The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

Iva Betova, Martin Bojinov (Corresponding Author), Timo Laitinen, Kari Mäkelä, Pekka Pohjanne, Timo Saario

    Research output: Contribution to journalArticleScientificpeer-review

    40 Citations (Scopus)

    Abstract

    The effect of pH and solution anion on the kinetics of transpassive dissolution of highly alloyed austenitic stainless steels (AISI 904L, 254SMO and 654SMO) was studied by a combination of electrochemical techniques. The experiments were performed in 0.5 M sulphate and 0.5 M chloride solutions, and in an equimolar mixture of the two. The transpassive dissolution was found to start at higher potentials in solutions with higher pH. The rate of transpassive dissolution was shown to decrease with increasing pH and to be the lowest in chloride solutions and the highest in sulphate electrolytes. The steady-state current vs. potential curves and the impedance spectra of the studied materials in the transpassive potential region were found to be consistent with a proposed kinetic model. The model describes the process as dissolution of Cr as Cr(VI) and Fe as Fe(III) through the anodic oxide film via parallel reaction paths. The kinetic parameters of the model in solutions with different pH values and different anions were determined. The role of pH and solution anion in the transpassive dissolution process is discussed in relation to changes induced by these parameters in the composition of the anodic passive film. The factors determining the efficiency of Fe as a secondary passivating agent are also considered.
    Original languageEnglish
    Pages (from-to)2699-2723
    JournalCorrosion Science
    Volume44
    Issue number12
    DOIs
    Publication statusPublished - 2002
    MoE publication typeA1 Journal article-refereed

    Fingerprint

    Stainless Steel
    Anions
    Dissolution
    Negative ions
    Stainless steel
    Kinetics
    Sulfates
    Chlorides
    Austenitic stainless steel
    Kinetic parameters
    Electrolytes
    Oxide films
    Chemical analysis
    Experiments

    Keywords

    • Stainless steel
    • EIS
    • RRDE
    • Modelling studies
    • Transpassivity
    • Kinetic parameters

    Cite this

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    title = "The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics",
    abstract = "The effect of pH and solution anion on the kinetics of transpassive dissolution of highly alloyed austenitic stainless steels (AISI 904L, 254SMO and 654SMO) was studied by a combination of electrochemical techniques. The experiments were performed in 0.5 M sulphate and 0.5 M chloride solutions, and in an equimolar mixture of the two. The transpassive dissolution was found to start at higher potentials in solutions with higher pH. The rate of transpassive dissolution was shown to decrease with increasing pH and to be the lowest in chloride solutions and the highest in sulphate electrolytes. The steady-state current vs. potential curves and the impedance spectra of the studied materials in the transpassive potential region were found to be consistent with a proposed kinetic model. The model describes the process as dissolution of Cr as Cr(VI) and Fe as Fe(III) through the anodic oxide film via parallel reaction paths. The kinetic parameters of the model in solutions with different pH values and different anions were determined. The role of pH and solution anion in the transpassive dissolution process is discussed in relation to changes induced by these parameters in the composition of the anodic passive film. The factors determining the efficiency of Fe as a secondary passivating agent are also considered.",
    keywords = "Stainless steel, EIS, RRDE, Modelling studies, Transpassivity, Kinetic parameters",
    author = "Iva Betova and Martin Bojinov and Timo Laitinen and Kari M{\"a}kel{\"a} and Pekka Pohjanne and Timo Saario",
    year = "2002",
    doi = "10.1016/S0010-938X(02)00074-4",
    language = "English",
    volume = "44",
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    }

    The transpassive dissolution mechanism of highly alloyed stainless steels : II. Effect of pH and solution anion on the kinetics. / Betova, Iva; Bojinov, Martin (Corresponding Author); Laitinen, Timo; Mäkelä, Kari; Pohjanne, Pekka; Saario, Timo.

    In: Corrosion Science, Vol. 44, No. 12, 2002, p. 2699-2723.

    Research output: Contribution to journalArticleScientificpeer-review

    TY - JOUR

    T1 - The transpassive dissolution mechanism of highly alloyed stainless steels

    T2 - II. Effect of pH and solution anion on the kinetics

    AU - Betova, Iva

    AU - Bojinov, Martin

    AU - Laitinen, Timo

    AU - Mäkelä, Kari

    AU - Pohjanne, Pekka

    AU - Saario, Timo

    PY - 2002

    Y1 - 2002

    N2 - The effect of pH and solution anion on the kinetics of transpassive dissolution of highly alloyed austenitic stainless steels (AISI 904L, 254SMO and 654SMO) was studied by a combination of electrochemical techniques. The experiments were performed in 0.5 M sulphate and 0.5 M chloride solutions, and in an equimolar mixture of the two. The transpassive dissolution was found to start at higher potentials in solutions with higher pH. The rate of transpassive dissolution was shown to decrease with increasing pH and to be the lowest in chloride solutions and the highest in sulphate electrolytes. The steady-state current vs. potential curves and the impedance spectra of the studied materials in the transpassive potential region were found to be consistent with a proposed kinetic model. The model describes the process as dissolution of Cr as Cr(VI) and Fe as Fe(III) through the anodic oxide film via parallel reaction paths. The kinetic parameters of the model in solutions with different pH values and different anions were determined. The role of pH and solution anion in the transpassive dissolution process is discussed in relation to changes induced by these parameters in the composition of the anodic passive film. The factors determining the efficiency of Fe as a secondary passivating agent are also considered.

    AB - The effect of pH and solution anion on the kinetics of transpassive dissolution of highly alloyed austenitic stainless steels (AISI 904L, 254SMO and 654SMO) was studied by a combination of electrochemical techniques. The experiments were performed in 0.5 M sulphate and 0.5 M chloride solutions, and in an equimolar mixture of the two. The transpassive dissolution was found to start at higher potentials in solutions with higher pH. The rate of transpassive dissolution was shown to decrease with increasing pH and to be the lowest in chloride solutions and the highest in sulphate electrolytes. The steady-state current vs. potential curves and the impedance spectra of the studied materials in the transpassive potential region were found to be consistent with a proposed kinetic model. The model describes the process as dissolution of Cr as Cr(VI) and Fe as Fe(III) through the anodic oxide film via parallel reaction paths. The kinetic parameters of the model in solutions with different pH values and different anions were determined. The role of pH and solution anion in the transpassive dissolution process is discussed in relation to changes induced by these parameters in the composition of the anodic passive film. The factors determining the efficiency of Fe as a secondary passivating agent are also considered.

    KW - Stainless steel

    KW - EIS

    KW - RRDE

    KW - Modelling studies

    KW - Transpassivity

    KW - Kinetic parameters

    U2 - 10.1016/S0010-938X(02)00074-4

    DO - 10.1016/S0010-938X(02)00074-4

    M3 - Article

    VL - 44

    SP - 2699

    EP - 2723

    JO - Corrosion Science

    JF - Corrosion Science

    SN - 0010-938X

    IS - 12

    ER -