216th ECS Meeting, Abstract #1773, The Electrochemical Society

Characterization of corrosion of pipeline steel under coating by localized electrochemical impedance spectroscopy
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Frank Y. Cheng Dept. of Mechanical and Manufacturing Engineering University of Calgary Calgary, Alberta, Canada T2N 1N4 Pipeline corrosion and stress corrosion cracking are associated with coating degradation and failure. Despite the application of cathodic protection (CP), the coating defects, depending on their number, size and geometry, will affect the CP effectiveness and, consequently, the corrosion of steel under coating. Electrochemical impedance spectroscopy (EIS) has been used extensively to study the coating performance and corrosion of steel under the coating. However, the measured impedance result is attributed to the electrochemical response of the whole electrode, reflecting an averaged behavior of the macroscopic electrode. As a consequence, local electrochemical process occurring at micro-defect such as pinhole in the coating is averaged out. In this work, localized EIS (LEIS) technique was used to investigate the fundamentals of localized corrosion of X65 pipeline steel at coating defect and, furthermore, to determine the effects of CP on local electrochemical environment and the resultant corrosion reaction at the base of defect. Fig. 1 shows the LEIS mapping over a coated X65 steel, with a 200 m defect. The defective area was identified by the central low-impedance area. Fig. 2 shows the Nyquist diagrams measured by LEIS at defect in a near-neutral pH solution as a function of time. It is seen that the localized corrosion of steel at defect experienced mechanistic change with time, as indicated by the different LEIS features. The diffusion process dominated the interfacial corrosion reaction, which was due to the blocking effect of the deposited corrosion product combined with the geometrical factor of a large coating thickness/defect width ratio. However, such changes cannot be revealed by conventional EIS measured on the identical electrode, as shown in Fig. 3.
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Fig. 2. Nyquist diagrams of LEIS measured directly at the defect as a function of time.
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Fig. 3. Nyquist diagrams of conventional EIS measured on a macroscopic coated steel electrode. impedance indicates that a mass-transfer step involving diffusion of reactants, such as oxygen, through the solution layer and the defect with a narrow, deep geometry (the depth/width ratio of defect is about 5.5) controls the corrosion process. Furthermore, even at very negative potential, e.g., -1200 mV (SCE), the measured LEIS is still associated with the diffusion-controlled corrosion reaction at the base of defect. The applied CP cannot penetrate through the defect to reach the steel surface, and is partially shielded due to the narrow, deep geometry of the defect, resulting in the generation of EIS plot that reflects the combination of both anodic and cathodic reactions.
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Fig. 1. LEIS map around a defect of 200 m in diameter. Fig. 4 shows the Nyquist diagrams measured by LEIS locally at the defect on the coated electrode at OCP (-510 mV, SCE) and various cathodic potentials after 7 days of immersion in a high pH solution. It is seen that all EIS plots were featured with a depressed semicircle in the high frequency range and a linear impedance in the low frequency range. While the high-frequency semicircle is attributed to the interfacial charge-transfer reaction occurring at the base of defect, the low-frequency linear

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Fig. 4. Nyquist diagrams measured at coating defect under various cathodic potentials.