Corrosion Science 48 (2006) 1733–1745

www.elsevier.com/locate/corsci

Corrosion behavior of steel bar embedded

in fly ash concrete
Yoon-Seok Choi a, Jung-Gu Kim a,*
, Kwang-Myong Lee b

a
Department of Advanced Materials Engineering, Sungkyunkwan University, 300 Chunchun-Dong,
Jangan-Gu, Suwon 440-746, Republic of Korea
b
Department of Civil and Environmental Engineering, Sungkyunkwan University, 300 Chunchun-Dong,
Jangan-Gu, Suwon 440-746, Republic of Korea

Received 31 August 2004; accepted 23 May 2005

Available online 8 August 2005

Abstract

Steel bar embedded in concrete without fly ash and with fly ash was tested under complete
immersion, in 3.5 wt.% NaCl solution. Monitoring of open-circuit potential, polarization
resistance measurement and electrochemical impedance spectroscopy (EIS) were used to eval-
uate the corrosion behavior of steel bar. ASTM C1202 test method was also used to estimate
the concreteÕs resistance to the penetration of chloride ions. The results obtained from electro-
chemical tests show that partial replacement of fly ash has led to an enhancement of corrosion
resistance and a reduction of corrosion rate due to the decrease of permeability to chloride
ions.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Corrosion; Fly ash; Chloride ion; Permeability; EIS

*
Corresponding author. Tel.: +82 31 290 7360; fax: +82 31 290 7371.
E-mail address: kimjg@skku.ac.kr (J.-G. Kim).

0010-938X/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2005.05.019
1734 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745

1. Introduction

Steel bars embedded in concrete are protected from corrosion by a thin oxide
layer that is formed and maintained on their surfaces because of the highly alkaline
environment of the surrounding concrete (pH  13) [1]. In spite of the advantages of
reinforced concrete, corrosion of the steel bar remains its most common durability
problem [2]. The most important cause of corrosion initiation of steel bar is the in-
gress of chloride ions to the steel surface [3–6]. Corrosion of steel bar damages the
reinforced concrete structures in two ways. First, it reduces the cross-sectional area
of steel bar. Secondly, it produces corrosion products with a larger volume than the
steel itself. The volume increase induces the tensile stress in concrete, which results in
cracking and eventual structural failure [7].
Use of fly ash as a cement replacement material has become common practice in
recent years. Fly ash is used in concrete for several economical and environmental
reasons. Moreover, the fly ash particles react with calcium hydroxide, producing
hydration products that strongly decrease concrete porosity [8]. Fly ash is used as
fine granulates and upon hydration it has the capability of partially obstructing voids
and pores. This leads to a decrease of pore size and to a smaller effective diffusivity
for either chloride or other species [9]. It is thought that these effects lead to an in-
crease of the concrete resistivity. In addition, the chloride diffusion coefficient de-
creases with decreasing W/B ratio [10].
The objective of this work is to investigate the effect of fly ash embedded in con-
crete with various water-to-binder (W/B) ratios on the corrosion behavior of steel
bar, exposed to 3.5 wt.% NaCl solution. Open-circuit potential (OCP) monitoring
and electrochemical impedance spectroscopy were applied to evaluate the corrosion
process. Also, ASTM C1202 test method was used to estimate the concreteÕs resis-
tance of chloride penetration in concrete.

2. Experimental methods

2.1. Materials and mix proportions of concrete

Type I Portland cement and low calcium fly ash were used as cementitious mate-
rials. The physical properties and chemical compositions of the materials are shown
in Table 1. Washed river sand and crushed granite were used as fine and coarse

Table 1
Physical properties and chemical compositions of cement and fly ash
Material Physical property Chemical composition, %
Specific Blaine SiO2 Al2O3 Fe2O3 CaO MgO SO3 LOI
gravity (cm2/g)
Cement 3.15 3.450 20.68 5.16 3.02 62.42 4.71 2.42 1.36
Fly ash 2.27 3.375 56.69 21.17 6.01 6.68 1.41 0.11 3.44
Note: LOI = loss on ignition.
 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745 1735

Table 2
Mix proportion of concrete (kg/m3)
Concrete type Water Cement Fly ash Fine aggregate Coarse aggregate W/B
OPC-0.50 185 370 – 754 969 0.5
FA20-0.50 185 296 74 744 956 0.5
OPC-0.35 158 450 – 672 1061 0.35
FA20-0.35 158 360 90 661 1043 0.35
OPC-0.31 155 500 – 626 1074 0.31
FA20-0.31 155 400 100 614 1054 0.31

aggregate, respectively. The fine and coarse aggregates had specific gravities of 2.51
and 2.64 and water absorption of 1.52% and 0.54%, respectively. The maximum size
of coarse aggregates was 20 mm in diameter.
The mix proportion of the tested concretes is shown in Table 2. The 28-day target
compressive strengths of ordinary Portland cement (OPC) concretes were 30, 45 and
55 MPa, and the corresponding water/binder ratio (W/B) were 0.50, 0.35 and 0.31,
respectively. Concrete mixes with fly ash content of 20% by weight of cementitious
materials were designated as FA20, whereas concrete without fly ash was designated
as OPC.
An air-entraining water reducer (AEWR), as much as 0.5% weight of cementi-
tious materials, was incorporated into concrete mix with W/B of 0.50, and a naph-
thalene sulfonate-based high range water reducer (HRWR) with solid content of
40% was used to improve the workability for concrete mix with W/B of 0.35 and
0.31.

2.2. Specimen preparation

Cylindrical concrete specimen is shown in Fig. 1. Steel bars with 12.7 mm dia-
meter, previously polished with a 600 grit SiC emery paper, were centered in the cyl-
inder, with a cover thickness of 21.5 mm. The chemical composition of the steel bar
is listed in Table 3. As illustrated in Fig. 1, in order to control the exposed area of

epoxy coated steel

Φ12 mm steel bar
concrete unpainted steel

150 mm 50 mm 55 mm

240 mm

Fig. 1. Schematic of cylindrical concrete specimen.

1736 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745

Table 3
Chemical composition of steel bar
Designation Composition (wt.%)
C Si Mn P S Fe
KS D3504 0.22 0.14 0.59 0.02 0.025 Bal.

steel, the steel bars were partially coated with Amercoat 90 epoxy paint, leaving an
exposed area of 57.68 cm2.
Concrete cylinders, B100 · 200 mm, were also prepared to measure compressive
strength of concrete; the cylinder molds were removed at 24 h after casting and cured
in a water bath of 20 C until testing.

2.3. Electrochemical measurements

Electrochemical tests of the concrete specimens were accomplished with an EG&G

Model 273A Potentiostat. A conventional three-electrode cell was used with a counter
electrode made of graphite and a saturated calomel electrode (SCE) as a reference elec-

Potentio stat

C W R

Reference
electrode
Counter
electrode

230 mm

Plastic tank

3.5 wt.% NaCl

solution

Fig. 2. Experimental setup for electrochemical measurements.

 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745 1737

trode. All electrochemical tests were conducted under complete immersion in 3.5 wt.%
NaCl solution. Fig. 2 is a schematic representation of the test setup. Open-circuit po-
tential (OCP) monitoring, and electrochemical impedance spectroscopy (EIS) were
used to evaluate the corrosion behavior. EIS measurements were conducted in the fre-
quency range between 100 kHz and 10 mHz. Sinusoidal voltage of ±10 mV was sup-
plied, and direct current (DC) potential was set to the corrosion potential.

2.4. Chloride ion penetration measurement

Chloride ion penetration test was carried out following ASTM C1202-91 [11]. The
concrete specimen (B100 · 50 mm) was inserted and the two halves of the test cell
were clamped together to seal. One side of the cell was filled with 3.5% NaCl solution
and the other side with 0.3 N NaOH solution containing the top surface of the speci-
men. DC 60 V was applied during 6 h and the current was recorded every 30 min for
the calculation of the total charge passed.

2.5. Surface analysis

After the completion of immersion tests, concrete specimens were broken and the
surface of steel bar was examined by scanning electron microscopy (SEM).

3. Results and discussion

3.1. Properties of fresh and hardened concrete

Initial slump, air content and compressive strength at the age of 7, 28, 90,
180 days were shown in Table 4. The slump of all concretes was greater than
19 cm, and air content varied from 2.1% to 5.0%. Compressive strengths of three
types of OPC concretes at 28 days were 31.1, 47.1 and 55.5 MPa, respectively. At
the early age, the compressive strength of FA20 concretes was lower than that of
OPC concretes with the same W/B ratio, however, its strength was comparable to
OPC concrete after 28 days.

Table 4
Properties of concrete
Concrete type Slump Air content Compressive strength (MPa)
(cm) (%) 7 days 28 days 90 days 180 days
OPC-0.50 19.0 5.0 25.3 31.1 38.0 40.7
FA20-0.50 19.0 4.7 20.7 29.3 39.5 41.8
OPC-0.35 21.0 4.8 43.0 47.1 49.8 56.7
FA20-0.35 23.5 3.3 37.4 45.9 52.3 56.9
OPC-0.31 22.5 2.4 49.4 55.5 60.7 63.1
FA20-0.31 24.5 2.1 40.7 52.6 59.7 64.8
1738 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745

3.2. Open-circuit potential monitoring

The potential evolution for the steel embedded in concrete is presented in Fig. 3.
The readings were ranging from 250 to 150 mVSCE until 10 days after immersion,
corresponding to a state of passivity based on the Pourbaix diagram [12]. After
30 days of immersion, large fluctuations between 400 and 600 mVSCE were
found. Until after about 90 days, more stable potential readings were registered.
Those readings were in the range of 450 to 550 mVSCE. Moreover, open-circuit
potential evolutions of concrete specimens with fly ash were more constant than
those of concrete specimens without fly ash.
According to ASTM C 876, if the potential of steel in concrete becomes more neg-
ative than 273 mVSCE, there is a 90% probability that corrosion will occur [13].
After 30 days, the potential of all the specimens became more negative than
273 mVSCE and fluctuated. Therefore, potential readings are not sufficient to eval-
uate the effect of fly ash, since they are affected by a factor, which includes polariza-
tion by limited diffusion of oxygen [14].

3.3. Electrochemical impedance spectroscopy (EIS)

Fig. 4 illustrates Nyquist plots of concrete specimens for impedance results after
28 days of immersion. At this stage corrosion resistance was independent of the pres-
ence of fly ash and W/B ratio. At lower frequencies a capacitive behavior was ob-
served indicating a situation of passivity for all the specimens. In the case of
passive stage, an equivalent circuit shown in Fig. 5 was applied to model the EIS
data [15,16]. The equivalent circuit consists of the following elements: a series resis-
tance (Rs) accounts for the ionic conduction in the electrolyte filling the pores, a con-
stant phase element (CPE) and a charge transfer resistance (Rct). The CPEs are
widely used in data fitting to allow for depressed semicircles. Generally, the de-
pressed semicircle is due to the heterogeneity of the alloy microstructure that

OPC-0.50 FA20-0.50
OPC-0.35 FA20-0.35
-200 -200
Potential (mV vs. SCE)

Potential (mV vs. SCE)

OPC-0.31 FA20-0.31

-273mVSCE -273mVSCE

-400 -400

-600 -600

0 50 100 150 200 250 0 50 100 150 200 250

a Immersion time (day) b Immersion time (day)

Fig. 3. Open-circuit potential evolution of concrete specimens immersed in a 3.5 wt.% NaCl solution:
(a) without fly ash, (b) with fly ash.
 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745 1739

4500

4000
b d
3500
c
3000 f

2500
z'' (ohm-cm )

e
2

a
2000

1500

1000

500

-500
0 200 400 600 800 1000 1200 1400 1600 1800 2000
2
z' (ohm-cm )

Fig. 4. Impedance spectra in Nyquist plot of specimens after 28 days immersion in 3.5 wt.% NaCl
solution: (a) OPC-0.50, (b) FA20-0.50, (c) OPC-0.35, (d) FA20-0.35, (e) OPC-0.31, (f) FA20-0.31.

CPE

Rs

R ct
Fig. 5. Equivalent circuit for passive steel in concrete.

promotes a surface with a certain degree of microscopic roughness or due to param-

eters distribution [17–19]. The impedance of CPE is given by
n
Z CPE ¼ Z 0 ðjxÞ ð1Þ
where Z0 is the adjustable parameter used in the nonlinear least squares fitting and
the factor n, defined as a CPE power, is the adjustable parameter that always lies be-
tween 0.5 and 1. When n = 1, the CPE describes an ideal capacitor [20]. In this sit-
uation the charge transfer resistance, obtained from fitting, is very high (>108 X cm2)
and could not be measured in the range of frequency tested.
The impedance spectra after 140 days of immersion are shown in Fig. 6. The sam-
ples of OPC-0.31 and FA20-0.31 still revealed a passive state. In contrast, the other
samples showed an active corrosion behavior with decreasing in diameter of the arc.
In these cases, the equivalent circuit shown in Fig. 7 was applied to fit the EIS data
1740 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745

4500

4000

3500

3000 e
2500
z'' (ohm-cm )
2

2000 f
c
1500

1000
d
500 a
b
0

-500
0 200 400 600 800 1000 1200 1400 1600 1800 2000
2
z' (ohm-cm )

Fig. 6. Impedance spectra in Nyquist plot of specimens after 140 days immersion in 3.5 wt.% NaCl
solution: (a) OPC-0.50, (b) FA20-0.50, (c) OPC-0.35, (d) FA20-0.35, (e) OPC-0.31, (f) FA20-0.31.

CPE1 CPE2

Rs
R HF R ct
Fig. 7. Equivalent circuit for pitting corrosion of steel in concrete.

[21–24]. This equivalent circuit includes the series resistance (Rs), discussed above,
the constant phase element (CPE2) and the charge transfer resistance (Rct), which
accounts for the dissolution processes at the steel/concrete interface. A parallel cir-
cuit (RHF, CPE1) was introduced to simulate high frequency loops that may be asso-
ciated with the dielectric properties of concrete. This high frequency process had a
CPE1 in the range of 4.1 · 106–5.1 · 105 F/cm2. The optimized values for the var-
ious parameters are given in Table 5 for specimens, respectively. The samples with fly
ash (FA20-0.50, FA20-0.35, FA20-0.31) showed higher resistance values than the
samples without fly ash (OPC-0.50, OPC-0.35, OPC-0.31). This indicated that a sub-
stitution of fly ash increased corrosion resistance of steel in concrete. For the con-
crete specimens with W/B ratio of 0.31, however, regardless of presence or
absence of fly ash, the charge transfer resistance is very high (>108 X cm2) due to
the passivation.
 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745 1741

Table 5
Electrochemical parameters obtained by equivalent circuit simulation
Immersion Mix type Rs CPE1 RHF CPE2 Rct
time (day) (X cm2) (·106 F/cm2) (X cm2) (·106 F/cm2) (X cm2)
140 OPC-0.50 4172.1 51.3 1154.8 71.21 82,953.3
FA20-0.50 6465.9 6.6 8340.5 84.9 84,789.6
OPC-0.35 7261.9 7.5 6339 74.7 438,829.4
FA20-0.35 10,162.3 4.1 20,127.2 79.8 650,917.7
OPC-0.31 7942.53 5.8 22,206.8 38.83 >108
FA20-0.31 17,926.94 14.9 35,876.9 74.54 >108
250 OPC-0.50 3934.7 55.3 1482.1 80.6 48,165.1
FA20-0.50 7210.8 9.0 15,400.5 107.2 60,794.7
OPC-0.35 11,022.6 9.7 6431.3 108.6 90,961.3
FA20-0.35 13,542.6 2.7 26,193.1 100.6 374,887.7
OPC-0.31 9188.4 4.5 38,818.6 33.9 >108
FA20-0.31 17,177.1 20.8 43,762.3 52.03 >108

The impedance spectra after 250 days of immersion are shown in Fig. 8. The sam-
ples of OPC-0.31 and FA20-0.31 still maintained a passivation. However, the active
corrosion process was accelerated for the other samples with decreasing in diameter
of the arc. The simulated values using the equivalent circuit (Fig. 7) for the relevant
parameters are also given in Table 5 for specimens. Although the values of Rct
decreased with increasing time, the samples with fly ash still maintained higher

4500
e
4000 d
500 c
3500
z'' (ohm)

b
3000
a f
e
2500
z'' (ohm-cm )
2

2000 0

0 200 400 600 800 1000 1200

1500 z' (ohm)
f
1000

500

-500
0 200 400 600 800 1000 1200 1400 1600 1800 2000
2
z' (ohm-cm )
Fig. 8. Impedance spectra in Nyquist plot of specimens after 250 days immersion in 3.5 wt.% NaCl
solution: (a) OPC-0.50, (b) FA20-0.50, (c) OPC-0.35, (d) FA20-0.35, (e) OPC-0.31, (f) FA20-0.31.
1742 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745

60000
140 days
250 days
Concrete resistance (ohm-cm2)
50000

40000

30000

20000

10000

0
OPC-0.50 FA20-0.50 OPC-0.35 FA20-0.35 OPC-0.31 FA20-0.31
Specimen

Fig. 9. Concrete resistance with time calculated from the simulation of the high frequency response of the
spectra at 140 days and 250 days.

resistance values than the samples without fly ash. In other words, the concretes with-
out fly ash absorb more water and ions because the more number and size of the surface
defects of concrete induce higher CPE1. These are corresponded to SEM images as the
concretes without fly ash produce more attack than those with fly ash.
The evolution of the concrete resistance with time shown in Fig. 9 is an important
parameter in understanding the behavior of the specimen. This resistance (Rs + RHF)
was calculated from the simulation of the high frequency response of the spectra [25].
The concrete resistance for all specimens increases between 140 and 250 days. Espe-
cially, FA20-0.35 and FA20-0.50 concretes indicated higher rate of increase in con-
crete resistance than OPC-0.35 and OPC-0.50 concretes between 140 and 250 days.

6000 OPC-0.50 6000 FA20-0.50

Total Charge Passed (C)

Total Charge Passed (C)

OPC-0.35 FA20-0.35
OPC-0.31 FA20-0.31
5000 5000

4000 4000

3000 3000

2000 2000

1000 1000

0 0
28 90 180 250 28 90 180 250
a Age (day) b Age (day)

Fig. 10. Total charge passed of concretes with age: (a) without fly ash, (b) with fly ash.
 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745 1743

For the concrete specimens with W/B ratio of 0.31, however, regardless of presence
or absence of fly ash, the charge transfer resistance was still high. Therefore, it is con-
cluded that the use of fly ash has beneficial effects on corrosion resistance of steel in
concrete, for the concrete specimens with W/B ratios of 0.5 and 0.35.

Fig. 11. SEM micrographs after 250 days immersion: (a) OPC-0.50, (b) FA20-0.50, (c) OPC-0.35,
(d) FA20-0.35, (e) OPC-0.31, (f) FA20-0.31.
1744 Y.-S. Choi et al. / Corrosion Science 48 (2006) 1733–1745

3.4. Chloride ion penetration measurements

Fig. 10 shows the chloride ion penetration test results. The values of total charge
passed represent the penetrability of aggressive ions into concrete. The higher the to-
tal charge passed, the lower the resistance for chloride ion intrusion.
At the same age, total charges of both OPC and FA20 concrete specimens de-
crease with the decrease of W/B ratio. In the case of FA20 concretes, the values de-
crease remarkably comparing with OPC concretes with the same W/B ratio after
28 days.

3.5. Surface analyses

Fig. 11 shows the scanning electron micrographs after 250 days of immersion in
3.5 wt.% NaCl solution. Many pits were formed on OPC-0.50 concrete, and the
number of pits were reduced for FA20-0.50, OPC-0.35 and FA20-0.35 concretes,
and few pits were found on OPC-0.31 and FA20-0.31 concretes. The size and the
number of pits decreased with decreasing W/B ratio, and steel embedded in fly
ash concretes behaved better than the steel embedded in OPC concretes. This result
especially corresponds to the results of EIS measurement.

4. Conclusions

The investigation of corrosion of steel embedded in concrete shows the following

results:

(1) Open-circuit potential evolutions of concrete specimens with fly ash were more
constant than those of concrete specimens without fly ash.
(2) The use of fly ash led to increase the charge transfer resistance which is well
correlated with lower corrosion rate and the small number and size of pits.
(3) Corrosion resistance increased with decreasing water-to-binder ratios. Further-
more, the use of fly ash had beneficial effects on corrosion resistance of steel in
concrete due to the decreased permeability of chloride ions.

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