Localization of formation reactions of protective heteropolynuclear complexes in the depth of oxide-hydroxide passivating films on the surface of mild steel

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Abstract

The laws of the formation of passivating films on the surface of mild steel in a borate buffer environment (pH = 7.4) containing additives of corrosion inhibitors nitrilotris(methylenephosphonato)zinc tridecahydrate Na4[Zn{N(CH2PO3)]·13H2O and nitrilotris(methylenephosphonatoaqua)cadmium heptahydrate Na4[Cd(H2O){N(CH2(PO3)3}]·7H2O have been investigated by X-ray photoelectron spectroscopy with layer-by-layer etching with Ar+ ions. The composition and structure of films, localization features of the processes of interaction of inhibitor ions with iron ions, related processes and products of these interactions in the depth of the films were established. The protective properties of passivating films and the anticorrosive properties of inhibitors have been studied using a potentiodynamic method.

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About the authors

I. S. Kazantseva

Udmurt Federal Research Center of the Ural Branch of the Russian Academy of Sciences

Email: chaus@udman.ru
ORCID iD: 0000-0003-4556-3854
Russian Federation, 426067, Izhevsk

F. F. Chausov

Udmurt Federal Research Center of the Ural Branch of the Russian Academy of Sciences

Author for correspondence.
Email: chaus@udman.ru
ORCID iD: 0000-0003-4950-2370
Russian Federation, 426067, Izhevsk

N. V. Lomova

Udmurt Federal Research Center of the Ural Branch of the Russian Academy of Sciences

Email: chaus@udman.ru
ORCID iD: 0000-0002-6568-4736
Russian Federation, 426067, Izhevsk

V. L. Vorob’yov

Udmurt Federal Research Center of the Ural Branch of the Russian Academy of Sciences

Email: chaus@udman.ru
ORCID iD: 0000-0002-9401-0802
Russian Federation, 426067, Izhevsk

N. Yu. Isupov

Udmurt Federal Research Center of the Ural Branch of the Russian Academy of Sciences

Email: chaus@udman.ru
ORCID iD: 0000-0002-2515-8117
Russian Federation, 426067, Izhevsk

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Supplementary files

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2. Fig. 1. The main structural fragments (a–c) and P2p XPS spectra (d–g) of the compounds ZnNTP (a, d), CdNTP (b, d), FeZnNTP (c, f), and FeCdNTP (c, g). Hydrogen atoms are not shown for clarity. Curves 1 correspond to the spectra of the initial reference compounds with the structure (a–c); curves 2 refer to the spectra of the corresponding compounds after etching with Ar+ ions with an energy of 1000 eV for 5 min.

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3. Fig. 2. Fragments of the XPS spectra measured at room temperature (a) and under conditions of thermal action on the sample in situ (b), from the surface of a St3kp steel sample subjected to polarization in a borate-borate buffer solution (pH = 7.4) at E = 0.5 V.

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4. Fig. 3. Spectra of Fe2p3/2 electrons measured during layer-by-layer etching of the surface of a St3kp steel sample subjected to polarization at a potential of E = 0.5 V in a borate-borate buffer solution (pH = 7.4).

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5. Fig. 4. The most characteristic fragments of the XPS spectra of St3kp steel samples polarized in a borate-borate buffer solution (pH = 7.4) at E = 0.5 V with the addition of 5 g/l ZnNTP (a), 1 g/l CdNTP (b).

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6. Fig. 5. P2p-electron spectra measured during layer-by-layer etching of the surface of St3kp steel samples polarized at a potential of E = 0.5 V in a borate-borate buffer solution (pH = 7.4) containing 5 g/l ZnNTP (a), 1 g/l CdNTP (b).

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7. Fig. 6. Atomic fraction of phosphorus included in the composition of the initial inhibitors ZnNTP, CdNTP, and heterometallic complexes FeZnNTP, FeCdNTP, depending on the etching depth δ of passive films formed on St3kp steel samples in a borate-borate buffer solution (pH = 7.4) at a potential of E = 0.5 V with the addition of 5 g/l ZnNTP or 1 g/l CdNTP.

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8. Fig. 7. Profiles of the elemental composition of the surface layers of St3kp steel samples subjected to polarization at a potential of E = 0.5 V in a borate-borate buffer solution (pH = 7.4) containing 5 g/l ZnNTP (a, b) and 1 g/l CdNTP (c, d).

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9. Fig. 8. Anodic polarization curves measured for St3kp steel samples in a borate-borate buffer solution (pH = 7.4) with the addition of various concentrations of ZnNTP (a) and CdNTP (b) inhibitors; the numbers on the curves indicate the concentration of inhibitors in g/l.

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10. Fig. 9. Micrographs of the surface of St3kp steel samples polarized in a borate-borate buffer solution (pH = 7.4) with the addition of 5 g/l ZnNTP at a potential of E = –0.1 V (a, b) and with the addition of 1 g/l CdNTP at a potential of E = 0.5 V (c, d).

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11. Fig. 10. Scheme of formation and structure of passivating films on the surface of steel in a borate-borate buffer solution containing ZnNTP (a) and CdNTP (b).

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