Anti-Corrosion Methods and Materials

Damage evolution of coated steel pipe under cathodic-protection in soil

Ximing Li Homero Castaneda
Article information:
To cite this document:
Ximing Li Homero Castaneda , (2017),"Damage evolution of coated steel pipe under cathodic-protection in soil ", Anti-Corrosion
Methods and Materials, Vol. 64 Iss 1 pp. 118 - 126
Permanent link to this document:
http://dx.doi.org/10.1108/ACMM-03-2015-1520
Downloaded on: 06 March 2017, At: 13:10 (PT)
References: this document contains references to 26 other documents.
To copy this document: permissions@emeraldinsight.com
The fulltext of this document has been downloaded 38 times since 2017*
Users who downloaded this article also downloaded:
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)

(2017),"3-Thiophenemalonic acid as corrosion inhibitor of copper", Anti-Corrosion Methods and Materials, Vol. 64 Iss 1 pp.
52-60 http://dx.doi.org/10.1108/ACMM-03-2015-1519
(2017),"The formation process of Zr-doped silane film on carbon steel during immersing in Zr(NO3)4/silane mixed solutions",
Anti-Corrosion Methods and Materials, Vol. 64 Iss 1 pp. 1-9 http://dx.doi.org/10.1108/ACMM-12-2015-1627

Access to this document was granted through an Emerald subscription provided by emerald-srm:203763 []
For Authors
If you would like to write for this, or any other Emerald publication, then please use our Emerald for Authors service
information about how to choose which publication to write for and submission guidelines are available for all. Please visit
www.emeraldinsight.com/authors for more information.
About Emerald www.emeraldinsight.com
Emerald is a global publisher linking research and practice to the benefit of society. The company manages a portfolio of
more than 290 journals and over 2,350 books and book series volumes, as well as providing an extensive range of online
products and additional customer resources and services.
Emerald is both COUNTER 4 and TRANSFER compliant. The organization is a partner of the Committee on Publication Ethics
(COPE) and also works with Portico and the LOCKSS initiative for digital archive preservation.

*Related content and download information correct at time of download.

 Damage evolution of coated steel pipe under
cathodic-protection in soil
Ximing Li
Department of Chemical and Bio-molecular Engineering, National Center for Education and Research on Corrosion and
Materials Performance, Akron, Ohio, USA, and
Homero Castaneda
National Corrosion and Materials Reliability Center, Texas A&M, College Station, Texas, USA

Abstract
Purpose – The purpose of this paper is to study the damage evolution (DE) of coated API5L-X52 steel pipe with cathodic protection (CP) in
nature soil. Also, different coating conditions, intact coating and coating with artificial holiday defect are considered to study the
electrochemical behavior combined with soil properties and CP potential. An approach of electrochemical impedance spectroscopy (EIS)
analysis is also developed.
Design/methodology/approach – This work developed a laboratory experimental set-up of coated pipeline under CP in nature soil. The
electrochemical behavior has been investigated using EIS. The CP potential provided by a DC power supplier has been adjusted and recorded
to maintain the protective potential of pipe at ⫺850 mV vs Cu/CuSO4.
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)

Findings – Various parameters were derived from the EIS fitting data by equivalent circuit models to illustrate the three DE stages of coated
carbon steel in soil. Each stage changes faster for the artificial defect coating system compared to intact coating, especially at the initial water
uptake and ion transport stage. The CP potential has been proved to be correlated to the soil properties, coating conditions and DE stages
of pipeline samples.
Originality/value – This work is the first one to study DE of coated pipeline system under CP in soil. It introduces an electrochemical method
to study coating defects which can promote to design the deterministic model to detect coating defects of buried pipe using AC impedance
technique.
Keywords Corrosion, Electrochemistry, Coatings and linings, Pipelines, Cathodic protection
Paper type Research paper

1. Introduction coating/soil interface was commonly described by simplified

Randles’ circuits (Skale et al., 2007; Ehrlich and Moran,
Underground pipelines are normally protected from corrosion
1989), and corrosion rates were predicted from polarization
by an insulating outer barrier (coating) enhanced by cathodic
resistance Rp. However, it is challenging to simulate and
protection (CP) using either a sacrificial anode bed or
analyze the EIS signal when it cannot be fitted by the simple
impressed current (Peabody, 2001). Disbondment and/or
equivalent circuits (Dong et al., 2008; Macdonald, 1990;
delamination of the coating are two of the main reasons for an
Hirayama and Haruyama, 1991; van Westing et al., 1994;
increasing degradation of the metallic substrate (Mansfeld and
Garcia-Belmonte and Bisquert, 2002; Hu et al., 2003). In
Tsai, 1991; Hirayama and Haruyama, 1991; Park et al.,
those cases, it is necessary to select the equivalent circuits
2003). The study of corrosion in soil is inherently complex
for accurate simulation of the studied interface with
because of its nature of a three-phase non-homogeneous
quantitative parameters (Magaña-Zavala et al., 2010).
system, raising the need to analyze the corrosion process of
Besides, studies on the dynamic process of coated pipeline
pipelines combined with soil properties and a dependable
under CP has been studied in soil simulation solution (Ding
monitoring technique (Alamilla et al., 2009; Cole and
et al., 2013), but rarely studied in natural soil, especially the
Marney, 2012).
initial processes before electrochemical corrosion occurs.
Electrochemical impedance spectroscopy (EIS) is
The purpose of the research described in this paper was
advantageous in coating studies because of its non-destructive
to identify and characterize the damage evolution of a
property, making it suitable for on-line monitoring of the
pipeline under CP with an intact coal tar coating, as well as
coating/metal interface (Castaneda et al., 2009; Dong et al.,
a pipeline with a damaged coating (holiday) in natural soil.
2008; Mansfeld et al., 1998; Sanjabi, 2011). The steel/
Different equivalent circuit models were used to analyze the

The current issue and full text archive of this journal is available on The authors would like to acknowledge SENER-CONACyT –
Emerald Insight at: www.emeraldinsight.com/0003-5599.htm hydrocarbons program – for the financial support through the project No.
159913.

Anti-Corrosion Methods and Materials Received 24 March 2015

64/1 (2017) 118 –126 Revised 27 April 2016
© Emerald Publishing Limited [ISSN 0003-5599] 19 June 2016
[DOI 10.1108/ACMM-03-2015-1520] Accepted 25 July 2016

118
 Damage evolution of coated steel pipe
Ximing Li and Homero Castaneda
impedance differences over time. The damage evolution
(DE) stages were proposed and analyzed by the effective
resistance Rt, calculated from the impedance fitting data.
The water volume fraction ␾ in the coating was also
analyzed. Corrosion products formed in each situation and
the DC power supplied potential were analyzed. This work
will be continued to study the electrochemical performance
and DE in soil simulated solution.
2. Experimental procedures
2.1 Preparation of pipeline samples and soil for
electrochemical testing
API 5L X52 carbon steel was used for this study. Sections
of pipeline with a length of 50 cm, outer diameter (OD) of
17 cm and inner diameter (ID) of 15 cm were exposed to
soil. Before experiments, all of the pipeline samples were
sprayed by coal tar coating (Bitumastic 50 coal tar coating
provide by Carboline Company), with a thickness of 300
␮m and coating resistivity of 2.9 ⫻ 109 ohm cm2. A copper
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)
cable was welded to the end of each pipeline sample for
electrical connections; and the welding site was protected
using the same coal tar coating. Both ends of the pipe were
covered using an acrylic sheet and coated by coal tar to
avoid the influence of internal corrosion. A 5.2 cm2 holiday
was scratched to some of the pipeline samples to simulate
the “defect condition” in the coating.
The soil was collected from a natural environment in the
State of Ohio in the USA, and it had no further preparation.
The parameters of the soil are shown in Table I. During
recent years, the corrosivity of soils has been discussed in
detail by considering critical physical and chemical
properties, including water content, pH and salt content
(Leis et al., 2005). Among ionic entities, the most important
species in soil are CO32⫺, SO42⫺ and Cl⫺ as previously
(Leis et al., 2005) indicated by the effects of these
properties on soil corrosivity. In general, when pH is larger
than 7.5, the soil is considered alkaline and mildly
corrosive. The soil is considered not corrosive when the
chloride concentration is smaller than 0.015 wt.%. The
effects of carbonate and sulfate content are complex
because of the possible microbe’s activity in the soil.
Following the ranking scale of soil corrosivity based on
these previous parameters, the soil used in this work is
mildly corrosive (Leis et al., 2005). In addition to the
previous parameters, the soil resistivity can be referred to as
an important indicator of soil’s physicochemical properties.
Normally, the higher soil resistivity, the lower corrosion
rate of pipeline steels. In this work, the soil resistivity
included a magnitude of 3 k⍀·cm, this number reflects a
mildly corrosive soil magnitude based on previous field
studies (Leis et al., 2005).
The soil resistivity is the parameter that characterizes the
soil aggressiveness and corrosion tendency for underground
Table I Chemistry of soil
Anion composition (wt.%)
pH wt.% water wt.% OC CO32ⴚ Clⴚ
8.22 18.78 2.81 1.78 0.007
119
Anti-Corrosion Methods and Materials
Volume 64 · Number 1 · 2017 · 118 –126
metallic structures. In this work, soil resistivity was
maintained by keeping approximately constant water
content; this was achieved by monitoring the weight change
of the soil and adding distilled water when necessary. Soil
resistivity was detected using a Digital resistometer (Miller
400D, ⫾5 per cent ⫾1LS Display Digit).
2.2 Experiment cell setup and tests
The rectangular acrylic tanks with dimensions of 76 ⫻ 45 ⫻
30 cm were set up to contain the pipeline sections and the
soils. The soil was compacted carefully around and atop the
pipeline sample; the distance between the pipeline sample
and soil surface was 19.5 cm.
A classic three-electrode system was used in this work.
The pipeline section was the working electrode; a graphite
rod was calomel electrode; and a saturated copper/copper
sulfate (Cu/CuSO4 sat) electrode was RE. During the
experiment, EIS measurements were carried out in a
frequency range from 100 kHz to 10 mHz and an amplitude
of 10 mV. The EIS data obtained were simulated by
different equivalent circuits. All the experiments were
carried out while applying CP of ⫺850 mV vs Cu/CuSO4,
supplied by a DC power supplier, and the output potential
of DC power supplier provided were adjusted and recorded
over time to maintain the potential of structure-soil to be
⫺850 mV.
After experiment, the corrosion products of each pipeline
sample were collected: from coating surface for intact
coating system and from the holiday surface for artificial
defect coating. The collected corrosion products were
characterized and analyzed by EDXA using a HITACHI®
TM3000 Tabletop Microscope.
3. Results and discussion
3.1 Characterization of the soil environment
The soil resistivity and water content were detected over
time, which were maintained approximately constant as
discussed above. Both of these two parameters for intact
coating and defective coating are similar, regardless the
defect. On average, the soil resistivity was 3 k⍀cm, and
the water content was 18 per cent, in agreement with the
“as-received” values (Table I).
The energy dispersive X-ray analysis results based on
corrosion products formed in different systems are
illustrated in Figures 1 and 2. For the pipeline with initial
coating defect, the cations elements, such as Ca2⫹, Mg2⫹
and Si2⫹, among others, were detected in the corrosion
products, this latter indicated that soil clusters participated
in the iron dissolution reaction. Following the activation
process at the defect site, the corrosion products were found
to be a mixture of iron oxides combined with soil particles;
this was in agreement with previous work (Sun et al., 2012).
For the intact coating conditions, yellowish brown products
Cation composition (wt.%)
SO42ⴚ Ca2ⴙ Mg2ⴙ Kⴙ Naⴙ
0.93 0.0307 0.0078 0.0144 0.0053
 Damage evolution of coated steel pipe Anti-Corrosion Methods and Materials
Ximing Li and Homero Castaneda Volume 64 · Number 1 · 2017 · 118 –126

Figure 1 EDXA results of corrosion products of pipeline with artificial defect coating buried in soil for 300 days

Figure 2 EDXA results of corrosion products of pipeline with intact coating buried in soil for 300 days
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)

were resolved on the coating surface. The resulted products Figure 3 Changes in DC power supplied potential over time
were sampled from the coating and characterized by
Soil-Intact Coating
EDXA. The results showed that there were iron oxides
– 800
Soil-Defect Coating
formed on the coating surface. This latter is due to ion
DC power supplied potential (mV)

transportation being in two ways:

1 the anion up taking the coating to reach the coating/steel –1,000
interface; and
2 the iron cation transporting to the surface of the coating. –1,200
Hence, the iron oxides were detected on the surface after 300 –1,400
days of exposure.
–1,600
3.2 Analysis of cathodic protection potential in
different systems –1,800 0 50 100 150 200 250 300
To provide the sufficient cathodic protection, the output Time (day)
potential of DC power supplier was adjusted in each
condition to keep the protective potential of pipeline tends to be resistive more than capacitive, and then the SP
constant at ⫺0.85 V vs Cu/CuSO4. Figure 3 shows the for both coating conditions become more negative. It is
changes of output potential provided by DC power supplier interesting to see that different stages can be distinguished
(SP) in response of exposure time. The SP for defect from SP evolution over time. SP became more negative at
coatings is more negative than the intact coating systems, the first 100 days, and then fluctuated, being more negative
which makes sense that pipeline with defect coating needs and stable after 200 days, correlated with the damage
more protective current. Over time, water and ions evolutions which will be discussed later. After 300 days of
transport through the coating interface, and the coating test, for the intact coating, the current protection density is

120
 Damage evolution of coated steel pipe Anti-Corrosion Methods and Materials
Ximing Li and Homero Castaneda Volume 64 · Number 1 · 2017 · 118 –126

0.011 mA/m2, whereas it is 0.062 mA/m2 for the defect
condition.
3.3 Electrochemical impedance spectroscopy
characterization of pipeline samples in soil
Equivalent circuit models are used to describe the
impedance response of the electrochemical system. Several
works (Le Thu et al., 2006; Akbarinezhad et al., 2009; Zhu
et al., 2011) have discussed common equivalent circuits
(ECs) applied in the EIS fitting for coated metals and the
respective interpretation. After tests, EIS results have been
simulated using different ECs, shown in Figure 4. In these
ECs, Rs represents the soil (electrolyte) resistance; and Qc
and Rc represent the constant phase element and resistance
of the coating. At the very beginning, Qc and Rc would
probably represent the constant phase element and
resistance of the soil clusters formed on coating surface for
intact coating and corrosion products combined with soil
particles on holiday surface for defect coating, which would
be specifically discussed in the following discuss. Qdl and
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)
A very good agreement with the proposed damage evolution
has also given a near perfect fitting. The selected fitting
parameters of ECs are listed in Tables II and III. The EIS
fitting process was performed by using complex non-linear
least squares principles, and ␹2 is the parameter that is used
as an accuracy stop criterion. Generally, the fitting results
are agreeable when ␹2 is smaller than 0.003. During our
fitting process, this value was maintained smaller than
0.00015. As a qualitative measure of good agreement can
also be seen by the experimental vs fitting comparison
displayed in Figures 5 and 6. The fitting errors for the
conditions of pipeline with defect coating during 300 days
are presented in Table IV.
The EIS characteristics for the pipeline sample with an
intact coating are shown in Figure 5. ECs [Figure 4(a) and
(b)] have been used to simulate the EIS results, the fitting
data listed in Table II. For the intact coating, the most
commonly used equivalent circuit is the two-constant phase
circuit [ECs Figure 4(a)] (Le Thu et al., 2006). The
impedance signal at high frequencies (larger than 100 Hz)

Rct represent the constant phase element associated with
the double layer capacitance and the charge transfer
resistance on the steel surface, respectively, and Ws
represents the Warburg impedance (Skale et al., 2007).
Different equivalent circuits are chosen based on the
mechanisms existing at the interface, which will be
discussed separately for intact and defect coating
conditions.
can be attributed to the characteristics of the soil clusters on
the coating surface, whereas the signal at medium
frequencies presents the combination of soil clusters and
coating. Water clusters formed in soil can cover current
distribution, in agreement with the much negative DC
power SP in Figure 3. During the initial 11 days, Rc
increased as a result of the assumed soil clusters on coating
surface. However, Qc, proportional to the coating

Figure 4 Different equivalent circuits used to simulate EIS results

Table II Fitting parameters of EIS by ECs Figure 4(a) and (b) of pipeline sample in soil with intact coating
Time/day Qc(10ⴚ11 S·sn·cmⴚ2) nc Rc(108 ⍀·cm2) Qdl(10ⴚ9 S·sn·cmⴚ2) ndl Rct(108 ⍀·cm2) WR(108 ⍀·cm2) WT(s) nw

1 3.78 0.85 8.88 1.05 0.51 16.4 – – –

11 8.20 0.79 20.9 3.75 0.77 3.78 – – –
31 7.41 0.81 2.92 3.09 0.46 6.28 – – –
102 6.11 0.83 4.96 0.51 0.50 10.8 – – –
200 6.13 0.83 5.57 3.66 0.40 4.42 – – –
300 5.59 0.84 2.06 0.13 0.71 0.90 1.02 41.5 0.26

121
 Damage evolution of coated steel pipe Anti-Corrosion Methods and Materials
Ximing Li and Homero Castaneda Volume 64 · Number 1 · 2017 · 118 –126

Table III Fitting parameters of EIS by ECs Figure 4(a), (c) and (d) of pipeline sample in soil with defect coating
Time/day Qc(10ⴚ11 S·sn·cmⴚ2) nc Rc(106 ⍀·cm2) Qdl(10ⴚ7 S·sn·cmⴚ2) ndl Rct(106 ⍀·cm2) WR(106 ⍀·cm2) WT(s) nw

1 4.89 0.82 1.31 4.35 0.66 8.76 – – –

10 5.84 0.81 1.17 2.21 0.73 58.7 – – –
40 7.38 0.81 1.15 4.89 0.74 56.4 – – –
60 5.98 0.83 1.14 7.28 0.79 36.8 1.07 2.52 0.39
160 11.8 0.78 5.57 – – – 4.56 3.47 0.18
300 8.34 0.83 1.55 19.7 0.76 2.84 1.50 1.98 0.29

Figure 5 Bode and phase angle representation for intact coating conditions exposed in soil with time

2x109
80

Phase degree
2x108
/Z/ / Ω⋅cm2

60

2x107 1d Exp. Fit.

40 1d Exp. Fit.
5d Exp. Fit.
5d Exp. Fit.
11d Exp. Fit.
11d Exp. Fit.
31d Exp. Fit.
2x106 59d Exp. Fit. 20
31d Exp. Fit.
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)

59d Exp. Fit.

102d Exp. Fit.
102d Exp. Fit.
200d Exp. Fit.
200d Exp. Fit.
300d Exp. Fit.
2x105 0 300d Exp. Fit.

10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105
Frequency / Hz Frequency / Hz
(a) (b)

Figure 6 Bode and phase angle representation for defect coating conditions exposed in soil with time
80
1d Exp. Fit. 1d Exp. Fit.
4d Exp. Fit. 4d Exp. Fit.
10d Exp. Fit. 10d Exp. Fit.
40d Exp. Fit. 40d Exp. Fit.
2x107 60d Exp. Fit. 60 60d Exp. Fit.
133d Exp. Fit. 133d Exp. Fit.
Phase degree

160d Exp. Fit.

/Z/ / Ω⋅cm2

160d Exp. Fit.

200d Exp. Fit. 200d Exp. Fit.
300d Exp. Fit.
300d Exp. Fit.
40
2x106

20

2x105 0

10-2
10 -1
100
10 1
10 2
103
104
10 5 10-2 10-1 100 101 102 103 104 105
Frequency / Hz Frequency / Hz
(a) (b)

Table IV Fitting errors of EIS data at Day 300 for pipeline with defect coating
Parameters Qc(10ⴚ11 S·sn·cmⴚ2) nc Rc(106 ⍀·cm2) Qdl(10ⴚ7 S·sn·cmⴚ2) ndl Rct(106 ⍀·cm2) WR(106 ⍀·cm2) WT(s) nw

Fitting value 8.34 0.83 1.55 19.7 0.76 2.84 1.50 1.98 0.29
Error (%) 5.70 0.56 1.47 6.79 0.75 0.01 2.06 1.10 6.70
␹2 0.001
Sum-square 0.26

capacitance, increased means that the coating starts to frequency constant describing the double layer in the
absorb water and becomes less capacitive. Once water starts coating/steel interface. As time passes, the coating becomes
to be transported, Rct also becomes lower than its initial saturated with water (Bellucci et al., 1992) and the process
value (Mansfeld et al., 1982); this represents the first stage of water and ion transport becomes more difficult, indicated
in the damage evolution concept (DE-Stage I), illustrated by the increasing Rct and decreasing Rc during this period.
in Figure 7(a). When water penetrated into the coating, this The water uptake and ion transport in the coating is
latter presented both, capacitive and resistive properties. At referred as DE- Stage II [Figure 7(b)]. After 110 days, the
Day 31, two time constants are distinguished, with the high impedance decreases at low frequencies. The electrolyte has
frequency constant representing the coating and the low been transported within the coating layer reaching the

122
 Damage evolution of coated steel pipe
Ximing Li and Homero Castaneda
Figure 7 Schematic diagrams of DE of intact (a, b, c) and artificial defect coatings (d, e, f)
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)
substrate surface, before anodic dissolution happens
(Bellucci et al., 1992), as it is considered in DE-Stage III,
illustrated in Figure 7(c). Rct is much lower, indicating that
the water uptake is accumulated at the substrate/coating
interface (van Westing et al., 1994). At around 300 days, a
diffusion-like signal appears at low frequency, which is the
transition of charge transfer control to diffusion control.
Hence, a two-constant phase and Warburg impedance
circuit is selected to fit the data [ECs Figure 4(b)].
Yellowish brown spots have been founded on the coating
surface, as seen in Figure 1, this latter supports the
diffusion process through coating interface. In addition, the
DC power SP became more negative at Stage I, and then
fluctuated during Stage II, being more negative at Stage III,
correlated with the DEs.
Figure 6 shows EIS plots for the pipeline sample with
induced pre-damage holiday and ECs. Figures 4(a), (c) and
(d) were applied to simulate different stages. During the
first 10 days, two time constants are observed: the first time
constant at high frequencies is associated to the coating
holiday/soil interface and produces a small impedance
magnitude. The second time constant at low frequencies is
related to the charge transfer magnitude due to
electrochemical reactions on the holiday surface and shows
a larger impedance magnitude. Then, the EC illustrated in
Figure 4(a) was selected to fit the EIS. For the particular
case of a coating with a holiday, corrosion products
combined with soil particles were formed on top of the
holiday surface at the beginning, which results in an
increasing Rct. However, Qc increased, which may be
because water uptake through the coating, especially
through the holiday, would destroy the insulating properties
of the coating. The initial anodic dissolution occurring at
the surface of the holiday and the water uptake in the
soil/coating holiday interface are referred as the first stage of
damage evolution concept (DE- Stage I), shown in Figure
7(d). When corrosion products form but cannot yet cover
the entire holiday surface, the transport of water and ions
cause the impedance to decrease after 40 days, which also
can be seen from Rc and Rct. A diffusion-related signal
123
Anti-Corrosion Methods and Materials
Volume 64 · Number 1 · 2017 · 118 –126
appears after 60 days, which indicates diffusion of water
and ions toward the coating/steel interface; this is
considered as DE-Stage II [Figure 7(e)]. At longer
exposure times, the diffusion process becomes the
dominant process. Consequently, the diffusion element is
in parallel with the second time constant [ECs Figure 7(d)].
After 110 days, corrosion products covered the entire
holiday surface; further anodic dissolution is no longer the
dominant process; diffusion becomes more dominant
because of increasing corrosion products and saturation of
the coating interface, which is represented by an increasing
WR, referred to as DE-Stage III [Figure 7(f)]. At around
160 days, the diffusion process is not dominant, and EIS
showed only one time constant. It does not mean that there
is no charge transfer process but diffusion process controls
the whole electrochemical process. In this latter case, EC
Figure 7(c) is selected to fit the EIS. As expected, the
impedance of the sample with a defective coating is much
lower than that with an intact coating, also illustrated by
DC power SP in Figure 3.
4. Discussion
EIS has been used to determine the volumetric water
content and the protective efficiency of the coatings. In
previous works, the coating protective efficiency was
calculated by the polarization resistance Rp and Rp0 in the
presence and absence of a coating. Rp normally is assumed
to be the sum of the coating resistance Rc and charge
transfer resistance Rct. This differentiation is reasonable
because different mechanisms are illustrated by the EIS
signal in a coated pipeline system in different stages: in the
initial period, mass transfer is the principal process;
however, Rc is more important when considering the whole
process. In other conditions, when the electrolyte is present
at the coating/steel interface, charge transfer is the
controlling process and Rct plays a main role in comparing
the coating performance; in these cases, the diffusion
process is normally ignored in the calculation of Rp. When
diffusion is the main process, the diffusion resistance Rw
 Damage evolution of coated steel pipe
Ximing Li and Homero Castaneda
Figure 8 Rt magnitude evolution with time for (a) intact coating conditions, (b) coating defect conditions
1010
Soil-Intact coating
Rt / Ω⋅cm2
Rt1
109
Rt2
108
0 50 100 150 200
Time / day
(a)
becomes the crucial parameter in the whole phenomenon.
In general, most of conditions involve mixed controlling
processes; to demonstrate the damage evolution in a
comprehensive manner, Rc, Rct and Rw should be
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)
considered altogether at the same time. Hence, the concept
of the “effective resistance” Rt would be proposed and
calculated using the following modified equation:
Rt ⫽ Rc ⫹ Rct ⫹ Rw,
where Rt represents the coating layer and double layer
resistances together and is more likely to show the real
coating performance than Rp.
Figure 8 illustrates the value of Rt over experiment. In
agreement with the EIS description, three DE stages are
recognized from the Rt-t diagram. The quantitative
relationship of Rt vs time for each stage has been fitted and
calculated and is shown in Table V. For the intact coating,
the first stage is water transport through the soil particles to
the coating, corresponding to the DE-Stage I (Table V,
intact coating). Over immersion time, coating would
become saturated with water, which agrees with the
increasing impedance. Then water and ions reach the
interface of coating/steel; electrolyte forms and corrosion
happens. For defect coating, corrosion products form on
the holiday surface, and diffusion becomes the main
mechanism. Over time, Rt increases after corrosion
products cover the holiday surface. It is interesting to see
that the slope of Rt-t for each system has the largest value in
DE-Stage I and then decreases, which relates directly to the
water uptake process that would be faster at the very
beginning under dry coating conditions. Over time, the
transport process slows down as the coating is saturated
with water and ionic diffusion is much slower than water
Table V Fitting equations of each stage in DEs
Systems Intact coating Defect coating
DE-Stage I logRt ⫽ 9.8293 ⫺ 0.02829t logRt ⫽ 6.8326 ⫹ 0.12149t
共10 ⱕ t ⱕ 30兲 共R2 ⫽ 0.92兲 共1 ⱕ t ⱕ 15兲 共R2 ⫽ 0.98兲
DE-Stage II logRt ⫽ 8.8835 ⫹ 0.00242t logRt ⫽ 7.8438 ⫺ 0.00396t
共30 ⱕ t ⱕ 150兲 共R2 ⫽ 0.54兲 共15 ⱕ t ⱕ 120兲 共R2 ⫽ 0.55兲
DE-Stage III logRt ⫽ 10.1184 ⫺ 0.00509t logRt ⫽ 6.0651 ⫹ 0.00576t
共150 ⱕ t ⱕ 300兲 共R2 ⫽ 0.84兲 共120 ⱕ t ⱕ 300兲 共R2 ⫽ 0.93兲
Anti-Corrosion Methods and Materials
Volume 64 · Number 1 · 2017 · 118 –126
Soil-Defect coating
108
Rt2
Rt3
Rt / Ω⋅cm2
Rt1
107 Rt3
106
250 300 0 50 100 150 200 250 300
Time / day
(b)
diffusion (Wei et al., 2006). Compared with the intact
coating system, the Rt-t curve at each stage has a larger
slope value for the defective coating, which means that each
stage changes faster because of the holiday site on the
coating, especially at the initial stage. The existence of
holiday on the coating would significantly promote the
process of water uptake and ion transport.
(1)
5. Conclusion
The performance evolution of coated steel pipe with
cathodic protection in nature soil was investigated for both
intact and pre-damage coating conditions. EIS technique
was used to monitor and quantify the status of the coating
condition when in a fully cathodic protection mode.
The experiment and analysis of results show three DE
stages of coated carbon steel in soil for each coating
condition. The soil clusters combined with water formed on
the coating surface influence the impedance at initial stage,
resulting in the first DE stage. Each of the three stages is
reached faster in the presence of a defect compared to intact
coating conditions. The most representative stage is the
initial or Stage I, where water uptake and ion transport
stage is the most dominant process for intact and defect
conditions. Each stage can be quantified and mitigated by
considering the dominant process at the interface.
This work helps to introduce an electrochemical method
to characterize and understand failure process of buried
steel pipes with CP, which can promote to design different
tools to mitigate and control the damage evolution of the
state of the coating of buried pipe using transfer function
AC-based techniques.
References
Akbarinezhad, E., Bahremandi, M., Faridi, H.R. and
Rezaei, F. (2009), “Another approach for ranking and
evaluating organic paint coatings via electrochemical
impedance spectroscopy”, Corrosion Science, Vol. 51
No. 2, pp. 356-363.
Alamilla, J.L., Espinosa-Medina, M.A. and Sosa, E.
(2009), “Modelling steel corrosion damage in soil
environment”, Corrosion Science, Vol. 51 No. 11,
pp. 2628-2638.
124
 Damage evolution of coated steel pipe
Ximing Li and Homero Castaneda
Bellucci, F., Nicodemo, L., Monetta, T., Kloppers, M.J.
and Latanision, R.M. (1992), “A study of corrosion
initiation on polyimide coatings”, Corrosion Science,
Vol. 33 No. 8, pp. 1203-1226.
Castaneda, H., Sosa, E. and Espinosa-Medina, M.A.
(2009), “Film properties and stability influence on
impedance distribution during the dissolution process of
low-carbon steel exposed to modified alkaline sour
environment”, Corrosion Science, Vol. 51 No. 4,
pp. 799-806.
Cole, I.S. and Marney, D. (2012), “The science of pipe
corrosion: a review of the literature on the corrosion of
ferrous metals in soils”, Corrosion Science, Vol. 56,
pp. 5-16.
Ding, Q., Li, Z. and Hao, H. (2013), “Effects of AC
interference on the optimum cathodic protection
potential of X70 steel in soil solution”, Anti-Corrosion
Methods and Materials, Vol. 60 No. 6, pp. 283-287.
Dong, C.F., Fu, A.Q., Li, X.G. and Cheng, Y.F. (2008),
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)
“Localized EIS characterization of corrosion of steel at
coating defect under cathodic protection”, Electrochimica
Acta, Vol. 54 No. 2, pp. 628-633.
Ehrlich, S.G. and Moran, P.J. (1989), “The use of
pseudocapacitance measurements for estimating the
corroding surface area on underground steel structures”,
Corrosion, Vol. 45 No. 8, pp. 689-696.
Garcia-Belmonte, G. and Bisquert, J. (2002), “Impedance
analysis of galvanostatically synthesized polypyrrole
films: correlation of ionic diffusion and capacitance
parameters with the electrode morphology”,
Electrochimica Acta, Vol. 47 No. 47, pp. 4263-4272.
Hu, J.M., Zhang, J.Q. and Cao, C.N. (2003),
“Determination of water uptake and diffusion of Cl- ion
in epoxy primer on aluminum alloys in NaCl solution by
electrochemical impedance spectroscopy”, Progress in
Organic Coatings, Vol. 46 No. 4, pp. 273-279.
Leis, B.N., Lamontagne, E.B.C.M. and Colwell, J.A. (2005),
“Improvement of external corrosion direct assessment
methodology by incorporating soils data”, US Department
of Transportation Research and Special Projects Agency,
Contract No. DTRS5603-T-0003, Final Report DOT
PHMSA, November 2015.
Le Thu, Q., Takenouti, H. and Touzain, S. (2006), “EIS
characterization of thick flawed organic coatings aged
under cathodic protection in seawater”, Electrochimica
Acta, Vol. 51 No. 12, pp. 2491-2502.
Macdonald, J.R. (1990), “Impedance spectroscopy: old
problems and new developments”, Electrochimica Acta,
Vol. 35 No. 10, pp. 1483-1492.
Magaña-Zavala, C., Angeles-San Martín, M.,
Rodríguez-Gómez, F., Acosta, D., Ávila-Godoy, R. and
Hidalgo-Prada, B. (2010), “Electrochemical impedance
spectroscopy (EIS) modelling of different behaviours of
Ni and Ni oxide thin films for corrosion prevention in
sour media”, Anti-Corrosion Methods and Materials,
Vol. 57 No. 3, pp. 118-125.
Mansfeld, F. and Tsai, C.H. (1991), “Determination of
coating deterioration with EIS I: basic relationships”,
Corrosion, Vol. 47 No. 12, pp. 958-963.
125
Anti-Corrosion Methods and Materials
Volume 64 · Number 1 · 2017 · 118 –126
Mansfeld, F., Kendig, M.W. and Tsai, S. (1982),
“Evaluation of corrosion behavior of coated metals with
AC impedance measurements”, Corrosion, Vol. 38 No. 9,
pp. 478-485.
Mansfeld, F., Han, L.T., Lee, C.C. and Zhang, G. (1998),
“Evaluation of corrosion protection by polymer coatings
using electrochemical impedance spectroscopy and noise
analysis”, Electrochimica Acta, Vol. 43 Nos 19/20,
pp. 2933-2945.
Park, J.H., Lee, G.D., Ooshige, H., Nishikata, A. and
Tsuru, T. (2003), “Monitoring of water uptake in
organic coatings under cyclic wet– dry condition”,
Corrosion Science, Vol. 45 No. 8, pp. 1881-1894.
Peabody, A.W. (2001), Control of Pipeline Corrosion,
NACE International, The Corrosion Society, Houston,
TX.
Hirayama, R. and Haruyama, S. (1991), “Electrochemical
I mpedance for Degraded coated steel having pores”,
Corrosion, Vol. 47 No. 12, pp. 952-958.
Sanjabi, S. (2011), “Corrosion behavior of organically
modified silicates coatings”, Anti-Corrosion Methods and
Materials, Vol. 58 No. 5, pp. 245-249.
Skale, S., Doleček, V. and Slemnik, M. (2007),
“Substitution of the constant phase element by Warburg
impedance for protective coatings”, Corrosion Science,
Vol. 49 No. 3, pp. 1045-1055.
Sun, C., Li, X., Xu, J., Yan, M., Wang, F. and Wang, Z.
(2012), “Effect of urea on microbiologically induced
corrosion of carbon steel in soil”, Acta Physica -Chim
Sinica, Vol. 28 No. 11, p. 10.
van Westing, E.P.M., Ferrari, G.M. and de Wit, J.H.W.
(1994), “The determination of coating performance
with impedance measurements – II, Water uptake of
coatings”, Corrosion Science, Vol. 36 No. 6,
pp. 957-977.
Wei, Y.H., Zhang, L.X. and Ke, W. (2006), “Comparison
of the degradation behaviour of fusion-bonded epoxy
powder coating systems under flowing and static
immersion”, Corrosion Science, Vol. 48 No. 6,
pp. 1449-1461.
Zhu, C., Xie, R., Xue, J. and Song, L. (2011), “Studies of
the impedance models and water transport behaviors of
cathodically polarized coating”, Electrochimica Acta,
Vol. 56 No. 16, pp. 5828-5835.
About the authors
Ximing Li is a PhD Candidate at National Center for
Education and Research on Corrosion and Materials
Performance (NCERCAMP), University of Akron. She got
her master’s degree in June 2012 in Institute of Metal
Research, Chinese Academy of Sciences, and majored in
Corrosion Science and Protection. Her research interest is
particularly focused on external corrosion of oil and gas
pipeline in coating/CP system and to set up the analysis model
to detect coating defects and studies of various coating
systems.
 Damage evolution of coated steel pipe
Ximing Li and Homero Castaneda
Homero Castaneda is an Associate Professor at the
Department of Materials Science and Engineering in Texas
A&M University. He used to work in Department of
Chemical Biomolecular Engineering in the University
of Akron. He got his PhD degree in the Department of
Materials Science and Engineering in Penn State University
in 2001. His current research interests are multi-scale tools
Downloaded by Ohio State University At 13:10 06 March 2017 (PT)
For instructions on how to order reprints of this article, please visit our website:
www.emeraldgrouppublishing.com/licensing/reprints.htm
Or contact us for further details: permissions@emeraldinsight.com
126
Anti-Corrosion Methods and Materials
Volume 64 · Number 1 · 2017 · 118 –126
for corrosion science and engineering in buried pipelines,
dynamic electrochemical characterization and monitoring
of operating batteries, corrosion assessment on storage
tanks and damage evolution of coatings/steel interface and
lifetime prediction determination. Homero Castaneda
is the corresponding author and can be contacted at:
hcastaneda@tamu.edu