Mechanism of transpassive dissolution of nickel-based alloys studies by impedance spectroscopy and rotating ring-disc voltammetry

Iva Betova, Martin Bojinov (Corresponding Author), Petri Kinnunen, Timo Laitinen, Pekka Pohjanne, Timo Saario

Research output: Contribution to journalArticleScientificpeer-review

12 Citations (Scopus)

Abstract

A generalised kinetic model of transpassive dissolution of industrial nickel-based alloys is presented in this paper.
It is based on electrochemical impedance spectroscopic (EIS) and rotating ring-disk (RRDE) measurements on several nickel-based alloys in 0.5 M sulphate and chloride solutions with pH ranging from 2 to 7.
The model assumes that the dissolution of Cr from the transpassive film occurs via a Cr(VI) surface intermediate species. The dissolution of Ni as Ni(II) is proposed to occur via two parallel paths featuring two reaction intermediates.
The role of Fe as a secondary passivating agent and Mo as an accelerator of transpassive dissolution is also taken into account.
The kinetic model has been found to reproduce quantitatively the current vs. potential curves and the impedance spectra for the studied nickel-based alloys in the transpassive region.
The proposed mechanism is sensitive to the impact of alloy and electrolyte composition on the dissolution process. Thus it can serve as a starting point to describe the transpassive behaviour of engineering alloys.
Original languageEnglish
Pages (from-to)2093-2107
JournalElectrochimica Acta
Volume47
Issue number13-14
DOIs
Publication statusPublished - 2002
MoE publication typeA1 Journal article-refereed

Fingerprint

Voltammetry
Nickel
Dissolution
Spectroscopy
Reaction intermediates
Kinetics
Electrolytes
Sulfates
Particle accelerators
Chlorides
Chemical analysis

Keywords

  • nickel-based alloys
  • transpassive dissolution
  • electrochemical impedance spectroscopy (eis)
  • rotating ring-disc electrode (rrde)
  • kinetic model

Cite this

@article{499325e1008e4b48982e6c14e52774e8,
title = "Mechanism of transpassive dissolution of nickel-based alloys studies by impedance spectroscopy and rotating ring-disc voltammetry",
abstract = "A generalised kinetic model of transpassive dissolution of industrial nickel-based alloys is presented in this paper. It is based on electrochemical impedance spectroscopic (EIS) and rotating ring-disk (RRDE) measurements on several nickel-based alloys in 0.5 M sulphate and chloride solutions with pH ranging from 2 to 7. The model assumes that the dissolution of Cr from the transpassive film occurs via a Cr(VI) surface intermediate species. The dissolution of Ni as Ni(II) is proposed to occur via two parallel paths featuring two reaction intermediates. The role of Fe as a secondary passivating agent and Mo as an accelerator of transpassive dissolution is also taken into account. The kinetic model has been found to reproduce quantitatively the current vs. potential curves and the impedance spectra for the studied nickel-based alloys in the transpassive region. The proposed mechanism is sensitive to the impact of alloy and electrolyte composition on the dissolution process. Thus it can serve as a starting point to describe the transpassive behaviour of engineering alloys.",
keywords = "nickel-based alloys, transpassive dissolution, electrochemical impedance spectroscopy (eis), rotating ring-disc electrode (rrde), kinetic model",
author = "Iva Betova and Martin Bojinov and Petri Kinnunen and Timo Laitinen and Pekka Pohjanne and Timo Saario",
year = "2002",
doi = "10.1016/S0013-4686(02)00080-4",
language = "English",
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pages = "2093--2107",
journal = "Electrochimica Acta",
issn = "0013-4686",
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Mechanism of transpassive dissolution of nickel-based alloys studies by impedance spectroscopy and rotating ring-disc voltammetry. / Betova, Iva; Bojinov, Martin (Corresponding Author); Kinnunen, Petri; Laitinen, Timo; Pohjanne, Pekka; Saario, Timo.

In: Electrochimica Acta, Vol. 47, No. 13-14, 2002, p. 2093-2107.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Mechanism of transpassive dissolution of nickel-based alloys studies by impedance spectroscopy and rotating ring-disc voltammetry

AU - Betova, Iva

AU - Bojinov, Martin

AU - Kinnunen, Petri

AU - Laitinen, Timo

AU - Pohjanne, Pekka

AU - Saario, Timo

PY - 2002

Y1 - 2002

N2 - A generalised kinetic model of transpassive dissolution of industrial nickel-based alloys is presented in this paper. It is based on electrochemical impedance spectroscopic (EIS) and rotating ring-disk (RRDE) measurements on several nickel-based alloys in 0.5 M sulphate and chloride solutions with pH ranging from 2 to 7. The model assumes that the dissolution of Cr from the transpassive film occurs via a Cr(VI) surface intermediate species. The dissolution of Ni as Ni(II) is proposed to occur via two parallel paths featuring two reaction intermediates. The role of Fe as a secondary passivating agent and Mo as an accelerator of transpassive dissolution is also taken into account. The kinetic model has been found to reproduce quantitatively the current vs. potential curves and the impedance spectra for the studied nickel-based alloys in the transpassive region. The proposed mechanism is sensitive to the impact of alloy and electrolyte composition on the dissolution process. Thus it can serve as a starting point to describe the transpassive behaviour of engineering alloys.

AB - A generalised kinetic model of transpassive dissolution of industrial nickel-based alloys is presented in this paper. It is based on electrochemical impedance spectroscopic (EIS) and rotating ring-disk (RRDE) measurements on several nickel-based alloys in 0.5 M sulphate and chloride solutions with pH ranging from 2 to 7. The model assumes that the dissolution of Cr from the transpassive film occurs via a Cr(VI) surface intermediate species. The dissolution of Ni as Ni(II) is proposed to occur via two parallel paths featuring two reaction intermediates. The role of Fe as a secondary passivating agent and Mo as an accelerator of transpassive dissolution is also taken into account. The kinetic model has been found to reproduce quantitatively the current vs. potential curves and the impedance spectra for the studied nickel-based alloys in the transpassive region. The proposed mechanism is sensitive to the impact of alloy and electrolyte composition on the dissolution process. Thus it can serve as a starting point to describe the transpassive behaviour of engineering alloys.

KW - nickel-based alloys

KW - transpassive dissolution

KW - electrochemical impedance spectroscopy (eis)

KW - rotating ring-disc electrode (rrde)

KW - kinetic model

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SP - 2093

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JF - Electrochimica Acta

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