Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada

IPC2012-90086

A REAL-TIME AC/DC MEASUREMENT TECHNIQUE FOR ASSESSMENT OF AC CORROSION OF BURIED PIPELINES

Cindy X. Su Dept. of Mechanical & Manufacturing Engineering University of Calgary Calgary, Alberta, Canada Luyao Xu Dept. of Mechanical & Manufacturing Engineering University of Calgary Calgary, Alberta, Canada

Frank Y. Cheng Dept. of Mechanical & Manufacturing Engineering University of Calgary Calgary, Alberta, Canada ABSTRACT In this work, a real-time AC/DC signal data acquisition (DAQ) technique was developed, which is capable of separating the DC and AC potential components from the recorded total potential, providing mechanistic information about the steel corrosion in the presence of AC interference. It was found that the corrosion of the steel is enhanced by the applied AC current density from 0 to 400 A/m2. With the further increase to 600 A/m2 and 800 A/m2, the corrosion rate of the steel decreases, which is attributed to passivation of the steel at sufficiently high AC current densities, and a compact film is formed on the steel surface. Moreover, the derived mathematic relationships between AC potential and AC current density provides a potential alternative to determine AC current density on pipelines based on measurements of AC potential in the field. INTRODUCTION With the increasing development of buried pipelines and the high-voltage power transmission lines as well as the rail transit systems, pipelines encounters frequently interference by alternating current (AC) (1). It has been acknowledged (2) that corrosion rate of most metallic structures can be accelerated in the presence of AC interference. In particular, there have been increasing reports of AC-induced corrosion and failure of oil/gas pipelines in recent years, drawing an increasing attention to this important problem (3-5). While AC corrosion of carbon steel pipelines and the effect on cathodic protection (CP) performance in the presence of AC have been studied recently (6-8), an accurate measurement of

AC potential or current density and thus the reliable assessment of AC corrosion of pipelines and the CP efficiency have remained challenging. CP potential monitoring in the presence of AC interference could lead to erroneous measurements since the IR drop contribution due to both DC and AC could affect potential readings. For example, Ormellese et al. (9) found that, in CP conditions, the effect of AC is the increase in potential toward more positive values, leading to the partial protection condition. A further investigation is mandatory in order to understand the meaning of the potential reading to avoid misinterpretations during potential monitoring. In this work, a real-time AC/DC data acquisition (DAQ) technique was developed to separate the AC and DC potential components from the recorded total potential for a reliable potential interpretation. The corrosion of a 16Mn pipeline steel in a simulated soil solution in the presence of AC interference was studied experimentally by corrosion measurements and surface characterization. A mechanistic model was developed to illustrated the AC corrosion process. EXPERIMENTAL Specimens used in this work were fabricated from a sheet of 16Mn steel pipe with a chemical composition (wt%): C 0.16, Mn 1.4, S 0.025, P 0.009, and Si 0.36. The steel coupons were embedded in epoxy resin, leaving a working area of 10 mm 10 mm. The test solution was a simulated soil solution, containing 8.933 g/L KCl, 1.1 70 g/L MgSO4.7H2O and 5.510 g/L NaHCO3. The solution pH was 8.95 and its conductivity was 0.0167 S/cm.

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The AC/DC real-time signal measurements were performed through a National Instruments USB-6009 multifunction data acquisition card and the home-developed NI-DAQ data-logging software package based on LabVIEW 2011 64 bit programming platform. The software package included three components, i.e., data analysis module to analyze AC/DC mixed signals obtained by data acquisition card, data operation and display interface for the real-time potential-time plots, and data storage module to save the analyzed data. The DAQ technique is capable of separating the DC and AC potential signals from the recorded total potential when an AC is applied on the steel specimen. The experimental setup for AC corrosion measurement is shown in Fig. 1, where the 16Mn steel electrode was used as the working electrode (WE), a platinum sheet as counter electrode (CE) and a saturated calomel electrode (SCE) as reference electrode (RE). The AC current was applied on WE through a capacitor (50 V, 1000 F) and a resistance (10 , 0.5 W). The AC current density was adjusted by a slide rheostat, and its value was obtained by measuring the voltage on the resistor and divided by resistance and the electrode area. The capacitor was used to block DC signals, and an inductor was used to prevent AC current to flow into the Solatron 1280C electrochemical workstation. The DAQ system was installed to measure the potential between WE and RE. Weight-loss tests were performed on the 16Mn steel coupons in the solution, where the coupons were under various AC current densities. Tests were conducted at 220C and open to air. After test, the corrosion product formed on the coupon surface was removed carefully by both mechanical and chemical methods. The mechanical methods, including light scraping and scrubbing, were used for removal of tightly adherent corrosion product. In chemical procedure, a descaling solution containing 500 mL HCl (special gravity 1.19), 3.5 g hexamethylenetetramine and 500 mL distilled water was used. The cleaning process was repeated several times to remove corrosion product thoroughly. The weight-loss of the steel was then measured using an electronic balance with an accuracy of 0.1 mg. The surface morphology of the steel electrode after AC corrosion test was observed by an optical microscope. RESULTS Real-time AC/DC potential signal measurements Fig. 2 shows the recorded AC+DC voltage signals at the time instant of the 2000th s. It is seen that the DC signal is not identifiable completely, and AC signal dominates the recorded signals. Fig. 3 shows the DAQ-separated real-time DC potentials recorded on the steel specimen at various AC current densities. Three potential regions are observed, i.e., (i) from 0 to 1000 s of testing, there is no AC applied on the specimen, and the recorded DC potential is corrosion potential; (ii) from 1000 s to 2000 s, the AC-ON potential is recorded, where iAC is applied; and (iii) after 2000 s, AC application is stopped and the AC-OFF potential is recorded. In the first region, DC potentials decrease rapidly and then reach a steady-state value of about 0.75 V(SCE). While AC current is applied at 1000 s, DC

potentials drop immediately. Moreover, the higher the iAC, the more negative the DC potential is. When iAC is lower than 400 A/m2, a steady-state potential would be achieved. When iAC is up to 600 A/m2 and 800 A/m2, DC potentials could increase to 0.63 V(SCE) and -0.60 V(SCE), respectively, which are much less negative than the original values of -0.75 V(SCE) prior to the AC application. When AC is stopped at 2000 s, DC potentials recover immediately back to a steady-state value at AC current densities below 400 A/m2. The steady state potential is more negative with the increasing iAC. However, for those with iAC of 600 A/m2 and 800 A/m2, DC potentials jump instantly to a higher value, and then decrease gradually to steady-state DC potentials which are more negative than those recoded at iAC below 400 A/m2. The effect of AC current density on the shift of DC potential, which is defined as the steady-state DC potential at stage (ii) subtracting corrosion potential at stage (i) in Fig. 3, is shown in Fig. 4. It is seen that, when AC current density is less than 400 A/m2, the shift of DC potential is negative, indicating that the DC potential at stage (ii) is more negative than corrosion potential of the steel, and decreases with the increasing iAC. However, when AC current density increases to 600 A/m2 and 800 A/m2, the shift of DC potential becomes positive. Fig. 5 shows the DAQ-separated AC potentials recorded on the steel electrode in the time domain under various iAC. It is seen that all curves show an ideal sine-wave shape and have the same frequency of 60 Hz. Moreover, the magnitude of AC potential increases with the AC current density. Fig. 6 shows the dependence of AC peak-to-peak potential (VPP), the most positive potential (VP+) and the most negative potential (VP-) on AC current density (iAC). Linear relationships are observed for the three potentials. Weight-loss measurements Fig. 7 shows the corrosion rate of the steel as a function of AC current density determined by weight-loss measurements after 48 h of immersion in the simulated soil solution. It is seen that, when iAC is less than 100 A/m2, the corrosion rate changes slightly with the AC current density. When iAC exceeds 100 A/m2, corrosion rate increases apparently and reaches a maximum value at 400 A/m2. With the further increase of iAC up to 600 A/m2 and 800 A/m2, corrosion rate decreases. Surface characterization Fig. 8 shows the optical views of 16Mn steel electrode after 7 h of test in the simulated soil solution under various AC current densities. In the absence of AC, most part of the electrode is still shining, with rust present on the surface, as seen in Fig. 8a. When a 50 A/m2 AC current density is applied, a thin layer of porous corrosion product is formed, covering almost all the electrode surface (Fig. 8b).With further increase of AC current density to 100, 200 and 400 A/m2, corrosion rust layer becomes denser and thicker, depositing on the whole surface of the electrode (Figs. 8c, 8d and 8e). When AC current

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density increases to 800 A/m2, the electrode surface is covered by a compact corrosion product film, as seen in Fig. 8f. DISCUSSION Mechanistic aspects of AC corrosion of pipelines The electrochemical anodic and cathodic reactions during corrosion of 16Mn steel in the simulated soil solution include the steel oxidation and reduction of oxygen. As AC current is applied, periodic fluctuations of potential occur, as recorded in Fig. 5. The most positive and negative potentials of the steel could be up to 2.25 V(SCE) and -3.46 V(SCE), respectively, under the AC current density of 800 A/m2 (Fig. 6). Consequently, the oxygen and hydrogen evolutions occur, accompanying corrosion of the steel, which is evidenced by a large quantity of small bubbles generated on the steel surface: At AC positive potentials: 2H2O - 4e O2 + 4H+ At AC negative potentials: 2H2O + 2e H2 + 2OH(1) (2)

Moreover, upon the application of AC, the steel is under periodic anodic and cathodic polarization. Dissolution of steel can be accelerated by anodic polarization, and mitigated temporarily by the cathodic one. A layer of corrosion product is formed and deposited on the steel surface by [4]: Fe2+ + 2OH- Fe(OH)2 6Fe(OH)2 + O2 2Fe3O4 + 6H2O 4Fe(OH)2 + O2 4FeOOH + 2H2O (3) (4a) (4b)

in the formation of surface oxide film, mitigating corrosion of the steel. The surface film morphology at 800 A/m2 is quite different from the corrosion product layer formed at low AC current densities, as seen in Fig. 8. Moreover, the weight-loss measurements also demonstrate the decreasing corrosion rate at sufficiently high iAC, such as 600 and 800 A/m2. However, it needs to pay attention that, while the average corrosion rate decreases at sufficiently high AC current densities, pitting corrosion could initiate, as seen in Fig. 8f. This is probably due to the attack of chloride ions contained in the solution to the formed oxide film. Authors previous work conducted in concentrated carbonate/bicarbonate solutions also found the formation of corrosion pits at high AC current densities (6). A further work will be conducted to determine the threshold AC current density to initiate pitting corrosion. When AC is removed, the DC potential reaches a new steady-state value which is more negative than corrosion potential at stage (i). This indicates the AC-induced activation effect of the steel will maintain even when AC application is stopped. Thus, the AC effect on the steel is irreversible. Moreover, the DC potential under 600 and 800 A/m2 is shifted negatively to corrosion potential after 1500 s, which indicates that the passivating effect would be maintained only in the presence of AC. When AC is removed, passivation will be eliminated gradually. Distribution of AC potential on the steel surface upon AC application Fig. 9 shows the schematic diagram of the equivalent circuit of corrosion of the steel in the presence of AC in the absence of corrosion pits. This circuit would be used for the average corrosion rate determination based on method discussed below. The equivalent circuit containing corrosion pits and thus the localized corrosion consideration is being developed in authors laboratory.
.

The oxide product film formed on the steel surface would decrease somewhat the corrosion rate of the steel, depending on the thickness and structure of the film. The DC potential, which is termed as corrosion potential of the steel, is shifted negatively by the AC application when iAC is lower than 400 A/m2, as seen in Fig. 3. Assume that the Tafel slope of cathodic partial reaction does not change with the AC application, this result indicates that the corrosion activity of the steel increases due to the AC superimposition. Moreover, a new, steady-state DC potential is established with AC-ON, indicating that the steel corrodes at a new state with a high corrosion rate, as confirmed by the weight-loss measurements in Fig. 7. With the further increase of iAC to 600 and 800 A/m2, DC potential drops immediately and then increases gradually with time. Fig. 4 also shows the steady-state DC potential at individual AC current density. For example, DC potential is 140 mV more negative than corrosion potential at iAC of 400 A/m2, while it is 100 mV less negative than corrosion potential at iAC of 600 A/m2. Apparently, a sufficiently high AC current density, such as 600 A/m2, would result in formation of a compact film on the steel surface and decrease its corrosion activity. As shown in Fig. 6, the most positive potential for anodic polarization could reach 1.95 V(SCE) and 2.25 V(SCE), and the most negative potential for cathodic polarization reach -3.24 V(SCE) and -3.46 V(SCE) under iAC of 600 and 800 A/m2, respectively. The oxygen evolution in reaction (1) could result

The total input AC potential, U , consists of three components, i.e., AC potential in solution, U s , AC potential in corrosion product film, U f , and AC potential in double-charge
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.
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layer, U dl . They are related quantitatively by: (5) where Zf and Zp are the impedance of corrosion product film and double-charge layer, respectively. Furthermore, the measured real-time potential between RE and the steel through
.

the developed DAQ, U x , is written as:

(6)

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where EDC is the DC potential of the steel, and U f U dl represents the measured AC potential on corrosion product film and the double-charge layer. As shown in Fig. 6, the VPP of AC
.

potential of U x increases with the increasing iAC. Although EDC decreases with iAC, the significant increment in VPP still results in a positive shift of VP+ and negative shift of VP- by:

Vp EDC 0.5Vpp V p EDC 0.5V pp

(7) (8)

The potentials VPP, VP+ and VP- at stage (ii) in Fig. 3 show steady-state values when iAC is lower than 400 A/m2. However, a gradual shifting phenomenon is observed when iAC is up to 600 and 800 A/m2, resulting from the formation of a compact surface film and probably the pit initiation under high AC current densities. Furthermore, approximate linear relationships are found between the AC potentials, including VPP, VP+ and VP-, and iAC. A linear fitting is performed on Fig. 5, and empirical equations are derived: (9) (10) (11) These empirical equations can be served to calculate iAC by the measurement of AC potentials. In pipeline industry, AC-induced corrosion is a serious problem. It is usually easy to measure AC potential, but very difficult to measure AC current density directly due to the lacking information about the coating defect size and the AC current flowing through it. However, it is feasible to measure AC potential components at defects by the developed DAQ technique in this work. The AC current density is thus expected to be determined, and used for average corrosion rate measurement. It is worthy pointing out that the empirical equations (9)-(11) are derived based on research conducted under the certain conditions described in this work. A further validation of the model and equations is required for generalization of the determination of AC current density in the field. In particular, tests will be performed on the coated steel specimens since this research is conducted on the freshly polished surface. CONCLUSIONS An advanced DAQ technique is developed, which is capable of separating the DC and AC potential components from the recorded total potential on the steel. Analysis of various AC potential components provides mechanistic information about the steel corrosion in the presence of AC interference. Moreover, the derived mathematic relationships between AC potential and AC current density provides a potential alternative

to determine AC current density on pipelines based on measurements of AC potential in the field, which is being under further validation. Corrosion of 16Mn pipe steel is enhanced by the applied AC current density from 0 to 400 A/m2. With the further increase to 600 and 800 A/m2, the corrosion rate of the steel decreases due to formation of a compact film on the steel surface. However, corrosion pits are initiated at high AC current densities. The response of DC potential, i.e., corrosion potential, to the applied AC is instantaneous and irreversible. The AC application shifts corrosion potential negatively at AC current density less than 400 A/m2. The DC potential would maintain at a more negative value than its original corrosion potential value even when AC is removed. The findings in this work are expressed as furthering the understanding of AC corrosion of pipelines, and not a full summary of knowledge since conditions in the field are far more complex than those listed here. ACKNOWLEDGMENTS This work was supported by Canada Research Chairs Program and Pipeline Storage & Transportation Company of SINOPEC. REFERENCES [1] L. Bortels, J. Parlongue, W. Fieltsch, S.M. Segall, Mater. Perf. 2010; 49: 2. [2] S. Goidanich, L. Lazzari, M. Ormellese, M. Pedeferri, Corrosion2005, NACE, paper no. 05189, Houston, 2005. [3] I. Ragault, Corrosion98, NACE, paper no. 557, Houston, 1998. [4] S. Goidanich, L. Lazzari, M. Ormellese, Corros. Sci. 2010; 52: 491. [5] S. Goidanich, L. Lazzari, M. Ormellese, Corros. Sci. 2010; 52: 916. [6] A.Q. Fu, Y.F. Cheng, Corros. Sci. 2010; 52: 612. [7] A.Q. Fu, Y.F. Cheng, Can. Metallur. Q. 2012; 51: 81. [8] Y. Hosokawa, F. Kajiyama, Y. Nakamura, Corros. 2004; 60: 304. [9] M. Ormellese, S. Goidanich, L. Lazzari, Corros Eng. Sci. Technol. 2011; 46: 618.

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Fig. 1. Schematic diagram of the experimental set-up for AC corrosion measurement in this work.
20 A/m 2 50 A/m 2 100 A/m 2 200 A/m 2 400 A/m 2 600 A/m 2 800 A/m
2

Fig. 4. Shift of DC potential of the steel under various AC current densities.

Potential (V,SCE)

-1

-2

-3 0.00 0.02 0.04 0.06 0.08

Time(sec)

Fig. 2. The actually recorded AC+DC potential signals under various AC current densities.

Fig. 5. AC potential signals recorded on the steel in the time domain under various AC current densities.

Fig. 3. The DAQ-separated DC potential recorded on 16Mn steel electrode at various AC current densities (a) corrosion potential before 1000 s; (b) AC-ON potential from 1000 s to 2000 s; (c) AC-OFF potential after 2000s.

Fig. 6. AC peak to peak potential (VPP), the most positive potential (VP+) and the most negative potential (VP-) as a function of AC current density (iAC).

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Fig. 7. Weight-loss measurements of 16Mn steel coupon under various AC current densities after 48 h of immersion in the simulated soil solution.

Fig. 8. Optical views of 16Mn steel electrode after 7 h of test in the simulated soil solution under various AC current densities (a) 0 A/m2; (b) 50 A/m2; (c) 100 A/m2; (d) 200 A/m2; (e) 400 A/m2; (f) 800 A/m2.

Fig. 9. Schematic diagram of the equivalent circuit of the steel corrosion in the presence of AC application.

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