Aropub Ijmsi 13 33

International Journal of Material Science Innovations (IJMSI) 1 (2): 73-86, 2013
ISSN: 2289-4063
Academic Research Online Publisher
Research Article
Effect of anodic inhibitors on corrosion of carbon steel bar reinforced
concrete
Saeid Kakooeia, S. Valid Jaberi b, Kourosh Sharifi b, Mokhtar Che Ismaila, Abolghasem
Dolatic
a
Center For Corrosion Research, Mechanical Engineering Department, Universiti Teknologi PETRONAS,
Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia.
b
Corrosion Engineering Group, Engineering Faculty, Kish University, Kish Island, Iran.
c
Department of Materials Engineering, Sharif University of Technology, Tehran, Iran
* Corresponding author. Tel.: 0060174958196;
E-mail address: saeid.k_g01663@utp.edu.my
ARTICLE INFO
Article history
Received:1May2013
Accepted:10May2013
Keywords:
Inhibitor
Steel reinforced concrete
Marine environment
Corrosion
Abstract
The effect of a mixture of anodic inhibitors used to mitigate the corrosion rate
of steel embedded in concrete caused by chloride ion has presented. For this
purpose, two different ratio combinations of Calcium Nitrite and Sodium
Molybdate were employed to study their functions and synergistic effects. For
corrosion accelerating of steel, different amounts of Sodium Chloride were
added to the designed solution and samples were exposed to wet and dry
cycles for one, two and six months. Three electrochemical methods including
linear polarization, impedance spectroscopy and cyclic potentiodynamic
polarization were used to evaluate inhibitor behavior on the corrosion rate of
steel embedded in concrete. Inherent permeability, compression strength, fourpin electrical resistance, and pH measurement tests have been done to study
the effect of inhibitors on the mechanical properties of concrete. It was
observed that the mixture of Calcium Nitrite and Sodium Molybdate improved
inhibition corrosion of steel embedded in concrete and improving concrete
mechanical properties as well.
Academic Research Online Publisher. All rights reserved.
1. Introduction
As a construction material, reinforced concrete offers various properties such as good
formability, low cost, high strength and durability which have good function in different
work conditions. Concrete coating on steel bars makes both physical and chemical obstacles
against corrosive agents. Concrete has naturally high alkalinity that forms a protective
passive layer on steel bars. The specific electrical resistivity of concrete could be up to 30
k.cm [1]. The above reasons cause reinforced concrete structures to be more corrosion
resistant than metallic ones. Some factors such as chloride ion diffusion in the concrete and
S. Kakooei et al. / International Journal of Material Science Innovations (IJMSI) 1 (2): 73-86, 2013
pH drop due to carbonating destroy the passive layer and the corrosion of steel bars begins.
One of the most important factors in destruction of concrete structures is the corrosion of
steel bars [2-5].
The degradation of concrete structures due to the corrosion of steel bars starts with the
formation of corrosion production at the surface of the steel and continues with the reduction
of the cross section area of bars and consequently increasing in stress applied to concrete
structures [6, 7]. In addition, the integration of corrosion products at the surface of steel bars
causes volume expansion and concrete cracking. The mentioned factors cause the structure to
fail [8]. Corrosion inhibitors influence Cathodic/anodic reaction or both and since all these
reactions are in equilibrium together, reduction in either rate of them causes the corrosion rate
to decrease [9]. Calcium Nitrite and Sodium Molybdate as two anodic inhibitors were
investigated in this work.
2. Experimental procedures
Raw material and test matrix for preparing concrete specimen are listed in Table 1. Samples
prepared in three different molds, a couple was made without carbon steel bar for mechanical
testing and one with the steel bar in the middle of the mold for corrosion studies (Figure 1).
After cleaning with acid and rust removing from the carbon steel bar, a part of them were
painted as shown in figure 1 to prevent crevice corrosion which can make error in real
corrosion measuring. Table 2 shows the Portland cement component. Concrete specimens
pulled out from molds after 24 hours and located in fresh water for seven days, then
submerge into sea water. The immersion mode was done in wet and dry cycles (three days in
water and four days in a dry place). Corrosion cell includes Ag/AgCl reference electrode,
steel bar inside concrete as working electrode and 316L semicircle stainless steel plate with a
surface area of 1020 cm2 as counter electrode.
74 | P a g e
Fig.1: SEM image of schematic of concrete sample
To study the corrosion of embedded carbon steel bars, linear polarization and
electrochemical impedance curves were employed according to ASTM G102 and G3
standards, respectively. Zahner potentiostat Model IM6 was used for polarization curves. To
measure potential and electrical resistivity measurement a digital potentiometer (CANIN
model) and RESI equipment from Switzerland were applied, respectively. Since the concrete
is not carbonated, pH is assumed to be fixed. Wet and dry cycles applied simulate to the real
sea tide. The number of samples for each mix design were calculated and named based on the
number of experiments (Table 3).
Table1. The raw materials used in the presented mixture design

Cement Type
The amount of cement
(kg/m3)
Water/cement ratio
P
0.45
Sand or aggregate 0-8

mm (kg/m3)
Aggregate 8-16 mm
(kg/m3)
[NO 2 -/Cl-]
990
[MolybdateNitrite/Chloride]
[NO 2 -/MoO 2 -]
75 | P a g e
Portland type
II
350
RP
RP
750
RP
Table 2. Hormozgan cement composition type II
SiO 2
R
Al 2 O
R
Fe 2 O 3
CaO
MgO
SO 3
K2O
3.68
C3S
42.13
62.7
C2S
28.72
2.01
C3A
7.55
2.38
C 4 AF
11.2
0.86
C 4 AF+2C 3 A
26.75
21.1
Na 2 O
0.22
R
5.2
L.O.I
0.8
Table 3. Introducing the samples containing inhibitors and chloride ion [index x shows the time
(month)].
[Cl-/0H-]
Inhibitor
Sample
[N02- /MoO4-]
0.6
1
15
Ca(N0 2 ) 2
2
1
P
A 2x
---
---
---
B 2x
---
---
---
---
C 2x
---
---
---
---
A 3x
---
---
---
B 3x
---
---
---
C 3x
---
---
A 4x
---
---
---
B 4x
---
---
---
C 4x
---
---
---
---
---
3. Results and discussion

Figure 2 shows the cyclic polarization of steel bars without inhibitor and chloride ions. No
significant change in polarization curves is observed on the wet and dry cycles of reinforced
concrete by time. Nevertheless, the repassivation potential of sample A11 decreases from 800
mV to 300 mV for A13 after six months. The corrosion densities increased with time even in
the absence of chloride ion. It shows the electrical resistance of passive layer, formed on the
surface of steel bar, decreases even in the absence of chloride ion only by applying wet and
dry cycles.
76 | P a g e
Fig. 2. Cyclic polarization diagram of steel bars embedded in concrete without chloride ion and
inhibitor in different times.
Figure 3 and Figure 4 demonstrate the corrosion behavior of steel bars in concrete
containing chloride ion with [Cl-/OH-]=1 and [Cl-/OH-]=15, respectively. It is seen that the
pitting potential (E pit ) for samples including chloride ion, increases by time, so that anodic
potential is transected before approaching to E pit . Because it is not reaching the transpassive
area and polarization keeps going in reverse direction.
Figures.5, 6 and 7 show the Nyquist curves for steel bars embedded in the concrete without
inhibitor and chloride ion. It demonstrates an increase in the number of wet and dry cycles
makes the impedance curves smaller and reduces the resistance Rp, while raises the corrosion
rate. Its obvious that impedance and Rp for samples without chloride ion are considerably
more than samples with chloride ion which remarks less corrosion rate for them.
Table 4 represents the extracted values of Cdl, Rct and Rs via extra-polarization curve (Z
Z). According to Rct data, the maximum values belong to samples without chloride ion
and by the time its going to reduce that mark more corrosion. It could be deduced that Rct
values decreased due to increasing of chloride ion in samples including chloride ion with the
ratio of [Cl-/OH-]=1 and 15.
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Fig.3. Cyclic polarization diagram of steel bars embedded in concrete in the presence of chloride ion
with the value of [Cl-/OH-]=1 without inhibitor.
Fig.4. Cyclic polarization diagram of steel bars embedded in concrete in the presence of chloride ion
with the value of [Cl-/OH-]=15 without inhibitor.
Table 4. The parameter values of Rct, Rs, and Cdl extracted by extrapolation diagrams (ZZ).
78 | P a g e
Cdl(f/cm2)x (106)
76.5
94.5
145
1260
610
3000
580
3000
5690
Rct(ohm.cm2) Rs(ohm)
365740
142330
84610
14980
11400
3730
10730
2300
1940
6100
5250
5900
5830
6850
6980
4220
4830
5200
Name
A11
A12
A13
B11
B12
B13
C11
C12
C13
Typically the effect of increasing of chloride ion concentration on the impedance spectrum
of carbon steel appears as a reduction of the second arc that is created due to the destruction
of the passive layer. Several researchers stated when passive layer is not being damaged,
chloride ion is not consumed and the consequently corrosion rate would not decrease by time
[8].
The function of nitrite ion as anodic inhibitor in the forming/mending of passive layer on
the metal surface in solutions with pH higher than 4.5 is as below[8, 10]:
9Fe(OH) 2 +NO 2 -3Fe 3 O 4 +
(1)
NH 4 +
2OH-
6H 2 O
In addition another iron oxide with higher purity might form following reaction:
9Fe(OH) 2
+NO 2 -
3(Fe 2 O 3 )+NH 4 ++2OH-
+3H 2 O
(2)
As shown in Table 3, index number shows what inhibitors are used for samples. Samples
with index 2 just include Calcium Nitrite whereas samples with index 3 and 4 contain both
Nitrite and Molybdate with 1:2 and 1:1 ratio, respectively. In this study cyclic
potentiodynamic polarization, linear polarization and impedance spectrometry were hired to
evaluate the inhibitors electrochemical function.
79 | P a g e
Fig.5.Nyquist diagrams and circuits of the steel bars inside the concrete without chloride ion.
Figure 8 shows the cyclic polarization of concrete samples containing various levels of
chloride ion and Nitrite Calcium inhibitor. It is observed that the noticeable variation in these
diagrams happens in the repassivation potential and passive current densities. Moreover,
diagrams of samples with chloride ion and without inhibitor have transferred to the low
values of current densities after the presence of Nitrite ion. It shows the constructive effect of
Nitrite ion in the reduction of passive current density. Figures 9 and 10 are cyclic polarization
diagrams of samples include Nitrite and Molybdate together. The main contrast is in their
current densities. Overall, the third group samples (index 3) were inhibited better than others
with passive current density. More positive E corr values have shown better prohibition.
R
Research done about the role of Nitrite in the corrosion behavior of steel in aqueous
environment has shown protection by oxidizing Fe2+ (created from the corrosion process) to
P
Fe+3 and forming an insoluble ferric oxide on the metal surface while in pH<4.5 it
accelerates the corrosion instead of inhibition [11].As an anodic inhibitor, Molybdate, has
weak oxidizing properties and must be utilized with a strong oxidizer. Molybdate accelerates
the corrosion of steel in pH<6 as well. So its usage for protecting the steel specimens is just
limited to neutral and alkaline environments.
80 | P a g e
Figure 6- Nyquist diagrams and circuits of the steel bars embedded in the concrete with chloride ion
[Cl-/OH-] =1.
Figure 7- Nyquist diagrams and circuits of the steel bars embedded in the concrete with chloride ion
[Cl-/OH-] =15.
According to Figure 8, a noticeable difference in the repassivation potential and passive

current densities was detected. Specimens with chloride ion and without inhibitor have shown
a shift to the low values of current densities. Presence of Nitrite ion clearly shows the
constructive effect of Nitrite ion in the reduction of passive current density.
Figure 8- The cyclic polarization of concrete samples containing chloride ion in the present of
Calcium Nitrite.
81 | P a g e
Figure 9- The cyclic polarization of concrete samples containing chloride ion in the presence of
Calcium Nitrite and Molybdate with a ratio of [NO2-]/[MoO4-]=2.
Figure 10- The cyclic polarization of concrete samples containing chloride ion in the presence of
Calcium Nitrite and Molybdate with a ratio of [NO2-]/[MoO4-]=1.
Table 5. The obtained values of Rp from linear polarization of steel bars embedded in the concrete.
Sample
Rp :Polarization Resistance
(k.ohm.cm2)
X=1
X=2
X=3
First Week
8th
25thWeek
Week
A1
56.6
90
56.8
B1
14.4
21.8
14.2
C1
15
7.1
8.6
A2
27.1
51.8
24.6
B2
42
57.2
28
C2
12.9
51.4
24
A3
44.8
91.2
149.6
B3
48
85.1
121.1
C3
70.7
111
154.6
A4
21
111.5
92.5
B4
47.4
94.2
116.4
C4
92
84
112.2
82 | P a g e
Table 6. The obtained values of inhibitor efficiency from linear polarization of steel bars embedded in
the concrete.
Sample
Rp1
Rp2
Rp3
IE1%
IE2%
A2
37.1
51.8
34.6
61
57
B2
43
57.3
28
66
61
C2
12.9
51.4
24
12
57
A3
44.8
91.3
149.6
67
76
B3
48
85.1
131.1
70
74
C3
70.7
111
154.6
79
80
A4
31
111.5
92.5
53
80
B4
47.4
94.2
116.4
69
76
C4
92
84
113.3
84
74
Table 7. Evaluation of mechanical properties evaluation of concrete samples containing various

inhibitor components.
Compression
Inherent
Electrical
Density of
pH
strength of
permeability X
resistance
concrete
concrete
10-8 (m2)
(kohm.cm2)
(kg.cm3)
(kg/cm3)
non inhibitor
260
8.5
4.8
2151.3 12.8
2With [NO ]
257
8.4
4.1
2186.7 12.75
With [NO2268
7.4
4.6
2221.3 12.81
4/MoO ]=2
With [NO2263
7.6
4.4
2208.4 12.71
/MoO4-]=l
Table 8. Concretes classification based on the permeability [12]
Quality of
Cover concrete
Very bad
Bad
Normal
Good
Very good
-16
Index
kT(10 m )
5
4
3
2
1
10
1.0-10
0.1-1.0
0.01- 0.1
0.01
Form figures 9 and 10, it can be understood the third group samples (index 3) were
inhibited better than the others in terms of passive current density and more positive E corr
values.
Polarization resistance (Rp) values related to E-Logi curves of steel bars embedded in the
concrete after 1 week and 2 and 6 months are presented in Table.4. It is seen that generally
linear polarization resistance of samples containing Nitrite-Molybdate increases by time
whereas it decreases in the samples containing Calcium Nitrite. Also Rp for NitriteMolybdate with a ratio of [NO2-]/[MnO4-]=2 after 6 months exposing to wet and dry cycles
showed the highest value. Based on whatever mentioned above, it is found out Molybdate
83 | P a g e
particularly with the ratio of [NO2-]/[MnO4-]=2 applies a synergistic effect on Nitrite to

reduce the corrosion rate. The efficiency of various components of consuming inhibitors is
calculated by following equation[13], and presented in Table.6.
IE(Inhibitor Efficiency) =
(3)
RP R P
RP
100
Where R P and R P are the polarization resistance of concrete samples with and without
inhibitors, respectively.
Three concrete samples were prepared for the compression strength test. Table 7 shows the
triple average strength. All samples were chloride ion free, and according to the Table 7 were
compared with respect to the reference sample which was free of additives. Concrete
permeability will be highlighted when there are some aggressive factors such as chloride ion
and oxygen attack. The inherent permeability depends on the type of material and fluid (is
inversely proportional to the fluid viscosity) and its unit is square meter. A cubic sample with
the size of 101015 cm3 after 28 days curing and drying in the ambient environment was
chosen for permeability measurements (Fig. 11) that is taken from different components.
According to Table 7 the obtained values are more than 10-19. In comparison with presenting
data in Table 8 they are considered moderate from the inherent permeability viewpoint. As it
can be understood from Table 7, concrete inhibitor does not show significant changes in
concrete strength. Although, a mix combination of Calcium Nitrite and Sodium Molybdate
slightly increased concrete strength.
4. Conclusions
The following conclusions can be drawn from this research:
1.
Corrosion current density of steel rebar has increased in the present of chloride ion in
concrete. It means in samples containing chloride ion with a little more than critical limit,
passive layer probably has destroyed and the existence of chloride ion will not let passive
layer reform. Then corrosion rate was enhanced.
2.
The lower arc of Nyquest diagram of steel bars embedded in the concrete appears in
frequencies less than 1 KHz that might belong to the interface reactions that have been
formed from passive film formation and transfer reaction processes.
84 | P a g e
3.
The result shows that Calcium Nitrite has less inhibition in comparison to MolybdateNitrite and the efficiency decreases by the time. Among the two combinations of NitriteMolybdate the inhibition of ratio equal to 2:1 is the highest and the efficiency increases
by time.
4.
Adding Molybdate to the concrete component does not have a significant effect on the
mechanical properties of the concrete.
Acknowledgments
Facilities and funding for this study were provided by Kish University, Iran. Also authors
would like to thank Universiti Teknologi PETRONAS for supporting the research work.
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International Journal of Material Science Innovations (IJMSI) 1 (2): 73-86, 2013

Fig.1: SEM image of schematic of concrete sample

Table1. The raw materials used in the presented mixture design

Sand or aggregate 0-8

3. Results and discussion

3(Fe 2 O 3 )+NH 4 ++2OH-

According to Figure 8, a noticeable difference in the repassivation potential and passive

Table 7. Evaluation of mechanical properties evaluation of concrete samples containing various

particularly with the ratio of [NO2-]/[MnO4-]=2 applies a synergistic effect on Nitrite to

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