Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
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.
804
CORROSIONOCTOBER 1994
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. 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
CORROSION ENGINEERING
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.
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.
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.
806
CORROSIONOCTOBER 1994
CORROSION ENGINEERING
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).
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.
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
CORROSION ENGINEERING
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
CORROSIONOCTOBER 1994
CORROSION ENGINEERING
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.
CORROSION ENGINEERING
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.
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.
CORROSIONOCTOBER 1994
CORROSION ENGINEERING
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)
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)
PC was pulsed at potentials between open circuit and Von at a duty cycle of 0.5.
CORROSION ENGINEERING
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.
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
CORROSIONOCTOBER 1994
CORROSION ENGINEERING
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
CORROSION ENGINEERING
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:
(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.
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.
CORROSIONOCTOBER 1994
CORROSION ENGINEERING
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
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. 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).
REFERENCES
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.
10.
17. 18.
19. 20.
21.
22.
23.
24. 25.
816
CORROSIONOCTOBER 1994