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Interpretation of Cyclic Potentiodynamic Polarization Test Results for Study of

Corrosion Behavior of Metals: A Review

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DOI: 10.1134/S207020511805026X

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ISSN 2070-2051, Protection of Metals and Physical Chemistry of Surfaces, 2018, Vol. 54, No. 5, pp. 976–989. © Pleiades Publishing, Ltd., 2018.

INVESTIGATION METHODS
FOR PHYSICOCHEMICAL SYSTEMS

Interpretation of Cyclic Potentiodynamic Polarization Test Results

for Study of Corrosion Behavior of Metals: A Review1
S. Esmailzadeha, M. Aliofkhazraeia, *, **, and H. Sarlakb
aDepartmentof Materials Engineering, Tarbiat Modares University, Tehran, P.O. Box: 14115-143 Iran
b
Department of Materials Engineering, Isfahan University of Technology, Isfahan, 84156-83111 Iran
*e-mail: maliofkh@gmail.com
**e-mail: khazraei@modares.ac.ir
Received June 22, 2017

Abstract—The cyclic potentiodynamic polarization technique is a method for evaluating the susceptibility of
a metal to localized corrosion such as pitting and crevice corrosion. This paper provides the information to
conduct the cyclic polarization test correctly and to help performing the interpretation of the polarization
scan properly. The effect of critical parameters including solution resistivity, scan rate, point of scan reversal,
aggressive ions, corrosion inhibitors, metastable pits, metallurgical variables, temperature, dissolution gases,
pH, immersion duration and surface roughness on the cyclic polarization curve and results interpretation are
discussed. Then a number of cyclic potentiodynamic polarization curves for common metals and alloys in
prevalent environments are given.

Keywords: Cyclic potentiodynamic polarization, Corrosion, Corrosion inhibitor, Localized corrosion, Pit-
ting corrosion, Protective surface film, Scan rate
DOI: 10.1134/S207020511805026X

1. INTRODUCTION putting the passivized metal in a solution containing

Corrosion as a natural phenomenon is the material
destructive reaction with its surrounding environment.
During the past years, it has caused irreparable dam-
ages for human life [1]. Human safety, economic costs
and conservation of materials have been the most
important reasons to control corrosion [1, 2]. The use
of corrosion inhibitors [3–6], cathodic protection [7–
9], different types of coatings on the surface [10–13],
alloying elements and additives [11, 14] are a number
of methods for controlling corrosion. In addition to
these methods, passivity is a property of some metals
or alloys, which are thermodynamically unstable, and
react inherently with environment (water or oxygen)
and form a stable passive oxide film on the material
surface. The metal surface is protected against the
atmosphere by the passive layer [15]. Thickness of pas-
sive films varies in a wide range. For metals such as
(Fe, Cr, Co, Ni, Mo) and their alloys it is tens to hun-
dreds of angstroms while the thickness of passive film
for the other metals (Zn, Cd, Mg, Cu, Pb) could be in
micro meter range. In the case of aluminum, the
thickness of oxide film changes from nano meter size
(air form film) to much thicker (anodized film) [2].
The protective oxide film could be destroyed by elec-
trochemical and mechanical methods. For example,
1 The article was translated by the authors.
the aggressive ions is a common degrading condition.
Localized corrosion (pitting corrosion, crevice corro-
sion and stress corrosion cracking) can occur by
breakdown of the passive film in the presence of
aggressive ions. Electrochemical investigation of pas-
sivity is used to evaluate the materials resistance to
localized corrosion. Studying the material polariza-
tion treatment by polarization techniques specially
cyclic potentiodynamic polarization (CPDP) tech-
nique is a suitable way for investigation of the begin-
ning of passivity, breakdown of oxide film, susceptibil-
ity to repassivation and calculation of the rate of pit-
ting corrosion due to the vast range of scanning
potential [2, 16, 17]. Although the CPDP test is a rapid
and reasonable method, it is not possible to interpret
all kinds of CPDP curves. Therefore, the aim of this
review is to study the CPDP technique and more
accurate interpretation of its results in order to predict
materials corrosion behavior appropriately.
2. CYCLIC POTENTIODYNAMIC
POLARIZATION
CPDP test was introduced for the first time in the
1960s. It is widely used to determine resistance to
localized corrosion or degradation rate in a short time
[18, 19]. Thus this technique is applicable as a method

976
 INTERPRETATION OF CYCLIC POTENTIODYNAMIC
(a)
2H2O
Potential
Ef
Ecorr
Log (Current Density)
Fig. 1. Schematic illustration of, (a) CPDP curve of a susceptible material to pitting corrosion, (b) potential-time curve during
CPDP test.
for prediction of localized corrosion also beneficial for
alloys that are passivized spontaneously and under-
went localized corrosion [19].
General shape of CPDP curve is as follows; after
passing through the region of active corrosion, the
current density decreases to a critical potential, called
the “Flade potential” or “primary passivation poten-
tial”. This decrease is due to the formation of the pas-
sive layer on metal surface.
The passive current density is the current density in
the passive region. With further increase in the poten-
tial in the passive region, a rapid rise in the anodic cur-
rent can be detected. This rise is due to either the evo-
lution of oxygen by the decomposition of water or
breaking the passive film and localized corrosion. If
the increase of current density is due to the decompo-
sition of water and evolution of oxygen gas, the region
is called “transpassive region” (Fig. 1a) [2].
2H2O = O2 + 4H++ 4e−,
(1)
E = 1.228 − 0.0591 pH (T = 25C, PO2 = 1 atm)
Observation of the transpassive region occurs at
different potentials for various materials. For instance
E for copper in 1 N H2SO4 is about 1800 mV (SHE)
and for stainless steel 304 in 1N H2SO4 is 1200 mV
(SHE) approximately. For Some materials such as
titanium, the range of passivation is very wide. This
behavior is due to the high ohmic resistance of protec-
tive film (TiO2). However, this film is unstable in the
presence of chloride ions and it may be destroyed [20].
The reason of increase in anodic current density at the
potential below the oxygen evolution potential is the
initiation of pitting and occurrence of localized corro-
sion (Epit). In order to compare the resistance of differ-
ent samples, the current density at which scanning
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
977
(b)
+
O2+4H +4e
Potential
Time
direction is reversed should be constant in various
experiments. According to the ASTM standards, this
current density is called as threshold current density
(it) and is about 5 mA/cm2 or 2 times (decades) more
than the passive current density. The vertex potential is
the potential at which the scan direction is reversed
(Eν). The direction of scanning potential is reversed
toward potentials that are more active (Fig. 1b) [16, 21,
22]. The test is performed by the defined instructions
by ASTM standards in this field [2].
In order to assess the corrosion susceptibility of
small implant devices and localized corrosion suscep-
tibility of iron, nickel, or cobalt-based alloys CPDP
measurements should be carried out according to the
defined ASTM standards (F2129, G61) [21, 23].
Implant devices made of metals with high corrosion
resistance are used instead of organs and damaged tis-
sues in body. Thus, it is needed to determine their cor-
rosion behavior and susceptibility to localized corro-
sion. The following section describes the general pro-
cedure of the test that is the same in two standards, but
for more information about preparation of the speci-
mens and more details of conducting the test such as
corrosive solution, pH and temperature, it should be
referred to the references [21] and [23]. After the
preparation of the test specimen according to the stan-
dards, for stabilizing the rest potential Er (the potential
of working electrode to the reference electrode under
the open circuit condition (OCP)), the specimen is
immersed in a prepared electrolyte (according to the
standard) Before that, it should be purged sufficiently
(minimum of 1h) with a gas for removing oxygen
(according to the standards). The specimen is
immersed until the OCP variation rate is less than
3 mV/min. Then the potential scan starts at the OCP
and moves in the more noble direction in a cyclic path
Vol. 54 No. 5 2018
978
(a)
Epit Eb
Potential
Erep
Potential
Ef
Ecorr Ecorr
Log (Current Density)
Fig. 2. Schematic illustration of CPDP tests for three different conditions, (a) exhibiting protection potential, (b) with oxygen
evolution, (c) without protection potential.
with a slow scan rate (0.6 V/h ≈ 1.66 mV/s (±5%)
between the working electrode and auxiliary elec-
trode. Finally, the scanning potential direction is
reversed to the starting point. Along with the continu-
ous scanning potential, the current response is moni-
tored. According to ASTM F2129 standard, there are
three different states: the scanning potential continues
until the hysteresis loop is completed indicating repas-
sivation (Fig. 2a) or oxygen evolution occurs and the
anodic to cathodic transition potential is reached
(Fig. 2b) or the hysteresis loop is not completed and
corrosion potential is reached (Fig. 2c). According to
ASTM G61 standard, the reverse scan continues until
the hysteresis loop is completed or the corrosion
potential is reached [21, 23].
The interpretation of the CPDP scan is difficult.
The extracted parameters from the cyclic curves are
not constant for each material. They are empirical
parameters and change in different experimental con-
ditions. The parameters used to interpret the CPDP
curves include: pitting potential, repassivation or pro-
tection potential, potential of anodic to cathodic tran-
sition, hysteresis and active passive transition (anodic
nose). The first three potentials are based on the dif-
ference of corrosion potential [19]. In the CPDP test,
relative position of pitting potential and repassivation
potential or protective potential with respect to the
corrosion potential are the most important parameters
for evaluating the pitting corrosion behavior [24].
2.1. Pitting Potential
In the anodic polarization scan, scanning starts
from corrosion potential after reaching the steady
state. Before reaching the potential of oxygen evolu-
tion, a rapid increase in the current density may occur.
Two reasons have been mentioned for this increase. If
the surface of oxide is not perfect, for example, some
defects exist on the film; the passive film will not be
stable over the passive region. At a potential below the
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
ESMAILZADEH et al.
(b) (c)
Epit
Hystersis Loop
Potential
Anodic to Cathodic
Ef Transition
Ecorr
Log (Current Density) Log (Current Density)
oxygen evolution potential, the surface defects will be
active and begin to propagate which can increase the
current density.
The other reason for the increase in the current
density earlier than the oxygen evolution could be the
breakdown of the oxide film and occurrence of the pit-
ting corrosion in the presence of aggressive ions. In the
absence of aggressive ions, the passive film will be sta-
ble over the electrode potential of O2 evolution.
The potential at which the current density increases
rapidly for either of two above reasons is given differ-
ent names: critical pitting corrosion, pitting corrosion,
breakdown potential or rupture potential [25–27].
Also in some studies, the numerical values of pitting
corrosion resistance, Rpit, have been calculated from
the equation: Rpit = |Ecorr – Epit| corresponding logi
versus E plot of Fig. 3 [28–30].
For some materials, the pitting potential coincides
with the corrosion potential, which occurs when there
is an oxide film on the material surface prior to the
polarization. Due to the intersection of cathodic
branch with the transpassive region of anodic branch,
the value of pitting potential is the same as corrosion
potential. The curve shown in Fig. 3 is related to the
CPDP of Al alloy after 24 h immersion in 3.5 wt %
NaCl. Due to the high activity of Al and formation of
an air-form oxide layer on its surface, the increase in
the current density at corrosion potential shows that
the values of the corrosion potential and pitting poten-
tial are the same [24, 31, 32].
2.2. Protective Potential
In the CPDP curve, for investigating the material
resistance to localized corrosion after increasing the
current density at pitting corrosion, the scanning
direction changes. Then with the potential reduction
toward the negative potentials, the current density in
the reverse scan will be higher than the current density
in the forward scan (positive hysteresis). The scanning
Vol. 54 No. 5 2018
 INTERPRETATION OF CYCLIC POTENTIODYNAMIC
Ecorr = Epit
Potential
Log (Current Density)
Fig. 3. Schematic illustration of CPDP of Al in 3.5 wt %
NaCl solution.
continues until the reverse curve crosses the forward
polarization curve. This intersection point is named
protection potential and it is introduced as a potential,
at which the anodic current density reaches the lowest
value on the reverse polarization scan [33, 34]. Repas-
sivation potential is the potential at which the growth
rate of pits is stopped. The amount of hysteresis or in
the other words, the difference between Epit – Erp indi-
cates the amount of localized corrosion. If the current
density in the reverse curve is more than the current
density in the forward scanning curve, it will be indic-
ative of pitting corrosion. Actually pitting is the major
form of corrosion in this condition [29, 35]. The resis-
tance of material to localized corrosion is evaluated on
the basis of the Erep measurement to the Ecorr. If Erep
lies in the more noble values than the Ecorr the propa-
gation of active pits is diminished or stopped. There-
fore, at the potentials between the protection potential
and corrosion potential, the passive film is stable and
no pits will initiate or grow. Also in this region crevice
corrosion and crack initiation and propagation will
not take place. This region is called perfect passivity.
At the potential between the pitting potential (Epit) and
protection potential (Erp), only old pits propagate and
no new pits nucleate (Fig. 4). If Ecorr lies between Epit
and Erep, the repassivation of pits will not take place
completely and preformed pits continue to grow and
propagate (Fig. 2c) [2, 19].
Pitting potential is the minimum potential at which
the material tends to the pitting corrosion. Above the pit-
ting potential, new pits will initiate and develop [29].
The difference between the Epit and Erp and also the
area of the hysteresis loop indicate the probability of
pitting corrosion. The more difference between the
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
979
Pitting initiates
and propagates
Epit
Hystersis Loop
Only prior pitting
propagate
Erep
Potential
Anodic to Cathodic
Transition
Pitting will not
initiate or
Ef propagate
Ecorr
Log (Current Density)
Fig. 4. Schematic illustration of CPDP curve and corro-
sion parameters. The arrows show the direction of polar-
ization.
Epit and Erp and the larger area of positive loop demon-
strate the probability of low pitting corrosion resis-
tance [2, 26, 36].
2.3. Hysteresis
The occurrence of hysteresis in the CPDP curve is
when the forward curve is not overlaid with the reverse
scanning curve. The difference between forward and
reverse current density at the same potential demon-
strates the size of hysteresis. The more difference
between the current densities is the result of disruption
of the surface passivity at high potentials. Thus the big-
ger size of hysteresis loop means more passive film dis-
ruption, following with more difficulty for restoring
the damaged passive film [37]. There are two types of
hysteresis at the more positive potentials: negative hys-
teresis happens when the degree of surface passivation
is greater at more noble potentials, which causes the
current densities in the reverse scan to be lower than
the current densities in the same potentials of forward
scan (Fig. 2b). Positive hysteresis is related to the
decrease of the passivity due to the localized corrosion
(pitting and crevice corrosion) that causes the increase
of the current density in reverse scan, in comparison to
the current density in the forward scan at the same
potential (Fig. 4). In the positive hysteresis, the direc-
tion of the current density changes toward the lower
current densities. Therefore, the slow decrease of cur-
rent density in the reverse scan in positive hysteresis is
indicative of the difficulty in surface repassivation or
stopping the growth of pits [2]. Sometimes in different
literatures, the definition of the type of hysteresis is
switched but in this paper, the meaning of positive and
Vol. 54 No. 5 2018
980 ESMAILZADEH et al.
Potential
Log (Current Density)
Fig. 5. Schematic illustration of CPDP curve with step
potential called pit transition potential (Eptp).
negative hysteresis is according to the above descrip-
tions.
The absence of hysteresis loop during the potential
scan (the forward curve coincides with the reverse
curve) means that the localized corrosion does not
occur but it could be a sign of an active surface and
general corrosion [37, 38]. Sometimes there is a
potential step in the positive hysteresis loop during the
reverse scan as shown in Fig. 5. It was proposed that
the potential step is called pit transition potential (Eptp)
at which the repassivation of small pits is completed
but deeper pits require a further drop of potential to
repassivation [24, 39]. In the positive hysteresis, at the
point of reversal potential, two types of behaviors can
be seen. Either the anodic current density is decreased
or increased as shown in Figs. 4 and 6 respectively.
Decrease of the current density immediately after
reversing scan is due to the reduce of the pits growth
rate which stops at repassivation potential while the
higher current is concerned to increase of the growth
rate of pits even after reverse of scan [28, 40].
2.4. Anodic to Cathodic Transition Potential
It is the potential at which the anodic current den-
sity varies to the cathodic current density. At the
reverse curve, the drastic decrease of the corrosion
current density at a potential called active-passive
transition potential (anodic nose) that is more noble
than Ecorr occurs for alloys that are susceptible to pas-
sive and restore the damaged oxide film (Fig. 4) or
the alloys that are not susceptible to pitting corrosion
(Fig. 2b). For these two groups of the alloys, the dif-
ference between the anodic to cathodic transition
potential and Ecorr are used to determine the per-
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
Epit
Hystersis Loop
Potential
Ecorr
Log (Current Density)
Fig. 6. Schematic illustration of CPDP curve with positive
hysteresis.
sistence of the passive film. According to the place of
anodic to cathodic transition potential relative to the
Ecorr, the passive layer stability is evaluated. If in the
reverse scan, the anodic to cathodic transition poten-
tial is more noble than Ecorr, the passive layer will not
be stable at Ecorr (Fig. 4), while the passivity will per-
sist, if Ecorr gets more noble than the anodic to
cathodic transition potential [19, 37]. For example,
the corrosion behavior of AZ91D and Mg–1.5Zn–
0.6Zr by CPDP curves after immersion in 5 wt %
NaCl solution saturated with Mg(OH)2 at 25°C for
30 min has shown that the breakdown potential or pit-
ting potential is obvious in the anodic polarization
curve of Mg–1.5Zn–0.6Zr whereas the point of
increasing in the current density (Ebd) is not obvious
for AZ91D. It can be said that the existence of a dense
and protective corrosion film on the surface of Mg–
1.5Zn–0.6Zr alloy is the reason of it. According to the
CPDP curves of alloys, for Mg–1.5Zn–0.6Zr the
anodic to cathodic transition potential on the reverse
scan is higher (more positive) than the corrosion
potential on the forward curve but for the AZ91D it is
opposite, anodic to cathodic transition potential is
lower (more negative) than the Ecorr on the forward
scanning curve. Therefore, for Mg–1.5Zn–0.6Zr, the
potential of the corroded areas is more positive than
the uncorroded area, leading them to act as the
cathodic areas and pitting corrosion is stopped while
for AZ91D the corroded areas as the anodic areas con-
tinue to corrode. Finally the result of this behavior is
the corrosion spread to the depth and formation of
deep pits for AZ91D but the corrosion spread to the
width and stopping the growth of pits for Mg–1.5Zn–
0.6Zr alloy [41].
Vol. 54 No. 5 2018
 INTERPRETATION OF CYCLIC POTENTIODYNAMIC
3. EFFECTIVE PARAMETERS
ON CPDP CURVE
In the following, the effect of critical parameters on
corrosion behavior and their effects on the interpreta-
tion of results have been brought.
3.1. Solution Resistivity
In an electrochemical cell, the arrangement of
electrodes in the cell must be in a way that voltage drop
between the working electrode and reference electrode
gets minimum value. The drop voltage is usually
resulted from the solution resistance, film resistance
on the surface and electrical resistance of electrodes
and leads. If the drop voltage is significant, it will
cause disruptions including: difference between the
effective potential (scan rate) on an alloy surface and
applied potential (scan rate) by potentiostat. By
increasing the current density, the created deviation in
voltage or scan rate increases. The increase of the solu-
tion resistance and following the increased voltage
drop affects the polarization scan by the change of
potentials and current densities. One of the effective
parameters on the voltage drop is electrolyte rotation
rate. For example, the CPDP of steel in the acetone
cyanohydrins showed that by increase the fluid rota-
tion rate, the primary passivation potential increases.
It means that in higher rotation rate and higher voltage
drop, the more noble potential for initiation of passiv-
ation is needed [19, 37].
3.2. Scan Rate
Scan rate is the value of potential that changes per
unit of time. If the surface defined as a simple resistor
(polarization resistance) and a capacitor (double layer
capacity) in parallel, the polarization scan rate should
be slow enough. Because in low scan rate the relation-
ship between current and voltage only reveals the cor-
rosion process at the interface of material surface with
the electrolyte for each potential. Otherwise the cur-
rent obtained from the polarization scan, not only
shows the value of current at the corrosion process but,
it includes the charge of surface capacitor. Therefore,
if the scan rate is not small enough, the current density
obtained from CPDP curve will be greater than the
current density derived from the corrosion reactions.
The methodology for choosing the lowest value of the
scan rate has been described previously [37]. It has
been suggested that the maximum permissible scan
rate at which the capacity is not considered is very low
for alloys susceptible to passivity [19, 37]. Also scan
rate is an effective parameter on the value of pitting
potential because pit nucleation and its propagation
are dependent on the amount of time at each potential
[2]. For example in the CPDP curve of Al alloy in
3.5 wt % NaCl solution at a scanning rate of 1 mV/s at
room temperature the pitting potential is absent. In
other words, at scanning rate of 1 mV/s, the potential
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
981
gap of the alloy is small and undistinguishable. There-
fore, the test should be carried out at a relative low
scan rate (less than 0.1 mV/s) to appear the pitting
potential in the curve [18]. The change of scan rate
from 0.2 mV/s to 5 mV/s did not show notable influ-
ence on the pitting potential of AA5083 aluminum
alloy, but the protective potential of the alloy shifted to
more negative potentials. The effect of scan rate is pre-
sented by a linear relationship between the protection
potential and scan rate,
E p = –0.921 – 0.013V , (2)
where V is the scanning rate [42].
3.3. Point of Scan Reversal
The image of polarization scan and the measure-
ment of the repassivation potential are depended on
the current density or potential at which the scan is
reversed. Scanning to high positive potentials causes
the surface to be exposed to more vulnerability. The
procedure used for polarization scan and choice of
maximum current density (potential) in the forward
scan, must be in accordance to the practical condi-
tions. The following example has been brought for bet-
ter understanding the effect of point of scan reversal.
Incoloy 825 (UNS NO8825) showed two different
corrosion behaviors in an atmosphere with low pH 1–
2. By changing the reverse point in CPDP scan, the
appearance of curve changed. At the high potential of
scan reversal a positive hysteresis loop was observed
that means the specimen has experienced the localized
corrosion. Furthermore, being the repassivation
potential more active than the corrosion potential was
indicative of non-restorable of the passive surface. But
there was no evidence of localized corrosion in prac-
tice. In the second CPDP test, the point of reversal
was chosen lower than the prior. In this condition a
negative hysteresis loop was generated. It means that
the localized corrosion does not occur on the surface
of the specimen and it confirmed the observations.
The reason of this behavior is because of an electro-
chemical transformation CrIII–CrVI at the potentials
above the 0.8–1.0 V (SCE). Thus in practical condi-
tions, as long as the specimen is not exposed to the
potentials above this rang, the passive film will not be
damaged [37]. The point of reversal scan is effective
not only on the repassivation potential and on behav-
ior of the reverse scan but its influence has been
observed on the corrosion parameters on the forward
scan. The CPDP scan of gold in deaerated 0.6 M NaCl
changed with the increase of the point of scan reversal
(vortex potential). The changes included the decrease
of corrosion potential on the forward scan and rise in
corrosion potential (anodic to cathodic transition) on
the reverse scan. The change of species activity such as
gold-oxygen complex has been proposed as the proba-
ble reasons [43]. Two parameters ΔE = Eν – Ecorr and
Vol. 54 No. 5 2018
982 ESMAILZADEH et al.
Potential
Ecorr
Log (Current Density)
Fig. 7. Schematic illustration of CPDP scan of Al alloy in
3.5 wt % NaCl at 1 mV/s.
ΔE' = Eν – Ecorr
' have been used for comparing the sta-
bility of the protective oxide layer in different condi-
tions, that Eν is the point of scan reversal (vortex
' are the corrosion poten-
potential) and Ecorr and Ecorr
tials in the forward scan and reverse scan respectively.
The greater amount of ΔE and ΔE' indicate of more
corrosion resistance [44].
3.4. Effect of Aggressive Ions
The presence of some ions such as chloride ions in
the electrolyte connected with a material has an
aggressive effect on durability of a passive film formed
on the material surface. The chloride ions cause the
material suffering from the localized corrosion by gen-
erating pits on the surface. The critical pitting poten-
tial reduces (shift to the active direction), as the chlo-
ride ions concentration increases in the solution and
conversely, as the solution containing chloride ions is
more dilute the value of the pitting potential will be
found at the high (more noble) potentials. For 304
stainless steel and aluminum, a linear relationship has
been found between the chloride ion concentration
and pitting potential [2, 45]. In addition, the change of
behavior of polarization scan for high chromium cast
irons (HCCLs) has been completely obvious by adding
of chloride ions to the 0.01 M NaOH. It includes, for-
mation of negative hysteresis in the absence of Cl–, the
observation of metastable pits in the SEM images after
adding 100 mg/L and occurrence of pitting corrosion
by creation of stable and irreparable pits in the pres-
ence of 500 mg/L and 1g/L [46].
In some cases the presence of chloride ions in the
solution only decreases the stability of passive film by
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
Epit
Potential
Log (Current Density)
Fig. 8. Schematic illustration of CPDP scan of Al alloy in
0.1 m/L NO2SO4 + 10 mmol/L NaCl at 1mV/s.
lowering the breakdown potential and does not cause
pitting corrosion [43]. In addition to Cl– ion, F– ions
and Br– decrease the pitting corrosion resistance by
shifting the pitting potential or protective potential to
the more active direction. For example, Epit (Erep) of
α-brass alloy has a linear relationship with the loga-
rithmic concentration of F– ions [47, 48]. One of the
effects of aggressive ions is prevention from the
appearance of localized corrosion parameters such as
Epit in the CPDP curve of a material. Figure 7 shows a
schematic figure of the CPDP curve of Al alloy in
3.5 wt % NaCl at scanning rate of 1 mV/s. As it can be
seen, although the pitting potential and rapid increase
in current density are absent in the curve, in the
reverse curve the anodic to cathodic point is more
active than the open circuit potential. Thus for
describing the corrosion behavior of the passive film,
it is required to increase the potential gap. In order to
increase the potential gap and appear the pitting
potential, a solution containing trace chloride ions
should be replaced instead of 3.5 wt % NaCl solution
Fig. 8 [18].
To evaluate the aggressive effect of chloride ions on
corrosion behavior of materials, the CPDP curves of
304 stainless steel and a duplex stainless steel in two
solutions, without and with chloride ions, for compar-
ison have been exhibited in Figs. 9 and 10 respectively
[49, 50].
3.5. Effect of Corrosion Inhibitor
One of the methods to prevent the localized corro-
sion is the addition of corrosion inhibitors to the elec-
trolyte. Corrosion inhibitors (anodic and cathodic)
increase the material resistance against corrosion by
Vol. 54 No. 5 2018
 INTERPRETATION OF CYCLIC POTENTIODYNAMIC 983

(a) (b)

Potential

Potential
Log (Current Density) Log (Current Density)

Fig. 9. Schematic illustration of CPDP scan of 304 stainless steel in (a) 3.5 wt % NaCl, (b) 1N H2SO4.

(a) (b)
Potential

Potential

Log (Current Density) Log (Current Density)

Fig. 10. Schematic illustration of CPDP scan of a duplex stainless steel in (a) 0.1 M H2SO4, (b) 0.1M H2SO4 + 0.1M NaCl.

different mechanisms. Therefore, it is expected that
the appearance of polarization scan will be under the
influence of corrosion inhibitors. In general, it can be
said that the addition of corrosion inhibitors increase
the critical pitting potential [34, 51–54]. For example
Na2SO4 as corrosion inhibitor in a 0.1 M NaCl solu-
tion increases the pitting potential of type 304 stainless
steel [2]. 5-(3-Aminophenyl)-tetrazole as corrosion
inhibitor in 3.5 wt % NaCl changes the CPDP curve of
Mg/Mn alloy by decreasing in cathodic current den-
sity, anodic current density and following that the
decrease of the corrosion current density, also the shift
of Ecorr and Eprot toward the negative potentials and
positive potentials respectively [55]. In some cases, the
corrosion inhibition effect of corrosion inhibitors on
localized corrosion is when its concentration reaches
to sufficient values. For example, the higher concen-
trations of nitrite (NO2− ) ions than 250 ppm could
inhibit the localized corrosion of 2205 duplex stainless
steel in acetic acid solution [48].
3.6. Metastable Pits
When CPDP scan is done at electrode potentials
below the pitting potential the curve often contains
some fluctuations. The reason of this transient is due

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 54 No. 5 2018

984 ESMAILZADEH et al.
to metastable pits which nucleate and grow but their
growth is stopped quickly and repassivized. Although
both of the stable pit and metastable pit cause the
increase in the anodic current density, it takes place for
metastable pit in a limited time due to the insufficient
development of the concentrated acidic chloride solu-
tion within the metastable pits. In relation to the
repassivation mechanism of metastable pits, it is sug-
gested that the presence of salt films prevents the
transfer of cations out and further growth of the prop-
agation pits [19, 37]. The observation of these fluctu-
ations in anodic branch of the CPDP curves has been
reported in literatures [46, 56, 57].
3.7. Effect of Metallurgical Variables
Metallurgical variables have various effects on the
passive film stability such as heterogeneity at grain
boundaries, disorder in the passive film by impurity
atoms or inclusions. For example, sulfide inclusions
(MnS) in the material microstructure act as sites for
pit nucleation. Observation the positive hysteresis
loop for a crystalline alloy (ASM1651) and an amor-
phous alloy (C-22) indicate the occurrence of local-
ized corrosion. The values of the breakdown potentials
and the repassivation potentials for the ASM1651 have
been nobler than the C-22 alloy. Therefore, the crys-
talline alloy has the higher corrosion resistance than
the amorphous alloy [58].
3.8. Effect of Temperature
Temperature changes have influences on the cor-
rosion rate. Therefore, it should be effective on the
CPDP parameters. For some materials, there is a crit-
ical pitting temperature (CPT). CPT is the minimum
temperature at which stable pits start to grow and fol-
lowing that, the corrosion pitting occurs. A higher
critical pitting temperature belongs to the alloys with
higher pitting corrosion resistance [2]. It is observed
that there is a breakdown potential transition from
high potentials to low potentials by the increase in
temperature. At temperature lower than the critical
pitting potential temperature, the meta stable pits gen-
erate and the increase in current density is not due to
the pitting but at temperatures above the CPT, the sta-
ble pits generate and pitting occurs [59]. For types 304
and 316 stainless steels in a chloride solution, the
increase in the temperature decreases the pitting
potential. The effect of temperature on the anodic
branch of CPDP curve for cold rolled steel in the pres-
ence of Cl– ions has been observed while the changes
of cathodic branch were not visible [60]. In addition to
the change of corrosion parameters on the anodic
branch, the decrease of the pits numbers and the
increase in pit size and its depth has been reported for
304 stainless steel in the range of temperatures 20–
50°C [56].
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
3.9. Effect of Dissolved Gases in the Electrolyte
The atmosphere, at which a specimen is tested, is
very effective on its behavior during the CPDP test.
The dissolution of different gases such as H2, O2 and
CO2 influences the corrosion behavior, formation of
the passive film and pitting corrosion. Destructive
effects of hydrogen on high alloyed stainless steel
include the decrease of Ecorr, Erep, Epit and the stability of
the protective passive film [61]. The CPDP scan of car-
bon steel is the same with and without oxygen gas, so it
has a little influence on the corrosion behavior of car-
bon steel. But the presence of CO2 gas changes the car-
bon steel behavior from passive to active-passive [62].
3.10. Effect of pH
Chromium-nitrogen steel and chromium-nickel
steel with chemical compositions of Cr23N1.2 and
Cr18Ni9 respectively have shown three different cor-
rosion behaviors in 3.5 wt % NaCl solution with the
range of pH 1–12. In the pH 1–2, the electrolyte is an
acidic solution so steel has an active corrosion. By the
increase in pH, the active corrosion behavior of two
alloys become active-passive and breakdown of the
passive film is observed due to pitting corrosion. The
size of passive region that means the durability of pas-
sivation, increasing in basic solution with pH 12.0 and
occurring the transpassivity in high positive potentials
[63]. The typical CPDP curves for galvanized steel in
simulated rust layer solution containing 0.6 M NaCl
with pH of 7.0, 10.0 and 13.0 has shown different
behaviors of the specimen. At pH 7.0 the increase in
rate of anodic current density was high and then it
became slow with the increase in the potential and the
specimen did not corrode locally. At pH 10.0 the
reverse anodic curve showed the transition from
unpassivized to passivized corrosion behavior and a
classical passive region was observed at potentials
more than the Epit = –0.56 V vs. SCE. At pH 13.0 the
current density in the reverse anodic curve increased
which was indicative of the formation of corrosion
products [60]. Al based alloy in acidic, neutral and
alkaline chloride solutions have shown the same pit-
ting potential while the values of corrosion potential
and cathodic current density have changed.
3.11. Effect of Immersion Duration
One of the effective parameters on the CPDP test
is the exposure time of alloy in the corrosive electro-
lytes. The increase in the immersion duration of
monel-400 (a nickel based alloy) causes the negative
shift of Ecorr and Eprot. In other words, it causes the
more agglomeration of chloride ions inside the pits. It
also leads to pits growth and the decrease of the pitting
corrosion resistance [64]. The rise of immersion dura-
tion of Mg in naturally aerated stagnant seawater and
3.5 wt % NaCl from 60 min to 6 days decreases the
Vol. 54 No. 5 2018
 INTERPRETATION OF CYCLIC POTENTIODYNAMIC
corrosion current density. Thus the further exposure
time of Mg in contact with the aggressive ions reduces
the uniform corrosion whereas it increases the pitting
corrosion [65].
3.12. Effect of Fluid Velocity
Fluid velocity is one of the effective parameters on
pitting resistance of some alloys. For alloys such as
nickel-chromium high molybdenum alloy and tita-
nium alloys, due to the stability of passive film, the
rate of corrosion is nil even at high velocity. For a
group of alloys such as copper based alloys, cast iron
and carbon steel, the corrosion rate increases by
increasing the velocity. It is due to more availability of
dissolved oxygen at high velocity and increase in the
oxygen limiting current density. For example, the
application of magnetic stirring in deaerated 0.6 M
NaCl causes the increase in the limiting current den-
sity of pure gold in the cathodic region of reverse scan
[66]. Another group of alloys, nickel copper alloy,
nickel chromium alloy and stainless steel types 316,
304 have exhibited less occurrence of pitting on the
surface at higher velocity of electrolyte. For these
alloys, the high velocity of fluid does not permit to
deposit suspended solids on the surface and formation
pit under the deposits [20].
3.13. Effect of Surface Roughness
Pits initiate at specific sites on the surface such as
sulfide inclusions and roughness. According to stud-
ies, at temperatures above the critical pitting tempera-
ture the available sites for pit initiation change. The
effect of roughness for 904 stainless steel in 1 M NaCl
was observed on the critical pitting temperature. The
average of CPT decreases with the increase in surface
roughness. By potentiostatic technique, the biggest
CPT for 904 S.S polished to 3 μm finished was 56°C
while for the 60 grit surface finished, it was 46°C [59].
The initiation of pits was evaluated for type 301 stain-
less steel with different surface roughness (range of sil-
icon carbide papers was 240, 400, 800, 1000 and 1500
grits). The pitting potential for 301 S.S with smooth
surface and low roughness was higher than the samples
with rougher surfaces. It was because of the difficulty
in initiation of meta stable and stable pits on the
smoother surface [67]. The effect of roughness on the
passive film of SS316VM has been investigated in two
different conditions. The efficiency of passive film
formed naturally, exhibited dependency to the surface
roughness, as the pitting potential rose with the
decline of surface roughness. It means that the surface
roughness is effective on the nucleation and propaga-
tion of metastable and stable pits. But for the passive
film formed by CPDP passivation method, the effect
of roughness was observed on the both pitting corro-
sion and general corrosion and it was related to the
change of roughness only in the range of higher surface
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
985
roughness. Therefore, the pitting corrosion of 316
stainless steel modified by CPP method was not sensi-
tive to the surface roughness [68].
4. EXPERIMENTAL POURBAIX
DIAGRAMS BY CPDP CURVES
Experimental Pourbaix diagram for different alloys
in the environments containing aggressive ions is con-
structed by electrochemical methods such as CPDP
curves. It is one of the other applications of CPDP test
[69]. Pourbaix diagram as an equilibrium diagram is
used for describing the corrosion behavior of pure
metals in pure water or simple aqueous solutions.
There are three main domains, immunity, passivity
and corrosion in the pourbaix diagram that show the
equilibrium state of metal in the specified condition (E
and pH). In the region of immunity, the metal is ther-
modynamically stable and is not corroded. Passivity is
the region where an oxide protective film is formed on
the metal surface and acts as a corrosion barrier and
the region where the metal undergoes general corro-
sion and metal ions are thermodynamically stable is
called corrosion region [2, 35]. Although the calcu-
lated pourbaix diagram is a useful tool for determining
the corrosion behavior of a material in different condi-
tions of potential and pH, it is often available for pure
metals and is not applicable for complicated industry
alloys. The other limitations for pourbaix diagram are
that the plot does not consider localized corrosion in
the presence of aggressive ions in the real solution and
in the passive region of pourbaix diagram, the quality
of passive film and degree of corrosion protection by
the film could not be considered [69]. These limita-
tions have caused the construction of experimental
pourbaix diagrams by CPDP curves for industry
alloys. For this construction, at first the CPDP is car-
ried out at constant conditions and at constant con-
centration of aggressive ions for example chloride ions
at different pH. Corrosion potential, flade potential
(primary passivation potential), protection potential
and pitting potential are determined from the CPDP
curve with respect to the pH of solution and trans-
ferred on the E-pH diagram. Transition of the corro-
sion parameters causes to establish five regimes within
the Pourbaix diagram. Immunity, general corrosion,
imperfect passivity, perfect passivity and pitting are
the equilibrium domains for the corrosion behavior of
the alloy at different potentials and pH. Figure 11 is
related to the construction of an experimental Pour-
baix diagram by anodic polarization curves for iron at
constant concentration of Cl– and at different pH.
According to the anodic polarization curves, the cor-
rosion behavior of iron varies with the increase of pH.
At acidic solution (pH 5) the metal shows general cor-
rosion only, the metal undergoes pitting corrosion and
repassivation by the increase of pH (pH 9) and finally
at basic solution (pH 13) the metal shows a passivation
behavior in a large range of potentials with no pitting
Vol. 54 No. 5 2018
986 ESMAILZADEH et al.
Potential
pH 5 pH 9 pH 13
Log (Current Density)
Fig. 11. Schematic illustration of the experimental Pourbaix diagram for iron in 0.01 M Cl− (right) constructed from experimental
anodic polarization curves (left).
[2]. It can be seen that in the experimental Pourbaix
diagram, the immunity is the region below the corro-
sion potentials, the general corrosion region is an area
at the potentials between the corrosion potential and
Flade potential also the potential range between the
Flade potential and protective potential is called per-
fect passivity. In the region of perfect passivity, there
are no pits which initiate or grow, while in the imper-
fect passivity region that exists between the protection
potential and pitting potential, the pits that initiated
previously, have the chance to grow. In the pitting
region that lies at the regime above the pitting poten-
tial, there is the risk of initiation and growth for pits on
the surface of passive film [69].
Therefore the experimental pourbaix diagram con-
structed from the CPDP curves is more useful than the
calculated pourbaix diagram due to their application
for various alloys, determination general and localized
corrosion of the alloys in chloride solution and evalu-
ation of passivation degree for protected film.
5. THE CPDP CURVES
OF SOME COMMON METALS AND ALLOYS
In this section, the behavior of localized corrosion
of some more common metals and alloys (iron [70],
316L [71], 420 [34] and 430 [33] stainless steels, alu-
minum [72], 6061 aluminum alloy [73], magnesium
[74], AZ31 [75] and AZ91D [76] magnesium alloys,
brass (copper based alloy) [77], low carbon mild steel
[78]) by their CPDP curves in NaCl and H2SO4 solu-
tions as more applicable solutions with the CPDP
curves of titanium alloy (Ti-6Al-4V) in Ringer physi-
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
E in V vs. S.H.E.
1.0
General Pitting
corrosion
0 Imperfect
passivity
Perfect
passivity
Immunity
1.0
0 9 14
pH
ological solution [79] and nitinol alloy in PBS (phos-
phate buffered saline) and bile according to ASTM F
2129 standard [80] for determining the localized cor-
rosion of materials, has been shown in Fig. 12. Due to
the effect of different parameters on the shape of
CPDP curves and material corrosion resistance (men-
tioned in the previous sections), the given curves are
related to the given conditions and they probably
change in different conditions.
In the CPDP curve for iron in 3.5 wt % NaCl a
short active- passive region is observed. Reduction of
anodic current density at the flade potential is an indi-
cation of passivation behavior of iron, due to either
formation of a passive layer or precipitation of corro-
sion products on the surface. The positive hysteresis
loop in the reverse scan, higher than Ecorr shows that
pitting corrosion is occurred at potentials more posi-
tive than Ecorr but it is stopped by the repassivation of
pits on the surface [53]. The localized corrosion
behavior of 316L stainless steel in 3.5 wt % NaCl solu-
tion is similar to that expressed for iron. The difference
is that the surface area of hysteresis loop for 316L
stainless steel is larger than that observed for iron. It
means that 316L stainless steel suffered severe pitting
corrosion [81]. As can be seen in the CPDP curves
presented for 316L, 420 and 430 stainless steel the
exact value of flade potential is not recognizable, that
is typical for steel substrates. Due to the more positive
value of Erep than Ecorr for 420 and 430 stainless steel,
they are not susceptible for repassivation of pits and
stopping the localized corrosion even at potentials
below Ecorr [33, 34]. A notable issue in the CPDP
curves for Al and 6061 Al alloy is the same value of
Vol. 54 No. 5 2018
 INTERPRETATION OF CYCLIC POTENTIODYNAMIC 987

Iron in 3.5 wt % NaCl 316L stainless steel in 420 stainless steel in

3.5 wt % NaCl 3 wt % NaCl

Potential

430 stainless steel Aluminum in 6061 Al Alloy in

in 3 wt % NaCl 3.5 wt % NaCl 3.5 wt % NaCl
Potential

Magnesium in AZ31 alloy in AZ91D alloy in

3.5 wt % NaCl 3.5 wt % NaCl 3.5 wt % NaCl
Potential

Brass in 1 wt % LC mild steel Ti-6Al-4V in Ringer

H2SO4 in 3.5 wt % physiological solution
Potential

Log (Current Density) Log (Current Density) Log (Current Density)

Nitinol in PBS solution Nitinol in bile solution
Potential

Log (Current Density) Log (Current Density)

Fig. 12. Schematic illustration of CPDP curves of common metals and alloys.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 54 No. 5 2018

988 ESMAILZADEH et al.
Ecorr and Epit, that is due to the intersection of cathodic
branch with the transpassive region [24]. Active disso-
lution in the anodic branch of CPDP curve for Mg and
its alloys exhibits that no passivation behavior
observed in 3.5 wt % NaCl solution. Also a large pos-
itive hysteresis loop in the reverse scan indicates that
Mg and its alloys are susceptible to pitting corrosion
[82]. In the reverse scan of potential for brass in 1 wt %
H2SO4, a small positive hysteresis is observed. It is due
to the type of localized corrosion, removing more
active zinc from brass selectively, that is usually called
dezincification [83]. In the CPDP curve for mild steel,
a sharp anodic current increase at potentials above
Ecorr indicates an active corrosion behavior of surface.
Also the absence of hysteresis loop in the reverse scan
can be a sign of uniform corrosion [78]. Stability of
passive behavior at higher potentials than Ecorr and the
negative hysteresis in the CPDP curve of Ti-6Al-4V
confirm the high localized corrosion resistance of this
alloy [84]. Comparing the CPDP curves for Nitinol
stents in both PBS and reconstituted bile, it is obvious
that the passivized corrosion behavior is preserved for
Nitinol in bile solution at high potentials so that no
localized corrosion occurs [80].
6. CONCLUSION
In this review, the CPDP technique as an applica-
ble and useful method to evaluate the susceptibility of
different metals and alloys to localize corrosion has
been described. This study includes the information
that helps us to conduct the CPDP test and predict the
corrosion behavior of the materials correctly. Some of
this information can be summarized as follows:
(1) ASTM G61 and F2129 standards are the stan-
dards to conduct the CPDP test for iron, nickel or
cobalt based alloys and small implant devices respec-
tively.
(2) The parameters used to interpret the CPDP
curve are including: pitting potential, repassivation or
protection potential, anodic to cathodic transition
potential, hysteresis and active-passive transition
potential.
(3) The difference between pitting potential and
protective potential with corrosion potential is the
most important parameters for evaluating the material
pitting corrosion resistance.
(4) Scan rate, point of scan reversal, aggressive ions
and temperature are some of different effective param-
eters on the corrosion behavior and the shape of
CPDP curves. Therefore the effects of these parame-
ters should be determined for predicting the localized
corrosion resistance of a material correctly.
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