Construction and Building Materials 286 (2021) 122916

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Synergetic effect of two inhibitors for enhanced corrosion protection on

the reinforcing steel in the chloride-contaminated carbonated solutions
Danqian Wang a,b, Chonggen Pan a,b,⇑, Zhicheng Liu a,b, Keyu Chen a,b, Na Chen a,b, Shuhua Liu a,b
a
Ningbo Institute of Technology, Zhejiang University, No.1, Qianhu South Road, Ningbo, Zhejiang 315100, China
b
School of Water Resources and Hydropower Engineering, Wuhan University, Wuhan 430000, China

h i g h l i g h t s

-

Corrosion inhibition in carbonated solution with Cl was studied.

A mixture of BTA and Na2HPO4 effectively inhibit corrosion of carbon steel.

BTA inhibitor acts as anodic inhibitor, while Na2HPO4 acts as a mixed type.

Different inhibition mechanisms were identified for two inhibitors.

Formation of hydrogen bonding contributes to synergistic inhibiting.

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

Article history: The synergetic inhibiting effect of benzotriazole (BTA) and Na2HPO4 for the corrosion of reinforcing steel
Received 17 July 2020 in the chloride-contaminated carbonated solutions was preliminarily investigated by electrochemical
Received in revised form 10 February 2021 measurements, as well as X-ray photoelectron spectroscopy and scanning electron microscopy/energy
Accepted 26 February 2021
dispersive X-ray techniques. Results show that a mixture of BTA and Na2HPO4 acts as an anodic inhibitor.
Available online 19 March 2021
An optimum enhanced inhibition efficiency was obtained for a mixture of 0.05 M BTA and 0.05 M
Na2HPO4. The synergistic inhibiting mechanism for steel was proposed, which was by forming a protec-
Keywords:
tive film consisting of Fen(BTA)m complex and iron phosphates, as well as hydrogen bonding between
Localized corrosion
pH
them on the steel surface. On the contrary, a mixture of unequal amount of BTA and Na2HPO4 showed
Reinforcing steel an antagonistic effect on corrosion inhibition resulting from the competition between the phosphate ions
Concrete pore solution and BTA- on the steel surface.
Inhibitor Ó 2021 Published by Elsevier Ltd.

1. Introduction required higher concentration of phosphate ions to inhibit pitting

Chloride-induced corrosion and carbonation-induced corrosion
are two main causes of the deterioration of reinforced concrete
structures. In order to reduce the corrosion of carbon steel, various
corrosion inhibitors were used in concrete conditions [1–3]. Benzo-
triazole (BTA) and phosphate ions have been adopted in concrete
as the corrosion inhibitors for steel embedded [4–6]. BTA and
phosphate ions can effectively inhibit pitting corrosion under chlo-
ride attack by forming iron-BTA complexes and iron phosphates,
respectively, at weak points of the passive film formed on the steel
surface [4,7]. On the other hand, good inhibition of carbonation-
induced corrosion had also been verified for both BTA and phos-
phate ions [3,8]. The reduced alkalinity of concrete pore solution
⇑ Corresponding author at: Ningbo Institute of Technology, Zhejiang University,
No.1, Qianhu South Road, Ningbo, Zhejiang 315100, China.
E-mail address: panchonggen@zju.edu.cn (C. Pan).
corrosion when compared with that required in high alkalinity
[7]. Furthermore, it has been reported that BTA showed better cor-
rosion inhibition efficiency than phosphate ions in concrete condi-
tion [9].
The synergetic effect of two types of inhibitors on the corrosion
inhibition had been reported widely [10–12]. An enhancement of
corrosion inhibition efficiency of BTA in accompany with another
inorganic or organic inhibitor had been well established in the pre-
vious studies [13–17]. These researches attributed the improved
corrosion inhibition to the synergetic effect of BTA and other inhi-
bitors. Rammelt et al.[16] claimed that the combination of ben-
zoate and benzotriazole showed the highest corrosion resistance
due to the formation of insoluble benzoate complex with BTA
strongly adsorbed on top of it. Moreover, some other researchers
drew the same conclusion for the BTA/Na3PO4 system or BTA/Na2-
MnO4 system in different conditions [15,17,18]. On the other hand,
hydrolytic polycondensation occurring between these inhibitors

https://doi.org/10.1016/j.conbuildmat.2021.122916
0950-0618/Ó 2021 Published by Elsevier Ltd.
D. Wang, C. Pan, Z. Liu et al.
on the steel surface had been considered as another synergetic
mechanism of inhibitors [13,14]. However, the corrosion inhibition
of a mixture of BTA and phosphate ions for steel in carbonated
solutions with contamination of chloride ions and its possible inhi-
bition mechanism, which could help to improve the carbonation-
induced and chloride-induced corrosion resistance of reinforced
concrete structure with higher efficiency, has not been
investigated.
The aim of the present study is to preliminarily investigate the
synergetic effect of BTA and Na2HPO4 as corrosion inhibitors for
reinforcing steel immersed in the chloride-contaminated carbon-
ated solutions. In this work, the corrosion behaviour was moni-
tored by electrochemical measurements including open circuit
potential (OCP), electrochemical impedance spectroscopy (EIS),
potentiodynamic polarization and Mott-Schottky curves. In addi-
tion, X-ray photoelectron spectroscopy (XPS) and scanning elec-
tron microscopy (SEM)/energy dispersive X-ray (EDS) techniques
were adopted to detect the chemical composition and morphology
of passive film formed on the steel surface.
2. Experimental
2.1. Sample preparation
Carbon steels of 8 mm in diameter were used in this study. The
chemical composition and mechanical properties of carbon steel
are listed in Table 1 and 2, respectively. Carbon steels were ground
with SiC grinding papers up to 3000 grits, followed by polishing to
1 mm. Subsequently, carbon steels were rinsed with deionized
water and degreased in alcohol. The steel electrode was connected
to iron wires and sealed with epoxy resin in order to facilitate the
electrochemical measurements. The total exposure surface area of
steel electrode is 0.5 cm2.
2.2. Preparation of concrete pore solutions
Carbonated concrete pore solution was prepared and used as
the low alkaline carbonated solution in this study. Type I 42.5 N
ordinary Portland cement (OPC) with the chemical composition
listed in Table 3. Schematic illustration of preparation of the pore
solutions used in this study is displayed in Fig. 1. Cement paste
specimens were made by mixing water and OPC of water/cement
ratio 0.45 for 3 min, as shown in Fig. 1a. After 1 h, the pore solution
was extracted by filtering the pastes through 0.45 mm filter paper,
as present in Fig. 1b. The extracted pore solution was then put in
the carbonation chamber with 5% CO2 at 20 °C for 24 h so that car-
bonated pore solution of pH = 9.8 was obtained, as displayed in
Fig. 1c. The carbonated pore solution with addition of NaCl
([Cl-] = 0.1 M) was prepared to simulate the simultaneous
carbonation-induced corrosion and pitting corrosion condition
(Fig. 1d). Moreover, the carbonated pore solutions with addition
of different concentrations of inhibitors used in the experiments
were listed in Table 4.
2.3. Electrochemical tests
Several electrochemical measurements were carried out at room
temperature (20 °C) in a glass cell to obtain both the kinetic and ther-
modynamic information related to the corrosion of carbon steel.
Table 1
The chemical composition of the carbon steel used in this study.
Element C Si
Content / wt.% 0.12 0.14
2
Construction and Building Materials 286 (2021) 122916
Table 2
The mechanical properties of the carbon steel used in this study.
Mechanical Tensile strength Yield strength Elongation
property (MPa) (MPa) (%)
387 239 25%
Specifically, OCP was measured in order to assess the corrosion of
carbon steel thermodynamically. In addition, corrosion resistance
and corrosion current density were obtained from EIS and potentio-
dynamic polarization, respectively. Moreover, Mott-Schottky curves
were measured in order to assess the semiconductive behaviour of
the oxide film formed on the surface of carbon steel. A platinum elec-
trode was used as the counter electrode and Ag/AgCl electrode as the
reference electrode, respectively. The electrochemical tests were
conducted via Gamry Instrument Potentiostat/Galvanostat/ZRA.
OCP of specimens with different concentrations of inhibitors were
recorded in the initial 25 min, followed by OCP tests at 4 h, 24 h
and 48 h. Thereafter, EIS measurements are carried out at 48 h
within the frequency range from 104 Hz to 10-2 Hz. During EIS mea-
surement, an applied AC signal amplitude of 10 mV RMS was applied
at open circuit potential. EIS data was fit by ZSimpWin software.
Subsequently, the potentiodynamic polarization tests were per-
formed from 1.2 VAg/AgCl to a potential higher than the pitting
potential at a scan rate of 0.16 mV/s. Mott-Schottky plots were mea-
sured ranging from 1.5 to 1.5 VAg/AgCl, with a potential step of
50 mV at the frequency of 1000 Hz.
2.4. X-ray photoelectron spectroscopy
The surface composition of carbon steel at 48 h was analysed by
XPS technique ESCALAB 250Xi (XPS, UK). The XPS system was
equipped with a monochromated Al-Ka X-ray excitation source
(1486.7 eV). A spot size of 200 lm was used on all the specimens.
All the XPS spectra were calibrated by standard C 1 s peak at
284.6 eV. Data analysis of the spectra was based on the background
elimination by Shirley background subtraction followed by 20%
Lorentzian and 80% Gaussian.
2.5. Scanning electron microscope (SEM)/energy dispersive
spectroscopy (EDS)
The surface morphologies and composition of carbon steel at
48 h were analyzed on FEI Quanta 250 scanning electron micro-
scope (SEM) coupled with energy dispersive spectroscopy (EDS).
3. Results and discussion
3.1. Open circuit potential
Fig. 2a and b presents the variation of OCP of the carbon steel dur-
ing the initial 2000 s in the carbonated pore solution with various con-
centrations of inhibitors in the absence and presence of chloride ions,
respectively. The evolution of OCP during the initial exposure period
provides information which is related to the interaction between the
bare steel surface and the carbonated solution without and with inhi-
bitors. From Fig. 2a it can be observed that the OCP of P0carb specimen
starts at a low value, –332 mVAg/AgCl, and decreased with exposure
period, which indicates that the carbonated solution promotes the
Mn S P Fe
0.74 0.0028 0.012 Bal.
D. Wang, C. Pan, Z. Liu et al. Construction and Building Materials 286 (2021) 122916

Table 3
Clinker compounds of the cement (wt.%).

SiO2 CaO MgO Fe2O3 Al2O3 SO3

20.47 59.64 3.74 4.80 5.90 2.08

Fig. 1. Schematic illustration of preparation of electrolytes used in this study.

Table 4
The carbonated solutions with different concentrations of inhibitors used in this
study.

BTA / M Na2HPO4 / M NaCl / M Specimen

0 0 0.1 P0
0.1 0 P1
0 0.1 P2 Fig. 2. The evolution of OCP of carbon steel during the initial 2000 s in the
0.09 0.01 P3 carbonated solution without and with inhibitors: (a) in the absence of chloride ions
0.05 0.05 P4 and (b) in the presence of 0.1 M chloride ions.
0.01 0.09 P5
0 0 P0carb
0.1 0 0 P1carb
0 0.1 P2carb
OCP values of specimens at 2000 s with comparison to those with-
0.09 0.01 P3carb out inhibitors. This implies that the dissolution of iron from the
0.05 0.05 P4carb steel substrate could be hindered due to the interaction between
0.01 0.09 P5carb the inhibitors and the steel surface, such as adsorption of BTA or
phosphate ions on the steel surface. In particular, P1carb, P3carb, P1
and P3 specimens experienced a marked increase of the OCP values
dissolution of Fe from the steel substrate. This is consistent with the from low values during the 2000 s. This suggests that iron could
previous literature reporting that generalized corrosion occurs when initially dissolve form the bare steel surface, followed by the inter-
carbon steel is exposed to a low pH environment, which leads to the action between BTA and the initially dissolved iron ions, which
formation of a porous and less protective oxide film on the steel sur- hinders the further dissolution of iron [20]. On the contrary, P2carb,
face [19]. Moreover, as shown in Fig. 2b, when chloride ions are pre- P4carb, P5carb, P2, P4 and P5 specimens show similar patterns of OCP
sent in the carbonated solution, the OCP values of P0 specimen are evolution, which start at high values (more positive than 235
even lower than those of P0carb specimen during the initial 2000 s. This mVAg/AgCl) and slightly change with exposure time. This suggests
could be attributed to the further dissolution of iron caused by the that inhibitors can impede corrosion process immediately after
presence of chloride ions in the carbonated solution, which would the carbon steel was exposed to the carbonated solutions without
lead to more serious generalized corrosion [19]. or with chloride ions.
In both chloride-containing and chloride-free carbonated solu- Fig. 3 displays the evolution of OCP during the exposure period up
tions, the addition of inhibitors leads to the ennoblement of the to 48 h. From the figure it can be observed that the OCP values of

3
D. Wang, C. Pan, Z. Liu et al. Construction and Building Materials 286 (2021) 122916

P0carb and P0 specimens decrease at a fast rate within the first 4 h, Fig. 4 display a cathodic region of Tafel behaviour. However, the
while at a much slower rate during the following period. This sug-
gests that the corrosion mainly occurs during the first hours and
the steel surface becomes relatively stable at 48 h. In addition, the
OCP values become more positive with addition of inhibitors when
compared with those without inhibitors, suggesting that the corro-
sion is inhibited during the exposure period. Moreover, it can be
noted that the OCP values of the specimens in the chloride-
containing carbonated pore solution are lower than the correspond-
ing OCP values in the chloride-free carbonated pore solution, which
could be attributed to more severe corrosion caused by both chloride
attack and carbonation than that caused only by carbonation. Fur-
thermore, it can be noticed that the OCP of P2 and P5 specimens
are significantly lower than those of P1, P3 and P4 specimens. This
implies that the corrosion inhibition mechanism of phosphate ions
could be different from that of BTA [21,22].

3.2. Potentiodynamic polarization curves

Fig. 4 display the potentiodynamic polarization curves of the

specimens in the carbonated solution without and with chloride
ions, respectively. It is obvious that all the polarization curves in

Fig. 3. The evolution of OCP of carbon steel within 48 h in the carbonated solution Fig. 4. The potentiodynamic polarization curves of the carbon steel tested: (a)
without and with inhibitors: (a) in the absence of chloride ions and (b) in the without inhibitors, (b) with inhibitors in the chloride-free carbonated solution; and
presence of 0.1 M chloride ions. (c) with inhibitors in the chloride-containing carbonated solution.

4
D. Wang, C. Pan, Z. Liu et al. Construction and Building Materials 286 (2021) 122916

anodic polarization curves do not show an extensive Tafel region, 0

which could be ascribed to the passivation and pitting process in
the anodic polarization [22]. Therefore, the corrosion current den-
sity was evaluated by Tafel extrapolation using the cathodic branch
as exemplified in Fig. 4a [23]. Table 5 summarizes the electrochem-
ical corrosion kinetic parameters, including corrosion potential
Ecorr, breakdown corrosion Eb, corrosion current density icorr and
cathodic Tafel slope bc obtained from the Tafel extrapolation of
the polarization curves. It can be noted from the table that the icorr
value of P0 specimen is higher than that of P0carb specimen, indi-
cating that more severe corrosion occurs in the presence of chlo-
ride ions, which is consistent with the OCP results. Moreover, the
addition of inhibitors leads to the decrease of the icorr value in both
chloride-free and chloride-containing carbonated solution, which
is indicative of the corrosion inhibition role of the inhibitors.
The inhibitor type can be identified from the comparison
between the Ecorr values of the specimens with inhibitors and that
without inhibitors. It can be observed form Fig. 4 that the Ecorr of
P1carb and P1 specimens are both higher than those of the corre-
sponding P0carb and P0 specimens, which suggests that the BTA
acts as an anodic inhibitor in both chloride-free and chloride-
containing carbonated solution [24]. On the contrary, the Ecorr of
P2carb and P5carb specimens are significantly lower than that of
P0carb specimen, indicating the cathodic inhibition role of the phos-
phate ions in the chloride-free carbonated solution [21]. As com-
parison, P2 and P5 specimens exhibit a slightly lower Ecorr value
than P0 specimen does, which is indicative of the mixed type inhi-
bitor for the phosphate ions in the chloride-containing carbonated
solution [25]. Analogously, a slight difference between the Ecorr of
P3carb and P4carb specimens and that of P0carb specimen demon-
strates a mixed type inhibitor in the absence of chloride ions. How-
ever, the inhibitors in P3 and P4 specimens act as an anodic type in
the presence of chloride ions as shown in Fig. 4b. Thus, based on
these information, it can be deduced that the corrosion inhibition
mechanism of a mixture of phosphate ions and BTA as well as sin-
gle phosphate ions may be altered when chloride ions are present
in the carbonated solution. It was reported in the previous litera-
ture that a protective passive film mainly consisting of iron oxide
and hydroxide can be formed in the phosphate-containing solution
of pH above 9.1, which inhibits the corrosion of iron [26]. On the
other hand, in the phosphate-containing solution in the presence
of chloride ions, iron phosphates form on the surface of carbon
steel which inhibits the corrosion of steel [27].
The corrosion inhibition efficiency can be calculated from the
following equation [28,29]:
0
icorr  icorr
g¼ 0
 100
icorr
where icorr and icorr represents the corrosion current density with-
out and with inhibitors, respectively. The calculated corrosion inhi-
bition efficiency g is listed in Table 5. It can be noted from the table
that the corrosion inhibition efficiency of P4 specimen, i.e., a mix-
ture of 0.05 M Na2HPO4 and 0.05 M BTA, is the highest among all
the specimens in the chloride-containing carbonated solution.
Moreover, the Eb of P4 specimen is also the highest among all
the specimens in the chloride-containing carbonated solution,
which is an indication of the highest anodic inhibition in the pres-
ence of 0.05 M BTA and 0.05 M Na2HPO4.
3.3. Electrochemical impedance spectroscopy (EIS)
3.3.1. EIS spectra
The impedance spectra, in the form of Nyquist plots (Fig. 5a)
and Bode phase plots (Fig. 5b), recorded for the carbon steel at
an age of 48 h in the chloride-containing carbonated solutions with
and without inhibitors are presented in Fig. 5. It is observed from
Fig. 5a that all the specimens in the presence of inhibitors (P1,
P2, P3, P4 and P5 specimens) show higher diameters of the
depressed semicircles than that in the absence of inhibitors (P0
specimen), which demonstrates that all the inhibitors can work
effectively to inhibit corrosion of carbon steel at the prolonged
exposure period. Moreover, P4 specimen exhibits the highest
diameter of depressed semicircle among all the specimens, which
indicates that a synergistic behaviour between BTA and Na2HPO4
exists in terms of corrosion inhibition. This is consistent with the
potentiodynamic polarization results.
The Bode phase plots at 48 h are present in Fig. 5b. The shape of
the Bode plots for all the specimens in the presence of inhibitors
exhibit broader peaks within a large range of frequency when com-
pared with that in the absence of inhibitors, which indicates the
formation of a protective oxide layer on the surface of carbon steel.
Moreover, for P5 specimen, the appearance of high Bode phase in
the high frequency range (104 Hz ~ 101 Hz) possibly indicates an
adsorption of inhibition species which is closer to electrolyte
[30]. On the contrary, the Bode phase in the high frequency range
(104 Hz ~ 101 Hz) of P4 specimen is the lowest among those of all
the specimens with BTA, which could be related to the compact
and thin adsorption of inhibitors on the surface of carbon steel.
3.3.2. EIS modelling
In order to quantitatively describe the behaviour of carbon steel
in the chloride-containing carbonated solutions in the presence of
inhibitors, the equivalent element circuit with two time constants,
as shown in Fig. 6, was adopted to fit the EIS data of specimens,
ð1Þ which shows a good fitting. The model was also used in the
previous studies on the corrosion inhibitors [31]. In this equivalent

Table 5
Polarization parameters of potentiodynamic polarization curves in the carbonated solution without and with chloride ions.

Specimen Ecorr (mV) Eb (mV) icorr (mA/cm2) bc (mV/dec) g (%)

P0carb 421.9 247.7 6.23 190.3 /
P1carb 205.0 122.9 0.70 217.4 0.89
P2carb 762.2 89.8 4.62 153.4 0.26
P3carb 520.8 162.7 0.32 178.5 0.95
P4carb 481.3 127.2 0.21 181.8 0.97
P5carb 818.3 70.7 5.38 150.6 0.14
P0 749.6 362.5 8.35 149.9 /
P1 567.5 241.9 0.75 186.8 0.91
P2 793.9 260.3 5.48 171.4 0.34
P3 610.2 188.5 0.79 185.2 0.91
P4 498.6 159.2 0.46 187.7 0.94
P5 766.7 197.9 8.12 148.3 0.03

5
D. Wang, C. Pan, Z. Liu et al.
Fig. 5. EIS spectra of the rebars immersed in the carbonated solution containing
0.1 M NaCl at 48 h: (a) Nyquist plots; (b) Bode plots; and (c) equivalent circuit for
modelling EIS results.
circuit, Rs represents the resistance of electrolyte. Meanwhile, Rf
and CPEf stand for the resistance and capacitance of oxide film,
respectively, while Rct and CPEdl represent the charge transfer
resistance and the capacitance of electric double layer, respec-
tively. It should be mentioned that a constant phase element
CPE, which represents the deviation from the ideal behaviour of
capacitance, is used for both capacitances in the equivalent circuit.
The presence of the CPE element is often related to the electrode
roughness or the inhomogeneity in the semiconductor [32]. The
capacitance of CPE is defined by [33]:
Fig. 6. Equivalent circuit adopted to fit the EIS data in this study.
6
Construction and Building Materials 286 (2021) 122916
C ¼ gQðqee0 Þ1n ð2Þ
g ¼ 1 þ 2:88ð1  nÞ2:375 ð3Þ
where e is the relative dielectric constant of oxide film, which is
assumed to be about 12 for iron oxides [34]. e0 represents permit-
tivity vacuum (8.8542  10-14F∙cm1). Q is a pseudo-capacitance
parameter and n is the power constant of CPE. q is assumed as a
constant value of 500 O∙cm2 in this study. Built upon this, the
capacitance of oxide film Cf and electric double layer Cdl can be cal-
culated based on the pseudo-capacitance parameter of oxide film
Qf and electric double layer Qdl, together with their power constant
nf and ndl.
The fitting results are listed in Table 6. From the table, it can be
observed that the low chi-square (103) is obtained for all the EIS
spectra, which demonstrates that the EIS data in Fig. 5a and b can
be fitted well with the equivalent circuit. It can be noted from the
table that both Rf and Rct values of the specimens with inhibitors
are significantly higher than those of specimen without inhibitors,
which indicates that corrosion is effectively inhibited in the pres-
ence of inhibitors. In particular, the Rf and Rct of P4 specimen are
the highest, suggesting that the passive film formed in this condi-
tion can efficiently inhibit the attack of chloride ions and carbona-
tion during the immersion period.
The film thickness, df, can be estimated from the EIS modelling
results based on Eq. (4) as shown below:
ee0
df ¼ ð4Þ
Cf
The values of df are listed in Table 6. It can be noted from the
table that the values of df are significantly decreased when inhibi-
tors were added, which indicates that compact and protective
oxide films were formed on the surface of carbon steel.
3.4. Mott-Schottky curves
The semiconductive properties of the passive films were
assessed by electrochemical capacitance. When potentials E where
the states are depleted are applied, there is a linear relationship
between 1/C2 and E, as expressed by the Mott–Schottky equation
in Eq. (4) [35].
1 2 kT
¼ ðEFB  E þ Þ ð5Þ
C2 ee0 qNq e
where C represents the space charge region developed in the pas-
sive film, Nq is the doping density, including acceptor Na or donor
Nd, for a p-type or n-type semiconductor, respectively. q is the ele-
mentary charge (e for electron and + e for holes; e = 1.6  1019-
C), k is the Boltzmann constant (1.38  1023 J∙K1), T is the
temperature, E is the applied potential, and EFB is the flat band
potential.
Fig. 7 presents Mott-Schottky plots for the passive films formed
on the carbon steel at 48 h in the chloride-containing carbonated
pore solutions without and with inhibitors. It can be observed from
Fig. 7a that, generally, six distinct regions of the film’s behaviour
are present in all the Mott-Schottky plots. The illustration of the
regions divided in the Mott-Schottky plot of P1 specimen is shown
in Fig. 7b. In region I and VI, the capacity value is very high and
independent of the applied potential E. In region I, the film is in
electric charge accumulation and allows current flow, while in
region VI, the semiconducting properties cannot be correlated
due to the formation of inversion layer in which the concentration
of the holes increases in the valence band [36]. Meanwhile, linear
relationships between 1/C2 and E, with two positive slopes, are pre-
sent in region II and IV, respectively. This behaviour corresponds to
the depletion of donors and the existence of the space charge layer.
D. Wang, C. Pan, Z. Liu et al. Construction and Building Materials 286 (2021) 122916

Table 6
Fitting results of EIS measurements in the chloride-containing carbonated solutions without and with inhibitors.

Specimen Rs (O∙cm2) Qf (105∙s∙ns ∙cm2) nf Cf (mF∙cm2) Rf (kO∙cm2) Qdl (105∙s∙ns ∙cm2) ndl Cdl (mF∙cm2) Rct (kO∙cm2) df (nm) Chi-squared
(∙10-3)
P0 44 24.56 0.71 0.46 0.03 22.32 0.81 3.40 14.16 22.93 1.27
P1 35 7.89 0.84 2.65 2.50 0.36 1.00 3.56 165.20 4.01 1.52
P2 21 29.11 0.82 5.62 1.38 1.47 1.00 14.71 101.20 1.89 1.31
P3 30 6.91 0.82 1.42 2.07 0.58 1.00 5.80 138.71 7.46 1.98
P4 22 7.02 0.86 3.35 2.52 0.32 1.00 3.20 202.50 3.17 5.86
P5 22 10.37 0.85 3.98 1.47 1.82 1.00 18.18 73.39 2.67 2.67

Based on Eq. (5), two donor density, Nd1 and Nd2, corresponding
to shallow donor density and deep donor density respectively,
were calculated and listed in Table 7. It can be observed from the
table that all the Nd1 values are much higher than the correspond-
ing Nd2 values, which was also reported by the previous literature
[38]. According to the literature, the presence of the shallow donor
was attributed to the outer layer consisting of Fe(III) hydroxide,
which contributes to the semiconductivity [38]. In this study, the
shallow donors could be assigned to donors from the adsorption
layer covered on top of the oxide layer, while the deep donors
are from the oxide layer beneath the adsorption layer.
From Table 7, it can be noted that the Nd1 and Nd2 values of all
the specimens with inhibitors are significantly lower than those of
the specimen without inhibitors. This indicates that the conductiv-
ity of passive film decreases and thus the corrosion resistance
increases when inhibitors were added in the chloride-containing
carbonated solution, which is consistent with the abovementioned
EIS results. Moreover, it can be observed that the specimens with
mixed inhibitors exhibit much lower Nd1 values than specimens
with a single inhibitor, which indicates that more compact adsorp-
tion layers were possibly formed on the carbon steel when mixed
inhibitors were added. Thus, based on this information, it can be
deduced that BTA and Na2HPO4 could interact with each other,
which influences the structure of adsorption layer. In addition, P4
specimen shows the lowest Nd2 value among all the specimens,
indicating the lowest conductivity of the oxide layer formed for
P4 specimen. This is consistent with the EIS results that P4 speci-
men shows higher resistance of the oxide layer than the other
specimens.

3.5. Surface analysis

The surface morphology and the corresponding composition of

the carbon steel was obtained after 48 h of immersion in the
chloride-free carbonated solution without inhibitors, as shown in
Fig. 8a. It can be observed that the porous corrosion products con-
sisting of Fe and O exist on the surface of carbon steel. As compar-
ison, it can be observed from Fig. 8b that the localized corrosion
products, which are possibly composed of b-FeOOH (EDS results
in Fig. 8b) [41], were observed on the steel surface of P0 specimen
when chloride ions were added in the carbonated solution. In addi-
Fig. 7. (a) Mott-Schottky plots of C-2 as a function of potential E for passive films on tion, cracks in the corrosion products were also observed in Fig. 8b,
the carbon steel at 48 h immersed in the chloride-containing carbonated solution which is indicative of severe generalized corrosion occurring on
without and with inhibitors and (b) an illustration of the typical Mott- Schottky
curve.
Table 7
Electronic properties of the passive film formed on the carbon steel in the chloride-
The presence of two positive slopes could be attributed to the exis- containing carbonated solutions without and with inhibitors.
tence of two donor levels in the passive film [37,38]. The presence
Specimen Nd1 (1021  cm3) Nd2 (1021  cm3)
of the positive slope of these linear regions indicates that all the
passive films formed behave as n-type semiconductors, with two P0 38.41 4.34
P1 13.45 1.27
donor levels. On the other hand, region III possibly represents a P2 17.00 1.38
potential interval in which the film growth is perturbed [39]. In P3 4.49 1.31
addition, the behaviour of the passive film is only dielectric in P4 8.31 1.25
region V [40]. P5 9.01 1.35

7
D. Wang, C. Pan, Z. Liu et al.
Fig. 8. SEM images and EDX spectra of carbon steel immersed for 48 h in the carbonated pore solutions: (a) P0carb; (b) P0 and (c) P4.
the steel surface. On the contrary, as displayed in Fig. 8c of P4 spec-
imen, a clean surface on which mainly Fe element was detected is
present, indicating that corrosion was suppressed in the presence
of inhibitors. The other specimens with inhibitors show identical
SEM images and EDS spectra as P4 specimen.
3.6. Composition of oxide film
XPS spectra were recorded on the surface region of film formed
on the carbon steel kept for 48 h immersed in each solution. Fig. 9
presents the high-resolution XPS spectra of Fe 2p3/2, O 1 s, N 1 s
and P 2p for each specimen in the chloride-containing carbonated
solutions with inhibitors. The Fe 2p3/2 peak contains contributions
from Fe0 at a binding energy (BE) of 706.9 eV, Fe(II) at 709.0, Fe(III)
at 710.8 and Fe(III) satellite at 714.6 [42,43]. As regards to the O 1 s
peak, deconvolution of the high-resolution O 1 s peak includes four
basic components, that is, O2 at 529.6 eV, OH at 531.4 eV, PO3 4 at
531.9 eV and adsorbed H2O at 533.0 eV [42,44]. Moreover, the peak
of N 1 s at 399.6 eV corresponds to nitrogen species in the BTA
molecules (=N– or –NH-) [17], while the N 1 s peak at 400.6 eV
is associated with the probable formation of the surface complex
(N-Fe) [17]. In addition, the N 1 s peak of higher BE at 401.5 eV
can be assigned to more electropositive nitrogen, which could be
assigned to the presence of hydrogen bonded or protonated nitro-
8
Construction and Building Materials 286 (2021) 122916
gen atoms in the BTA molecule (N. . .H-O-) [45,46]. Additionally,
P 2p peak at about 133.5 eV is ascribed to the presence of PO3- 4 [44].
The ratios of different species obtained from the deconvolution of
XPS spectra were calculated and listed in Table 8. It can be noted
from Table 8 that the surface regions of P0 specimen has the highest
Fe3+/Fe2+ and OH/O2 ratios when compared with the specimens
with inhibitors. This indicates that Fe(III) hydroxide mainly exists
in the surface region of film formed on the carbon steel immersed
in the chloride-containing carbonated pore solution without inhibi-
tors. On the other hand, P4 specimen exhibits the lowest OH/O2
ratio, which is indicative of the highest relative amount of iron oxide.
It also can be found from Table 8 that the P/Fe ratio, which is
defined as the ratio of the intensity of P peak to the intensity of
peaks of Fe(II) and Fe(III), increases with the concentration of Na2-
HPO4 in the solutions. This suggests that the iron phosphate com-
pounds precipitates [27] or phosphate ions adsorb in the oxide [47]
in the film formed on the carbon steel, the amount of which
increases with the increasing content of Na2HPO4 in the solutions.
In this way, the phosphate ions block the anodic dissolution of
some surface sites, contributing to the inhibition of the corrosion
of carbon steel, which had also been claimed in the previous liter-
ature [15]. Moreover, for P1, P3 and P4 specimens, BTA molecules
could adsorb in the oxide film by the formation of Fen(BTA)m due to
the presence of N-Fe bonds as detected in XPS spectra (Fig. 9).
D. Wang, C. Pan, Z. Liu et al.
Additionally, P1 specimen exhibits the largest amounts of N-Fe
bonds, which suggests the most Fen(BTA)m complexes form in
the surface region of oxide film in the presence of 0.1 M BTA. Apart
from the N-Fe bond, for P1, P3 and P4 specimens, hydrogen bonds
between N atoms from BTA and H-O- from Na2HPO4, i.e. N. . .H-O-,
could also exist in the surface region of oxide films as shown in
Fig. 9. Furthermore, P4 specimen exhibits the highest intensity of
the N. . .H-O- bond, which suggests that the mixture of 0.05 M Na2-
HPO4 and 0.05 M BTA promotes the formation of the N. . .H-O-
bond. On the other hand, as for P5 specimen, the lowest amounts
of Fe-N and N. . .H-O- bonds are present in the oxide film, which
demonstrates that a mixture of 0.01 M BTA and 0.09 M Na2HPO4
is adverse to the adsorption of BTA on the surface of carbon steel.
In order to differentiate the role of inhibitors in the
carbonation-induced corrosion and chloride-induced corrosion,
the composition of oxide film formed in the carbonated pore solu-
tions without chloride ions was detected. Fig. 10 displays the high-
resolution XPS spectra of Fe 2p3/2, O 1 s, N 1 s and P 2p for each
specimen in the carbonated pore solutions without and with inhi-
bitors. The ratios of different species obtained from the deconvolu-
tion of XPS spectra were listed in Table 8. It can be noticed from the
table that the specimens with inhibitors exhibit much lower Fe3+/
Fe2+ and OH/O2 ratios than P0carb specimen. This indicates that
the presence of inhibitors effectively hinders the corrosion of car-
bons steel in the carbonated solution. Moreover, it can be found
that Fe3+/Fe2+ ratios of specimens in the chloride-free carbonated
solution are remarkedly reduced when compared with the corre-
sponding ones in the chloride-containing carbonated pore solu-
Fig. 9. XPS spectra of specimens immersed in chloride-containing carbonate pore solution with various inhibitors: (a) P0; (b) P1; (c) P2; (d) P3; (e) P4; and (f) P5.
9
Construction and Building Materials 286 (2021) 122916
tions. This indicates that the amount of Fe(III) oxide/hydroxide
decreased in the oxide film when chloride ions are absent in the
solution. Moreover, the presence of the N 1 s peak representing
Fe-N bond of P1carb specimen is indicative of the chemisorption
of BTA in the oxide film in the carbonated pore solution, which
shows the same adsorption mechanism of BTA in the chloride-
containing carbonated pore solution. On the contrary, when phos-
phate ions are present in P2carb specimen, the phosphate ions
hardly precipitate in the oxide film formed in the carbonated pore
solution. This is consistent with the previous literature which
claims that the oxide film formed in the phosphate-containing
alkaline solution was mainly composed of iron oxide/hydroxide
while few iron phosphates adsorb on the surface of iron [26].
Moreover, N element is absent for P4carb specimens, which indi-
cates that BTA can hardly precipitate in the oxide film formed
when a mixture of 0.05 M BTA and 0.05 M Na2HPO4 is present. This
could be related to the presence of phosphate ions, favouring the
formation of compact iron oxide instead of Fen(BTA)m complex.
Therefore, when comparing the XPS results in the presence of chlo-
ride ions with those in the absence of chloride ions, it could be
plausible that phosphate ions can inhibit the carbonation-
induced corrosion by promoting the formation of compact iron
oxide/hydroxide, while inhibiting the chloride-induced corrosion
by the precipitation of iron phosphates. On the other hand, both
carbonation-induced corrosion and chloride-induced corrosion
are inhibited by forming Fen(BTA)m complex when BTA is present
in the solutions. However, when both phosphate ions and BTA
were added into the chloride-containing carbonated solution, the
D. Wang, C. Pan, Z. Liu et al. Construction and Building Materials 286 (2021) 122916

Fig. 9 (continued)

Table 8
The different ratios of species in the surface films of carbon steel immersed in different solutions obtained from XPS deconvolution.

Chloride-containing carbonated pore solution

Fe3+/Fe2+ OH/O2 P/Fe Fe-N/=N- N. . .H-O-/=N-
P0 24.53 9.07 / / /
P1 11.39 5.04 / 0.26 /
P2 11.45 4.90 0.85 / /
P3 11.72 4.65 0.09 0.19 0.10
P4 11.68 2.27 0.20 0.11 0.14
P5 11.09 7.18 0.42 0.03 0.09
Carbonated pore solution
P0carb 29.54 8.13 / / /
P1carb 1.55 2.00 / 0.18 /
P2carb 1.73 1.99 0.023 / /
P4carb 3.56 2.34 0.028 / /

carbonation-induced corrosion is mainly inhibited by the forma-
tion of compact iron oxide/hydroxide, while the chloride-induced
corrosion is hindered by the precipitation of iron phosphates and
Fen(BTA)m complex.
3.7. Corrosion inhibition mechanism
Based on the abovementioned results in the presence of Na2-
HPO4 and BTA, a schematic illustration of corrosion inhibition
mechanism of Na2HPO4 and BTA in the chloride-containing
carbonated pore solution is displayed in Fig. 11. As shown in
10
Fig. 11a, phosphate ions from NaH2PO4 chemically adsorb in the
oxide film by forming iron phosphates via Fe-O-P bonds, inhibiting
the dissolution of Fe ions in the defective surface regions, which
had also been reported in the previous literature [27]. Moreover,
the presence of phosphate ions was reported to promote the for-
mation of compact oxide film consisting of c-Fe2O3 formed in the
uniform areas of steel surface, which leads to a more compact
oxide film and thus effectively inhibits corrosion [48]. This is con-
sistent with the XPS results obtained in this study that the relative
amount of iron oxide in the oxide film increased when the phos-
phate ions are present in the carbonated solution.
D. Wang, C. Pan, Z. Liu et al.
Fig. 10. XPS spectra of specimens immersed in the carbonate pore solution with various inhibitors: (a) P0carb; (b) P1carb; (c) P2carb; and (d) P4carb.
The interaction between the BTA molecules with the surface of
carbon steel can be physisorption and/or chemisorption. According
to the previous literature, BTA adsorbed on the surface of carbon
steel mainly chemically in the solution with contamination of chlo-
ride ions [4,5]. Moreover, the chemisorption of BTA could be
enhanced when another inhibitor was introduced into the system
[17,49]. In this study, BTA molecules are mainly negatively
charged, i.e. BTA-, as a result of deprotonation in alkaline condition
[50]. Consequently, Fen(BTA)m complex can form in the surface
region of carbon steel via dative bonding interactions between
Fen+ and deprotonated nitrogen, as shown in Fig. 11b [51]. The
Fen(BTA)m complex blocks the defects in the surface region of oxide
11
Construction and Building Materials 286 (2021) 122916
film and hence hindering the dissolution of Fe from carbon steel,
leading to the enhancement of corrosion resistance. Moreover, pre-
vious research had shown that a better corrosion resistance to
chloride attack in the solution was obtained in the presence of
BTA than Na3PO4 [9]. This was claimed to be possibly due to the
formation of polymeric complex [Fen(BTA)m]z via the bidentate
bonds between the triazolic nitrogen ring and the steel surface,
which acts as an effective barrier to chloride ions [9,52]. This is
consistent with the electrochemical results in this study as dis-
played in Fig. 5, which demonstrates that BTA has higher corrosion
efficiency than NaH2PO4 in the chloride-containing carbonated
solution.
D. Wang, C. Pan, Z. Liu et al.
Fig. 11. Models proposed to visualize the structure of layer formed on the surface of carbon steel immersed in the chloride-containing carbonated pore solutions in the
presence of: (a) Na2HPO4; (b) BTA; (c) a mixture of equal amount of BTA and Na2HPO4; and (d) a mixture of unequal amount of BTA and Na2HPO4.
The corrosion inhibition mechanisms of a mixture of BTA and
NaH2PO4 with different proportions are illustrated in Fig. 11 c and
d. Based on the XPS results, hydrogen bonding between N atoms
from BTA- and H-O- from HPO2- 4 can form in the surface region of
oxide film when a mixture of BTA- and HPO2- 4 are present in the
chloride-containing carbonated solution [51]. The formation of
hydrogen bonding strengthens the interlink between BTA- and
HPO2-4 in the surface region of oxide film. When the amount of
BTA- is equal to that of HPO2- - 2-
4 , BTA and HPO4 could adsorb in
the oxide film, in other words, both Fen(BTA)m and FexHy(PO4)z
could exist in the surface region of oxide film, as illustrated in
Fig. 11c. In this scenario, the hydrogen bonding between Fen(-
BTA)m and Fe2HPO4 enhances the interlink between each other,
and thereby leading to a stronger sealing adsorption layer on
top of the oxide film, as displayed in Fig. 11c. Meanwhile, the
oxide film consisting of iron oxide/hydroxide formed in the uni-
form areas when the amount of BTA- is equal to that of HPO2- 4 .
As comparison, when the content of BTA- is much lower than that
of HPO2-4 , only a small amount of positions of FeOOH/Fe2O3 oxy-
gen atoms could be occupied by BTA- since much more strict con-
ditions are required for BTA- to adsorb, for example, inclination of
BTA molecule plane is required at the adsorbed sites [53]. As a
result, FeOOH/Fe2O3 oxygen atoms in the surface region of oxide
film mainly interact with HPO2- -
4 , while the remaining BTA mole-
2-
cule could possibly only adsorb on top of HPO4 via hydrogen
bonding, as illustrated in Fig. 11d. In this scenario, the adsorption
of BTA- could be weaker since hydrogen bonds are weaker than
fully covalent or ionic bonds. As a result, the adsorption layer of
BTA- and HPO2- 4 could be weaker, which leads to lower corrosion
inhibition efficiency.
12
Construction and Building Materials 286 (2021) 122916
Overall, a synergistic effect of BTA and NaH2PO4 on the corro-
sion occurs in the P4 specimen, leading to the highest corrosion
inhibition efficiency, which can be attributed to the formation of
an adsorption layer consisting of Fen(BTA)m and FexHy(PO4)z as
well as large amounts of N. . .H-O- hydrogen bonding. The hydro-
gen bonding could enhance the interlink between compounds in
the adsorption layer. On the contrary, the absence of hydrogen
bonding between the adsorption layers formed in single BTA or
could lead to defective points at the interface between the Fen(-
BTA)m or FexHy(PO4)z compounds. Thus, due to the large amount
of bonds between BTA- and HPO2- 4 , the compactness of the adsorp-
tion layer in the case of a mixture of 0.05 M BTA and 0.05 M NaH2-
PO4 is significantly higher than that the surface layers from
solutions containing single BTA or NaH2PO4.
4. Conclusion
This study preliminarily investigates the corrosion inhibition of
carbon steel in the chloride-contaminated carbonated solutions
without and with different concentration of BTA and Na2HPO4
and their mixtures by electrochemical methods including OCP,
EIS, potentiodynamic polarization and Mott-Schottky, as well as
XPS and SEM/EDS techniques. Based on the results obtained in this
study the following conclusions can be drawn:
1. BTA shows better corrosion inhibition efficiency than Na2HPO4
for carbon steel immersed in the chloride-contaminated car-
bonated solutions (which are low alkaline). The inhibition
action of BTA inhibitor acts as an anodic type, while Na2HPO4
acts as a mixed inhibition type.
D. Wang, C. Pan, Z. Liu et al.
2. Na2HPO4 inhibits the corrosion by forming compact iron oxide/
hydroxide in the absence of chloride ions, while forming iron
phosphates in the presence of chloride ions. BTA inhibits the
corrosion by the formation of insoluble Fen(BTA)m complex.
3. The mixture of 0.05 M BTA with 0.05 M Na2HPO4 shows a syner-
getic inhibiting effect due to the formation of hydrogen bonding
between Fen(BTA)m complex and iron phosphates in oxide film.
4. An adverse effect on corrosion inhibition was observed with
addition of a mixture of unequal amount of BTA and Na2HPO4,
which is possibly due to the competition between the phos-
phate ions and BTA- for the occupation of the sites in the oxide
film on the steel surface.
CRediT authorship contribution statement
Danqian Wang: Conceptualization, Writing - original draft.
Chonggen Pan: Supervision, Project administration. Zhicheng
Liu: Writing - review & editing. Keyu Chen: Investigation, Writing
- review & editing. Xu Li: Investigation, Writing - review & editing.
Shiyuan Xu: Investigation, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (Grant No.
51878610, 51778578), the Natural Science Foundation of Ningbo
(Grant No. 2019C50015), the Natural Science Foundation of Zhe-
jiang Province (Grant No. LGG21E080006), Research topics of
higher education in Zhejiang Province (Grant No.KT2020157),
Ningbo 2025 Science and Technology Major Project (Grant No.
2019B10049, 2020Z035, 2020Z040), and Ningbo Education Science
Planning Project (Grant No. 2019YGH025).
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