coatings

Article
Effect of a DC Stray Current on the Corrosion of X80
Pipeline Steel and the Cathodic Disbondment
Behavior of the Protective 3PE Coating in 3.5%
NaCl Solution
Xinhua Wang, Zuquan Wang, Yingchun Chen *, Xuting Song and Yong Yang
College of Mechanical Engineering and Applied Electronics Technology, Beijing University of Technology,
Beijing 100124, China; wangxinhua@bjut.edu.cn (X.W.); 2534005625@emails.bjut.edu.cn (Z.W.);
18811521053@emails.bjut.edu.cn (X.S.); yangyong-jd@emails.bjut.edu.cn (Y.Y.)
* Correspondence: yingchun.c@bjut.edu.cn




Received: 5 November 2018; Accepted: 27 December 2018; Published: 7 January 2019


Abstract: The influence of a direct current (DC) stray current on the corrosion and cathodic
disbondment of X80 steel coated with a polyethylene (3PE) coating in 3.5% NaCl solution was
studied by immersion experiments, electrochemical tests, three-dimensional microscopy, and a
surface analysis. The results showed that the potential of the X80 steel sample shifts under the direct
current. After 100A/m2 DC interference was applied, the potential of the sample in the anode region
positively shifted from –0.68 to –0.43 V. At the same time, the sample in the cathode region negatively
shifted to –1.45 V. Under the DC anode action, the X80 steel corrosion exhibited no passivation and
followed Faraday’s law of electrolysis, in which the corrosion rate is proportional to the current density.
Three-dimensional (3D) digital microscopy showed that, as the DC current increased, the depth of
the corrosion pit also increased (gradually), indicating a higher corrosion degree. The sample in the
cathode region only underwent a hydrogen evolution reaction, which caused cathodic disbondment
of the coating. The stray current had a critical current density for the coating disbonding: the coating
delamination area reached its maximum and then remained unchanged.

Keywords: X80 pipeline steel; coating damage; DC stray current; anodic corrosion;
cathodic disbondment

1. Introduction
Due to the complexity of the coating process and mechanical damage during construction, pipeline
coatings will inevitably be damaged and/or destroyed. These coatings are also severely affected by
various long-term corrosion factors in the soil during the life of the pipe and its service, and these factors
often cause coating disbonding. Corrosive media, such as soil solutions, infiltrate into the interface
between the pipeline and the damaged coating, forming a favorable corrosion microenvironment
and corroding the pipeline [1,2]. Stray currents refer to the currents that occur outside of a specific
loop. Stray currents accelerate pipeline corrosion and are one of the most important factors affecting
corrosion-related leakage of buried metal pipelines [3,4]. Stray current interference is typically divided
into alternating current (AC) and direct current (DC). Corrosion caused by DC is considered to be the
most serious [5,6], and a lot of research efforts are dedicated to this issue. Berziou et al. [7] summarized
major characteristics of corrosion caused by a DC stray current: the corrosion intensity is high and is
localized. Cui et al. [8] used the BEASY software to simulate DC interference with a negative protection
system under different soil resistivity conditions as well as its influence on the failure rates of corrosion
protection layers and anode parameters. Cheng et al. [9] analyzed the mechanism and drastic influence

Coatings 2019, 9, 29; doi:10.3390/coatings9010029 www.mdpi.com/journal/coatings

Coatings 2019, 9, 29 2 of 12

of stray current corrosion on buried metal pipelines in a subway and discussed potential measures to
minimize and eliminate the influences of stray current corrosion. Zhu et al. [10] proposed an effective
stray current drainage method based on the mechanism of stray current interference to minimize
corrosion. Currently, scientists have a good agreement on the mechanism by which DC stray currents
cause corrosion, i.e., that it is caused by an electrochemical reaction and the amount of corrosion is
proportional to the stray current’s density, which follows Faraday’s law of electrolysis [11–13].
The main focus of the research efforts is whether or not the buried pipelines experience DC
interference and the resulting corrosive damage. However, cathodic disbondment of the coating due to
DC stray currents in the pipeline area is less studied. When a DC current passes through the damaged
portion of the coating of buried long-distance pipelines, an anode region forms that causes electrolytic
corrosion of the metal pipeline, resulting in a corrosion piercing [14,15]. In contrast, DC passing through
the cathode region does not cause stray current corrosion of the pipeline because of the protection by
the cathode current. However, if the potential of the cathode area is too negative, a cathodic hydrogen
evolution reaction (HER) and an oxygen reduction reaction (ORR) occur on the pipeline’s surface,
causing cathodic disbondment of the coating [16–18]. Nielsen et al. [19], after field investigations and
tests, determined that the surface of buried steel pipelines under cathodic protection (CP) generates
large amounts of OH− that raise the localized pH around the defect areas, which eventually leads
to a pH increase in the majority of the area around the buried pipe’s coating. Due to the extremely
large stray current density in buried pipelines (up to 200 A/m2 ), delamination of the coating occurs
very easily [20]. Therefore, while studying a DC stray current’s influence on buried metal pipelines,
it is necessary to consider both corrosion of the pipeline and cathodic disbondment of the coating to
improve the anticorrosion performance of the organic coatings that protect metal pipelines.
In this work, we used immersion experiments, electrochemical tests, three-dimensional (3D)
microscopy, and a surface analysis to study the cathodic disbondment of a polyethylene (3PE) coating
caused by the inflow of a DC stray current and the corrosion behavior of the pipeline steel caused by
the outflow of a DC stray current in 3.5% NaCl solution.

2. Experimental

2.1. Experimental Materials

The chemical composition of the X80 pipeline steel that was used in this study was 0.06 wt % of C,
0.216 wt % of Si, 1.80 wt % of Mn, 0.0137 wt % of P, 0.0009 wt % of S, 0.105 wt % of Nb, and 0.013 wt %
of Ti (Fe balance). A 40 × 40 × 2 mm3 sample was machined using a wire-cutting method. After that,
the surface of the sample was polished sequentially with SiC60#, 200#, 400#, and 600# water sandpaper
until a uniform metallic luster was obtained and then thoroughly cleaned with ethanol and acetone.
A three-layer structure of polyethylene (3PE) tape was used as a coating material. 3PE supporting
primer was evenly applied to the surface of the X80 steel and allowed to dry for 3–5 min. After that,
3PE tape was applied and uniformly pressed to ensure a good bond. Several holes (2.5 mm in diameter)
were then
Coatings 2018,drilled
8, x FORthrough the coating without touching the metal substrate (see Figure 1).
PEER REVIEW 3 of 12

Figure 1. A photograph
photograph of prefabricated coating damage points drilled only through the coating (The
scale is 1 mm).

2.2. Electrochemical Test

A 3.5% NaCl solution (pH = 7) was prepared with analytical reagents and deionized water to
simulate the coastal environment. The electrochemical testing and stray current loading device is
shown in Figure 2. We used a constant voltage adjustable DC power supply (KXN-305D, Zhaoxin,
 Figure 1. A photograph of prefabricated coating damage points drilled only through the coating (The
Coatings is 9,
2019,
scale 29
1 mm). 3 of 12

2.2. Electrochemical Test

2.2. Electrochemical Test
A 3.5% NaCl solution (pH = 7) was prepared with analytical reagents and deionized water to
A 3.5% NaCl solution (pH = 7) was prepared with analytical reagents and deionized water to
simulate the coastal environment. The electrochemical testing and stray current loading device is
simulate the coastal environment. The electrochemical testing and stray current loading device is
shown in Figure 2. We used a constant voltage adjustable DC power supply (KXN-305D, Zhaoxin,
shown in Figure 2. We used a constant voltage adjustable DC power supply (KXN-305D, Zhaoxin,
Shenzhen, Guangdong, China) as a stray current source. S is a switch. R is a resistor. Samples 1 and
Shenzhen, Guangdong, China) as a stray current source. S is a switch. R is a resistor. Samples 1 and 2
2 were connected to the positive and negative electrodes, respectively. A carbon rod was placed in
were connected to the positive and negative electrodes, respectively. A carbon rod was placed in the
the middle to form a closed circuit. In this configuration, DC flowed out of the damage point of
middle to form a closed circuit. In this configuration, DC flowed out of the damage point of Sample 1
Sample 1 to form an anode metal corrosion area. In contrast, a cathode area formed on Sample 2.
to form an anode metal corrosion area. In contrast, a cathode area formed on Sample 2.

Figure 2. A schematic of the stray direct current (DC) loading and electrochemical testing device. WE,
Figure 2. A schematic of the stray direct current (DC) loading and electrochemical testing device. WE,
working electrode; RE, reference electrode; CE, counter electrode.
working electrode; RE, reference electrode; CE, counter electrode.
The electrochemical workstation (PARSTAT2273, Hampshire, UK) used a three-electrode system,
The an
in which electrochemical workstation
X80 pipeline steel sample was (PARSTAT2273, Hampshire,
used as the working electrodeUK)(WE),
usedplatinum
a three-electrode
plate was
system, in which an X80 pipeline steel sample was used as the working electrode
used as a counter electrode (CE), and a saturated calomel electrode (SCE) was used as a reference (WE), platinum
plate was used as a counter electrode (CE), and a saturated calomel electrode (SCE)
electrode (RE). Prior to the electrochemical tests, samples were kept for 30 min in the solution. After was used as a
reference
that, electrode
DCs with (RE).
different Prior to(0,
intensities the20,electrochemical
40, 60, 80, and 100tests,
A/m samples
2 ) were were
appliedkept for the
to test 30 min
DC’sin the
effect
solution. After that, DCs with different intensities (0, 20, 40, 60, 80, and 100 A/m 2) were applied to test
on the corrosion potential of the X80 steel. After the corrosion potential reached a relatively stable state
the DC’s
(within 30effect
min), on the corrosion
potential potential
polarization curves ofwere
the X80 steel. at
recorded After the corrosion
a 1 mV/s scan rate.potential reached
Experimental dataa
relatively
were stableusing
simulated state (within 30 min),
the Origin potential
software. polarization
The corrosion curves
current were(irecorded
density at a 1 mV/s scan
corr ) was calculated using
rate. Experimental data were
the Tafel extrapolation method. simulated using the Origin software. The corrosion current density
(𝑖 All) was calculated using the Tafel extrapolation method.
experimental samples were tested electrochemically and microscopically using a new batch for
All experimental
each analysis. samples was
A set of samples wereused
tested electrochemically
to analyze and microscopically
the electrochemical usingparameters
kinetic corrosion a new batch of
for each analysis. A set of samples was used to analyze the electrochemical
X80 steel under DC interference. DC power was applied for 24 h to another set of samples to kinetic corrosion
analyze
parameters
the corrosionofofX80
X80steel
steelunder
and theDC interference.
cathodic DC power
disbonding was applied
morphology for 24 h to another set of
of the coating.
samples to analyze the corrosion of X80 steel and the cathodic disbonding morphology of the coating.
2.3. Analysis of Pitting Corrosion Morphology
Sample 1 was removed at the end of the experiment. A digital camera (DSC-HX400 Sony, Tokyo,
Japan) was then used to record the surface corrosion morphology, after which the 3PE coating was
scraped off. The surface was then treated with Clarke’s solution containing 1 L of hydrochloric acid
(specific gravity 1.19 g/cm3 ), 20 g of antimony trioxide (pure chemical reagent grade), and 50 g of
stannous oxide (pure chemical reagent grade) to remove corrosion products and then washed with
deionized water. After drying, the corrosion pit depth was measured using a three-dimensional (3D)
digital microscope (HIROX KH-8700, Tokyo, Japan).
Japan) was then used to record the surface corrosion morphology, after which the 3PE coating was
scraped off. The surface was then treated with Clarke’s solution containing 1 L of hydrochloric acid
(specific gravity 1.19 g/cm3), 20 g of antimony trioxide (pure chemical reagent grade), and 50 g of
stannous oxide (pure chemical reagent grade) to remove corrosion products and then washed with
deionized water. After drying, the corrosion pit depth was measured using a three-dimensional (3D)
Coatings 2019, 9, 29 4 of 12
digital microscope (HIROX KH-8700, Tokyo, Japan).

2.4. Analysis
2.4. of Cathodic
Analysis of Disbondment Area
Cathodic Disbondment Area
Figure 33 shows
Figure showsaadiagram
diagramofofhowhowthethe measurements
measurements of the
of the cathodic
cathodic disbondment
disbondment areaarea of3PE
of the the
3PE coating were performed. Measurements were performed using Sample 2,
coating were performed. Measurements were performed using Sample 2, which was removed from the which was removed
from theat
solution solution
the endatofthe
theend of the experiment.
experiment. The area
The area around thearound thedivided
hole was hole was divided
into into eight
eight parts parts
(as shown
(as shown in Figure 3) around the damaged point. The coating was then cut with
in Figure 3) around the damaged point. The coating was then cut with a knife until the metal substratea knife until the
metal substrate became exposed. After that, the knife was inserted into the bottom of
became exposed. After that, the knife was inserted into the bottom of the coating from the center of the coating from
the damaged
the center of the damaged
hole, and the hole, andwas
coating thepeeled
coatingoff
was peeled
in the off in the
horizontal horizontal
direction along direction
the cut along the
line until
cut line until the coating showed significant disbonding resistance. By measuring the
the coating showed significant disbonding resistance. By measuring the distance of each cutting line distance of each
cutting
and line anddiameter
the reduced the reduced diameterpoint,
of the damage of the
we damage point,thewe
thus obtained thus obtained
cathodic disbondment the distance,
cathodic
disbondment
which was then distance,
used towhich wasthe
calculate then used todisbondment
cathodic calculate thearea.
cathodic disbondment area.

Figure 3.3.AA
Figure schematic of the
schematic of measurement patternpattern
the measurement of the cathodic
of the disbondment area of the polyethylene
cathodic disbondment area of the
(3PE) coating.
polyethylene (3PE) coating.

3. Results and Discussion

3. Results and Discussion
3.1. Potential Values of the 3PE-Coated X80 Steel in the 3.5% NaCl Solution under Various DC
3.1. Potential
Current Values of the 3PE-Coated X80 Steel in the 3.5% NaCl Solution under Various DC Current
Densities
Densities
When the DC passed through the X80 steel, the balanced electrode reactions became disturbed,
When
causing the DC passed
polarization of thethrough
X80 steelthe X80
and steel, the
shifting thebalanced
electrodeelectrode
potentialreactions
away from became disturbed,
the equilibrium
causing polarization
electrode of the 4a
potential. Figure X80 steel potential
shows and shifting the of
values electrode potentialX80
the 3PE-coated away from
steel the equilibrium
samples under DC
electrode potential. Figure 4a shows potential values of the 3PE-coated X80 steel
anodic polarization interference at different currents. The potential values shifted positively samples underas DC
the
anodic
DC polarization
increased. interference
The potential at different
shifted currents.
from –0.68 V (the The
value potential values shifted
corresponding positively
to the state without as DC
the
DC increased.toThe
interference) potential
–0.43 shifted2 from
V at 100A/m of DC–0.68 V (the value
interference. Thus,corresponding
the potential to
of the
the state without
X80 steel DC
sample
interference)
shifted by 0.25 toV.
–0.43 V at4b100A/m
Figure shows 2theof DC interference.
potential values of Thus, the potential
3PE-coated of the
X80 steel X80 DC
under steelcathodic
sample
shifted by 0.25
polarization V. Figure 4b
interference shows thecurrents.
at different potentialThe
values of 3PE-coated
potential X80 steel
values shifted under DC
negatively ascathodic
the DC
polarization interference at different currents. The potential values shifted negatively
increased: from –0.68 V (the value corresponding to the state without DC interference) to –1.45 as the VDC
at
increased: 2 from –0.68 V (the value corresponding to the state without DC interference)
100 A/m of DC current interference. Thus, the potential of the X80 steel shifted by 0.78 V. Therefore, to –1.45 V at
100 A/m
under 2 of DC current interference. Thus, the potential of the X80 steel shifted by 0.78 V. Therefore,
the same DC conditions, the degree of the cathodic potential shift was greater than that of
under the
the anode. same DC conditions, the degree of the cathodic potential shift was greater than that of the
anode.This result agrees with previously reported results. Yang et al. [21] studied the influence of DC
stray currents on the surface morphology and electrochemical behavior of X65 steel. They found that,
as the DC current density increased, the corrosion potential of the X65 steel also increased, making
the X65 steel more susceptible to corrosion. Qian et al. [22] found that, under DC interference, the
potential of X52 steel shifted positively and negatively in the anodic and cathodic zones, respectively.
The cathodic potential shifts were larger than the anodic ones.
 -0.40 20A/m
40A/m2
-0.8 40A/m2
60A/m2
-0.45 60A/m2

Potential (V.SCE)

Potential (V.SCE)
80A/m2 -0.9
80A/m2
100A/m2
-0.50 -1.0 100A/m2

-1.1
-0.55
Coatings 2018, 8, x FOR PEER REVIEW -1.2
5 of 12
Coatings 2019, 9, 29 5 of 12
-0.60
-1.3

-0.65 -1.4
-0.35 -0.6
(a) 0A/m2 -1.5 (b)
-0.70 0A/m2
20A/m2 -0.7
-0.40 -200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 -200 0 200 400 600 800 1000 1200 1400 1600 1800 200020A/m2
40A/m2
Time(s) -0.8 Time(s) 40A/m2
60A/m2
-0.45 60A/m2
Potential (V.SCE)

Potential (V.SCE)
80A/m2 -0.9
80A/m2
100A/m2 2
Figure 4. Potential measurements of the results of a 3PE-coated
-0.50 -1.0 X80 steel sample under DC 100A/m
(a) anode
and-0.55
(b) cathode polarization. -1.1

-1.2
-0.60
This result agrees with previously reported results. -1.3
Yang et al. [21] studied the influence of DC
-0.65 -1.4
stray currents on the surface morphology and electrochemical behavior of X65 steel. They found that,
-1.5
as the DC
-0.70 current density increased, the corrosion potential of the X65 steel also increased, making
-200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 -200 0 200 400 600 800 1000 1200 1400 1600 1800 2000
the X65 steel more susceptible Time(s) to corrosion. Qian et al. [22] found that, under DC interference, the
Time(s)
potential of X52 steel shifted positively and negatively in the anodic and cathodic zones, respectively.
Figure 4. Potential measurements of the results of a 3PE-coated X80 steel sample under DC (a) anode
The cathodic potentialmeasurements
Figure 4. Potential shifts were larger of the than
resultsthe
of anodic
a 3PE-coatedones.X80 steel sample under DC (a) anode
and (b) cathode polarization.
and (b) cathode polarization.
3.2. Polarization of 3PE-Coated X80 Steel Samples Samples at at Different
Different DC DC Currents
Currents
This result agrees with previously reported results. Yang et al. [21] studied the influence of DC
Figure 5 shows
shows the the polarization
polarization curves curves ofof 3PE-coated
3PE-coated X80 X80 steel
steel samples
samples underunder DCDC polarization
polarization
stray currents on the surface morphology and electrochemical behavior of X65 steel. They found that,
interference at different currents. The kinetic parameters parameters listed listed in in Tables 1 and 2 were obtained by
as the DC current density increased, the corrosion potential of the X65 steel also increased, making
the polarization
fitting the polarization curves, curves, performed
performed as described
described elsewhere
elsewhere [23–26]. Bertocci [27] pointed pointed out out
the X65 steel more susceptible to corrosion. Qian et al. [22] found that, under DC interference, the
that the metal corrosion potential shifts under the influence of stray
metal corrosion potential shifts under the influence of stray currents, but the direction ofcurrents, but the direction of this
potential of X52 steel shifted positively and negatively in the anodic and cathodic zones, respectively.
shiftshift
this depends
depends on the onratio
the of theof
ratio absolute valuesvalues
the absolute of the Tafel
of theslope Tafelbetween the anode
slope between theand
anode the and
cathode
the
The cathodic potential shifts were larger than the anodic ones.
(|𝑏 ⁄𝑏 |).(|bAt
cathode a /b |𝑏
c |) ⁄
. 𝑏
At| = 1,
| a c |=
b /b the corrosion
1 , the potential
corrosion will
potential notwillshift.
not At |𝑏
shift. ⁄𝑏
At | < 1
| a c |<
b /b or 1|𝑏 or ⁄ 𝑏 | > 1,
| a c |>the
b /b 1,
corrosion
the corrosionpotential
potential will shift
will shift negatively or positively, respectively. In general, the DC polarization
3.2. Polarization of 3PE-Coated X80negatively or positively,
Steel Samples at Differentrespectively.
DC CurrentsIn general, the
has aa great
has great influence
influenceon onthe
theTafel
Tafelconstant.
constant.From
FromFigureFigure5a, 5a,it itcan
canbebe seen
seen that,
that, when
when anode
anode potential
potential is
is Figure
applied to 5 shows
the the
system, polarization
the Tafel curves
constant ofofthe3PE-coated
anode and X80 steel
cathode
applied to the system, the Tafel constant of the anode and cathode side are obviously changed, and the samples
side are under
obviously DC polarization
changed, and
interference
the effect
effect on theon at different
the
cathodic currents.
cathodic The
sidekinetic
polarization
polarization is parameters
plotside listed in
plot is obviously
obviously greater Tables
that 1ofthan
greater
than and
the 2anode
wereofpolarization.
that obtained
the anode by
fitting
It can betheseen
polarization.polarization
Itfrom
can be curves,
seen
Figure from performed
5b that,Figure as to
5b that,
contrary described
contrary
the direct elsewhere
tocurrent
the direct [23–26].
current
anodic Bertocci
anodic [27]
polarization, pointed
polarization,
the influenceout
the
that the
influence metal
of thecorrosion
direct potential
current shifts
cathode under
on the the influence
anodic of
polarizationstray currents,
side
of the direct current cathode on the anodic polarization side plot process of X80 steel is significantly plot but the
process direction
of X80 of this
steel is
shift depends
significantly
greater on
greater
than that the ratio
than
of the of the absolute
that ofpolarization
cathodic values
the cathodicprocess.of the Tafel
polarization process. slope between the anode and the cathode
(|𝑏 ⁄𝑏 |). At |𝑏 ⁄𝑏 | = 1, the corrosion potential will not shift. At |𝑏 ⁄𝑏 | < 1 or |𝑏 ⁄𝑏 | > 1, the
0.2 -0.2
corrosion potential (a) will shift negatively or positively, 0 A/m respectively.
(b) In general, the DC 2
0A/mpolarization
2

2 2
20 A/m -0.4 20A/m
has a great influence
0.0
on the Tafel constant. From 40 A/m
Figure 5a, it can be seen that, when anode
2
40A/m potential 2

-0.6 2 2
60A/m
is applied to the system, the Tafel constant of the anode and cathode side are obviously changed, and
-0.2 60 A/m
2 2
80 A/m -0.8 80A/m
Potential (V.SCE)

Potential (V.SCE)

the effect on -0.4 the cathodic polarization side plot is

100A/m
-1.0
obviously greater than that 100A/m of the anode
2 2

polarization.-0.6It can be seen from Figure 5b that, contrary -1.2

to the direct current anodic polarization, the
influence of -0.8the direct current cathode on the anodic-1.4 polarization side plot process of X80 steel is
significantly -1.0greater than that of the cathodic polarization -1.6 process.
-1.8
-1.2
0.2 -0.2 2
(a) 0 A/m
2 -2.0
(b) 0A/m
-1.4 2 2
0.0 20 A/m -0.4 20A/m
-6 -5 -4 -3 -2 -1 0 -7 -6 -5 -4 -3 -2 -1 0 2
2
40 A/m 40A/m
-0.2 log i(A/cm2) 60 A/m
2 -0.6 log i(A/m2) 60A/m
2

2 2
80 A/m -0.8 80A/m
Potential (V.SCE)

Potential (V.SCE)

2 2
Figure 5. The
-0.4 polarization curves of 3PE-coated X80 steel under DC anode (a) and cathode (b) polarization. 100A/m 100A/m
Figure 5. The polarization curves of 3PE-coated X80 -1.0
steel under DC anode (a) and cathode (b)
-0.6
-1.2
polarization.
Table 1. The electrochemical parameters of 3PE-coated X80 steel samples under DC anode polarization
-0.8 -1.4
at different DC current densities.
-1.0 -1.6

i -1.2 (A/m2 ) Ecorr (mV) icorr (µA/cm2 )-1.8 ba bc |ba /bc |

-2.0
0 −859.03 36.38
-1.4 69.75 −150.46 0.46
-6 -5 -4 -3 -2 -1 0 -7 -6 -5 -4 -3 -2 -1 0
20 −546.53 393.18 86.77 −61.12 1.42
log i(A/cm2
) log i(A/m2)
40 −510.55 441.99 71.73 −63.51 1.13
60 −470.81 478.10 94.24 −85.36 1.11
Figure 5. 80
The polarization curves of 3PE-coated
−453.57 708.91 X80 steel88.89
under DC−anode75.10 (a) and1.12
cathode (b)
polarization.
100 −435.26 843.20 113.56 −103.06 1.10
Coatings 2019, 9, 29 6 of 12

Table 2. The electrochemical parameters of 3PE-coated X80 steel samples under DC cathode
polarization at different DC current densities.

i (A/m2 ) Ecorr (mV) icorr (µA/cm2 ) ba bc |ba /bc |

0 −858.03 36.37 69.75 −150.46 0.46
20 −1247.9 213.57 57.71 −68.02 0.84
40 −1256.7 381.98 53.58 −86.10 0.62
60 −1324.1 612.06 50.01 −122.92 0.41
80 −1357.3 875.98 53.88 −159.25 0.34
100 −1352.0 982.97 58.59 −186.56 0.31

The kinetic parameter |ba /bc |, shown in Table 1 and corresponding to the DC anodic polarization
interference conditions, is >1; thus, the corrosion potential Ecorr shifts positively. Our experimental
results also showed that, as the DC current increased, the potential of the X80 steel shifted positively
(see Figure 4a). The kinetic parameter |ba /bc |, shown in Table 2 and corresponding to the DC cathodic
polarization interference, is >1; thus, Ecorr shifts negatively. Figure 4b confirms this result, as it shows
an increase in the DC as the potential of the X80 steel shifted negatively. These results are also consistent
with the polarization curve fitting results.
When DC is added to the system, the Ecorr and icorr values change significantly (see Tables 1
and 2). The magnitude of Ecorr represents the strength of the electrode polarization potential; icorr
indicates the degree of corrosion and the corrosion rate. The X80 steel demonstrated no passivation
in the anode area during the corrosion process. According to Faraday’s law of electrolysis [11], the
corrosion rate of a metal is directly proportional to the corrosion current density. Thus, the greater
the anode corrosion current density, the more obvious the active dissolution tendency of X80 steel is.
However, due to the protection of the cathode current, the metal in the cathode region usually does not
corrode. At this time, the increase of the cathode corrosion current density represents not the corrosion
of the X80 steel but the acceleration of the cathode hydrogen evolution reaction on the surface of the
X80 steel metal substrate.

3.3. Corrosion Morphology and Pitting Corrosion Depth at Different DC Anode Currents
Because of the 3PE coating, a stray current can only flow out of the damaged coating areas to
initiate the electrochemical reaction. The corrosion reactions of X80 steel under the DC anode can be
summarized as follows [28]:
Fe → Fe2+ + 2e− (1)

Fe2+ + 2H2 O → Fe(OH)2 + 2H+ (2)

4Fe(OH)2 + O2 → 2Fe2 O3 + 4H2 O (3)

In this paper, since the anode and cathode are separated from each other on the same sample,
Sample 1 is the anode region. At the anode area, metallic Fe oxidizes and generates Fe2+ by undergoing
an electrolysis reaction and then combines with H2 O and O2 to oxidize further and to form corrosion
products, such as Fe2 O3 , which then deposit in the anode region.
When the pipeline is electrochemically corroded by a DC stray current, the metal corrosion
complies with Faraday’s law:
w = kIt, v = wI/A (4)

where w is the metal corrosion in g; k is the electrochemical equivalent of metal in kg/(A·s); I is the
value of the current flowing out of the anode metal in A; t is the corrosion duration in h; A is the anode
metal corrosion area in cm2 ; and v is the corrosion rate of the metal in kg/(cm2 ·h).
Equation (4) can help to estimate damages caused by the DC stray current. Thus, a DC stray
current equal to 1 A can corrode 9.13 kg of steel in one year [28].
 complies with Faraday’s law:
w = kIt, v = wI/A (4)
where w is the metal corrosion in g; k is the electrochemical equivalent of metal in kg/(A∙s); I is the
value of the current flowing out of the anode metal in A; t is the corrosion duration in h; A is the
Coatings 2019, 9, 29 7 of 12
anode metal corrosion area in cm2; and v is the corrosion rate of the metal in kg/(cm2∙h).
Equation (4) can help to estimate damages caused by the DC stray current. Thus, a DC stray
current equal to 1 A can corrode 9.13 kg of steel in one year [28].
Figure 6 shows the depth of the corrosion pits of the X80 steel samples under DC anode
Figure 6 shows the depth of the corrosion pits of the X80 steel samples under DC anode
interference obtained using three-dimensional (3D) digital microscopy. Figure 7 shows the relationship
interference obtained using three-dimensional (3D) digital microscopy. Figure 7 shows the
between the corrosion
relationship betweenpit
thedepth andpit
corrosion thedepth
corresponding current density
and the corresponding currentatdensity
the damage point of the
at the damage
coating. The corrosion pits deepened as the DC increased. The depth of the pits represents the severity
point of the coating. The corrosion pits deepened as the DC increased. The depth of the pits represents
of thethe
corrosion [29]; thus, in our experiments, the corrosion rate was higher at higher DC
severity of the corrosion [29]; thus, in our experiments, the corrosion rate was higher at higher current
DC current
densities, whichdensities, which
is in good is in good
agreement agreement
with with
Equation Equation (6).
(6).

(a) (b)

78.9μm 168.1μm

(c) (d)

Coatings 2018, 8, x FOR PEER REVIEW 212.8μm 232.7μm 8 of 12

(e) (f)

258.9μm 325.6μm

Figure 6. The corrosion pit depth (obtained using three-dimensional (3D) digital microscopy) of
Figure 6. The corrosion pit depth (obtained using three-dimensional (3D) digital microscopy) of the
the 3PE-coated X80 steel samples at DC anode current densities equal to (a)2 0 A/m2 , (b) 20 A/m2 ,
3PE-coated
2
X80 steel samples
2
at DC 2anode current densities
2
equal to (a) 0 A/m , (b) 20 A/m2, (c) 40
(c) 40 A/m , (d) 60 A/m , (e) 802 A/m , and (f) 2100 A/m .
A/m , (d) 60 A/m , (e) 80 A/m , and (f) 100 A/m .
2 2

350

300
pth (um)

250
 258.9μm 325.6μm

Figure 6. The corrosion pit depth (obtained using three-dimensional (3D) digital microscopy) of the
3PE-coated X80 steel samples at DC anode current densities equal to (a) 0 A/m2, (b) 20 A/m2, (c) 40
Coatings 2019, 9, 29 8 of 12
A/m2, (d) 60 A/m2, (e) 80 A/m2, and (f) 100 A/m2.

350

300

Corrosion pit depth (um)

250

200

150

100

50
0 20 40 60 80 100

i (A/m2)

Figure 7. The
Figure 7. The corrosion
corrosion pit
pit depth
depth of
of the
the 3PE-coated
3PE-coated X80
X80 steel
steel samples
samples under
under DC
DC anode
anode polarization
polarization
interference with various current densities.
interference with various current densities.

Chen et al. [30] designed and assembled some indoor equipment to simulate DC stray current
Chen et al. [30] designed and assembled some indoor equipment to simulate DC stray current
interference. They noticed that the corrosion rate of the 16MnR was proportional to the outcoming DC
interference. They noticed that the corrosion rate of the 16MnR was proportional to the outcoming
current density in different soil solutions. Wang et al. [31] studied the effect of a stray current on the
DC current density in different soil solutions. Wang et al. [31] studied the effect of a stray current on
corrosion of X70 steels with a damaged coating. They pointed out that, as the stray current increased
the corrosion of X70 steels with a damaged coating. They pointed out that, as the stray current
and the coating damage rate decreased, the corrosion rate and the depth of the corrosion pit increased
increased and the coating damage rate decreased, the corrosion rate and the depth of the corrosion
as well, ultimately increasing the corrosion degree. Thus, our results on DC current anode corrosion
pit increased as well, ultimately increasing the corrosion degree. Thus, our results on DC current
processes are very consistent with previously reported ones.
anode corrosion processes are very consistent with previously reported ones.
3.4. Cathodic Disbondment of the 3PE Coating from the X80 Steel at Various DC Cathode Currents
3.4. Cathodic Disbondment of the 3PE Coating from the X80 Steel at Various DC Cathode Currents
Corrosion of the pipeline in the cathode region does not occur easily. However, if the potential
Corrosion of the pipeline in the cathode region does not occur easily. However, if the potential
value in the cathode region is extremely negative, HER and ORR occur on the surface of the metal of
value in the cathode region is extremely negative, HER and ORR occur on the surface of the metal of
the pipeline, easily causing the cathodic disbondment of the coating in this region [16]. Sample 2 is a
the pipeline, easily causing the cathodic disbondment of the coating in this region [16]. Sample 2 is a
cathode region, and the DC negative electrode supplies electrons that need to be removed during the
cathode region, and the DC negative electrode supplies electrons that need to be removed during the
cathode process, usually by oxygen reduction and/or hydrogen generation. In the cathode area, the
cathode process, usually by oxygen reduction and/or hydrogen generation. In the cathode area, the
cathodic reactions of X80 steel under the action of the DC cathode at the damage of the coating occur
cathodic reactions of X80 steel under the action of the DC cathode at the damage of the coating occur
as follows [32]:
as follows [32]:
O2 + 2H2 O + 4e− → 4OH− (5)

2H2 O + 2e− → H2 + 2OH− (6)

Generally, in aerobic neutral or alkaline solutions, the electrochemical corrosion of metals is called
oxygen uptake corrosion, and the cathodic reaction at this time is called an oxygen uptake reaction.
However, due to the large stray current in the buried metal pipeline, the cathode potential is negative.
As Figure 4 showed, when the current densities were 20 and 40 A/m2 , the reaction potentials were
lower than the standard potential of HER (EV,SCE = −1.056 V [33]). Therefore, cathodic reactions of
stray currents are dominated by the hydrogen evolution reactions.
Figure 8 shows cathodic disbondment of the 3PE coating of the X80 steel samples caused by a
DC stray current. Figure 9 demonstrates the relationship between the cathodic disbondment area
and the stray current density. During our experiments, we observed a large number of bubbles at the
damaged areas. We speculate that the cathodic reaction of stray currents generated both H2 and OH−
ions. However, the hydrogen evolution process dominated, weakening adhesion between the coating
and the metal substrate and leading to the coating delamination. The delamination area of the coating
first increased as the initial stray current increased but then stabilized and remained unchanged. Thus,
stray current has a critical current density value for the disbonding failure of the buried metal pipeline
coating. When the stray current density is less than its critical value, the peel area of the coating varies
the stray current density. During our experiments, we observed a large number of bubbles at the
damaged areas. We speculate that the cathodic reaction of stray currents generated both H2 and OH−
ions. However, the hydrogen evolution process dominated, weakening adhesion between the coating
and the metal substrate and leading to the coating delamination. The delamination area of the coating
Coatings 2019, 9, 29 9 of 12
first increased as the initial stray current increased but then stabilized and remained unchanged. Thus,
stray current has a critical current density value for the disbonding failure of the buried metal
pipeline coating.density.
with the current When the
Whenstray
thecurrent density
stray current is lessisthan
density its than
greater critical
its value,
criticalthe peeldelamination
value, area of the
coating varies with the current density. When the stray current density is greater
area of organic coatings remains unchanged as the current density changes. Cao [34] observed than its critical value,
the
delamination area of organic coatings remains unchanged as the current density changes.
same behavior of the disbondment as a function of the DC current density even though his experiments Cao [34]
observed the same
were performed behavior
under of the
different disbondment as a function of the DC current density even though
conditions.
his experiments were performed under different conditions.

(a) (b) (c)

(d) (e) (f)

Figure 8. Photographs of the cathodic disbondment of the 3PE coating of the X80 steel samples under
Figure 8. Photographs of the cathodic disbondment of the 3PE coating of the X80 steel samples under
DC cathode current densities equal to (a) 0 A/m2 , (b) 20 A/m2 , (c) 40 A/m2 , (d) 60 A/m2 , (e) 80 A/m2 ,
Coatings 2018, 8, x FOR
DC cathode currentPEERdensities equal to (a) 0 A/m , (b) 20 A/m2, (c) 40 A/m2, (d) 60 A/m2, (e) 80 A/m10
REVIEW 2 2, of 12
and (f) 100 A/m2 .
and (f) 100 A/m . 2

70

60
Delamination area (mm2)

50

40

30

20

10

0 20 40 60 80 100

i (A/m2)

Figure 9. Cathodic disbondment of the 3PE coating of the X80 steel samples as function of the DC
Figure 9. Cathodic disbondment of the 3PE coating of the X80 steel samples as function of the DC
current density under DC cathode polarization.
current density under DC cathode polarization.
3.5. Corrosion and Cathodic Disbondment Mechanism of the Pipeline under the Action of the DC Stray Current
3.5. Corrosion and Cathodic Disbondment Mechanism of the Pipeline under the Action of the DC Stray
From our and previously reported literature data, the following mechanism of the corrosion
Current.
and organic cathodic disbondment of the pipeline under the action of a DC stray current in neutral
From our [35,36]
environments and previously reported(see
can be proposed literature
Figuredata,
10). the following mechanism of the corrosion and
organic cathodic disbondment of the pipeline under the action of a DC stray current in neutral
environments [35,36] can be proposed (see Figure 10).
3.5. Corrosion and Cathodic Disbondment Mechanism of the Pipeline under the Action of the DC Stray
Current.
From our and previously reported literature data, the following mechanism of the corrosion and
organic cathodic disbondment of the pipeline under the action of a DC stray current in neutral
Coatings 2019, 9, 29 10 of 12
environments [35,36] can be proposed (see Figure 10).

Figure 10.
Figure Aschematic
10. A schematic of
ofthe
thecorrosion
corrosion and
andorganic
organic cathodic
cathodic disbondment
disbondment mechanism
mechanism of
of the
the pipeline
pipeline
under the DC stray current conditions.
under the DC stray current conditions.

Under a DC stray current, the iron in the anode region generates Fe2+ through the electrolysis
Under a DC stray current, the iron in the anode region generates Fe2+ through the electrolysis
reaction (see Figure 10a), which then reacts with H O and O to be further oxidized into Fe O (see
reaction (see Figure 10a), which then reacts with H22O and O22 to be further oxidized into Fe22O33 (see
Figure 10b) and deposited in the anode region. The damage point is rapidly covered by the corrosion
Figure 10b) and deposited in the anode region. The damage point is rapidly covered by the corrosion
product as the reaction continues, which causes the anode reaction to spread to the surrounding areas.
product as the reaction continues, which causes the anode reaction to spread to the surrounding areas.
Due to the electrolysis of the direct current, the corrosion pit will expand in both directions at the point
Due to the electrolysis of the direct current, the corrosion pit will expand in both directions at the
of damage of the coating. Longitudinal expansion results in thinning of the tube wall, manifesting
point of damage of the coating. Longitudinal expansion results in thinning of the tube wall,
as corrosion perforation. Lateral expansion causes the metal matrix under the coating to dissolve,
manifesting as corrosion perforation. Lateral expansion causes the metal matrix under the coating to
manifesting as anode destruction of the coating.
dissolve, manifesting as anode destruction of the coating.
ORR and dominating HER occur in the stray current cathode region, producing H2 and OH− ions.
ORR and dominating HER occur in the stray current cathode region, producing H2 and OH− ions.
Driven by the electrostatic forces, H2 and OH− migrate between the interface of the organic coating and
Driven by the electrostatic forces, H2 and OH− migrate between the interface of the organic coating
the metal substrate forming bubbles and an alkaline environment that weaken the adhesion between
and the metal substrate forming bubbles and an alkaline environment that weaken the adhesion
the coating and the metal substrate and eventually lead to the cathodic disbondment of the coating.
between the coating and the metal substrate and eventually lead to the cathodic disbondment of the
coating.
4. Conclusions
Under the effect of a DC stray current, the balance of the electrode reaction becomes interrupted,
causing polarization of the X80 steel. The potentials of the X80 steel move in the positive direction
during anodic polarization and in the negative direction during the cathode polarization process. At the
same DC interference level, the potential deviation of the cathode is greater than that of the anode.
No passivation of the X80 steel occurs during the DC anodic corrosion process. The corrosion
process of the pipeline steel follows Faraday’s law of electrolysis: the corrosion amount and corrosion
rate are proportional to the current intensity. Three-dimensional (3D) digital microscopy showed
that the corrosion pit depths increase as the DC stray current increases. At the same time, the X80
steel in the cathode region does not corrode. However, due to the negative cathodic potential, the
cathodic reaction is dominated by hydrogen evolution, resulting in the cathodic disbondment of the
protective coating.
The cathodic disbondment area of the coating increases as the DC cathode current increases, and
a critical current density of the DC cathode current exists. When the stray current density is less than
the critical current density, the coating delamination area changes with the current density. However,
if the stray current density is greater than the critical value, the delamination area of the coating does
not change substantially with the change of the current density.

Author Contributions: Conceptualization, X.W. and Y.C.; Methodology, X.W. and Z.W.; Software, Z.W.; Validation,
Y.C.; Formal Analysis, Y.C. and X.S.; Investigation, X.W.; Resources, X.W.; Data Curation, Y.C.; Writing—Original
Draft Preparation, Z.W.; Writing—Review and Editing, Y.Y.; Visualization, X.S.; Supervision, Y.C.; Project
Administration, X.W.; Funding Acquisition, X.W. and Y.C.
Coatings 2019, 9, 29 11 of 12

Funding: This research was funded by the National Natural Science Foundation of China (No. 51471011) and the
“Rixin Scientist” of the Beijing University of Technology.
Conflicts of Interest: The authors declare no conflict of interest.

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