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

&

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

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is largely a result of the inability of imposed cathodic protection systems to pass sufficient protective current to the corroding sites on the pipeline. The disbonded pipe coating acts as a shield against the flow of cathodic current to the pipe surface beneath it.6-7 The cathodic current must flow through the holiday opening into the crevice, 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 0.85 V vs a copper sulfate reference electrode (CSE) to a less negative value at which the cathodic protection fails to stop the corrosion process. Toncre and Ahmad studied cathodic protection against crevice corrosion of mild steel in seawater, saline water, and brackish water.4 They simulated the crevice that would be found under a disbonded pipeline coating and measured the potential along the crevice length. Their results showed cathodic protection in low-resistivity solutions could be achieved if the potential at the crevice opening was more negative than 1.0 V vs a saturated calomel electrode (SCE). Similar potential measurements were carried out by Peterson and Lennox.8 They found it was not always necessary to pass current into the crevice to protect the metal surface cathodically.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. Berry,9 Fletcher, et al.,10 and Fessler, et al.,11 studied polarization of pipeline steel in a solution containing 1 N sodium carbonate (Na2CO3) and 1 N sodium bicarbonate (NaHCO3). 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. The steel samples that had a mill scale needed a longer time to polarize and attained a less negative potential than clean steel samples. Using a segmented specimen, Fessler, et al., showed the protective current density decreased along the crevice from the opening.11 Proper protection could be achieved with a controlled holiday potential of 1.0 VSCE in the Na2CO3 and NaHCO3 solution. At a more negative controlled potential, hydrogen gas (H2) bubbles were produced at the holiday opening and caused fluctuations in the current/potential measurement. Toncre found that, by extending the testing time, proper polarization of the steel surface beneath disbonded coatings could be achieved in a lowresistance solution for crevice thickness-to-depth ratios up to 1:1,200.12 A field study on the effectiveness of cathodic protection under disbonded coatings on a pipeline

was carried out by Orton in eastern Saudi Arabia.13 The soil environment consisted of rocks and desert sands. In a large area, the saline water table was only a few feet below ground. The water resistivity ranged from 30 -cm to 200 -cm. The current required to maintain the holiday potential at 0.85 VCSE and 1.0 VCSE was almost the same, whereas at a 1.5 VCSE setting, additional current was necessary because of H2 evolution on the pipe surface. In most of Ortons experiments, steel was polarized only within a short distance from the crevice opening. McCoy reported the cathodic protection of the Dampier-to-Perth natural gas pipeline in Australia buried in a high-resistivity soil (50,000 -cm to 100,000 -cm).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. When using a controlled potential of 1.1 VCSE, the potential within the crevice was only 0.6 VCSE. Apparently, polarization within the crevice was not achieved. On a pipeline in Saudi Arabia, Toncre measured the pipe-to-soil potential circumferentially around pipe.12 There was general corrosion on the pipe when the circumferential potential was 0.99 VCSE. Where the coating was disbonded extensively, pitting corrosion occurred on the pipe surface, and the circumferential potential was 0.5 VCSE to 0.6 VCSE. 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. However, in a high-resistivity environment, it is difficult to achieve the 0.85 VCSE protective polarization potential inside a crevice. At a high applied potential, H2 evolution occurred at the holiday opening, whereas at a low holiday potential, cathodic protection was not achieved. No experimental study has been reported for the current/ potential distribution within a crevice filled with a high-resistivity electrolyte. A detailed review of the cathodic protection of underground pipelines against crevice corrosion was given by Sabde, et al.15 Recently, 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, water heaters, and steel pipes.16-20 Although no particular benefit was identified, PC reduced energy consumption while maintaining the protection efficiency afforded by the direct current (DC) cathodic protection system. In electroplating, PC has been reported to possess a larger microthrowing power than DC plating.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

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distribution than DC when used in cathodic protection against crevice corrosion. In the present study, 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 local pipe potential and solution pH within the crevice were monitored as a function of time. The relative merits of PC vs DC were examined experimentally. To account for a large difference in the behavior of local crevice potential between the low-resistivity and highresistivity solutions, a model crevice cell was used to examine the effect of solution resistivity on cathodic protection.

Pipe Coating and Crevice Configuration

The exterior surface of the steel pipe was polished manually using 600-grit sandpaper, cleaned with detergent, degreased with acetone, and dried. The pipe then was wrapped circumferentially with a new polyethylene pipeline tape.(2) The tape was 1.3 mm thick by 10.2 cm wide and was fastened to the pipe with two stainless steel pipe clamps. At both ends of the pipe, the space between the tape and exterior surface of the pipe was sealed using an adhesive strip 1 mm thick and 1.3 cm wide. The overlap sections of the tape on the pipe also were sealed with adhesive. In this way, a watertight crevice 1 mm thick was formed circumferentially between the exterior pipe surface and the polyethylene coating. 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). The ratio of the crevice opening area to the total pipe surface within the crevice was 1:1,400 (i.e., 0.5 cm2 of holiday area to 700 cm2 of pipe area in the crevice). The crevice thickness-to-length ratio along the circumferential direction was 1:500.

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. The resistivity of the soil water was in the range 3,050 -cm to 4,400 -cm. 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 4,200 -cm.

Corrosion Cell and Test Soil

Figure 1 shows the schematic of cell construction. The cell was a rectangular acrylic container 48 cm wide by 36 cm deep by 50 cm high. 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. The pipe, plates, and cell wall were bolted together using eight titanium (Ti) bolts. The Ti bolts also served as the anode during the cathodic protection experiments. One holding plate served as a partition between the soil in the cell and the interior of the test pipe. The other holding plate, which faced the cell wall, had an opening to the atmosphere. 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. 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. To simulate the temperature of warm petroleum oil flowing in the pipe, an electric heat gun inserted through the opening was used to heat the air in the pipe to 50C 2C. The pipe interior temperature was measured using a thermistor probe and was controlled by a temperature controller. In this way, two horizontal pipe test sections were mounted on each acrylic cell. 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 160.5 in Atigun Valley, Alaska. The soil was mixed with deionized water in a volume ratio of 1:1. The resulting soil water(3) had

Test Pipe
The test pipe was a steel pipe (API Standard SL Grade X65(1)) of 32.4-cm outer diameter (OD) and 0.714 cm wall thickness. The pipe was sandblasted, machine smoothed, and cut into sections 10.2 cm long. On each pipe section, four back-reference taps and four pH monitoring holes were drilled through the pipe wall at the 12:00 (12 oclock; top), 3:00, 6:00 (bottom), and 10:30 positions. 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 pH monitoring holes were sealed with a rubber stopper, which permitted the insertion of a pH microelectrode probe from the interior of the pipe for measurement of the crevice solution pH.

(1)

(2)

(3)

Steel composition: carbon (C), max. 0.16%; silicon (Si), max. 0.35%; manganese (Mn), max. 1.5%; phosphorus (P), max. 0.025%; sulfur (S), 0.01% to 0.035%; copper (Cu), max. 0.2%; chromium (Cr), 0.3%; vanadium (V), max. 0.1%; aluminum (Al), max. 0.04%; nitrogen (N), max. 0.008%; and iron (Fe), remainder. The electric resistance and capacitance of tape in the test soil water at 50C, as measured by an alternating current (AC) impedance technique, were > 1011 and 3.0 pF/cm2, respectively. The water adsorption was 1.2% of its weight after 80 days immersion in the soil water at 50C. Water composition in milligrams per liter: calcium ions (Ca2+), 50; magnesium ions (Mg2+), 26; sodium ions (Na+), 6; chloride ions (Cl), 6; bicarbonate ions (HCO3), 98; sulfate ions (SO42), 66; total solids, 302.

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a pH of 6.4 to 8.4 and an electric resistivity of 3,050 -cm to 4,400 -cm at a steady-state soil temperature of 35C during the experiments. Air was bubbled through the soil water continuously, and the water was recirculated in the soil using an air-lift pump (Figure 1).

Electric Circuit and Cathodic Protection Procedures

The electric circuit for cathodic protection experiments is shown schematically in Figure 2. 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. During the experiment, the anode-to-cathode cell voltage was monitored with a digital multimeter (V1) and its waveform was checked periodically on an oscilloscope. The protective cell current was determined by measuring the voltage drop across a standard resistor (R) with a second multimeter (V2). The current waveform was examined using the oscilloscope. The SCE was used to determine the local crevice potential at the 12:00, 3:00, 6:00, and 10:30 positions on the test pipe. A high-input impedance electrometer (V3) was used for the potential measurement. Prior to filling the cell with the test soil, 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. Then, the cell was filled with the 1:1 soil-water mixture to cover the test pipe completely. The test began by connecting the pipe and Ti anode to the cathodic protection circuit and by switching on the pipe temperature controller. During the test, the local crevice potential was measured daily, and the local crevice pH values were measured weekly with a combination pH microelectrode. To avoid contamination of the crevice solution by the reference electrode fluid, the SCE was inserted into the pipes reference tap only during the measurement, which took a few minutes. At the end of test, the crevice solution was collected, and its final pH and electric resistivity were measured using a pH meter and a conductivity meter. The cell then was disassembled, and the test pipe was stripped of the polyethylene tape and washed with water. The pipe surface was examined for corrosion damage visually, and its surface condition was recorded on videotape.

FIGURE 1. Schematic of the corrosion cell used to test the cathodic protection of a steel pipe with a disbonded coating in wet soil.

FIGURE 2. Electric circuit for cathodic protection and locations of reference and pH measurement taps on the steel pipe sample.

Model Crevice Cell Experiment

The electrolyte used in the model crevice cell experiment was an aqueous NaCl solution at 25C.

The solution was prepared by dissolving an appropriate amount of analytical-grade NaCl in deionized water. Three NaCl concentrations were used: 0.06 M, 0.006 M, and 0.002 M. The corresponding electric resistivities of these solutions at 807

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FIGURE 3. Model crevice cell for testing the effect of solution resistivity on potential distribution within a crevice.

potential (i.e., the potential difference between the steel rod and the reference electrode in the main compartment) using a potentiostat. Direct and pulsed potential were used. The pulsed potential was generated by feeding a rectangular pulse signal from a pulse function generator to the potentiostat. A multimeter was used to measure the cell current during the tests. The local crevice potentials were measured using a high-input impedance electrometer. The test lasted 7 h in the 0.06 M NaCl solution and 70 h in the 0.002 M NaCl solution. At the end of each test, the solution pH was measured in the bulk electrolyte as well as in the crevice electrolyte. The surface of the steel rod was examined visually for corrosion damage.

RESULTS
room temperature were 158 -cm, 1,440 -cm, and 4,200 -cm. Figure 3 shows the construction of the model crevice cell. It consisted of a horizontal glass tube 10 cm long with an 11.8 mm inner diam (ID). One end of the glass tube was open to a large glass vessel, which was used to hold the bulk of the test electrolyte. The other end of the glass tube was sealed with a rubber stopper. A cylindrical steel rod of 9.3 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. 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. The resulting model crevice had a crevice width of 1.3 mm and a crevice width-to-depth ratio of 1:80. The main electrolyte compartment contained 110 mL of test electrolyte, a Ti anode, a SCE, and an air bubbling tube. The reference electrode was inside a Luggin capillary tube, 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. Three vertical reference taps were mounted on the glass tube 1.5 cm, 4.5 cm, and 7.4 cm from the crevice opening. A SCE was inserted into the reference taps to measure the local crevice potential. The reference compartments were separated from the crevice solution with a sintered glass and were filled with the same test electrolyte during the test. Air was bubbled into the electrolyte in the main compartment throughout the test. 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. Each set tested four coated steel pipe samples buried in the test soil. Cathodic protection was carried out using DC and PC at controlled anode-to-cathode cell voltage settings of 10 V, 15 V, and 20 V. For the pulsed cathodic protection, the cell voltage was pulsed between the open circuit and a controlled voltage setting (Von) at a duty cycle of 0.5. Two pulse frequencies were used: 1 Hz and 10 Hz. The experiment lasted from 20 days in Test 1 to 45 days in Test 3. Tests 1 and 2 included a coated pipe undergoing natural corrosion within the crevice of a disbonded coating holiday without any protective measures. Table 1 lists the controlled cell voltage, the surface condition after the tests, the amount of electric charge passing through the cell (Q), and the total electric energy consumption during the test (E). The pH values of the bulk soil water and crevice solutions at the 12:00, 3:00, 6:00, and 10:30 positions at the end of the test also are listed. 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.

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, and the entire surface was covered with a layer of brownish corrosion products; Corrosion The pipe surface was covered with a thin rust layer, and a lustrous metal color was visible under the brownish coating; Slight Corrosion The pipe surface was covered with a light blackish film. A few patches of light brownish rust were scattered around the

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FIGURE 4. Local crevice potential of a steel pipe protected by a DC cell voltage of Von = 20 V. The pipe was wrapped in a disbonded polyethylene coating with a holiday at the 12:00 position.

FIGURE 5. Local crevice potential of a steel pipe protected by PC. 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 0.5.

surface, and in some areas, the pipe surface was bright and lustrous; and Very Slight Corrosion Most of the pipe surface was bright and lustrous, with only a few small patches of light blackish film and brownish rust. For the steel pipes undergoing the natural corrosion, severe corrosion was found in the neighborhood of the holiday opening. Heavy brownish rust covered almost the entire pipe surface. For the steel pipes protected by cathodic protection, the surface condition after the tests depended on the controlled cell voltage settings. The most effective settings were PC of 1 Hz at Von = 20 V and DC at Von = 15 V, for which only very slight corrosion was found on the pipe surface. The next most effective settings were PC of 1 Hz at Von = 15 V and DC at Von = 20 V, for which slight corrosion occurred on the test pipes. The least effective settings were PC of 10 Hz at Von = 20 V and DC or PC of 1 Hz at Von = 10 V, for which the pipe surface after the tests was classified at a level between slight corrosion and corrosion. In general, for the pipe samples protected by cathodic protection, the pipe surface in the neighborhood of the holiday opening was grayish-silver and free of rust. 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. The size of the area ranged from 2.5 cm to 13 cm diam depending on the controlled cell voltage. White calcareous deposits were beneath the holiday openings. Farther downstream from the grayish-silver area, some form of corrosion always took place, the extent of which depended on the cell voltage settings.

Local Potential Within the Crevice of Disbonded Coating

For the pipe samples undergoing natural corrosion beneath the disbonded coating with a holiday, the pipe potential at different locations within the crevice all changed to a steady value of 0.76 VSCE to 0.78 VSCE after 3 days of experiments. The steady-state potential value was more negative than that of an uncoated pipe steel sample in the bulk soil (0.3 VSCE to 0.6 VSCE), probably because of the depletion of dissolved O2 in the crevice. For the cathodically protected pipe samples, the local crevice potential at the holiday opening at 12:00 invariably became more negative than 1.0 VSCE. However, the local crevice potential at the 3:00 and 6:00 positions all were more positive than 0.85 VSCE. Figure 4 shows the crevice potential-vs-time curves for the pipe protected at a DC cell voltage of Von = 20 V. For this pipe there was no significant difference between the local crevice potential at the 3:00 and 6:00 positions. The crevice potential at these two positions reached a steady-state value of 0.83 VSCE. The pipe surface at these two locations were protected technically in accordance with the 0.78 VSCE cathodic protection criterion set by NACE International.23 Figure 5 shows the crevice potential-vs-time curves for the pipe protected at a PC of 1 Hz at Von = 20 V. For this pipe sample, there was a sudden shift of local crevice potential at the 3:00 and 6:00 positions from 0.8 VSCE toward a more positive value. The shift occurred after 250 h of testing. The potential shift first occurred at the 3:00 position, and 809

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FIGURE 6. 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. For comparison, the pH of the bulk soil water in two corrosion cells are shown also.

FIGURE 7. 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.

then at the 6:00 position within 24 h. The steadystate potentials were 0.6 VSCE at the 3:00 position and 0.5 VSCE at the 6:00 position. 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). 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. However, for this pipe the potential shift occurred after a longer test time( 600 h). The potential shift again corresponded to the time for pH to increase to 12 (Figure 6). This phenomenon indicated the pipe surface may have become passivated under the alkaline condition, reducing the corrosion rate in the crevice.

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. 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, the pH values of the bulk soil water of two test cells also are given in Figure 6. They were nearly constant at 8.5 throughout the test duration. 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, with a steady pH value of 7.2 to 7.4. 810

For the pipes protected by cathodic protection, the crevice pH increased with time and reached a steady-state value after 2 weeks of test. The rate of pH increase and the final pH values in the crevice increased with the cell voltage settings. The highest pH measured was 12.3. The local crevice pH was the highest at the holiday opening (i.e., at the 12:00 position). The crevice pH generally decreased with increasing distance from the holiday opening. Pulsed cell voltage seemed to give a more uniform pH distribution than DC at the same Von setting. With the exception of the steel pipe protected by a PC of 10 Hz at Von = 20 V, 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. The crevice solution for each pipe sample in Tests 2 and 3 was collected at the end of the test, and its average resistivity at its steady-state temperature of 43C was measured using a conductivity cell and a conductivity bridge (Table 1). There was a substantial decrease in the crevice solution resistivity when compared with the resistivity of the bulk soil water. In some cases, the decrease was more than tenfold. The cathodically protected pipes had a lower crevice solution resistivity than the pipe without any cathodic protection. The effectiveness of cathodic protection seemed to correlate with the extent of decrease in the resistivity of the crevice solution.

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TABLE 1 Results of Cathodic Protection Tests for Steel Pipes Buried in Soil
Protective Cell Voltage (Von) Resistivity (-cm) Bulk Crevice (35C) (43C) 3,830 4,230 3,830 4,230

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, 10 V(A) Slight corrosion PC 1 Hz, 20 V(A) Very slight corrosion Test Number 2 (42 days) Natural corrosion Severe corrosion DC 20 V Slight corrosion PC 1 Hz, 20 V(A) Very slight corrosion PC 10 Hz, 20 V(A) Corrosion Test Number 3 (45 days) DC 10 V Slight corrosion PC 1 Hz, 10 V(A) Corrosion DC 15 V Very slight corrosion PC 1 Hz, 15 V(A) Slight corrosion
(A)

0.20 0.57 2.3

2.0 5.7 45.2

8.3 8.4 8.3 8.4

10.9 6.9 3.1

219 139 62.8

8.4 8.5 8.5 8.4

7.4 11.3 11.6 12.2

7.2 8.9 11.2 12.2

7.2 9.1 12.1 12.3

7.2 10.8 12.1 12.3

3,100 3,050 3.050 3,100

1,900 380 264 202

4.5 1.4 4.9 3.9

44.8 13.5 74.1 59.6

6.5 6.5 6.4 6.4

10.5 9.3 12.2 11.0

8.1 8.1 7.8 7.9

8.0 8.5 9.5 7.9

8.5 7.6 9.9 10.9

4,400 4,400 4,200 4,200

720 2,550 605 1,320

PC was pulsed at potentials between open circuit and Von at a duty cycle of 0.5.

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. For a given pipe, the current density curve was characterized by large fluctuations. Sometimes, the fluctuation was as high as 200% over only a few hours of test time. The exact nature of current fluctuation was not clear. In a high-resistivity soil, the magnitude of cell current was controlled by the soil resistance at the holiday opening. Any disturbances at the holiday opening, including the formation of H2, accumulation of calcareous deposits, and changes in soil porosity, could affect the current flowing into the pipe crevice. The protective cathodic current for a given pipe decreased with increasing test time. The cell current generally increased with the applied cell voltage. For a given Von setting, the time-averaged current of a pulsed voltage was smaller than that of the DCcontrolled voltage. The current-vs-time curves were integrated to give the Q and E values for the pipes used in the tests (Table 1). Results indicated that, at the same Von setting, the energy consumption of pulsed voltage control was less than that of the DC voltage control. A similar conclusion also was reported by Juchniewicz, et al., on the use of PC for cathodic protection.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: 0.06 M, 0.006 M, and 0.002 M. The initial pH of the solutions was in the range 5.2 to 6.0. The experiments were carried out at three controlled DC holiday potentials: 1.03 VSCE, 1.28 VSCE, and 1.53 VSCE. For the 0.06 M NaCl solution that had a low resistivity of 158 -cm, the steel surface was polarized immediately after the potentiostat was turned on at all the controlled potentials investigated. The local potentials at the three crevice locations became more negative than 0.8 VSCE within 30 min after the start of experiment. The steady-state potential distribution within the crevice was normal, as expected (i.e., with the No. 1 reference electrode tap 1.5 cm from the crevice opening having the most negative value and the No. 3 reference tap [7.6 cm from the crevice opening] having the least negative value). No H2 evolution was observed for the runs at the controlled potentials of 1.03 VSCE and 1.28 VSCE. At the more negative controlled potential of 1.53 VSCE, H2 evolution occurred at the crevice opening. At the end of test in the 0.06 M NaCl solution, the crevice pH increased to 10.4, and the steel surface showed no sign of corrosion. For the 0.002 M NaCl solution with a high resistivity of 4,200 -cm, the steel surface within the 811

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FIGURE 8. Time-averaged protective current density vs time for the pipes protected by DC and PC at Von = 20 V.

test was in the range 5.5 to 6.1, which was about the same as the initial pH of the test solution. Corrosion occurred 2 cm from the crevice opening. However, no corrosion was observed near the crevice entrance or at the sealed end of the crevice. For the 0.006 M NaCl solution, which had a moderately high resistivity of 1,440 -cm, the potential distribution within the crevice exhibited a transition from the behavior in the 0.002 N NaCl (high-resistivity) solution to that in the 0.06 M NaCl (low-resistivity) solution. Figure 9 shows the local crevice potential in the 0.006 M NaCl solution at a controlled holiday potential of 1.28 VSCE. No H2 evolution was observed in this run. During the initial period of this run, the potential distribution in the crevice was in the reverse order, with the least negative potential occurring at the No. 1 reference tap and the most negative potential occurring at the No. 3 reference tap. This behavior was similar to that in the 0.002 M NaCl solution. As the cathodic protection continued, the local crevice potential gradually shifted toward the negative direction. However, the rate of potential shift was the highest at the No. 1 reference tap. This was followed by the No. 2 and then by the No. 3 reference tap. After 16 h of test, the order of potential distribution was changed to the normal order (the No. 1 reference electrode tap exhibited the most negative potential and the No. 3 reference tap the least negative potential [Figure 9]). This indicated that, in a moderately dilute NaCl solution, an initial incubation period was necessary for the current to penetrate into the crevice. The crevice solution at the end of the run (22 h) had a pH of 10. The steel surface exhibited only minor corrosion 2 cm from the crevice opening.

Effect of Pulsed Potential

FIGURE 9. Crevice potential of a steel rod in the model crevice cell containing 0.006 M NaCl at a controlled DC holiday potential of 1.28 VSCE.

crevice could not be polarized to a more negative potential than 0.8 VSCE at any controlled potential setting within a test duration of 70 h. The crevice potential distribution for this solution was in the reverse order from that for the 0.06 M solution, with the least negative value occurring at the No. 1 reference tap and the most negative value occurring at the No. 3 reference tap. This result indicated the current did not penetrate into the crevice, 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 0.006 M and 0.002 M NaCl solutions. The controlled holiday potential was pulsed between 1.03 VSCE and 1.53 VSCE at a frequency of 1 Hz and a duty cycle of 0.5. This gave a time-averaged holiday potential of 1.28 VSCE. Figure 10 shows the crevice potential-vs-time curves for a run in the 0.006 M NaCl solution. Comparing Figure 10 to Figure 9, which shows the results for DC potential control at the same time-averaged potential, the pulsed potential improved the rate of potential change of steel in the crevice. The pulsed potential eliminated the initial incubation period, and the potential of the No. 1 reference tap shifted to the neighborhood of 0.8 VSCE immediately after the current was switched on. A normal potential distribution in the crevice was observed, with the most negative value occurring at the No. 1 reference

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Chemical Changes Inside the Crevice

During cathodic protection, hydroxyl ions (OH) are produced by O2 reduction at the cathode surface, and the pH of solution inside the crevice is increased. In turn, the excess negatively charged OH ions attract such positively charged cations as hydrogen ions (H+), sodium ions (Na+), calcium ions (Ca2+), and magnesium ions (Mg2+) in the soil, which migrate into the crevice and increase their concentrations, decreasing the electric resistance of the crevice solution. In addition, 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. 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. 3 reference tap. The pH of the crevice solution increased to 10, and there was no visible corrosion on the steel rod at the end of the test. For the 0.002 M NaCl solution, the crevice potential distribution of pulsed cathodic protection was similar to that of DC cathodic protection. However, the pulsed potential increased the crevice solution pH to 10. Corrosion on the steel rod at the end of the test was less than that occurring on rods under DC cathodic protection. Mg 2+ + 2OH = Mg(OH) 2 H + + OH = H 2 O (2) (3) (4) (1)

FIGURE 10. Crevice potential of a steel rod in the model crevice cell containing 0.006 M NaCl under pulsed cathodic protection. The controlled holiday potential was pulsed between 1.03 VSCE and 1.53 VSCE with a frequency of 1 Hz and a duty cycle of 0.5. The time-averaged holiday potential was 1.28 VSCE.

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. Corrosion on the pipe surface in the immediate vicinity of a holiday opening could be stopped by the cathodic current. In the crevice area away from the holiday, the corrosion rate may be reduced substantially by eliminating dissolved O2 in the crevice. During cathodic protection, the solution inside the crevice undergoes chemical changes, including an increase in pH and a decrease in solution resistivity. These changes are favorable to the mitigation of crevice corrosion in a high-resistivity environment.

During cathodic protection, there is a constant transport of ionic species between the bulk and crevice solutions to maintain electric neutrality. The OH ions formed inside the crevice are transported to the bulk solution through the holiday opening. The H+, Ca2+, and Mg2+ ions are transported from the bulk soil water into the crevice, and the above reactions occur to compensate for the pH increase in the crevice. The Ca(OH)2 and Mg(OH)2 subsequently precipitate out in the crevice and at the holiday opening. The solution pH inside the crevice is limited by the solubility products of Ca(OH)2 and Mg(OH)2, which would not permit the pH to increase beyond a theoretical limit of 12. 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. They meet the outgoing OH, and the above 813

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Lennox have shown that it is not necessary to force the electric current into a crevice to protect it cathodically.8 Sufficient cathodic protection can be achieved by applying an appropriate potential to suppress the differential O2 cell within the crevice. 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. Using a simple O2 diffusion model, the steady-state local O2 concentration, C(x), within a cathodically protected crevice may be described by the differential equation:

k d2C C=0 dx2 D

at
FIGURE 11. O2 concentration inside crevice as a function of distance from the crevice opening for three values of a dimensionless parameter, k/D.

(10)

x = 0, C = Cb; and at x = ,

dC =0 dx

(11)

reactions take place in the neighborhood of the holiday opening. 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, is the crevice thickness, Cb is the O2 concentration at the crevice opening, D is the diffusivity of dissolved O2, and k is a first-order reaction rate constant for the reduction of O2 at the steel surface inside the crevice. The above equations may be integrated to give:
1 2

C(x) kd = exp Cb D

(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.

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. In the present study, steel pipes with a disbonded coating in a high-resistivity solution also were protected cathodically, even though the electric current was not able to penetrate deep into the crevice. Two possible mechanisms for the cathodic protection of pipe surfaces within the crevice of a disbonded coating with a holiday were examined. O2 Depletion Mechanism In aerated neutral and alkaline environments, the corrosion of steel is controlled by the O2 reduction reaction. Peterson and 814

Figure 11 shows the variation of O2 concentration inside the crevice for three values of a dimensionless parameter, k/D. For a value of k/D 0.1, the local O2 concentration inside the crevice is reduced to < 0.001 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, the corrosion rate in the crevice eventually is reduced to a low level. This situation is illustrated schematically by the polarization curves in Figure 12, in which A represents the anodic polarization curve of steel in a neutral crevice solution, C refers to the O2 reduction curve at the initial stage of corrosion, and C refers to the O2 reduction curve after the application of cathodic protection. The limiting current for C is smaller than that for C because of a decrease of O2 concentration in the crevice. 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, icorr. The corrosion potential in the crevice is shifted from Ecorr to a more negative value of Ecorr because of the depletion of O2.

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FIGURE 12. Schematic of a potential-vs-current diagram showing the changes in corrosion rate and corrosion potential during cathodic protection of steel inside a crevice. Curve A anodic polarization of steel in neutral crevice solution; 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; Curve C cathodic polarization curve after O2 concentration in the crevice has been reduced by cathodic protection.

FIGURE 13. Anodic (A) and cathodic (C) polarization curves of a pipe steel in aerated soil water at controlled pH values of 7.9 and 12.3.

pH Increase and Passivation Mechanism The O2 reduction reaction caused by cathodic protection generates OH at the crevice opening as shown by Equation (1). Some of the OH diffuses into the interior of the crevice and causes an increase in the pH of the crevice solution, as demonstrated by the present experimental data. According to a potentialvs-pH diagram of Fe,24 the pipe surface can become passivated with the formation of a ferrosoferric oxide (Fe3O4) film in the pH range 9 to 13. When the crevice solution becomes sufficiently alkaline, the steel passivates and the anodic polarization curve shifts from the initial behavior of curve A to curve A (Figure 12). The corrosion rate is decreased to a low value of icorr, and the corrosion potential in the crevice shifts to a positive value of Ecorr. 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 0.5 VSCE to 0.6 VSCE. To further elaborate the passivation mechanism in a highresistivity medium, 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. The measurement was carried out at 50C and at two controlled pH values (7.9 and 12.3) corresponding to the initial and final pH values of the crevice solution in the cathodic protection experiments. Results are shown in Figure 13, in which A1 and C1 represent the anodic and cathodic polarization curves in the pH 7.9 water, and A2 and C2 represent the anodic and cathodic polarization curves in the pH 12.3 water. At pH 7.9, curve A1 indicates the steel was corroding in an active state. The cathodic curve (C1) exhibited a limiting current regime for the O2 reduction reaction, followed by the onset of H2 evolution at 1.0 VSCE. This result implied that the corrosion of pipe steel in neutral soil water was controlled by the diffusion of O2 to the cathodic sites. At pH 12.3, the anodic polarization curve (A2) exhibited a passive potential regime similar to the vertical portion of curve A, shown in Figure 12, and the cathodic polarization curve (C2) exhibited a Tafel potential-current relationship for O2 reduction in the neighborhood of the corrosion potential. This result indicated that, in the pH 12.3 water, the corrosion of steel was taking place in the passive state, and the corrosion rate as calculated using the Tafel extrapolation method was nearly 10 times smaller than that in the pH 7.9 water. 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.25 815

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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. 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. The pipe was buried in a wet soil in which the resistivity of the soil water was 3,050 -cm to 4,400 -cm. 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 4,200 -cm. 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 the present study, 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, (b) depletion of dissolved O2 in the solution inside the crevice, and (c) a pH increase in the crevice and passivation of the steel surface in the alkaline environment. O The applied cell voltage is an important parameter for cathodic protection in a high-resistivity environment. A low cell voltage would not permit sufficient polarization of the steel surface within the crevice. A high voltage induced excessive H2 evolution at the holiday opening, which blocked the penetration of cathodic protection current into the crevice. In the present laboratory cell, the optimal cell voltage settings were: (a) PC of a frequency of 1 Hz and a duty cycle of 0.5 at Von = 15 V to 20 V and (b) DC at a controlled cell voltage of 15 V to 20 V. O Cathodic protection increases the pH and decreases the resistivity of solution inside the crevice. The maximum crevice pH measured in the present experiment was 12.3. The resistivity of the crevice solution was reduced from an initial value of 3,050 -cm to 4,400 -cm to a final value of 200 -cm to 600 -cm. The chemical changes were favorable to the cathodic protection of the steel pipe beneath the disbonded coating. O With a properly controlled voltage, both DC and pulsed cathodic protection can protect a steel pipe buried in high-resistivity soil. There was no significant difference in overall protection effectiveness between the DC- and PC-controlled modes. A low-frequency PC of 1 Hz at a duty cycle of 0.5 provided better protection than a high-frequency PC of 10 Hz. When using PC, the protective current and energy

consumption were smaller and the pH distribution in the crevice was more uniform than when using DC cathodic protection.

ACKNOWLEDGMENTS
The authors acknowledge the support of Alyeska Pipeline Service Co. (TAPS); E.D. Burger (ARCO Exploration and Production Technology); and the members of a TAPS task group including L. Bone (ARCO Exploration and Production Technology), J. Hotchkiss and E.W. Klechka (Alyeska Pipeline Service Co.), J. Nunn (Mobil Pipe Line Co.), E. Pierson (Exxon Pipeline Co.), S.N. Smith (Exxon Production Research), and T. Widin (BP Research).
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1. 2. 3. 4. 5. 6. 7. 8. 9. G. Mills, MP 28, 12 (1988): p. 13. M. Roche, J.P. Samaran, MP 27, 11 (1987): p. 28. H.M. Smith, M.F. Bird, R.H. Penna, MP 28, 11 (1988): p. 19. A.C. Toncre, N. Ahmad, MP 19, 6 (1980): p. 39. R.R. Fessler, Oil Gas J. 74, 7 (1976): p. 81. A.W. Peabody, Control of Pipeline Corrosion (Houston, TX: NACE, 1967), p. 26. R.L. Wenk, Proc. 5th Symp. Line Pipe Research (Arlington, VA: American Gas Association, 1974), p. T-15. M.H. Peterson, T.J. Lennox Jr., Corrosion 29 (1973): p. 406. W.E. Berry, Stress Corrosion Cracking Laboratory Experiences, Proc. 5th Symp. on Line Pipe Research (Arlington, VA: American Gas Association, 1977), p. 43. A.A. Fletcher, L. Fletcher, R.J. Morrison, The Effect of Pipe Surface Oxide upon Crevice Polarization and Stress Corrosion Cracking Under Fusion-Bonded, Low-Density Polyethylene Coatings, 5th Int. Conf. on the Internal and External Protection of Pipes, paper F4 (Bedford, UK: BHRA Fluid Eng. 1983). R.R. Fessler, A.J. Markworth, R.N. Parkins, Corrosion 39 (1983): p. 20. A.C. Toncre, MP 23, 8 (1984): p. 22. M.D. Orton, MP 24, 6 (1985): p. 17. J. McCoy, MP 28, 2 (1989): p. 16. G. Sabde, F. Gan, D.-T. Chin, J. Chin. I. Ch. E. 24 (1993): p. 417. E.W. Haycock, D.M. Seid, Cathodic Protection by Intermittent and Pulsed Currents, CORROSION/73, paper no. 69 (Houston, TX: NACE, 1973). T. M. Doniguian, Oil Gas J. 80, 26 (1982): p. 221. E.E. Fletcher, T.J. Barlo, A.J. Markworth, E.W. Brooman, W.E. Berry, R.N. Parkins, W.C. McGary, R.R. Fessler, Relative Merits of Pulsed Rectifiers for Controlling Stress Corrosion Cracking, NG-18 Report No. 127 to the American Gas Association (Columbus, OH: Battelle Columbus Laboratories, 1982). R. Juchniewicz, J. Szukalski, E. Stankiewicz, B. Electrochem. 3 (1987), p. 531. B.N. Bauman,Protection of Well Casings by Pulsed Cathodic Currents, NACE-CRCW Meeting, Saskatoon, Saskatchewan, Canada, Feb. 19-21, 1991. J-C. Puippe, F. Leaman, eds., Theory and Practice of Pulse Plating, (Orlando, FL: American Electroplaters and Surface Finishers Society, 1986). D.-T. Chin, Periodic Electrode Processes: AC Corrosion and Pulse Plating, in Trends in Electrochemistry, Vol. 1 (Sreekanteswaram, Trivandrum, India: Council of Scientific Research Integration, 1992), p. 215. NACE Standard RP01-69, Recommended Practice, Control of External Corrosion on Underground or Submersed Metallic piping Systems (Houston, TX: NACE, 1983). H.H. Uhlig, R.W. Revie, Corrosion and Corrosion Control (New York, NY: John Wiley & Sons, 1985), p. 414. R.W. Cherry, A.N. Gould, MP 29, 8 (1990): p. 22.

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