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Article history:
Received 10 March 2010
Received in revised form
18 September 2010
Accepted 29 November 2010
Keywords:
Corrosion
Austenitic stainless steel
Polarization
Pyrimidine derivatives
a b s t r a c t
5-Benzoyl-4-(substitutedphenyl)-6-phenyl-3,4-dihydropyrimidine-2(1H)-(thio)ones (DHPMs) (I and II)
were synthesized using the Biginelli three component cyclocondensation reaction of an appropriate
-diketone, arylaldehyde, and (thio) urea. The effect of these corrosion inhibitors on the corrosion of
austenitic stainless steel in 0.5 M H2 SO4 has been studied by electrochemical methods using Tafel plot,
linear polarization and electrochemical impedance spectroscopy at 298 K. The inhibition efciencies
obtained from all the methods employed are in good agreement. The adsorption of the DHPMs onto the
stainless steel surface was found to follow Langmuir and DubininRadushkevich adsorption isotherm
models. Negative values of Gads in the acidic media ensured the spontaneity of the adsorption process. Results show DHPM I to be the best inhibitor with a mean efciency of 91% at 2 103 M additive
concentration.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Stainless steel has a wide scope of applications in different
industries. This type of stainless steel is covered with a protective
lm rich in chromium (oxides/hydroxides) that imparts corrosion
resistance to its surface. Amount of chromium prevents the formation of rust in unpolluted atmospheric environments. However,
acidic solutions are aggressive to this lm layer and results in
severe pitting formation [1,2]. Acid solutions are widely used in
industries for pickling, acid cleaning of boilers, descaling and oil
well acidizing [3,4]. Sulfuric acid is generally the choice in the
steel surface treatment basically due to its lower cost, minimal
fumes and non-corrosive nature of the SO4 2 ion [5]. Corrosion
inhibitors are needed to reduce the corrosion rates of metallic
materials in this area. Most of the well-known acid inhibitors are
heterocyclic compounds containing bonds, heteroatom phosphorus, sulfur, oxygen and nitrogen [6] as well as aromatic rings
in their structure which are the major adsorption centers [7].
The compounds containing both nitrogen and sulfur can provide
excellent inhibition, compared with compounds containing only
nitrogen or sulfur [4,8]. Generally, a strong interaction causes
higher inhibition efciency, the inhibition increases in the sequence
O < N < S [9,10].
Recently, some studies have been presented on heterocyclic
compounds, such as pyrimidine [9,11], pyridazine [10], bicycloisox-
The working electrode was mounted in polyester with following chemical composition (wt.%) C: 0.0425; Si: 0.421; Mn: 2.13; P: 0.0133; S: 0.113; Cr: 18.51; Mo:
984
Scheme 1. The molecular structure and name of inhibitor used 5-benzoyl-4,6diphenyl-1,2,3,4-tetrahydro-2-thiopyrimidin (DHPM I); 5-Benzoyl-6-phenyl-4-ptolyl-3,4-dihydropyrimidin-2(1H)-one (DHPM II).
0.563; Ni: 8.34; Al: 0.0334; Co: 0.0901; Cu: 0.358; Fe: balance. The steel electrode was coated with polyester except its bottom surface with surface area of
0.19625 cm2 .
Fig. 1. Polarization curves for steel in 0.5 M H2 SO4 in the absence and presence of
different concentrations of DHPM I at 298 K.
calculated by:
2.2. Materials
A mixture of 1,3-diphenyl-1,3-propanedione (1.6 mmol), aryl aldehyde
(1.1 mmol), (thio)urea (1.1 mmol) and 20 ml of glacial acetic acid containing a few
drops concentrated hydrochloric acid was heated under reux for 8 h. After the
precipitate were ltered off, the solution was held at the room temperature 25 C
for one night and recrystallized from suitable solvents. The synthesis method of
DHPM II was not able to be reached, in spite of it is available the theoretical calculations [25a]. Therefore, it has been thought that the synthesis method applied in the
present study is different [25b]. DHPM I synthesized according to Ref. [26]. DHPMs
were characterized on the basis of their spectral data and elementary analyses. The
molecular structures of DHPM I and II are shown in Scheme 1.
2.3. Test solutions
Solvents and material synthesis chemicals are commercially available (Aldrich,
Fluka, Merck) and were used without further purication. 0.5 mol dm3 H2 SO4 and
inhibitor solutions were prepared using double distilled water. Inhibitor concentrations were chosen as 1 104 , 5 104 , 1 103 and 2 103 mol dm3 . Solutions
were mixed with a magnetic stirrer. For each experiment, a freshly prepared solution
was used.
Rp = A
dE
di
where A is the surface area of the electrode. The Rp values were used to calculate the
inhibition efciencies (Rp , %), using the following equation. Rp and Rp are the polarization resistances in the presence and absence of the organic additive, respectively.
Rp (%) =
R
Rp
100
Rp
R
Rp
Rp
100
where Rp and Rp are uninhibited and inhibited polarization resistances, respectively.
pol (%) =
=
i i
i
100
i i
i
where i and i are the corrosion current densities without and with inhibitor. The
corrosion currents were determined from the intersection of the Tafel plots for each
case.
LPR measurements were carried out by recording the electrode potential
10 mV around open circuit potential with 0.1 mV s1 scan rate [27]. Polarization
resistance values were obtained from the slope of the potentialcurrent lines and
Fig. 2. Polarization curves for steel in 0.5 M H2 SO4 in the absence and presence of
different concentrations of DHPM II at 298 K.
985
Table 1
Corrosion parameters for steel in 0.5 M H2 SO4 in the absence and presence of DHPM I and II.
DHPMs
Ecorr (V)
a (mV dec1 )
c (mV dec1 )
pol (%)
a
None
1 104
5 104
1 103
2 103
0.393
0.339
0.320
0.296
0.259
0.0465
0.0124
0.0062
0.0057
0.0046
93
62
68
49
42
85
89
101
136
176
73
87
88
90
0.73
0.87
0.88
0.90
II
None
1 104
5 104
1 103
2 103
0.393
0.356
0.343
0.341
0.340
0.0465
0.0234
0.0189
0.0102
0.0081
93
51
55
57
58
85
110
105
103
100
50
59
78
83
0.50
0.59
0.78
0.83
the inhibitors, but the reduction in the anodic current was greater
than that of the cathodic current.
These results showed that the addition of DHPMs reduces anodic
dissolution and also retards the hydrogen evolution reaction.
The corresponding electrochemical parameters, i.e., corrosion
current density (icorr ), Tafel slope constants (a and c ), corrosion
potential (Ecorr ), inhibition efciency, (%) and surface coverage
degrees () values were calculated from these curves and are given
in Table 1. The inhibition efciency follows order, DHPM I > DHPM
II.
In acidic solutions, the anodic reaction of corrosion is the passage of metal ions from the metal surface into the solution, and
the cathodic reaction is the discharge of hydrogen ions to produce
hydrogen gas or to reduce oxygen. The inhibitor may affect either
the anodic or the cathodic reaction, or both [29,30]. The values of
the anodic Tafel constant, a , calculated for inhibited solutions are
smaller than obtained for the uninhibited in H2 SO4 concentration;
this indicates that the inhibitors affected anodic reactions. The values of the cathodic Tafel constant, c , showed an opposite trend.
Also corrosion potentials shifted to the positive direction. A compound can be classied as an anodic- or a cathodic-type inhibitor
when the change in the Ecorr value is larger than 85 mV [30,31].
Since the largest displacement exhibited by DHPM I was 134 mV
(Table 1), it may be concluded that this molecule should be considered as an anodic-type inhibitor, meaning that the addition of
compounds to a 0.5 M H2 SO4 solution reduces the anodic dissolution of steel. The change of Ecorr was observed 53 mV; therefore the
DHPM II is a mixed-type inhibitor (Table 1), meaning that the addition of compounds to a 0.5 M H2 SO4 solution reduces the anodic
dissolution of steel and also retards the cathodic hydrogen evolution reaction. The corrosion inhibition increased with inhibitor
concentration. Particularly, the DHPM I exhibited higher inhibition effect than DHPM II. The process of inhibition is inuenced
by the nature and the charge of the metal, chemical structure of
the organic inhibitor and the type of electrolyte [32].
The surface charge of the metal is due to the electrical eld which
emerges at the interface by immersion in the electrolyte. This surface charge can be determined by comparing the potential of zero
charge (PZC) and the stationary potential of the metal in the corresponding medium [4]. As PZC corresponds to the potential at which
the surface of electrode is charge-free, at the corrosion potential
the metal surface can be positively or negatively charged. The surface charge of immersed iron in the H2 SO4 solution is positive or
slightly negative compared with PZC [4,32]. Corrosion mechanism
of the acid dissolution of stainless steel is dependent not only on
the hydrogen ion concentration but also on the counter ion of the
acid. The majority of corrosion inhibition studies of steel in H2 SO4
media using different organic compounds showed less inhibition
efciency than in HCl medium [33]. Therefore some studies are also
continuing in our laboratory on pyrimidine compounds on stainless
steel in hydrochloric acid.
986
Table 2
Polarization resistances and inhibition efciencies obtained from the linear polarization method for steel in 0.5 M H2 SO4 .
DHPMs
Ecorr (V)
Rp ( cm2 )
Rp
None
1 104
5 104
1 103
2 103
0.396
0.340
0.320
0.300
0.266
87.52
244.92
607.30
750.69
858.12
64
86
88
90
II
None
1 104
5 104
1 103
2 103
0.396
0.363
0.351
0.345
0.340
87.52
149.26
185.54
344.43
458.22
41
53
75
81
Fig. 5. Nyquist diagrams for steel in 0.5 M H2 SO4 in the absence and presence of
different concentrations of DHPM II at 298 K.
1
1
Rp
2fmax
Fig. 4. Nyquist diagrams for steel in 0.5 M H2 SO4 in the absence and presence of
different concentrations of DHPM I at 298 K.
DHPMs
Inhibitor
concentration
(mol dm3 )
Rp ( cm22 )
Cdl (F cm2 )
fmax
EIS (%)
None
1 104
5 104
1 103
2 103
65.78
252.82
693.44
721.94
812.21
235.0
67.0
31.4
18.1
16.1
10.3
9.4
7.3
12.2
12.2
74
91
91
92
II
None
1 104
5 104
1 103
2 103
65.78
121.95
179.03
344.49
445.22
235.0
113.5
90.75
53.74
45.27
10.3
11.5
9.8
8.6
7.9
46
63
81
85
987
1
+ C(inh)
K(ads)
Fig. 6. Langmuir adsorption plot for steel in 0.5 M H2 SO4 containing different concentrations of DHPM I and DHPM II.
= RT ln 1 +
Cinh
Gads = RT ln K
The standard free energy of adsorption values of 20 kJ mol1
or less negative are associated with an electrostatic interaction
between charged molecules and charged metal surface (physical adsorption); those of 40 kJ mol1 or more negative involves
charge sharing or transfer from the inhibitor molecules to the metal
surface to form a co-ordinate covalent bond (chemical adsorption)
[37].
The calculated standard free energy of adsorption values were
found 28.81 and 26.81 kJ mol1 for DHPM I and DHPM II,
respectively. (Thermodynamic parameters were determined from
the potentiodynamic polarization measurements.) The decreasing
value of Gads reects the increasing adsorption capability. The
988
0.5
In the present work were less than those expected for chemical
adsorption process, thereby suggesting that the adsorption mechanism may be a combination of electrostatic interaction and physical
sorption.
4. Conclusions
The inhibition and adsorption effect of DHPMs on the corrosion
behavior of the stainless steel in 0.5 M H2 SO4 was studied using
different techniques. The following points can be emphasized:
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
1. The pyrimidine compounds studied are good inhibitors for stainless steel in 0.5 M H2 SO4 .
2. The inhibition efciency increases with inhibitor concentration.
3. The addition of DHPM I and DHPM II induces a decrease in both
anodic and cathodic currents. The corrosion potential (Ecorr ) of
DHPM I was observed to shift towards more noble potentials
with increasing additive concentration, indicating the inhibitors
to be of anodic character and formation of a surface lm. Since
the largest displacement exhibited by DHPM II was 53 mV, it
may be concluded that this inhibitor should be considered as a
mixed-type inhibitor. The presence of the sulfur atom increases
the inhibition efciency.
4. The negative values of Gads show that the adsorption of
inhibitor molecules on the metal surface is spontaneous.
5. The adsorption DHPMs on stainless steel surface can be approximated by Langmuir and DubininRadushkevich isotherm
models. DubininRadushkevich model suggests that DHPMs are
adsorbed on stainless steel surface by physical adsorption mechanism.
Acknowledgement
This study was supported by the Research Fund of Yznc Yl
University, Van, Turkey.
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