Effects of dissolved gases on partial anodic passivation phenomena at copper microelectrodes immersed in aqueous NaCl

Langley, Amelia R.; Fletcher, Philip; Dawes, Jonathan; Marken, Frank

doi:10.1016/j.jelechem.2019.113589

Cited by 5 publications

(6 citation statements)

References 54 publications

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“…0.2 V vs. SCE is attributed to the formation of Cu(II) causing strain in the passive film and leading to instabilities observed as current noise thereafter (see Figure 1a-c). [15,34] For constantan, only one anodic peak is observed at approx. 0.2 V vs. SCE during the first cycle (see Figure 3b).…”

Section: Resultsmentioning

confidence: 99%

“…The first anodic peak at 0.0 V vs. SCE is attributed to CuCl formation (equation 1). [15,34] The second anodic peak at approx. 0.2 V vs. SCE is attributed to the formation of Cu(II) causing strain in the passive film and leading to instabilities observed as current noise thereafter (see Figure 1a-c).…”

Section: Resultsmentioning

confidence: 99%

“…[15] This process has been shown to be dependent on the presence of dissolved gases in the solution phase, probably due to gas bubble nucleation and implosion during breakdown. [34] The Cu(II/I) redox transition (see Figure 2a) produces current associated with copper dissolution relatively uniformly with some spikes up to + 5 V vs. SCE applied potentials.…”

Section: Resultsmentioning

confidence: 99%

“…In a recent study for copper, it has been shown that also electrode diameter and the nature of the gaseous species dissolved in the solution phase can affect breakdown of passive films. [34] This directly implied for the Cu j CuCl system in aqueous 0.5 M chloride solution the absence of anodic gas evolution processes (oxygen or chlorine) even at high positive applied potentials.…”

Section: Introductionmentioning

confidence: 93%

“…[32,33] Additional pathways for breakdown could be linked to redoxinduced strain within the passive interfacial layer. [34] This could be caused by redox processes in the solid state at the metal j ion conductor interface or also due to the redox induced formation of traces of gaseous species. The nature of the passive film generally dictates the breakdown pathway, which can cause, for example, phenomena such as pitting.…”

Section: Introductionmentioning

confidence: 99%

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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

et al. 2020

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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.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%