Ocean Engineering 115 (2016) 149–158

Contents lists available at ScienceDirect

Ocean Engineering
journal homepage: www.elsevier.com/locate/oceaneng

Cathodic protection criteria of ship hull steel under flow condition

in seawater
Jin-Ho Kim, Yong-Sang Kim, Jung-Gu Kim n
School of Advanced Materials Engineering, Sungkyunkwan University, 300 Chunchun-Dong, Jangan-Gu, Suwon 440
746, South Korea

art ic l e i nf o a b s t r a c t

Article history: The effect of flow velocity on the cathodic protection criteria of ship hull steel was studied in synthetic
Received 29 June 2015 seawater. Sufficient protection could not be obtained at
800 mV versus SCE (
781 mV versus Ag/AgCl)
Accepted 7 February 2016 under the flow condition. The anodic Tafel lines were used to determine the protection potential at each
Available online 22 February 2016
flow condition. The protection potential was shifted to the more negative value as the flow velocity
Keywords: increased. From the surface analysis, the change of cathodic protection potential criteria was due to the
Cathodic protection criteria formation of the magnetite (Fe3O4) on the surface under the flow condition. There was a good agreement
Flow velocity between electrochemical impedance spectroscopy (EIS), weight loss and numerical simulation results.
Tafel slope & 2016 Elsevier Ltd. All rights reserved.
Ship hull steel

1. Introduction of hydrogen embrittlement was increased due to the water dis-

Cathodic protection is one of the corrosion prevention methods
of marine structures (Degiorgi et al., 1998; Baeckmann, 1997)
commonly prevented from external corrosion by a combined
application of coatings and cathodic protection (Li et al., 2004;
Peabody, 2001; Roberge, 1999; Enos and Williams, 1997, Zamani,
1993; Fontana, 1986; Kuhn, 1933). An Evan's diagram schemati-
cally shown in Fig. 1 gives the theoretical basis of cathodic pro-
tection. The anodic dissolution and cathodic reaction show the
activation and diffusion limited polarization. As the applied
cathodic current density is increased, the potential of anode falls,
and the anodic dissolution rate is decreased accordingly (Gum-
mow, 1986). From this theory, the cathodic protection criteria in
various conditions are calculated.
For the appropriate application of cathodic protection to mar-
ine structure, the cathodic protection criteria have been postulated
(Kim and Kim, 2001; Schwedtfeger and Madorman, 1952).
According to the National Association of Corrosion Engineers
(NACE) standard RP-0169, the criteria for cathodic protection at
room temperature is a negative (cathodic) potential of at least
770 mV versus saturated calomel electrode (SCE), which is the
same with
751 mV versus silver/silver chloride electrode (Ag/
AgCl), and the corrosion rate should be lower than 0.0254 mm/y
under the cathodic protection (Heidersbach, 1987; Barlo and Berry,
1984). Also, under the over protection potential below the

1000 mV versus SCE (
981 mV versus Ag/AgCl), the possibility
n
Corresponding author.
E-mail address: kimjg@skku.ac.kr (J.-G. Kim).
sociation reaction (Hartt, 2012). Thus, appropriate cathodic pro-
tection range would appear to be from
770 to
1000 mV versus
SCE (from
751 mV to
981 mV versus Ag/AgCl).
The cathodic protection criteria can be changed by chloride ion,
type of cathodic potential pulse, temperature and flow velocity
(Yamamoto et al., 2013; Büchler et al., 2012). Especially, the flow
effect on the cathodic protection has been studied in many years.
Lee and Ambrose (1988) reported the influence of flow velocity
(actually, rotating cylinder speed 500 and 1000 rpm) on the cal-
careous deposit, such as calcium carbonate (CaCO3) and magne-
sium hydroxide (Mg[OH]2) formation which can affect the catho-
dic protection design. They investigated that the rate of calcareous
deposit formation increases with the increase of flow velocity due
to the increase in OH
generation rate on metal surface. However,
the increase in flow velocity has little influence on the calcareous
deposit formation. Hugus and Hartt (1999) reported the effect of
velocity (0.03, 0.09 and 0.30 m/s) on the current density for
cathodic polarized steel by aluminum anode in seawater. They
showed the increase of calcareous deposit thickness, change of
porosity and phase with the increase of the flow velocity.
Although the flow effect on the cathodic protection was studied
in various researches, it was almost focused on the calcareous
deposit effect. Not only calcareous deposit but also state of oxide
film on the metal surface can be important factors of the cathodic
protection criteria because the anodic Tafel slope, which was used
to determine the cathodic protection potential, can be affected.
Additionally, the experimental flow velocities of previous studies
were too slow as compared with the average sailing velocities for
container ship and oil tanker (5–15 Kn E3–7 m/s). Thus, in this
study, we focused on the oxide film state under higher flow

http://dx.doi.org/10.1016/j.oceaneng.2016.02.024
0029-8018/& 2016 Elsevier Ltd. All rights reserved.
150 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158

Potential a pH of 8.2 at 25 °C. Table 2 gives the chemical composition of the

Anodic reaction
synthetic seawater from ASTM D1141-98 (2013).

Cathodic reaction 2.2. Electrochemical tests

Potential The effect of flow velocity on cathodic protection criteria in

without CP seawater was examined using potentiodynamic polarization,
electrochemical impedance spectroscopy (EIS) and potentiostatic
polarization in the RCE system. All electrochemical tests were
Potential performed by VMP2 multi-channel potentiostat. As saturated
with CP
Applied
calomel electrode (SCE) and mesh type platinum were used as the
current density
reference and counter electrodes, respectively, as shown in Fig. 2.
Potentiodynamic polarization tests were performed to demon-
Anodic Anodic
Log current density strate the overall corrosion properties according to the flow velocity
dissolution rate dissolution rate
with cathodic without cathodic with a potential sweep of 0.166 mV/s from an initial potential of
protection protection
250 mV versus the open-circuit potential (Ecorr) to a final potential
Fig. 1. Evan's diagram, illustrating the shifting of the potential and corrosion cur- of 1000 mV versus SCE (
981 mV versus Ag/AgCl).
rent density after applied cathodic protection current. The EIS tests were performed at Ecorr,
800 mV versus SCE
(
781 mV versus Ag/AgCl) and
900 mV versus SCE (
881 mV
versus Ag/AgCl) under the flow velocities of 0 m/s, 2 m/s and 5 m/s
Table 1 to investigate the surface properties and the satisfaction of
Chemical composition of ship hull steel (wt%). cathodic protection criteria. The frequency range of EIS tests was
from 100 kHz to 10 mHz and an alternating current amplitude was
Elements C Mn P S Cu Ni Cr Mo Fe
7 10 mV. The impedance plots were interpreted on the basis of an
Composition 0.30 1.20 0.05 0.45 0.50 0.40 0.40 0.15 Balance equivalent circuit using a suitable fitting procedure by ZsimpWin
software.
The potentiostatic polarization tests were performed with and
without constant cathodic potentials for the corrosion rate mea-
Table 2 surements. The specimens had been held without and with the
Chemical composition of synthetic seawater. applied cathodic protection potential of
800 mV versus SCE
(
781 mV versus Ag/AgCl, NACE-recommended) for 7 days during
Component Concentration (g/L).
the potentiostatic tests. The cathodic current density was mea-
NaCl 24.53 sured for 7 days. At the end of the test, the corrosion products on
MgCl2 5.20 the carbon steel surface were removed and cleaned for 10 min in
Na2SO4 4.09 the cleaning solution containing 500 ml HCl, 3.5 g hexamethyle-
CaCl2 1.16
netetramine (C6H12N4) and distilled water to make 1000 ml. The
KCl 0.695
NaHCO3 0.201 specimens were then rinsed in distilled water and weighed to
KBr 0.101 10
4 g for weight-loss measurements.
H3BO3 0.027
SrCl2 0.025 2.3. X-ray diffraction analysis
NaF 0.003

The corrosion products on the carbon steel surface formed after

velocity than previous studies in seawater and determined the
appropriate cathodic protection potential. Additionally, electro-
chemical impedance spectroscopy, weight loss tests were con-
ducted for the reliability of cathodic protection and the oxide film
state was investigated by surface analyses. Finally, to confirm the
determined cathodic protection criteria, the numerical simulation
of real ship model was carried out.
2. Experimental procedures
2.1. Materials and test condition
The chemical composition of the ship hull steel used for the
experiment is listed in Table 1. The dimensions of the rotating
cylinder electrode (RCE) were 30 mm in diameter, 52 mm in
length and 3 mm in thickness, as shown in Fig. 1. For the elec-
trochemical test, the specimen was abraded with 600-grit silicon
carbide (SiC) paper, rinsed ultrasonically with ethanol and finally
dried with air. The preparation process for all specimens was
completed within 10 min before the subsequent corrosion tests to
obtain an identical condition of surface oxide film. The flow
velocity of the synthetic seawater was controlled at 0, 2 and 5 m/s,
the 7-day weight-loss tests were characterized by X-ray diffraction
(XRD). Bulk XRD patterns were taken on Burker D8 Advance with a
Ni-filtered Cu-Kα radiation operated at 18 kW and the scanning
speed was 2°/min.
2.4. Computer modeling for cathodic protection
A 3D theoretical simulation was introduced to analyze the effect of
flow velocity on the cathodic protection of ship structure. The simu-
lation was accomplished by BEASY software based on the boundary
element method and 3D ship structure model was used. The polar-
ization curves of uncoated steel under different flow conditions were
set as the boundary condition of ship hull with the length of 115 m.
The impressed current for cathodic protection system included three
electrodes and the input current of 150 A and the solution con-
ductivity was set to common seawater conductivity of 3.75 S/m.
3. Result and discussion
3.1. Potentiodynamic polarization tests
Fig. 3 shows the polarization curves of uncoated ship hull steel
as a function of flow velocity in synthetic seawater. All of the
 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158 151

Working electrode

Reference electrode

Counter electrode

Luggin
27 mm
probe
30 mm

5 mm

Specimen
Teflon

Fig. 2. Schematic diagram of RCE system and specimen geometry.

polarization curves exhibited active corrosion behavior in syn-

0.0 thetic seawater. Also, the polarization curves were shifted to right
0 m/s direction with the increase of flow velocity.
2 m/s
Table 3 summarized the potentiodynamic polarization data.
-0.2 5 m/s
Corrosion rate can be inferred from the corrosion current density
Potential ( VSCE )

(icorr) based on Faraday's law:

-0.4
3:16  108  icorr  M
Corrosion rate ðmm=yrÞ ¼ ` ð1Þ
zF ρ
-0.6
where icorr is the corrosion current density (A/cm2), M is the molar
mass of the metal (g/mol), z is the number of electrons transferred
-0.8 per metal atom, F is Faraday's constant, and ρ is the density of the
metal (g/cm3) (Jones, 1996). As listed in Table 3, the corrosion rate
is increased with the increase of flow velocities. This result is
-1.0
10
-7
10
-6
10
-5
10
-4 -3
10
-2
10 10
-1 generally considered due to the increase of cathodic reaction rate.
2 The cathodic reaction in aerated seawater solution is the reduction
Current density ( A/cm ) of dissolved oxygen as the following (Begum and Basha, 2010):
Fig. 3. Polarization curves of carbon steel as a function of the flow velocity in the
synthetic seawater at 25 °C.
O2 þ2H2O þ4e
-4OH
(2)

The rate of reaction can be determined by oxygen (O2) con-

centration in solution. At high rates, the cathodic reaction is lim-
Table 3 ited due to the limited diffusion rate of O2 in solution and the
Electrochemical parameters of potentiodynamic polarization tests as a function of limited cathodic reaction is indicated as a limiting current density
flow velocity in synthetic seawater at 25 °C. (iL) which is the current density in vertical part of cathodic
polarization curve. The limiting current density can be calculated
Flow Ecorr Ecorr icorr (A/ iL (A/cm2) βa βc Corrosion
velocity (mV (mV cm2) (mV/ (mV/ rate (mm/
by the following equation (Evans, 1969):
(m/s) versus versus dec.) dec.) yr) Doxy nFC B
SCE) Ag/ iL ¼ ð3Þ
AgCl)
δ
where n is the number of equivalents exchanged, F is the Faraday's
0
705
686 1.79  10
5 2.91  10
5 75.2 711.8 0.208 constant, Doxy is the diffusivity of O2, CB is the O2 concentration of
2
555
536 2.46  10
4 4.27  10
4 134.2 702.6 2.867
5
508
489 8.49  10
4 9.21  10
4 191.3 672.5 9.892
the uniform bulk solution and δ is the thickness of the con-
centration gradient in solution. As listed in Table 3, the limiting
152 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158

Concentration of oxygen

Distance
Fig. 4. Schematic of concentration profile of O2 in solution near the steel surface
with and without flow velocity.

current density was increased with the increase of flow velocity. It

is implied that the oxygen concentration on the steel surface is
increased with the increase of flow velocity. The oxygen con-
centration profile with and without flow on the surface is illu-
strated in Fig. 4. In Eq. (3), the other parameters are the same
regardless of flow velocity, except for δ. Therefore, the increase of
limiting current density is related to the decrease of thickness of
the concentration gradient as shown in Fig. 4. The increase of
concentration gradient caused the increase of oxygen concentra-
tions on the steel surface so that the kinetics of oxygen reduction
reaction increased.
Fig. 5 shows the calculated applied current density (iapp), ano-
dic current density (ia) and anodic Tafel slope (βa) for carbon steel
at the potential of
800 mV versus SCE (
781 mV versus Ag/AgCl)
as a function of the flow velocity in synthetic seawater at 25 °C.
Table 4 summarized the calculated electrochemical parameters of
the carbon steel at the potential of
800 mV versus SCE
(
781 mV versus Ag/AgCl) as a function of the flow velocity. It
indicated that the applied current density, anodic Tafel slope and
anodic current density increased with the increase of flow velocity.
At the flow velocities of 2 m/s and 5 m/s, the corrosion rates of
carbon steel at the potential of
800 mV versus SCE (
781 mV
versus Ag/AgCl) were not satisfied with the corrosion rate of
cathodic protection criteria (less than 0.0254 mm/yr).
Fig. 6 represent the measured cathodic protection potential
which satisfied the corrosion rate of cathodic protection criteria for
the carbon steel under different flow velocities. Anodic Tafel slope
determines the corrosion rate at each applied potential and pro-
vides the cathodic protection potential criteria which satisfied the
current density of 2.1810
6 A/cm2 (¼ 0.0254 mm/yr) at the flow
velocities of 2 m/s and 5 m/s. It indicated that the values of mea-
sured potential under the flow condition were lower than that of Fig. 5. Calculated applied current density (iapp), anodic current density (ia) and
anodic Tafel slop from polarization curves for carbon steel at
800 mV versus SCE
the NACE-recommended criteria (
800 mV versus SCE,
781 mV
(
781 mV versus Ag/AgCl) as a function of the flow velocity in the synthetic sea-
versus Ag/AgCl). Fig. 7 shows the cathodic potentials to satisfy the water at 25 °C: (a) 0 m/s, (b) 2 m/s, and (c) 5 m/s.
corrosion rate less than 0.0254 mm/yr at each flow velocity, hence
the cathodic protection was obtained satisfactorily at
836 mV
versus SCE (
817 mV versus Ag/AgCl, 2 m/s),
906 mV versus SCE
(
887 mV versus Ag/AgCl, 5 m/s), respectively.
Table 4
3.2. Electrochemical impedance spectroscopy (EIS) Calculated electrochemical parameters from potentiodynamic polarization curves
under
800 mV versus SCE (
781 mV versus Ag/AgCl) as a function of flow velo-
city in synthetic seawater at 25 °C.
Fig. 8 shows the Nyquist plots obtained for the carbon steel
with the flow velocity and the applied cathodic protection Flow velocity (m/s) iapp (A/cm2) ia (A/cm2) Corrosion rate (mm/yr)
potential in synthetic seawater at 25 °C. All of the plots indicated

5
7
the depressed semicircles and the capacitive can be related to the 0 2.26  10 8.31  10 0.009
2 4.86  10
4 4.31  10
6 0.050
charge transfer reaction and electrical double layer formed on the 5 1.15  10
3 9.17  10
5 1.068
carbon steel surface (Ahamed et al., 2010). Fig. 9 shows the
 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158 153

-0.2

-0.4
Potential ( VSCE )

-0.6

-0.8

-1.0

-1.2
-8 -7 -6 -5 -4 -3 -2 -1
10 10 10 10 10 10 10 10
2
Current density ( A/cm )
Fig. 6. Anodic Tafel slope and measured cathodic potential criteria at each flow
velocity.

NACE criterion
-0.75 Measured criteria

-800
-0.80
Potential ( VSCE )

-0.85
-836

-0.90
-906

-0.95

-1.00
0 2 5
Flow velocity (m/s)
Fig. 7. Effect of flow velocity on the potential for cathodic protection.

equivalent circuit containing two relaxation time constants, which

is used to show the formation of oxide film on the metal surface
(Nam et al., 2014; Lee et al., 2013; Kim et al., 2013). The equivalent
circuit in Fig. 9 consists of the following elements: Rs is the solu-
tion resistance, Rfilm is the electrical film resistance from the for-
mation of an ionic conduction path through pores in the oxide
film, Cfilm (CPE1) is the film capacitance generated by the dielectric
properties of the film, Rct is the charge transfer resistance from the
Fig. 8. Nyquist plots for carbon steel in synthetic seawater at 25 °C at (a) 0 m/s flow
metal dissolution, Cdl (CPE2) is the double-layer capacitance gen-
velocity under OCP,
800 mV versus SCE (
781 mV versus Ag/AgCl), (b) 2 m/s and
erated by the electric double layer capacitance at the water/sub- (c) 5 m/s flow velocities under Ecorr,
800 mV versus SCE (
781 mV versus Ag/
strate interface. The constant phase element (CPE) has been used AgCl) and
900 mV versus SCE (
881 mV versus Ag/AgCl).
in the equivalent circuit instead of the pure capacitor to get more
accurate fit (Cottis and Turgoose, 1999). The impedance CPE is Mansfeld, 2001):
expressed as:
n
1
C ¼ Y 0 2π f max ð5Þ
1
Z CPE ¼ ð4Þ where fmax is the frequency at which the imaginary component of
Y0 ðjωÞ
n

where Y0 is the magnitude of the CPE, j is the imaginary number

effect of flow velocity and cathodic potential on the parameters
(j2 ¼
1), α is the phase angle of the CPE and n ¼ α= π =2 . The
parameter n usually lies between 0.50 and 1.0 and the CPE
describes an ideal capacitor when n ¼ 1, which measures the
deviation from the ideal capacitive behavior (Bentiss et al., 2009;
Lopez and Simison, 2003).
Table 5 summarized the impedance parameters of carbon steel
under different potentials as a function of the flow velocities in
synthetic seawater at 25 °C. The CPE is converted into the capa-
citance (C) by using the following conversion equation (Hsu and
the impedance reaches the maximum value. The Fig. 10 shows the
related to the film properties (Rfilm, Cfilm), Rct and Cdl.
In Fig. 10(a), Rfilm is decreased with the increase of flow velocity,
indicating that the resistance of oxide film to the corrosion
decreases due to the increase of cathodic reaction. This tendency is
similar to Rct shown in Fig. 10(c). However, in case of the cathodic
potential, these two resistance values (Rfilm, Rct) have different
tendency. The Rfilm is decreased with the increase of cathodic
protection potential. When the cathodic potential is applied, the
anodic reaction on the surface is suppressed. The oxide film is
154 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158

formed from the reaction of dissolved metal ion and hydroxide or
oxide in the electrolyte. Therefore, the obstruction of anodic dis-
solution by cathodic potential decreases the formation of oxide
film, which caused the decrease of Rfilm. The Rct is increased with
the increase of cathodic potential as shown in Fig. 10(c). The result
is well matched with the cathodic protection theory mentioned in
Evan's diagram, i.e., the increase of cathodic potential increases the
corrosion resistance.
The capacitance related to oxide film (Cfilm) and Helmholtz
electrical double layer (EDL) (Cdl) between water/substrate can be
indicated as the following equation (Hassan, 2006; Baraillon and
Brunet, 1994).
εε0 A
C¼
d dielectric constant and then decreases the Cdl, consequently.
where ε is the dielectric constant of the oxide film or EDL, ε0 the
vacuum permittivity, A is the effective surface area of electrode
and d is the thickness of the iron oxide film or EDL (Wang et al.,
2006). In Fig. 10(b), the Cfilm is decreased with the increase of flow
velocity at Ecorr. Although the Rfilm is decreased with the increase of
flow velocity, the Cfilm is decreased, implying that the thickness of
oxide film is increased. Also, the parameter n of the Cfilm is
increased with the increase of flow velocity at Ecorr. The n indicates
various surface conditions such as roughness, heterogeneity,
inhibitor adsorption or porous layer (Li et al., 2011). Thus, the
oxide film not only increased the thickness but also formed new
CPE1
Rs
RE CPE2
WE
CE
Rfilm
Rct
Oxide film Substrate
Fig. 9. Equivalent circuit for fitting the EIS result of carbon steel under the different
flow velocities in synthetic tap water at 25 °C (WE: working electrode, CE: counter
electrode, RE: reference electrode).
oxide layer with the increase of flow velocity. On the other hands,
the Cfilm is increased with the increase of cathodic potential. This is
also due to the obstruction of anodic dissolution, which is related
to the decrease of Rfilm. The decrease of oxide film formation
causes the decrease of oxide film thickness, which results in the
decrease of Cfilm. The Cdl decreases with the increase of flow
velocity and cathodic potential as shown in Fig. 10(d). The cathodic
reaction (2) is increased in both cases (the increase of flow velocity
and cathodic potential), meaning that the water molecules in
reaction (2) and other ions are more adsorbed on the metal surface
due to the increase of diffusion by the flow velocity and electrical
charged surface which attracts water molecules by the cathodic
polarization. It increases the thickness of the EDL and changes the
ð6Þ
The corrosion current density in Table 5 was calculated by the
Tafel extrapolation method as the following equation (Mansfeld,
2005):
βa  βc
icorr ¼ ð7Þ
2:3  Rtotal  ðβa þ βc Þ
where Rtotal is the sum of Rfilm and Rct, βa and βc are the anodic and
cathodic Tafel slope, respectively. The corrosion rate was calcu-
lated by Eq. (1). In all cases of E, the βa and βc obtained from the
potentiodynamic polarization results for accurate calculation. The
corrosion rate calculated by obtained Tafel slopes is well correlated
with the potentiodynamic polarization results. However, under
the applied cathodic potential, the Tafel slopes cannot be obtained.
Therefore, the approximate value (βa ¼ βc ¼100 mV/dec.) from the
Stern and Weisert (1959) was used.
The corrosion rate under the stationary condition is 0.018 mm/
yr at the potential of
800 mV versus SCE. It indicated that the
cathodic protection potential criteria are almost sufficient to
satisfy the corrosion rate criteria (0.0254 mm/yr). Under the flow
condition, the corrosion rate of carbon steel (0.093 and 0.135 mm/
yr under 2 m/s and 5 m/s, respectively) did not sufficiently satisfy
the criteria at the cathodic protection potential of
800 mV versus
SCE (
781 mV versus Ag/AgCl). These results are in good agree-
ment with the potentiodynamic polarization results to determine
the adequate cathodic protection potential. The more negative
potential (
900 mV versus SCE,
881 mV versus Ag/AgCl) was
applied to the specimen under the flow condition in the synthetic
seawater. As listed in Table 5, the corrosion rates of carbon steel at
the applied potential of
900 mV versus SCE (
881 mV versus Ag/
AgCl) were 0.022 mm/yr and 0.028 mm/yr at the flow velocities of
2 m/s and 5 m/s, respectively. These corrosion rates almost satis-
fied the corrosion rate criteria. It meant that under the flow con-
dition more negative cathodic protection potential is required so
that the criteria of cathodic protection potential should be changed
according to the flow velocity.

Table 5
Impedance parameters for carbon steel under different potentials as a function of flow velocity in synthetic seawater at 25 °C.

Flow velo- Potential Potential (mV Rs (Ω cm2) Rfilm n Cfilm (μF/ Rct (Ω cm2) n Cdl (μF/cm2) Rtotal icorr (A/cm2) Corrosion
city (m/s) (mV versus versus Ag/ (Ω cm2) cm2) ¼ Rfilm þ Rct rate (mm/yr)
SCE) AgCl) (Ω cm2)

0 Ecorr 5.43 260.9 0.725 87.91 1505 0.661 37,250 1765.9 1.67  10
5 0.194

800
781 5.29 222.4 0.705 226.7 13,270 0.662 660.5 13,492 1.61  10
6 0.018
2 Ecorr 6.05 136.4 0.708 76.3 57.47 0.669 25,530 193.87 2.52  10
4 2.931

800
781 6.44 112.3 0.682 642.8 2578 0.659 19,550 2690.3 8.08  10
6 0.093

900
881 5.65 93.47 0.644 988 11,254 0.619 453.4 11,347 1.90  10
6 0.022
5 Ecorr 4.38 72.35 0.972 27.37 18.2 0.678 3818 90.5 8.46  10
4 9.819

800
781 5.25 65.25 0.865 856.2 3292 0.612 1223.43 1860.2 1.17  10
5 0.135

900
881 3.89 22.21 0.734 1325.2 9132 0.654 11.2 9154.2 2.37  10
6 0.028
 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158 155

Fig. 10. Effect of flow velocity and cathodic potential on film resistance/capacitance and charge transfer resistance and double layer capacitance in synthetic seawater at
25 °C: (a) Rfilm, (b) Cfilm, (c) Rct, and (d) Cdl.

2.5
Corrosion Rate (mm/yr)

2.0
(c)
M, F
1.5 M
HH M A M
AM
intensity (a.u.)

0.5 F

0.0 M, F
0 2 5 (b)
A M A
Flow velocity (m/s)
Fig. 11. Measured corrosion rates of carbon steel by weight loss at Ecorr and

800 mV versus SCE (
781 mV versus Ag/AgCl) as a function of flow velocity in
F
synthetic seawater at 25 ˚C.

3.3. Weight loss measurements

(a)
A F
Fig. 11 shows the corrosion rate of carbon steel determined by
weight loss with and without the applied cathodic protection
30 40 50 60 70
potential (
800 mV versus SCE,
781 mV versus Ag/AgCl) as a
2 theta (degree)
function of flow velocity for 7 days immersion in the synthetic
seawater at 25 °C. At the potential of
800 mV versus SCE Fig. 12. XRD Patterns of each specimen immersed in synthetic seawater for 7 days
at the different velocities: (a) 0 m/s, (b) 2 m/s and (c) 5 m/s. A-akaganeite
(
781 mV versus Ag/AgCl), satisfactory protection could not be
(β-FeOOH), M-magnetite (Fe3O4), H-maghemite (γ-Fe2O3) and F-iron (Fe).
obtained under the flow condition. The corrosion rates at the flow
velocities of 2 m/s (0.063 mm/yr) and 5 m/s (0.127 mm/yr) did not 3.4. Surface analyses
satisfy the cathodic protection criteria. These results indicated that
the cathodic protection criteria should be changed under the flow Fig. 12 shows the XRD patterns of corrosion products on the
condition as mentioned above. steel surface as a function of flow velocity in the synthetic
156 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158
1. FeOOH formation
OH
OH -
OH-
-
Fig. 13. Schematic formation mechanism of oxide product.
Potential
log i
Fig. 14. Variation of E versus log i as a function of flow velocity for carbon steel.
seawater at 25 ˚C. Patterns at the flow velocity of 0 m/s possessed
α-Fe and akaganeite (β-FeOOH) diffraction peak. The β-FeOOH
rust is formed in Cl
containing environment such as seawater
(Keller, 1969) so that the β-FeOOH peak is detected in all condi-
tions. The Fe3O4 diffraction peaks were firstly appeared at the flow
velocity of 2 m/s. At the flow velocity of 5 m/s, the number of
Fe3O4 diffraction peaks and peak intensities increased and
maghemite (γ-Fe2O3) peaks were appeared. The XRD result reveals
that the flow velocity affected the formation of Fe3O4 on the car-
bon steel surface in the synthetic seawater at 25 °C.
By Fick's first law, carbon steel can have high oxygen con-
centration at the carbon steel surface with increasing flow velocity
as shown in potentiodynamic polarization tests. The rate of reac-
tion (2) increases due to the high oxygen concentration at the steel
surface with the increase of flow velocity, hence the OH
con-
centration at the steel surface increases. The anodic reaction is the
dissolution of steel in seawater as the following reaction:
Fe-Fe2 þ þ 2e

The total rate of anodic reactions must be equal to the total rate
of cathodic reactions, hence the rate of reaction (8) increases with
the increasing rate of reaction (2). In short, by the increase of
anodic and cathodic reactions, the Fe2 þ and OH
concentration at
the steel surface increases. The increase of Fe2 þ and OH
con-
centration has an effect on the formation of Fe3O4 by oxidation of
iron and reduction of FeOOH.
First, the oxidation of steel in alkali solutions occurs as the
following reactions (Evans and Taylor, 1972):
Fe þOH
2FeOHads þe

2. Reduction of FeOOH 3. Fe3O4 formation
FeOOH
Fe3O4
F e 2+
F e 2+
steel sustrate
þ
FeOHads2FeOHads þ e
(10)
þ
FeOHads þOH
2Fe(OH)2 (11)
Fe(OH)2 þOH
-FeOOH þH2Oþ e
(12)
Therefore, the increase of OH
concentration at the steel sur-
face makes reactions (9), (10), (11) and (12) more active so that the
more FeOOH can be produced.
Second, this FeOOH transforms to Fe3O4 by reduction reaction
with Fe2 þ as the following reactions (Cornell and Schwertmann,
2003; Stratmann and Hoffman, 1989, 1983; Marsh, 1966).
3FeOOHþ H þ þe
-Fe3O4 þH2O (13)
2FeOOHþ Fe2 þ -Fe3O4 þ 2H þ (14)
Fe2 þ þ8FeOOHþ2e
-Fe3O4 þ H2O (15)
Therefore, the increase of Fe2 þ concentration at the steel sur-
face activated the formation reaction of Fe3O4 Briefly, Fe2 þ and
OH
concentration at the steel surface increases with the increase
of flow velocity, which activates Fe3O4 formation. These series of
formation reaction is illustrated in Fig. 13.
Fe3O4 is well known as the compound which protects the
substrate by forming thin film layer (Tanaka et al., 2014). Thus, the
increase of oxygen concentration due to the flow velocity activates
the formation of Fe3O4 and makes the anodic reaction rate of
carbon steel lower. It is considered that not only the anodic
reaction rate but also the cathodic reaction rate affects the corro-
sion rate. Although the anodic reaction decreased and βa increased
with the flow velocity, the corrosion rate of carbon steel increased
as shown in Fig. 14 because the flow condition had a major effect
on the corrosion rate.
3.5. Computer simulation
(8) Fig. 15 shows the BEASY simulation results which show the
potential distribution at the applied current of 150 A as a function
of flow velocity. At the flow velocity of 0 m/s, the potential was

795 mV versus SCE (
776 mV versus Ag/AgCl) and it was almost
appropriate for the cathodic protection criteria of
800 mV versus
SCE (
781 mV versus Ag/AgCl). However, at the flow velocities of
2 m/s and 5 m/s, the potentials were
571 mV versus SCE
(
552 mV versus Ag/AgCl) and
511 mV versus SCE (
492 mV
versus Ag/AgCl), respectively as given in Table 6. Both potentials
were not satisfied with the cathodic protection potential criteria.
Thus, when the ship is on a voyage or the berth, the impressed
(9) current for cathodic protection of the ship should be changed.
 J.-H. Kim et al. / Ocean Engineering 115 (2016) 149–158
0.5
0.0
Potential (V vs. SCE)
-0.5
-1.0
-1.5
-2.0
-2.5
0 10 20 30 40 50 60
Distance (m)
Fig. 15. Potential distribution of the ship structure model for the cathodic protection under different flow velocities.
Table 6
Cathodic potential results at impressed 150 A current under different flow
velocities.
Flow velocity (m/s) Potential (mV versus SCE) Potential (mV versus Ag/AgCl)
0
795
776
2
571
552
5
511
492
4. Conclusion
Based on laboratory experiments to investigate the effect of
flow velocity on the cathodic protection criteria of carbon steel in
the synthetic seawater, the following conclusions were drawn:
(1) From potentiodynamic polarization, EIS, weight loss and
computer simulation results, it was confirmed that sufficient
protection could not be obtained under the flow condition at
the protection potential of
800 mV versus SCE (
781 mV
versus Ag/AgCl).
(2) The cathodic protection potential obtained by anodic Tafel line
was shifted to more negative value under the flow condition.
The result had a good correlation with potentiostatic EIS
results.
(3) Under the flow condition, the magnetite (Fe3O4) was formed
due to the increase of oxygen reduction reaction at the surface,
which affected the cathodic protection criteria.
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