materials

Article
Effect of Elemental Sulfur and Sulfide on the
Corrosion Behavior of Cr-Mo Low Alloy Steel
for Tubing and Tubular Components in Oil
and Gas Industry
Ladan Khaksar 1, * and John Shirokoff 2
1 Department of Mechanical Engineering, Faculty of Engineering and Applied Science,
Memorial University of Newfoundland, St. John’s, NL A1B 3X5, Canada
2 Department of Process Engineering, Faculty of Engineering and Applied Science,
Memorial University of Newfoundland, St. John’s, NL A1B 3X5, Canada; shirokof@mun.ca
* Correspondence: lk6514@mun.ca

Academic Editor: Peter J. Uggowitzer

Received: 16 February 2017; Accepted: 17 April 2017; Published: 20 April 2017

Abstract: The chemical degradation of alloy components in sulfur-containing environments is a major

concern in oil and gas production. This paper discusses the effect of elemental sulfur and its simplest
anion, sulfide, on the corrosion of Cr-Mo alloy steel at pH 2 and 5 during 10, 20 and 30 h immersion
in two different solutions. 4130 Cr-Mo alloy steel is widely used as tubing and tubular components
in sour services. According to the previous research in aqueous conditions, contact of solid sulfur
with alloy steel can initiate catastrophic corrosion problems. The corrosion behavior was monitored
by the potentiodynamic polarization technique during the experiments. Energy dispersive X-ray
spectroscopy (EDS) and scanning electron microscopy (SEM) have been applied to characterize the
corrosion product layers after each experiment. The results show that under the same experimental
conditions, the corrosion resistance of Cr-Mo alloy in the presence of elemental sulfur is significantly
lower than its resistance in the presence of sulfide ions.

Keywords: corrosion behavior; elemental sulfur; sulfide; 4130 Cr-Mo alloy; potentiodynamic
polarization

1. Introduction
For more than 40 years, elemental sulfur deposition in pipelines and facilities has become a major
concern in the sour oil and gas industry [1]. In conjunction with reservoir souring, the incidence of
sulfur corrosion will likely increase. It is known from prior research that the presence of dry elemental
sulfur in contact with carbon steel is not considered as a corrosion threat to steel; however, by adding
water to the system, the corrosion process may be dramatically accelerated [2].
Elemental sulfur usually appears in an aqueous system due to the oxidation of sulfide species
where the possible reaction for the formation of elemental sulfur (S8 ) may involve high oxidation state
metals or oxygen [3]:

8 H2 S (aq) + 16 Mn+ (aq) → S8 (s) + 16 H+ (aq) + 16 M(n−1)+ (aq) (1)

8 H2 S (aq) + 4 O2 (g) → S8 (s) + 8 H2 O (l(2)) (2)

Materials 2017, 10, 430; doi:10.3390/ma10040430 www.mdpi.com/journal/materials

Materials 2017, 10, 430 2 of 12

MacDonald et al. hypothesized that an electrochemical reaction between iron and polysulfide
could be the driving force for a corrosion process where elemental sulfur is present [4]:

(x − 1)Fe (s) + Sy−1 S2− (aq) + 2 H+ (aq) → (x − 1) FeS (s) + H2 S (g) + Sy−x (s) (3)

In recent years, Fang et al. investigated the corrosion behavior of carbon steel at different
temperatures with molten sulfur on the steel surface [5,6]. These investigations comprehensively
studied the sulfur hydrolysis and direct sulfur/iron reaction, with either an electrically insulating or
conductive barrier placed between the sulfur droplet and the metal surface.
The investigation of Fang et al. proved that the electrical connection and physical proximity
between sulfur and steel are critical characteristics for elemental sulfur corrosion of mild steel. They also
identified that an electrochemical reaction is the likely mechanism of elemental sulfur corrosion of mild
steel. However, there are few electrochemical investigations on the corrosion behavior of an alloy steel
such as 4130 in the presence of elemental sulfur. In this paper, the effect of elemental sulfur and its anion
on corrosion mechanism and the behavior of the Cr-Mo low alloy steel were investigated at varying
pH levels and immersion time through corrosion simulation tests and electrochemical measurements.

2. Experimental Procedure

2.1. Material and Sample Preparation

According to National Association of Corrosion Engineering (NACE) MR0175/ISO 15156,
the most common steel alloy for tubular and tubular components in sour service is Unified Number
System (UNS) G41XX0, formerly American Iron and Steel Institute (AISI) 41XX [7]. 4130 steel is
among the most common low alloys used in the oil and gas industry. This steel typically consists
of 0.80–1.1 Cr, 0.15–0.25 Mo, 0.28–0.33 C, 0.40–0.60 Mn, 0.035 P, 0.040 S, 0.15–0.35 Si and balance Fe.
The working electrode was machined from the parent material into cylinders having dimensions of
approximately 9 mm in length and 9 mm in diameter. Prior to the experiments, all specimens were
polished with Coated Abrasive Manufacturers Institute (CAMI) grit designations 320, 600 and 1000,
corresponding to average particle diameters 36.0, 16.0 and 10.3 microns and finally 6-micron grit
silicon carbide paper, then cleansed with deionized water until a homogeneous surface was observed.
Following this, the specimens were quickly dried using cold air to avoid oxidation.
After preparing the samples, they were transferred into a multi-port glass cell, which was filled
with 3.5% sodium chloride solution. The pH was adjusted by adding deoxygenated hydrochloric acid
or sodium hydroxide. Prior to the start of each electrochemical test, the sample was immersed in the
solution for 55 min in accordance with ASTM G5-82 [8].

2.2. Direct Sulfur/Iron and Sulfide/Iron Reactions Preparation

Two series of experiments have been performed to investigate the effects of elemental sulfur (S8)
and its simplest anion, sulfide (S2− ), on the corrosion behavior of Cr-Mo low alloy steel at varying pH
and immersion times. In the first series of experiments, all of the tests were carried out in a multi-port
glass cell, which was filled with solved thioacetamide (2 M) in 420 mL de-ionized water. According to
the literature and the authors’ previous studies [9,10], the addition of thioacetamide into the water
would produce free sulfide ions through the bulk solution. Decomposition of thioacetamide is an
irreversible reaction that has been considered as the sulfur source, generating S2− by a hydrolytic
method [11–14]. The following equation shows the presence of dissolved free sulfides in di-ionized
water, which are super active to react with samples. Table 1 describes the experimental conditions of
the first series of experiments.
In the second series, a similar method to the method of Fang et al. with maximum uniform
coverage of adherent sulfur to the coupon surface was employed for all of the tests [1,5,15]. In this
series of experiments, samples’ surfaces were covered with sublimed elemental sulfur 99.9999%
Materials 2017, 10, 430 3 of 12

(ACROS) deposited onto polished samples. Table 2 describes the experimental conditions of the second
series of experiments.
CH3 CSNH2 + H2 O ↔ S2− + CH3 CONH2 + 2H+ (4)

Table 1. Experimental condition of the first series.

Condition No. T (◦ C) pH Immersion Time (h)

1 80 2 10
2 80 2 20
3 80 2 30
4 80 5 10
5 80 5 20
6 80 5 30

Table 2. Experimental condition of the second series.

Condition No. T (◦ C) PH Immersion Time (h)

7 80 2 10
8 80 2 20
9 80 2 30
10 80 5 10
11 80 5 20
12 80 5 30

2.3. Electrochemical Measurements

Electrochemical corrosion experiments, and in particular the potentiodynamic polarization scan,
can provide considerable information on the corrosion rate, pitting susceptibility and passivity, as well
as the cathodic behavior of an electrochemical system [16]. During this study, experiments were
conducted in a multi-port glass cell with a three-electrode setup at atmospheric pressure based on the
ASTM G5-82 standard for potentiodynamic anodic polarization measurements [8].
A graphite rod was used as the counter electrode (CE) and saturated silver/silver chloride
(Ag/AgCl) was used as the reference electrode (RE). Furthermore, as was mentioned in the material
and sample preparation, 4130 low alloy steel was used as the working electrode (WE).
An Ivium Compactstat Potentiostat monitoring system was used to perform electrochemical
corrosion measurements. The potentiodynamic polarization technique was applied to investigate the
corrosion behavior. The applied scan rate for this measurements was 0.125 mV/s.

2.4. Surface Morphology Observation and Corrosion Product Layers Analysis

Upon completion of corrosion testing, morphological characterization of the surface was
conducted using an FEI Quanta 400 scanning electronic microscope (SEM) with Bruker energy
dispersive X-ray (EDS) spectroscopy. The SEM was operating at 15 kV, with a working distance
of 15 mm and beam current of 13 nA.

3. Results and Discussion

3.1. First Series of Experiments; Effect of Sulfide (S2− ) on the Corrosion Mechanism of Cr-Mo Low Alloy Steel
As was mentioned in the experimental procedure, in order to investigate the effect of sulfide (S2− )
on the corrosion behavior of 4130 alloy, the samples were immersed into the solution containing solved
thioacetamide (2 M) in 420 mL de-ionized water for 10, 20 and 30 h at 80 ◦ C, pH 2 and 5.
Materials 2017, 10, 430 4 of 12

3.1.1. Corrosion Behavior of Cr-Mo Low Alloy Steel

The potentiodynamic curves of 4130 Cr-Mo low alloy steel in thioacetamide solution at different
immersion times, 10, 20 and 30 h at 80 ◦ C, pH 2, are illustrated in Figure 1. The scan rate was
0.125 mV/s.
Figure 1 indicates the stable behavior of anodic curves with increasing the immersion time from
10 to 30 hMaterials ◦ C,10,pH
at 802017, 430
2. It illustrates that the corrosion potential, Ecorr , at pH 2 for 4 of 12
20 and 30 h
immersion time is time
immersion almost the same
is almost the sameand
andmore positive
more positive than
than thatthat
of 10of 10 h immersion
h immersion in the solution;
in the solution;
theMaterials
however, however,
values 2017, 10, 430
the of difference
values are not
of difference significant.
are not significant. It canbebealso
It can also observed
observed thatcurrent
that the
4 of 12
the current
density density of
of 10 h immersion
10 h immersion is higher is higher than those ofand
20 and 30 h immersion.
immersion time isthan
almostthose of 20
the same and 30positive
more h immersion.
than that of 10 h immersion in the solution;
however, the values of difference are not significant. It can be also observed that the current density
-3.60E-01is higher than those of 20 and 30 h immersion.
of 10 h immersion
-3.70E-01
Potential (V, Ag/AgCl)

-3.60E-01
-3.80E-01
-3.70E-01
Potential (V, Ag/AgCl)

-3.90E-01 E/I 30 h
-3.80E-01
-4.00E-01
E/I 20 h
-3.90E-01 E/I 30 h
-4.10E-01
-4.00E-01
E/I 10 h
-4.20E-01 E/I 20 h
-4.10E-01
-4.30E-01 E/I 10 h
-4.20E-01
1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02
-4.30E-01 Current density (A)
1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02

The potentiodynamic curves Current

ofof4130 densityalloy
(A) steel in thioacetamide solution at different
Figure 1. Figure 1. The potentiodynamic curves 4130 Cr-Mo
Cr-Mo alloy steel in thioacetamide solution at different
immersion times: 10, 20 10,
and ◦
immersion times: 20 30
andh30ath80
at 80C,
°C,pH
pH 2.
2.
Figure 1. The potentiodynamic curves of 4130 Cr-Mo alloy steel in thioacetamide solution at different
immersion
Figure times:
2 shows 10,stable
the 20 andbehavior
30 h at 80 °C, pH 2. curves with increasing the immersion time from
of anodic
Figure 2 shows the stable behavior of anodic curves with increasing the immersion time from 10
10 to 30 h at 80 °C, pH 5. The potentiodynamic polarization curves indicate that Ecorr of 10 h immersion
80 ◦relatively
to 30 h at was C,Figure
pH 5.2more
shows the stable behavior ofpolarization
Thepositive than that of 30 hanodic
potentiodynamic curves with
immersion, increasing
curves
which more the
wasindicate immersion
thatthan
positive Ecorrtime from
ofof10
that 20hh.immersion
10 to 30 h at 80 °C, pH 5. The potentiodynamic polarization curves indicate that Ecorr of 10 h immersion
was relatively moredensity
The current positiveof 10than that of is30slightly
h immersion h immersion,
lower thanwhich was
that of the 30 more positive
h immersion time,than
was relatively more positive than that of 30 h immersion, which was more positive than that of 20 h.
which that of 20 h.
The currentis significantly
density of higher
10 h than the current
immersion is density oflower
slightly 20 h immersion
than in the
that of solution.
the 30 h immersion time, which is
The current density of 10 h immersion is slightly lower than that of the 30 h immersion time, which
significantly higher than the current density of 20 h immersion in the solution.
is significantly higher than the current density of 20 h immersion in the solution.
-0.34
-0.36
-0.34
Potential (V, Ag/AgCl)

-0.38
-0.36
Potential (V, Ag/AgCl)

-0.4
-0.38
E/I 30 h
-0.42
-0.4
E/I
E/I30
20hh
-0.42
-0.44
E/I
E/I20
10hh
-0.44
-0.46
-0.46 E/I 10 h
-0.48
-0.48
-0.5
1.00E-08
-0.5 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02
1.00E-08 1.00E-07 1.00E-06 1.00E-05
Current 1.00E-04
density(A) 1.00E-03 1.00E-02
Current density(A)
Figure 2. The potentiodynamic curves of 4130 Cr-Mo alloy steel in thioacetamide solution at different
The potentiodynamic
Figure 2. immersion
Figure 2. times: 10, 20 andcurves
The potentiodynamic of°C,
30 h curves
at 80 4130
pH Cr-Mo
of 4130 alloy
5.Cr-Mo alloy steel
steel in thioacetamide
in thioacetamide solution
solution at different at different
immersion
immersion times: 10,times:
20 and10, 20
30and
h at h at◦80
30 80 C,°C,
pH pH5.5.
During a corrosion process, the rate of the reactions is determined by the corrosion mechanism.
During
The growth of aa corrosion
corrosionprocess,
productthe ratelimits
layer of the the
reactions
rate ofisfurther
determined by theby
corrosion corrosion
acting asmechanism.
a diffusion
During a
The corrosion
growth of a process,
corrosion the rate
product of
layer the
limitsreactions
the rate of is determined
further corrosion by
by the
acting
barrier for the species involved in the process [17,18]. After 20 h immersion at pH 5, the formation corrosion
as a diffusionofmechanism.
barrier forcorrosion
the speciesproduct
involved in the process [17,18]. Aftercorrosion
20 h immersion at pH 5,surface;
the formation of
The growth of a corrosion product layer limits the rate of further corrosion by acting as a diffusion
a protective layer prevented the further of the sample however,
a protective corrosion product layer prevented the further corrosion of the sample
whichsurface; behowever,
barrier forafter
the 30 h immersion,
afterspecies
30 h immersion,
the
involved corrosion current
in the process
the corrosion
density
[17,18].
current density
significantly
After 20increased,
significantly h immersion
increased,
may
at
which may pH related
5, to
thetoformation
be related of
the breaking down of the protective corrosion product layer on the alloy surface. The values of anodic
a protective corrosion
the breaking downproduct
of the layer prevented
protective the
corrosion product further
layer oncorrosion of the
the alloy surface.
( ) and cathodic ( ) Tafel slopes of the samples of each experiment were obtained by potentiostat
Thesample
values ofsurface;
anodic however,
after 30 h as ( ) and cathodic
immersion, ( ) Tafel slopes of thedensity
samples significantly
of each experiment were obtained by potentiostat
illustrated inthe corrosion
Table 3. current increased, which may be related to the
as illustrated in Table 3.
breaking down of the protective corrosion product layer on the alloy surface. The values of anodic
(β a ) and cathodic (β c ) Tafel slopes of the samples of each experiment were obtained by potentiostat as
illustrated in Table 3.
Materials 2017, 10, 430 5 of 12

Table 3. The values of anodic (β a ) and cathodic (β c ) Tafel slopes of first series.

Experiment β a (mV·Decade−1 ) β c (mV·Decade−1 )

1 0.022 0.019
2 0.029 0.020
3 0.020 0.019
4 0.034 0.023
5 0.021 0.018
6 0.028 0.020

3.1.2. Corrosion Rate of Cr-Mo Low Alloy Steel

The corrosion current (icorr ) was calculated using the following equations [19]:

B
icorr = (5)
RP

where, icorr is the corrosion current density in A·m−2 ; R P is the polarization resistance in Ω·m2 and B
is the proportionality constant in mV·decade–1 :

βa βc
B= (6)
2.3 ( β a + β c )

which can be calculated by the given values of anodic (β a ) and cathodic (β c ) Tafel slopes of the samples
of each experiment.
Finally, the corrosion rate (CR) was calculated using the following equation:

icorr w
CR = (7)
ρF

where, w is the equivalent weight of 4130 alloy; F is the Faraday constant, and ρ is the density of
4130 alloy.
Table 4 indicates the corrosion rate of each experiment.

Table 4. The corrosion rate of the first series.

Experiment 1 2 6 4 5 6
pH 2 2 2 5 5 5
Corrosion Rate (CR) (mm/year) 0.368 0.325 0.318 0.066 0.044 0.224

As can be observed in Table 4, in thioacetamide solution, the corrosion rate of Cr-Mo alloy at pH 2
is greater than that of pH 5, which is usually related to the formation of a corrosion protective layer at
higher pH. At pH 2, iron is dissolved, and iron sulfide is not significantly precipitated on the surface of
the alloy due to the high solubility of iron sulfide phases at pH values less than 2 [20–22]. In this case,
sulfide exhibits only the accelerating effect on the dissolution of iron. At pH 5, the inhibitive effect of
sulfide is seen due to the formation of iron sulfide protective film on the alloy surface [16].
Table 4 shows that the corrosion rate has a maximum of 0.368 mm/year after 10 h immersion at
pH 2, which slightly decreases to 0.318 mm/year after 30 h immersion. The corrosion rates of pH 5
indicate a small decrease and a large increase during 20 and after 30 h immersion, respectively, due to
the formation and breakdown of the corrosion product layer. These results are consistent with data
obtained from the potentiodynamic polarization technique.
Materials 2017, 10, 430 6 of 12

3.2. Second Series of Experiments: the Effect of Elemental Sulfur (S8 ) on the Corrosion Mechanism of Cr-Mo
Low Alloy Steel
As was mentioned in the experimental procedure, in order to investigate the effect of elemental
sulfur (S8 ) on the corrosion behavior of 4130 Cr-Mo alloy, the surfaces of the samples were covered by
melted elemental sulfur 99.999% (ACROS) and then immersed in a glass cell, which was filled with the
3.5% sodium chloride solution.

3.2.1. Corrosion Behavior of Cr-Mo Low Alloy Steel

The Materials
potentiodynamic
2017, 10, 430 curves of 4130 Cr-Mo low alloy steel covered with elemental 6 of 12 sulfur in

the 3.5% sodium chloride

Materials 2017, 10, 430 solution at different immersion times, 10, 20 and 30 h 6at 80 ◦ C, pH 2,
of 12
3.2.1. Corrosion Behavior of Cr-Mo Low Alloy Steel
are illustrated in Figure 3. The scan rate was 0.125 mV/s. Figure 3 presents that Ecorr at pH 2 for
TheCorrosion
3.2.1. potentiodynamic
Behavior curvesof Cr-Mo of Low
4130 Alloy
Cr-MoSteel low alloy steel covered with elemental sulfur in the
the 20 h immersion time is more positive than that of 30 h immersion in the solution; however,
3.5% sodium chloride solution at different immersion times, 10, 20 and 30 h at 80 °C, pH 2, are
the difference isThe
illustrated notpotentiodynamicIt
in significant.
Figure 3. The scan
curves
canrate
of 4130
be Cr-Mo low
observed
was 0.125 mV/s. thatalloy
thesteel
Figure
covered with elemental
current
3 presentsdensitythat Ecorrof 30 hsulfur
at pH
in the
immersion
2 for the 20 h is higher
3.5% sodium chloride solution at different immersion times, 10, 20 and 30 h at 80 °C, pH 2, are
than that immersion
ofillustrated
20 h immersion.
time is more
in Figure 3. positive
The scanthan that 0.125
rate was of 30 mV/s.
h immersion
Figure 3inpresents
the solution;
that Ehowever, the difference
corr at pH 2 for the 20 h
is not significant.
Figureimmersion
3 also shows It
time isthatcan be observed
moreEpositive that the current density of 30 h immersion is higher than thatone.
of It can be
corr at than
pH that2 for of 10
30 hhimmersion
immersion in thetime is the
solution; most the
however, negative
difference
20ish not
immersion.
significant. It can be observed that the current density of 30 h immersion is higher than that of
observed that current density of 10 h immersion is higher than that at 20 and 30 h immersion.
20 Figure 3 also shows that Ecorr at pH 2 for 10 h immersion time is the most negative one. It can be
h immersion.
Figure 4 shows
observed the
Figure 3current
that stable
also shows
behavior
density
thatof 10at
Ecorr hof anodic
immersion
pH 2 for 10 h
curves
higherof
isimmersion samples
than thatisatthe
time 20covered 30 hwith
and negative
most
elemental sulfur with
immersion.
one. It can be
increasing the immersion time from 10hto 30 h at is80 ◦ C and pH 5.20 The
Figure
observed 4 shows
that current thedensity
stable behavior
of 10 of anodic
immersion curves
higher of samples
than that at andpotentiodynamic
covered 30with elemental sulfur
h immersion. polarization
with increasing
curves indicate Figure
that E theof
4 corr
shows immersion
the30stable time from
behavior
h immersion 10more
of is
anodicto 30 h atof80samples
curves
positive °Cthan
andcovered
pH 5.of
that The
with potentiodynamic
20 elemental
h immersion sulfur in the 3.5%
polarization
with increasingcurvesthe indicate that Etime
corr of from
30 h immersion
10 to 30 h isatmore positive than that of 20 h immersion
sodium chloride solution. Itimmersion
can be observed that current 80 °C and pH
density of 5.20The potentiodynamic
h immersion is higher than
in polarization
the 3.5% sodium curveschloride
indicate solution.
that Ecorr of It 30
can be observed
h immersion that current
is more positivedensity
than that of of
2020h himmersion
immersionis
that of 30 higher
h inimmersion.
thethan
3.5%that The values
of 30chloride
sodium h immersion.of anodic
solution. (β
TheIt values a
can be of ) and cathodic
anodic that
observed (β
( ) current c )
and cathodicTafel slopes
density( of) 20Tafel of the samples
slopes of the
h immersion is of each
experimentssampleswere
higher of determined
than
each that
experiments as were
illustrated
of 30 h immersion. in Table
The values
determined asof 5. ( in) Table
anodic
illustrated and cathodic
5. ( ) Tafel slopes of the
samples of each experiments were determined as illustrated in Table 5.
-6.10E-01
-6.10E-01
-6.20E-01
Potential (V, Ag/AgCl)

-6.20E-01
Potential (V, Ag/AgCl)

-6.30E-01
-6.30E-01
-6.40E-01
-6.40E-01 E/I 30 h
E/I 30 h
-6.50E-01 E/I 20 h
-6.50E-01 E/I 20 h
-6.60E-01 E/I 10 h
-6.60E-01 E/I 10 h
-6.70E-01
-6.70E-01
-6.80E-01
-6.80E-01
1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02
1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02
Current density (A)
Current density (A)

The potentiodynamic
Figure 3. Figure 3. 3.
Figure TheThe
curves
potentiodynamic
potentiodynamiccurves
of of
4130
curvesof 4130 Cr-Mo
4130Cr-Mo
alloy
Cr-Mo alloy
steel
alloy steel
covered
covered
steel covered
with elemental
withelemental
with elemental sulfur in 3.5%
sulfurinin3.5%
sulfur 3.5%
sodium chloride
sodium solution
chloride at different
solution at immersion
different immersion times:
times: 10,
10, 20 20
and and
30 h 30
at h
80 at
°C, 80
pH ◦2.C, pH 2.
sodium chloride solution at different immersion times: 10, 20 and 30 h at 80 °C, pH 2.

-0.61
-0.61
-0.62
-0.62
Potential(V,Ag/AgCl)
Potential(V,Ag/AgCl)

-0.63
-0.63
-0.64
-0.64
E/I3030h h
E/I
-0.65
-0.65
E/I
E/I2020h h
-0.66
-0.66
E/I
E/I1010h h
-0.67
-0.67
-0.68
-0.68
-0.69
-0.69
1.00E-08 1.00E-07
1.00E-08 1.00E-07 1.00E-06
1.00E-06 1.00E-05
1.00E-05 1.00E-04
1.00E-04 1.00E-03
1.00E-03 1.00E-02
1.00E-02
Currentdensity
Current density (A)
(A)

Figure
The 4. The potentiodynamic
potentiodynamic
Figure 4. Figure curvescurves
ofofof 4130Cr-Mo
4130 Cr-Mo alloy
alloysteel covered
steel with elemental
covered sulfur in 3.5%
with elemental sulfur in 3.5%
4. The potentiodynamic curves 4130 Cr-Mo alloy steel covered with elemental sulfur in 3.5%
sodium chloride solution at different immersion times: 10, 20 and 30 hat pH 5.
sodium chloride solution
sodium chloride at different
solution immersion
at different times:10,10,
immersion times: 20 and
20 and 30pH
30 hat hat
5. pH 5.
Materials 2017, 10, 430 7 of 12

Table 5. The values of anodic (β a ) and cathodic (β C ) Tafel slopes of second series.

Experiment β a (mV·Decade−1 ) β C (mV·Decade−1 )

7 0.032 0.015
8 0.030 0.013
9 0.023 0.020
10 0.022 0.021
11 0.022 0.019
12 0.020 0.019

3.2.2. Corrosion Rate of Cr-Mo Low Alloy Steel

The corrosion rates of the second series of the experiments were calculated with the same method
as the first series. Table 6 indicates the corrosion rate of each experiment.

Table 6. The corrosion rates of second series.

Experiment 7 8 9 10 11 12
pH 2 2 2 5 5 5
Corrosion Rate (CR) (mm/year) 0.615 0.605 0.595 0.381 0.367 0.318

As Table 6 indicated, generally the corrosion rates of Cr-Mo alloy in the presence of elemental
sulfur are greater than those in the presence of sulfide ions. Furthermore, it can be observed that at
pH 2, the rates of corrosion are higher than those of pH 5, which is due to the formation of protective
corrosion product layers on the alloy surface at pH greater than 2. The corrosion rate after 10 h
immersion at pH 2 has a maximum of 0.615 mm/year, which slightly decreased to 0.595 mm/year
after 30 h immersion. The corrosion rates of pH 5 gradually decreased by increasing the immersion
time due to the formation of protective corrosion product layer. These results are consistent with data
obtained from the potentiodynamic polarization technique.

3.3. Analysis of Corrosion Product Layers on the Surface of the Alloy

Figure 5 shows the SEM micrograph of the corrosion product layers that form on the surface of
each sample at pH 2 under 10, 20 and 30 h immersion time in thioacetamide solution. Figure 5 shows
that by increasing the immersion time, a thin corrosion product layer gradually covered the alloy
surface and protected it from further corrosion. EDS results indicate that this corrosion product layer
contains iron and sulfur and so, likely, compounds of iron sulfide.
The EDS spectrum of Figure 5a illustrates that once the corrosion product layer formed on the
sample surface, in some areas, the elemental sulfur was observed as the predominant constituent with
a high ratio compared to elemental iron. The same features have been reported by F. Alabbas et al. [23].
Figure 6 shows the SEM micrograph of the corrosion product layers that form on the surface of
each sample at pH 5 under 10, 20 and 30 h immersion time in thioacetamide solution.
Figure 6a,b shows that generally, a much thicker film was deposited on the alloy surface at pH 5
after 10 and 20 h immersion in thioacetamide solution. The composition of this film was shown by
EDS to consist of iron and sulfur. After 30 h immersion in the solution, the corrosion product layer
was broken and exposed the sample surface to the corrosive solution.
Comparison of Figures 5 and 6 and also the cross-section of the corrosion product layers show that
at pH 2, a very thin and open structure layer formed, which could not display a protective role against
corrosion. However, at pH 5, the corrosion product layer was more dense, adherent and protective
due to a higher volume of precipitated products on the sample surface.
Materials 2017, 10, 430 8 of 12
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10, 430
430 88 of
of 12
12

Figure
Figure 5.
Figure5. SEM
5.SEM micrograph
SEMmicrograph and
micrographand EDS
andEDS
EDSofof the
ofthe corrosion
thecorrosion product
corrosionproduct layers
productlayers that
layersthat form
thatform on
formon the
onthe surface
thesurface of
surfaceof each
ofeach
each
sample
sample at pH
sampleatatpH 2 under
pH22under (a)
under(a) 10,
(a)10, (b)
10,(b) 20
(b)20 and
20and (c)
and(c) 30
(c)30 h immersion
30hhimmersion time
immersiontime
timeinin thioacetamide
inthioacetamide solution.
thioacetamidesolution.
solution.

Figure 6. SEM micrograph and EDS of the corrosion product layers that form on the surface of each
Figure
Figure 6.atSEM
sample6. SEM micrograph
pH 5micrograph and
and
under (a) 10, EDS
(b)EDS of the
of
20 and the corrosion
(c) corrosion
30 product
product
h immersion layers
layers
time that form
that form on
on solution.
in thioacetamide the surface
the surface of
of each
each
sample at pH 5 under (a) 10, (b) 20 and (c) 30 h immersion time in thioacetamide solution.
sample at pH 5 under (a) 10, (b) 20 and (c) 30 h immersion time in thioacetamide solution.
Higher pH would generally decrease the solubility of the corrosion products layer and
Higher pH
Higher pH would
would generally
generally decrease
decrease the
the solubility
solubility ofof the
the corrosion
corrosion products
products layer
layer and
and
consequently result in an increase of precipitation rate, faster formation of protective layers and
consequently result
consequently result in
in an
an increase
increase of
of precipitation
precipitation rate,
rate, faster
faster formation
formation of
of protective
protective layers
layers and
and the
the
the reduction of corrosion rates [21].
reduction of
reduction of corrosion
corrosion rates
rates [21].
[21].
Figure 7 shows the SEM micrograph of the corrosion product layers that formed on the surface of
Figure 77 shows
Figure shows thethe SEM
SEM micrograph
micrograph of
of the
the corrosion
corrosion product
product layers
layers that
that formed
formed onon the
the surface
surface
each sample covered with elemental sulfur at pH 2 under 10, 20 and 30 h immersion time.
of each sample covered with elemental sulfur at pH 2 under 10, 20 and 30 h immersion
of each sample covered with elemental sulfur at pH 2 under 10, 20 and 30 h immersion time. time.
 Materials 2017, 10, 430 9 of 12
Materials
Materials2017, 10,10,
2017, 430430 9 of 1212
9 of

Figure
Figure7.7.7.SEM
Figure SEMmicrograph
SEM micrographand
micrograph andEDS
and EDSofof
EDS ofthe
thecorrosion
the corrosionproduct
corrosion productlayers
product layersthat
layers thatform
that formon
form onthe
on thesurface
the surfaceofof
surface ofeach
each
each
sample
sample covered
covered with
with elemental
elementalsulfur
sulfuratat pH
pH 2 2under
under(a)
(a)10,
10,(b)
(b)20
20and
and (c)
(c)30
30hhimmersion
immersion
sample covered with elemental sulfur at pH 2 under (a) 10, (b) 20 and (c) 30 h immersion time. time.
time.

Figure
Figure777illustrated
Figure illustratedthat
illustrated thatthe
that thehighest
the highestpercentage
highest percentageofof
percentage ofcracks
cracksand
cracks andpits
and pitscan
pits canbe
can beobserved
be observedinin
observed inthese
these
these
experimental
experimental conditions;
conditions; however,
however, the
the corrosion
corrosion product
product layers’
layers’ formation
formation
experimental conditions; however, the corrosion product layers’ formation on the alloy surface on onthe
the alloy
alloy surface
surface
gradually
graduallyincreased
gradually increasedwith
increased with time,
withtime, which
time,which
which slightly
slightly
slightly reduced
reduced
reduced the
thethecorrosion
corrosion
corrosion rate.
rate.rate.
TheThe
The
EDSEDS
EDS analysis
analysis
analysis shows
showsshows
the
the
thepresence
presence ofofdifferent
different values
values ofofiron
iron and
and sulfur,
sulfur, which
which also
alsoindicates
indicates the
the presence
presence of different values of iron and sulfur, which also indicates the presence of various compoundspresence ofofvarious
various
compounds
compounds
of ofofiron
iron sulfide iron
on sulfide
thesulfideonon
surface the
of surface
the surfaceofofsamples.
samples. samples.
Figure 8 shows
Figure88shows
Figure the
showsthe SEM
theSEM micrograph
SEMmicrograph
micrographof of the
thecorrosion
ofthe corrosionproduct
corrosion productlayers
product layersthat
layers thatform
that formon
form onthe
on thesurface
the surfaceofof
surface of
each
eachsample
sample covered
covered with
withelemental
elemental sulfur
sulfur at pH
at pH 5 under
5 under 10,
10,2020and
and 30
each sample covered with elemental sulfur at pH 5 under 10, 20 and 30 h immersion time.
h
30 himmersion
immersion time.
time.

Figure
Figure8.8.8.SEM
Figure SEMmicrograph
SEM micrographofof
micrograph ofthethecorrosion
the corrosionproduct
corrosion productlayers
product layersthat
layers thatform
that formon
form onthe
on thesurface
the surfaceofof
surface ofeach
eachsample
each sample
sample
covered
coveredwith
covered withelemental
with elementalsulfur
elemental sulfuratatatpH
sulfur pH555under
pH under(a)
under (a)10,
(a) 10,(b)
10, (b)20
(b) 20and
20 and(c)
and (c)30
(c) 30hhhimmersion
30 immersiontime.
immersion time.
time.
Materials 2017, 10, 430 10 of 12
Materials 2017, 10, 430 10 of 12

Comparison of Figures 7 and 8 shows that by increasing pH from 2 to 5, the corrosion product
layer became more even and continuous, which is consistent with data from corrosion rate and
potentiodynamic polarization tests. At At pH
pH 5 and after 30 h immersion in the solution, the corrosion
product
product layers
layersbecame
becamefiner
finerand
andcompact, indicative
compact, of good
indicative protection
of good for the
protection foralloy compared
the alloy to those
compared to
of 10 and 20 h immersion. The formation of this condensed corrosion product layer slightly
those of 10 and 20 h immersion. The formation of this condensed corrosion product layer slightly prevents
further
preventscorrosion and consequently
further corrosion decreasesdecreases
and consequently the corrosion rate with time.
the corrosion rate with time.

General
General Comparison
Comparison of
of the
the Corrosion
Corrosion Product
Product Layers
Layers in
in Two
TwoSeries
Seriesof
ofExperiments
Experiments
Figure
Figure 9a,b
9a,b shows
shows the
the cross-section of corrosion
cross-section of product layers
corrosion product layers of
of the
the first
first and
and second
second series
series of
of
experiments at pH 5 after 10 h immersion time, respectively.
experiments at pH 5 after 10 h immersion time, respectively.

Figure 9. Cross-section of corrosion product layer of the (a) first and (b) second series of experiments
at pH 5 after 10 h immersion time.

In the presence of sulfide ions, Figure 9a, a thin, dense and adherent layer covered the sample
In the presence of sulfide ions, Figure 9a, a thin, dense and adherent layer covered the sample
surface with a thickness of approximately 7 µm, which provided a barrier against further corrosion;
surface with a thickness of approximately 7 µm, which provided a barrier against further corrosion;
however, in the presence of elemental sulfur, Figure 9b, the top surface layer indicates a flaky
however, in the presence of elemental sulfur, Figure 9b, the top surface layer indicates a flaky structure.
structure. The thickness of this layer is about 10.15 µm, which still cannot provide enough protection
The thickness of this layer is about 10.15 µm, which still cannot provide enough protection due to the
due to the structure being too porous and detached from the sample surface.
structure being too porous and detached from the sample surface.
The results of cross-sectional analysis verified the results from the corrosion rate calculation and
The results of cross-sectional analysis verified the results from the corrosion rate calculation and
potentiodynamic measurements.
potentiodynamic measurements.
The XRD patterns of 4130 Cr-Mo alloy steel exposed to sulfide ions and elemental sulfur are
The XRD patterns of 4130 Cr-Mo alloy steel exposed to sulfide ions and elemental sulfur are
displayed in Figure 10. As has been mentioned in the cross-sectional analysis, the corrosion product
displayed in Figure 10. As has been mentioned in the cross-sectional analysis, the corrosion product
layer thickness is extremely low for most of the samples, which made them undetectable with XRD
layer thickness is extremely low for most of the samples, which made them undetectable with XRD
measurements. Figure 10a indicates the XRD pattern for the sample covered with elemental sulfur at
measurements. Figure 10a indicates the XRD pattern for the sample covered with elemental sulfur
pH 5 after 30 h immersion. As can be seen, iron is the only element that was detected on the
at pH 5 after 30 h immersion. As can be seen, iron is the only element that was detected on the
sample surface.
sample surface.
The XRD patterns in Figure 10b,c confirmed the formation of iron sulfide compounds on the
The XRD patterns in Figure 10b,c confirmed the formation of iron sulfide compounds on the
surface of the samples at pH 5 after 10 h immersion time in the first and second series of experiments
surface of the samples at pH 5 after 10 h immersion time in the first and second series of experiments
respectively, where the corrosion product layers were thick enough to be detected by X-ray spectra.
respectively, where the corrosion product layers were thick enough to be detected by X-ray spectra.
Materials 2017, 10, 430 11 of 12
Materials 2017, 10, 430 11 of 12

Figure10.
Figure 10. XRD
XRD pattern
pattern for
for the
the samples
samples in
in (a)
(a) the
the second
second series
series of
of experiment
experiment at
at pH
pH 55 after
after 30
30 hh
immersion, (b) the first series of experiments at pH 5 after 10 h immersion and (c) the second
immersion, (b) the first series of experiments at pH 5 after 10 h immersion and (c) the second series of series
of experiment
experiment at pH
at pH 5 after
5 after 10 h10immersion.
h immersion.

4.4.Conclusions
Conclusions

• Corrosionresistance
Corrosion resistanceofof Cr-Mo
Cr-Mo alloy
alloy in the
in the presence
presence of elemental
of elemental sulfur
sulfur is significantly
is significantly lowerlower
than
than its resistance in the presence of sulfide ions with the same experimental
its resistance in the presence of sulfide ions with the same experimental conditions. conditions.
• Increasingthe
Increasing thepHpHsignificantly
significantlydecreases
decreases the
the corrosion
corrosion rate
rate of of Cr-Mo
Cr-Mo alloy
alloy steel
steel in the
in the presence
presence of
of elemental sulfur, which is due to the formation of evener and compact
elemental sulfur, which is due to the formation of evener and compact corrosion product layers corrosion product
layers
on on the
the alloy alloy surface.
surface.
• Theeffect
The effect of
of immersion
immersion timetime on
onthe
thecorrosion
corrosionbehavior
behaviorofofthe alloy
the is is
alloy moremorecomplicated
complicated than the
than
effect of pH. Results suggest that a number of factors such as microstructure,
the effect of pH. Results suggest that a number of factors such as microstructure, composition composition and
the the
and stability of corrosion
stability of corrosionproduct
product layers
layersand
andimmersion
immersiontime timecan
can increase
increase oror decrease
decrease thethe
corrosionrate.
corrosion rate.
 How stable the corrosion product layers are from elemental sulfur corrosion in various
• How stable the corrosion product layers are from elemental sulfur corrosion in various aggressive
aggressive environments needs to be further investigated.
environments needs to be further investigated.
Acknowledgments: The research in this paper is supported by the Suncor Reservoir Souring Initiative at
Memorial UniversityThe
Acknowledgments: of Newfoundland.
research in this paper is supported by the Suncor Reservoir Souring Initiative at
Memorial University of Newfoundland.
Author Contributions: Ladan Khaksar and John Shirokoff conceived and designed the experiments;
Author performedLadan
Contributions:
Ladan Khaksar Khaksar and
the experiments; LadanJohn
KhaksarShirokoff conceived
and John Shirokoffand designed
analyzed theLadan
the data; experiments;
Khaksar
Ladan Khaksar performed the experiments; Ladan Khaksar and John Shirokoff analyzed the data; Ladan Khaksar
contributed reagents/materials/analysis tools; All authors co-wrote the manuscript.
contributed reagents/materials/analysis tools; All authors co-wrote the manuscript.
ConflictsofofInterest:
Conflicts Interest:The
Theauthors
authorsdeclare
declareno
noconflict
conflictofofinterest.
interest.

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