Corrosion Science 51 (2009) 2242–2245

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Short Communication

Effect of cathodic protection on corrosion of pipeline steel under disbonded coating

X. Chen a, X.G. Li a,*, C.W. Du a, Y.F. Cheng b,*
a
Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 100083, China
b
Dept. of Mechanical & Manufacturing Engineering, University of Calgary, Calgary, AB, Canada T2N 1N4

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a test rig was developed to study the effect of cathodic protection (CP) on corrosion of X70
Received 25 February 2009 pipeline steel in the crevice area under disbonded coating through the measurements of local potential,
Accepted 19 May 2009 solution pH and dissolved oxygen concentration. Results demonstrated that, in the early stage of corro-
Available online 23 May 2009
sion of steel, CP cannot reach the crevice bottom to protect steel from corrosion due to the geometrical
limitation. Corrosion of steel occurs preferentially inside crevice due to a separation of anodic and catho-
Keywords: dic reaction with the depletion of dissolved oxygen in the crevice solution. The main role of CP in miti-
A. Steel
gation of sequential corrosion of steel in crevice under disbonded coating is to enhance the local solution
C. Cathodic protection
C. Crevice corrosion
alkalinity. With the increase of distance from the open holiday, a high cathodic polarization is required to
C. Oxygen reduction achieve appropriate CP level at crevice bottom. A potential difference always exists between the open
C. Polymer coating holiday area and inside crevice, reducing the CP effectiveness.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction by the water reduction under cathodic polarization. Perdomo and

Pipeline integrity is maintained by simultaneous application of
protective coating and cathodic protection (CP) [1]. Disbondment
is one of the most common failure modes in pipeline coating, while
the coating membrane is still highly resistant [2–5]. However,
corrosive gases, water and/or chemical species may enter the disb-
onded crevice area, creating an electrochemical environment sup-
porting pipeline corrosion and/or stress corrosion cracking (SCC)
[6–10].
Effects of CP on local electrochemical environment and corro-
sion of steel under disbonded coating have been paid much atten-
tion. For example, Brousseau and Qian [11] found that pH of the
trapped electrolyte increases with time due to generation of hy-
droxyl ions from the reduction of H2O. Cherry and Gould [12] be-
lieved that hydroxyl ions would tend to diffuse out of the crevice
under the concentration gradient, altering the electrochemical
condition of the trapped solution. Fessler et al. [13] showed that
the potential in the disbonded crevice area is always less negative
than the applied cathodic potential, and the crevice bottom is
thus insufficient protected. Song et al. [14–16] modeled the elec-
trochemical reactions and mass-transfer steps occurring across
the coating, and indicated that the depletion of oxygen under
the disbonded coating is not affected by the applied cathodic po-
tential. The increase of solution alkalinity in the crevice is caused
* Corresponding authors. Tel.: +86 10 6233 4005 (X.G. Li); tel.: +1 403 220 3693;
fax: +1 403 282 8406 (Y.F. Cheng).
E-mail addresses: lixiaogang99@263.net (X.G. Li), fcheng@ucalgary.ca (Y.F.
Cheng).
Song [6,17] measured potential, pH and oxygen concentration
within a crevice, and concluded that the electrochemical corro-
sion of pipeline steel is due to the gradual chemical and electro-
chemical changes produced along the crevice. Dong et al. [18]
investigated localized corrosion of steel at coating defect, and
determined the effect of CP on local electrochemical environment
and the resulting corrosion reaction at the base of defect. It was
demonstrated that corrosion of steel is dependent on CP potential
and the defect geometry. Mass-transfer of oxygen through the de-
fect with a narrow, deep geometry is the rate-limiting step for the
corrosion process of steel. The applied CP is partially shielded by
the narrow, deep defect. Furthermore, Stratmann’s group [19–21]
used scanning Kelvin probe to investigate the delamination of
polymeric coatings from steel, and demonstrated that the interfa-
cial electrochemical reactions were responsible for the coating
disbondment. During coating disbondment, the electrode poten-
tial drops significantly from very positive values, which are char-
acteristic for the intact interface, to negative values, which are
typical for disbonded coating under which corrosion reaction
occurs.
Corrosion of steel under disbonded coating has been simulated
frequently as crevice corrosion [22,23]. To further understand the
corrosion behavior of pipeline steel in the crevice solution under
disbonded coating in the presence of applied CP, a rectangle crevice
assembly was developed in this work to investigate the effective-
ness of CP on mitigation of corrosion of X70 pipeline steel under
the disbonded coating through measurements of local potential,
solution pH and concentration of dissolved oxygen. The electro-
chemical corrosion mechanism was analyzed.

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.05.027
 X. Chen et al. / Corrosion Science 51 (2009) 2242–2245 2243

a -600

-700

-800

E (mV/SCE)
-900

-1000

-1100

-1200 OCP
-775 mV
-1300 -1000 mV
-1200 mV
-1400
0 5 10 15 20 25
Fig. 1. Test rig for simulation of a crevice under disbonded coating. Distance (cm)

14
b OCP
2. Experimental 13 -775 mV
-1000 mV
12
Test specimen was cut from a X70 steel pipe, with the chemical -1200 mV
composition (wt.%): C 0.045, Si 0.24, Mn 1.48, S 0.0001, Cr 0.031, P 11
0.017, Ni 0.16, Mo 0.23, Cu 0.21 and Nb 0.033. A three-electrode
10
cell system was used for simulation of a crevice created by coating
disbondment, as shown in Fig. 1. The cell consisted of an X70 steel 9
pH
working electrode with 33.5 cm  7.5 cm  1 cm in dimension, 8
which was ground sequentially to #1000 grit emery paper. A satu-
rated calomel electrode (SCE) was used as reference electrode, and 7
a platinum wire (1 cm in diameter) as counter electrode. A rectan- 6
gle thermoplastic shim (0.9 mm in thickness) was used to create
the crevice, with a Lucite as a coating membrane. The plastic shim 5
was adjustable to control the crevice width. A hole of 3.5 cm  4
1 cm was opened to simulate a holiday. Three ports were then 0 5 10 15 20 25
drilled at an interval of 5 cm from the holiday along the Lucite Distance (cm)
block to position the microelectrodes for measurements of local
potential, solution pH and oxygen concentration, respectively. In c 9
OCP
particular, the local potentials of steel at individual ports were
8 -755 mV
measured by microelectrodes when various CP potentials were ap-
-1000 mV
plied at the holiday. The local solution pH was measured ex-situ, 7 -1200 mV
using a capillary to sample the local solution in a beaker, through
a Thermo Orion 9863BN pH meter. The local oxygen concentration 6
was measured in situ through a Unisense OX100 dissolved oxygen
[O2] (mg/L)

5
micro-glass electrode with a 5 micron tip. The oxygen microelec-
trodes were sealed tightly with Lucite using a 732 Multi-purpose 4
Sealant (Dow Corning) in order to avoid diffusion of oxygen
through the port openings. 3
The test solution was 0.01 M Na2SO4 solution, with a pH of 6.8.
2
The solution was made of analytical agent and distilled water.
All tests were conducted at room temperature (22 °C), and 1
open to air.
0
0 5 10 15 20 25
Distance (cm)
3. Results
Fig. 2. Potential (a), pH (b) and oxygen concentration (c) profiles within crevice
Fig. 2 shows the local potential, solution pH and the oxygen after 0.5 h of test.
concentration as a function of distance from the open holiday
after 0.5 h of immersion in the solution at corrosion potential
(680 mVSCE), 775 mVSCE, 1000 mVSCE and 1200 mVSCE, day, and there was the lowest solution pH at the crevice bottom
respectively. The concentration of dissolved oxygen in the bulk (Fig. 2b). Furthermore, the oxygen concentration dropped from
solution was 8.3 mg/L. It is seen that the applied cathodic poten- 8.3 mg/L at holiday to 1 mg/L at crevice bottom no matter if CP
tial could not penetrate into the crevice bottom. With the increase was applied.
of distance from holiday, the local potential became positive Fig. 3 shows the local potential, solution pH and oxygen concen-
(Fig. 2b). Even at 1200 mVSCE, the potential at 10 cm point was tration after 72 h of application of CP potentials. It is seen that
approximately corrosion potential. Moreover, local solution pH there was a similar local potential distribution to that shown in
decreased (more acidic) with the increase of distance from holi- Fig. 2a, i.e., local potential became less negative towards the cre-
2244 X. Chen et al. / Corrosion Science 51 (2009) 2242–2245

a -600 4. Discussion

-700
The anodic and cathodic reactions during corrosion of pipeline
steel in aerated Na2SO4 solution are oxidation of iron and the
reduction of oxygen, respectively:
-800
Fe ! Fe2þ þ 2e ð1Þ
E (mV/SCE)

-900 O2 þ H2 O þ 4e ! 4OH ð2Þ

During corrosion of steel, the dissolved oxygen diffuses towards the
-1000 electrode surface, and mass-transport step thus plays an essential
role in the steel corrosion. Furthermore, the generation of hydroxyl
OCP
-1100 -775 mV ions accompanying reduction of oxygen increases the local solution
-1000 mV pH. The present work shows that a high concentration of oxygen at
-1200 -1200 mV open holiday supports corrosion of steel, resulting in a high solution
pH (Figs. 2b and 3b). The oxygen concentration decreases appar-
0 5 10 15 20 25 ently inside crevice due to the limited diffusion through the crevice
Distance (cm) solution layer. At crevice bottom, there was the lowest oxygen con-
centration (Fig. 2c) and the lowest solution pH.
b 14 After 72 h of test, oxygen inside crevice, especially at the crevice
bottom, is almost depleted, as seen in Fig. 3c. It is expected that a sep-
arated anodic and cathodic reaction zones exist, with crevice as the
12 anodic reaction zone and the holiday for cathodic reduction of oxy-
gen. Consequently, corrosion occurs preferentially inside crevice.
Furthermore, the solution pH at crevice bottom drops from 8 at
10 0.5 h to about 6.8 at 72 h, which is due to the local acidification effect:
pH

Fe2þ þ H2 O ! FeOHþ þ Hþ ð3Þ

8
The present results (Figs. 2a and 3a) also show that CP cannot reach
inside crevice to protect effectively steel from corrosion due to the
6
OCP geometrical limitation. However, a more negative potential would
-775 mV
-1000 mV decrease the local potential of steel in the crevice, and thus provide
-1200 mV somewhat protection over steel. However, a potential difference al-
4 ways exists between the open holiday area and inside crevice. It is
0 5 10 15 20 25
worthy pointing out that an applied cathodic potential cannot be
Distance (cm)
too negative since an over-protection would enhance the hydrogen
evolution, generating hydrogen atoms to permeate into the steel [3].
c OCP Depletion of oxygen inside crevice is not dependent on applica-
8 -775 mV tion of CP (Fig. 3c), which is consistent with Song et al.’s results
-1000 mV [14]. The geometrical factor limits the diffusion of oxygen in cre-
-1200 mV vice. However, the solution pH inside crevice is enhanced by appli-
6 cation of CP, as seen in Fig. 3b. With the negative shift of potential,
water would be reduced to generate hydroxyl ions, resulting in a
[O2] (mg/L)

high solution pH in crevice:

4
H2 O þ e ! H þ OH ð4Þ

Therefore, it is concluded that the key role of CP in mitigation of cor-

2 rosion of the steel under disbonded coating is to enhance the local
solution alkalinity. However, an elevated alkalinity of trapped elec-
trolyte would enhance the disbondment of coating from the steel
0 substrate [6,9,14–17]. Therefore, the effects of CP on local solution
0 5 10 15 20 25 pH and the coating disbondment should be taken into account
Distance (cm) simultaneously.

Fig. 3. Potential (a), pH (b) and oxygen concentration (c) profiles within the crevice
5. Conclusions
after 72 h of test.

In the early stage of corrosion of steel under disbonded coating,

vice bottom. Furthermore, the potential difference between the
open holiday and the crevice bottom decreased, i.e., the potential
at crevice bottom became more negative than that after 0.5 h of
immersion, as shown in Fig. 3a.
The solution pH inside crevice tended to approach that at holi-
day with time. There was a higher pH when the applied potential
was more negative (Fig. 3b). The dissolved oxygen concentration
decreased to almost zero at crevice bottom after 72 h of test.
CP cannot reach the crevice bottom to protect effectively the steel
from corrosion due to the geometrical limitation. Corrosion of steel
occurs preferentially inside crevice due to the separation of anodic
and cathodic reaction sites. Local solution pH decreases with the
increase of distance from the open holiday due to local acidificat-
ion effect.
The solution pH inside crevice goes up with time. There is a high-
er solution pH when the applied potential is more negative. The
 X. Chen et al. / Corrosion Science 51 (2009) 2242–2245 2245

main role of CP in mitigation of corrosion of steel in crevice area un- [2] N. Sridhar, D.S. Dunn, M. Seth, Corrosion 57 (2001) 598.
[3] D.T. Chin, G.M. Sabde, Corrosion 5 (1999) 229.
der disbonded coating is to enhance the local solution alkalinity.
[4] M.C. Yan, J.Q. Wang, E.H. Han, Corrosion Science 50 (2008) 1331.
With the increase of distance from the open holiday, a high [5] T.R. Jack, G. van Boven, M. Wilmott, Materials Performance 33 (1994)
cathodic polarization is required to achieve appropriate CP level 17.
at crevice bottom. A potential difference always exists between [6] J.J. Perdomo, M.E. Chabica, I. Song, Corrosion Science 43 (2001) 515.
[7] Z.F. Li, F.X. Gan, X.H. Mao, Corrosion Science 44 (2002) 689.
the open holiday area and inside crevice, reducing the CP effective- [8] G.W. Walter, Corrosion Science 32 (1991) 1059.
ness. The oxygen concentration drops significantly inside crevice [9] A.Q. Fu, Y.F. Cheng, Corrosion Science 51 (2009) 914.
no matter if CP is applied. [10] W. Furbeth, M. Stratmann, Corrosion Science 43 (2001) 207.
[11] R. Brousseau, S. Qian, Corrosion 50 (1994) 907.
[12] B.W. Cherry, A.N. Gould, Material Performance 29 (1990) 22.
Acknowledgements [13] R.R. Fessler, A.J. Markworth, R.N. Parkins, Corrosion 39 (1983) 20.
[14] F.M. Song, N. Sridhar, Corrosion Science 50 (2008) 70.
[15] F.M. Song, D.W. Kirk, J.W. Graydon, D.E. Cormack, Corrosion 58 (2002)
This work was supported by Chinese National R&D Infrastructure
1015.
and Facility Development Program (Project # 2005DKA10400) and [16] F.M. Song, D.A. Jones, D.W. Kirk, Corrosion 61 (2005) 145.
Canada Research Chairs Program. [17] J.J. Perdomo, I. Song, Corrosion Science 42 (2000) 1389.
[18] C.F. Dong, A.Q. Fu, X.G. Li, Y.F. Cheng, Electrochimica Acta 54 (2008) 628.
[19] A. Leng, H. Steckel, M. Stratmann, Corrosion Science 41 (1999) 547.
References [20] A. Leng, H. Steckel, M. Stratmann, Corrosion Science 41 (1999) 579.
[21] A. Leng, H. Steckel, M. Stratmann, Corrosion Science 41 (1999) 599.
[1] National Energy Board, Report of Public Inquiry Concerning Stress Corrosion [22] Zhengfeng Li, Fuxing Gan, Xuhui Mao, Corrosion Science, 44 (2002) 689.
Cracking on Canadian Oil and Gas Pipelines, MH-2-95, 1996. [23] D.T. Chin, G.M. Sabde, Corrosion 55 (1999) 229.