Construction and Building Materials 221 (2019) 232–243

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Construction and Building Materials

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Enhanced seawater corrosion resistance of reinforcement in nanophase

modified fly ash concrete
Sudha Uthaman a, R.P. George b,⇑, Vinita Vishwakarma a, Manu Harilal b,c, John Philip b,c
a
Centre for Nanoscience and Nanotechnology, Sathyabama Institute of Science & Technology, Chennai 600 119, India
b
Corrosion Science and Technology Division, IGCAR, Kalpakkam 603 102, India
c
Homi Bhabha National Institute, Mumbai 400 094, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Corrosion resistance of reinforcement

by nanophase modification of fly ash
concrete.

Nano-CaCO3 particles prevented
leakage of chloride ions to the rebar.

Nano-CaCO3 modified fly ash
exhibited the most noble OCP, LPR
and corrosion rate.

Particle size analysis confirmed lesser
agglomeration of nano-CaCO3.

Natural electrochemical results
complemented accelerated corrosion
test results.

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

Article history: This paper presents a method for enhancing the corrosion resistance of reinforcements through nano-
Received 6 January 2019 phase modification of fly ash concrete. A combination of natural and accelerated corrosion tests were per-
Received in revised form 4 June 2019 formed to evaluate the corrosion resistance of reinforcements. The tests were conducted on four types of
Accepted 7 June 2019
fly ash concrete specimens with and without nanoparticles designated as fly ash concrete with 40 wt% fly
ash (FA), fly ash concrete with 2 wt% nano-CaCO3 (FAC), fly ash concrete with 2 wt% nano-TiO2 (FAT) and
fly ash concrete with 1 wt% nano-CaCO3 and 1 wt% nano-TiO2 (FATC). Electrochemical measurements
Keywords:
showed that reinforcements in nano-CaCO3 modified fly ash concrete (FAC) exhibited noble potential
Fly ash
Nanophase modification
value, high polarization resistance and lower corrosion rate. Impressed voltage test also corroborate
Reinforcement the enhanced corrosion resistance of FAC specimens, which was evident from the longer crack initiation
Corrosion resistance time with minimum anodic current as compared to fly ash concrete without nano additives. Corrosion
Impressed voltage test products of cover concrete showed a comparatively lesser amount of detrimental phases like lepi-
docrocite and goethite which was in agreement with the corrosion results. The least depth of chloride
ion penetration indicated the effective plugging of pores by nano-CaCO3 particles that prevent diffusion
and movement of chloride ions to surface of the rebar and thereby maintaining the passivity of the thin
iron oxide layer around the steel rebar.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
The corrosion of steel rebar reduces the life expectancy and
structural stability of concrete structures. The thin iron oxide layer
⇑ Corresponding author. Tel.: +91 44 27480121; fax: +91 44 27480121.
E-mail address: rani@igcar.gov.in (R.P. George).
formed over the surface of the steel rebar makes it passive and
stable in highly alkaline environments (pH 11–13) [1]. The corro-
sion process involves the disintegration of the protective passive
layer and an expansion in the cross-section of the reinforced steel
due to the formation of high volume corrosion products [2]. The
utilization of mineral admixtures like fly ash, blast furnace slag
and silica fume in concrete is found to improve its properties and

https://doi.org/10.1016/j.conbuildmat.2019.06.070
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243
resistance against corrosion [3–5]. When the concrete structures
are submerged in marine environments, chloride ions permeate
through the pores, causing localized corrosion and premature fail-
ure of structures [6,7]. Studies conducted with 10–50 wt% partial
replacement of cement with fly ash, showed an enhanced corrosion
resistance and a drastic decrease in chloride permeability com-
pared to ordinary Portland cement (OPC) concrete [8–10].
The spherical shaped fly ash particles react with calcium
hydroxide ((Ca(OH)2) and form calcium silicate hydrate (CASAH)
that drastically decreases the concrete porosity, thereby, making
the concrete structures less permeable to aggressive chemicals
[11]. Fly ash modified concrete is reported to have closed voids
and pores, thereby reducing the diffusibility of truculent chemicals
[12]. Further, they also exhibit superior properties with respect to
strength and durability.
One of the drawbacks associated with fly ash concrete is early
age performance as a result of its slow hydration [13]. Since poz-
zolanic reaction is a slow process, fly ash contributes to the devel-
opment of strength in concrete only at a later age [14,15]. Fly ash
concrete is also reported to undergo carbonation at significantly
faster rates than concrete without fly ash [16]. A holistic study
by Ramachandran et al. [17] on fly ash concrete revealed some
other drawbacks of fly ash like low early-age strength, delayed set-
ting and higher carbonation depth.
Nanoparticles are incorporated in fly ash concrete to overcome
the low-early-age strength and delayed setting problems associ-
ated with fly ash [18]. It is also reported that nano-additives can
reduce reinforcement corrosion in concrete [19]. Enhanced corro-
sion resistance, durability and antibacterial activity was also
observed in nanophase modified fly ash concrete exposed to mar-
ine environment [20].
In general, nanoparticles act as fillers and densify the
microstructure of concrete. Further, they can also form heteroge-
neous nuclei for accelerating cement hydration, contributing to a
reduction in porosity [21]. The combination of fly ash and nano
materials can produce tightly bonded hydration products, which
can accelerate the pozzolanic reaction and compensate for the
increased early strength development [18]. The addition of TiO2
nanoparticles in cement is increases the heat of hydration, acceler-
ates the rate of reaction at early stages of hydration and enhances
the antimicrobial activity when the concrete structures are
exposed to marine environments [22]. Initially, CaCO3 nanoparti-
cles were considered only as fillers to replace OPC, but subsequent
studies showed positive benefits such as improved strength and
acceleration of hydration rate with incorporation of nano-CaCO3
[23]. Compare to other nano additives, lower concentrations of
nano CaCO3 can provide denser microstructure and formation of
hydration products contributing to the early age strength and
durability [24]. The addition of nano-TiO2 offers benefits in terms
of antimicrobial activity in a marine atmosphere. This is the ratio-
nale for choosing TiO2 and CaCO3 nanoparticles as additives in the
present study.
The main objective of this study was to evaluate the synergis-
tic effect, if any, of fly ash and nanoparticles on the corrosion
resistance of steel rebars in fly ash modified concrete specimens.
A combination of natural electrochemical techniques along with
accelerated corrosion test by impressed current method was
used to evaluate the corrosion resistance of reinforcements.
The depth of chloride ion penetration was also measured to
determine the extent of chloride permeability. Corrosion param-
eters of the concrete specimens were continuously monitored
using open circuit potential (OCP) and linear polarization resis-
tance (LPR) measurements and the post exposure characteriza-
tions of the concrete extracts near the corroded rebar was
carried out to evaluate the changes in pH, morphology and
chemical composition.
233
2. Experimental methods
2.1. Materials
The test specimens for the present study was fabricated using
commercial OPC (43 Grade) conforming to IS 8112-2013 [25] and
class-F fly ash procured from a thermal power plant (Ennore, Tamil
Nadu). The physical properties and chemical composition of these
materials are listed in Table 1. Crushed hard blue granite rocks
with a maximum size of 20 mm and 12 mm in compliance with
the requirements of IS 383-1970 was used as the coarse aggregates
[26]. Washed river sand (river bed, Palar) with a maximum size of
4.75 mm was used as the fine aggregates. The coarse and fine
aggregates had specific gravities of 2.72 and 2.64, respectively.
Supaplast HP (SP-430, M/s. Fosroc Chemicals Ltd., India), a high
range water reducer cum retarding plasticizer having sulphonated
naphthalene formaldehyde as a base conforming to ASTM C-494
type G [27] was used as the admixture. The commercial grade
titanium-di-oxide (TiO2), (anatase) and calcium carbonate (CaCO3)
were purchased and finely powdered using a ball mill (SPEX
8000M-230 dual mixer mill, 230 V/50 Hz) to reduce the size to
the range of 50–80 nm [20,28].
2.2. Mix design and proportioning
Four different types of concrete specimens were fabricated and
designated as fly ash concrete with 40 wt% replacement of OPC
(FA), FA admixed with 2 wt% nano-TiO2 (FAT), FA admixed with
2 wt% nano-CaCO3 (FAC) and FA admixed with 1 wt% nano-TiO2
and 1 wt% nano-CaCO3 (FATC). The total content of the cementi-
tious materials such as cement, fly ash and nanoparticles for all
mixes was 375 kg/m3. The water to cement (w/c) ratio was 0.44,
fly ash content was 150 kg/m3, fine aggregate 784 kg/m3, coarse
aggregate 1130 kg/ m3 and chemical admixture was 4.5 kg/ m3.
The detailed mix design used in the casting of concrete specimens
is given in Table 2.
2.3. Particle size analysis of nanoparticles
TiO2 and CaCO3 nanoparticles suspension of different concen-
trations (1% and 2%) used for concrete fabrication was imaged
using an electrochemical atomic force microscope (EC-AFM, M/s.
NT-MDT Solver ProEC, Russia) and the mean particle size was
obtained. At higher concentrations, nanoparticles have a tendency
to agglomerate and hence exhibit higher particle size [29,30].
Agglomeration can reduce the capacity of nanoparticles to act as
effective fillers in concrete.
2.4. Specimen preparation and exposure details
Cylindrical concrete specimens of 150 mm diameter and
300 mm height embedded with thermo mechanically treated
(TMT) rebars of 10 mm diameter and 325 mm length were cast
and cured for 28 days in fresh water. The chemical composition
of the steel bar is listed in Table 3. The schematic diagram of the
cylindrical concrete specimens used for the electrochemical mea-
surements is shown in Fig. 1a. Two steel bars were placed at a dis-
tance of 35 mm from the edge and the distance between the rods
was 60 mm. A small area of the steel rebar at the interface of con-
crete and air (20 mm at the top and 15 mm at the bottom) was
given an epoxy adhesive coating to avoid the localized attack due
to differential aeration. Electrical connections were provided
through copper wires which were fixed to the top uncoated end
of the rebar by brazing. Thus, two rebars with an exposed area of
270 mm length were used with one of the steel bar acting as a
234 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243

Table 1
Physical properties and Chemical composition of cement and fly ash.

Materials Physical properties Chemical composition (%)

2
Specific gravity Fineness (cm /g) LOI SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O
Cement 3.09 2602 3.26 19.28 6.32 3.83 61.9 1.01 2.70 0.60 0.50
Fly ash 2.24 4527 1.00 59.44 33.53 2.87 Traces 1.01 0.42 0.40 1.10

Note: LOI = Loss on ignition.

Table 2
Mix proportions of concrete specimens (kg/m3).

Specimen Cement Fly ash Fine aggregate Coarse aggregate Admixture Water Nano-TiO2 Nano-CaCO3
designation (kg/m3) (kg/m3) (kg/m3) (kg/m3) (kg/m3) (kg/m3) (kg/m3) (kg/m3)
FA 225.0 150 784 1130 4.5 165 – –
FAT 220.5 150 784 1130 4.8 165 4.5 –
FAC 220.5 150 784 1130 4.8 165 – 4.5
FATC 220.5 150 784 1130 4.8 165 2.25 2.25

Table 3 Rebars having a length of 10 cm and 10 mm dia. was embedded

Chemical composition of TMT steel rebar used. at 30 mm cover. Mortar specimens of size 100  100  100 mm
Element Concentration (%) were also cast for the measurement of chloride ion penetration
Carbon 0.10 ± 0.01
depth.
Phosphorous 0.022 ± 0.005 The schematic of the experimental set up used for exposing the
Sulphur 0.035 ± 0.005 concrete specimens is given in Fig. 1b. The concrete specimens
Sulphur + Phosphorus 0.070 ± 0.005 were placed inside a non-conductive plastic tank filled up to a
Carbon Equivalent 0.26 ± 0.005
height of 285 mm with seawater taken from the Kalpakkam Coast,
India and exposed for a period of four months. The water level was
kept constant throughout the study by weekly replenishment.
working electrode (WE) and the other as counter electrode (CE). A
silver-silver chloride (Ag/AgCl) electrode was used as the reference 2.5. Electrochemical measurements
electrode (RE).
The accelerated corrosion measurements were performed on The OCP measurements on the rebars embedded inside con-
cylindrical concrete specimens of 70 mm diameter and 110 mm crete specimens were carried out at 25 °C using an ACM Galvo Gill
height cast using the mix proportion of cement, sand and aggre- electrochemical workstation (Gill 12, M/s. ACM Instruments, UK)
gates as 1:2.11: 3.13 with a water/cement (w/c) ratio of 0.44. as per ASTM C311-05 [31]. The typical three electrode system

Fig. 1. (a) Schematic representation of the concrete specimen embedded with TMT rebars (b) schematic representation of concrete specimens immersed in seawater under
laboratory conditions. Note: Fig. 1(b). The distance between reference electrode and test specimens were maintained same during testing of all specimens.
 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243
[32] was used for the measurements where, a saturated Ag/AgCl
electrode was used as the reference electrode and the working
and counter electrodes were the TMT rebars embedded in the spec-
imen. The OCP measurements were carried out weekly for 1 h.
The LPR technique is generally used to determine the corrosion
rate of the reinforcement embedded in concrete specimen. The
specimens were subjected to LPR test with DC current and poten-
tial sweep range from 10 mV to +10 mV [33] with respect to the
corrosion potential found from OCP test at a sweep rate of
10 mV min1. Polarization resistance of the steel was then calcu-
lated by dividing the applied potential with the induced current.
The current density (icorr) was calculated from the polarization
resistance and the Stern-Geary equation [34].
B 25 mm cover both at the top and bottom. In order to get conductiv-
icorr ¼
Rp
where, Rp is the polarization resistance and B is the Stern-Geary
constant. The value of B is usually assumed to be in the range of
26 mV–52 mV [35]. In the present study, the value of 26 mV was
adopted for B with the maximum error in the measurement a factor
of 2 [36].
The corrosion rates of the four different types of concrete spec-
imens were determined in terms of corrosion current density
according to ASTM G102 – 89 [37] and represented in mm/year.
icorr
C:R ¼ K 1 EW
q per ASTM-C876 [40]. The experiment was performed on duplicate
where, C.R represents the corrosion rate in mm/yr, icorr is the corro-
sion current density in mA/cm2, K1 = 3.27  103 mm g/mA cm y, q is
the density of the steel in g/cm3 and EW is the equivalent weight of
the metal in g.
2.6. Post exposure studies
On completion of electrochemical experiments, the concrete
specimens were cut open and the rods were visually examined.
The photographs of the steel rebars embedded inside different con-
crete specimens were taken using a high resolution DSLR camera.
Concrete samples were extracted from the near vicinity of the
rebar from all the four test specimens for pH measurement, scan-
ning electron microscopy (SEM) analysis, X-ray diffraction (XRD)
and Fourier transmittance infra-red (FTIR) spectroscopy measure-
ments. The test method proposed by Ha et al. [38] was followed
to measure the pH. The extracts were powdered and then passed
through a sieve of 80 mm to obtain very finely ground particles.
5 g of this well-grounded powder was then mixed with 50 ml of
double distilled water. The solution was then placed in a beaker
and stirred properly using a magnetic stirrer. After 1 h, the solution
was filtered and pH of the filtrate was measured using a flat surface
electrode pH meter (HI 98191, M/s. HANNA Instruments, USA).
Four readings were noted for each concrete system and the average
pH value was recorded. The gold coated concrete extract specimen
was examined for detailed morphological changes using Desktop
mini SEM (Nano Eye, SEN-3000M, Korea) [39].
The pulverized concrete extract specimens were analyzed by X-
ray Diffraction technique to understand the phases evolved after
exposure in seawater. The XRD analysis was done using an X-ray
diffractometer (Inel make, Equinox-2000, France) with a X-ray
source of Co-Ka radiation (k = 1.789 Å) over a 2h range of 10–80°.
The phases were identified using the standard database (JCPDS
database) after obtaining the diffraction spectra.
The powdered concrete extracts were mixed with IR grade KBr
(Merck, Germany) and made into a uniform mixture using a mortar
and pestle. This mixture was pelletized using a hydraulic pelletizer
connected with a mechanical pump. The pellet was placed in the
235
FTIR sample holder to record the spectra for analysis. A Fourier-
transform infrared spectrometer (M/s. Bruker, Germany) was used
to collect the spectra in the range of 500–4000 cm1.
2.7. Accelerated Corrosion Test (ACT)
The primary objective of accelerated corrosion or impressed
voltage test is to understand the reinforcement corrosion and its
effects within a realistic time-scale under accelerated conditions.
ACT method is used frequently to reduce the time taken for a crit-
ical level of chlorides to reach the surface of the reinforcement. Ini-
tial weights of the rebars were recorded before embedding inside
the specimen. The rebars were embedded vertically with a
ð1Þ ity for the electrochemical measurement, copper wire was brazed
at one end of the rebar and that was sealed using insulation tape.
Measurement was carried out over an exposed length of 8 cm
and the remaining area was sealed. The steel rod embedded into
concrete acts as the anode, a stainless steel mesh acts as the cath-
ode and Ag/AgCl electrode was used as the reference electrode. The
corrosion behaviour of the rebar embedded inside the concrete
specimens was determined by conducting the accelerated corro-
sion test in 5% NaCl solution. A constant DC voltage of 12 mV
was applied between the electrodes. The time taken for the obser-
vation of the first crack in the specimen was noted and the corre-
sponding anodic current was recorded. This test was carried out as
ð2Þ
specimens and the average values are reported.
2.8. Chloride ion penetration test
The ability of the mortar specimens admixed with nanoparticles
to prevent chloride ion penetration was assessed under accelerated
conditions. The specimens were cured for 28 days in a curing tank
with relative humidity 95% and temperature 20 ± 2 °C. After this
age, the specimens were exposed in a non-conductive plastic con-
tainer filled with 3.5% NaCl solution which was revived every week
up to a period of one month. Then the specimens were broken in
dry condition with a compression testing machine into two halves
and sprayed with an indicator solution which is a mixture of 0.1%
sodium fluorescein and 0.1 N silver nitrate [41]. When silver
nitrate solution is sprayed on a fresh concrete surface containing
chlorides ions, chlorides bind with silver to produce silver chloride,
a substance which is white in appearance. In the absence of chlo-
ride ions, the silver binds with hydroxides present in the concrete
leading to the formation of silver oxide, a brown precipitate
[42,43]. The regions where chloride ions have penetrated were
seen white in colour and the depth was measured using a Digi-
matic Vernier caliper (M/s. Mitutoyo, Japan). The pictorial repre-
sentation of mortar specimens sprayed with indicator solution
and the corresponding colour change along with different mea-
surement locations are shown in Fig. 2a and b respectively. The test
was performed on duplicate specimens. Four points on each longi-
tudinal side were measured to get a total of eight-point depth mea-
surement for each specimen.
3. Results and discussion
3.1. Natural electrochemical corrosion studies
Fig. 3 represents corrosion potential (Ecorr) versus duration of
exposure for the rebars embedded in FA, FAT, FAC and FATC con-
crete specimens exposed in seawater for a period of over four
months. The corrosion potential values of all the specimens were
compared with the ASTM table of standard potential value
236 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243

Fig. 2. Pictorial representation of mortar specimens (a) sprayed with indicator solution, (b) corresponding colour change in the specimens with different measurement
locations.

300 mV to 700 mV. This was attributed to the further loss of

integrity of the passive film formed over the reinforcement in the
concrete specimens. The most active behaviour was shown by
FATC and the least loss of passivity was shown by FA.
As soon as the specimens were exposed in the chloride medium,
all the fly ash based specimens known for their slow hydration
resulted in easy penetration of the chloride ions and thereby affect-
ing the integrity of the passive film. Thus, by four weeks the OCP
values of all the specimens shifted to the active range (300 to
600 mV). With more time of exposure, the hydration accelerated
in the fly ash specimens resulting in the formation of more cemen-
titious products. This helped to achieving repassivation of the film
formed over the reinforcement. Thus, the OCP values again shifted
to the uncertainity region. Thus, reinforcements in all the speci-
mens achieved ennoblement in the OCP values in the order of
FATC > FAC > FAT > FA.
Fig. 4 shows the variations in the linear polarization resistance
values (Rp) of steel rebar embedded inside different concrete

Fig. 3. Corrosion potential vs. duration of exposure in seawater for steel rebars
embedded in different concrete specimens.

corresponding to corrosion probability (Table 4) and the results

were interpreted [40]. Initially the potential values of FA, FAC
and FATC specimens were in the uncertain region (140 to
250 mV vs. Ag/AgCl). However, FAT showed comparatively lesser
negative potential value of 68 mV, which was in the passive
region. With exposure time, the corrosion potential of all the spec-
imens shifted towards the active region and was in the general
range of 150 to 185 mV. After 3rd and 4th weeks of exposure,
the potential values of all the specimens shifted to the range of

Table 4
ASTM standard table Potential, mV vs Ag/AgCl (ASTM C 876–09, 2001).

Potential, mV vs Ag/AgCl Probability of Corrosion (%)

More negative than 255 > 90 (active)
Between 255 and 105 Uncertain
More positive than 105 <10% (passive) Fig. 4. Variations in the linear polarization resistance with exposure period for steel
rebars embedded in different concrete specimens exposed to seawater.
 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243
specimens with exposure time in seawater. The LPR results are
compared with the standard Rp values and the corresponding cor-
rosion probability was determined [44]. The results showed that
the initial Rp values were in the order of FAT > FAC > FA > FATC.
With time, the Rp values decreased for all the specimens. However,
after four months, FAC concrete specimens showed the highest
polarization resistance value as compared to all the other speci-
mens and FAT specimens showed the lowest polarization resis-
tance indicating that nano-CaCO3 can improve the corrosion
resistance of the embedded rebar.
The variations in the current density (icorr) values, estimated
from the LPR measurements, versus duration of exposure (weeks)
for the steel rebars embedded in concrete specimens are shown
in Fig. 5. Initially all the specimens showed negligible corrosion
current densities and the corrosion current density followed the
order of FAT < FAC < FA < FATC. With time, icorr values of all the
specimens were found to increase. However, all the specimens
showed a moderate corrosion severity as per the standard table
of icorr versus corrosion severity [45,46]. Among the different types
of specimens, FAT (1.06 mA/cm2) and FA (0.66 mA/cm2) showed
higher icorr values when compared to FAC (0.43 mA/cm2) and FATC
(0.50 mA/cm2), which confirms the improved corrosion resistance
of reinforcement inside concrete incorporated with nano-CaCO3
particles.
Fig. 6 represents the corrosion rate of rebars inside concrete
specimens exposed in seawater after four months. As reported in
earlier investigations [47], corrosion rate up to 0.0058 mmpy indi-
cates the passive state of reinforcement. Corrosion rate in the range
of 0.0058 mmpy to 0.023 mmpy and 0.023 mmpy to 0.058 mmpy
corresponds to negligible and low corrosion severity, respectively.
According to this criteria, FAC and FATC specimens maintained the
passive state. Among the different concrete specimens, FAC
(0.0049 mmpy) and FATC (0.0058 mmpy) showed least rates of
degradation, whereas, FA (0.0077 mmpy) and FAT (0.012 mmpy)
showed comparatively higher corrosion rates. Thus, addition of
nano-CaCO3 to fly ash concrete appears to be a potential strategy
to increase its resistance against corrosive media.
Thus in our study, after 4 months of exposure in seawater, FAC
concrete specimens showed the most noble corrosion potential,
maximum polarization resistance, least corrosion current density
and lowest corrosion rate among all the specimens. This is possibly
due to the effective filling of pore space and pore connectivity by
nano-CaCO3 and thus, preventing the penetration and diffusion
of chloride ions. Addition of nano-CaCO3 is reported to fill up the
pores of loose net structure around the cement particles and thus
Fig. 5. Current density (icorr) vs. duration of exposure in seawater for steel rebars
embedded in different concrete specimens.
237
Fig. 6. Corrosion rate (mmpy) vs. duration of exposure in seawater for steel rebars
embedded in different concrete specimens.
decreasing the porosity of hardened cement paste [48]. Initially
on the first day of exposure, FAT specimens showed a passive cor-
rosion potential, highest polarization resistance and least current
density indicating very good corrosion resistance. A study showed
that nano TiO2 can act as inert filler and also help in faster hydra-
tion [49]. This explains the reason for the better performance of
FAT during the initial period. However, after exposure to chloride
environments, the performance of FAT is found to deteriorate,
whereas performance of FAC increased significantly. The improve-
ment in the corrosion properties of concrete admixed with
nanoparticles is reported earlier [50]. In this study, we could
observe some variations in the corrosion characteristics with addi-
tion of different nanoparticles. In chloride environments, rate of
diffusion of chloride ions through the concrete cover determines
the loss of passivity and corrosion of reinforcements [51]. The dif-
fusion depends on the pore structure of concrete [52]. Thus, addi-
tion of nanoparticles which fill the pores appears to provide better
corrosion resistance to the reinforcements.
Owing to the high surface area to volume ratio, nanoparticles
are known for their outstanding chemical reactivity [53]. Transport
of ionic and molecular species in mortar is mainly through the pore
solution. Thus, nano-materials often work as nanosized fillers that
aid in the development of denser and less permeable microstruc-
ture of concrete [50]. Shaikh et.al [21] has reported that addition
of nanoparticles and fly ash together in conventional concrete
can provide better corrosion protection due to the synergistic
effect of both the additives. Studies by Nguyen et.al [50] on the cor-
rosion resistance of epoxy-coated steel in salt contaminated mor-
tars using potentiodynamic polarization and electrochemical
impedance spectroscopy showed that nano-SiO2 and nano-Fe2O3
can improve the chloride ion penetration resistance in the mortar.
The effect of addition of TiO2 nanoparticles on the mechanical
properties of concrete and corrosion behavior of reinforcements
was examined by Mosad et.al [54]. They found that corrosion resis-
tance increased with increasing nano-TiO2 content up to 1.5 wt%
and thereafter the corrosion resistance decreased, which was
attributed to the agglomeration of nanoparticles at higher concen-
trations. The presence of aggregate induced voids and nanopores
allows the permeation of water and aggressive ions to the surface
of the rebar. With increase in the number of voids in FAT speci-
mens, the rate of electrochemical reaction was found to increase
[54]. Nguyen et al. [50] have reported that quantity of nano-
materials (1% by weight of cement) play a major role in improving
238 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243
the resistance against chloride ion penetration and nanoparticles
agglomerate at a faster rate at higher concentrations [55].
In order to check the probability of agglomeration of nano-TiO2
at higher concentrations, the mean particle size was calculated
using EC-AFM and the results are shown in Table 5. The mean par-
ticle size of nano-TiO2 in 1% and 2% suspension was found to be
0.784 mm and 1.176 mm, respectively. The mean particle size of
nano-CaCO3 in 1% and 2% suspension was 0.588 mm and
0.980 mm, respectively which were comparatively lower than that
in nano-TiO2 for the same concentration. This shows that nano-
CaCO3 particles are better pore fillers. Nano-TiO2 tends to agglom-
erate and form more clusters in concrete than acting as pore filler.
The schematic representation of agglomeration of nanoparticles at
increasing concentrations is shown in Fig. 7.
Bonavetti et al. [56] have shown that calcium carbonate powder
acts as effective filler on concrete. Also, it reacts with aluminum
phase of the cement paste to form calcium carboaluminate
hydrates [57–59] and accelerates the hydration of C3S and C3A
phases [60]. It was also reported that increased C3A content in con-
crete significantly reduces the free chloride concentration in the
pore solution, which greatly influences the corrosion of concrete
[61]. The hydration of overwhelmingly increased C3A content
forms denser pore structure leading to a reduction in the ionic
transport. The high reactivity of C3A with chloride ions in the pore
solution of concrete often results in the formation of crystallized
salts like Friedel’s salt, which has an ability to remove chlorides
Table 5
Mean particle size of nanoparticles at different concentration used for concrete
fabrication.
Type and concentration of nanoparticles Mean particle size (mm)
1% TiO2 0.784
2% TiO2 1.176
1% CaCO3 0.588
2% CaCO3 0.980
Fig. 7. Schematic representation of the proposed mechanism where incorporation of nanoparticles at increasing concentration results in their agglomeration (a) Concrete
with micro and nano size pores, (b) concrete with reduced pores (c) pores retained due to the agglomeration of nanoparticles.
from the pore solution and hence do not participate in the corro-
sion process. Thus, a high concentration of C3A is considered to
be inhibitive against chloride-induced corrosion of steel in con-
crete. Hence, in our study also, high concentration of C3A content
and comparably low agglomeration of 2 wt% CaCO3 nanoparticles
would have reduced the penetration of the aggressive chloride ions
from seawater and thereby reduced the extent of corrosion in the
reinforcement which is in agreement with the results in the liter-
ature [62].
The average pH values of the extracts from all the concrete sys-
tems before exposure and after exposure to seawater are given in
Table 6. Before exposure, all the nanophase modified concrete
specimens showed pH values in the range of 12.1–12.4 as com-
pared to 12.0 for the fly ash concrete, which is in agreement with
earlier studies [63]. After exposure to seawater, it was found that
there is a reduction in pH value and among all specimens, FAT
specimens showed the maximum reduction in pH (10.9). How-
ever, the least reduction in pH values was observed for FAC and
FATC specimens. The reduction in the pH values is due to the fact
that mineral admixtures absorb some CH through the pozzolanic
reaction. Further, the addition of mineral admixtures reduces the
relative content of cement. Thus, amount of CH produced as a
result of cement hydration is reduced. This results in a drop in
the pH values [38].
Fig. 8 shows the SEM images of concrete samples extracted
from surfaces surrounding the corroded rebar. Sample extracted
Table 6
pH of unexposed and seawater exposed concrete specimens.
Specimen Before Concrete extracted from surfaces surrounding the
type exposure corroded rebar after exposure
FA 12.0 11.1
FAT 12.1 10.9
FAC 12.4 11.4
FATC 12.2 11.3
 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243
Fig. 8. SEM images of concrete samples extracted from vicinity of the corroded rebar (a) FA, (b) FAT, (c) FAC, (d) FATC.
from FA concrete showed cracks and micro pores indicating degra-
dation in FA specimens. The crack is shown in the inset image of FA
(Fig. 8a). FAT specimens showed bigger macro pores of approxi-
mately 0.1 mm size (Fig. 8b). However, FAC and FATC concrete spec-
imens were devoid of any micro or macro pores. FATC showed
uniformly packed morphology of calcium silicate hydrate (CASAH)
gel (Fig. 8d) [64]. As observed in Fig. 8c, a completely hydrated
region covered with CASAH gel morphology is reported to reduce
pore structure of concrete in FAC specimen. Babak et al. [65], have
reported that CASAH, the main hydration product observed in the
form of a dense sponge matrix, can gradually spread, merge and
strengthen the concrete and reduce its permeability. Reduction in
permeability prevents penetration of aggressive chemicals that
leads to reduced corrosion of reinforcements [65]. Saraswathy
et al [66], have also reported that CASAH gel enhanced the corro-
sion resistance properties of reinforcement in concrete structures
to a greater extent.
Fig. 9 shows the XRD patterns of concrete samples extracted
from surfaces surrounding the corroded rebar. All the four concrete
specimens showed cementitious hydration products like CASAH
and quartz. The corrosion products like lepidocrocite and goethite
originating from the mild steel rebar were also observed in the
spectra of all the concrete specimens. The intensity of lepidocrocite
and goethite peaks were maximum for FA concrete compared to
nanophase modified concrete specimens. Among all the nanophase
modified specimens, FAC showed less intense peaks of corrosion
products especially goethite, a more stable polymorph of iron oxy-
hydroxides, which results in its enhanced corrosion resistance.
When chloride ions move into the concrete, they disrupt the pas-
sive layer protecting the steel, causing it to rust and pit [67]. Chlo-
ride ions can also act as a catalyst for the anodic reaction of the
corrosion process once they penetrate the concrete cover and reach
a threshold level high enough to disrupt the passive film on the
rebar surface [68,69]. Lepidocrocite is reported as the primary crys-
239
talline corrosion product formed on the steel rebar embedded in
concrete. As the initial corrosion product of steel, lepidocrocite
increases with different concentrations of Fe(II) ion and with expo-
sure time, it gets partially transformed into goethite and magnetite
[70,30]. Lepidocrocite and goethite produces the highest volume
expansion ratio leading to cracking in reinforced concrete struc-
tures [71].
FTIR spectra of concrete samples extracted from surfaces sur-
rounding the corroded rebar are shown in Fig. 10. The major peak
of lepidocrocite is found on all the spectra at 874 and 1035 cm1. It
is reported that lepidocrocite is the initial corrosion product that is
formed on steel when exposed to a saline environment [72]. The
peak at 774 cm1 observed on all the specimens correspond to
goethite, which is a more stable polymorph formed on transforma-
tion of lepidocrocite [73]. Even though the transformation of lepi-
docrocite to goethite was seen in all the specimens, the spectrum
of FA concrete specimens showed distinct high intensity peaks,
which indicates higher corrosion. FAC and FATC specimens showed
less intense peaks indicating less corrosion severity on these spec-
imens. The broad peak at 1436 cm1 attributed to the asymmetric
stretching vibrations of the C-O corresponding to carbonate ions
was present in all the concrete specimens [74]. The peak at 1634
and 3444 cm1 in all the specimens can be attributed to the water
molecules [75].
3.2. Accelerated corrosion test
Fig. 11 shows the photographs of steel rebars taken out from
different concrete specimens exposed to 5% NaCl solution. The
extent of rust was visibly more on FA and FAT concrete specimens,
whereas, FAC and FATC concrete specimens showed lesser rust
marks. It is reported that in fly ash incorporated concrete speci-
mens adhere extraordinarily well to reinforcement, thereby favor-
ing high-volume stability even in aggressive environments [76,77].
240 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243
Fig. 9. XRD pattern of concrete samples extracted from surfaces surrounding the corroded rebar.
The visual examination of rebars embedded in concrete specimens
after exposure to seawater showed that the adherence of concrete
on the rod was more for all the concrete specimens.
The time taken for crack initiation (h) and the corresponding
anodic current (mA) developed in different concrete specimens
subjected to accelerated corrosion test in 5% NaCl solution is
shown in Fig. 12. It can be observed that the time taken for initia-
tion of the first crack was found to be highest in FAC (122 h) fol-
lowed by FATC (109 h). The minimum anodic current was also
observed to be 10.5 mA and 12.7 mA in FAC and FATC specimens,
respectively. However, FAT (54 h) concrete showed the lowest time
for crack initiation with maximum anodic current (22.3 mA)
among all four specimens.
Corrosion of steel is a quite slow process. It takes a reasonably
longer duration for corrosion initiation due to the alkaline nature
of concrete even under exposure to severe corrosive conditions.
The long time periods involved in replicating reinforcement corro-
sion within laboratories has resulted in the development of accel-
erated corrosion test methods. Among the various accelerated
corrosion test methods, impressed voltage technique is known to
be an effective and quick method that dramatically reduces the
corrosion initiation period required for depassivation from years
to days [78]. Hence, the electrochemical implications of applying
an external current are explored and the results are used to com-
plement the natural electrochemistry of reinforcement corrosion.
When an external electric field is applied to passive steel embed-
ded in concrete, the evolution of oxygen generates hydrogen ions
that diffuse into the pore water adjacent to the steel rebar and
lower the pH [79]. In the present study, impressed voltage test also
showed an enhanced corrosion resistance for reinforcements in
FAC concrete which was in good agreement with the results
obtained from natural electrochemical test.
3.3. Chloride ion penetration test
The depth of chloride ion penetration under accelerated condi-
tions measured at different locations is shown in Fig. 13. The FAT
concrete specimens showed the highest average value of depth of
chloride ion penetration at all the measurement points. The depth
of chloride ingress was seen significantly lower on FAC concrete,
indicating enhanced resistance against penetration of chloride ions
into these specimens. The assessment of chloride ion penetration by
colorimetric method using the combination of silver nitrate and
sodium fluorescein is the most reliable method [80]. Upon spraying
the silver nitrate solution, formation of Ag2O and AgCl takes place.
Fluorescein is a week organic acid that dissociates in solution to a
yellowish green ion. Using the simplest method of chloride ion pen-
etration test, the least depth of penetration was seen in nano-CaCO3
incorporated fly ash concrete. This reduction in the permeability
could be due to consolidation of the microstructure, refinement of
the concrete pore structure [81] and the formation of more C-S-H
that contribute to the formation of a dense matrix with higher
strength and lower permeability [82,83].
Thus, the experimental investigations by natural electrochemi-
cal techniques on corrosion resistance of reinforcements in fly ash
concrete using two types of nano additives showed that the addi-
 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243 241

Fig. 10. FTIR spectra of concrete samples extracted from surfaces surrounding the corroded rebar (a) FA, (b) FAT, (c) FAC, (d) FATC.

Fig. 12. Time taken for crack initiation and the corresponding maximum anodic
current developed for different specimens exposed in 5% NaCl solution.

anodic current confirming enhanced corrosion resistance. Particle

Fig. 11. Photographs of the steel rebars embedded in different concrete specimens
after exposure to 5% NaCl solution (a) FA, (b) FAT, (c) FAC, (d) FATC.
tion of 2 wt% nano-CaCO3 provides excellent corrosion resistance.
FAC exhibited the most noble potential values, highest polarization
resistance and maximum crack initiation time with a minimum
size analysis confirmed lesser agglomeration of nano-CaCO3 as
compared to nano-TiO2. SEM micrographs showed a compact
microstructure devoid of micro and macro pores on FAC in com-
parison to FAT. The depth of chloride ion penetration was the least
in FAC as compared to FAT that prevented the permeation of chlo-
ride ions to the rebar in the FAC specimens.
242 S. Uthaman et al. / Construction and Building Materials 221 (2019) 232–243
Fig. 13. Depth of chloride ion penetration (mm) vs. measurement locations for
mortar specimens exposed to 3.5% NaCl solution.
4. Conclusions
This study investigated the corrosion behaviour of four types of
concrete specimens exposed to natural and accelerated environ-
ments under controlled laboratory conditions by immersing in sea-
water and 5% NaCl solution, respectively. Key findings are
summarised as follows:
1. OCP and LPR studies showed that reinforcements in nano-
CaCO3 modified fly ash concrete exhibited the most noble
potential, maximum polarization resistance, least corrosion
current density and lowest corrosion rate.
2. The mean particle size of nano-CaCO3 up to 2% suspension was
found to be comparatively lower than that of nano-TiO2 with
the same concentration.
3. Post exposure characterization studies of the concrete extracts
near the reinforcements showed least reduction in pH, homoge-
neous and completely hydrated microstructure, absence of
macro and micro pores and corrosion products in FAC
specimens.
4. Accelerated corrosion test results showed maximum crack initi-
ation time with minimum anodic current for FAC concrete
specimens.
5. The depth of chloride ion penetration was significantly lower in
FAC concrete indicating enhanced resistance against attack by
chloride ion.
Declaration of Competing Interest
None.
Acknowledgements
Financial support from Board of Research in Nuclear Sciences
(BRNS), Mumbai, India (2013/36/33-BRNS/2355 dated 26 Novem-
ber, 2013) is greatly acknowledged. The authors would also like
to thank Chancellor, Sathyabama Institute of Science and Technol-
ogy, Chennai and Director, IGCAR, Kalpakkam for guidance, encour-
agement and motivation. The authors would like to sincerely
acknowledge Dr. B. Anandkumar, CSTD, IGCAR and Mr. K. Thya-
garajan, CSTD, IGCAR for their help in electrochemical experiments
and engineering artwork respectively.
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