Growth kinetics of anodic oxide layers on cobalt silicides in sulphuric acid solutions

Keywords: Cobalt silicide, Passivity, Oxide film, Growth kinetics, High field model, Point defect model


        The aim of this research was to study the growth kinetics of anodic oxide films on cobalt silicides in sulphuric acid solutions under potentiostatic conditions with various pretreatment of the electrode surface. For the study, we used low and high silicon silicides (Co2Si and CoSi2) in 0.05 and 0.5 M H2SO4.
        We obtained the chronoamperograms in the time interval t = 0.3–3000 s with the oxide formation potentials of Ef = 0.2, 0.5, and 1.0 V (SHE). It was determined that the kinetics of the growth of oxide layers on cobalt silicides in acidic solutions greatly depends on the method of the silicide surface pretreatment (mechanical polishing; cathodic pre-polarisation in a H2SO4 solution; exposure to H2SO4 solution at the open circuit potential; exposure in a 2 M KOH solution; and exposure to 2% HF solution). In most cases, at low t (up to 30–50 s), the oxide films grew due to the ion migration in the strong electric field generated in the film during anodic polarisation.
         In some cases (Co2Si silicide with higher cobalt content; pretreatment of Co2Si in alkaline solution, further enriching the silicide surface with cobalt; and the region of high values of t), the point defect model seemed to be executed. 


Download data is not yet available.

Author Biographies

Anatoliy B. Shein, Perm State National Research University, 15 Bukireva ul., Perm 614990, Russian Federation

Dr. Sci. (Chem.), Full Professor,
the Department of Physical Chemistry, Perm State
University (Perm, Russian Federation)

Vladimir I. Kichigin, Perm State National Research University, 15 Bukireva ul., Perm 614990, Russian Federation

Cand. Sci. (Chem.), Research
Fellow at the Department of Physical Chemistry, Perm
State University (Perm, Russian Federation)


Maurice V., Marcus P. Current developments of nanoscale insight into corrosion protection by passive oxide films. Current Opinion in Solid State and Materials Science. 2018;22(4): 156–167.

Shein A. B. Electrochemistry of silicides and germanides of transition metal*. Perm: Perm State Univ. Publ., 2009. 269 p. (In Russ)

Schmidt C., Strehblow H.-H. The passivity of Fe/Si alloys in aqueous electrolytes at pH 5 and 9 studied by X-ray photoelectron spectroscopy and ion scattering spectroscopy. Journal of the Electrochemical Society. 1998; 145(3):834–840.

Strehblow H.-H., Maurice V., Marcus P. Passivity of metals. In: Corrosion Mechanisms in Theory and Practice. P. Marcus (ed.). CRC Press, Taylor & Francis Group; 2012. pp. 235–326.

Wolff U., Schneider F., Mummert K., Schultz L. Stability and electrochemical properties of passive layers on Fe-Si alloys. Corrosion. 2000;56(12): 1195–1201.

Chen H., Ma Q., Shao X., Ma J., Huang B. X. Corrosion and microstructure of the metal silicide (Mo1-xNbx)5Si3. Corrosion Science. 2013;70: 152–160.

Tang C., Wen F., Chen H., Liu J., Tao G., Xu N., Xue J. Corrosion characteristics of Fe3Si intermetallic coatings prepared by molten salt infiltration in sulfuric acid solution. Journal of Alloys and Compounds. 2019;778: 972–981.

Hu L., Hu B., Gui, Y. Study on the melting and corrosion resistance of Fe-Cr-Si dual phase alloy. IOP Conference Series: Materials Science and Engineering. 2020;782(2): 022031.

Zhang Y., Xiao J., Zhang Y., Liu W., Pei W., Zhao A., Zhang W., Zeng, L. The study on corrosion behavior and corrosion resistance of ultralow carbon high silicon iron-based alloy. Materials Research Express. 2021; 8(2): 026504.

Shadrin K. V., Panteleeva V. V., Shein A. B. Passivation of chromium dicilicide in acidic media. Bulletin of Perm University. Chemistry. 2021;11(3): 202–211 (In Russ., abstract in Eng.).

Baklanov M. R., Badmaeva I. A., Donaton R. A., Sveshnikova L. L., Storm W., Maex K. Kinetics and mechanism of the etching of CoSi2 in HF-based solutions. Journal of the Electrochemical Society. 1996; 143(10): 3245–3251.

Strehblow H.-H. Passivity of metals. In: Advances in Electrochemical Science and Engineering. Vol. 8. R. C. Alkire (ed.). Wiley; 2002. pp. 271–374.

Panteleeva V. V., Shein A. B. Growth of anodic oxide films on iron-triad metal monosilicides in sulfuric acid electrolyte. Russian Journal of Electrochemistry. 2014;50(11): 1036–1043.

Behazin M., Biesinger M. C., Noël J. J., Wren J. C. Comparative study of film formation on high-purity Co and Stellite-6: Probing the roles of a chromium oxide layer and gamma-radiation. Corrosion Science. 2012; 63: 40–50.

Lutton K., Gusieva K., Ott N., Birbilis N., Scully J. R. Understanding multi-element alloy passivation in acidic solutions using operando methods. Electrochemistry Communications. 2017;80: 44–47.

Lutton Cwalina K., Ha H. M., Ott N., Reinke P., Birbilis N., Scully J. R. In operando analysis of passive film growth on Ni-Cr and Ni-Cr-Mo alloys in chloride solutions. Journal of the Electrochemical Society. 2019; 166(11):C3241–C3253.

Wang Z., Di-Franco F., Seyeux A., Zanna S., Maurice V. , Marcus P. Passivation-induced physicochemical alterations of the native surface oxide film on 316L austenitic stainless steel. Journal of the Electrochemical Society. 2019;166(11): C3376–C3388.

Choudhary S., Thomas S., Macdonald D. D., Birbilis N. Growth kinetics of multi-oxide passive film formed upon the multi-principal element alloy AlTiVCr: Effect of transpassive dissolution of V and Cr. Journal of the Electrochemical Society. 2021;168: 051506.

Burstein G. T. Passivity and localized corrosion. In: Corrosion. Vol. 1. Metal/Environment Reactions. L. L. Shreir, R. A. Jarman, G. T. Burstein (eds.). Oxford: Butterworth-Heinemann; 1994. pp. 1:118–1:150.

Zhang L., Macdonald D. D., Sikora E., Sikora J. On the kinetics of growth of anodic oxide films. Journal of the Electrochemical Society. 1998;145(3): 898–905.

Kichigin V. I., Shein A. B. Effect of anodising on the kinetics of the hydrogen evolution reaction on cobalt silicides in sulphuric acid solution. Condensed Matter and Interphases. 2017;19(3): 359–367 (In Russ., abstract in Eng.).

Liu D. Q., Blackwood D. J. Mechanism and dissolution rates of anodic oxide films on silicon. Electrochimica Acta. 2013;105: 209–217.

Thissen P., Seitz O., Chabal Y. J. Wet chemical surface functionalization of oxide-free silicon. Progress in Surface Science. 2012;87(9-11): 272–290.

Seidel H., Csepregi L., Heuberger A., Baumgärtel H. Anisotropic etching of crystalline silicon in alkaline solutions. I. Orientation dependence and behavior of passivation layers. Journal of the Electrochemical Society. 1990;137(11): 3612–3626.

Kichigin V. I., Shein A.B . Anodic behavior of Co2Si in potassium hydroxide solutions. Bulletin of Perm University. Chemistry. 2011;1(3): 4–14 (In Russ., abstract in Eng.). Available at:

Sukhotin A. M. (ed.). Handbook of Electrochemistry*. Leningrad: Khimiya Publ.; 1981. 488 p. (In Russ.).

Lohrengel M. M. Thin anodic oxide layers on aluminium and other valve metals: high field regime. Materials Science and Engineering: R: Reports. 1993;11(6): 243–294.

Vanhumbeeck J. F., Proost J. Current understanding of Ti anodisation: fundamental, morphological, chemical and mechanical aspects. Corrosion Reviews. 2009;27: 117–204.

Macdonald D. D. The point defect model for the passive state. Journal of the Electrochemical Society. 1992; 139(12):3434–3449.

Roh B., Macdonald D. D. Passivity of titanium: part II, the defect structure of the anodic oxide film. Journal of Solid State Electrochemistry. 2019;23: 1967–1979.

Bösing I., La Mantia F., Thöming J. Modeling of electrochemical oxide film growth – a PDM refinement. Electrochimica Acta. 2022;406: 139847.

Seyeux A., Maurice V., Marcus P. Oxide film growth kinetics on metals and alloys. I. Physical model. Journal of the Electrochemical Society. 2013;160(6): C189–C196.

Momeni M., Behazin M., Wren J. C. Mass and charge balance (MCB) model simulations of current, oxide growth and dissolution during corrosion of Co- Cr alloy Stellite-6. Journal of the Electrochemical Society. 2016; 163(3): C94–C105.

Lutton K., Scully J. R. Kinetics of oxide growth of passive films on transition metals. Encyclopedia of Interfacial Chemistry, Surface Science and Electrochemistry. 2018;284–290.

Burstein G. T., Davenport A. J. The current-time relationship during anodic oxide film growth under high electric field. Journal of the Electrochemical Society. 1989; 136(4): 936–941.

Franssila S. Introduction to Microfabrication. John Wiley & Sons; 2010. 518 p. 37. Nascimento M. L. F., Zanotto E. D. Diffusion processes in vitreous silica revisited. Physics and Chemistry of Glasses - European Journal of Glass Science and Technology Part B. 2007;48(4): 201–217. Available at:

Koel G. J., Gellings P. J. The contribution of different types of point defects to diffusion in CoO and NiO during oxidation of the metals. Oxidation of Metals. 1972;5: 185–203.

Razina N. F. Oxide electrodes in aqueous aolutions*. Alma-Ata: Nauka Publ.; 1982. (In Russ.).

Deml A. M., Holder A. M., O’Hayre R. P., Musgrave C. B. Intrinsic material properties dictating oxygen vacancy formation energetics in metal oxides. The Journal of Physical Chemistry Letters. 2015;6(10): 1948–1953.

Vargas R., Carvajal D., Galavis B., Maimone A., Madriz L., Scharifker B. R. High-field growth of semiconducting anodic oxide films on metal surfaces for photocatalytic application. International Journal of Photoenergy. 2019: 2571906.

Ma L., Pascalidou E.-M., Wiame F., Zanna S., Maurice V., Marcus P. Passivation mechanisms and pre-oxidation effects on model surfaces of FeCrNi austenitic stainless steel. Corrosion Science. 2020;167; 108483.

How to Cite
Shein, A. B., & Kichigin, V. I. (2022). Growth kinetics of anodic oxide layers on cobalt silicides in sulphuric acid solutions. Condensed Matter and Interphases, 24(4), 559-571.
Original articles