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10.1016 - J.matchemphys.2010.08.058 Corrosion Inhibition Performance of Three Imidazole Derivatives On Mild Steel in 1 NBSP M Phosphoric Acid
10.1016 - J.matchemphys.2010.08.058 Corrosion Inhibition Performance of Three Imidazole Derivatives On Mild Steel in 1 NBSP M Phosphoric Acid
10.1016 - J.matchemphys.2010.08.058 Corrosion Inhibition Performance of Three Imidazole Derivatives On Mild Steel in 1 NBSP M Phosphoric Acid
a r t i c l e i n f o a b s t r a c t
Article history: The effect of benzimidazole (BI), 2-methyl benzimidazole (2MBI) and 2-aminobenzimidazole (2ABI) on
Received 8 September 2009 the corrosion of mild steel was evaluated in 1 M phosphoric acid at various concentrations using electro-
Received in revised form 13 August 2010 chemical techniques (Electrochemical Impedance Spectroscopy (EIS) and DC polarization). Inhibition of
Accepted 18 August 2010
imidazole derivatives was evaluated at concentrations between 5 × 10−2 –10−4 M. It was observed that
inhibition efficiency increased with increasing inhibitor concentration. Adsorption of imidazole deriva-
Keywords:
tives on the metal surface was investigated to consider basic information on the interaction between the
Phosphoric acid
inhibitors and the metal surface. Flory–Huggins adsorption isotherm model showed that each inhibitor
EIS
Polarization
replaces 3–5 molecules of water on the metal surface.
Inhibitor © 2010 Elsevier B.V. All rights reserved.
1. Introduction The following adsorption isotherms are the most common mod-
els to study the mechanism of corrosion inhibition [17–21]:
Metallic corrosion is attracting the attention of researchers. Langmuir adsorption isotherm:
Researchers all over the world are searching for some methods to
avoid corrosion damage. Using inhibitors is an effective method to C · kad = (1)
1−
reduce corrosion rate [1].
An acid wash process is widely used in many industries in order Flory–Huggins adsorption isotherm:
to cleaning and descaling of steel substrates [2]. In acid pickling pro-
cess, hydrochloric acid, phosphoric acid and sulfuric acid are used log = log(kad ) + x · log(1 − ) (2)
C
due to their special chemical properties [3]. By considering the fact
that mentioned mineral acids are aggressive solution for metallic Tempkin adsorption isotherm:
substrates, using corrosion inhibitors in acidic bath is one of the
C · kad = exp(f · ) (3)
most practical methods for preventing the corrosion of metals. As a
result, corrosion inhibitors for acidic media have attracted increas- Freundlich adsorption isotherm:
ing attention due to their extended applications [3–5]. The use
C f · kad = (4)
of organic compounds containing oxygen, sulfur and nitrogen has
been studied in some details to reduce corrosive attack on steel in Frumkin adsorption isotherm:
phosphoric acid media [6–13]. Replacement of common phospho-
ric acid inhibitors by eco-friendly inhibitors is a subject of current C · kad = exp(f · ) (5)
1−
research. The imidazole derivatives investigated in this paper are
eco-friendly and safe inhibitors. Imidazole derivatives are useful as In the above, C is the concentration of inhibitor, kad the adsorption
potential corrosion inhibitors for iron as well as for copper, zinc and constant and the surface coverage. The parameter ‘x’ in Eq. (2) is
their alloys [14]. The inhibition performance of organic inhibitors is the number of water molecules replaced by an inhibitor molecule
due to physisorption and/or chemisorption on the surface of met- on metal surface. The parameter ‘f’ in Tempkin, Freundlich and
als [15,16]. To characterize the adsorbed layer and the interaction Frumkin isotherms is called “surface heterogeneity”, “adsorption
between adsorbed species, adsorption isotherms are used. intensity” and “interaction parameter”, respectively.
Different methods including weight loss measurement [22],
electrochemical AC [23] and DC [24] methods or combination of
these methods [25] have been used to determine surface cover-
∗ Corresponding author. Tel.: +98 2164542404; fax: +98 2166468243. age () and the adsorption isotherms of inhibitor molecules in the
E-mail address: attar@aut.ac.ir (M.M. Attar). corrosive media.
0254-0584/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.08.058
1206 A. Ghanbari et al. / Materials Chemistry and Physics 124 (2010) 1205–1209
2. Experimental Table 1
Electrochemical parameters of mild steel at various concentrations of imidazole
1 M phosphoric acid was prepared from laboratory grade phosphoric acid derivatives in 1 M H3 PO4 at 298 K.
detained from Mojalali Company (Iran). Three imidazole derivatives including BI,
Concentration (M) Ecorr (mV/Ag-AgCl) Icorr (A cm−2 ) E (%)
2MBI and 2ABI were obtained from Merck (Germany) and used without further
purification. Mild steel sheets (ST37 with thickness of 6 mm) were obtained from Blank 0 −474 392 –
Mobarake Steel Company (Iran). Samples were polished with a magnetic polisher BI 10−4 −475 368 6.1
to remove mill scale from the surface and degreased twice by acetone. A 1.0 cm2 10−3 −476 323.4 17.5
sample area was exposed to electrolytes while the rest of each plate was sealed via 10−2 −476 218.3 44.3
a beeswax-colophony mixture. Each sample was immersed in 75 cm3 of the pre- 5 × 10−2 −477 148.9 62
pared electrolytes. Each test was carried out at 298 K and after 7 h immersion in 2MBI 10−4 −474 375.5 4.2
test solutions to ensure complete adsorption of inhibitors on the surface. EIS and 10−3 −474 327.3 16.5
DC polarization were carried out using an Autolab PG STAT12 (Italy). EIS was used 10−2 −475 257 34.43
to confirm the DC polarization results and to study the inhibition mechanism in 5 × 10−2 −476 174 55.60
more details. EIS was carried out at open circuit potential within frequency range 2ABI 10−4 −474 363.3 7.3
of 10−2 –104 Hz with 10 mV perturbation. DC polarization was carried out at a scan 10−3 −474 289.2 26.20
rate of 1 mV s−1 . The reference electrode and counter electrodes were silver–silver 10−2 −475 181.6 53.67
chloride and platinum, respectively. pHs of solutions were measured using a pH315i 5 × 10−2 −476 120.4 69.28
WTW pH-meter (Germany).
3. Results and discussion relatively similar behavior in polarization testing. Fig. 1 shows that
imidazole derivatives do not change the profile of the anodic and
3.1. DC polarization cathodic curves, indicating that they block the reaction sites of iron
without affecting the anodic and cathodic reaction mechanisms.
The polarization curves of mild steel in 1 M H3 PO4 (pH 1.09) in With the inhibitors, both anodic and cathodic current densities are
the both absence and presence of BI, 2MBI and 2ABI at different con- reduced, suggesting that these compounds behave as mixed type
centrations are presented in Fig. 1. All imidazole derivatives show inhibitors.
The measured parameters such as corrosion potential (Ecorr ),
corrosion current density (Icorr ) and inhibition efficiency (E%) are
listed in Table 1. Eq. (6) determines the inhibition efficiency:
Icorr − Icorr(inh)
E% = × 100 (6)
Icorr
where Icorr and Icorr(inh) are corrosion current densities without
and with inhibitors respectively, as determined by extrapolation
of Tafel lines.
Table 1 shows that inhibition efficiency of these inhibitors is
not significant at concentration of 10−4 M on mild steel. It can be
seen that with increasing inhibitor concentration, corrosion current
density decreases and inhibition efficiency increases. The corrosion
inhibition efficiency of the imidazole derivatives increases in the
order 2ABI > BI > 2MBI.
The inhibition of corrosion of mild steel by heterocyclic com-
pounds can be explained by their adsorption on the metal surface
[14–16]. These compounds can be adsorbed by interaction between
the lone pairs of electrons of inhibitor nitrogen atoms and the metal
surface [17]. Fig. 2 shows their chemical structures of imidazole
derivatives. According to Fig. 2, the number of nitrogen atoms in the
2ABI is greater than that in 2MBI and BI. As a result, adsorption of
2ABI on the steel substrate is more probable. The methyl side chain
in 2MBI prevents adsorption of this molecule on the metal surface.
Hence adsorption of BI molecules is easier than MBI molecules on
the steel surface.
According to Table 1, the highest inhibition efficiency is 69.28%
showing that imidazole derivatives had limited inhibition effi-
ciency in phosphoric acid media. Table 2 shows the change in the pH
of phosphoric acid after addition of 0.01 M imidazole derivatives in
which the initial pH was 4.0. Although pH of 1 M H3 PO4 is 1.09, pH
changing of the solutions is more significant in the pH 4 in compari-
son to pH 1.09. According to Table 2, it is obvious that in acidic media
Fig. 1. Polarization curves of mild steel in 1 M H3 PO4 containing (a) benzimidazole, Fig. 2. Chemical structure of inhibitors, (a) benzimidazole, (b) 2-methyl benzimi-
(b) 2-methyl benzimidazole and (c) 2-aminobemzimidazole. dazole and (c) 2-aminobemzimidazole.
A. Ghanbari et al. / Materials Chemistry and Physics 124 (2010) 1205–1209 1207
Table 2
pH of phosphoric acid in the absence and presence of 0.01 M imidazole derivatives
at 298 K.
Rct(inh) − Rct
E% = × 100 (7) Fig. 3. EIS plots of the mild steel in 1 M H3 PO4 containing (a) benzimidazole, (b)
Rct(inh) 2-methyl benzimidazole and (c) 2-aminobemzimidazole.
where Rct(inh) and Rct are charge transfer resistances with and with-
out inhibitors, respectively.
According to Table 3, as the concentration of imidazole deriva-
tives increases, the charge transfer resistance (Rct ) increases
slightly, indicating formation of an insulated inhibitor layer on
metal surface. In Table 3 the double layer capacitance Cdl was cal-
culated by Eq. (8):
(Y0 · Rct )1/n Fig. 4. Equivalent electrical circuit corresponding to the corrosion process on the
Cdl = (8)
Rct mild steel in phosphoric acid.
Table 3
Characteristic parameters evaluated from the impedance diagram for mild steel in 1 M H3 PO4 at various concentrations of imidazole derivatives at 298 K.
Concentration (M) Rct ( cm2 ) Rs ( cm2 ) Y0 (sn −1 cm−2 ) ndl Cdl (F cm−2 ) E (%)
Table 4 Table 6
Curve fitting results of inhibitors for different adsorption isotherms. Theoretical surface area of water and imidazole derivatives obtained by “semiem-
pirical, PM3, quantum chemical calculation” method.
R2 Log(kad )
Surface area (square Å) Inhibitor surface/water surface
BI 2MBI 2ABI BI 2MBI 2ABI
Water 11 –
Langmuir 0.891 0.837 0.843 1.45 1.25 1.58 BI 21.82 1.98
Frumkin 0.973 0.968 0.962 1.36 0.89 0.65 2MBI 28.17 2.56
Tempkin 0.977 0.987 0.988 4.11 4.07 4.32 2ABI 24.11 2.19
Freundlich 0.969 0.936 0.943 3.9 4.52 3.76
Flory–Huggins 0.982 0.993 0.990 2.73 2.57 3.03
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