Corrosion Science 74 (2013) 214222

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Characterization of AISI 1005 corrosion lms grown under cyclic

voltammetry of low sulde ion concentrations
N. Perini a, P.G. Corradini a, V.P. Nascimento b, E.C. Passamani b, M.B.J.G. Freitas a,
a
Laboratory of Research and Development of Methodologies for Analysis of Oils, Chemistry Department, Federal University of Esprito Santo, Av. Fernando Ferrari 514, Goiabeiras,
Vitria, Esprito Santo 29075-910, Brazil
b
Physical Department, Av. Fernando Ferrari 514, Goiabeiras, Vitria, Esprito Santo 29075-910, Brazil

a r t i c l e

i n f o

Article history:
Received 4 December 2012
Accepted 24 April 2013
Available online 3 May 2013
Keywords:
A. Carbon steel
B. EIS
B. Cyclic voltammetry
B. Mssbauer spectroscopy
C. Sulphide cracking

a b s t r a c t
The mechanism of AISI 1005 corrosion in sulde ion solutions has been investigated using cyclic voltammetry, electrochemical impedance spectroscopy, X-ray diffraction (XRD) and Mssbauer spectroscopy
(MS). The proposed mechanism occurs with the initial formation of oxygenated ferrous species followed
by adsorption of HS species, precipitation of iron monosuldes and their partial conversion to bisulde
iron. This mechanism was demonstrated by XRD results that revealed Fe-O and Fe-S phases and by MS
results that detected pyrite as the major proportion (94%) of the iron species in the corrosion product.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Steel corrosion is a problem that affects many types of industries, especially the petroleum manufacturing industry. Oil production is usually accompanied by the presence of water. The solids
content and ionic composition of the water present in oil wells differ from those of sea water [1]. The presence of sulfur in petroleum
and in the existing water in oil wells causes problems such as localized corrosion and the formation of various iron anodic lms [25].
The iron lms can passivate the steel and may also induce dissolution of the metal either through the anodic lm or in regions where
no iron lm is present [68]. The kinetic mechanism of iron anodic
lm formation depends primarily on pH, temperature and sulde
concentration [3,9]. The crystal structure, morphology, composition and other properties of the iron lms formed depend on the
kinetic mechanism involved in their formation.
Several investigations of iron lm formation have been conducted with pure iron and carbon steel in sulde ion solutions. Certain aspects of the initial formation of such lms in solutions
containing low sulde concentrations are difcult to elucidate.
The widely accepted initial corrosion mechanism was proposed
by Iofa et al. [10]. These authors demonstrated that H2S at low
pH or SH at medium pH forms a monolayer lm through chemisorption on iron. This behavior is similar to OH adsorption on
iron, which promotes its dissolution [11]. The initial steps in thin
Corresponding author. Tel.: +55 27 33352486; fax: +55 27 33352460.
E-mail address: marcosbj@hotmail.com (M.B.J.G. Freitas).
0010-938X/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2013.04.045

sulde lm formation may involve the formation of cubic iron sulde (FeS), tetragonal mackinawite (FeS1x), and hexagonal troilite
(FeS) [1214]. The stability of these compounds, in descending order, is troilite > mackinawite > cubic iron sulde. Therefore, in
principle, cubic iron sulde is the most unstable and easily converts to mackinawite, which is thermodynamically more stable.
Troilite is a stable monosulde but can be considered metastable
compared to pyrite, a disulde. Iron sulde phases such as mackinawite, troilite, marcasite and pyrite are formed even at low sulde
ion concentrations, e.g., parts per million (ppm) [14]. The chemical
and electrochemical processes that occur during the formation of
these minerals are represented by the following equations [11].

Fes HSaq ! FeHSads

FeHSads ! FeHSads 2e

The adsorbed FeHS

ads species may be dissolved (Eq. (3)) and/or
form a mackinawite lm (Eq. (4)):

FeHSads H2 O ! Fe2
aq H2 S OHaq

FeHSads xFe2
aq ! Fe1x Ss Haq

Depending on the pH and electrochemical potential, other species of iron sulde may be formed. In sulde solutions with pH values between 6.5 and 8.0 and under open circuit conditions,
mackinawite is the major corrosion product formed on the interfacial iron [14,15]. At pH values lower than 6.5, mackinawite has

N. Perini et al. / Corrosion Science 74 (2013) 214222

high solubility and Eq. (4) dominates, resulting in enhancement of

the corrosion rate. The results of some studies using high sulde
ion concentrations in the presence of cations such as K+, Mg2+
and Ca2+ to simulate eld operation conditions [2,9,16] have been
reported in the literature. These ions may interact with the HxS
(x = 1, 2) adsorbate at the interface and produce dubious electrochemical results.
In this work, the corrosion of AISI 1005 under low sulde solution concentration was studied in an attempt to elucidate the initial processes of sulde lm formation. This work concisely
elucidates the formation and aging mechanisms of sulde lms.
The iron anodic lms were grown using cyclic voltammetric techniques. The characterization of the corrosion products was performed using electrochemical impedance spectroscopy, scanning
electron microscopy (SEM), energy dispersive X-ray spectroscopy
(EDX), X-ray diffraction (XRD) and Mssbauer spectroscopy (MS).
2. Experimental procedures
2.1. Electrochemical experiments
The sulde ion solutions containing 0.013 mmol L1,
0.19 mmol L1, 0.38 mmol L1 and 0.83 mmol L1 were prepared
with the reagent Na2S9H2O. The supporting electrolyte solution
was 0.1 mol L1 Na2SO4. The solution pH was adjusted to 6.5 with
diluted solutions of H2SO4 and NaOH. All solutions were freshly
prepared before each experiment using deionised water. A conventional three-electrode cell with a thermostatic bath was used. The
cell consisted of a counter electrode of platinum plate with an area
of 3.7 cm2 and a working electrode of AISI 1005 steel with an area
of 0.20 cm2 and of the following composition (% w/w): 0.063% C,
0.009% Si, 0.015% P, 0.060% Al, 0.015% S, 0.302% Mn and balanced
Fe. The surface was mechanically polished with 320, 400 and 600
grit sandpaper. The surface was washed with water, placed in an
ultrasonic bath with acetone for 10 min, cleaned in water for
5 min, dried and immediately immersed in the working solution.
The reference electrode contained Ag/AgCl (3.0 mol L1 KCl).
In electrode Ag/AgCl used in the electrochemical tests the contact with electrolyte was accomplished through a ceramic junction point, which allows low electrolyte ow rate, in order
to hinder the electrolyte solution test contamination with the reference electrolyte and vice versa. For verify the implications of
the reference Ag/AgCl in the electrochemical tests, the potential of
the Ag/AgCl used in the electrochemical tests was monitored relative to another Ag/AgCl (not used in these electrochemical
measurements). The potential difference between the Ag/
AgCl electrode used in this paper vs. other Ag/AgCl electrode (not
used in these electrochemical measurements) was always less
than 4 mV. Indeed, analyzing the several voltammograms obtained
during this work, all of them (including theirs triplicates) presenting the anodic and cathodic peaks current at the same potential
values, irrespective of sulde concentration Therefore, the low
electrolyte ow does not affect the results obtained.
All obtained potential values were corrected to the standard
hydrogen electrode (SHE).
The cyclic voltammetry experiments consisted of 10 cycles
starting from an initial potential of 590 mVSHE and sweeping until
480 mVSHE; the scan direction was then reversed until
890 mVSHE was reached at a sweep rate of 10 mV s1.
After these experiments were performed, the corrosion product
on the steel electrode surface was washed with distilled water to
eliminate the excess of sulde and sulfate ions in the lms and immersed in a solution of 0.1 mol L1 Na2SO4 (pH 6.5) to record electrochemical impedance spectroscopy data over a frequency range
of 104103 Hz with 10 points per decade and a sinusoidal signal
of 10 mV amplitude.

215

The stability of iron sulde lms deposited onto carbon steel

surfaces depends on several factors, including the presence of corrosive anions, e.g., CN, Cl, H+, F, NO
3 , in the solution, temperature and pressure. As a rst step in this work, we decided to
perform electrochemical impedance spectroscopy in a solution
with pH near that of the water found in the petroleum reservoirs
of the state of Espirito Santo. We used sodium sulfate as a supporting electrolyte because it is less aggressive on lms grown on steel.
All electrochemical measurements were performed with the
AUTOLAB PGSTAT 302N potentiostat/galvanostat.
2.2. Preparation of carbon steel samples for morphological and
structural characterization
Carbon steel samples were machined with silicon carbide (SiC)
paper from 320 to 1500 grit, washed with water and acetone, immersed for ten seconds in 2.5%v/v HNO3 in ethanol solution and
immediately analyzed by SEM [1719]. The corrosion products
formed on the carbon steel surface in the absence and presence of
low concentrations of sulde ions were analyzed by SEM/EDX to
provide morphological and compositional information on the surface lm and on the clean carbon steel surface that remained after
removal of the corrosion products. The lms formed in the voltammetry experiments at 0.83 mmol L1 sulde ions were maintained
in an argon atmosphere, removed from the substrate, and then
characterized by X-ray diffraction and Mssbauer spectroscopy.
XRD was performed using a Rigaku diffractometer with Cu Ka radiation (k = 1.5418 ), scanning from 10 to 100 with a step scan of
0.05 per minute. Mssbauer spectroscopy of 57Fe was performed
using a spectrometer operated in constant acceleration mode under
transmission settings. 57Co in an Rh matrix (25 mCi) at room temperature (RT) was used as a radioactive source. The Mssbauer data
were tted using the NORMOS program. The isomer shift values are
given with respect to metallic iron at RT. Micrographs were collected with a scanning electron microscope (Shimadzu SS550)
operating at 20 kV at a working distance of 17 mm.
3. Results and discussion
3.1. Characterization of the carbon steel surface
The SEM image in Fig. 1a shows only scratches caused by the
surface treatment and several black spots that represent structural
defects and inclusions formed during the production of the AISI
1005 carbon steel. Exposure of the carbon steel surface to 2.5%v/
v HNO3 alcoholic (ethanol) solution highlighted the grain cores of
the ferrite phase and also the grain boundaries. In Fig. 1b, no other
phases such as perlite or cementite are observed, conrming the
result of the AISI 1005 carbon steel metallography. Fig. 1c shows
one of many inclusions at the steel surface; defects of this type
usually appear in the grain boundary regions. Some authors have
attributed the beginning of the corrosion process to the presence
of inclusions [20,21]. Fig. 1d and e presents the EDX spectra recorded at the approximate middle of the grain and in the inclusion,
respectively. The EDX spectrum recorded in the grain detected only
iron and carbon, a composition close to that found in the ferrite
phase. The EDX spectrum recorded in the inclusion detected sulfur
and oxygen in addition to iron and carbon; this may have resulted
in the presence of oxygenated and sulfured iron species, as will be
shown in the results described later in the paper.
3.2. Cyclic voltammetry analysis of AISI 1005 corrosion occurring at
low sulde ion concentrations
Fig. 2 displays the voltammetric prole of AISI 1005 steel in a
solution without sulde ions (Fig. 2a) and in solutions with sulde

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N. Perini et al. / Corrosion Science 74 (2013) 214222

Fig. 1. (a) SEM of steel after surface treatment; (b) metallographic analysis by SEM of AISI 1005 steel; (c) inclusion on the grain boundary and corresponding EDX composition
of the (d) grain and (e) inclusion.

ion concentrations of 0.013 mmol L1 (Fig. 2b), 0.19 mmol L1
(Fig. 2c), 0.38 mmol L1 (Fig. 2d) and 0.83 mmol L1 (Fig. 2e).
Fig. 2a shows that the formation of iron hydroxide lms on the carbon steel surface started at 390 mVSHE and continued in the positive direction. In the negative direction, a peak current at
740 mVSHE can be attributed to the reduction of the iron hydroxide lms. The rst two cycles shown in Fig. 2b have similar proles
to those obtained without sulde ion solutions, presenting just one
current peak close to 740 mVSHE. From the third cycle onward, it
was possible to distinguish two anodic peaks at 540 mVSHE (a1)
and 440 mVSHE (a2); these are due to the formation of sulde iron
species on the steel surface. In the last cycles, two additional cathodic peaks related to the formation of different iron suldes appeared (Fig. 2b). In Fig. 2ce, in which the amount of sulde ion
in the solution was 0.19 mmol L1, 0.38 mmol L1 and
0.83 mmol L1, respectively, the anodic peaks a1 and a2 appeared
after the rst voltammetric cycle, representing higher denition
and density of the current.
The second cycles for the solutions of different sulde ion concentrations are plotted in Fig. 3. Fig. 3a displays the entire potential
range of the voltammograms. It is evident that current density increased with the increase in the amount of sulde ions in solution.
At potential values more positive than 300 mVSHE, the current

density increased for 0.013 mmol L1 and 0.19 mmol L1 and decreased for 0.38 mmol L1 and 0.83 mmol L1. This is evidence that
the corrosion process was inhibited in this potential region as a
consequence of the higher amount of sulde present. Fig. 3b represents the anodic process, for which it was observed that the onset
potential was 640 mVSHE and that peaks a1 (540 mVSHE) and a2
(440 mVSHE) increased with increasing sulde ion concentration.
In the solution containing 0.013 mmol L1 sulde ions, the onset
potential was 740 mVSHE, and no anodic peaks were obtained.
From these results, it can be inferred that iron sulde compounds
are not formed during the rst cycle.
3.2.1. Mechanism of AISI 1005 corrosion under cyclic voltammetric
polarization at low sulde ion concentrations
No peaks were detected during the rst positive sweep, and the
initial cyclic voltammetric proles appear similar for synthesis
solutions with and without sulde ions (Fig. 2). In the presence
of water, iron and steel surfaces are thermodynamically unstable,
as suggested by the Pourbaix diagram, and these surfaces immediately form an iron hydroxide layer with low solubility close to neutral pH [22]. The formation of iron anodic lms on the steel surface
is independent of the sulde ion concentration. This process may
be associated with the formation of oxygenated ferrous species, a

N. Perini et al. / Corrosion Science 74 (2013) 214222

217

Fig. 2. Cyclic voltammetric proles of AISI 1005 steel in solutions of 0.1 mol L1 Na2SO4with (a) no sulde, (b) 0.013 mmol L1, (c) 0.19 mmol L1, (d) 0.38 mmol L1 and (e)
0.83 mmol L1 of sulde ion concentration, at 10 mV s1.

process that begins with the adsorption of OH. During the initial
stage, the OH
ad promotes the dissolution of iron atoms in a potential-determining step reaction, as shown in the following equation
[11].

Fes OHaq ! FeOHaq 2e

When the FeOH

aq solubility is exceeded, iron (II) hydroxide is
precipitated, according to the following equation:

FeOHaq OHaq ! FeOH2s

Considering that the HS species has a higher adsorption constant on the iron atoms compared with OH, it follows that displacement of OH by HS can occur according to the following
equation [23]:

FeOH2s HSaq ! FeHSads 2OHaq

After the rst cycle, two anodic peaks were detected for the
solutions with 0.19 mmol L1, 0.38 mmol L1 and 0.83 mmol L1
sulde ion (for 0.013 mmol L1, two peaks were detected after
the fourth cycle). These two anodic peaks, a1 (540 mVSHE) and
a2 (440 mVSHE), could be attributed to the formation of iron
monosulde and iron bisulde, respectively. The density charge

throughout the interface increased with cycle number and reached

a plateau for the peak a2 (440 mVSHE). At higher sulde ion concentrations, 0.38 mmol L1 and 0.83 mmol L1, the peak a1
(540 mVSHE) was not detected after the sixth cycle. The formation
of the sulde lm, at least initially during the corrosion process,
may inhibit the dissolution of iron at more positive potential values, as was shown in a previous section.
It is widely accepted that the chemical step represented in Eq.
(7) is followed by a mackinawite formation phase, which can be
represented by:

FeHSads xFe2
ads ! Fe1x Ss Haq

The mackinawite phase is very unstable and is quickly converted into iron monosulde, FeS [24]. The latter species may react
with itself or with aqueous HS at the interface to produce bisulde iron species, as suggested by the following equations below.

FeSs FeSs ! Fe2
aq FeS2aq 2e

FeSs HSaq ! FeS2aq Haq 2e

10

Based on the results shown in Figs. 2 and 3, it seems reasonable

to assume that the process that occurs at potentials near

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N. Perini et al. / Corrosion Science 74 (2013) 214222

3.2.2. Structural characterization of the iron lms by XRD and

Mssbauer spectroscopy
Fig. 4 presents the X-ray diffraction pattern for the iron lm
formed on the carbon steel surface at 0.83 mmol L1 of sulde
ion solution during cyclic voltammetric experiments (nal corrosion product obtained at 0.83 mmol L1 of sulde ion solution).
The X-ray diffraction pattern of this sample is complex and clearly
shows the presence of several crystalline phases. According to the
results reported in the JCPDS database, it was possible to identify
the presence of the following crystalline phases: (a) solid sulfur
(S) with Bragg peaks at 2h = 32.0, 33.8, 48.7 and 54.6 (card 80247); (b) iron bisuldes identied as marcasite (FeS2), with peaks
at 2h = 33.8, 38.5, 39.2, 54.6, 68.4 and 71.2 (card 37-475)) and
pyrite (FeS2), with peaks at 2h = 28.7, 57.2, 61.5, 78.9 and 88.2
(card 42-1340). In addition to the Fe-S phases, iron hydroxide III
(Fe(OH)3), with peaks at 2h = 18.5, 35.0, 43.0, 62.7 (card 220346), lepidocrocite (FeOOH, 2h = 27.0 and 68.4, card 44-1415)
and iron sulfate hydrate (FeSO4nH2O), with peaks at 2h = 26.9,
32.0, 38.5, 44.5 and 48.7 (card 22-0633) could also be identied
in the X-ray pattern [25]. The presence of the sulfur can be attributed to oxidation of the iron monosuldes [26].
Fig. 5 displays the 57Fe Mssbauer spectrum recorded at RT for
the 0.83 mmol L1 sample. This spectrum basically consists of two
components, one sextet and one doublet. However, it was tted
assuming three components (two doublets D1 and D2 and one sextet S). The second doublet was used to account for the absorption
line asymmetry observed at velocities close to 3 mm/s when compared with the line at approximately 3 mm/s. The doublet D1
covers most of the area of the spectrum and is the component with
the major fraction of the Fe-phases. It has a relatively broad
absorption resonance line width, suggesting either an atomic disordered effect or the presence of multiple Fe-phases with similar
isomer shift values (d) and quadruple splitting (DEQ) hyperne
parameters. The hyperne parameters of the doublet D1 obtained
by tting are: 85% of the total relative area; d value of
0.33 0.06 mm s1; and DEQ equal to 0.69 0.06 mm s1. It
should be stressed that these hyperne parameter values are commonly found in Fe3+ states. Because the absorption Mssbauer line
of the doublet D1 is relatively broad, the doublet may be associated
with the presence of the different Fe3+ phases observed in the Xray pattern of this sample. However, it should also be emphasized
that these hyperne values are relatively comparable (within
experimental error) to those found in disulde iron phases, i.e.,
FeS2 (d = 0.32 0.01 mm s1 and DEQ = 0.61 0.01 mm s1)
[2729]. Therefore, because we do not have sufcient energy

Fig. 3. (a) Second cycle for AISI 1005 steel in a solution of 0.1 mol L1 Na2SO4
containing different concentrations of sulde. (b) Region of the anodic peaks a1 and
a2. (c) Region of the cathodic peaks c0, c1 and c2.

540 mVSHE is exhausted after a few cycles, while the process that
occurs at potentials near 440 mVSHE increases until saturation. In
contrast, at lower concentrations of sulde ions, i.e.,
0.013 mmol L1, the two oxidation processes coexist throughout
the test cycles. X-ray diffraction and Mssbauer spectroscopy were
therefore conducted as complementary methods to investigate the
proposed mechanism for the most interesting sample, i.e., the sample in which the sulde ion concentration was 0.83 mmol L1.

Fig. 4. X-ray diffraction patterns for the corrosion products formed on the surface
of AISI1005 steel during cyclic voltammetry in solutions containing
0.83 mmol L1sulde.

N. Perini et al. / Corrosion Science 74 (2013) 214222

219

the Mssbauer spectra in Fig. 5). As the sulde ion concentration

was increased to 0.013 mmol L1, the surface lm coverage increased, and the relative amounts of iron and oxygen became
nearly equal. At 0.19 mmol L1 and 0.38 mmol L1, the sulfur/iron
ratio was almost one, and at 0.83 mmol L1 it was approximately
two. These results are consistent with the results presented in
the previous sections.
The micrographs in the right panel, which show the iron surface
after removal of the lms, show that the corrosion is localized for
solutions without sulde ions and that it is intergranular for lms
formed in solutions containing 0.013 mmol L1, 0.19 mmol L1,
0.38 mmol L1 and 0.83 mmol L1.

57

Fig. 5. Room temperature Fe Mssbauer spectrum of the corrosion product

formed on the surface of AISI 1005 carbon steel after cyclic voltammetry in
solutions containing 0.83 mmol L1 sulde ions. The dark points are the experimental data, while the grey line is the tting using NORMOS program. The dark
lines represent the subspectra used to t the experimental data.

resolution to separate the subspectra of the Fe3+ phases observed

in XRD and because the temperature dependence of the Mssbauer
experiments could not be determined in our setup, we attribute
the doublet D1, according to its hyperne parameters, basically
to disulde iron phases. On the other hand, doublet D2 has a relative total area of 5%. Its d and DEQ values, also obtained from the
tting, are 1.87 0.06 mm s1 and 1.92 0.06 mm s1, respectively. These values are similar to those found in Fe2+ phases. Thus,
according to the X-ray data obtained using this sample, it can be
associated with the hydrated ferrous sulfate phase.
Finally, the magnetic component observed in this spectrum was
tted with a broad sextet S. The hyperne parameters of the Scomponent are similar to those of Fe-rich Fe-C phases (a-Fe-like
phase). Therefore, it is attributed to the a-Fe-like phase obtained
when we removed the sample powder from the steel plate treated
in 0.83 mmol L1 sulde ion solution. It should be mentioned that
the S-component represents 10% of the total contribution to the
spectrum. Thus, after subtracting the a-Fe like contribution, it
can be estimated that the disulde phases represent approximately
94% of the iron-containing corrosion products and that ferrous sulfate hydrate represents approximately 6%. Almost all of the monosulde produced during voltammetry experiments was converted
to bisulde. The physical characterization of the lms formed in
sulde solutions corroborates the mechanism proposed in Section
3.2.1.
3.2.3. Morphological characterization of the lms formed by cyclic
voltammetry
Fig. 6 shows the SEM/EDX characterization of iron lms formed
during cyclic voltammetry from 890 mVSHE to 110 mVSHE with 10
cycles at a scan rate of 10 mV s1. The left panel of Fig. 6 shows
micrographs of these iron lms. The central panel presents the
EDX spectra of the iron lms, and the right panel shows the electrode surfaces after removal of the iron lms. In the left panel
(Fig. 6be) can be seen the iron lms grown in the presence of
0.013 mmol L1, 0.19 mmol L1, 0.38 mmol L1 and 0.83 mmol L1
sulde ions. The electrode coverage increases with increasing sulde content of the solution. The iron lm formed in solution containing 0.83 mmol L1 sulde ions has a compact form and
exhibits some cracks on the surface. The EDX spectra of lms
formed in solutions lacking sulde have high relative amounts of
iron compared to oxygen; due to the low lm coverage, the iron
of the steel surface is still detected. Some sulfur, which was presumably present due to the use of a (Na2SO4) support electrolyte
and which led to the formation of iron sulfate, was detected (see

3.2.4. Electrochemical impedance spectroscopy of iron lms formed by

cyclic voltammetry
The iron lms still adhered on the carbon steel were analyzed
by electrochemical impedance spectroscopy after the cyclic voltammetric experiments, and the open circuit potential was measured. The results are displayed in Fig. 7. After immersion of the
iron electrodes in the solution, the potential increased until the
equilibrium of the iron lm in contact with the solution was
reached. Because the solution is not saturated with iron ions, the
potential difference at the lm/solution interface depends on the
oxygen activity in the oxide and the concentration of protons in
the solution. The potential for iron lm became more positive in
solution without sulde and in solutions with low content
(0.013 mmol L1) of sulde ions; in these solutions, the steady
state was reached in 10 min. At the other tested concentrations
of sulde ions, the steady state was reached in approximately
100 min. The electrochemical impedance spectroscopy data were
recorded in the stationary potential for each case. Fig. 8 presents
the electrochemical impedance spectroscopy data as a Nyquist diagram. All of the curves have similar shapes. At high frequencies,
distorted semicircles appear. At low frequencies, straight lines that
show a tendency to form semicircles at the lowest frequencies are
observed. This behavior was very clear for lms formed in
0.013 mmol L1 sulde. The semicircle diameter decreased for
lms formed at intermediate concentrations of sulde
(0.19 mmol L1, 0.38 mmol L1) and increased again at
0.83 mmol L1. Fig. 9 shows a Bode diagram in which phase angle
data are presented in Fig. 9a and impedance module data are presented in Fig. 9b. The electrochemical impedance spectroscopy
parameters were obtained by tting the experimental data to the
equivalent circuit shown in Fig. 10, which includes the solution
resistance (Rs), the lm resistance (Rlm) and capacitance (Clm), a
constant phase element of the double layer (CPEdl), the charge
transfer resistance (Rct) and a diffusional element (Zd). The parameter values together with their respective error values are summarized in Table 1. The ZView software version 3.3 (written by Derek
Johnson, Scrinbner Associates, INC) was used to t an electrical
model to the experimental data.
The CPE element is written as follows:

Z CPE

1
Y o jxa

11

where 0 < a < 1.

As shown in Figs. 8 and 9, the tted curves and the experimental data are in good agreement. This is further conrmed by the error values for each element listed in Table 1, which shows the
calculated values of the circuit elements. Because the same support
electrolyte was used in each case, Rs was approximately 5.0 X cm2
for all sulde ion concentrations tested. The Clm formed in the
presence of sulde is greater than that of lm formed in blank solution because of an increase in the dielectric constant or in the
thickness of the lm. The resistances attributed to the lms (Rlm)

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N. Perini et al. / Corrosion Science 74 (2013) 214222

(a)

(b)

(c)

(d)

(e)

Fig. 6. SEM and EDX of the carbon steel surface corrosion products formed during cyclic voltammetry (left side) and the surface after removal of the lm (right side) in (a) the
absence of sulde or the presence of (b) 0.013 mmol L1, (c) 0.19 mmol L1, (d) 0.38 mmol L1 and (e) 0.83 mmol L1 sulde.

formed in the presence of sulde were slightly smaller than those

found in the blank solution. The CPE parameters increased with the
sulde ion concentration, most likely due to decreasing lm
roughness or/and porosity.

The changes in Rct and Zd may be related primarily to the lm

thickness and composition. The lm diffusional resistance, Zd,
decreased for lms formed in the presence of greater amounts of
sulde. This result is related to the high conductivity of pyrite

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221

Fig. 7. Open circuit potential for the lms formed on the surface of AISI 1005 steel
immersed in 0.1 mol L1 Na2SO4.

Fig. 9. Bode (a) phase angle; (b) module of impedance for the lms formed on the
surface of AISI 1005 steel during cyclic voltammetry at different sulde concentrations in a solution of 0.1 mol L1 Na2SO4 at pH 6.5.

Fig. 8. Nyquist diagram for the lms formed on the surface of AISI 1005 steel during
cyclic voltammetry at different sulde concentrations in a solution containing
0.1 mol L1 Na2SO4 at pH 6.5.

compared to that of iron hydroxides, which promotes high mass

transport between the lm and the solution.
The Rct increased from 197 X cm2 for lms formed in the absence of sulde to 284 X cm2 for lms formed in the presence of
0.013 mmol L1 sulde. This low concentration of sulde was not
sufcient to achieve high coverage of the iron sulde compounds.
Additionally, the charge transfer resistance increased due to the
low conductivity of the iron hydroxide lm, which presented a
higher coverage as indicated by the EDX results shown in Fig. 6b;
the relative quantities of iron and oxygen are very similar. The
SEM image on the left side of Fig. 6 shows low coverage by the lm;
in this gure, it is still possible to observe the scratches on the steel
surface that occurred during its pre-treatment.
In the case of lms formed in solutions with sulde contents of
0.19 mmol L1 and 0.38 mmol L1, the Rct values decreased to
113 X cm2 and 71 X cm2, respectively. These results can be attributed to the high coverage of the steel surface by the iron sulde
lms compared to lms formed at 0.013 sulde or no sulde.

The EDX shows that the relative amounts of iron and sulfur are
similar (Fig. 6c and d). For lms formed at 0.83 mmol L1 sulde,
the Rct increased to 142 X cm2, and EDX indicated a large amount
of sulfur relative to iron (Fig. 6e). As indicated by cyclic voltammetric experiments and corroborated by the XDR and MS data, the increase in pyrite may act as an inhibitor and cause the lm to
become more resistive under formation conditions involving
0.83 mmol L1 of sulde ions. This behavior shows that at
0.83 mmol L1 the corrosion rate decreases signicantly and most
likely indicates that iron lms containing sulfur species passivate
the carbon steel.

Fig. 10. Equivalent circuit for the lm formed on the surface of AISI 1005 steel in a
solution of 0.1 mol L1 Na2SO4 at pH 6.5.

222

N. Perini et al. / Corrosion Science 74 (2013) 214222

Table 1
Electrochemical impedance spectroscopy parameters obtained by equivalent circuit tting as represented in Fig. 8.
[S2]
mmol L

Rs
1

No sulde
0.013
0.19
0.38
0.83

Clm
2

Rlm
2

CPEdl
2

X cm

mF cm

X cm

5.78(0.02)
7.66(0.01)
4.21(0.01)
4.01(0.01)
4.76(0.01)

0.08(0.01)
0.20(0.06)
1.15(0.08)
11.0(0.3)
9.6(0.4)

6.3(0.2)
3.1(0.2)
0.6(0.4)
5.0(0.4)
2.9(0.2)

4. Conclusions
The effect of dilute solutions of sulde ions on carbon steel corrosion has been investigated using various electrochemical techniques and by ex situ physical characterization. Variation of the
sulde concentration changed the type of anodic lm formed on
the steel surface. Using cyclic voltammetry techniques, no peaks
were detected for the rst cycle during the positive sweeping. After
the rst cycle, two oxidation processes, the formation of monosulde iron (540 mVSHE) and the formation of bisulde iron
(440 mVSHE), were found to coexist. Nearly all of the monosulde
produced during the voltammetry experiments was converted to
bisulde and pyrite because the rst observed process ceased to
occur. XRD characterization indicated the presence of bisulde
species. MS results on the corrosion product formed in
0.83 mmol L1 sulde solution indicated that the major compounds formed were pyrite and iron sulfate. The lms with low
coverage of iron sulde exhibited higher charge transfer resistance.
With increased coverage of iron sulde, this parameter decreased;
it then increased again for lms formed at higher sulde ion concentrations (0.83 mmol L1). This effect can be related to the presence of the pyrite phase as a major Fe species of the formed
supercial lm. Based on these results, the initial stages of AISI
1005 carbon steel corrosion at low sulde concentrations are characterized by the formation of oxygenated ferrous species, high
adsorption of HS species, precipitation of monosulde and, nally,
interconversion of monosulde to a bisulde iron phase.
Acknowledgments
The authors acknowledge PETROBRAS, CNPq, UFES, FAPES and
CAPES for their nancial support.
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Y0 (10

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