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 chrono-amperometry 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.
Original languageEnglish
JournalChemElectroChem
Early online date13 Dec 2019
DOIs
Publication statusE-pub ahead of print - 13 Dec 2019

Cite this

@article{ea0c008fabfc4c728dc3777d0ef86169,
title = "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 chrono-amperometry 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.",
author = "Frank Marken and Amelia Langley and Aisling Elmer and Philip Fletcher",
year = "2019",
month = "12",
day = "13",
doi = "10.1002/celc.201901927",
language = "English",
journal = "ChemElectroChem",
issn = "2196-0216",
publisher = "John Wiley and Sons Inc.",

}

TY - JOUR

T1 - 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

AU - Marken, Frank

AU - Langley, Amelia

AU - Elmer, Aisling

AU - Fletcher, Philip

PY - 2019/12/13

Y1 - 2019/12/13

N2 - 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 chrono-amperometry 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.

AB - 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 chrono-amperometry 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.

U2 - 10.1002/celc.201901927

DO - 10.1002/celc.201901927

M3 - Article

JO - ChemElectroChem

JF - ChemElectroChem

SN - 2196-0216

ER -