stress and breaking of a passive CuCl film. For Cu−Ni alloy, two stages are observed at 0.3 V vs. SCE due to a Cu(II/I) process and at 1.7 V vs. SCE due to a sub‐interfacial Ni(IV/II) process. A breakdown mechanism is proposed based on redox processes at the buried interface at the metallic conductor | passive ion conductor junction.

Elemental partitioning and corrosion resistance of Ni–Cr alloys revealed by accurate ab-initio thermodynamic and electrochemical calculations

“…High-fidelity calculations using exact nonlocal exchange potentials can be used to obtain accurate Δ f G values, from which reliable Pourbaix diagrams for transition-metal systems can be constructed and validated 36,37,39,40 . The first-principles Poubaix diagrams for transition metals have also been widely referred to by many recent electrochemical experiments in the fields of, e.g., corrosion [41][42][43][44][45] , catalysis, and energy [46][47][48][49][50][51][52][53][54] , where these diagrams guide the design and characterization of many related materials, and even have been applied to understand geological processes (rock weathering in acid rains) on both the ancient Earth and Mars 55,56 .…”