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Corrosion and time dependent passivation of Al 5052 in the presence of H2O2

Article in Metals and Materials International · July 2016

DOI: 10.1007/s12540-016-5699-0

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Met. Mater. Int., Vol. 22, No. 4 (2016), pp. 609~620
doi: 10.1007/s12540-016-5699-0

Corrosion and Time Dependent Passivation of Al 5052 in the Presence of H2O2

Farhad Batmanghelich1,*,†, Mohiedin Bagheri Hariri2,†, Samin Sharifi-Asl3, Yadollah Yaghoubinezhad4,

4 1
Golsa Mortazavi , and Youngwoo Seo

1
Department of Chemical and Environmental Engineering, University of Toledo, Ohio 43606,
United States
2
Department of Chemistry and Biochemistry, New Mexico State University,
New Mexico 88003, United States
3
Department of Materials Science and Engineering, University of California at Berkeley,
California 94720, United States
4
Materials Science and Engineering Department, Sharif University of Technology,
Tehran 11365-9466, Iran
(received date: 20 December 2015 / accepted date: 26 February 2016)

Corrosion and time–dependent oxide film growth on AA5052 Aluminum alloy in 0.25M Na2SO4 solution
containing H2O2 was studied using electrochemical impedance spectroscopy, potentiodynamic polarization,
chronoamperometric and open circuit potential monitoring. It was found that sequential addition of H2O2 pro-
vokes passivation of AA5052 which ultimately thickens the oxide film and brings slower corrosion rates
for AA5052. H2O2 facilitates kinetics of oxide film growth on AA 5052 at 25° and 60 °C which is indicative of
formation of a thick barrier film that leads to an increment in the charge transfer resistance. Pitting incuba-
tion time increases by introduction of H2O2 accompanied by lower pitting and smoother surface morpholo-
gies. At short exposure (up to 8 h) to H2O2–containing solution, the inductive response at low frequencies
predominantly determined the corrosion mechanism of AA5052. On the other hand, at prolonged expo-
sure times (more than 24 h) to 0.25M Na2SO4+1vol% H2O2 solution, thicker oxide layers resulted in the
mixed inductive–Warburg elements in the spectra.
Keywords: alloys, metals, corrosion, electrochemistry, surface

1. INTRODUCTION respect, it is of vital importance to study degradation and

The current plethora of interest in Al-Mg alloys stems from
the necessity of a quest for high strength to density ratio, good
formability, and weldability together with acceptable corrosion
resistance. Consequently, Al series alloyed with Mg (5xxx)
have found a wide spectrum of applications, especially in
the marine and vehicle industries [1-4]. Hydrogen peroxide,
H2O2, as a powerful oxidizer, remarkably affects passivation
and corrosion behavior of metals and alloys. In spite of the
tremendous oxidizing power, H2O2 is unstable and naturally
decomposes to form water and oxygen. Nevertheless, many
grades of 5xxx series of Al alloys, ex. 5052 and 5254, are among
the few metallic materials that do not significantly catalyze
the natural decomposition process of H2O2; therefore, they are
broadly used in applications where H2O2 contact is inevitable
such as H2O2 reaction vessels and storage tanks [5]. In this
*Corresponding author: farhad.batmanghelich@rockets.utoledo.edu
†
First and second authors contributed equally.
KIM and Springer
time–dependent corrosion behavior of 5xxx series of Al
alloys. Decomposition process of aqueous H2O2 at water–
ceramic interfaces has been investigated elsewhere [6] and it
was found that the rate of H2O2 decomposition in order of the
most to the least is as follows SiO2, Al2O3, TiO2, CeO2 and ZrO2.
At initial stages of exposure to passivating media, chemical
composition of the thin layer created on Al and its alloys
was claimed [7] to be AlOOH (boehmite/pseudoboehmite).
However, at longer exposure times of up to 10–20 h, gibbsite
phase (Al(OH)3) takes the lead in electrolytes with near–neutral
pH values.
Early mathematical models of passivation postulated an
inverse correlation among the electric field strength and passive
film thickness (high–field model) [8]. However, these models
fail to predict the limiting current plateau during the poten-
tiostatic passivation process. Therefore, the models were modi-
fied to the point defect model (PDM) where the electric field
strength through the growing passive film is independent of
the applied potential and film thickness. According to the PDM,
potential drop across the metal/oxide interface decreases as
610 Farhad Batmanghelich et al.
the film thickness gradually increases. Hence, the diminish-
ing driving force for the migration of cation/oxygen vacan-
cies coincides well with the steady–state current [9]. A plausible
model for time–dependent growth kinetics of passive film is
presented elsewhere based on the correlation between the
electric field strength and the passive film thickness [10].
The electrochemical impedance spectroscopy (EIS) as a
powerful and sensitive technique is broadly considered to
characterize the phenomena occurring at the electrode/elec-
trolyte interface [11,12]. The effect of various surface treatments
on the electrochemical behavior of self–assembly monolayer
treated AA5052 alloys in sulfate solution has been studied
by means of EIS [13]. Additionally, the influence of alloying
elements on the corrosion characteristics of Al and Al–Sn
alloys has been reported by Gudić et al [14] using EIS tech-
nique. Metikoš-Huković et al. [15] have investigated the
passivation behavior of Al–Mo alloys as a function of alloy
composition in hydrochloric acid solutions. They have indi-
cated that the pseudoinductive behavior in impedance spectra
is attributed to the transport of oxygen vacancies through
the passive film which is accelerated by negative charge resulted
by the accumulation of metal vacancies at the film/solution
interface. However, mechanisms of time–dependent passivation
and corrosion of Al alloys in the presence of are H2O2 are
not well understood yet.
Therefore, this work aims to address current knowledge
gap investigating the effect of temperature and H2O2 concentra-
tion on the corrosion and time–dependent passivation behav-
ior of AA5052 Al alloys in a 0.25 M sulfate solution at pH 4.5.
The chronoamperometric, potentiodynamic polarization experi-
ments, open circuit potential (OCP) monitoring, and EIS
were implemented in order to shed more light into the pas-
sivation mechanism of AA5052. Surface morphology was
further evaluated using stereo, optical and scanning electron
microscopes (SEM).
2. EXPERIMENTAL PROCEDURE
2.1. Electrochemical apparatus and techniques
Electrochemical measurements were performed by a Potentio-
stat/Galvanostat Autolab (model PGSTAT302N, Metrohm,
USA) equipped with Nova 1.8 software. A Pt sheet (1 ×10 ×
10 mm) and a saturated calomel electrode (SCE; 0.238 V vs.
standard hydrogen electrode (SHE)) were used as counter and
reference electrodes respectively in a conventional three–
electrode setup. In the potentiodynamic polarization experi-
ment, potential was ramped from –0.8 to 1.9 V around OCP
in sodium sulfate solutions (0.25 M Na2SO4, pH ~ 4.5 in the
presence or absence of H2O2); scan rate was set at 5 mV/s.
Electrochemical experiments were conducted at ambient
(25 °C) and 60 °C. In order to provide reproducible and homo-
geneous conditions for working electrode surfaces, they were
cathodically polarized at –1 VSCE for 60 s. Chronoampero-
metric experiments were performed through a single–poten-
tial–step procedure with addition of H2O2 every 5ks at the
step potentials of 0.5, 0.6, 0.7 and 0.8 VSCE. As H2O2
decomposition sharply increases above pH 5 in all cases,
pH was adjusted to 4.5 with diluted NaOH or H2SO4 solu-
tions. In order to record the impedance spectra, a high–fre-
quency response analyzer (model SI 1255, Schlumberger, USA)
connected to a Potentiostat / Galvanostat (model 273A, EG&G,
USA) was employed. The impedance data were collected at
the OCP. Prior to each EIS measurement; electrodes were
immersed in the solution (0.25 M Na2SO4) for about 20 min
to assure that the electrodes have sufficient time for OCP
stabilization. The signal amplitude was ± 10 mV in the frequency
range from 1 MHz to 1 mHz. ZSimpWin 3.30 (EChem soft-
ware, USA) was used to fit and analyze the impedance date.
To ensure reproducibility, at least two separate runs of each
experiment were conducted. All tests were carried out in a
0.25 M sulfate solution at pH 4.5 with continuous aeration
(21% O2) and without stirring (stagnant condition).
2.2. Electrode preparation
4 mm thick plates were cut from a rolled sheet of AA5052
(chemical composition (wt%): Mg 2.36, Fe 0.37, Si 0.12,
Cu 0.02, Mn 0.06, and Cr 0.19) and used as the working
electrode. Rolled sheet was initially cold rolled from an as-cast
ingot. The ingots had been homogenized at 470 °C for 13 h
and cooled in the air followed by cold rolling to the afore-
mentioned dimensions (43% rolling reduction). After rolling
the alloys have not been annealed to intensify corrosion sus-
ceptibility in order to increase sensitivity towards corrosion.
The surface area exposed to the test solution was 1 cm2. Conven-
tional H2O2 solution contains 30 wt% H2O2 and is slightly
acidic (pH~4) at this concentration. All materials were from
analytical grade (Merck, Germany). AA5052 plates were abraded
up to 3000 grit emery paper and subsequently degreased in
acetone solution under ultrasonic agitation for 5 min. At the end,
they were rinsed with distilled water and dried under gentle
warm air blow.
2.3. Morphological analysis
Stereomicroscopic observations were made using an Olym-
pus LG–PS2 system with a SZH10 camera. After etching with
a mixture of hydrochloric acid (37 vol%), nitric acid (65 vol%),
and potassium chromate solutions, the optical microscopy
(Olympus model PME3) was utilized to reveal corrosion
deteriorations. Figure 1 illustrates the optical micrograph of
AA5052 alloy after polishing and exposing to the etchant
for 20 s. Al 5052 microstructure mainly consists of primary
α-Al (solid solution of Mg in Al) and Magnesium aluminide
(mostly Mg5Al8, Mg2Si, Al3Fe [16]). The microstructure con-
sists of equiaxed α-Al grains with sparse intermetallics at the
grain boundaries. Field–emission scanning electron micros-
copy (FESEM; Hitachi S4160) was also used to verify the
 Corrosion and Time Dependent Passivation of Al 5052 in the Presence of H2O2
Fig. 1. Optical micrograph of AA5052 alloy after 20 s of etching.
surface morphologies after exposure to sulfate solution con-
taining H2O2.
3. RESULTS AND DISCUSSION
3.1. Open circuit potential monitoring
Influence of H2O2 stepwise addition on the evolution of
OCP for AA5052 immersed in sulfate solution (pH 4.5) is
depicted in Fig. 2.
After immersion, OCP values stabilized around –0.83 VSCE
due to the formation of initial Al(OH)3 [17]. The decomposition
Fig. 2. Rest potential variations with time for AA5052 in 0.25 M Na2-
SO4 solution by sequential addition of 0.5 vol% and 2 vol% H2O2.
The insets show the stereomicroscopic macrographs after (a) 7 ks, (b)
11 ks, and (c) 15 ks exposure to the solution and FESEM micrographs
(d) before and (e) after 0.5 vol% H2O2 addition to Na2SO4 solution.
611
of H2O2 may take place through the following pathway [18]:
 +
H2 O2  HO2 + H (1)
  1
HO2  OH + --- O2 (2)
2
In the presence of Al(s) in the medium [19]:
 
2Al  s   2HO2 + OH + H2 O (3)

AlO2 contributes to further passivation as follows [20]:
 +
2AlO2 (aq) + H => Al2O3·3H2O (4)
Al2 O3 + 3H2 O  2Al  OH 3 (5)
Increase in the production of Al hydroxide with addition of
H2O2 has been observed before [18].
As shown in Fig. 2, by addition of 0.5 vol% H2O2, the stable
average value of OCP shifts toward more positive potentials
(from –832 to –822 mVSCE). After around 4000 s, further addition
of H2O2 (2 vol%), exerts another positive shift in OCP value
(from –822 to –810 mVSCE).
+  0
H2 O2 + 2H + 2e  2H2 O EH2O2/H2 O = 1.78V (6)
According to the reduction reaction (6), the equilibrium redox
potential for H2O2 decomposition (+1780 mV) is considerably
higher than OCP potential in the absence of H2O2 (-830 mV);
Ultimately, corrosion potential moves towards more noble
values and an increment in the OCP occurs [21]. Furthermore,
the mere presence of H2O2 favors hydration of the oxide film
(reactions 1-5) which prevents the dissolution process of
pre–formed oxide layer and thickens the oxide film on the
surface, therefore OCP displaces towards nobler values [22].
Fluctuation of the rest potential arises from the consecutive
breakdown and localized repassivation of the pits [23]. Figure
2(a)–(c) illustrates corresponding stereograph images of AA5052
after 7, 11 and 15 ks exposure to the electrolyte during OCP
recording. After exposure for 11 ks, several randomly distrib-
uted pits were observed on the part of the surface and these were
caused by local destruction of the passive film. The localized
attacks commonly nucleate and propagate at the weaker points
of the passive layer [24]. By gradual addition of H2O2, the metal
has lost its reflective surface and the dark areas are extended
as a result of continuous thickening of the oxide film on the
surface. H2O2 facilitates formation of Al2O3/Al(OH)3 layers
(reactions 1-5) which have a disordered crystal structure and
[25] therefore appear as the dark areas in the optical micro-
graphs. For a better understanding, the influence of sequen-
tial H2O2 addition on the surface morphology of AA5052 was
also examined by FESEM. Apparently, in the absence of H2O2
(Fig. 2(d)), higher surface roughness with many cavities is
dominant indicating the enhanced metal dissolution. How-
ever, surface morphology after 9 ks exposure to the media
612 Farhad Batmanghelich et al.
Fig. 3. Potentiodynamic polarization plots of AA5052 in 0.25 M Na2-
SO4 solution at different temperatures and in the presence or absence
of H2O2, pH = 4.5. The inset depicts a zoom of the polarization plots.
Scan rate = 5 mV/s.
containing H2O2 (Fig. 2(e)) turned smoother with fewer pits,
which implies that H2O2 serves as an effective barrier against
local corrosion attacks in our electrolyte.
3.2. Potentiodynamic polarization studies
Figure 3 exhibits the potentiodynamic polarization curves
of AA5052 in 0.25 M Na2SO4 solution at pH = 4.5 and at
different temperatures in the presence or absence of H2O2.
Extracted electrochemical data; i.e. corrosion potential Ecorr.,
corrosion current density jcorr, pitting potential Epit and passive
current density jpass (current density at the beginning of the
passive region) are summarized in Table 1.
According to polarization plots presented in Fig. 3, H2O2
decreased vulnerability and enhanced corrosion resistance
of AA5052 compared to media without H2O2, at both tempera-
tures. At 25 °C, 0.5 vol% H2O2 decreases corrosion current
density from 6.8 to 4.2 µA/cm2 and shifts the Ecorr in positive
direction from –1.08 to –0.82 VSCE. This effect was more promi-
nent at 60 °C; in a way that jcorr has changed from 28.2 to
11.2 µA/cm2 and Ecorr has increased from –1.21 to –0.81 VSCE.
Moreover, at both temperatures, in the presence of H2O2, Epit
has been increased which is indicative of the advantageous
influence of H2O2 on the pitting corrosion resistance of AA5052.
However, since Epit is a thermodynamic property of the system
and shows the direction, the extent of pitting by temperature
is more prominent than H2O2. Oxygen reduction reaction
Table 1. Summary of Ecorr., jcorr., Epit and jpass. values obtained from polarization measurements of AA5052 in 0.25 M Na2SO4 solution at
different temperature and in presence or absence of H2O2, pH = 4.5
H2O2 Conc. (vol%) Temp. (°C) Ecorr. vs. SCE (V)
0 25 –1.08
0 60 –1.21
0.5 25 –0.82
0.5 60 –0.81
predominantly occurs on the more noble Al–Mg intermetal-
lic phase; subsequently localized alkalinization in the area
surrounding these phases results in a local dissolution of the
passive layer. This behavior is due to the amphoteric nature
of Al. Initially in the vicinity of intermetallic phases, Al is
anodic and intermetallic phases are cathodic. However, because
of the amphoteric nature of Al, pH values would change
around the Al area towards alkaline values. This would ren-
der the intermetallic regions cathodic and triggers the oxygen
reduction reaction of alkaline media (O2 + 2H2O + 4e => 4OH-).
Again because of the amphoteric nature of the Al, every-
thing turns back to initial conditions and this process occurs
repeatedly, resulting in corrosion of noble intermetallics
and Al in their vicinity [1,26]. Hence, the pits are expected
to nucleate and grow at these favorable sites on the surface
of AA5052 alloy. The ennoblement of Ecorr by H2O2 addition, is
mainly attributed to the added cathodic reaction from peroxide
reduction which results in in the formation of a thick Al2O3 /
Al(OH)3 layer [23]. This observation is in accord with that
attained in section 3.1. Final OCP value during the monitoring
stage (Fig. 2) is indicated by an arrow on the polarization curve
in the inlet of Fig. 3. Final OCP values of AA5052 at different
H2O2 concentrations at 25 °C (–810, –822 and –832 mVSCE
for 2, 0.5, and 0 vol%, respectively) entirely reside in the passive
region of AA5052, therefore, observation of oxide film forma-
tion at the final stages of OCP recording was expected. Addi-
tionally, it is worth mentioning that the sample exposed to
H2O2 –containing electrolyte exhibits a far lower value of jpass
at 60 °C (11.2 µA/cm2) compared to the specimen polarized
in H2O2–free solution at same temperature (95.5 µA/cm2).
The jpass decrement at both temperatures reveals that H2O2 is
able to facilitate passivation kinetics of AA5052, which is
indicative of formation of a thicker barrier film that leads to
an increment in the charge transfer resistance. It has been
reported [27] that further addition of H2O2 associates with
the disappearance of the active–passive transition area in the
polarization curves, as it was clearly exhibited in Fig. 3. Indeed,
the current density which is assigned to the anodic oxidation
of H2O2 can interfere with the overall anodic branch; hence,
no appreciable region of passivity might be specified in the
presence of H2O2. Additionally, elevated temperatures affect
the cathodic reactions in a way that shifted cathodic braches
towards higher current values. This reveals that the elevated
temperature can facilitate the cathodic reactions and more
especially, it accelerates hydrogen evolution reaction [28]. With
Epit vs. SCE (V) jcorr. (μA/cm2) jpass. (μA/cm2)
–0.68 6.81 8.12
–0.64 28.19 95.50
–0.49 4.22 7.58
–0.67 11.23 11.22
 Corrosion and Time Dependent Passivation of Al 5052 in the Presence of H2O2 613

of the system; therefore although more positive Epit is indic-

ative of lower pitting vulnerability it does not show the extent
of resistance which is a subject of kinetics. It can be inferred that
under our experimental conditions, pitting corrosion is mostly
affected by temperature variation rather than H2O2 addition
during the polarization measurements.

3.3. Chronoamperometric measurements

In order to gain more insights on the effect of temperature
and H2O2 on the passivation and pitting corrosion of AA5052,
chronoamperometric measurements were conducted at four
different step potentials which had been selected in the passive
and trans-passive region of the polarization curves. The recorded
plots of j-t in 0.25 M Na2SO4 solution at the step potentials
of –0.5, –0.6, –0.7 and –0.8 VSCE are indicated in Fig. 5.
Fig. 4. Optical micrographs of AA5052 coupons after potentiody- As it is evident, current density sharply drops right after
namic polarization measurements in 0.25 M Na2SO4 solution (a) at
25 C, (b) at 60 C, (c) containing 0.5 vol% H2O2 at 25 C, and (d)
chronoamerometric process initiates where this acute decrease
containing 0.5 vol% H2O2 at 60 C. in current density at the initial stages is attributed to the forma-
tion and growth of the oxide film. As it is evident, steady–state
current density (jss) values show a descending trend at higher
an increase of the electrolyte temperature from 25 to 60 °C, potentials due to the enhanced chemical stability and thick-
passive current density has remarkably increased from 8.1 to ening of the oxide layer which leads to an increase in the charge
95.5 µA/cm2. Furthermore, jcorr showed an obvious increase transfer resistance [30]. The upsurge increment of the current
from 6.8 to 28.2 µA/cm2 at high temperatures. In fact, tempera- density at the pit incubation time (tinc) mainly ascribes to the
ture enhances kinetics of the corrosion reaction and it acceler- nucleation and growth of the corrosion pits. Moreover, the
ates the anodic dissolution of AA5052. As shown in Fig. 3 Al–Mg beta–phases are anodic with respect to AA5052 matrix,
and Table 1, pitting corrosion potential (Epit) in the presence hence, formation of a continuous network of beta–phase
of H2O2 decreases by increasing the electrolyte temperature. around grain boundaries intensifies sensitivity of the alloy
It has been reported that at lower temperatures, oxide film is towards localized attacks [1]. It has been postulated else-
composed of Al(OH)3 and Al2O3.3H2O, while at higher tempera- where that by increasing potential there would be a competition
tures it is mostly made of AlOOH and Al2O3.H2O where the among two surface phenomena; pitting corrosion suscepti-
easier breakdown of the oxide film coincides with the dec- bility and passive film thickening [31,32]. At first sight, it
rement of pitting potential [29]. Figure 4 depicts morphological might be conjectured that the potential increment increases
structures of AA5052 after potentiodynamic polarization
experiments at 25 and 60 °C without (Figs. 4(a) and (b))
and with (Figs. 4(c) and (d)) H2O2.
The relatively high number of corrosion pits in the optical
micrographs is indicative of transpassive breakdown of the
barrier film around Epit. At higher temperature levels (Figs. 4(b)
and 4(d)), pitting condition has been exacerbated accompa-
nied by numerous, wide and deep hemispherical pits on the
surface. More intense pitting at higher temperatures is attributed
to the enhanced anodic dissolution of intermetallic phases
by temperature which leads to the formation of a large number
of randomly distributed pits [28]. Some small corrosion pits
are observed on the surface of specimens exposed to the solu-
tion at lower temperature (Figs. 4(a) and 4(c)). These micro-
graph observations are consistent with the Epit values presented
in Table 1 where higher temperatures enhanced vulnerability
60 C 25 C
of AA5052 to pitting attack ( Epit << Epit ). Although Epit has
also increased by H2O2 introduction, as optical micrographs
show (Fig. 4), pitting is not intensified as did temperature. Fig. 5. Current density variation vs time for AA5052 in 0.25 M Na2-
As previously mentioned, Epit is a thermodynamic property SO4 solution at different applied overpotentials; T = 25 C (pH 4.5).
614 Farhad Batmanghelich et al.

Fig. 6. (a) Effect of solution temperature on current transient curves of AA5052 in 0.25 M Na2SO4 solution containing 0.5 vol% H2O2 and (b)
influence of H2O2 concentration on the current transient curves of AA5052 in 0.25 M Na2SO4; pH 4.5, step potential = –0.5 VSCE. Insets show the
correlated morphology of corrosion attacks after chronoamperometric experiment.

the number of active nucleation sites and more severe pit
formation; however, as it is depicted in Fig. 5, tinc increases
by overpotential which is indicative of the fact that the film
thickening predominantly controls passivation behavior of
AA5052 in this system.
The effect of electrolyte temperature and H2O2 concentration
on chronoamperometric responses (at step potential = 0.5 VSCE)
of AA5052 in 0.25 M Na2SO4 solution are presented in Figs.
6(a) and (b), respectively. In almost all cases, j variations
obey similar trend: after a sudden acute drop, reaches a current
plateau and ultimately increases in view of the pits incubation.
According to Fig. 6, jss increases from 0.06 mA/cm2 to
2
0.40 mA/cm as temperature increases, nevertheless, no obtru-
sive plateau of steady–state current was observed. Addition-
ally, tinc decreases from 44s at ambient temperature to 25s at
60 °C. During amperometric monitoring, oxide film thick-
ening and dissolution occur simultaneously, therefore, at initial
stages, an overall decrement in the current level takes place
since the dissolution rate is negligible (oxide film formation
rate dominates over its dissolution rate) [9]. Current density
fluctuations have increased at 60 °C due to the localized
breakdown and further repassivation of the corrosion pits
[33]. Apparently at 60 °C, pits have been increased in terms
of population, as more acute localized attacks are observed
after amperometric monitoring (inset of Fig. 6(a)). These
observations suggest higher vulnerability to pitting corrosion
at higher temperatures, as noted previously. In the absence
2
of H2O2 (Fig. 6(b), 0 vol% H2O2), j decreases to 0.12 mA/cm
2
and after a small rise and drop, it reaches 0.15 mA/cm ; no
discernible current density plateau is achieved because of
metastability of the oxide film. The underlying reason for the
initial increment in the overall current density lies in the fact that
the dissolution rate of the oxide film overcomes film growth
rate at initial stages of potential exertion in the absence of H2O2
[9]. In fact, fluctuation of j at early stages corresponds to the
pit nucleation and quick passivation of the pit bottoms [34].
Further addition of H2O2 (2 vol%) diminishes jss from 0.12
mA/cm2 to 0.03 mA/cm2 due to the enhanced chemical stability
and thickening of the passive film [30]. As shown in the insets
of Fig. 6(b), there exists several conspicuously large and hemi-
spherical pits on the sample exposed to H2O2–free solution;
nevertheless no obtrusive pits are detectable on the surface
of specimens in the presence of H2O2. Moreover, pit incubation
time roughly increases by introduction of 0.5 and 2 vol%
H2O2. According to the aforementioned observations, it can be
inferred that the pitting resistance enhances by gradual introduc-
tion of H2O2. Kinetics of oxidation/hydroxidation reactions
at the bottom of the pits has been accelerated by H2O2 and
thereby a protective layer against pitting has been formed at
the bottom of the pits [27]. These results well agree with our
findings in polarization studies where the presence of H2O2
enhanced corrosion resistance and decreased susceptibility
to pitting attack.
3.4. Electrochemical impedance spectroscopy (EIS)
EIS provides more information about the ongoing processes
at the metal/electrolyte interface. Experimental and simulated
impedance spectra in ZSimpWin environment for AA5052
exposed to 0.25M Na2SO4 solution in the absence or pres-
ence of H2O2 are represented in Figs. 7(a) and (b), respec-
tively. Characteristics of EIS spectra are exactly similar to
those which were observed by Reis et al. [13] in the case of
 Corrosion and Time Dependent Passivation of Al 5052 in the Presence of H2O2 615

Fig. 7. Experimental ( ) and fitted ( ) impedance data obtained in ZsimpWin environment for AA5052 in 0.25M Na2SO4 containing (a) 0
vol% and (b) 1 vol% H2O2; (c) relevant electrical equivalent circuit used to analyze the EIS data.

AA5052–H32 alloy in naturally aerated 0.5 M Na2SO4 solution.
The impedance data were interpreted using Rs(Q(Rf(LRL)))
electrical equivalent circuit (EEC) that is shown in Fig. 7(c).
Q is the constant phase element (CPE) and its impedance can
be described as Z(Q) = [Y0(jω)n]-1, where Y0 is a factor of
proportionality having numerical values, j2 = 1, ω is angu-
lar frequency and n is CPE exponent and when n = 1, 0 or
0.5 then the CPE represents an ideal capacitor, a pure resistor
or a Warburg element impedance, respectively [35]. Because
of the deviation from an ideal capacitor, Q element is used
instead of a pure capacitor so as to adequately describe the
interfacial properties of the obtained oxide layer. Such a
deviation is mainly ascribed to the frequency dispersion, mass
transport resistant, and surface heterogeneities resulting from
dislocations, impurities, grain boundaries and formation of
a porous film on the surface [36].
Rs refers to the solution resistance, Rf stands for the oxide
film resistance, L represents the inductance behavior and RL
is the inductive resistance. The Nyquist and Bode plots for
AA5052 after 8 h of exposure to 0.25 M Na2SO4 solution
containing different levels of H2O2 are illustrated in Fig. 8.
As a first remark, all Nyquist spectra exhibit similar behavior,

Fig. 8. (a) Nyquist, (b) Bode–phase and (c) Bode–absolute diagrams for AA5052 in 0.25M Na2SO4 solution containing various concentrations of
H2O2 at 25 °C (pH 4.5); exposure time = 8 h.
616 Farhad Batmanghelich et al.

manifesting that the features of the surface passivity and
corrosion mechanism of AA5052 are alike after 8h of exposure
at 25 °C. At high frequencies (10 kHz), the impedance data
are dominantly influenced by the electrolyte resistance, while
at lower frequencies a semi-circle emerges below the ZRe axis in
Nyquist plot due to the presence of an inductive response.
The effective capacitive (Ceff) loop can be the result of a series
connection between double layer capacity and oxide film capacity
(Ceff-1 = CDL-1 + Cf-1) where CDL and Cf are related to the charge
transfer processes in Helmholtz double layer and mass transfer
of ions through oxide film formed on the AA5052 surface,
respectively [37]. There are two distinguishable peaks in Bode
diagrams. At medium frequency range from 0.01 to 1 kHz,
slope of log|Z| vs. logƒ plots approaches –1 and the phase angle
comes close to –80° and correlates to the capacitance behavior
of AA5052 in sulfate solution. At lower frequency ranges, the
relaxation processes of adsorbed species which are formed
due to the local dissolution of film/electrolyte interface con-
tributes to the appearance of inductive semi–circular arcs in
Nyquist diagrams [38]. In all Bode–phase spectra, two time
constants (inductive and capacitive loops) are seen after 8 h
of exposure. The increase in diameter of Nyquist semi–circles
implies that AA5052 corrosion rate has been impeded by
gradual addition of H2O2 which confirms our observation in
polarization experiments. The measured impedances were fitted
to the EEC of Rs(Q(Rf(LRL))) using a complex nonlinear
least–square algorithm; corresponding values of the electro-
chemical elements are presented in Table 2.
Along with gradual addition of H2O2 in sulfate solution,
the resistance of oxide film has been increased from 16.1 to
26.2 kΩcm2, which is indicative of passive film growth; this
hinders the charge transfer phenomena at the metal/electro-
lyte interface. Hirschorn et al. [39] have reported that the
effective capacitance associated with a CPE is proportional
to the effective film thickness as follows:
–1
deff = 0 Ceff (5)
where the vacuum permittivity (0) value is 8.85×10-14
Fcm-1 and  is the dielectric constant of the film. As a result
of increasing H2O2 content of the sulfate solution from 0.5 to
1.5 vol% at 25 °C, the effective capacitance has been decreased
-
from 11.3 to 4.3 Fcm 2. Hence, the increment of recipro-
1
cal capacitance (Ceff ) by increasing the H2O2 level can be
assigned to the oxide film growth [14]. For a better clarification,
the variation of Ceff, Rf and the product of Rf C are depicted
in Figs. 9(a)–(c).
After a sudden decrement of Ceff (Fig. 9(a)), capacitance
reaches a relatively steady state value after 4 h of immersion due
to the formation of a stable and thick passive film. A significant
oscillation in both Rf and Ceff data for specimen immersed in
0.25 M Na2SO4 + 0 vol%H2O2 electrolyte is observed; nev-
ertheless, Rf is approximately stabilized after about 6 h
immersion in samples exposed to 0.25 M Na2SO4 +X(0.5
< X < 1.5) vol%H2O2 solution that implies the impressive
effect of H2O2 on formation and complete surface coverage
of barrier film. Final values of Rf are relatively high which

Table 2. Summary of the electrochemical parameters extracted from best–fitted EEC (Fig .7(c)) to the impedance data for AA5052 in
0.25 M Na2SO4 solution (exposure time = 8 h)
Exp. No. Temp. (°C) vol% H2O2 Rs (kcm2) Rf (k cm2) Y0 (Ωsncm-2) n Ceff10-6 (Fcm-2) L (H) RL (k cm2)
-6
1 25 0 0.009 14.7 7.5210 0.92 6.2 325500 2.56
-5
2 25 0.5 0.005 16.1 1.2110 0.96 11.3 13070 3.67
-6
3 25 1 0.013 19.4 9.1810 0.93 10.6 11740 3.73
-6
4 25 1.5 0.005 26.2 5.0010 0.93 4.3 16410 1.60
-6
5 30 1 0.009 13.8 6.0010 0.90 4.5 221400 2.57
-5
6 50 1 0.008 11.3 1.5110 0.87 11.6 420.7 0.28
-5
7 75 1 0.008 7.8 1.2510 0.94 14.7 1960 1.17

Fig. 9. Evaluation of (a) capacitance, (b) Rf, and (c) RfC vs. time for AA5052 in 0.25M Na2SO4 solution containing different level of H2O2 at
25 °C (pH 4.5).
 Corrosion and Time Dependent Passivation of Al 5052 in the Presence of H2O2
might be attributed to the insulative nature of oxide layer
formed on AA5052 alloy in sulfate solution containing H2O2. In
H2O2–free solution, Rf fluctuations probably arise from the
simultaneous occurrence of localized dissolution of Al–Mg
intermetallic compounds and formation of the corrosion product
layer [40]. As can be seen in Fig. 9(b), general trend inclined
towards increasing film resistance with introduction of H2O2.
Additionally it should be noted that the highest values of Rf are
observed for the solution containing 1.5 vol% H2O2 (Fig. 9(b))
which manifests the persistent effect of H2O2 on oxide film
thickening over time, as proposed earlier. The EIS results show
a good agreement with those acquired by both OCP and
polarization studies. The specific resistivity ( = RfCeff / 0)
of a material, as a chemical and structural–dependent param-
eter is not a function of film thickness. As shown in Fig. 9(c),
the product of RfC for oxide film in H2O2–free electrolyte (blue
colored curve) has a more stable value compared with that of
specimens exposed to the solutions containing H2O2. Hence,
the variation of Rf and C versus time significantly correspond to
the film thickening in the absence of H2O2, while for specimens
submerged in H2O2 containing media this dependency might
be slightly impressed by other phenomena, especially by the
change in the concentration of point defect vacancies through
the oxide film [21]. In the situations where the diffusion of oxy-
gen vacancies in the passive film dominantly controls the
overall rate of film thickening, the Warburg–like impedance
emerges in the plots and the passive film growth could be
well described based upon the PDM [8]. Such a Warburg–type
behavior was not observed in our experiments after 8 h of
exposure and that is why we did not deal with PDM anymore.
The inductive loops are generally assigned to the relaxation
process of adsorbed species such as Al(OH)3ads and subse-
quent local dissolution of oxide layer around Al–Mg inter-
metallic compound at low frequencies [41]. The magnitude
of inductive changed irregularly at different concentrations
of H2O2. It has been speculated that larger inductive values
are probably representative of faster adsorption–desorption
process of Al(OH)3ads species on the surface [42].
Fig. 10. (a) Nyquist, (b) Bode–phase, and (c) Bode–absolute plots for AA5052 in 0.25M Na2SO4 electrolyte containing 1 vol% H2O2 at various
temperatures; exposure time = 8 h.
617
Moreover, by rising solution temperature from 30 to 75 °C,
overall impedance value and corrosion resistance follow a
descending trend (Fig. 10) which is in accordance with the
corrosion data presented in Table 1. It has been claimed that
the oxidizing power of H2O2 slightly diminishes at higher
temperatures due to the enhanced decomposition of H2O2 [6].
By rising the temperature from 30 to 75 °C, the Ceff has been
increased from 4.5 to 14.7 cm-2 and Rf has been decreased
from 13.8 to 7.8 kcm2. This indicates that at higher tempera-
tures, a thinner and looser oxide film is probably formed which
facilitates the dissolution process [14]. By investigating Fig.
10 with more scrutiny, one could clearly detect just one time
constant at 50 °C which manifests that the overall passiva-
tion behavior is predominantly determined by the growth of
the oxide film and the alloy is in its active–passive transition
region at this temperature. It has been speculated that the
disappearance of the inductive loop is correlated to the forma-
tion of a protective film that hinders further local dissolution
of metal [42].
The influence of longer exposure times of 24 h, 48 h, and
72 h on the characteristics of oxide layer formed on AA5052
in 0.25 M Na2SO4 solution with 1 vol% H2O2 is also exam-
ined. After such a long exposure time, AA5052 surface was
completely covered in a slightly black oxide layer (similar
to what was seen in Fig. 2(c)). The Nyquist and Bode plots
of AA5052 after different exposure times of 24 h, 48 h, and
72 h in 0.25 M Na2SO4 solution containing 1 vol% H2O2 are
presented in Fig. 11. Interestingly, the straight line tails in
Nyquist diagrams indicate the presence of a Warburg com-
ponent that is attributed to the activation of the diffusion–
controlled phenomena after prolonged exposures. As a matter
of fact, a lengthened exposure to 0.25 M Na2SO4 solution
containing 1 vol% H2O2 leads to the formation of thicker oxide
layer on the surface. Meanwhile, the diffusion of point defects
across this thick film becomes the rate controlling step, and
thereby a Warburg–like impedance spectrum is just developed
at low frequencies. Conversely, in some cases where the imped-
ance response is completely and entirely determined by dif-
618 Farhad Batmanghelich et al.
Fig. 11. (a) Nyquist, (b) Bode–phase, and (c) Bode–absolute plots for AA5052 in 0.25M Na2SO4 solution containing 1 vol% H2O2 after different
exposure times of 24 h, 48 h and 72 h at 25 C.
fusion of anionic or cationic vacancies through the oxide film,
the more intense Warburg impedance is obtained at early stages
of impedance spectroscopy [8]. The collected spectra in Fig. 11
could not be accurately fitted to the EEC of Rs(Q(Rf (LRL)))
anymore. A Warburg diffusion element should be placed in
series with inductive element in EEC of Rs(Q(Rf (LRL)))
(Fig. 7(c)). When Rs(Q(Rf (LRL)W)) model was used as EEC, a
good fit to the collected data for samples with exposure times
of more than 24 h was obtained. This equivalent circuit is
shown in the inset of Fig. 11(c), the outcome fitting values
for impedance data are listed in Table 3.
The magnitudes of CPE powers are generally lower than
those presented in Table 2 in the case of 8 h exposure time,
indicating that the localized defects probably begin to acti-
vate over longer times which led to the increment in the surface
heterogeneity due to the microscopic roughness [38]. Actually,
a highly porous film of corrosion products, in series with charge
transfer resistance, sometimes hinders the diffusion of ion
vacancies through the oxide film and as a result Warburg
element is appeared at low frequencies [43]. According to
the Bode–phase plot presented in Fig. 11(b), phase angle
maxima are quite broad compared with those recorded after
8h of exposure (compare Figs. 8(b) and 10(b) with Fig. 11(b)).
This broadening is possibly due to the dual protection mecha-
nism of the oxide film against corrosion. Firstly, oxide film
acts as a barrier layer to charge transfer as a result of the film
growth at longer exposure times and secondly the limitation
3+
of diffusion for Al cation during its electro–migrating through a
thicker film [44]. With increasing exposure time, the imped-
ance spectra appears to become capacitive in nature, con-
ceivably due to the film thickening which coincides with an
Table 3. Outcome values derived from the fitting of the EIS data after long exposure times of AA5052 to 0.25 M Na2SO4 solution
containing 1 vol% H2O2 at 25 C, pH = 4.5
Exp. No. Exposure time (h) Rs(kcm2) Rf (kcm2) Y0 (Ωsncm-2)
1 24 0.006 20.7 2.2810-5
-5
2 48 0.009 34.2 1.8310
-5
3 72 0.005 70.5 1.1710
obvious increase of |Z| in Bode diagram at low frequencies
(Fig. 11(c)). After a higher exposure time the magnitude of
Ceff (which is proportional to the reciprocal film thickness)
has decreased. Rf value augments by increasing exposure time
which confirms charge transfer hindrance at metal/electrolyte
interface as a consequence of oxide film growth. EIS spectra
in the form of Bode–absolute diagram clearly show a higher
absolute impedance |Z| after longer exposure times. Mean-
while, it is remarkably observed in Fig. 11(c) that as exposure
time increases, the absolute impedance maximum is displaced
to higher values. The product of Rf Ceff has not a similar value
for exposure times of 24 h, 48 h, and 72 h. So, it can be deduced
that in long–term exposure, characteristics of the AA5052
passive/oxide layer in the presence of H2O2, except for film
thickness is distinctively affected by oxygen vacancy trans-
portation at low frequencies. The possible reactions for creation
of the oxygen vacancies in AA5052 oxide film can be expressed
by Eq. (6) [45]:

2Al  2AlAl + 3VO + 6e
or

Mg  MgMg + VO + 2e (6)
As time progressed, with reference to Eq. (6), the concen-
tration of oxygen vacancy would change, and subsequently
the relative permittivity of the oxide layer probably varies.
As a consequence, with regard to Eq. (5) it would result in
alteration of Rf Ceff product over time. The models which
are proposed to analyze the low–frequency features were
based upon the reasonable chemical and physical hypothe-
ses. Nevertheless, the model for AA5052 passivation in the
n Ceff10-6 (Fcm-2) L(H) RL (k cm2) W (Ω-1s0.5cm-2)×105
0.82 19.3 17160 10.10 164
0.8 16.5 242000 8.21 188
0.83 11.2 153200 11.44 273
 Corrosion and Time Dependent Passivation of Al 5052 in the Presence of H2O2
presence of H2O2 is more complex in detail and requires
additional investigation and scrutiny to shed more light on
the variation trend of impedance data over time with more
scrutiny. It is worth noting that by increasing the immersion
time from 24 h to 72 h and accompanied thickening of the
oxide film, Warburg impedance has slightly increased from
1640 to 2730 -1s0.5cm-2. This increment might be due to
the combined effects of charge transfer resistance and dif-
fusion limitations related to thick oxide film [44]. In long term
exposure, the relaxation effects of adsorbed Al(OH)3ads. and
mass transfer of point defects concurrently determine the
overall passivation process which is accompanied by the
emergence of combined inductive and Warburg–like spectra
at low frequencies. Nevertheless, as it was mentioned earlier at
shorter exposure times of 8 h, the rate controlling phenomenon
was mainly adsorption–desorption processes, consequently
an inductive behavior was conspicuously observed at the
lowest frequencies.
4. CONCLUSIONS
The corrosion and passivation behavior of AA50520 alloy
in 0.25 M Na2SO4 solution in the absence or presence of
H2O2 during short and long term exposure was studied by a
diverse range of electrochemical techniques. Conclusive remarks
from the present work can be summarized briefly as follows:
(1) Based on the potentiodynamic polarization measure-
ments, a lower advance of corrosion for AA5052 in sulfate
solution was observed after introduction of H2O2.
(2) Analysis of the j-t transients revealed some important
pitting corrosion parameters, namely tinc. and jss. It was confirmed
that H2O2 is able to improve pitting resistance through grad-
ual augmentation of H2O2 concentration from 0.5 to 2 vol%,
tinc increased and jss decreased from 0.12 to 0.03 mA/cm2. At
higher temperature, corrosion parameters were intensified
probably due to the emergence of a thinner and looser oxide
film.
(3) OCP transient together with FESEM observations indi-
cated that the mere presence of H2O2 in the electrolyte boosts
formation of an effective barrier film against corrosion attacks.
In this respect, addition of 2 vol% H2O2to 0.25M Na2SO4
solution culminated in a shift in stable OCP value towards
more noble potentials (from –832 to –810 mVSCE).
(4) EIS results also revealed that by increasing H2O2 con-
centration from 0.5 to 1.5 vol%, oxide film resistance Rf
2
expanded from 16.1 to 26.2 kcm , indicative of the impressive
impact of H2O2 on passive film thickening. Moreover, by
increasing exposure time from 24 h to 72 h, Rf increased from
2
20.7 to 70.5 kcm as a result of oxide film growth and charge
transfer limitation. At these prolonged exposure times, further
film thickening and diffusion controlled processes led to the
appearance of the Warburg–like spectra at the lowest frequen-
cies.
619
(5) At shorter exposure times (up to 8 h) to H2O2–containing
solution, the impedance spectra were predominantly deter-
mined by the adsorption–desorption process of adsorbed spe-
cies which was manifested as an inductive response at lowest
frequencies. However, after more than 24 h of exposure time,
the corrosion mechanism of AA5052 was obviously switched
to mixed inductive–Warburg behavior.
The present results show that H2O2 facilitates kinetics of
oxide film formation on the surface of AA5052 and decreases
corrosion rate at ambient and elevated temperatures. These
finding suggest that in applications where H2O2 contact is
inevitable, at ambient temperatures AA 5052 is a good can-
didate to be considered for material selection since H2O2
increases protective oxide film growth, however at higher
temperatures pitting exacerbates even in the presence of
H2O2, therefore special care should be given to pitting con-
trol and inspection at higher temperatures.
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