Corrosion Science 126 (2017) 247–254

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

Synergistic inhibition effects of octadecylamine and tetradecyl trimethyl MARK

ammonium bromide on carbon steel corrosion in the H2S and CO2 brine
solution
⁎
Chen Zhanga, Jingmao Zhaoa,b,
a
College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
b
Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing 100029, China

A R T I C L E I N F O A B S T R A C T

Keywords: The corrosion inhibition performances of octadecylamine (OCT) and tetradecyl trimethyl ammonium bromide
A. Acid solution (TTAB) for carbon steels in H2S and CO2 brine solution were investigated by weight loss, potentiodynamic
A. Carbon steel polarization, molecular dynamic simulation and XPS analysis. TTAB showed better inhibition effects on H2S and
B. Polarization CO2 induced corrosion than OCT. Synergistic corrosion inhibition effect was found between OCT and TTAB with
B. Weight loss
proper mass ratios and the best inhibition performance was achieved with 10 mg L−1 OCT and 20 mg L −1
B. XPS
TTAB. The synergism was correlative to the fractional free volume of the inhibitor film of OCT and TTAB.
C. Acid corrosion

1. Introduction inhibitors by many scholars in recent years [22–29]. However, it is

The combined corrosion effects of CO2 and H2S on carbon steels is a
serious issue in the oil and gas production. Various advanced corrosion
protection technologies have been developed [1,2], among which the
injection of corrosion inhibitors is one of the most economical and ef-
fective methods to minimize the CO2 and H2S induced corrosion of
carbon steels. Organic compounds containing heteroatoms and aro-
matic rings, such as imidazoline [3–6], amine [7,8], quinoline [9], and
so on, are effective corrosion inhibitors. They are able to form an iso-
lation film on the metal surface to retard the corrosion in aggressive
solutions [10–12].
Generally, a single inhibitor can rarely achieve the desired corrosion
inhibitions. Synergism of two or more inhibitors can usually enhance
the corrosion inhibition and reduce costs [13]. Previous studies have
been focused on the synergistic corrosion inhibition effects of inhibitors
on carbon steels in inorganic acid solutions, such as HCl, H2SO4, H3PO4,
and so on [13–19], and CO2-saturated brine solutions [20,21]. The
synergistic corrosion inhibition of steels in H2S and CO2 coexisting
brine solution has rarely been reported.
The synergistic inhibition effects of various inhibitors are usually
determined by weight loss method, electrochemical measurements,
surface analysis and other techniques to screen and develop new high
efficiency composite inhibitors. Molecular simulation techniques,
which offset the deficiencies of experimental methods, have also been
used to evaluate the corrosion inhibition performance of various
rarely used for the study of the synergistic inhibition effects.
In the present work, the synergistic inhibition effects of octadecy-
lamine (OCT) and tetradecyl trimethyl ammonium bromide (TTAB) on
carbon steel corrosion in the H2S and CO2 co-existing brine solution
were determined by weight-loss method and potentiodynamic polar-
ization measurements. XPS analysis and molecular dynamic (MD) si-
mulation were used to conjecture the synergistic inhibition mechanism.
2. Experimental
2.1. Materials
All tests were performed on Q235 steels composed of 0.19 wt.% C,
0.59 wt.% Mn, 0.3 wt.% Si, 0.044 wt.% P, 0.05 wt.% S and bal. Fe. The
steel was cut into coupons with the sizes of 50 mm × 10 mm × 3 mm
for weight loss test, 10 mm × 10 mm × 3 mm for polarization mea-
surements, and 5 mm × 5 mm × 2 mm for XPS analysis. The coupons
were wet abraded with silicon carbide abrasive papers up to 3000 grit,
degreased in acetone, rinsed with ethanol, and dried by a hot air stream
Analytical grade octadecylamine (OCT) and tetradecyl trimethyl
ammonium bromide (TTAB) were used as the corrosion inhibitors in
present work. Their chemical structures are shown in Fig. 1. An ag-
gressive solution of 3.5 wt.% NaCl solution was prepared with analy-
tical grade sodium chloride and distilled water.

⁎
Corresponding author at: No. 15 of Beisanhuan East Road, Chao Yang District, Beijing 100029, China.
E-mail address: jingmaozhao@126.com (J. Zhao).

http://dx.doi.org/10.1016/j.corsci.2017.07.006
Received 6 August 2016; Received in revised form 11 July 2017; Accepted 12 July 2017
Available online 14 July 2017
0010-938X/ © 2017 Elsevier Ltd. All rights reserved.
C. Zhang, J. Zhao
Fig. 1. Chemical structures of TTAB (a) and OCT (b).
2.2. Weight loss
Three identical coupons were weighed by an electric balance with
precision of ± 0.1 mg and immersed in 700 ml aggressive solutions
containing various concentrations of the inhibitors. The solutions were
purged with pure N2 gas for 1 h to remove the oxygen, then H2S
(20 ml min−1) and CO2 (20 ml min−1) were simultaneously introduced
into the solution for 1 h. The H2S/CO2 brine solutions containing the
coupons were seal with silicone sealants and incubated at 60 ± 1 °C
for 72 h. The coupons were then taken out, immersed in a Clarke’s
solution (6 g 1,3,5,7-tetraazatricyclo [3.3.1.1(3,7)]decane + 500 ml
distilled water and hydrochloric acid to make 1000 ml) for 5 min to
remove the corrosion products, washed under running water, degreased
in acetone, rinsed with ethanol, dried, and re-weighed accurately. The
corrosion rate (VCR) of the carbon steel was calculated by Eq. (1).
ΔW
VCR =
Sm × t
where ΔW is the average weight loss of the three coupons, Sm is the
total surface area of the coupon, and t is the immersion time.
The inhibition efficiency (ηw) of inhibitors was defined as follows:
VCR (inh)
ηw = (1 − ) × 100%
VCR (uninh)
where VCR(inh) and VCR(uninh) are the corrosion rates of the steel in the
solution with and without inhibitors, respectively.
Corrosion Science 126 (2017) 247–254
2.3. Potentiodynamic polarization measurements
The potentiodynamic polarization measurements were performed
on a Gamry interface 1000 electrochemical system at 60 ± 1 °C. A
conventional three-electrode cell with a platinum foil as the counter
electrode and a saturated calomel electrode as the reference electrode
was used. The test solutions for the polarization measurements were
prepared as described in the weight loss test except that the solution
volume was 200 ml. To achieve a stable status of the working electrode,
the working electrode was immersed in the test solution for 1 h before
the measurements to ensure an open circuit potential (OCP) fluctuation
less than ± 5 mV (Fig. 2). The potentials were then scanned from −200
to +200 mV vs. OCP at a scan rate of 0.16 mV s−1. The electrochemical
parameters were fitted in the software Cview [30]. The inhibition ef-
ficiency (ηp) of the corrosion inhibitor was defined as follows:
icorr − icorr (inh)
ηp = × 100%
icorr (3)
where icorr and icorr(inh) are the corrosion current densities of the steel in
the aggressive solutions with and without inhibitors added, respec-
tively.
Each measurement was repeated at least three times to obtain ac-
curate data.
2.4. Molecular dynamics (MD) simulation
A simplified amorphous model was constructed to calculate fraction
free volume (FFV) with Materials Studio software in the present work
(Fig. 3). The simulation was conducted in four steps:
1. A cubic model containing 50 inhibitor molecules in three-dimen-
sional periodic boundary conditions was constructed by the
(1)
Amorphous Cell module in Materials Studio. The initial density of
the model was set to 0.6 g cm−3 and the model was then minimised
by the smart minimisation method until the convergence reached to
0.042 kJ mol−1.
2. To evaluate the stable density of the model, a 500 ps MD simulation
with a time step of 1 fs was carried out at NPT ensemble. The final
density of the model was defined as the average density of the last
(2)
200 frames that were recorded at every one frame per ps.
3. Step 1 was repeated with the density of the model set to the value
obtained in step 2.
4. A 1000 ps MD simulation with a time step of 1 fs was carried out at
NVT ensemble to calculate the FFV of the model by the Atom
Fig. 2. OCP curves of Q235 carbon steel in H2S and CO2 co-existing 3.5 wt.
% NaCl solutions containing different inhibitors at 60 °C.
248
C. Zhang, J. Zhao
Fig. 3. Model for FFV calculation.
Volumes and Surfaces Tool in Materials Studio. The FFV values of
nine structures chosen every five frames in the last forty frames were
calculated and the maximum and minimum values were omitted.
The mean value of the rest seven values was defined as the FFV
value of the model.
COMPASS force field was used in all simulation steps [31]. The si-
mulation temperature and pressure of the model were controlled at
333 K and 1 × 105 Pa by Andersen thermostat and Berendsen barostat,
respectively. The long-range coulomb and Van der Waals interactions
were handled by the Ewald and Atom Based methods, respectively. The
cutoff was set to 1.25 nm.
2.5. X-ray photoelectron spectroscopy (XPS) analysis
The coupons were immersed in CO2 and H2S co-existing solutions
containing 10 mg L−1 OCT and 20 mg L−1 TTAB at 60 ± 1 °C for 5,
15, 25 and 40 min, respectively, taken out from the solutions, dried by a
hot air, and kept in a desiccator before use. XPS spectra were recorded
on a PHI-5300ESCA spectrometer (Perkin–Elmer, USA) equipped with
an Al Kα excitation source. The survey scan was set to 0–1155 eV with a
step size of 1 eV. The high-resolution spectra of N1s were achieved over
Fig. 4. ηw vs concentration plots of TTAB and OCT (a) and ηw vs TTAB content plot and S vs TTAB content plot of the composite inhibitor at a total addition concentration of 30 mg L−1
(b) for the Q235 carbon steel measured in 3.5 wt.% NaCl solution containing H2S and CO2 at 60 °C.
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Corrosion Science 126 (2017) 247–254
391–414 eV with a step size of 0.05 eV. All binding energies were ca-
librated with the binding energy of C1s peak at 284.6 eV. The data were
fitted and analysed in XPSPEAK version 4.1 software.
3. Results and discussion
3.1. Weight loss
Weight loss experiments were conducted at 60 °C to investigate the
synergistic corrosion inhibition performances of OCT and TTAB in the
brine solution containing H2S and CO2. As shown in Fig. 4a for the
inhibition efficiencies (ηw) of OCT and TTAB, the ηw values of both OCT
and TTAB increased with the increase of concentration. Fig. 4b shows
the ηw measured in the aggressive solutions containing various con-
centrations of TTAB and OCT with a total concentration of 30 mg L−1.
As can be seen, the ηw of the composite inhibitor increased with the
portion of TTAB (C%TTAB) and remained steady at ∼95% as C%TTAB
increased to over 67%.
To compare the synergistic degrees of the different combinations of
TTAB and OCT, the synergistic parameter, S, was calculated as follows
[32,33]:
1 − ηA − ηB + ηAηB
S=
1 − ηAB (4)
where ηA, ηB and ηAB are the inhibition efficiencies of inhibitor A, in-
hibitor B and the mixture of A + B, respectively. Generally, S = 1 in-
dicates that there is no synergistic effect between inhibitor A and B.
Alternatively, S > 1 if the synergistic effects manifest themselves and
S < 1 if there is an antagonistic effect between inhibitor A and B. The
synergistic corrosion inhibition effects of OCT and TTAB were found at
C%TTAB = 50–83% and peaked at C%TTAB = 67%. In addition, the ηw
of 10 mg L−1 OCT + 20 mg L−1 TTAB is higher than the sum of those
of 10 mg L−1 OCT and 20 mg L−1 TTAB, indicating the good corrosion
inhibition synergistic effect between OCT and TTAB.
3.2. Potentiodynamic polarization
To further confirm the synergistic corrosion inhibition effect of OCT
and TTAB, potentiodynamic polarization experiments were performed
at 60 °C. Fig. 5 shows the polarization curves of mild steels in the ag-
gressive solutions containing different inhibitors. As can be seen, the
inhibitors can affect both anodic dissolution and cathodic reactions on
the steel surface. The corrosion potential (Ecorr) of the steel in the
presence of composite inhibitors obviously shifted toward positive di-
rection in the TTAB concentration (cTTAB) range of 20–30 mg L−1 and
C. Zhang, J. Zhao Corrosion Science 126 (2017) 247–254

Fig. 5. Polarization curves of Q235 carbon steel measured in H2S and CO2
co-existing 3.5 wt.% NaCl solutions containing various concentrations of
TTAB and OCT at 60 °C.

slightly shifted at cTTAB below 20 mg L−1. It has been reported that
TTAB and OCT are anodic-type and mixed-type inhibitors, respectively
[34,35]. Therefore, the composite inhibitors evolved from mixed-type
to anodic-type with the increase of cTTAB, which eventually retarded the
anodic dissolution of the mild steel [36,37].
Table 1 shows the electrochemical parameters fitted from the po-
larization curves. It is clear that ηp of OCT and TTAB composite in-
hibitor is significantly higher than those of OCT or TTAB alone. The ηp
of the composite inhibitors increased dramatically with the increasing
of cTTAB to 20 mg L−1 and gradually increased with the increasing of
cTTAB from 20 mg L−1 to 30 mg L−1. Although the absolute ηp values
differ from those obtained by the weight loss method, their changing
trends with the increase of cTTAB obtained by these two methods are
consistent.
3.3. Fractional free volume (FFV)
Organic inhibitors can usually adsorb on the metal surface sponta-
neously and form an inhibitor film to retard corrosion. Co-adsorption of
two or more inhibitors, which is usually conducive to the formation of a
more compact inhibitor film on the metal surface, may occur if the
corrosion inhibitors are adsorption-type and have a synergistic corro-
sion inhibition effect [38,39]. Although the inhibitor film can prevent
the contact of metal surface with corrosive media to some extent, cor-
rosive particles may still be able to diffuse to the metal surface through
large cavities in the inhibitor film [25]. The diffusion rate of the
Table 1
Electrochemical parameters fitted from the polarization curves of Q235 steel in H2S and
CO2 co-existing 3.5 wt.% NaCl solutions containing various concentrations of TTAB and
OCT at 60 °C.
corrosive particles in the film with large cavities is faster than that in
the film with small cavities. Therefore, the size of the cavities in the
inhibitor film is an important factor determining the inhibition per-
formance of the inhibitor. To determine the free volume inside an in-
hibitor film, the fractional free volume (FFV) was calculated as follows
[40,41]:
Vfree
FFV = × 100%
Vfree + Voccupy (5)
where Vfree is the total volume of the large cavities where the corrosive
particles can enter. The small cavities where the corrosive particles
cannot diffuse into are excluded from the Vfree. Voccupy is the volume of
the film excluding Vfree. The FFV of an inhibitor film depends on the
radiuses of the corrosive particles and the properties of the inhibitor. A
low FFV indicates fewer cavities with smaller sizes where the corrosive
particles can diffuse, and thus the good inhibition performance of the
inhibitor. In the present work, the corrosive particles including H3O+,
HS−, Cl−, HCO3−, and H2O were selected as the probe species to
evaluate the FFV of the inhibitor films. The Van der Waals radiuses
(Rvdw) of the corrosive particles were calculated by the radial dis-
tribution function (Table 2) [24]. The calculated Rvdw are consistent to
the experimental results reported in the literatures, suggesting that the
radial distribution function method adopted in the present work is
credible.
The inhibitor films were then established with OCT and TTAB at
mass ratios of 1:0, 1:0.5, 1:1, 1:2, 1:3, 1:5, 1:8 and 0:1, respectively, and
their FFV were calculated. As shown in Fig. 6, the FFV of the films
constructed with 50–90% TTAB in the composite inhibitor are rela-
tively low for all probe species. The lowest FFV was achieved with 75%
TTAB i.e. a 1:3 mass ratio of OCT to TTAB.

cOCT cTTAB βa (mV/ βc (mV/dec) Ecorrvs.SCE icorr ηp (%) Table 2

(mg/L) (mg/L) dec) (mV) (μA/ Calculated and experimental Van der Waals radiuses of corrosive particles.
cm2)
Corrosive Particle Calculated (nm) Experimental (nm)
0 0 54.38 −231.33 −736.31 141.8 –
0 30 62.48 −149.1 −600.24 3.35 97.64 H2O 0.1365 0.1450 [42]
5 25 57.66 −186.16 −628.73 1.37 99.03 H3O+ 0.1405 –
10 20 68.51 −100.25 −654.65 1.72 98.79 Cl− 0.1725 0.1810 [43]
15 15 61.41 −155.56 −701.08 21.2 85.05 HCO3− 0.1835 –
20 10 58.68 −176.29 −724.08 48.9 65.51 HS− 0.1885 –
25 5 58.09 −181.91 −731.82 84.2 40.62
30 0 51.78 −294.05 −716.63 48.1 66.08

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C. Zhang, J. Zhao
The S curve of the composite inhibitor peaked at 70% TTAB and
showed an opposite changing tendency to FFV values with the increase
of C%TTAB (Fig. 4b vs 6), indicating that there is a negative correlation
between FFV and S although their extreme points were at different
C%TTAB values. Based on this negative correlation, the optimal mass
ratio range of the inhibitors in a composite inhibitor may be con-
jectured out by theoretical calculations. However, further work is
needed to develop a method for accurately determining the optimal
compositions of different composite inhibitors.
3.4. X-ray photoelectron spectroscopy (XPS) analysis
To further investigate the co-adsorption of OCT and TTAB, XPS
spectra of the carbon steel surfaces covered with different inhibitor
films were recorded. The inhibitor films were prepared by immersing
the steel coupons in the H2S and CO2 co-existing brine solution con-
taining 10 mg L−1 OCT and 20 mg L−1 TTAB at 60 °C for 5, 15, 25, 40,
and 60 min respectively. Fig. 7 shows a typical wide-scan spectrum of
the inhibitor film prepared by a 40 min immersion. The F2p, O1s, N1s,
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Corrosion Science 126 (2017) 247–254
Fig. 6. FFV vs TTAB content curves for different probe species.
C1s, and S2p peaks were observed in the wide-scan spectrum. The C1s
and N1s signals were mainly attributed to the OCT and TTAB molecules
adsorbed on the steel surface. The signals of O1s and S2p were due to
the oxide, oxycarbide, and sulfide of iron. Fe2p peak can be ascribed to
the substrate and its corrosion products.
Fig. 8 shows the high-resolution spectra of N1s of the inhibitor films
prepared at a 1:3 mass ratio of OCT to TTAB. Two peaks at 402.3 eV
and 399.8 eV were observed, which were assigned to the −N+(CH3)3
in TTAB [44,45] and the −NH2 in OCT, respectively [46]. The ratio of
peak areas of −N+(CH3)3 to −NH2 and other parameters obtained
from the N1s spectra are listed in Table 3. The peak areas of
−N+(CH3)3 and −NH2 of the inhibitor film formed in 5 min are almost
equal, indicating that TTA+ cations and OCT molecules almost are
equally adsorbed on the steel surface in the initial immersion stage. The
peak area of −NH2 gradually became larger than that of −N+(CH3)3
with the increasing immersion time, indicating that more OCT mole-
cules were adsorbed on the steel surface than TTA+ cations in the late
immersion stage.
Fig. 7. Wide-scan spectrum of the Q235 carbon steel immersed in H2S and
CO2 co-existing 3.5 wt.% NaCl solution containing 10 mg L−1 OCT and
20 mg L−1 TTAB for 40 min at 60 °C.
C. Zhang, J. Zhao Corrosion Science 126 (2017) 247–254

Fig. 8. High-resolution XPS spectra of N1s of the Q235 carbon steel coupons immersed in H2S and CO2 co-existing 3.5 wt.% NaCl solution containing 10 mg L−1 OCT and 20 mg L−1
TTAB for 5 min (a), 15 min (b), 25 min (c), and 40 min (d) at 60 °C.

3.5. The synergistic inhibition mechanism of OCT and TTAB
In the H2S and CO2 co-existing solution, HS− ions might pre-
ferentially adsorb on the carbon steel surface and negatively charged
the surface [47,48]. The lone pair electrons of N atom in OCT tend to
bind the hydrogen ions to form amide cations in the acidic solution
[49,50]. TTAB molecules could be hydrolysed to TTA+ cations in the
test solution. The quaternary ammonium ions and the protonated pri-
mary amine could simultaneously bind to the HS− layer adsorbed on
the metal surface through electrostatic interaction [51–53], which was
a physisorption process. Subsequently, the N atoms of both TTAB and
OCT donated their lone pair electrons to the empty d-orbitals in Fe
atoms to form coordinate covalent bonds between the inhibitors and the
metal surface, which was a chemisorption process. The physisorption
and chemisorption of TTA+ cations and protonated OCT molecules on
the steel surface are demonstrated in Fig. 9a.
As demonstrated by the XPS analysis, TTA+ cations and OCT
molecules simultaneously adsorbed on the steel surface to form an inner
inhibitor film in the initial immersion stage (Fig. 9b). With the
prolonging of the immersion, both OCT and TTAB tended to adsorb on
the inner film to form an outer inhibitor film. However, the TTA+ ions
in the outer film were easily desorbed due to the high water-solubility
of TTAB [54]. Therefore, the relative OCT content on the steel surface
was much higher than that of TTA+ in the later immersion stage. The
ideal structure of the inhibitor film is illustrated in Fig. 9c [55]. The
molecular dynamics simulation indicated that this inhibitor film had a
low FFV for all corrosive particles and thus could effectively prevent
corrosive particles from diffusing to the steel surface. In addition, FFV is
negatively correlative to S, which could be used to establish a low-cost
method to explore new high-effective composite inhibitors. However,
further work is needed to establish an effective method to screen
composite inhibitors by the correlation between FFV and S.
4. Conclusion

Table 3 In the present work, the synergistic corrosion inhibition effect of

Parameters of the high-resolution spectra of N1 s of the Q235 steel in the H2S and CO2 co- OCT and TTAB on the carbon steels in the H2S and CO2 co-existing
existing 3.5 wt.% NaCl solution containing 10 mg L−1 OCT and 20 mg L−1 TTAB at 60 °C.
brine solution was reported for the first time. Their combination was
Immersion Time -N+(CH3)3 Peak -NH2 Peak Ratio of Peak Area able to effectively retard the H2S and CO2 induced corrosion of carbon
(min) Area Area (-NH2:-N+(CH3)3) steel. TTAB and OCT are anodic-type and mixed-type inhibitors, re-
spectively. Their combinations evolved from mixed-type to anodic-type
5 2710 2692 0.993
with the increase of TTAB concentration. The molecular dynamics si-
15 2543 4468 1.757
25 2023 5526 2.732 mulation indicated that the FFV of the inhibitor film formed with OCT
40 1322 4464 3.377 and TTAB was negatively correlated to the degree of synergistic cor-
rosion inhibition effect, which could be used to screen new composite
corrosion inhibitors. The XPS measurements showed that TTA+ cations
and OCT molecules simultaneously adsorbed on the steel surface in the

252
C. Zhang, J. Zhao
initial immersion stage, and more OCT molecules adsorbed on the
surface than TTA+ cations in the late immersion stage.
Acknowledgment
The authors thank National Natural Science Foundation of China for
the financial supports for this work (No. 51471021).
253
Corrosion Science 126 (2017) 247–254
Fig. 9. Schematic diagram of the interactions between the inhibitors and
metal surface (a), co-adsorption process of TTAB and OCT (b), and the
ideal structure of the inhibitor film (c) formed in H2S and CO2 co-existing
3.5 wt.% NaCl solution containing OCT and TTAB at 60 °C.
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