CORROSION ENGINEERING

Cathodic Protection to Mitigate External Corrosion of Underground Steel Pipe Beneath Disbonded Coating&
F. Gan, Z.-W. Sun, G. Sabde, and D.-T. Chin*

ABSTRACT
A study was conducted to determine the feasibility of cathodically protecting the steel surface beneath a disbonded coating with a holiday using an external power source. A laboratory cell was used to simulate the field condition of a steel pipe buried in a soil saturated with ground water that had resistivity of 3,050 ⍀-cm to 4,400 ⍀-cm. The local pipe potential and solution pH within the crevice of the disbonded coating during cathodic protection were measured over time. The relative advantages of using a pulsed current (PC) vs those of a direct current (DC) were examined. Results indicated applied cell voltage was an important factor for proper protection of a coated steel pipe in high-resistivity soils. A low cell voltage would not permit sufficient polarization of the steel surface within the crevice. A high voltage induced excessive hydrogen evolution at the crevice opening, which blocked penetration of cathodic current into the crevice. The optimal cell voltage was: (a) PC of a frequency of 1 Hz and a duty cycle 0.5 at a controlled voltage setting (Von) = 15 V to 20 V and (b) DC at Von = 15 V to 20 V. Both DC and PC protected the steel pipe adequately in the test soil. The mechanism of cathodic protection in the high-resistivity environment was identified as: (a) polarization to a “corrosion immunity” potential for the steel surface in the vicinity of crevice opening, (b) oxygen depletion for the solution in the interior of the crevice, and (c) a pH increase in the crevice and passivation of the steel in the alkaline environment.

KEY WORDS: cathodic protection, coating holiday, crevice corrosion, disbonded coating, high-resistivity soil, potential distribution, pulsed current

INTRODUCTION
Crevice corrosion beneath disbonded coating is a common problem on underground steel pipelines.1-2 Underground gas and oil pipelines are protected against corrosion by combined application of coatings and cathodic protection. Coatings usually are in the form of fusion-bounded epoxy or polyethylene and polyvinyl chloride tapes with an adhesive backing, which are wrapped helically on the pipe surface.3 Holidays are the pinholes and ruptures on a pipe coating. They are caused by defects in the coating, coating misapplication, and mechanical damage during or after pipeline installation. The development of a holiday leads to the loss of adhesion between the pipe and coating in the surrounding areas. Water in the soil then flows through the holiday opening into the crevice between the pipe and disbonded coating and initiates corrosion on the pipe surface. Field studies have shown that crevices beneath disbonded coatings range from 5 mm to 125 mm in diam.3 The corrosion within the crevice occurs in the form of elongated pits. Stress corrosion cracking can develop if sufficient amounts of carbonates and bicarbonates are present in the soil water.4-5 Cathodic protection has not been able to mitigate crevice corrosion properly beneath disbonded coatings, especially on pipes buried in high-resistivity soil. This

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Submitted for publication November 1993; in revised form, March 1994. * Department of Chemical Engineering, Clarkson University, Potsdam, NY, 13699-5705.

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0010-9312/94/000187/$5.00+$0.50/0 © 1994, NACE International

CORROSION–OCTOBER 1994

1 VCSE. steel was polarized only within a short distance from the crevice opening.. Toncre found that. proper polarization of the steel surface beneath disbonded coatings could be achieved in a lowresistance solution for crevice thickness-to-depth ratios up to 1:1.21-22 This raises the possibility that PC might be able to penetrate deeper into the crevice and provide a more uniform potential and current 805 CORROSION–Vol. Where the coating was disbonded extensively. The water resistivity ranged from 30 ⍀-cm to 200 ⍀-cm.0 VCSE was almost the same. PC reduced energy consumption while maintaining the protection efficiency afforded by the direct current (DC) cathodic protection system.12 There was general corrosion on the pipe when the circumferential potential was –0.CORROSION ENGINEERING is largely a result of the inability of imposed cathodic protection systems to pass sufficient protective current to the corroding sites on the pipeline.11 studied polarization of pipeline steel in a solution containing 1 N sodium carbonate (Na2CO3) and 1 N sodium bicarbonate (NaHCO3). Toncre measured the pipe-to-soil potential circumferentially around pipe. The current required to maintain the holiday potential at –0. et al. At a high applied potential. On a pipeline in Saudi Arabia. hydrogen gas (H2) bubbles were produced at the holiday opening and caused fluctuations in the current/potential measurement.9 Fletcher. and brackish water.85 VCSE protective polarization potential inside a crevice.8 Corrosion could be mitigated when a sufficiently negative potential was applied to the crevice opening so that the concentration of dissolved oxygen (O2) within the crevice was reduced. Their results showed cathodic protection in low-resistivity solutions could be achieved if the potential at the crevice opening was more negative than –1. whereas at a low holiday potential.85 VCSE and –1. 10 .5 VCSE to –0. and the circumferential potential was –0.6-7 The cathodic current must flow through the holiday opening into the crevice. pulsed current (PC) in the form of an intermittent on-and-off current wave has been studied for the cathodic protection of oil well casings. 50. showed the protective current density decreased along the crevice from the opening.4 They simulated the crevice that would be found under a disbonded pipeline coating and measured the potential along the crevice length.6 VCSE.0 VSCE in the Na2CO3 and NaHCO3 solution. Results of the above studies indicate it is possible to achieve cathodic protection of a metal surface in a crevice containing a low-resistivity electrolyte. whereas at a –1.5 VCSE setting. et al. and steel pipes. by extending the testing time.6 VCSE. additional current was necessary because of H2 evolution on the pipe surface. In electroplating.99 VCSE. water heaters. polarization within the crevice was not achieved.10 and Fessler. et al. it is difficult to achieve the –0. McCoy reported the cathodic protection of the Dampier-to-Perth natural gas pipeline in Australia buried in a high-resistivity soil (50. pitting corrosion occurred on the pipe surface. No experimental study has been reported for the current/ potential distribution within a crevice filled with a high-resistivity electrolyte. H2 evolution occurred at the holiday opening. In most of Orton’s experiments. saline water.. The steel samples that had a mill scale needed a longer time to polarize and attained a less negative potential than clean steel samples. Apparently. A detailed review of the cathodic protection of underground pipelines against crevice corrosion was given by Sabde. Similar potential measurements were carried out by Peterson and Lennox. in a high-resistivity environment.12 A field study on the effectiveness of cathodic protection under disbonded coatings on a pipeline was carried out by Orton in eastern Saudi Arabia.16-20 Although no particular benefit was identified.0 V vs a saturated calomel electrode (SCE). Toncre and Ahmad studied cathodic protection against crevice corrosion of mild steel in seawater. Their data indicated the potential of a clean steel surface inside a crevice could be maintained within the protected range by keeping the potential at the holiday opening at an appropriate level. PC has been reported to possess a larger microthrowing power than DC plating. When using a controlled potential of –1.. cathodic protection was not achieved. At a more negative controlled potential. The disbonded pipe coating acts as a shield against the flow of cathodic current to the pipe surface beneath it. In a large area.000 ⍀-cm to 100. However. the saline water table was only a few feet below ground.000 ⍀-cm).8 They found it was not always necessary to pass current into the crevice to protect the metal surface cathodically. No. Berry. Fessler.85 V vs a copper sulfate reference electrode (CSE) to a less negative value at which the cathodic protection fails to stop the corrosion process. the potential within the crevice was only –0. and the excess ohmic potential drop across the electrolyte within the crevice reduces the true pipe-to-electrolyte polarization potential from a protected value of –0.200.15 Recently.14 Corrosion coupons were installed along the pipeline to simulate disbonded coating holidays and to determine the degree of polarization on the pipe by measuring coupon potential using a current interruption technique. Using a segmented specimen.13 The soil environment consisted of rocks and desert sands.11 Proper protection could be achieved with a controlled holiday potential of –1. et al.

The pH monitoring holes were sealed with a rubber stopper. On each pipe section.3 mm thick by 10. 26. The crevice thickness-to-length ratio along the circumferential direction was 1:500. max. which permitted the insertion of a pH microelectrode probe from the interior of the pipe for measurement of the crevice solution pH.2 cm wide and was fastened to the pipe with two stainless steel pipe clamps.3 cm wide. One holding plate served as a partition between the soil in the cell and the interior of the test pipe. as measured by an alternating current (AC) impedance technique. The space between the cell and coated pipe samples was filled with soil taken from an excavation site on the TransAlaska Pipeline at mile post 160. In this way. max. phosphorus (P). respectively.. The effect of electrolyte resistivity on cathodic protection and crevice potential distribution was studied using a model crevice cell filled with a dilute sodium chloride (NaCl) solution over a resistivity range of 158 ⍀-cm to 4. a model crevice cell was used to examine the effect of solution resistivity on cathodic protection. 0.400 ⍀-cm. sulfur (S). 0.5%. total solids. copper (Cu). The water adsorption was 1. manganese (Mn). 6. machine smoothed. chloride ions (Cl–). 806 CORROSION–OCTOBER 1994 . Each reference tap was fitted with a plastic tube on the inside surface of the pipe and was connected by flexible plastic tubing to an external reference electrode compartment. The overlap sections of the tape on the pipe also were sealed with adhesive. an electric heat gun inserted through the opening was used to heat the air in the pipe to 50°C ± 2°C. cleaned with detergent. The cell was a rectangular acrylic container 48 cm wide by 36 cm deep by 50 cm high. a watertight crevice ≈ 1 mm thick was formed circumferentially between the exterior pipe surface and the polyethylene coating. silicon (Si). A circular hole of 0.78 cm diam was cut through the tape at the 12:00 position to simulate the holiday (or crevice opening). aluminum (Al). and 10:30 positions.1%.2 cm long. The other holding plate. In the present study.400 (i. and cell wall were bolted together using eight titanium (Ti) bolts.008%. 0. Corrosion Cell and Test Soil Figure 1 shows the schematic of cell construction. which faced the cell wall. max. The resistivity of the soil water was in the range 3. 98. The relative merits of PC vs DC were examined experimentally. four back-reference taps and four pH monitoring holes were drilled through the pipe wall at the 12:00 (12 o’clock. Pipe Coating and Crevice Configuration The exterior surface of the steel pipe was polished manually using 600-grit sandpaper.04%.5 cm2 of holiday area to 700 cm2 of pipe area in the crevice). (1) (2) (3) Steel composition: carbon (C). Alaska.3%.5 in Atigun Valley. bicarbonate ions (HCO3–).035%.(2) The tape was 1. In this way. and dried.025%. 0. 50. To simulate the temperature of warm petroleum oil flowing in the pipe. 302. The soil was mixed with deionized water in a volume ratio of 1:1.2%. The pipe was sandblasted. The Ti bolts also served as the anode during the cathodic protection experiments. 0. The opening was used for connecting reference capillary tubes to the reference taps on the steel pipe and for making pH measurements during the test. two horizontal pipe test sections were mounted on each acrylic cell. the space between the tape and exterior surface of the pipe was sealed using an adhesive strip 1 mm thick and 1. 1. The pipe then was wrapped circumferentially with a new polyethylene pipeline tape.200 ⍀-cm. The ratio of the crevice opening area to the total pipe surface within the crevice was 1:1. At both ends of the pipe.2% of its weight after 80 days’ immersion in the soil water at 50°C. max. top). max. To account for a large difference in the behavior of local crevice potential between the low-resistivity and highresistivity solutions. had an opening to the atmosphere. 0. Water composition in milligrams per liter: calcium ions (Ca2+). and iron (Fe). sodium ions (Na+).16%. 0. vanadium (V). 66.01% to 0. The electric resistance and capacitance of tape in the test soil water at 50°C. 6:00 (bottom). chromium (Cr). 0. 3:00. EXPERIMENTAL A laboratory corrosion cell was used to simulate the field condition of a steel pipe having a disbonded coating with a holiday buried in a soil saturated with water. magnesium ions (Mg2+). The resulting soil water(3) had Test Pipe The test pipe was a steel pipe (API Standard SL Grade X65(1)) of 32. degreased with acetone. and cut into sections 10. 0. sulfate ions (SO42–). A neoprene O-ring was placed between each holding plate and the steel pipe to prevent soil water from leaking into the interior of the test pipe. were > 1011 ⍀ and 3.e.CORROSION ENGINEERING distribution than DC when used in cathodic protection against crevice corrosion. plates. max. The steel pipe with the disbonded polyethylene coating was sandwiched between two acrylic holding plates and was mounted on one side of the cell wall. max. 6.35%.050 ⍀-cm to 4.4-cm outer diameter (OD) and 0. 0. The local pipe potential and solution pH within the crevice were monitored as a function of time.714 cm wall thickness. the effectiveness of cathodic current using an impressed current to mitigate the crevice corrosion of a steel pipe beneath a disbonded coating holiday in high-resistivity soil was investigated. The pipe interior temperature was measured using a thermistor probe and was controlled by a temperature controller. remainder. The pipe.0 pF/cm2. max. nitrogen (N).

FIGURE 1. To avoid contamination of the crevice solution by the reference electrode fluid. The protective cell current was determined by measuring the voltage drop across a standard resistor (R) with a second multimeter (V2). the local crevice potential was measured daily. Then. 50. During the experiment.06 M. a leakage test was carried out to ensure that the crevice between the exterior surface of the pipe and disbonded coating was sealed properly and the soil water could enter the crevice only through the holiday opening at the 12:00 position. Schematic of the corrosion cell used to test the cathodic protection of a steel pipe with a disbonded coating in wet soil. The solution was prepared by dissolving an appropriate amount of analytical-grade NaCl in deionized water.050 ⍀-cm to 4. and its final pH and electric resistivity were measured using a pH meter and a conductivity meter. Air was bubbled through the soil water continuously. and its surface condition was recorded on videotape. Model Crevice Cell Experiment The electrolyte used in the model crevice cell experiment was an aqueous NaCl solution at 25°C. and 0. and the test pipe was stripped of the polyethylene tape and washed with water. No. the crevice solution was collected. and 10:30 positions on the test pipe.CORROSION ENGINEERING a pH of 6. The pipe surface was examined for corrosion damage visually. and the local crevice pH values were measured weekly with a combination pH microelectrode. the cell was filled with the 1:1 soil-water mixture to cover the test pipe completely. 3:00. Three NaCl concentrations were used: 0. Electric Circuit and Cathodic Protection Procedures The electric circuit for cathodic protection experiments is shown schematically in Figure 2.002 M.006 M. which took a few minutes. At the end of test. During the test. 0. 6:00.4 to 8. The cell then was disassembled. The current waveform was examined using the oscilloscope. 10 . FIGURE 2. and the water was recirculated in the soil using an air-lift pump (Figure 1).4 and an electric resistivity of 3.400 ⍀-cm at a steady-state soil temperature of 35°C during the experiments. A high-input impedance electrometer (V3) was used for the potential measurement. the SCE was inserted into the pipe’s reference tap only during the measurement. The SCE was used to determine the local crevice potential at the 12:00. Prior to filling the cell with the test soil. A pulse power supply or a DC power supply was used to supply the controlled cell voltage between the Ti anode and the steel pipe cathode. The test began by connecting the pipe and Ti anode to the cathodic protection circuit and by switching on the pipe temperature controller. Electric circuit for cathodic protection and locations of reference and pH measurement taps on the steel pipe sample. The corresponding electric resistivities of these solutions at 807 CORROSION–Vol. the anode-to-cathode cell voltage was monitored with a digital multimeter (V1) and its waveform was checked periodically on an oscilloscope.

The reference electrode was inside a Luggin capillary tube.002 M NaCl solution. 1. and the total electric energy consumption during the test (E). the surface condition after the tests. and 20 V. The experiment lasted from 20 days in Test 1 to 45 days in Test 3. the cell voltage was pulsed between the open circuit and a controlled voltage setting (Von) at a duty cycle of 0. Table 1 lists the controlled cell voltage. a Ti anode. potential (i. and 4.5 cm. The reference compartments were separated from the crevice solution with a sintered glass and were filled with the same test electrolyte during the test. The electric resistivities of the bulk soil water and crevice solution at the end of the tests are presented in the last two columns of the table. 6:00. It consisted of a horizontal glass tube 10 cm long with an 11. A cylindrical steel rod of 9. A few patches of light brownish rust were scattered around the CORROSION–OCTOBER 1994 .8 mm inner diam (ID). the solution pH was measured in the bulk electrolyte as well as in the crevice electrolyte. The pH values of the bulk soil water and crevice solutions at the 12:00. the potential difference between the steel rod and the reference electrode in the main compartment) using a potentiostat. and the entire surface was covered with a layer of brownish corrosion products. A multimeter was used to measure the cell current during the tests. The resulting model crevice had a crevice width of 1. Two pulse frequencies were used: 1 Hz and 10 Hz.3 mm and a crevice width-to-depth ratio of 1:80. Cathodic protection of the steel rod within the crevice was carried out by controlling the holiday 808 Cathodic Protection of Steel Pipe in Soil Three sets of cathodic protection tests were carried out. The test lasted ≈ 7 h in the 0. The surface of the steel rod was examined visually for corrosion damage. and an air bubbling tube. 3:00.. 15 V.CORROSION ENGINEERING FIGURE 3. Slight Corrosion — The pipe surface was covered with a light blackish film. Figure 3 shows the construction of the model crevice cell. whose sintered glass tip was placed near the crevice opening. This reference electrode in the main electrolyte compartment was used to control the holiday potential of the steel rod during the cathodic protection experiments.440 ⍀-cm.e. At the end of each test.06 M NaCl solution and 70 h in the 0. One end of the steel rod was insulated from the test electrolyte with an epoxy glue and was placed at the open end of the glass tube to serve as the crevice (or holiday) opening. 4. which was used to hold the bulk of the test electrolyte. Model crevice cell for testing the effect of solution resistivity on potential distribution within a crevice. Air was bubbled into the electrolyte in the main compartment throughout the test.5 cm. Corrosion —The pipe surface was covered with a thin rust layer. RESULTS room temperature were 158 ⍀-cm. The pulsed potential was generated by feeding a rectangular pulse signal from a pulse function generator to the potentiostat. Each set tested four coated steel pipe samples buried in the test soil. and 10:30 positions at the end of the test also are listed. and a lustrous metal color was visible under the brownish coating. the amount of electric charge passing through the cell (Q). The other end of the glass tube was sealed with a rubber stopper.3 mm diam and having the same composition as the steel pipe samples was inserted into the glass tube through a central hole on the rubber stopper to simulate a model crevice. Pipe Surface Condition After Test The condition of the pipe surface after the cathodic protection tests was classified into one of the following categories: Severe Corrosion — The pipe surface rusted heavily. Three vertical reference taps were mounted on the glass tube 1. Cathodic protection was carried out using DC and PC at controlled anode-to-cathode cell voltage settings of 10 V. A SCE was inserted into the reference taps to measure the local crevice potential. For the pulsed cathodic protection. Direct and pulsed potential were used.5. The local crevice potentials were measured using a high-input impedance electrometer.200 ⍀-cm. The main electrolyte compartment contained 110 mL of test electrolyte. One end of the glass tube was open to a large glass vessel. a SCE. and 7. Tests 1 and 2 included a coated pipe undergoing natural corrosion within the crevice of a disbonded coating holiday without any protective measures.4 cm from the crevice opening.

No. there was a sudden shift of local crevice potential at the 3:00 and 6:00 positions from –0.78 VSCE cathodic protection criterion set by NACE International. the pipe potential at different locations within the crevice all changed to a steady value of –0. for which the pipe surface after the tests was classified at a level between slight corrosion and corrosion. and Very Slight Corrosion — Most of the pipe surface was bright and lustrous.5 cm to 13 cm diam depending on the controlled cell voltage. the surface condition after the tests depended on the controlled cell voltage settings.23 Figure 5 shows the crevice potential-vs-time curves for the pipe protected at a PC of 1 Hz at Von = 20 V. and in some areas. the pipe surface was bright and lustrous. for which slight corrosion occurred on the test pipes.5. For the cathodically protected pipe samples. the extent of which depended on the cell voltage settings.83 VSCE. In general. The controlled cell voltage was pulsed between the open circuit and a Von of 20 V at a frequency of 1 Hz and a duty cycle of 0. The pipe was wrapped in a disbonded polyethylene coating with a holiday at the 12:00 position. The pipe surface at these two locations were “protected” technically in accordance with the –0. The size of the area ranged from 2. The most effective settings were PC of 1 Hz at Von = 20 V and DC at Von = 15 V. Local crevice potential of a steel pipe protected by PC. The crevice potential at these two positions reached a steady-state value of –0.78 VSCE after 3 days of experiments. Figure 4 shows the crevice potential-vs-time curves for the pipe protected at a DC cell voltage of Von = 20 V. the local crevice potential at the 3:00 and 6:00 positions all were more positive than –0. “severe corrosion” was found in the neighborhood of the holiday opening.85 VSCE. White calcareous deposits were beneath the holiday openings. Local Potential Within the Crevice of Disbonded Coating For the pipe samples undergoing natural corrosion beneath the disbonded coating with a holiday. the pipe surface in the neighborhood of the holiday opening was grayish-silver and free of rust. For the steel pipes protected by cathodic protection. For this pipe sample. Farther downstream from the grayish-silver area. The least effective settings were PC of 10 Hz at Von = 20 V and DC or PC of 1 Hz at Von = 10 V. The shift occurred after ≈ 250 h of testing.CORROSION ENGINEERING FIGURE 4. some form of corrosion always took place. For the steel pipes undergoing the natural corrosion. The potential shift first occurred at the 3:00 position. This could be considered as an area at which the cathodic current penetrated into the crevice and protected the pipe at a sufficiently negative potential.0 VSCE. and 809 CORROSION–Vol. Heavy brownish rust covered almost the entire pipe surface. probably because of the depletion of dissolved O2 in the crevice. 10 . surface. Local crevice potential of a steel pipe protected by a DC cell voltage of Von = 20 V.8 VSCE toward a more positive value. for which only very slight corrosion was found on the pipe surface. 50.6 VSCE).3 VSCE to –0. for the pipe samples protected by cathodic protection. For this pipe there was no significant difference between the local crevice potential at the 3:00 and 6:00 positions. the local crevice potential at the holiday opening at 12:00 invariably became more negative than –1. The next most effective settings were PC of 1 Hz at Von = 15 V and DC at Von = 20 V. The steady-state potential value was more negative than that of an uncoated pipe steel sample in the bulk soil (–0. with only a few small patches of light blackish film and brownish rust.76 VSCE to –0. However. FIGURE 5.

They were nearly constant at 8. A similar potential shift at the 3:00 and 6:00 positions also was observed for the pipe protected with a PC of 10 Hz at Von = 20 V. for this pipe the potential shift occurred after a longer test time(≈ 600 h).2 to 7. FIGURE 7. The steadystate potentials were –0. reducing the corrosion rate in the crevice. The crevice solution for each pipe sample in Tests 2 and 3 was collected at the end of the test.5 VSCE at the 6:00 position. The characteristics of crevice pH changes could be summarized as follows: — For the natural corrosion pipe. the crevice solution was slightly more acidic than the bulk soil water. The highest pH measured was 12. In some cases. — Pulsed cell voltage seemed to give a more uniform pH distribution than DC at the same Von setting. The crevice pH generally decreased with increasing distance from the holiday opening. and its average resistivity at its steady-state temperature of 43°C was measured using a conductivity cell and a conductivity bridge (Table 1). Crevice solution pH at the 6:00 position vs time for a pipe without cathodic protection and for the pipes protected by DC and PC at Von = 20 V. with a steady pH value of 7.6 VSCE at the 3:00 position and –0. then at the 6:00 position within 24 h. However. the pH values of the bulk soil water of two test cells also are given in Figure 6. This phenomenon indicated the pipe surface may have become passivated under the alkaline condition. The effectiveness of cathodic protection seemed to correlate with the extent of decrease in the resistivity of the crevice solution. The potential shift again corresponded to the time for pH to increase to 12 (Figure 6). the pH of the bulk soil water in two corrosion cells are shown also. pH and Resistivity Changes Inside the Crevice Figure 6 shows pH-vs-time curves at the 6:00 position for the four pipe samples in Test 2. — The rate of pH increase and the final pH values in the crevice increased with the cell voltage settings. — With the exception of the steel pipe protected by a PC of 10 Hz at Von = 20 V.. The time of the potential shift corresponded approximately to the time of a crevice solution pH increase from 8 to 12 for this sample (Figure 6).CORROSION ENGINEERING FIGURE 6. There was a substantial decrease in the crevice solution resistivity when compared with the resistivity of the bulk soil water. CORROSION–OCTOBER 1994 .5 throughout the test duration. 810 — For the pipes protected by cathodic protection.3. For comparison. at the 12:00 position).4. the crevice pH increased with time and reached a steady-state value after ≈ 2 weeks of test. — The local crevice pH was the highest at the holiday opening (i. the decrease was more than tenfold. Figure 7 shows the local crevice solution pH of the four pipes at the end of Test 2 as a function of circumferential tap location. For comparison. there was less corrosion on the steel pipe when the crevice pH at the 12:00 and 10:30 position was in the 10 to 12 range.e. Local crevice solution pH at the end of Test 2 for a pipe without cathodic protection and for the pipes protected by DC and PC at Von = 20 V. The cathodically protected pipes had a lower crevice solution resistivity than the pipe without any cathodic protection.

the time-averaged current of a pulsed voltage was smaller than that of the DCcontrolled voltage.4 7.4 8.9 8.20 0.9 6.8 13.4.06 M NaCl solution. Cell Current and Electric Energy Consumption The time-averaged cathodic current densities for the three DC and PC protected pipes in Test 2 are plotted against the time in Figure 8. The exact nature of current fluctuation was not clear. and –1. the crevice pH increased to 10.5 7.4 10. 1 reference electrode tap 1.2 12. the current density curve was characterized by large fluctuations.4 11.3 7. At the end of test in the 0.8 7.050 3.3 3.e.2 9.9 3.53 VSCE.1 12. as expected (i.1 8.0. For a given Von setting.8 12.9 3.5 7.230 3.006 M. and changes in soil porosity. The protective cathodic current for a given pipe decreased with increasing test time.5 cm from the crevice opening having the most negative value and the No.5 9.100 3.2 7. on the use of PC for cathodic protection.3 8. and the steel surface showed no sign of corrosion. The steady-state potential distribution within the crevice was normal.2 11. the steel surface within the 811 CORROSION–Vol.050 3.100 1. 0. At the more negative controlled potential of –1.5 74.9 4.400 4.1 12. 15 V(A) Slight corrosion (A) 0.3 12.9 44.5 1. the steel surface was polarized immediately after the potentiostat was turned on at all the controlled potentials investigated.6 6.9 8. the fluctuation was as high as 200% over only a few hours of test time. 20 V(A) Corrosion Test Number 3 (45 days) DC 10 V Slight corrosion PC 1 Hz. The experiments were carried out at three controlled DC holiday potentials: 1. with the No. 10 V(A) Corrosion DC 15 V Very slight corrosion PC 1 Hz.6 12.03 VSCE.8 VSCE within 30 min after the start of experiment.5 9. 20 V(A) Very slight corrosion Test Number 2 (42 days) Natural corrosion Severe corrosion DC 20 V Slight corrosion PC 1 Hz. Sometimes.0 5.1 7.4 8.7 45. 10 V(A) Slight corrosion PC 1 Hz. 50.2 8.19 Effect of Electrolyte Resistivity on Crevice Potential Distribution The effect of electrolyte resistivity on the potential distribution in the model crevice cell was examined at three NaCl concentrations: 0.200 720 2. 10 . could affect the current flowing into the pipe crevice.1 219 139 62.2 8.03 VSCE and –1.5 6.830 4.6 cm from the crevice opening] having the least negative value).2 7. Results indicated that.900 380 264 202 4..400 4.830 4.550 605 1. –1.002 M NaCl solution with a high resistivity of 4.1 59.200 4. 20 V(A) Very slight corrosion PC 10 Hz. H2 evolution occurred at the crevice opening. and 0.4 10.9 11.06 M.0 8. A similar conclusion also was reported by Juchniewicz. including the formation of H2.5 8.3 2..3 11. The local potentials at the three crevice locations became more negative than –0.5. accumulation of calcareous deposits.53 VSCE. No. the energy consumption of pulsed voltage control was less than that of the DC voltage control. In a high-resistivity soil. Any disturbances at the holiday opening.4 6.0 8.8 8.57 2. 3 reference tap [7.CORROSION ENGINEERING TABLE 1 Results of Cathodic Protection Tests for Steel Pipes Buried in Soil Protective Cell Voltage (Von) Resistivity (⍀-cm) Bulk Crevice (35°C) (43°C) 3.4 4.9 10. The initial pH of the solutions was in the range 5. For the 0.6 9. The current-vs-time curves were integrated to give the Q and E values for the pipes used in the tests (Table 1).230 Surface Condition Q (kCoul) E (kJ) pH at Position Bulk 12:00 3:00 6:00 10:30 Test Number 1 (20 days) Natural corrosion Severe corrosion DC 10 V Corrosion PC 1 Hz.002 M. the magnitude of cell current was controlled by the soil resistance at the holiday opening.28 VSCE.28 VSCE.2 to 6. at the same Von setting.2 10. et al. No H2 evolution was observed for the runs at the controlled potentials of –1. For the 0. For a given pipe.320 PC was pulsed at potentials between open circuit and Von at a duty cycle of 0.200 ⍀-cm. The cell current generally increased with the applied cell voltage.1 12.5 6.06 M NaCl solution that had a low resistivity of 158 ⍀-cm.5 8.3 8.

which was about the same as the initial pH of the test solution.002 M NaCl solution. 3 reference tap. Corrosion occurred ≈ 2 cm from the crevice opening.8 VSCE at any controlled potential setting within a test duration of 70 h. The crevice solution at the end of the run (22 h) had a pH of 10.006 M NaCl at a controlled DC holiday potential of –1. in a moderately dilute NaCl solution. However. no corrosion was observed near the crevice entrance or at the sealed end of the crevice. with the least negative value occurring at the No. For the 0. However.002 N NaCl (high-resistivity) solution to that in the 0. No H2 evolution was observed in this run. After 16 h of test.CORROSION ENGINEERING FIGURE 8. This gave a time-averaged holiday potential of –1.006 M NaCl solution.8 VSCE immediately after the current was switched on.006 M and 0. 1 reference tap and the most negative potential occurring at the No.002 M NaCl solutions. and the potential of the No. which had a moderately high resistivity of 1.03 VSCE and –1. A normal potential distribution in the crevice was observed. 3 reference tap the least negative potential [Figure 9]). The steel surface exhibited only minor corrosion 2 cm from the crevice opening. As the cathodic protection continued. The controlled holiday potential was pulsed between –1. test was in the range 5. This behavior was similar to that in the 0.53 VSCE at a frequency of 1 Hz and a duty cycle of 0. the rate of potential shift was the highest at the No.06 M NaCl (low-resistivity) solution. 1 reference tap and the most negative value occurring at the No.1. crevice could not be polarized to a more negative potential than –0. 1 reference CORROSION–OCTOBER 1994 . Figure 10 shows the crevice potential-vs-time curves for a run in the 0. Time-averaged protective current density vs time for the pipes protected by DC and PC at Von = 20 V. During the initial period of this run.5 to 6. the order of potential distribution was changed to the normal order (the No.5. with the least negative potential occurring at the No. the potential distribution in the crevice was in the reverse order. 3 reference tap. with the most negative value occurring at the No. The pulsed potential eliminated the initial incubation period.006 M NaCl solution. Effect of Pulsed Potential FIGURE 9. Figure 9 shows the local crevice potential in the 0.440 ⍀-cm. This indicated that. the local crevice potential gradually shifted toward the negative direction.06 M solution.28 VSCE. This was followed by the No. 2 and then by the No. the potential distribution within the crevice exhibited a transition from the behavior in the 0. the pulsed potential improved the rate of potential change of steel in the crevice. 1 reference tap shifted to the neighborhood of –0.28 VSCE.28 VSCE. 3 reference tap. This result indicated the current did not penetrate into the crevice. Crevice potential of a steel rod in the model crevice cell containing 0. an initial incubation period was necessary for the current to penetrate into the crevice. The crevice potential distribution for this solution was in the reverse order from that for the 0. Comparing Figure 10 to Figure 9. which shows the results for DC potential control at the same time-averaged potential. and the steel surface was not protected by the cathodic current. The solution pH within the crevice after the 812 The effect of rectangular pulsed potential on the potential distribution in the model crevice cell was tested in the 0. 1 reference tap.006 M NaCl solution at a controlled holiday potential of –1. 1 reference electrode tap exhibited the most negative potential and the No.

28 VSCE. For the 0. sodium ions (Na+). They meet the outgoing OH–. and the above reactions occur to compensate for the pH increase in the crevice. Corrosion on the steel rod at the end of the test was less than that occurring on rods under DC cathodic protection. which migrate into the crevice and increase their concentrations.CORROSION ENGINEERING Chemical Changes Inside the Crevice During cathodic protection. The H+. During cathodic protection. and the above 813 CORROSION–Vol. The controlled holiday potential was pulsed between –1. and the pH of solution inside the crevice is increased. decreasing the electric resistance of the crevice solution.006 M NaCl under pulsed cathodic protection. 10 . — Decomposition of bicarbonate ions and formation of calcium carbonate (CaCO3) precipitates: HCO 3 – + OH – = H 2 O + CO 3 2– Ca 2+ + CO 3 2– = CaCO 3 (5) (6) The bicarbonate ions are transported by diffusion and migration from the bulk soil water into the crevice. The pH of the crevice solution increased to 10. including an increase in pH and a decrease in solution resistivity. The Ca(OH)2 and Mg(OH)2 subsequently precipitate out in the crevice and at the holiday opening. the crevice potential distribution of pulsed cathodic protection was similar to that of DC cathodic protection. DISCUSSION Experimental results indicated cathodic protection with a sufficiently high impressed cell voltage could mitigate external corrosion of a buried steel pipe beneath a disbonded coating in highresistivity soils. and Mg2+ ions are transported from the bulk soil water into the crevice. During cathodic protection. In addition.002 M NaCl solution.53 VSCE with a frequency of 1 Hz and a duty cycle of 0. which would not permit the pH to increase beyond a theoretical limit of ≈ 12. calcium ions (Ca2+). there is a constant transport of ionic species between the bulk and crevice solutions to maintain electric neutrality. In the crevice area away from the holiday. and magnesium ions (Mg2+) in the soil. However. calcareous deposits of hydrated calcium hydroxide (Ca[OH]2) and magnesium hydroxide (Mg[OH]2) form on the pipe surface when sufficient amounts of Ca2+ and Mg2+ ions move into the crevice. and there was no visible corrosion on the steel rod at the end of the test. In turn. 50. the solution inside the crevice undergoes chemical changes. The nature of the chemical environmental changes within the crevice may be summarized as: — O2 reduction reaction at the cathodic steel surface: O 2 + 2H 2 O + 4e – = 4OH – — Formation of Ca(OH)2 and Mg(OH)2 precipitates and neutralization of OH–: Ca 2+ + 2OH – = Ca(OH) 2 tap and the least negative value occurring at the No. hydroxyl ions (OH–) are produced by O2 reduction at the cathode surface. These changes are favorable to the mitigation of crevice corrosion in a high-resistivity environment. the pulsed potential increased the crevice solution pH to 10. Ca2+. the excess negatively charged OH– ions attract such positively charged cations as hydrogen ions (H+). Crevice potential of a steel rod in the model crevice cell containing 0. Mg 2+ + 2OH – = Mg(OH) 2 H + + OH – = H 2 O (2) (3) (4) (1) FIGURE 10. No.03 VSCE and –1. The solution pH inside the crevice is limited by the solubility products of Ca(OH)2 and Mg(OH)2. Corrosion on the pipe surface in the immediate vicinity of a holiday opening could be stopped by the cathodic current. The time-averaged holiday potential was –1. 3 reference tap. the corrosion rate may be reduced substantially by eliminating dissolved O2 in the crevice.5. The OH– ions formed inside the crevice are transported to the bulk solution through the holiday opening.

1. — Corrosion of iron (Fe) and subsequent hydrolysis and oxidation of the corrosion product: Fe = Fe 2+ + 2e – Fe 2+ + 2OH – = Fe(OH) 2 4Fe 2+ + O 2 + 10H 2O = 4Fe(OH) 3 + 8H + (7) (8) (9) where x is the distance from the crevice opening. the corrosion of steel is controlled by the O2 reduction reaction. Cathodic protection effectively can stop the diffusion of dissolved O2 into the crevice by reducing all available O2 at the pipe surface directly beneath the crevice opening. dC =0 dx (11) reactions take place in the neighborhood of the holiday opening.CORROSION ENGINEERING Lennox have shown that it is not necessary to force the electric current into a crevice to protect it cathodically. ␦ is the crevice thickness. k␦/D. the corrosion rate in the crevice eventually is reduced to a low level. Peterson and 814 Figure 11 shows the variation of O2 concentration inside the crevice for three values of a dimensionless parameter. i´corr. O2 Depletion Mechanism — In aerated neutral and alkaline environments. In the present study. D is the diffusivity of dissolved O2. The above equations may be integrated to give: 1 2 C(x) kd = exp – Cb D x δ (12) The formation of Fe corrosion products were evident from the blackish and rusty films on pipe sample surfaces and the yellowish precipitates in the crevice solutions collected at the end of experiments. and at x = ∞. even though the electric current was not able to penetrate deep into the crevice. C refers to the O2 reduction curve at the initial stage of corrosion. The corrosion potential in the crevice is shifted from Ecorr to a more negative value of E´corr because of the depletion of O2. The limiting current for C´ is smaller than that for C because of a decrease of O2 concentration in the crevice. Two possible mechanisms for the cathodic protection of pipe surfaces within the crevice of a disbonded coating with a holiday were examined. the local O2 concentration inside the crevice is reduced to < 0. For a value of k␦/D ≥ 0. within a cathodically protected crevice may be described by the differential equation: k d2C – C=0 dx2 δD at FIGURE 11. and C´ refers to the O2 reduction curve after the application of cathodic protection. (10) x = 0. This situation is illustrated schematically by the polarization curves in Figure 12. C(x). Mechanism of Cathodic Protection Against Crevice Corrosion Past results have shown that cathodic polarization of steel inside the crevice of a disbonded coating can be achieved in low-resistivity solutions.8 Sufficient cathodic protection can be achieved by applying an appropriate potential to suppress the differential O2 cell within the crevice.001 of the bulk O2 concentration outside the crevice at a distance of x = 25␦ from the crevice opening. Since no O2 is transported into the crevice. O2 concentration inside crevice as a function of distance from the crevice opening for three values of a dimensionless parameter. The point of intersection between the anodic and cathodic polarization curves gives a high initial corrosion rate of icorr and a low corrosion rate after the application of cathodic protection. CORROSION–OCTOBER 1994 . k␦/D. and k is a first-order reaction rate constant for the reduction of O2 at the steel surface inside the crevice. the steady-state local O2 concentration. in which A represents the anodic polarization curve of steel in a neutral crevice solution. Using a simple O2 diffusion model. steel pipes with a disbonded coating in a high-resistivity solution also were protected cathodically. Cb is the O2 concentration at the crevice opening. C = Cb.

in the pH 12. Curve C´ — cathodic polarization curve after O2 concentration in the crevice has been reduced by cathodic protection. No.CORROSION ENGINEERING FIGURE 12. the anodic and cathodic polarization curves of the present pipe steel in the test soil water were measured using a laboratory cell and a computer-interfaced potentiostat.0 VSCE. Curve A — anodic polarization of steel in neutral crevice solution. At pH 12. At pH 7. and A2 and C2 represent the anodic and cathodic polarization curves in the pH 12.9 and 12.9 water.3. 10 . To further elaborate the passivation mechanism in a highresistivity medium.25 815 CORROSION–Vol. and the corrosion rate as calculated using the Tafel extrapolation method was nearly 10 times smaller than that in the pH 7. 50. Curve A´ — anodic polarization of steel showing passivity after sufficient alkali has been introduced into the crevice by cathodic protection. Curve C — cathodic polarization at the initial stage of corrosion. According to a potentialvs-pH diagram of Fe.6 VSCE. followed by the onset of H2 evolution at ≈ –1. and the corrosion potential in the crevice shifts to a positive value of E´´corr. in which A1 and C1 represent the anodic and cathodic polarization curves in the pH 7. This result indicated that. The cathodic curve (C1) exhibited a limiting current regime for the O2 reduction reaction. and the cathodic polarization curve (C2) exhibited a Tafel potential-current relationship for O2 reduction in the neighborhood of the corrosion potential. Some of the OH– diffuses into the interior of the crevice and causes an increase in the pH of the crevice solution.9 and 12. shown in Figure 12. Results are shown in Figure 13. FIGURE 13. The measurement was carried out at 50°C and at two controlled pH values (7.9 water. the steel passivates and the anodic polarization curve shifts from the initial behavior of curve A to curve A´ (Figure 12). This result implied that the corrosion of pipe steel in neutral soil water was controlled by the diffusion of O2 to the cathodic sites. pH Increase and Passivation Mechanism — The O2 reduction reaction caused by cathodic protection generates OH– at the crevice opening as shown by Equation (1). the corrosion of steel was taking place in the passive state. the anodic polarization curve (A2) exhibited a passive potential regime similar to the vertical portion of curve A´. curve A1 indicates the steel was corroding in an active state. as demonstrated by the present experimental data.24 the pipe surface can become passivated with the formation of a ferrosoferric oxide (Fe3O4) film in the pH range 9 to 13. Schematic of a potential-vs-current diagram showing the changes in corrosion rate and corrosion potential during cathodic protection of steel inside a crevice.5 VSCE to –0.3.9.3) corresponding to the initial and final pH values of the crevice solution in the cathodic protection experiments.3 water. The corrosion rate is decreased to a low value of i´´corr. The passivation mechanism also was discussed by Cherry and Gould for the cathodic protection of steel in a crevice filled with a dilute NaCl solution. When the crevice solution becomes sufficiently alkaline. This passivation mechanism is consistent with the present cathodic protection data of a pH increase in the crevice to 10 to 12 and a shift in the local crevice potential at the 3:00 and 6:00 positions to a more positive value of –0. Anodic (A) and cathodic (C) polarization curves of a pipe steel in aerated soil water at controlled pH values of 7.3 water.

1967).E.W. India: Council of Scientific Research Integration. E. 21.W.E. 221. Berry.” CORROSION/73.). I. 1985). Juchniewicz. 1983). Corrosion 29 (1973): p. Wenk.C. D. eds. Smith (Exxon Production Research). the protective current and energy consumption were smaller and the pH distribution in the crevice was more uniform than when using DC cathodic protection. 24. L. 80. R. Pierson (Exxon Pipeline Co.C. F. Toncre. MP 28. The maximum crevice pH measured in the present experiment was 12. which blocked the penetration of cathodic protection current into the crevice.3. Fletcher. 26 (1982): p. Bone (ARCO Exploration and Production Technology). In the present study. A. 13.W. VA: American Gas Association. T. Fessler. 5..R. NY: John Wiley & Sons. 215. 1992). M. Leaman.. A.J. J. Gan.H.W. (TAPS). p. 20.J. Line Pipe Research (Arlington. 6. The pipe was buried in a wet soil in which the resistivity of the soil water was 3.200 ⍀-cm. Burger (ARCO Exploration and Production Technology). Trivandrum. Samaran. Ahmad. on the Internal and External Protection of Pipes. The resistivity of the crevice solution was reduced from an initial value of 3. Chin. 5th Symp. R. p.“ 5th Int. 8 (1990): p. both DC and pulsed cathodic protection can protect a steel pipe buried in high-resistivity soil. the optimal cell voltage settings were: (a) PC of a frequency of 1 Hz and a duty cycle of 0. Corrosion and Corrosion Control (New York. (b) depletion of dissolved O2 in the solution inside the crevice. There was no significant difference in overall protection effectiveness between the DC. (Orlando. “Recommended Practice. 1982). 19. H. 20. 7 (1976): p.N. 406. When using PC. 1977). 19-21. A.W. 1986). Puippe. Toncre. 15. Stankiewicz.” NACE-CRCW Meeting. 39. 11 (1988): p. OH: Battelle Columbus Laboratories. MP 28.N. Control of External Corrosion on Underground or Submersed Metallic piping Systems” (Houston. J.-T.M. p. 8. Chin. Hotchkiss and E. R. Proc. Sabde. Corrosion 39 (1983): p. 19.M. REFERENCES 1. “The Effect of Pipe Surface Oxide upon Crevice Polarization and Stress Corrosion Cracking Under Fusion-Bonded. Revie. O Cathodic protection increases the pH and decreases the resistivity of solution inside the crevice.W.-T. Conf. and (c) a pH increase in the crevice and passivation of the steel surface in the alkaline environment. E.P. Barlo.050 ⍀-cm to 4.C. T-15. Klechka (Alyeska Pipeline Service Co. T. E. 13. O Cathodic protection by means of an impressed current was shown to be potentially effective in mitigating the external corrosion of steel pipe beneath a disbonded coating with a holiday in a highresistivity soil.).” in Trends in Electrochemistry. Feb. O With a properly controlled voltage. A. VA: American Gas Association. 81. and the members of a TAPS task group including L. A high voltage induced excessive H2 evolution at the holiday opening.J. 10.N. 1983). p. paper no. 26. 17. MP 24.050 ⍀-cm to 4. 9. 816 CORROSION–OCTOBER 1994 . 12 (1988): p. R. 22. S. 74.J. R. MP 23. paper F4 (Bedford. A. Doniguian. 531. J. TX: NACE. MP 28. R. G. J-C. W.L. 3.D. Fletcher. Control of Pipeline Corrosion (Houston.F. Seid. Oil Gas J. Markworth. 1974).” Proc.”Protection of Well Casings by Pulsed Cathodic Currents. J. E. Bauman. 12.E. A low-frequency PC of 1 Hz at a duty cycle of 0. Markworth. E. 14. 25. MP 27. R. MP 19. Roche. TX: NACE. T. 18. MP 29. Saskatoon. Parkins. Smith. 8 (1984): p. Electrochem.). 2. 6 (1980): p. 127 to the American Gas Association (Columbus. R. O The applied cell voltage is an important parameter for cathodic protection in a high-resistivity environment. 6 (1985): p. R. 69 (Houston. “Periodic Electrode Processes: AC Corrosion and Pulse Plating. 23. N. p. Theory and Practice of Pulse Plating. M.” NG-18 Report No.J. Peterson.5 provided better protection than a high-frequency PC of 10 Hz. B. 28. D.N. 2 (1989): p. Fessler. A low cell voltage would not permit sufficient polarization of the steel surface within the crevice. R. 22. Lennox Jr. 43. W. Peabody. McCoy. Widin (BP Research). Bird. Oil Gas J. Penna. 16. 17. 414.5 at Von = 15 V to 20 V and (b) DC at a controlled cell voltage of 15 V to 20 V. Saskatchewan. F.400 ⍀-cm to a final value of 200 ⍀-cm to 600 ⍀-cm. on Line Pipe Research (Arlington. 11 (1987): p.H. The chemical changes were favorable to the cathodic protection of the steel pipe beneath the disbonded coating. E. J. A. NACE Standard RP01-69. 3 (1987). J. 1973). Fletcher. p. H. 417. “Relative Merits of Pulsed Rectifiers for Controlling Stress Corrosion Cracking. Mills. FL: American Electroplaters and Surface Finishers Society. McGary. and T. 22. 4. M. 11. Canada. Brooman.CORROSION ENGINEERING CONCLUSIONS Experiments were conducted to determine the effectiveness of cathodic protection to mitigate external corrosion of a steel pipe beneath a disbonded coating with a holiday. Morrison. B. Haycock. Cherry. Fessler. Vol. Chin. 24 (1993): p.R. “Cathodic Protection by Intermittent and Pulsed Currents. G. Berry. 1991. Nunn (Mobil Pipe Line Co. Low-Density Polyethylene Coatings. Gould. D. The relative merits of using PC vs DC were examined for a steel pipe having a crevice that had a thickness-to-length ratio of 1:500.and PC-controlled modes. ACKNOWLEDGMENTS The authors acknowledge the support of Alyeska Pipeline Service Co. Szukalski. 1 (Sreekanteswaram.N.400 ⍀-cm.H. E. M. In the present laboratory cell. A. R. the protection mechanism was identified to be: (a) cathodic polarization of pipe surface in the immediate vicinity of the holiday opening to a “corrosion immunity” potential. A model crevice cell was used to examine the effect of solution resistivity on the behavior of the crevice potential for solution resistivities from 158 ⍀-cm to 4. 5th Symp. Uhlig. 7. Orton.R. 16. W.D. Parkins. TX: NACE. UK: BHRA Fluid Eng. “Stress Corrosion Cracking Laboratory Experiences. M.A. Ch.