Corrosion Science 75 (2013) 123–133

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

Electrochemical and XPS studies of the corrosion inhibition

of carbon steel in hydrochloric acid pickling solutions
by 3,5-bis(2-thienylmethyl)-4-amino-1,2,4-triazole
M. Tourabi a, K. Nohair a, M. Traisnel b, C. Jama b, F. Bentiss a,b,⇑
a
Laboratoire de Catalyse et de Corrosion des Matériaux (LCCM), Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco
b
UMET-ISP, CNRS UMR 8207, ENSCL, Université Lille Nord de France, BP 90108, F-59652 Villeneuve d’Ascq Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: Corrosion inhibition of carbon steel in normal hydrochloric acid solution at 30 °C by new 4-amino-1,2,4-
Received 25 March 2013 triazole derivative, namely 3,5-bis(2-thienylmethyl)-4-amino-1,2,4-triazole (2-TMAT) has been studied
Accepted 28 May 2013 by electrochemical impedance spectroscopy (EIS) and polarization techniques. The experimental results
Available online 5 June 2013
have showed that this organic compound revealed a good corrosion inhibition and that the inhibition effi-
ciency is increased with the inhibitor concentration. Two time constants determined by the charge-trans-
Keywords: fer and the adsorption of the inhibitor, respectively, can be readily outlined. Potentiodynamic
A. 4-Amino-1,2,4-triazole
polarization showed that 2-TMAT is a mixed type of inhibitor. The adsorption of 2-TMAT on the carbon
A. Carbon steel
A. HCl
steel surface in 1 M HCl solution obeyed to the Langmuir isotherm with a very high negative value of the


B. EIS standard Gibbs free energy of adsorption DGads (chemisorption). X-ray photoelectron spectroscopy (XPS)
C. Adsorption analyses were carried out to establish the mechanism of corrosion inhibition of carbon steel in 1 M HCl
medium by 3,5-bis(2-thienylmethyl)-4-amino-1,2,4-triazole (2-TMAT).
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction 3,5-bis(2-thienylmethyl)-4-amino-1,2,4-triazole (2-TMAT), is

Acid solutions are generally used for the removal of rust and
scale in industrial processes. Hydrochloric acid is widely used in
the pickling of steel and different alloys. Inhibitors are generally
used in these processes to control the metal dissolutions. Most
well-known acid corrosion inhibitors are organic compounds con-
taining nitrogen, sulfur, and oxygen atoms; nitrogen-containing
organic compounds are known to be efficient corrosion inhibitors
in hydrochloric acid solutions, while sulfur-containing compounds
are sometimes preferred for sulfuric acid solutions [1,2]. Among
them, N-heterocyclic compounds are considered to be the most
effective corrosion inhibitors for steel in acid media [3–5].
Previously, some 1,2,4-triazole derivatives have been reported
as potential corrosion inhibitors [6–33]. Our previous investiga-
tions showed that the inhibitive effectiveness of these compounds
is affected mostly by the molecular structure, the position of the
substituents, the temperature and the acidic media [11,16–
18,22,23]. In this work we continue our investigations on 1,2,4-
aminotriazole derivatives as inhibitors of steel corrosion in acid
media. The investigated 4-amino-1,2,4-triazole derivative, namely
⇑ Corresponding author at: UMET-ISP, CNRS UMR 8207, ENSCL, Université Lille
Nord de France, BP 90108, F-59652 Villeneuve d’Ascq Cedex, France. Tel.: +33 320
337 746; fax: +33 320 436 814.
E-mail address: fbentiss@enscl.fr (F. Bentiss).
tested for the first time as corrosion inhibitor on carbon steel in
1 M HCl medium at 30 °C. The inhibitive activity of 2-TMAT is
examined successively via electrochemical impedance spectros-
copy (EIS), polarization, isotherm calculations, scanning electron
microscopy (SEM) and X-ray photoelectron spectroscopy (XPS)
techniques.
2. Experimental details
2.1. Materials
The tested inhibitor, namely 3,5-bis(2-thienylmethyl)-4-amino-
1,2,4-triazole (2-TMAT), was synthesised according to a previously
described experimental procedure [34,35]. The molecular structure
of 2-TMAT is shown in Fig. 1. The structure of the 2-TMAT was con-
firmed by 1H and 13C NMR, mass spectroscopy and elemental
analysis:
Yield 87%; mp 144 °C; 1H NMR (dimethyl-d6 sulfoxide;
300 MHz): d (ppm) 4.34 (s, 4H); 6.89 (m, 4H); 7.16 (d, 2H); 7.26
(s, 2H); 13C NMR (dimethyl-d6 sulfoxide; 75 MHz): d (ppm)
25.68, 125.27, 126.61, 127.56, 137.74, 153.96; MALDI-TOFMS: m/
z 277 (M+1). Anal. Calcd. for C12H12N4S2: C, 52.17; H, 4.35; N,
20.29; S, 23.19. Found: C, 52.29; H, 4.22; N, 20.41; S, 23.05.
The material used in this study is a carbon steel (Euronorm:
C35E carbon steel and US specification: SAE 1035) with a chemical

0010-938X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2013.05.023
124 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133
NH2
S Tafel experiment, the carbon steel electrode was pre-polarized at
N 800 mVSCE for 10 min and thereafter the WE was allowed to cor-
N S
N
Fig. 1. Chemical structure of 3,5-bis(2-thienylmethyl)-4-amino-1,2,4-triazole (2-
TMAT).
composition (in wt%) of 0.370% C, 0.230% Si, 0.680% Mn, 0.016% S,
0.077% Cr, 0.011% Ti, 0.059% Ni, 0.009% Co, 0.160% Cu and the
remainder iron (Fe). The steel samples were pre-treated prior to
the experiments by grinding with emery paper SiC (120, 600 and
1200); rinsed with distilled water, degreased in acetone in an
ultrasonic bath immersion for 5 min, washed again with bidistilled
water and then dried at room temperature before use. The acid
solutions (1 M HCl) were prepared by dilution of an analytical re-
agent grade 37% HCl with doubly distilled water. The solubility
of the 2-TMAT is about 104 M in 1 M HCl. The concentration range
of 2-TMAT employed was 5  106 M to 104 M in order to com-
pare their corrosion inhibition properties with those of similar het-
erocyclic compounds.
2.2. Corrosion tests
Electrochemical impedance spectroscopy (EIS), linear polariza-
tion resistance (LPR) and potentiodynamic polarization are three
classical electrochemical techniques which were used to deter-
mine the corrosion inhibitor characteristics of 2-TMAT in 1 M HCl.
Ac impedance tests were performed in a polymethyl methacry-
late (PMMA) cell with a capacity of 1000 ml at 30 ± 1 °C, using a
thermostat. A saturated calomel electrode (SCE) was used as the
reference; while a platinum leaf was used as a counter electrode.
All potentials are reported vs. SCE. The working electrode was pre-
pared from a square sheet of carbon steel such that the area ex-
posed to solution was 7.55 cm2. All impedance spectra were
recorded at the steady state of open circuit potential, i.e., at the
corrosion potential, after 24 h of the exposure of the working elec-
trode to the solution (no deaeration and no stirring).
Ac impedance measurements were performed using a potentio-
stat Solartron SI 1287 and a Solartron 1255B frequency response
analyzer and ZPlot 2.80 software was used to run the tests and
to collect the experimental data. The response of the electrochem-
ical system to ac excitation with a frequency ranging from 105 Hz
to 102 Hz and peak to peak amplitude of 10 mV was measured
with data density of 10 points per decade. All EIS diagrams were
recorded at the open circuit potential, i.e., at the corrosion poten-
tial Ecorr. One EIS spectrum is recorded usually within 10 min.
The impedance data were analyzed and fitted with the simulation
ZView 2.80, equivalent circuit software.
Linear polarization resistance (LPR) and potentiodynamic polar-
ization measurements were performed in a conventional three-
electrode cylindrical Pyrex glass cell. The temperature is thermo-
statically controlled. Pure carbon steel specimen was used as the
working electrode, a platinum electrode as the counter electrode
and a saturated calomel electrode (SCE) as the reference electrode.
The working electrode (WE) in the form of disk cut from steel has a
geometric area of 1 cm2 and is embedded in polytetrafluoroethyl-
ene (PTFE). A fine Luggin capillary was placed close to the working
electrode to minimize IR drop. All test solutions were de-aerated in
the cell by using pure nitrogen for 10 min prior to the experiment.
During each experiment, the test solution was mixed with a mag-
netic stirrer and the gas bubbling was maintained. Solartron
Instruments SI 1287 potentiostat monitored by a personal com-
puter via a GPIB Interface and CorrWare 2.80 software were used
to run the tests and to collect the experimental data. Before each
rode freely and its open circuit potential (OCP) was recorded as a
function of time up to 1 h, the time necessary to reach a quasi-sta-
tionary value for the open-circuit potential. This steady-state OCP
corresponds to the corrosion potential (Ecorr) of the WE. For LPR
measurements, the WE was polarized only in the range ±20 mV
vs. Ecorr at a scan rate of 0.125 mV s1. After studying the open cir-
cuit potential and LPR tests, the potentiodynamic Tafel measure-
ments were scanned from cathodic to the anodic direction,
E = Ecorr ± 200 mV, with a scan rate of 0.5 mV s1. The Tafel and
LRP data were analyzed and fitted using the polarization CorrView
2.80 software (Scribner Associates, Inc.).
2.3. Scanning electron microscopy (SEM)
The morphologies of the uninhibited and inhibited carbon steel
surface were analyzed by scanning electron microscope (JEOL
5300). The energy of the acceleration beam employed was 6 kV.
2.4. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) spectra were recorded
by a XPS KRATOS, AXIS UltraDLD spectrometer with the monochro-
matized Al Ka X-ray source (hm = 1486.6 eV) and an X-ray beam
of around 1 mm. The analyzer was operated in constant pass
energy of 40 eV using an analysis area of approximately
700 lm  300 lm. Charge compensation was applied to compen-
sate for the charging effects that occurred during the analysis.
The C 1s (285.0 eV) binding energy (BE) was used as internal refer-
ence. The spectrometer BE scale was initially calibrated against the
Ag 3d5/2 (368.2 eV) level. Pressure was in the 1010 torr range
during the experiments. XPS spectra were deconvoluted using a
non-linear least squares algorithm with a Shirley base line and a
Gaussian–Lorentzian combination. CasaXPS software was used
for all data processing. XPS analyses were practiced on pure 2-
TMAT and on protected steel surface with 2-TMAT. The disk carbon
steel (1 cm2) was pre-treated by the same procedure as for the
gravimetric test. After 24 h of immersion at 30 °C, the carbon steel
sheet was rinsed with acetone and ultra pure water.
3. Results and discussion
3.1. Corrosion inhibition evaluation
3.1.1. Ac impedance study
The electrochemical impedance spectroscopy (EIS) is a good
technique in investigating corrosion inhibition processes. It pro-
vides information on both the resistive and capacitive behavior
at interface and makes it possible to evaluate the performance of
the tested compounds as possible inhibitors against metals’ corro-
sion. Figs. 2 and 3 show a typical set of impedance diagrams for
carbon steel in 1 M HCl without and with various concentrations
of 2-TMAT. The Nyquist diagram in the absence of inhibitor
(Fig. 2a) shows only one depressed capacitive loop at the higher
frequency range (HF) with one capacitive time constant in the
Bode-phase plot (Fig. 2b). In this case, the standard Randles’ circuit
model of Fig. 4a, which has been previously used [36], fits well our
experimental results. In this equivalent circuit, Rs is the solution
resistance, Rct present the charge transfer resistance whose value
is a measure of electron transfer across the surface and CPE is
the constant phase element. The constant phase element, CPE, is
 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133 125

-40 -300
HCl 1 M a 10-4 M a
510-5 M
10-5 M
510-6 M

-30 -200

Zi (Ωcm )
2
50.1 Hz 25.1 Hz

100 Hz 10 Hz
Z i (Ωcm )
2

7.9 Hz 5 Hz
-20 199.5 Hz
-100 12.6 Hz
2.5 Hz
10 Hz 1 Hz
5 Hz 0.5 Hz 0.1 Hz
25.1 Hz 25.1 Hz
0.01Hz
2.5 Hz 2 Hz
-10 50.1 Hz 0
1 Hz
0 100 200 300 400 500
100 Hz
0.1 Hz Zr (Ωcm2)

0 103 -75
0 10 20 30 40 50 10-4 M
510-5 M
b
2
Z r (Ωcm ) 10-5 M
510-6 M
-55
10
2 -50
HCl 1 M b

Phase angle (Degree)

102

-40 -35

|Z| (Ωcm2)
Phase angle (Degree)

-30 -15
101
|Z| (Ωcm2)

10
1 -20
5

-10
100 25
10-2 10-1 100 101 102 103 104 105

0 Frequency (Hz)

Fig. 3. (a) Nyquist and (b) Bode diagrams for carbon steel in 1 M HCl containing
different concentrations of 2-TMAT after 24 h of immersion period at 30 °C. Key: h
100 10 – 5  106 M, s – 105 M, r – 5  105 M, } – 104 M.
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10
Frequency (Hz)
a depressed semicircle at the high frequency part of the spectrum
Fig. 2. (a) Nyquist and (b) Bode diagrams for carbon steel in 1 M HCl after 24 h of
immersion period at 30 °C.
was observed and a second time constant appeared at low fre-
quency region (Fig. 3). The increase in size of the semicircle with
introduced in the circuit instead of a pure double layer capacitor in 2-TMAT concentration means that the inhibitor effect increases
order to take into account the electrode surface heterogeneity as well. The first capacitive loop (the larger) appearing at high fre-
resulting from surface roughness, impurities, dislocations, grain quency region can be attributed to the charge transfer, the second
boundaries, adsorption of inhibitors, formation of porous layers one (the smaller) at low frequencies can be related to the adsorp-
[37,38] and therefore to give a more accurate fit [39]. The imped- tion of inhibitor molecules on the metal surface and/or all other
ance of the CPE is expressed as: accumulated kinds at the metal/solution interface (inhibitor mole-
n
cules, corrosion products, etc.) [43]. In this case, the structural
Z CPE ¼ A1 ðixÞ ð1Þ model of Fig. 4a is inadequate (see Fig. 5, representative example)
and a two-time-constant model should be used to describe the
where A is the magnitude of CPE (in X1 sn cm2), x is the sine
electrochemical impedance spectra in the presence of 2-TMAT, as
wave modulation angular frequency (in rad s1), i2 = 1 is the imag-
presented in Fig. 4b, that permits the determination of the adsorp-
inary number, and n is an empirical exponent (0 6 n 6 1) which
tion parameters Ra and CPEa (Aa and na, respectively). In Fig. 4b, Rs
measures the deviation from the ideal capacitive behavior [40,41].
represent the solution resistance, Rct is the charge transfer resis-
The corresponding fitting results are listed in Table 1. In this table
tance and CPEd represent the capacitance of the high frequency
are also shown the calculated double layer capacitance (Cdl) derived
semicircle that can be attributed to the charge transfer process.
from the CPE parameters according to the following equation [42]:
Ra represents the resistance of the adsorbed inhibitor and CPEa is
C dl ¼ ðAd R1n d 1=nd
Þ ð2Þ the capacitance of the inhibitor film due to the inhibitor’s adsorp-
ct
tion on the steel surface. The time constant of the adsorption pro-
and the relaxation time constant (sd) of charge-transfer process cess is sa = Ca Ra, the adsorption capacitance being again replaced
using the following equation [42]: by a CPE, and Ca is calculated using Eq. (2). The experimental data
were very well fitted according to the proposed equivalent circuit
sd ¼ C dl Rct ð3Þ
and as an example; the calculated curves are presented in Fig. 6.
The addition of 2-TMAT to the aggressive solution leads to a This model is valid for all concentrations of 2-TMAT and it is well
change of the impedance diagrams in both shape and size, in which representative of the phenomena which may occur in the
126 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133

Rs CPEd

Rct CPEa

Ra

(a) (b)
Fig. 4. Electrical equivalent circuit used for modeling the interface carbon steel/1 M HCl solution (a) without and (b) with 2-TMAT.

Table 1
Impedance parameters and inhibition efficiency values for carbon steel after 24 h immersion period in 1 M HCl containing different concentrations of 2-TMAT at 30 °C.

Conc. Rs (X cm2) Rct (X cm2) 106 Ad nd Cdl sd (s) Ra (X cm2) 104 Aa na Ca sa (s) Rp E
(M) (X1 sn cm2) (lF cm2) (X1 sn cm2) (mF cm2) (X cm2) (%)
Blank 5.70 ± 0.02 37.05 ± 0.13 844.4 ± 0.09 0.879 ± 0.001 524.1 0.0194 – – – – – 37.05 –
5  106 6.36 ± 0.02 155.5 ± 0.9 45.20 ± 0.09 0.906 ± 0.003 27.0 0.0042 97.4 ± 1.6 19.1 ± 1.1 0.64 ± 0.02 0.75 0.073 252.9 85.3
1  105 6.49 ± 0.02 160.7 ± 1.0 32.61 ± 0.09 0.927 ± 0.003 21.6 0.0035 130.9 ± 1.2 12.9 ± 0.8 0.61 ± 0.02 0.42 0.054 291.6 87.3
5  105 6.40 ± 0.02 208.0 ± 2.0 41.79 ± 0.08 0.916 ± 0.003 26.6 0.0055 160.0 ± 1.6 15.7 ± 1.2 0.55 ± 0.02 0.51 0.081 368.0 89.7
1  104 6.38 ± 0.02 279.4 ± 5.6 41.20 ± 0.08 0.913 ± 0.003 26.9 0.0075 179.8 ± 4.6 15.5 ± 1.1 0.61 ± 0.03 0.67 0.121 459.2 91.9

investigated steel/2-TMAT/HCl system, both in the HF and in the LF with inhibitor concentration). A large Rct is associated with a
parts of the spectra. The main fitted parameters are given in Ta- slower corroding system [38,44]. Furthermore, the decrease in
ble 1. Estimates of the margins of error calculated for the parame- the Cdl with increase in 2-TMAT concentrations may be attributed
ters are also presented in this Table. The data are found to be to the formation of a protective layer on the carbon steel surface
sufficiently well fitted within the limits of experimental error [45]. The increase of the nd value after addition of 2-TMAT in the
and reproducibility of data. Inspection of the fitting results (Ta- corrosive solution can corroborate this assumption. Indeed, the
ble 1), shows clearly that Rct and Cdl values have opposite trend
at the whole concentration range (Rct increases and Cdl decreases
-300

-300
Experimental curve
FitResult
a
Experimental curve a
FitResult
-200
Zi (Ωcm )
2

-200
Zi (Ωcm )

25.1 Hz 10 Hz
2

50.1 Hz 5 Hz
25.1 Hz 10 Hz -100
2.5 Hz
5 Hz 100 Hz
50.1 Hz 1 Hz
-100 2.5 Hz 0.1 Hz
100 Hz
1 Hz 0.01 Hz
0.1 Hz
0
0.01 Hz 0 100 200 300 400 500
0 Zr (Ωcm2)
0 100 200 300 400 500

Zr (Ωcm2) 3
10 -75
Experimental curve
3
FitResult b
10 -75
Experimental curve
FitResult
b -55

-55
2
10
Phase angle (Degree)

2
10 -35
Phase angle (Degree)

|Z| (Ωcm2)

-35
|Z| (Ωcm2)

-15
-15 10
1
1
10

5
5

0
0
25 10 25
10 -2 -1 0 1 2 3 4 5
10 -2
10 -1
10 0
10 1
10 2
10 3
10 4
10 5 10 10 10 10 10 10 10 10
Frequency(Hz) Frequency (Hz)
5
Fig. 5. (a) EIS Nyquist and (b) Bode diagrams for carbon steel/1 M HCl + 5  10 M Fig. 6. (a) EIS Nyquist and (b) Bode diagrams for carbon steel/1 M HCl + 5  105 M
of 2-TMAT interface: (  ) experimental; (–) fitted data using EEC in Fig. 4a. of 2-TMAT interface: (  ) experimental; (–) fitted data using EEC in Fig. 4b.
 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133 127

Table 2
Some 1,2,4-triazole derivatives investigated as corrosion inhibitors by other authors (the values of inhibition efficiency were obtained by EIS method at 0.1 mM in 1 M HCl).

Inhibitor Inhibition efficiency (%) Reference

3,5-Bis(2-thienylmethyl)-4-amino-1,2,4-triazole (2-TMAT) 91.9 This work
3,5-Bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT) 94.8 [24]
4-Amino-5-phenyl-4H-1,2,4-trizole-3-thiol (APTT) 90 [47]
3,5-Di(m-tolyl)-4-amino-1,2,4-triazole (m-DTAT) 86.9 [17]
3,5-Di(m-tolyl)-4H-1,2,4-triazole (m-DTHT) 63.8 [17]
3,5-Diphenyl-4-amino-1,2,4-triazole (DAT) 92.8 [10]
3,5-Dibenzyl-4-amino-1,2,4-triazoles (BAT) 91.1 [10]
3,5-Bis(2-thienyl)-4-amino-1,2,4-triazole (2-TAT) 97.5 [8]
3,5-Bis(4-methylthiophenyl)-4H-1,2,4-triazole (4-MTHT) 99.1 [15]
3,5-Diphenyl-4H-1,2,4-triazole (DHT) 84.1 [22]
3,5-Bis(4-pyridyl)-4H-1,2,4-triazole (4-PHT) 93.9 [22]
4-Amino-5-(2-hydroxy)phenyl-4H-1,2,4,-triazole-3-thiol (AHPTT) 70.5 [48]
4-Amino-5-styryl-4H-1,2,4,-triazole-3-thiol (ASTT) 76.7 [48]
4-Salicylideneamino-3-methyl-1,2,4-triazole-5-thione(SAMTT) 76 [49]
4-(2,4-Dihydroxybenzylideneamino)-3-methyl-1H-1,2,4-triazole-5(4H)-thione (DBAMTT) 79 [49]

value of nd grows as well (0.906–0.927), when compared to that 0

10
obtained in pure 1 M HCl (0.879). This can be attributed to a certain
decrease in the initial surface in homogeneity resulting from the 10-1
adsorption of 2-TMAT molecules on the most active adsorption
-2 a
centers at the carbon steel surface [38]. Also, the addition of 2- 10
TMAT to the corrosive solution increases slightly the time constant
-3
(sd) value with opposite trend of Cdl (Table 1). For example, when A cm2) 10 b c
the 2-TMAT concentration is increased to 104 M in HCl medium, d
10-4
-
I (A/

the interface (sd) parameter increases from 0.0194 to 0.075 s while

the Cdl value decreases from 524 to 26.9 lF cm2, signifying that -5 e a: Blank
10
the charge and discharge rates to the metal–solution interface is b: 5×10-6 M
c: 1×10-5 M
greatly decreased. This shows that there is agreement between 10-6 d: 5×10-5 M
the amount of charge that can be stored (i.e., capacitance) and e: 1×10-4 M
the discharge velocity in the interface (sd) [46]. In the case of 2- 10
-7

TMAT addition, the resistance Ra has small values compared to
Rct values (the total resistance Rp is dominated by Rct) and increases
significantly with 2-TMAT concentration. However, the Ca values
have opposite trend as that of Ra values at the whole concentration
range, while practically no change is observed in the value of na.
The values of na are lower than that of nd, probably connected with
energy dissipation within the adsorbed layer [42]. The time con-
stants sa shows a marked tendency to increase with concentration
and its values are much greater than sd. This behavior can be re-
lated to the adsorption process.
In the absence of inhibitor molecules, the ac resistance polariza-
tion, Rp, consists of only charge transfer resistance (Rct), while in
the presence of inhibitor, the sum of Rct and Ra are equivalent to
Rp. The related inhibition efficiency, gZ (%), is calculated from
Rp = (Rct + Ra) using the following equation:
RPðiÞ  Rp
gZ ð%Þ ¼  100
RPðiÞ
where Rp and Rp(i) are the ac polarization resistance of carbon steel
electrode in the uninhibited and inhibited solutions, respectively. It
is obvious that the increase in inhibitor concentration enhances Rp,
and consequently improves the inhibition efficiency till reaching
-0.70 -0.65 -0.60 -0.55 -0.50 -0.45 -0.40 -0.35 -0.30 -0.25 -0.20
E (V/SCE)
Fig. 7. Polarization curves for carbon steel in 1 M HCl containing different
concentrations of 2-TMAT. Key: (a) Blank, (b) 5  106 M, (c) 105 M, (d)
5  105 M, and (e) 104 M.
their maximum value at 0.1 mM (Rp = 459.2 X cm2, gZ (%) = 91.9).
The comparison of the inhibitive performance of 2-TMAT for the
steel corrosion in 1 M HCl with other 1,2,4-triazole derivatives, pre-
viously described in the same conditions, is given in Table 2. A sur-
vey of these data shows that 2-TMAT can be considered as excellent
organic inhibitor for the corrosion of carbon steel in 1 M HCl.
3.1.2. Polarization studies
Potentiodynamic polarization measurements were carried out
in order to gain knowledge concerning the kinetics of the cathodic
ð4Þ
and anodic reactions. Fig. 7 presents the results of the effect of
2-TMAT concentration on the cathodic and anodic polarization
curves of carbon steel in 1 M HCl, respectively. It could be observed
that the anodic and cathodic reactions are affected by the addition
of 2-TMAT. Indeed, the addition of this 4-amino-1,2,4-triazole
derivative to HCl solution reduces the anodic dissolution of steel

Table 3
Polarization parameters and the corresponding inhibition efficiency for the corrosion of carbon steel in 1 M HCl containing different concentrations of 2-TMAT at 30 °C.

Inhibitor conc. (M) Tafel data LPR data

Ecorr vs. SCE (mV) jcorr (lA cm2) ba (mV dec1) bc (mV dec1) gTafel (%) Rp (X cm2) gLRP (%)
Blank 451 717 110 108 – 30.9 –
5  106 469 140 65 117 80.5 150.4 79.5
1  105 475 71 68 111 90.1 208.8 85.2
5  105 466 50 57 105 93.0 243.9 87.3
1  104 476 40 68 113 94.4 398.6 92.2
128 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133
and also retards the cathodic hydrogen evolution reaction. The
inhibiting effect of 2-TMAT may be related to its adsorption and
formation of a barrier film on the electrode surface [50].
Electrochemical corrosion kinetic parameters, i.e., corrosion
potential (Ecorr), corrosion current density (jcorr), cathodic and ano-
dic Tafel slopes (bc, ba), obtained from the extrapolation of the
polarization curves are given in Table 3. The data were fitted using
non-linear least square algorithm based on the Tafel-LEV (Leven-
berg–Marquardt) method used along with CorrView 2.80 software.
Table 3 also included percentage inhibition efficiency, gTafel (%),
which was calculated from the following equation [50]:
jcorr  jcorrðiÞ
gTafel ð%Þ ¼  100
jcorr
where jcorr and jcorr(i) are the corrosion current densities for steel
electrode in the uninhibited and inhibited solutions, respectively.
The LPR experiments were carried out in order to exclude the influ-
ence of the surface changes which may occur during polarization at
higher overpotentials in the case of potentiodynamic polarization
method. The polarization resistance (Rp) obtained by LPR method
is used to calculate the corrosion current (jcorr) based on the
Stern–Geary kinetics equation [51]. In this case, the inhibition effi-
ciency, gLRP (%), is calculated from Rp using the following equation:
R  Rp
gLRP ð%Þ ¼ PðiÞ  100
RPðiÞ
where Rp and Rp(i) are the polarization resistance of carbon steel
electrode in the uninhibited and inhibited solutions, respectively.
The parallel cathodic Tafel curves in Fig. 7 suggest that the
hydrogen evolution is activation-controlled and the reduction
mechanism is not affected by the presence of the inhibitor. The val-
ues of bc show a slight change with increasing inhibitor concentra-
tion, indicating the influence of the aminotriazole derivative on the
kinetics of hydrogen evolution. This may probably be due to a dif-
fusion or barrier effect [51]. The values of the slopes of the anodic
Tafel lines, ba, also change with the addition of 2-TMAT suggesting
Fig. 8. SEM micrographs of the carbon steel surface: (a) Metallic surface after being polished, (b) metallic surface after 24 h immersion in 1 M HCl and (c) metallic surface
after 24 h immersion in 1 M HCl with 1  104 M of 2-TMAT.
that this studied inhibitor was first adsorbed onto the metal sur-
face and impeded by merely blocking the reaction sites of the me-
tal surface without affecting the anodic reaction mechanism [52].
The values of Rp increase and jorr values decrease considerably with
the increase of the concentration of 2-TMAT, with a slight negative
shift in corrosion potential (maximum displacement  25 mV)
compared to that of uninhibited solution. From these data one
can conclude that 2-TMAT is of mixed type with predominantly
cathodic action.
The inhibition efficiency values calculated by LPR and potentio-
dynamic polarization curves are comparable (Table 3). The coinci-
dence between these two methods can suggest that no significant
surface changes occur during the polarization measurements at
ð5Þ
±200 mV vs. Ecorr. The polarization data also confirm the ac imped-
ance results, i.e., 2-TMAT is a good inhibitor and its inhibition effi-
ciency depends on the inhibitor concentration. The values obtained
by means of the polarization experiments are somewhat lower
than in the ac impedance tests but the trends are the same. These
differences are probably due to a greater extent to the different
exposure time in the corrosive solution.
3.2. Adsorption isotherm and surface analysis
Scanning electron microscopy (SEM) micrographs (Fig. 8a–c) of
carbon steel strips were recorded in order to see the changes oc-
ð6Þ curred during corrosion process before and after immersion in
1 M HCl with and without corrosion inhibitor (2-TMAT). Parallel
features on the polished steel surface before exposure to the corro-
sive solution were observed, which are associated with abrading
scratches (Fig. 8a). Fig. 8b and c show the steel surface after 24 h
of immersion in 1 M HCl without and with 2-TMAT. The resulting
of the high resolution SEM micrograph (Fig. 8b) shows that the
steel surface was strongly damaged in the absence of the 2-TMAT
with the increased number and depth of the pits. However, in pres-
ence of 2-TMAT (Fig. 8c), the surface was remarkably improved and
less pits and cracks were observed in comparison to the steel
surface in absence of inhibitor. This improvement in surface
 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133
morphology is probably due to the formation of protective film of
2-TMAT on steel surface which is responsible for the corrosion
inhibition. Indeed, 2-TMAT has a strong tendency to adhere to
the steel surface and can be regarded as good inhibitor for steel
corrosion in normal hydrochloric medium. The high inhibitive per-
formance suggests a strong bonding of the 2-TMAT derivative on
the metal surface due to presence of lone pairs from heteroatom
(nitrogen and sulfur) and p-orbitals, blocking the active sites and
therefore decreasing the corrosion rate.
In hydrochloric medium, the 4-amino-1,2,4-triazole molecules
(2-TMAT) give cationic species with respect to the pKa of the pro-
tonated function as shown in the following scheme:
S
NH2
N
+ H+
N N
S N
I II
It is assumed that Cl ions are first adsorbed on the metal sur-
face and the net positive charge on the steel surface enhances the
specific adsorption of chloride ions [15,24]. Due to the electrostatic
attraction, the cationic forms of inhibitor (2-TMATH+) are adsorbed
through electrostatic interactions (physical adsorption) between
positively charged nitrogen atoms (form II) and negatively charged
carbon steel surface [53]. The adsorption of the 2-TMAT molecules
can also occur due to the formation of links between the d-orbital
of iron atoms, involving the displacement of water molecules from
the metal surface, by the lone sp2 electron pairs present on the
nitrogen and sulfur atoms and p-orbitals (chemisorption) [53,54].
If it is assumed, that adsorption of the organic molecules or ions
on the metal surface is the cause for the inhibitor action in both
acid media, then the surface coverage (h) can be estimated using
from the inhibitor efficiency as h = g(%)/100 [53]. An attempt was
made to find a suitable adsorption isotherm, which can describe
the concentration dependence of the inhibitor efficiency. Adsorp-
tion isotherms were determined, using the data of the ac imped-
ance data, which are collected in a time interval of 24 h,
0.12
0.1
0.08
C inh /θ (mM)
0.06
0.04
0.02
0 
0 0.02 0.04 0.06 0.08
Cinh (mM)
Fig. 9. Langmuir adsorption plot for carbon steel in 1 M HCl containing 2-TMAT at
30 °C.
129
considered sufficient for adsorption equilibrium to be achieved
[55]. Several adsorption isotherms (Langmuir, Temkin, Frumkin,
. . .) were assessed and the Langmuir adsorption isotherm was
found to fit well with the experimental data obtained for 2-TMAT.
The Langmuir isotherm is given by the following equation [56]:
C inh 1
¼ þ C inh ð7Þ
h K ads
where h is the fractional surface coverage; Cinh is the inhibitor con-
centration; and Kads is the equilibrium constant of the adsorption
process. The plot of Cinh/h vs. Cinh, in Fig. 9, yields straight line with
S
+
NH 3
N
N
S
the regression coefficient (R2) very higher than 0.99, which suggests
that the experimental data are well described by Langmuir iso-
therm and exhibit single-layer adsorption characteristic. This kind
of isotherm involves the assumption of no interaction between
the adsorbed species on the electrode surface [36,57]. This behavior
can be explained by the fact that the 2-TMAT molecule possesses
non-planar structure that can make important steric effects, and
therefore a strong repulsive interaction between adsorbed 2-TMAT
molecules in the adsorbed layer can occur (formation of single-
layer).
From the intercepts of the straight lines Cinh/h – axis (Fig. 9), the
Kads can be calculated; Kads = 1.35  106 M1. Kads is related to the

standard Gibbs free energy of adsorption, DGads , according to the
following equation [58]:
 
1 DGoads
K ads ¼ exp ð8Þ
55:55 RT
where R is the universal gas constant and T is the absolute temper-
ature. The value 55.55 in the above equation is the concentration of

water in solution in mol/l. The calculated DGads value is

45.68 kJ mol1. The high values of Kads and DGads refer to high
adsorption and good inhibiting effect [59,60]. Generally, the energy

values of DGads around 20 kJ mol1 or less negative are associated
with an electrostatic interaction between charged inhibitor mole-
cules and charged metal surface, physisorption; those of
40 kJ mol1 or more negative involve charge sharing or transfer
from the inhibitor molecules to the metal surface to form a coordi-
nate type bond i.e., chemisorptions [61–64]. It is difficult to distin-
guish between chemisorption and physisorption only based on
these criteria, especially when charged species are adsorbed. The
possibility of Coulomb interactions between adsorbed cations and
specifically adsorbed anions can increase the Gibbs energy even if
no chemical bond appears [62]. According the obtained value of
0.1 0.12
DGads (45.68 kJ mol1), it can be suggested that the adsorption of
the 2-TMAT is mainly due to chemisorption. This behavior is in
accordance with the findings of other researchers in the case of
the thiadiazoles [53,65], 1,3,4-oxadiazoles [36], 1,2,4-triazoles
[22,24] and the macrocyclic polyether compounds [66].
130 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133

C 1s a N 1s b

Intensity (a.u.)

Intensity (a.u.)
289 288 287 286 285 284 283 282 404 403 402 401 400 399 398 397
Binding Energy (eV) Binding Energy (eV)

S 2p c
Intensity (a.u.)

S 2p 3/2

S 2p 1/2

168 167 166 165 164 163 162

Binding Energy (eV)

Fig. 10. The XPS deconvoluted profiles of (a) C 1s, (b) N 1s and (c) S 2p for pure 2-TMAT.

C 1s a
N 1s
b
Intensity a.u.)
Intensity (a.u.)

290 288 286 284 282 403 402 401 400 399 398
Binding Energy (eV) Binding Energy (eV)

Fe 2p 3/2
S 2p c O 1s d e
Intensity (a.u.)
Intensity (a.u.)
Intensity (a.u.)

170 168 166 164 162 160 535 533 531 529 527 717 715 713 711 709 707

Binding Energy (eV) Binding Energy (eV) Binding Energy (eV)

Fig. 11. The XPS deconvoluted profiles of (a) C 1s, (b) N 1s, (c) S 2p, (d) O 1s and (e) Fe 2p3/2 for 2-TMAT treated carbon steel.
 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133 131

Table 4
Binding energies (eV), relative intensity and their assignment for the major core lines observed pure 2-TMAT and 2-TMAT treated carbon steel substrate.

Substrate C 1s N 1s S 2p O 1s Fe 2p3/2
BE (eV) Assignment BE (eV) Assignment BE (eV) Assignment BE (eV) Assignment BE (eV) Assignment
Pure 2-TMAT 285.0 CAC/C@C/ 399.5 NH2 group/ 164.2 (60 %) Thiophen (S – – – –
(60%) CAH (40%) RACN 2p3/2)
286.2 CAN/C@N/ 400.6 @NA 165.4 (40 %) Thiophen (S – – – –
(40%) CAS (34%) structure 2p1/2)
– – 401.6 @N+H – – – – – –
(26%)
2-TMAT treated 285.0 CAC/C@C/ 399.6 @NA/RACN 161.8 (20 %) Disulfide 529.6 Fe2O3/ 707.8 Fe0
carbon steel (50%) CAH (39%) (FeS2) (30 %) Fe3O4 (1.2 %)
286.4 CAN/CAS 400.9 @NAFe 163.7 (27 %)/ Thiophen 531.1 FeOOH 711.5 Fe2O3/Fe3O4/
(26%) (49%) 164.9 (20 %) (>S) (54 %) (51.8 %) FeSO4/FeOOH
+
288.4 C@N 401.8 NHþ +
3 /@N H
168.5 (33 %) >S+ 532.6 Adsorbed 713.0 (31 FeCl3
(24%) (12%) (16 %) H2O %)
– – – – – – – – 714.6 (16 Satellite of Fe(III)
%)

In order to confirm this assumption (chemisorption of 2-TMAT)

and elucidate the nature of the organic thin film formed on the
steel surface, X-ray photoelectron spectroscopy (XPS) analyses
are given and discussed below. For comparison purpose, the XPS
spectra were obtained from the pure 2-TMAT, and the steel surface
which was treated by 104 M of 2-TMAT after 24 h of immersion in
1 M HCl. The XPS spectra, shown in Figs. 10 and 11, were obtained
both from pure 2-TMAT (C 1s, N 1s and S 2p) and the 2-TMAT-trea-
ted carbon steel surface (C 1s, N 1s, S 2p, O 1s and Fe 2p). All XPS
spectra show complex forms, which were assigned to the corre-
sponding species through a deconvolution fitting procedure. The
binding energies (BE, eV) and the corresponding quantification
(%) of each peak component are summarized in Table 4.
The deconvoluted C 1s spectrum for pure 2-TMAT shows two
main peaks (Fig. 10a, Table 4). The first peak located at approx.
285.0 eV has the largest contribution and is attributed to the
CAC, C@C and CAH aromatic bonds [24]. The second peak at
286.2 eV is attributed to the CAN and C@N bonds in the triazole
ring [24] and the CAS bond in the thienyl rings [67]. After acidic
immersion, the deconvoluted C 1s spectrum for 2-TMAT-treated
carbon steel shows three main peaks (Fig. 11a, Table 4). Indeed,
the first component at a BE  285.0 eV is attributed to the CAC,
C@C and CAH aromatic bonds which the largest contribution;
the second component at 286.4 eV may be assigned to the carbon
atoms bonded to: (i) nitrogen in CAN and C@N bonds in the tria-
zole ring and (ii) sulfur in CAS bond in the thienyl ring; the last
component at higher binding energy (located at approx.
288.4 eV) may be ascribed to the carbon atom of the C@N+ in the
triazole ring [67], resulting probably from the protonation of the
@NA structure in the triazole ring and/or the coordination of nitro-
gen in triazole ring with the steel surface.
For the pure 2-TMAT molecule, the N 1s spectrum can be
decomposed into three components centered at 399.5 eV,
400.6 eV and 401.6 eV (Fig. 10b, Table 4). The first component
has the largest contribution and is mainly are attributable to the
bonds of CAN and the unprotonated N atoms (@NA structure) in
the triazole ring [68,69]. The second peak may be assigned to neu-
tral amino nitrogen (˜NANH2 in aminotriazole) [70]. The last peak
at higher binding energy (401.6 eV) is attributed to positively
charged nitrogen, and could be related to protonated nitrogen
atoms (@N+HA) in the triazole ring [12]. Indeed, the molecular
conformation of 2-TMAT can yield intermolecular hydrogen bond-
ing which leads to a positive polarization of the nitrogen atom and
therefore an increased binding energy [71]. Thus, the presence of
the positively charged nitrogens (@N+HA structure) can be ex-
plained by hydrogen bonding between one hydrogen atom bonded
to a nitrogen atom of the amino group and lone electron pair of a
H H
N
S
N
N S
N
δ(+)
H H δ(−)
N
S
N
N S
N
Fig. 12. Intermolecular hydrogen bonding of 2-TMAT.
nitrogen atom of another aminotriazole molecule as illustrated in
Fig. 12. The high-resolution N 1s spectrum of the carbon steel sam-
ple treated by 2-TMAT shows peaks indicative of different chemical
forms of N presence on the steel surface (Fig. 11b, Table 4). The
appearance of nitrogen species on the protected steel surface pro-
vides thus the evidence that the investigated 4-amino-1,2,4-tria-
zole (2-TMAT) was chemically adsorbed on the steel surface.
Moreover, the N 1s analyze of untreated carbon steel shows the ab-
sence of the nitrogen in this substrate [72]. Similarly, three compo-
nents located at BE  399.6, 400.9 and 401.8 eV were used to fit the
spectrum of treated steel and the relative proportion of nitrogen
species are quite different from those observed with pure 2-TMAT.
The first component is attributed to CAN and the unprotonated N
atom (@NA structure) in the triazole ring [69] while the second is
mainly attributed to the coordinate nitrogen in triazole ring with
the steel surface. Indeed, the NAFe bond complex can cause the
peak shift to higher binding energy compared to uncoordi-
nated @NA structure [73]. The same behavior was observed in
our previously papers concerning the corrosion inhibition of mild
steel using 3,5-bis(n-pyridyl)-1,2,4-oxadiazoles [36], 3,5-bis(4-
methoxyphenyl)-4-amino-1,2,4-triazole [24] and 3,6-bis(3-pyri-
dyl)pyridazine [50]. The last component at 401.8 eV is attributable
to the oxidized nitrogen as a result of the protonation of the nitro-
gen in the amino group ðANHþ 3 Þ, which leads to a positive polariza-
tion of the nitrogen atom, and therefore a core-level chemical shift
to higher binding energy is produced [74].
The S 2p core-level of the pure 2-TMAT is best resolved with at
least two spin-orbit-split doublets (S 2p3/2 and S 2p1/2), with
132 M. Tourabi et al. / Corrosion Science 75 (2013) 123–133
binding energy (BE) for S 2p3/2 peak lying at about 164.2 eV
(Fig. 10c, Table 4). This former can be assigned to the neutral thio-
phen as mentioned previously [75,76]. After immersion in 1 M HCl
containing 2-TMAT, the S 2p spectrum shows the presence of sulfur
on the steel surface but in low content (Fig. 11c). This spectrum
could be deconvoluted into four main components centered at
161.9 eV, 163.7 eV, 164.9 eV and 168.5 eV. The first one can be
attributed to the sulfide species [77,78]; the second and third are
attributed to the neutral thiophen and the last peak observed at
168.5 eV may be assigned to the SAFe bound complex and/or the
sulfur atoms in a more positive environment [76].
The O 1s spectrum for carbon steel surface after immersion in
1 M HCl solution containing 2-TMAT could be fitted into three
main peaks (Fig. 11d, Table 4). The first peak, at approx.
529.6 eV, is ascribed to O2 and could be related to oxygen atoms
bonded to Fe3+ in the Fe2O3 and/or Fe3O4 oxides [79]. The second
peak, observed at a BE  531.1 eV, is attributed to OH, can be
associated to the presence of hydrous iron oxides, such as FeOOH
[79]. Finally, the third peak at 532.9 eV may be assigned to oxygen
of adsorbed water [80].
The Fe 2p spectrum for carbon steel surface covered with 2-
TMAT exhibits two doublets, 711 eV (Fe 2p3/2) and 724.1 eV (Fe
2p1/2), with an associated ghost structure on the high energy side
showing the subsequent oxidation of the steel surface. The decon-
volution of the high resolution Fe 2p3/2 XPS spectrum consists in
four peaks (Fig. 11e, Table 4). The small peak at lower bending en-
ergy (707.8 eV) is attributable to metallic iron as previously re-
ported [81,82]. The second peak at a BE  711.5 eV assigned to
Fe3+ as mentioned in [83], was attributed to ferric compounds such
as Fe2O3 (i.e., Fe3+ oxide), FeOOH (i.e., oxyhydroxyde) [84,85], while
that located at around 713.0 eV is attributed to the presence of a
small concentration of FeCl3 on the metal surface [74,86]. The last
peak at BE  714.6 may be ascribed to the satellite of Fe(III) [87].
The comparison of the Fe2p3/2 XPS results for carbon steel after
immersion in 1 M HCl medium containing 2-TMAT with that for
untreated surface steel, previously described [72], shows that the
aggressive solution induces a significant decrease in Fe0 amount
in favor of oxidized species (Fe2+ and Fe3+) indicating therefore that
the oxide layer thickness is increasing. The formation of a stable
and insoluble oxide layer (FeOOH), which can reduce ions diffu-
sion, may be benefice in improving the corrosion resistance of car-
bon steel in HCl solutions.
On the basis of XPS analyses, the obtained results give evidence
of chemical interactions between the 2-TMAT inhibitor and carbon
steel surface. Indeed, the presence of nitrogen species on the steel
surface, such as @NA structure, thiophen and NAC, confirms that
the investigated aminotriazole was chemisorbed on the carbon
steel surface and corroborates the thermodynamic study. Thus 2-
TMAT can be regarded as good inhibitor for carbon steel corrosion
in normal hydrochloric acid medium.
4. Conclusions
2,5-Bis(2-thienylmethyl)-4-amino-1,2,4-triazole (2-TMAT)
shows excellent inhibition properties for the corrosion of carbon
steel in 1 M HCl at 30 °C, and the inhibition efficiency, g (%), in-
creases with increase in the inhibitor concentration. The EIS spec-
tra are well described by the proposed structural models. Based on
the Tafel polarization results, 2-TMAT can be classified as mixed
inhibitor. The ac impedance and polarization methods are in good
agreement. The corrosion process is inhibited by the adsorption of
2-TMAT on the steel surface and the adsorption of the inhibitor fits

a Langmuir isotherm model. The calculated value of DGads can sug-
gest that the adsorption mechanism of 2-TMAT on carbon steel
surface in 1 M HCl solution is mainly due to chemisorption. XPS
analysis corroborate the thermodynamic results and give evidence
of the chimisorption of 2-TMAT on the carbon steel surface in 1 M
HCl medium.
Acknowledgement
The authors gratefully acknowledge the EGIDE for its financial
support under Volubilis MA/10/234.
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