Corrosion and Electrochemical Properties of Aluminum and Lithium Alloys

Egyptian Journal of Petroleum (2016) xxx, xxxxxx
H O S T E D BY
Egyptian Petroleum Research Institute
Egyptian Journal of Petroleum

www.elsevier.com/locate/egyjp
www.sciencedirect.com
FULL LENGTH ARTICLE
Corrosion behavior and electrochemical properties

of carbon steel, commercial pure titanium, copper
and copperaluminumnickel alloy in 3.5% sodium
chloride containing sulfide ions
H. Nady a,b,*, M.M. El-Rabiei a, M. Samy a
a
b
Chemistry Department, Faculty of Science, Fayoum University, Fayoum, Egypt

Chemistry Department, Faculty of Science & Arts in Qurayat, Al-Jouf University, Saudi Arabia
Received 20 December 2015; revised 15 February 2016; accepted 28 February 2016
KEYWORDS
Corrosion resistance;
Titanium;
Copper and copper alloys;
Carbon steel;
EIS;
Passive films
Abstract In this research the electrochemical performance of Cu, Cu10Al10Ni, Cp-Ti and Csteel in 3.5% sodium chloride containing sulfide ions was investigated. Different electrochemical
methods such as polarization technique and electrochemical impedance spectroscopy, EIS, were
used. Surface examination and morphological studies were employed. The effect of immersion time
of the different alloys was extensively studied by EIS. A comparison was made between the electrochemical stability of the different alloys in this media. Polarization measurements reveal that Cp-Ti
and Cu10Al10Ni alloys possess lower corrosion rates than both Cu and carbon steel. EIS measurements, have shown that a more thicker and resistive passive film is formed on Cp-Ti alloy due to
the formation of TiO2 film of duplex nature. The incorporation of Ni in the Cu2O barrier film leads
to the stabilization of Cu10Al10Ni alloy and the stability is enhanced in the presence of Al. The
thickness and resistance of the barrier layer formed on the alloy surfaces increase with the increasing
the immersion time. The formation of such passive film on the surface of different alloys was discussed. An equivalent circuit model for the electrode/electrolyte interface under different conditions
was proposed. The experimental impedance data were fitted to the theoretical data according to the
proposed model.
2016 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction
* Corresponding author at: Chemistry Department, Faculty of
Science, Fayoum University, Fayoum, Egypt. Tel.: +20
01069878104, +966 535589807.
E-mail addresses: hashem_nady@yahoo.com, nhm00@fayoum.edu.eg
(H. Nady).
Peer review under responsibility of Egyptian Petroleum Research
Institute.
Hydrogen sulfide, H2S, corrosion has been a research topic for

several decades [1]. Most studies on this subject were based on
an engineering perspective because of fractures in metals
caused by H2S especially in the case of steel [24]. Also the
electrochemical analysis technology has been widely used in
http://dx.doi.org/10.1016/j.ejpe.2016.02.008
1110-0621 2016 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: H. Nady et al., Corrosion behavior and electrochemical properties of carbon steel, commercial pure titanium, copper and copper
aluminumnickel alloy in 3.5% sodium chloride containing sulfide ions, Egypt. J. Petrol. (2016), http://dx.doi.org/10.1016/j.ejpe.2016.02.008
2
recent decades to study the corrosion process and has been
proven to be effective [510]. Copper and copper alloys belong
to the group of alloys having sufficient resistance to corrosion
in seawater. However, they corrode under specific conditions.
Hydrogen sulfide is the most common pollutant which may
cause an intensive corrosion of copper and copper alloys in
seawater where the presence of sulfide ions lead to the modification of the oxide layer on copper and copper based alloys.
Acceleration of corrosion is due to the enhancement of the
cathodic process. One of the most important parameters playing a major part in the processes of corrosion of copper alloys
in seawater polluted with sulfides is their concentration. Traverso et al. [11] have found that the most intensive corrosion
is caused by sulfides at initial levels of 4 ppm. Gudas and Hack
[12] stated that wrought 90/10 CuNi is susceptible to accelerated attack in seawater containing only 0.01 ppm of sulfides.
Mukhopadhyay, Baskaran [13] and Chauhan, Gadiyar [14]
determined the chemical composition of corrosion products
created on 70/30 CuNi in sulfide polluted seawater. Instead
of Cu2O and green CuCl23Cu(OH)23H2O, a gray layer of
Cu2S(NiFe)3S4 and Cu2O was created. In our recent previous
paper the stability of Cu10Al05Ni alloy in chloride solutions
polluted by sulfide ions was studied [15]. Also the effect of Cl
and H2S on steel weld [1619] was studied. The results demonstrated that H2S could accelerate both the anodic iron dissolution and the cathodic hydrogen evolution in most cases, but
some results showed that H2S could also inhibit the corrosion
of iron under certain special conditions [20,21]. Zimer et al.
[22] recently studied the initial stage of pitting corrosion in
AISI 1040 steel through temporal series micrographs coupled
with an open-circuit potential and polarization curves in an
alkaline sulfide solution. Due to a set of excellent properties,
chemical and mechanical properties, Titanium and titanium
based alloys are commonly employed in many functions such
as chemical, marine, space and biomedical, dental and orthopedic applications [2325]. The high corrosion resistance of
titanium in aggressive environments is ensured by a compact
and chemically stable oxide film that spontaneously covers
the metal surface which is amorphous or poorly crystalline
and mainly composed of titanium oxide, TiO2 [26]. Though
much effort has been put into separate individual studies for
each alloy with the aggressive media, H2S and/or NaCl, little
research has been carried out on collection studies including
different alloys in these media. In this work, some common
alloys namely, Cu, Cu10Al10Ni, C-steel and commercially
pure titanium, Cp-Ti, are investigated in both 3.5%NaCl
and 3.5%NaCl polluted by sulfides. The mechanism of corrosion processes taking place at the electrode/solution interface
will be discussed, and a categorization of the different investigated alloys according to their stability in this aggressive medium can be made.
2. Experimental details
2.1. Materials and sample preparation
The working electrodes were made from commercial grade Cu,
Cu10Al10Ni, carbon steel and commercial pure Ti. The rods
were prepared in metallurgical work shop. The prepared alloys
are cast alloys without any special treatment. The metallic rods
are mounted into glass tubes by two-component epoxy resin
H. Nady et al.
leaving a surface area of 0.2 cm2 to contact the solution.
Chemical composition of Titanium in mass percent: 0.30 Fe,
0.25 O, 0.06 C, 0.03 N, 0.015 H and balance Ti. The chemical
composition of carbon steel is: 0.34 C, 0.93 Mn, 0.26 Si, 0.0.2
S, 0.04 P, 0.01 Cu, 0.01 Cr, 0.02 Ni and balance Fe. The chemical composition of pure Cu and Cu10Al10Ni alloy electrodes is: Cu (99.928 Cu, 0.001 Al, 0.02 Ni, 0.007 Zn, 0.003
Mn, 0.033Sn, 0.002 Fe, 0.004 Si, 0.001 Mg and 0.001 Ti) and
Cu10Al10Ni (76.00 Cu, 11.28 Al, 9.95 Ni, 0.10 Zn, 0.02
Mn, 0.14 Sn, 2.26 Fe, 0.24 Si, 0.01 Mg and 0.01Ti). The electrochemical cell is a three-electrode all-glass cell, with a platinum spiral counter electrode and saturated calomel, SCE,
reference electrode. Before each experiment, the working electrode was polished using successive grades emery papers down
to 2500 grit, washed thoroughly with bi-distilled water, then
transferred quickly to the electrolytic cell. The electrochemical
measurements were carried out in a stagnant, naturally aerated
3.5 (mass, m/volume, v)% NaCl containing 2 ppm S2 solution. The source of sulfide ions in this research is Na2S salt.
2.2. Electrochemical measurements
The corrosion behavior of the specimens under investigation
were monitored using electrochemical impedance spectroscopy, EIS, and DC polarization techniques during immersion in 3.5% NaCl and 3.5% NaCl containing 2 ppm S2
solution open to air and at room temperature. The polarization experiments and EIS, investigations were performed using
a Voltalab PGZ 100 All-in-one Potentiostat/Galvanostat.
The potentials were measured against and referred to the standard potential of the SCE (0.245 V vs. the standard hydrogen
electrode, SHE). To achieve quasi-stationary condition, the
polarization experiments were carried out using a scan rate
of 5 mV s1. The total impedance, Z, and phase shift, h, were
measured in the frequency range from 105 to 0.1 Hz. The
superimposed ac-signal amplitude was 10 mV peak to peak
as assigned by measuring system. To achieve reproducibility,
each experiment was carried out at least twice, where a range
of 23 mV was considered to be reasonable for open-circuit
potential measurements and 5 mV for the polarization experiments. The surface morphology of some electrodes was investigated by scanning electron microscopy, SEM (Model Quanta
250 FEG, FEI Company, Netherlands).
3. Results and discussion
3.1. Potentiodynamic polarization measurements
The electrochemical behavior of the different alloys was investigated by the polarization technique. Tafel extrapolation measurements were used. The shape of polarization curves can
obtain information on the kinetics of the corrosion reactions.
The polarization curves of the alloys were recorded after
240 min of electrode immersion in stagnant naturally aerated
3.5% NaCl containing 2 ppm S2 ions at a scan rate of
10 mV/s and 25 C. Polarization curves for Cu, Cu10Al
10Ni, C-steel and Cp-Ti are presented in Fig. 1. The fitted values of corresponding kinetic parameters such as anodic and
cathodic Tafel slope (ba and bc respectively), corrosion potentials, Ecorr, and corrosion current densities, icorr, are listed in
Table 1. Polarization curve for Cu shows an obvious anodic
2-
3.5% NaCl + 2 ppm S
-2
log (Current density /A cm )
-1
-2
-3
-4
C-Steel
-5
Cu
-6
Cp-Ti
Cu-10Al-10Ni
-7
-8
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2
0.0
Potential vs. SCE (V)
Figure 1 Potentiodynamic polarization curves of Cu, Cu10Al

10Ni, C-Steel and Ti measured in 3.5 wt.% NaCl + 2 ppm S2
aqueous solution at 25 C.
sented in Fig. 2. It presents the polarization curves of the four

alloys, Cu (a), Cu10Al10Ni (b), C-Steel (c) and Cp-Ti (d)
after 240 min of electrodes immersion in sulfide free chloride
solutions and containing sulfide ions. It is clear that the addition of sulfide ions to the chloride solution increases the corrosion current density; also, it shifts the corrosion potential to
more negative values for all alloys except in the case of titanium where it shifted to more positive values. Interestingly,
the current densities for Cu, Cu10Al10Ni, and C-Steel in
the anodic branch of the polarization curves increased in the
presence of sulfide while in the case of Cp-Ti the anodic current branches in the absence and presence of sulfide nearly
coincided with each other which may be meaning that the high
stability of Cp-Ti not much affected by the presence of sulfide
ions. For comparison, the characteristic parameter, corrosion
current densities, icorr, Tafel slops, (ba and bc), and corrosion
potentials, Ecorr of the different alloys in chloride 3.5% NaCl
solutions are presented in Table 2. The accepted cathodic reaction occurring on Cu and Cu-based alloys in aqueous solutions
is always represented by the oxygen reduction [27]:
O2 2H2 O 4e ! 4OH
Table 1 Polarization parameters of the different materials

under investigation after electrode immersion in 3.5% NaCl
containing 2 ppm S2 ions at 25 C.
Alloys
Ecorr/
mVSCE
icorr/
lA cm2
ba/
mV dec1
bc/
mV dec1
Cu
Cu10Al10Ni
Cp-Ti
Carbon steel
1351
609
972
1009
63.6
30
30
69.7
122.2
146
34.7
125.3
67
101
19.3
86.6
behavior with the most shifted corrosion potential to negative

values, Ecorr 1.351 V and a high corrosion current density
approximately of 63.6 lA cm2. As the electrode potential
was increased to above Ecorr, the anodic current increased
and gradually decreased resulting in an anodic peak at 0.9 V,
While the addition of the alloying elements, Al and Ni to pure
Cu results in shifting the corrosion potential, Ecorr to more
positive values 0.609 V and decreasing the corrosion current
density to a minimum value of 30 lA cm2 just as in the case
of Cp-Ti alloy, it exhibits the smallest current density of the
same value with corrosion potential at about 0.972 V. Ti
exhibited a passivation characteristic extending the widest passive region from 0.950 V to 0.35 V. Although the corrosion potential of carbon steel slightly shifted from, close to,
that of titanium by 37 mV, carbon steel showed an obvious anodic behavior with the largest corrosion current density
of approximately 69.7 lA cm2. The corrosion current density
increases gradually as the potential increases and the passive
region only extended from 0.9 to 0.6 V. Further
increasing the potential resulted in an abrupt current at
0.6 V indicating a passivity break down of non-protective
nature of film formed. As indicated from the polarization
parameters the corrosion rates of the different alloys obey
the sequence, C-steel > Cu > Cu10Al10Ni = Cp-Ti alloy.
The effect of the addition of sulfide ions to chloride solution
on the corrosion behavior of the different alloys is clearly pre-
The anodic dissolution and film formation on Cu surface in

chloride solutions can be represented by the reactions [27,28]:

Cu 2Cl ! CuCl
2 e
2
CuCl
2
It was suggested that the presence of

at the metal
surface leads to hydrolysis reaction and the formation of
Cu2O [29] according to:
2CuCl
2 H2 O ! Cu2 O 4Cl 2H
In Al containing alloys the surface dissolution of Al leads to

an additional passivation process and formation of Al2O3
according to [29,30]:

Al 4Cl ! AlCl
4 3e
2AlCl
4 3H2 O ! Al2 O3 6H 8Cl
Accordingly, the corrosion resistance of Cu10Al10Ni

alloy increases and is enhanced in the presence of Ni. The presence of Ni with copper leads to its segregation in the Cu2O
layer resulting in a doped Cu2O layer thus corrosion resistance
is increased [3034]. Therefore, Cu10Al10Ni alloy exhibits
lower current density than pure copper, 7.4 lA cm2, in chloride solutions. In sulfide containing solutions HS- will be
formed:
S2 H2 O $ HS OH
HS will combine with the metallic copper to form an

adsorbed precursor of the oxidation reaction:
Cu HS ! CuHS ads
The coupled anodic dissolution is then represented by Eq.

(8), which is followed by dissociation and recombination processes [35]:
CuHS ! CuHS e
CuHS ! Cu HS
2Cu HS OH ! Cu2 S H2 O
10
H. Nady et al.
(b)
Cu
-1
-2
-2
-3
-4
-5
3.5% NaCl
2-
3.5% NaCl + 2 ppm S
-6
log (current density, i /A cm-2)
log (current density /A cm-2)
(a)
-7
Cu-10Al-10Ni
-3
-4
-5
3.5 % NaCl
-6
3.5 % NaCl + 2 ppm S
-7
-8
-900 -800 -700 -600 -500 -400 -300 -200 -100
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
(c)
(d) -2.0
-1.0
C-Steel
-2.0
-2.5
-3.0
-3.5
3.5% NaCl
2-
3.5% NaCl + 2 ppm S
-4.0
-4.5
log (current density /A cm -2)
Cp-Ti
-1.5
log (current density /A cm-2)
--
-2.5
-3.0
-3.5
-4.0
-4.5
3.5% NaCl
-5.0
3.5% NaCl + 2 ppm S
2-
-5.5
-5.0
-6.0
-5.5
-1.2
-1.0
-0.8
-0.6
-0.4
-1.2
-1.0
-0.8
-0.6
-0.4
Figure 2 Potentiodynamic polarization curves of Cu (a),Cu10Al10Ni (b), C-Steel (c) and Cp-Ti (d), alloys after 3 h immersion in
stagnant naturally aerated 3.5% NaCl and 3.5% NaCl containing 2 ppm S2 solutions at 25 C.
Table 2 Polarization parameters of the different materials

under investigation after electrode immersion in 3.5% NaCl at
25 C.
Alloys
Ecorr/
mVSCE
icorr/
lA cm2
ba/
mV dec1
bc/
mV dec1
Cu
Cu10Al10Ni
Cp-Ti
Carbon steel
601
464
1096.6
999.6
53.5
7.4
22.6
54.9
125.3
122
41.9
112.9
66
118
35.7
84.7
Therefore the overall reaction is:

4Cu 2S
2
O2 2H2 O $ 2Cu2 S 4OH
11
However, the presence of Cu2S prevents the protective

effectiveness of Cu2O film which is always formed in aqueous
solutions, and so the passive film resistance of Cu and Cu
10Al10Ni decreases in sulfide polluted chloride solutions.
Under conditions of low (SH) and high Cl the formation
of the soluble chloride complex, CuCl

2 , by the reaction with
the surface intermediate, Cu(SH)ads, could compete with the
film formation reaction [36]. Dissolution as CuCl
2 via Eq.
(12), when SH concentration is low at the Cu alloy surface,
could lead to the transport of Cu+ through pores to the Cu2S/solution interface. At a higher SH- concentration, Cu2S formation would occur via Eq. (13) and this reaction will
dominate at the film/electrolyte interface:
CuHS 2Cl ! CuCl HS e
12

2CuCl
2 HS ! 2Cu2 S 4Cl H
13
Such a transportdeposition process would account for the

fine particles, which nucleate and grow on the alloy surfaces at
short times.
As a result of its higher corrosion rate compared to other
different alloys, C-steel exhibits passive region, only, extends
to a small range of potential then, the current suddenly raises
steeply without any sign for oxygen evolution, denoting
the breakdown of the passive film and the initiation and
propagation of pitting attack (cf. Fig 2c). Consequently the

influence of Cl ions on the corrosion rate, in case of Csteel, can be interpreted as a balance between two processes
competing on the metal surface, stabilization of the passive
film by OH adsorption and disruption of the film by Cl ions
adsorption. When the activity of chlorides overcomes that of
hydroxyls, corrosion occurs [37]. During corrosion, the reversible formation of Fe(OH)ad adsorbed on the bare metal is
the first process and followed by the following sequence
[38,39]:
Fe OH ! FeOH
ads
14

FeOH
ad ! FeOHads e
15
FeOHads OH ! FeOH2 e
16
FeOH2 OH ! FeOOH H2 O e
17
In the presence of chloride ions, the Fe(OH)ads coverage

decreases resulting in an increase in the anodic dissolution of
the metal where the following reactions occur:
Fe Cl ! FeClads e
18

FeClads ! FeCl
aq e
19
From the results of the potentiodynamic polarization curves

mentioned above (cf. Fig 2c) the cathodic behavior of C-steel
in the absence and presence of S2 was very similar, while
the anodic process of C-steel was accelerated in the presence
of S2. Also the passivity break down occurs at more negative
values in the presence hydrogen sulfide. This attributed to the
easy adsorption of S2 molecules on carbon steel surface and
those molecules will first occupy the active site on the steel surface, thereby accelerating the steel dissolution [21]. The anodic
and cathodic processes of C-steel in H2S-containing solution
could be described by the following reactions [19,40]:Anodic
reaction:
Fe ! Fe2 2e
in the corrosion products was worse than that of troilite (iron

sulfide with the simple formula, FeS) [21]. Consequently, even
if appreciable amounts of mackinawite deposited on carbon
steel surface at higher H2S concentration, what the sulfide film
did not exhibit contribution to the protective effect. Therefore,
the corrosion rates of C-steel increased [21].
In contrast to Cp-Ti, as the potential increases, extends
over a wide range of potentials, the current density is very
low and steady in the passive regions in both free and polluted
H2S sodium chloride solutions (cf. Fig. 2d). This is attributed
to the naturally formed stable passive film, TiO2. It is generally
accepted that the mechanism of the passive film formation is
determined completely by the diffusion of metal ions to the
surface and the subsequent transfer reactions at the interface.
The formation of passive layer requires transfer of titanium
and hydroxyl ions as follows [42]:
Ti ! Ti2 2e
27
2+
Ti is unstable and once it is formed it will react with H2O

to produce Ti3+:
2Ti2 2H2 O ! 2Ti3 2OH H2
28
Ti3 3OH ! TiOH3
29
Transformation of Ti(OH)3 might be taking place to

hydrated TiO2 layer in a dynamic equilibrium reaction as
follows:
2TiOH3 2TiO2 H2 O H2
30
Accordingly, TiO2 formed by migration and adsorption of

the OH ions through the structure defects on the thinnest
part of the oxide film [42]. The high corrosion resistance of
Cp-Ti is due to the strong adherence of oxide layer, TiO2,
20
Cathodic reaction:
2H 2e ! H2
and =or
21
2H2 S 2e ! 2HS H2
22
A probable formation mechanism of corrosion products

due to the easy adsorption of H2S or SH on the surface of
C-steel is as follows [20,21]:
Fe H2 S H2 O FeSH
ads H3 O
and=or
23
Fe HS FeSH
ads
24

FeSH
ads ! FeSHads 2e
25
FeSH+
ads
on the electrode surface could be

The species
incorporated directly into a layer of iron sulfide (mackinawite)
via the following reaction [41]:
FeSH
ads ! FeS1x xSH 1 xH
26
The amount of the corrosion products adsorbed also

increased as S2 concentration increases. However, the corrosion product film was loose and had some defects in its solid
structure. In addition, the protective ability of mackinawite
Figure 3 (a) Equivalent circuit model used in the fitting of the

impedance data at different conditions, Rs = solution resistance,
Rct = charge-transfer resistance, Cdl = double layer capacitance,
Rpf = passive film resistance and Cpf = passive film capacitance.
(b) Equivalent circuit model used in the fitting of the impedance
data for C-steel in 3.5% NaCl solution.
H. Nady et al.
where, a represents an empirical parameter (0 6 a 6 1) and f is
the frequency in Hz [43]. The dispersion formula takes into
account the deviation from the ideal capacitor (RC) behavior
in terms of a distribution of time constants due to surface inhomogeneity, roughness effects, and variations in properties or
composition of surface layers [44,45]. To account for the presence of a passive or barrier film, the impedance data were analyzed using the equivalent circuit model shown in Fig. 3, where
another combination of Rpf Cpf representing the passive film
resistance, Rpf, and the passive film capacitance, Cpf, was
introduced.
Fig. 4 represents the Bode and Nyquist plots of Cu electrode after different times of immersion in stagnant naturally
aerated 3.5% NaCl {cf. Fig. 4(a1 and b1} and 3.5% NaCl
+ 2 ppm S2 {cf. Fig. 4(a2 and b2)} solutions at 25 C. The
initial impedance (Z) recorded 15 min after electrode immersion drifts continuously toward an increasing value, which
indicates a decrease in the corrosion rate of Cu with time.
From the respective phase angle Bode plots {cf. Fig. 4(a1
and a2)}, two phase maxima were present, the major one at
lower frequencies and the other as a shoulder at intermediate
frequencies, such behavior indicates the presence of two time
constants representing the electrode processes. The phase max-
which exhibits a duplex structure with an inner layer (thick and

microcrystalline) and an outer layer (with grains). Substantially, the formation of the adherent TiO2 oxide layer and
the incorporation of Ni2+ into Cu2O layer explains why both
Cp-Ti and Cu10Al10Ni alloys exhibit the lowest corrosion
rates than both Cu and C-steel alloys.
3.2. Electrochemical impedance spectroscopic investigations
The experimental impedance spectra obtained, at OCP, with
the different materials, Cu, Cu10Al10Ni, Cp-Ti and Csteel exposed to 3.5% NaCl and 3.5% NaCl + 2 ppm S2 at
different intervals of electrode immersion are presented in
the form of Bode and Nyquist plots in (Figs. 47).The impedance data were analyzed using software provided with the
impedance system where the dispersion formula was used.
For a simple equivalent circuit model, consisting of a parallel
combination of a capacitor, Cdl, and a resistor, Rct, in series
with a resistor, Rs, representing the solution resistance, the
electrode impedance, Z, is represented by the mathematical
formulation:
3.0
Cu in 3.5% NaCl
15 min.
60 min.
120 min -60
180 min.
240 min.
2.5
2.0
log (Z / cm2)
b1
-80
-40
1.5
1.0
-20
210
Cu/ 3.5% NaCl
180
150
Phase / degree.
a1
31
- Zi / cm2
Z Rs Rct =1 2pfRct Cdl a
120
90
15 min.
60 min.
120 min
180 min.
240 min.
60
0.5
30
0
0.0
0
-2
log (f / HZ)
--
1.5
-60
-40
1.0
-20
0.5
0
0.0
400
--
Cu / 3.5% NaCl + 2pp S
500
15 min.
60 min.
120 min
180 min.
240 min.
100
80
- Zi / cm2
log (Z / cm2)
2.0
120
15 min.
60 min.
120 min
180 min.
240 min.
Phase / degree.
Cu / 3.5% NaCl + 2pp S
2.5
200
300
2
Zr / cm
b2
-80
a2
100
60
40
20
0
20
-2
2
log (f / HZ)
40
80
120
160
200
240
280
Zr / cm
Figure 4 Bode (a) and Nyquist (b) plots of Cu electrode after different times of immersion in stagnant naturally aerated 3.5% NaCl (a1
and b1) and 3.5% NaCl + 2 ppm S2 (a2 and b2) solutions at 25 C.
7
region in 3.5% NaCl {cf. Fig. 4b1}. This behavior is typical
Warburg impedance indicating the presence of diffusion process, diffusion of reactants and/or products to the interface
[46]. In case of Cu the appearance of the Warburg impedance
in the impedance spectrum could be attributed to the diffusion
of dissolved oxygen from the bulk solution to the Cu surface
[47]. With sulfide ion addition, the diffusion process, i.e. Warburg impedance disappeared and a complete capacitive loop
was observed {cf. Fig. 4b2}.
The same behavior was observed for Cu10Al10Ni alloy
in sulfide free and sulfide polluted 3.5% NaCl solution as
described in Fig. 5. But the presence of alloying elements, Al
and Ni result in the broadness of the phase angle more than
that recorded for Cu {cf. Figs. 4(a1 and a2) and 5 (a3 and
a4)}. Also it is clear that the total impedance increases with
the increase in the immersion time, and higher than that
recoded for Cu, which indicates that the protective film formed
on the Cu10Al10Ni alloy becomes more stable with time
ima appearing in the low frequency range were attributed to

the protective oxide film and the phase maximum at the intermediate frequency range corresponds to the electrical double
layer. The changes in the phase maximum with time indicate
the differences in the relaxation time constants at different
exposure times. From the corresponding phase angle Bode
plots, it can be seen that the angle values at the low frequency
zone increase with the immersion time, which indicates a
decrease in the corrosion rate of the alloy with time. But the
high of phase angle decrease in presence of sulfide. The total
impedance magnitude values of the Cu increases with the
increase in exposure time implying an increase in the corrosion
resistance due to the growth of the passive film till the steady
state is achieved {cf. Fig. 4(a1 and a2)}, where the passive film
resistance, Rpf, recorded after 240 min in 3.5% NaCl + 2 ppm
S2 decreases to half its value in 3.5% NaCl. Nyquist plot of
the impedance diagrams exhibited an incomplete capacitive
reactance and a slash with a tilt angle in the low-frequency
a3 3.5
b3 0.6
Cu-Al-Ni/ 3.5% NaCl
Cu-Al-Ni 3.5% NaCl

-60
3.0
0.5
1.5
-20
15 min.
60 min.
120 min
180 min.
240 min.
1.0
0.5
2.0
0.4
- Zi / cm
-40
Phase / degree.
log (Z / cm2)
2.5
0.3
0.2
15 min.
60 min.
120 min
180 min.
240 min.
0.1
0
0.0
0.0
-2
-0.2
0.0
0.2
0.6
0.8
Zr / cm
log (f / HZ)
1.0
1.2
1.4
b4
a4
--
Cu-Al-Ni/ 3.5% NaCl+ 2ppm S
--
-60
400
-40
1.5
-20
1.0
- Zi / cm
2.0
500
15 min.
60 min.
120 min
180 min.
240 min.
2.5
-80
Phase / degree.
Cu-Al-Ni/ 3.5% NaCl+ 2ppm S
3.0
log (Z / cm2)
0.4
300
15 min.
60 min.
120 min
180 min.
240 min.
200
100
0.5
0.0
-2
log (f / HZ)
20
6
-100
100 200 300 400 500 600 700 800 900

2
Zr / cm
Figure 5 Bode (a) and Nyquist (b) plots of CuAl10Ni electrode after different times of immersion in stagnant naturally aerated 3.5%
NaCl (a3 and b3) and 3.5% NaCl +2 ppm S2 (a4 and b4) solutions at 25 C.
H. Nady et al.
than that formed on Cu. This attributed to segregation of Ni,

where Ni2+ from the alloy dissolution incorporated into the
crystal lattice of Cu2O and the number of cation vacancies
decreases with increasing the nickel content [30,31], thats represents not inconsiderable ratio about 10% from the alloy content. Segregation into the Cu2O barrier layer occurs via a solid
state reaction and Ni2+ interacts with mobile cation vacancies
which leads to a decrease in the ionic conductivity and an
increase in the electronic conductivity of the barrier film leading to higher corrosion resistance [33,34]. Based on these studies and EIS observations, the electrical equivalent circuit
shown in Fig. 3a was used to fit the experimental data for
Cu and Cu10Al10Ni alloys, where the calculated equivalent
circuit parameters at different immersion time in 3.5%NaCl
and 3.5% NaCl + 2 ppm S2 are presented in (Tables 3 and
4). From the equivalent circuit parameters, it is evident that
passive film resistance, Rpf, recorded in the absence of sulfide
ions is bigger than that observed in the presence of sulfide ions.
This behavior was attributed to the diffusion of sulfide ions
into the protective oxide layer, reacting with Cu ions to form
a non-adherent copper sulfide film [48].
Bode and Nyquist plots impedance diagrams of C-steel during the early stages of corrosion for different immersion periods are shown in Fig. 6. When C-steel was immersed in
aqueous 3.5% NaCl solution from 15 min to 240 min the Bode
plots exhibited one phase maxima at the intermediate frequency{cf. Fig. 6(a5 and b5)}. Also Nyquist diagram approx-
Table 3
25 C.
imated by a single capacitive semi-circle, showing that the

corrosion process was mainly charge transfer controlled [49].
But when the electrode was immersed 3.5% NaCl was polluted
by 2 ppm sulfide ions {cf. Fig. 6(a6 and b6)}; the Bode plots
presented two phase maxima at high and low frequencies. In
addition to Nyquist plots the Nyquist presented two capacitive
reactance, the capacitive reactance in the high frequency region
corresponded to the electric double layer behavior at the interface, whereas the incomplete capacitive reactance arc corresponded to the corrosion products in the low frequency
region. The equivalent circuit model used to fit the impedance
data when the electrode was exposed in 3.5% NaCl solution is
illustrated in Fig. 3b. In the circuit, Rs is the solution resistance, Rcorr, corrosion resistance or charge transfer resistance,
while the equivalent circuit model for the C-steel immersed in
3.5% NaCl + 2 ppm S2 is illustrated in Fig. 3a. In this case,
Rct, is the charge transfer resistance, Cdl, charge transfer capacitance, Cpf, is the corrosion product film capacitance and Rpf,
represents the corrosion product resistance. The equivalent circuit parameters obtained in the two cases are depicted in
Table 5. Its clearly shown that the corrosion resistance
increases as the immersion time increases. This result is attributed to the generation and gradual increase of corrosion products at the electrode surface.
In case of Cp-Ti, the Nyquist plots, as seen in Fig. 7(b7 and
b8) showed two relaxation time constants. This is also indicated by the two peaks in the phase angle plot at the high
Equivalent circuit parameters for the Cu electrode in 3.5% NaCl solution in the absence and presence 2 ppm of sulfide ions at
Solutions
Time/min.
Rs/X
Rct/X cm2
3.5% NaCl
15
60
120
180
240
1.2
1.0
1.0
1.1
1.24
202.3
258.7
342.6
317.0
350.7
3.5% NaCl + 2 ppm S2
15
60
120
180
240
1.6
2.4
2.8
4.8
4.7
111.0
152.4
158.1
152.3
216.5
Cdl/lF cm2
a1
Rf/X cm2
Cf/lF cm2
a2
24.9
30.8
37.2
25.1
22.7
0.99
0.99
0.99
0.99
0.99
281.0
513.5
482.7
533.7
532.1
89.5
247.9
263.7
188.4
148.7
0.99
0.99
0.99
0.99
0.99
35.8
52.2
201.3
131.6
146.9
0.99
1.0
1.0
1.0
1.0
140.4
138.2
156.5
191.0
218.4
283.2
363.8
406.7
416.5
581.6
0.99
0.99
0.99
0.99
0.99
Table 4 Equivalent circuit parameters for the Cu10Al10Ni in 3.5% NaCl solution in the absence and presence 2 ppm of sulfide ions
at 25 C.
Solutions
Time/min.
Rs/X
Rct/X cm2
3.5% NaCl
15
60
120
180
240
2.5
2.5
2.6
2.8
2.9
260.5
432.0
938.7
734.5
1060.0
15
60
120
180
240
2.6
2.7
2.7
2.9
3.0
374.8
464.3
641.3
774.5
966.2
Cdl/lF cm2
12.2
18.4
13.6
5.42
4.7
84.9
108.2
99.3
129.8
164.7
a1
Rf/X cm2
Cf/lF cm2
a2
0.99
1.0
1.0
1.0
1.0
973.6
1049.0
1060.0
1430.0
1692.0
326.9
303.3
189.1
175.8
188.1
0.99
0.99
0.99
0.99
0.99
1.0
1.0
1.0
1.0
0.99
424.8
496.9
732.2
954.4
1418
187.2
320.2
434.6
666.9
897.4
0.99
0.99
0.99
0.99
0.99

-40
1.0
-30
-20
0.8
-10
0.6
0.4
15 min.
60 min.
120 min
180 min.
240 min.
10
8
- Zi / cm2
1.2
Steel/ 3.5% NaCl
12
15 min.
60 min.
120 min
180 min.
240 min.
1.4
log (Z / cm2)
b5
Steel/ 3.5 % NaCl
1.6
Phase / degree.
a5
6
4
2
0.2
0
0.0
2
log (f / HZ)
-30
-20
0.8
-10
0.6
0.4
Phase / degree.
1.0
10
15
20
2
Zr / cm
25
30
--
Steel/ 3.5% NaCl+ 2ppm S
-40
15 min.
60 min.
120 min
180 min.
240 min.
1.2
b6
20
Steel/ 3.5% NaCl + 2ppm S
1.4
log (Z / cm2)
-50
--
a61.6
15 min.
60 min.
120 min
180 min.
240 min.
15
- Zi / cm
-2
10
6
10
0.2
10
0.0
-2
-1
10
log (f / HZ)
15
20
2
Zr / cm
25
30
Figure 6 Bode (a) and Nyquist (b) plots of Carbon-steel electrode after different times of immersion in stagnant naturally aerated 3.5%
NaCl (a5 and b5) and 3.5% NaCl +2 ppm S2 (a6 and b6) solutions at 25 C.
Table 5
Equivalent circuit parameters for the C-steel in 3.5% NaCl solution in the absence and presence 2 ppm of sulfide ion at 25 C.
Solutions
Time/min.
Rs/X
Rct/X cm2
3.5% NaCl
15
60
120
180
240
1.8
1.7
1.5
1.8
1.7
25.6
39.6
47.8
39.3
23.9
15
60
120
180
240
1.8
1.9
1.7
1.8
1.9
2.12
1.91
1.87
1.82
1.67
and low frequencies where the phase angles increase as the

immersion time increased {cf. Fig. 7(a7 and a8)}. These behaviors observed evinced the formation of a duplex film over CpTi. According to reports, the duplex film formed is composed
of a dense inner barrier layer and a porous outer layer [50,51].
Cdl/lF cm2
1.97
10.1
21.1
8.1
8.4
555
995
1310
1150
1113
a1
Rf/X cm2
Cf/lF cm2
a2
25.8
48.3
54.6
60.6
68.8
6.8
7.5
9.2
13.1
18.5
0.99
0.99
0.99
0.99
1.0
0.99
0.99
0.99
0.99
0.99
0.98
0.93
0.94
0.96
0.97
Its clearly shown that, the phase angle at high frequency

depressed in the presence of H2S. In Bode plots, curves that
are represents the variation of frequency with total impedance,
a straight line were observed with the slope approaching 1
{cf. Fig. 7(a7 and a8)}. The resistance gradually increased with
10
H. Nady et al.
-80
a7
b7 11
Ti/ 3.5% NaCl
10
Ti/ 3.5% NaCl
15 min.
60 min.
120 min
180 min.
240 min.
7
6
- Zi / cm2
-40
Phase / degree.
log (Z / cm2)
-60
3
5
15 min.
60 min.
120 min
180 min.
240 min.
4
3
-20
2
1
0
0
-2
0
6
-1
-0.5
0.0
0.5
1.0
2.0
2.5
3.0
3.5
b8 6
-80
a8
--
--
Ti/ 3.5% NaCl + 2ppm S
1.5
Zr / cm
log (f / HZ)
Ti/ 3.5% NaCl+ 2ppm S

5
-60
2
15 min.
60 min.
120 min
180 min.
240 min.
-20
- Zi / cm2
-40
Phase / degree.
log (Z / cm2)
-2
15 min.
60 min.
120 min
180 min.
240 min.
2
1
0
0
0.0
0.3
0.6
0.9
1.2
1.5
1.8
2.1
Zr / cm
log (f / HZ)
Figure 7 Bode (a) and Nyquist (b) plots of Ti electrode after different times of immersion in stagnant naturally aerated 3.5% NaCl (a7
and b7) and 3.5% NaCl + 2 ppm S2 (a8 and b8) solutions at 25 C.
Table 6
Equivalent circuit parameters for the cp-Ti in 3.5% NaCl solution in the absence and presence 2 ppm of sulfide ion at 25 C.
Solutions
Time/min.
Rs/X
Rct/X cm2
Cdl/lF cm2
a1
Rf/kX cm2
3.5% NaCl
15
60
120
180
240
2.5
1.5
1.8
1.6
2.9
893.7
1590.0
2002.0
1710.0
3100.0
2.2
4.0
9.9
11.7
20.6
1.0
0.99
1.0
1.0
0.99
2.3
7.6
9.9
21.2
26.6
15
60
120
180
240
2.2
1.8
3.6
2.9
2.9
727.2
859.8
965.4
1002
930
34.6
18.5
26.04
24.6
21.9
0.98
0.98
0.98
0.98
0.99
the increase in the immersion time. This constant increase in

resistance attributed to a consequence progressive thickening
of the film. The obtained spectra were interpreted with the cir-
0.96
5.6
7.3
9.3
9.18
Cf/lF cm2
a2
13.6
10.5
8.0
7.5
6.0
0.99
0.99
0.99
0.99
1.0
104.5
22.6
27.5
21.6
13.9
0.99
1.0
0.99
0.99
1.0
cuit elements representing the electrochemical properties of the

alloy and its oxide film. Fig 3a shows the equivalent circuit
models used for fitting the spectra at different immersion
11
agreement and confirm that Cp-Ti alloy is the most stable
and suitable material to be used in these media.
Fig. 9(ac) represents the variation of the corrosion resistance of the barrier layer on Cu (a), CuAlNi (b), and
(a)
550
Cu
500
3.5% NaCl
450
2
400
Rf / cm
times, where, in this case, Rpf and Cpf, represent the resistance
and capacitance of barrier layer, and Rct and Cdl, present the
resistance and capacitance of the pours layer, respectively
[52]. The impedance parameters calculated for Cp-Ti are given
in Table 6.
A comparison between the impedance spectra, Bode and
Nyquist plots, for Cu, Cu10Al10Ni, C-steel and Cp-Ti alloy
after 240 min of electrode immersion in 3.5% NaCl + 2 ppm
S2 was obtained and is depicted in Fig. 8(a and b). It is obvious that the shape of the impedance spectra is very characteristics of each alloy as explained previously. The inset in Fig. 8b
is a close-up of Cu and C-steel data. In this figure the total
impedance magnitude for Cp-Ti is higher and Cu10Al10Ni
is much higher than that of Cu due to the duplex nature of film
and segregation of Ni2+ to Cu2O layer in both Cp-Ti and Cu
10Al10Ni alloys, respectively, while C-steel recorded the lowest corrosion resistance in this medium which means that sulfide ions have a significant effect on the corrosion rate of Csteel. Therefore, corrosion rate results obtained from both
potentiodynamic polarization and EIS methods are in good
350
300
250
--
3.5% NaCl + 2 ppm S
200
150
100
0
50
1650
--
log (Z / cm )
4
2
Cu
Cu-10Al-10Ni
C-Steel
Cp-Ti
-60
-40
2
3
-20
3
250
3.5% NaCl
1350
200
Cu-10Al-10Ni
1500
1200
2
1
2
3
4
1050
Rf / cm
-80
Phase / degree.
3.5% NaCl + 2 ppm S

2
4
150
Time /min.
(b)
(a)
100
900
750
3.5% NaCl + 2 ppm S
--
600
450
300
0
20
-2
50
(c)
log (f / HZ)
100
150
200
250
Time /min.
30
(b)
Cp- Ti
5000
3.5% NaCl
25
- Zi / cm
200
3000
Cu
Cu-10Al-10Ni
C-Steel
Cp-Ti
2000
400
Zr /cm
800
1000
Rf / cm
- Zi / cm2
400
4000
20
15
3.5% NaCl + 2 ppm S
--
10
5
0
0
300
600
900
1200
1500
1800
50
100
150
200
250
Time /min.
Zr / cm
Figure 8 Bode (a) and Nyquist (b) plots of Cu (jjj), Cu

10Al10Ni (ddd), C-Steel (NNN) and Ti (...) measured in
3.5 wt.% NaCl + 2 ppm S2 aqueous solution at 25 C.
Figure 9 Variation of the corrosion resistance of the barrier

layer on Cu (a), CuAlNi (b) and Cp-Ti (d) with the time of
immersion in stagnant naturally aerated 3.5% chloride solutions
of pH 7.0 in the absence and presence of sulfide ions at 25 C.
12
H. Nady et al.
a1 3.0
b1
200
-40
150
1.5
-20
1.0
- Zi / cm2
log (Z / cm2)
2.0
-60
Phase / degree.
Cu
2.5
Cu
100
3.5% NaCl
50
0.5
2-
3.5% NaCl
3.5% NaCl + 2 ppm S
3.5% NaCl + 2 ppm S
2-
0.0
20
-2
100
200
a2 3.5
300
400
500
Zr / cm
log (f / HZ)
b2 0.6
Cu-Al-10Ni
-80
3.5% NaCl
3.0
Cu-Al-10Ni
0.5
2-
3.5% NaCl + 2 ppm S
-60
2.5
-20
- Zi / cm2
-40
1.5
Phase / degree.
log (Z / cm2)
0.4
2.0
0.3
0.2
1.0
3.5% NaCl
0.5
2-
0.1
3.5% NaCl + 2 ppm S
0.0
0.0
20
-2
0.0
0.2
0.4
log (f / HZ)
18
-40
1.4
1.4
1.0
-20
0.8
-10
0.6
C-Steel
14
-30
12
- Zi / cm2
2-
3.5% NaCl + 2 ppm S
Phase / degree.
log (Z / cm2)
1.2
16
3.5% NaCl
0.4
10
8
6
4
3.5% NaCl
2-
0.2
3.5% NaCl + 2 ppm S
10
0.0
-2
-2
10
log (f / HZ)
-80
a4
b4
10
Cp-Ti
-60
2
-20
3.5% NaCl
1
25
30
4
3.5% NaCl
2-
3.5% NaCl + 2 ppm S
20
Cp Ti
- Zi / cm
-40
15
Zr / cm
Phase / degree.
log (Z / cm2)
1.0
b3 20
C-Steel
1.2
0.8
2
-50
a3
1.6
0.6
Zr / cm
3.5% NaCl + 2 ppm S
2-
0
0
-2
log (f / HZ)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Zr / cm
Figure 10 Bode and Nyquist plots of Cu (a1 and b1), Cu10Al10Ni (a2 and b2), C-Steel (a3 and b3) and Cp-Ti (a4 and b4), alloys after
3 h immersion in stagnant naturally aerated 3.5% NaCl and 3.5% NaCl containing 2 ppm S2 solutions at 25 C.

Cp-Ti (c) with the time of immersion in stagnant naturally aerated 3.5% chloride solutions in the absence and presence of
sulfide ions. The general behavior reflects the increase of barrier layer with time, In case of Cu and Cu10Al10Ni alloys
the presence of S2 decreases the passive film resistance than
that recorded in chloride solution due to the diffusion of sulfide ions into the protective oxide layer Cu2O [48]. Also, for
Cp-Ti alloy, the barrier layer resistance decreases in the presence of H2S, this suggests that the mixed chloride-hydrogen
sulfide solution is relatively corrosive for Cp-Ti alloy.
Bode and Nyquist plots in Fig. 10, presents a comparison of
the impedance spectra for each alloy after 3 h of exposure in
neutral 3.5% NaCl solution in the absence and presence of sulfide ions, Figs. (a1 and b1) for Cu, (a2 and b2) for Cu10Al
10Ni, (a3 and b3) for C-Steel and (a4 and b4) for Cp-Ti alloy.
For Cu and Cu-10Al-10Ni alloys, the magnitude of the total
impedance enhanced in the absence of sulfide ions which is
Figure 11
13
clearly shown in Nyquist plots {cf. Fig. 10(b1 and b2)}, where
passive film resistance, Rpf, recorded in the absence of sulfide
ions is bigger than that observed in the presence of sulfide ions,
therefore, the passive film resistance, Rpf, after 3 h from electrodes immersion in 3.5% NaCl solution were 532.1 and
1.692 k and decreased to 218 and 1.418 k in the presence
of sulfide ions for Cu and Cu10Al10Ni alloys, respectively.
This behavior was attributed to the diffusion of sulfide ions
into the protective oxide layer reacting with Cu ions to form
a non-adherent copper sulfide film [48]. Also the barrier layer
formed on Cp-Ti alloy after 3 h in 3.5% NaCl solution was
26.6 k and decreased to 9.3 k in the presence of sulfide ions.
In contrast to C-steel the magnitude of the total impedance
increased in presence of H2S {cf. Fig. 10(a3 and b3)}, where
in 3.5% NaCl solution the corrosion resistance was mainly
controlled by the charge transfer, while in the presence of sulfide ions another additional resistance which attributed to the
SEM micrograph (a) and EDX results (b) of Cu10Al10Ni alloy before electrochemical testing.
14
H. Nady et al.
Figure 12 SEM micrograph (a) and EDX results (b) of Cu10Al10Ni alloy after immersion in stagnant naturally aerated neutral NaCl
solution at 25 C.
formation of some corrosion products, the mackinawite grows

and adheres, thus, the film of corrosion products increased.
3.3. Surface analyses
Scanning electron microscopy analyses, SEM, were used to
define the morphology of surface attack and the chemical composition of corrosion products. Surface morphology of Cu
10Al10Ni alloy was subjected to SEM/EDX analysis as an
example. The SEM/EDX investigation was carried out and
depicted in Figs. 1113 of polished and after 72 h of alloy
immersion in sulfide free 3.5% sodium chloride and 3.5%
sodium chloride solutions polluted by 2 ppm sulfide ions. In
addition to the presence of boundary phases, before immersion, the electrode surface clearly seems smooth (Cf. Fig. 11).
The polished surface of Cu10Al10Ni alloy was subjected

to SEM/EDX analysis as an example after immersing in the
test solutions (Cf. Fig. 12). It is clear that the sulfide containing
solution is remarkably aggressive as can be seen on the SEM
image (Cf. Fig. 13). In the sulfide containing solution a granular layer with relatively large and irregular sized grains is
formed on the alloy surface compared to the smoother surface
recorded for sulfide free solutions, where in case of sulfide free
solution the corrosion sits present only at the boundary phases
(Cf. Fig. 12). It is also important to notice that the corrosion
products formed on the surface Cu10Al10Ni alloy in the
chloride containing 2 ppm S2 ions are relatively more than
that formed in the absence of sulfide. The results obtained
from the surface analysis are in good agreement with those
of polarization and impedance measurements.
15
Figure 13 SEM micrograph (a) and EDX results (b) of Cu10Al10Ni alloy after immersion in stagnant naturally aerated neutral 3.5%
NaCl containing 2 ppm S2 at 25 C.
4. Conclusions
Investigations of the electrochemical behavior of Cu, Cu
10Al10Ni, Cp-Ti and C-steel in sodium chloride and sodium
chloride polluted by 2 ppm hydrogen sulfide ions have shown
that:
1- The presence of sulfide ions enhances the corrosion process for different alloys, where the corrosion rate of the
Cp-Ti and Cu10Al10Ni alloy is less than half of Cu,
and C-steel alloy in 3.5% NaCl containing 2 ppm S2.
2- The passive film resistance formed on Cp-Ti was larger
than those of the passive film formed on the other three
alloys due to the protective nature of the film formed on
this alloy.
3- The dissolution of copper is inhibited in the Cu-alloys;
especially thats containing Ni. This is attributed to the
incorporation of Ni2+ into the Cu2O film leading to
its stabilization, but its resistance is still less than that
of Cp-Ti due to the duplex nature of the film formed

on its surface which is composed of a dense inner barrier
layer and a porous outer layer.
4- Only, for C-steel where the total impedance magnitude
increased in the presence of S2 ions, where, the resistance
increases due to the formation of some corrosion products, and the mackinawite grows and adheres with time.
References
[1] C. Ren, D. Liu, Z. Bai, T. Li, Mater. Chem. Phys. 93 (2005) 305.
[2] L.W. Tsay, Y.J. Lin, C. Chen, Corros. Sci. 63 (2012) 267.
[3] T.Y. Jin, Z.Y. Liu, Y.F. Cheng, Int. J. Hydrogen Energ. 35
(2010) 8014.
[4] B. Beidoknti, A. Dolati, A.H. Koukabi, Mater. Sci. Eng., A 507
(2009) 167.
[5] C. Plennevaux, J. Kittel, M. Fregonese, B. Normand, F.
Ropital, F. Grosjean, T. Cassagne, Electrochem. Commun. 26
(2013) 17.
16
[6] S.J. Kim, H.G. Jung, K.Y. Kim, Electrochim. Acta 78 (2012)
139.
[7] S.J. Kim, K.Y. Kim, Scr. Mater. 66 (2012) 1069.
[8] E. Abelev, T.A. Ramanarayanan, S.L. Bernasek, J.
Electrochem. Soc. 156 (2009) 331.
[9] Z.F. Yin, W.Z. Zhao, Z.Q. Bai, Y.R. Feng, W.J. Zhou,
Electrochim. Acta 53 (2008) 3690.
[10] S. Serna, H. Martinez, S.Y. Lopez, J.G. Gonzalez-Rodriguez, J.
L. Albarran, Hydrogen Energ. 30 (2005) 1333.
[11] P. Traverso, A.M. Beccaria, B. Poggi, Br. Corr. J. 29 (1994) 110.
[12] J.P. Gudas, H.P. Hack, Corrosion 35 (1979) 67.
[13] N. Mukhopadhyay, S. Baskaran, Corrosion 42 (1986) 113.
[14] P.K. Chauhan, H.S. Gadiyar, Corros. Sci. 25 (1985) 55.
[15] N.H. El Sayed, M.M. El-Rabiei, Egypt. J. Petrol. 23 (2014) 163.
[16] Y.S. Choi, J.G. Kim, Corrosion 56 (2000) 1202.
[17] H.H. Huang, W.T. Tsai, J.T. Lee, Mater. Sci. Eng., A 188 (1994)
219.
[18] H.H. Huang, J.T. Lee, W.T. Tsai, Mater. Chem. Phys. 58 (1999)
177.
[19] H.H. Huang, W.T. Tsai, J.T. Lee, Electrochim. Acta 41 (1996)
1191.
[20] H. Ma, X. Cheng, S. Chen, C. Wang, J. Zhang, H. Yang, J.
Electroanal. Chem. 451 (1998) 11.
[21] H. Ma, X. Cheng, G. Li, S. Chen, Z. Quan, S. Zhao, L. Niu,
Corros. Sci. 42 (2000) 1669.
[22] A.M. Zimer, M.A.S. De Carra, E.C. Rios, E.C. Pereira, Corros.
Sci. 76 (2013) 27.
[23] S. Tamilselvi, V. Raman, N. Rajendran, J. Appl. Electrochem.
40 (2010) 285.
[24] J. Chen, F.Y. Yan, B.B. Chen, J.Z. Wang, Mater. Corros. 62
(2013) 394.
[25] R. Narayanan, S.K. Seshadri, Corros. Sci. 50 (2008) 1521.
[26] A. Hugot-Le-Goff, Thin Solid Films 142 (1986) 193.
[27] G. Kear, B.D. Barker, K.R. Stokes, F.C. Walsh, J. Appl.
Electrochem. 34 (2004) 659.
[28] W.A. Badawy, M.M. El-Rabiee, N.H. Helal, H. Nady,
[29] G. Kear, B.D. Barker, K.R. Stokes, F.C. Walsh, I. Part, I.I.
Part, J. Appl. Electrochem. 34 (2004) 1235.
H. Nady et al.
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
R.G. Blundy, M.J. Pryor, Corros. Sci. 12 (1972) 65.

A.M. Beccaria, J. Crousier, Br. Corros. J. 2 (4) (1989) 49.
I. Milosev, M.H. Metikos, Electrochem. Acta 42 (1997) 1537.
M. Urquidi, D.D. Macdonald, J. Electrochem. Soc. 132 (1985)
555.
M. Metikos-Hukovic, R. Babic, I. Skugor, Z. Grubac Z, Corros.
Sci. 53 (2011) 347.
M.R. Reda, Al. Hajjaji, Br. Corros. J. 30 (1995) 56.
H.G. Ostlund, J. Alexander, J. Geophys. Res. 68 (1963) 3995.
M.A. Amin, K.F. Khaled, S.A. Fadl-Allah, Corros. Sci. 52
(2010) 140.
E. Poorqasemi, O. Abootalebi, M. Peikari, F. Haqdar, Corros.
Sci. 51 (2009) 1043.
H.H. Strehblow, Werkst. Korros. 35 (1984) 437.
S. Arzola-Peralta, J. Mendoza-Flores, R. Duran-Romero, J.
Genesca, Corros. Eng., Sci. Technol. 41 (2006) 321.
D.W. Shoesmith, P. Taylor, M.G. Bailey, D.G. Owen, J.
Electrochem. Soc. 127 (1980) 1007.
A.M. Magdy, D.Ibrahim Ponkao, M. Yashimura, J. Solid State
Electrochem. 6 (2002) 341.
K.M. Ismail, A.M. Fathi, W.A. Badawy, Corros. Sci. 48 (2006)
191.
K. Hladky, L.M. Calow, J.L. Dawson, Br. Corros. J. 15 (1980)
20.
J. Hitzig, J. Titz, K. Juettner, W.J. Lorenz, E. Schmidt,
D.D. MacDonald, Impedance Spectroscopy, John Wiley, 1987.
Y. Ma, S. Chen, S. Zhao, X. Liu, D. Li, J. Electrochem. Soc. 148
(2001) B482B488.
J.N. Al-Hajji, M.R. Reda, Corrosion 49 (1993) 809.
R. Rosliza, W.B. Wan Nik, H.B. Senin, Mater. Chem. Phys. 107
(2008) 28.
I.C. Lavos-Valereto, S. Wolynec, I. Ramires, A.C. Guastaldi, I.
Costa, J. Mater. Sci. Mater. Med. 15 (2004) 55.
N. Ibris, J.C.M. Rosca, J. Elect. Anal. Chem. 526 (2002) 53.
F. Mansfeld, M.W. Kending, J. Electrochem. Soc. 135 (1988)
828.

Corrosion and Electrochemical Properties of Aluminum and Lithium Alloys

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Corrosion and Electrochemical Properties of Aluminum and Lithium Alloys

Uploaded by

Copyright:

Available Formats

Egyptian Journal of Petroleum (2016) xxx, xxxxxx

Egyptian Petroleum Research Institute

Egyptian Journal of Petroleum

FULL LENGTH ARTICLE

Corrosion behavior and electrochemical properties

Chemistry Department, Faculty of Science, Fayoum University, Fayoum, Egypt

Received 20 December 2015; revised 15 February 2016; accepted 28 February 2016

Hydrogen sulfide, H2S, corrosion has been a research topic for

Corrosion behavior and electrochemical properties

3.5% NaCl + 2 ppm S

log (Current density /A cm )

-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2

Potential vs. SCE (V)

Figure 1 Potentiodynamic polarization curves of Cu, Cu10Al

sented in Fig. 2. It presents the polarization curves of the four

Table 1 Polarization parameters of the different materials

behavior with the most shifted corrosion potential to negative

The anodic dissolution and film formation on Cu surface in

It was suggested that the presence of

In Al containing alloys the surface dissolution of Al leads to

Accordingly, the corrosion resistance of Cu10Al10Ni

HS will combine with the metallic copper to form an

The coupled anodic dissolution is then represented by Eq.

2Cu HS OH ! Cu2 S H2 O

3.5% NaCl + 2 ppm S

log (current density, i /A cm-2)

log (current density /A cm-2)

3.5 % NaCl + 2 ppm S

Potential vs. SCE (V)

Potential vs. SCE (V)

3.5% NaCl + 2 ppm S

log (current density /A cm -2)

log (current density /A cm-2)

3.5% NaCl + 2 ppm S

Potential vs. SCE (V)

Potential vs. SCE (V)

Table 2 Polarization parameters of the different materials

Therefore the overall reaction is:

O2 2H2 O $ 2Cu2 S 4OH

However, the presence of Cu2S prevents the protective

of the soluble chloride complex, CuCl

Such a transportdeposition process would account for the

Corrosion behavior and electrochemical properties

propagation of pitting attack (cf. Fig 2c). Consequently the

FeOHads OH ! FeOH2 e

FeOH2 OH ! FeOOH H2 O e

In the presence of chloride ions, the Fe(OH)ads coverage

From the results of the potentiodynamic polarization curves

in the corrosion products was worse than that of troilite (iron

Ti is unstable and once it is formed it will react with H2O

Ti3 3OH ! TiOH3

Transformation of Ti(OH)3 might be taking place to

Accordingly, TiO2 formed by migration and adsorption of

2H2 S 2e ! 2HS H2

A probable formation mechanism of corrosion products

on the electrode surface could be

The amount of the corrosion products adsorbed also

Figure 3 (a) Equivalent circuit model used in the fitting of the

which exhibits a duplex structure with an inner layer (thick and

Cu/ 3.5% NaCl

Z Rs Rct =1 2pfRct Cdl a 

Cu / 3.5% NaCl + 2pp S

Cu / 3.5% NaCl + 2pp S

Corrosion behavior and electrochemical properties

Z Rs Rct =1 2pfRct Cdl a