Corresponding Author

Fa-he CAO(nelson_cao@zju.edu.cn)


Scanning electrochemical microscopy (SECM) is chemical microscopy with higher spatial resolution. After 24 years of development, SECM has been widely applied in mapping and kinetics study of heterogeneous electron transfer in localized processes at solid-liquid or liquid-liquid interfaces. The fundamentals and recent advances of SECM in corrosion applications are described, including SECM mapping and kinetics on localized corrosion of metal or coating. Research work of SECM in corrosion by our group is also introduced. Future applications of SECM in corrosion are highlighted.

Graphical Abstract


scanning electrochemical microscopy, metal, corrosion

Publication Date


Online Available Date


Revised Date


Received Date



[1] Bard A J, Fan F R F, Pierce D T, et al. Chemical Imaging of surfaces with the scanning electrochemical microscope[J]. Science, 1991, 254(5028): 68-74.

[2] Bard A J, Fan F R F, Kwak J, et al. Scanning electrochemical microscopy. Introduction and principles[J]. Analytical Chemistry, 1989, 61(2): 132-138.

[3] Isaacs H S. The localized breakdown and repair of passive surfaces during pitting[J]. Journal of Electroanalytical Chemistry, 1989, 29(2/3): 313-323.

[4] Lin C J(林昌健), Li Y(李彦), Lin B(林斌), et al. Developments of Scanning electrochemical probes and their applications in studying of localized corrosions[J]. Journal of Electrochemistry(电化学), 2009, 15(2): 121-128.

[5] Niu L, Yin Y H, Guo W K, et al. Application of scanning electrochemical microscope in the study of corrosion of metals[J]. Journal of Materials Science, 2009, 44(17): 4511-4521.

[6] Luo H(骆鸿), Wei D(魏丹), Dong C F(董超芳) et al. Development of electrochemical studies in microzone of metallic corrosion (1) scanning electrochemical microscopy[J]. Corrosion and Protection (腐蚀与防护), 2009, 30(7): 437-441.

[7] Wang L W(王力伟), Li X G(李晓刚), Du C W(杜翠微), et al. Recent advances in local electrochemical measurement techniques and appolications in corrosion research[J]. Journal of Chinese Society for Corrosion and Protection (中国腐蚀与防护学报), 2010, 30(6): 498-504.

[8] Wittstock G, Burchardt M, Pust S E, et al. Scanning electrochemical microscopy for direct imaging of reaction rates[J]. Angewandte Chemie-International Edition, 2007, 46(10): 1584-1617.

[9] Sun P, Laforge F O, Mirkin M V. Scanning electrochemical microscopy in the 21st century[J]. Physical Chemistry Chemical Physics, 2007, 9(7): 802-823.

[10] Kwak J, Bard A J. Scanning electrochemical microscopy. Apparatus and two-dimensional scans of conductive and insulating substrates[J]. Analytical Chemistry, 1989, 61(17): 1794-1799.

[11] Horrocks B R, Schmidtke D, Heller A, et al. Scanning electrochemical microscopy. 24. Enzyme ultramicroelectrodes for the measurement of hydrogen-peroxide at surfaces[J]. Analytical Chemistry, 1993, 65(24): 3605-3614.

[12] Alpuche-Aviles M A, Wipf D O. Impedance feedback control for scanning electrochemical microscopy[J]. Analytical Chemistry, 2001, 73(20): 4873-4881.

[13] Keddam M, Portail N, Trinh D, et al. Progress in scanning electrochemical microscopy by coupling with electrochemical impedance and quartz crystal microbalance[J]. Chemphyschem, 2009, 10(18): 3175-3182.

[14] Wipf D O, Bard A J. Scanning Electrochemical Microscopy.7. Effect of heterogeneous electron-transfer rate at the substrate on the tip feedback current[J]. Journal of the Electrochemical Society, 1991, 138(2): 469-474.

[15] Wipf D O, Bard A J. Scanning Electrochemical Microscopy.10. High-resolution imaging of active-sites on an electrode surface[J]. Journal of the Electrochemical Society, 1991, 138(5): L4-L6.

[16] Bard A J, Mirkin M V, Unwin P R, et al. Scanning electrochemical microscopy .12. theory and experiment of the feedback mode with finite heterogeneous electron-transfer kinetics and arbitrary substrate size[J]. Journal of Physical Chemistry, 1992, 96(4): 1861-1868.

[17] Wei C, Bard A J, Mirkin M V. Scanning electrochemical microscopy.31. application of secm to the study of charge-transfer processes at the liquid-liquid interface[J]. Journal of Physical Chemistry, 1995, 99(43): 16033-16042.

[18] da Silva C G, Margarit-Mattos I C P, Mattos O R, et al. The molybdate-zinc conversion process[J]. Corrosion Science, 2009, 51(1): 151-158.

[19] Eckhard K, Schuhmann W, Maciejewska M. Determination of optimum imaging conditions in AC-SECM using the mathematical distance between approach curves displayed in the impedance domain[J]. Electrochimica Acta, 2009, 54(7): 2125-2130.

[20] Liu X L, Zhang T, Shao Y W, et al. Effect of alternating voltage treatment on the corrosion resistance of pure magnesium[J]. Corrosion Science, 2009, 51(8): 1772-1779.

[21] Yin Y H, Niu L, Lu M, et al. In situ characterization of localized corrosion of stainless steel by scanning electrochemical microscope[J]. Applied Surface Science, 2009, 255(22): 9193-9199.

[22] Zhou H R, Li X G, Dong C F, et al. Corrosion behavior of aluminum alloys in Na2SO4 solution using the scanning electrochemical microscopy technique[J]. International Journal of Minerals Metallurgy and Materials, 2009, 16(1): 84-88.

[23] Zhu R K, Luo J L. Investigation of stress-enhanced surface reactivity on Alloy 800 using scanning electrochemical microscopy[J]. Electrochemistry Communications, 2010, 12(12): 1752-1755.

[24] Yuan Y, Li L, Wang C, et al. Study of the effects of hydrogen on the pitting processes of X70 carbon steel with SECM[J]. Electrochemistry Communications, 2010, 12(12): 1804-1807.

[25] Gonzalez-Garcia Y, Santana J J, Gonzalez-Guzman J, et al. Scanning electrochemical microscopy for the investigation of localized degradation processes in coated metals[J]. Progress in Organic Coatings, 2010, 69(2): 110-117.

[26] Souto R M, Gonzalez-Garcia Y, Izquierdo J, et al. Examination of organic coatings on metallic substrates by scanning electrochemical microscopy in feedback mode: Revealing the early stages of coating breakdown in corrosive environments[J]. Corrosion Science, 2010, 52(3): 748-753.

[27] Santana J J, Gonzalez-Guzman J, Izquierdo J, et al. Sensing electrochemical activity in polymer-coated metals during the early stages of coating degradation by means of the scanning vibrating electrode technique[J]. Corrosion Science, 2010, 52(12): 3924-3931.

[28] Souto R M, Fernandez-Merida L, Gonzalez S. SECM imaging of interfacial processes in defective organic coatings applied on metallic substrates using oxygen as redox mediator[J]. Electroanalysis, 2009, 21(24): 2640-2646.

[29] Souto R M, Gonzalez-Garcia Y, Gonzalez S. Characterization of coating systems by scanning electrochemical microscopy: Surface topology and blistering[J]. Progress in Organic Coatings, 2009, 65(4): 435-439.

[30] Souto R M, Gonzalez-Garcia Y, Gonzalez S, et al. Imaging the origins of coating degradation and blistering caused by electrolyte immersion assisted by SECM[J]. Electroanalysis, 2009, 21(23): 2569-2574.

[31] Gonzalez-Garcia Y, Mol J M C, Muselle T, et al. SECM study of defect repair in self-healing polymer coatings on metals[J]. Electrochemistry Communications, 2011, 13(2): 169-173.

[32] Malik M A, Kulesza P J, Pawlowska G. Surface analysis with scanning electrochemical microscopy in the feedback mode: Monitoring of reactivity and pitting precursor sites on the Nd-Fe-B-type magnet[J]. Electrochimica Acta, 2009, 54(23): 5537-5543.

[33] Walsh D A, Li L E, Bakare M S, et al. Visualisation of the local electrochemical activity of thermal sprayed anti-corrosion coatings using scanning electrochemical microscopy[J]. Electrochimica Acta, 2009, 54(20): 4647-4654.

[34] Blanc C, Pebere N, Tribollet B, et al. Galvanic coupling between copper and aluminium in a thin-layer cell[J]. Corrosion Science, 2010, 52(3): 991-995.

[35] Pust S E, Salomo M, Oesterschulze E, et al. Influence of electrode size and geometry on electrochemical experiments with combined SECM-SFM probes[J]. Nanotechnology, 2010, 21(10): 105709-105720.

[36] Xia Y, Cao F H, Chang L R, et al. Corrosion micro- and macro-electrochemical behavior of rusted carbon steel and weathering steel[J]. Chemical Journal of Chinese University(高等学校化学学报), 2013, 34(5): 1246-1253.

[37] Xia Y, Cao F H, Liu W J, et al. The formation of passive films of carbon steel in borate buffer and their degradation behavior in NaCl solution by SECM[J]. International Journal of Electrochemical Science, 2013, 8: 3057-3073

[38] Liu W J, Cao F H, Xia Y, et al. Localized corrosion of magnesium alloys in NaCl solutions explored by scanning electrochemical microscopy in feedback mode[J]. Electrochimica Acta, 2012, submitted

[39] Souto R M, Gonalez-Garcia Y, Gonzalez S. In situ monitoring of electroactive species by using the scanning electrochemical microscope. Application to the investigation of degradation processes at defective coated metals[J]. Corrosion Science, 2005, 47(12): 3312-3323.
[40] Volker E, Inchauspe C G, Calvo E J. Scanning electrochemical microscopy measurement of ferrous ion fluxes during localized corrosion of steel[J]. Electrochemistry Communications, 2006, 8(1): 179-183.
[41] Cornut R, Lefrou C. New analytical approximation of feedback approach curves with a microdisk SECM tip and irreversible kinetic reaction at the substrate[J]. Journal of Electroanalytical Chemistry, 2008, 621(2): 178-184.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.