CEMCON-05227; No of Pages 14

Cement and Concrete Research xxx (2016) xxx–xxx

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Cement and Concrete Research

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Influence of sulfate ion and associated cation type on steel reinforcement

corrosion in concrete powder aqueous solution in the presence of
chloride ions
Fouzia Shaheen, Bulu Pradhan ⁎
Department of Civil Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, India

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

Article history: State of rebar corrosion in concrete powder aqueous solution contaminated with chloride and sulfate ions has
Received 9 February 2016 been determined by conducting a potentiodynamic polarization test. XRD analysis and FTIR spectroscopy were
9 October 2016 also performed. From the results, different zones of corrosion in terms of potential ranges have been identified.
Accepted 11 October 2016
The presence of Na2SO4 has mitigated the effect of chloride ions whereas the presence of MgSO4 has stimulated
Available online xxxx
the effect of chloride ions on reducing the passivity of steel reinforcement in a chloride environment. Ordinary
Keywords:
Portland cement performed better against Mg-oriented sulfate attack whereas Portland pozzolana cement per-
Corrosion (C) formed better against Na-oriented sulfate attack in the presence of chloride ions.
Chloride (D) © 2016 Elsevier Ltd. All rights reserved.
Reinforcement (D)
Sulfate (D)
Concrete (E)

1. Introduction reinforcement corrosion by lowering corrosion-inducing free chlorides

Concrete is a heterogeneous material with many special characteris-
tics, including high alkalinity of the pore solution, high electrical resis-
tivity and has a structure that acts as a physical barrier for mass
transport and crack behaviour [1]. Concrete durability problems are
the major cause of concern all over the world especially in the coastal
areas where the structures are undergoing deterioration well before
their expected life and need proper attention and care [2]. In the marine
environment, chloride and sulfate salts do exist concomitantly. The con-
joint presence of these salts may cause deterioration of concrete due to
reinforcement corrosion and sulfate attack [3].
Chloride ions enter into concrete through two sources such as inter-
nal chloride (at the time of preparation of concrete, through chloride
contaminated aggregates, chloride-containing admixtures, or mixing
water) and external chloride (entering from the external environment
into the hardened concrete through deicing salts, sea water, soil and
ground water) [4]. In the hardened cement paste, when both chlorides
and sulfates exist conjointly, they react with tricalcium aluminate
(C3A) to form various compounds. Chloride ions react with C3A to
form calcium chloroaluminate (Friedel's salt) [5]. Sulfate ions react
with calcium hydroxide and hydrated C3A to form gypsum and
ettringite respectively, which lead to expansion and disruption of hard-
ened concrete. The higher proportions of C3A would reduce the level of
⁎ Corresponding author.
E-mail address: bulu@iitg.ernet.in (B. Pradhan).
from the concrete pore solution, but it would pose a serious concrete
durability problem in terms of sulfate attack [6]. The electrolytic pore
solution of concrete has a pH value between 12.5 and 13.5 due to the
presence of calcium hydroxide along with small amounts of Na2O and
K2O [1]. In this highly alkaline environment, a thin protective layer
known as a passive layer of γ-Fe2O3 is formed on the rebar surface [7–
9]. However the free chloride content (also known as water soluble
chloride) in the pore solution of concrete breaks down the passive
layer of steel and initiates corrosion [10]. Sulfate ions enter into concrete
externally from exposure condition and internally through aggregates,
mixing and curing water, and admixtures [3]. Sulfate ions can be associ-
ated with magnesium, calcium and sodium cations. Since the solubility
of calcium sulfate is very low, magnesium and sodium sulfate are mainly
responsible for the deterioration of concrete due to sulfate attack [11].
In the conjoint presence of chloride and sulfate ions, the mechanism
of deterioration of concrete becomes complex due to the simultaneous
interaction of these ions with hydrated cement phases. Further, the cat-
ion type associated with these aggressive ions makes the mechanism
even more complex. From the review of literature, it is inferred that dif-
ferent researchers have studied the corrosion behaviour of steel embed-
ded in concrete exposed to chloride, sulfate and mixed chloride-sulfate
environment. Zuquan et al. [12] reported that the presence of sulfate
ions in a composite solution enhanced the resistance to chloride pene-
tration into the concrete at the early stage of exposure, but the opposite
behaviour was observed at a later exposure period. Further from XRD
results, the authors observed the formation of a higher amount of

http://dx.doi.org/10.1016/j.cemconres.2016.10.008
0008-8846/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
2 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx
Nomenclature
CCA Calcium chloroaluminate
E Ettringite
G Gypsum
CH Calcium hydroxide
MH Magnesium hydroxide
CC Calcium carbonate
T Thaumasite
Q Quartz
gypsum and ettringite in the concrete exposed to sulfate solution as
compared to that exposed to composite sulfate-chloride solution. A
study conducted by Al-Amoudi and Maslehuddin [7] on the respective
effect of chloride and sulfate ions on corrosion of steel in cement paste
indicated that sulfate ions are hardly able to initiate reinforcement cor-
rosion. However considerable reinforcement corrosion was observed in
specimens immersed in mixed chloride-sulfate solution. Jarrah et al.
[13] reported that the time to initiation of reinforcement corrosion
was higher in blended cement than plain cement in all chloride and
chloride-sulfate solutions and the sulfate ions alone do not initiate the
reinforcement corrosion but they increase the corrosion activity once
the corrosion was initiated due to the conjoint presence of chloride
and sulfate salts. Dehwah et al. [14] have found that the presence of sul-
fate ions in a chloride environment did not affect the time to initiation of
reinforcement corrosion but corrosion current density increased with
an increase in the concentration of sodium sulfate and magnesium
sulfate.
The presence of chloride and sulfate salts significantly affects the
pore solution chemistry of concrete. The pore solution of concrete sig-
nificantly varies in the concentration of hydroxyl ions, sulfate ions, chlo-
ride ions, solubility of metal cations and temperature [15]. Different
researchers have investigated the corrosion behaviour of reinforcing
steel in simulated concrete pore solutions. Dehwah et al. [9] studied
the effect of chloride and sulfate contamination on the pore solution
chemistry in plain and blended cements and the results from the
study indicated that the chloride binding capacity of both plain and
blended cements decreased due to the concomitant presence of chlo-
ride and sulfate salts. It was also observed that the increase in chloride
and sulfate ions in mixed chloride-sulfate solution enhances the corro-
sion of steel reinforcement. Zhang et al. [16] have found that the passiv-
ity breakdown potential or pitting potential is lower with higher
chloride concentrations and they also observed that the higher pH of
the simulated concrete pore solution facilitates the passivation of
steel, whereas the higher concentration of Cl− leads to a passivity break-
down at relatively lower potential. Ghods et al. [17] have investigated
the growth of oxide film on steel surface in saturated calcium hydroxide
solution with different amounts of NaOH, KOH and Ca(SO)4. The authors
reported that pore solution composition has an effect on the protective
properties of passive oxide film and the presence of SO2− 4 ions in the
pore solution has a significant negative effect on the protective proper-
ties of the passive oxide film. Chen et al. [18] reported that in chloride
free saturated calcium hydroxide solution, steel remains in a passive
state and the corrosion current of steel was very low. On the other
hand in the saturated calcium hydroxide with 0.5 M NaCl, the corrosion
current density increased considerably and the steel surface was unsta-
ble with chloride attack and localized corrosion appeared with FeCO3
and Fe2O3 as main corrosion products on its surface. Padilla and
Alfantazi [19] found that the most severe corrosion damage in terms
of corrosion rate and degradation of the corrosion film formed on the
surface and was observed when galvanized steel was immersed in
NaCl + Na2SO4 solution whereas the best performance was observed
in MgCl2 + Na2SO4 solution. Pradhan and Bhattacharjee [20] have
Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
conducted a potentiostatic study on reinforcing steel in chloride con-
taminated concrete powder solution extracts. The authors reported
that chloride content has the strongest influence in governing zones of
corrosion of steel reinforcement as compared to other parameters. Aal
et al. [21] have reported that the pitting corrosion current density in
constant Ca(OH)2 solution increased with the increase in SO24 − and
Cl− ions, whereas under the constant concentrations of SO2− 4 and Cl−
ions, pitting corrosion current density decreased with an increase in
the concentration of Ca(OH)2.
From the review of past research work, it is observed that very few
studies have been conducted to evaluate the corrosion performance of
steel reinforcement in simulated concrete pore solutions contaminated
with composite chloride-sulfate salts. Further, in these studies mostly
saturated calcium hydroxide solution has been taken as the simulated
pore solution. On the other hand, concrete powder aqueous solutions
can also be taken as the electrolytic concrete pore solution. Since con-
crete powder from which the aqueous solution is extracted, is a mixture
of cement hydrates, coarse aggregates and fine aggregates, the aqueous
solution may represent the electrolytic pore solution of concrete more
closely as compared to saturated calcium hydroxide solution. From the
literature review, it is inferred that the work on corrosion performance
of steel in concrete powder aqueous solutions contaminated with chlo-
ride ions and/or composite chloride-sulfate ions is meager. Therefore, in
the present research work, an attempt has been made to study the elec-
trochemical behaviour of steel in electrolytic concrete powder aqueous
solutions contaminated with chloride and composite chloride-sulfate
ions through anodic polarization curves by conducting a potentiody-
namic polarization test. Further to analyze the effect of chemical compo-
sition of the concrete powder aqueous solutions on corrosion behaviour
of steel reinforcement, ionic concentration, pH and conductivity of con-
crete powder aqueous solutions were determined. In addition, for the
purpose of analyzing the changes in phase composition of hardened
concrete and for identifying different functional groups associated
with different products formed in concrete in the presence of chloride
ion and sulfate ions, X-ray diffraction (XRD) analysis and Fourier trans-
form infrared (FTIR) spectroscopy were conducted.
2. Experimental work
The experimental program has been designed to evaluate the corro-
sion performance of steel in ordinary Portland cement (OPC) and
Portland pozzolana cement (PPC) concrete powder aqueous solutions
contaminated with different concentrations of chloride ions and sulfate
ions. The details of materials used, test specimens and tests conducted
in the present investigation are presented below.
2.1. Materials used and specimen preparation
Concrete cube specimens with a size of 150 mm were prepared
using ordinary Portland cement satisfying IS: 12269-1987 [22] and
ASTM Type I [23]; and Portland pozzolana cement satisfying IS: 1489-
1991 [24] and ASTM Type IP [25] with a water-cement ratio (w/c) of
0.50. The chemical composition of OPC and PPC determined by XRF
(X-ray fluorescence) analysis are presented in Table 1. Locally available
river sand was used as fine aggregate. The specific gravity of sand is 2.61
and it is conforming to grading zone II as per IS: 383-1970 [26] and as
per ASTM C33/C33M-13 [27]. The coarse aggregate of quartzite origin
Table 1
Chemical composition of cement determined by X-ray fluorescence (XRF) analysis.
Compound (wt.%) CaO SiO2 Al2O3 Fe2O3 MgO Na2O K2O SO3 LOI
Ordinary Portland 65.2 19.2 5.2 2.4 3.4 0.3 0.62 1.5 1.4
cement (OPC)
Portland pozzolana 64.7 20.52 4.2 3.4 1.55 0.35 1.31 1.6 1.2
cement (PPC)
 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx 3

Table 2 Table 4
Chemical composition of coarse aggregate in wt%, determined by energy-dispersive X-ray Concentration of chloride and sulfate salts admixed in concrete mixes (added by weight of
(EDX) analysis. cement).

O Si Na K Ca Al Concentration of admixed
salts Abbreviation Group
42.8 29.2 0.1 15.7 0.2 8.7
3% NaCl 3NC Sodium chloride
5% NaCl 5NC
7% NaCl 7NC
is used and its chemical composition determined by energy-dispersive
3% NaCl + 3% Na2SO4 3NC + 3NS Sodium chloride plus sodium sulfate
X-ray (EDX) analysis is presented in Table 2. The coarse aggregates of 5% NaCl + 3% Na2SO4 5NC + 3NS
20 mm MSA (maximum size aggregate) with a specific gravity of 2.64 7% NaCl + 3% Na2SO4 7NC + 3NS
and 10 mm MSA with a specific gravity of 2.63 were used in the propor- 3% NaCl + 6% Na2SO4 3NC + 6NS
tion of 1.941:1 by mass of total coarse aggregate content to satisfy the 5% NaCl + 6% Na2SO4 5NC + 6NS
7% NaCl + 6% Na2SO4 7NC + 6NS
overall grading requirement of coarse aggregate as per IS: 383-1970 3% NaCl + 12% Na2SO4 3NC + 12NS
[26] and ASTM C33/C33M-13 [27]. Tap water from the laboratory was 5% NaCl + 12% Na2SO4 5NC + 12NS
used as mixing water in the preparation of concrete mixes. The water 7% NaCl + 12% Na2SO4 7NC + 12NS
content in all the concrete mixes was kept at 195 kg/m3. The mix pro- 3% NaCl + 3% MgSO4 3NC + 3MS Sodium chloride plus magnesium
5% NaCl + 3% MgSO4 5NC + 3MS sulfate
portion of concrete for both OPC and PPC is presented in Table 3.
7% NaCl + 3% MgSO4 7NC + 3MS
The concrete mixes were prepared with varying dosages of chloride 3% NaCl + 6%MgSO4 3NC + 6MS
and sulfate salts as shown in Table 4. The concrete mixes were admixed 5% NaCl + 6% MgSO4 5NC + 6MS
with only NaCl for chloride contamination. Sodium chloride (NaCl) is 7% NaCl + 6% MgSO4 7NC + 6MS
normally present in seawater and in contaminated soil and groundwa- 3% NaCl + 12% MgSO4 3NC +
12MS
ter in higher concentrations [28,12]. Further chloride ions may also
5% NaCl + 12% MgSO4 5NC +
enter into fresh concrete at the time of its preparation through chloride 12MS
contaminated aggregates, mixing water and chloride bearing admix- 7% NaCl + 12% MgSO4 7NC +
tures. In addition, as reported in literature, different researchers have 12MS
used sodium chloride in different concentrations as the source of chlo-
ride ions in their investigations [4,12,14]. On the basis of these factors,
in the present work, lower to very high concentrations of NaCl were square opening with a size of 150 μm. The sieved concrete powder
used to perform electrochemical measurements. The concentrations of was stored in air tight plastic containers. For the purpose of preparing
NaCl used in this investigation were 3%, 5% and 7% by weight of cement concrete powder aqueous solutions, the stored concrete powder was
content. Further in seawater and contaminated groundwater, sulfate mixed with distilled water in 1:1 proportion by mass and then stirred
salts mostly in the form of sodium sulfate and magnesium sulfate are for a period of half an hour followed by boiling for 15–20 min. After
also present along with chloride salts. In the present work, the concrete that, the concrete powder solution was allowed to settle and cool to
mixes were admixed with NaCl plus Na2SO4 and NaCl plus MgSO4 for room temperature. This solution was then filtered through Whatman
composite chloride-sulfate contaminations. The admixed concentra- no. 1 filter paper. The obtained filtered concrete powder aqueous solu-
tions of Na2SO4 and MgSO4 were 3%, 6% and 12% each by weight of ce- tion nearly represents all the species in the vicinity of the rebar in the
ment content. The required quantities of these salts were dissolved in contaminated concrete as it is extracted from concrete powder, which
the mixing water during the preparation of concrete mixes. Cube spec- is a mixture of cement hydrates, coarse aggregate, fine aggregate and
imens from different concrete mixes were prepared for obtaining con- admixed dosages of chloride and composite chloride-sulfate ions. The
crete powder samples. After 24 h of casting, the cube specimens were concrete powder aqueous solution was then used to perform a potenti-
demoulded and subjected to moist curing till the age of 28 days. Then odynamic polarization test on the prepared steel specimens.
the specimens were removed from the curing tank and kept in the lab-
oratory exposure condition till the period of crushing. The steel speci- 2.3. Test techniques
mens of 12 mm diameter and 70 mm length were used as steel
reinforcement and these were made from commonly used Tempcore 2.3.1. Chemical analysis of concrete powder aqueous solution
TMT (thermomechanically treated) ribbed steel bars. The chemical The chemical composition of the solution extracted from concrete
composition of steel reinforcement determined by energy-dispersive powder depends on the type of binder (OPC and PPC) used and also
X-ray (EDX) analysis is presented in Table 5. The steel specimens were on salt concentrations (NaCl, Na2SO4 and MgSO4), which are admixed
cleaned with wire brush to remove any surface scale. A hole of 3 mm di- at the time of preparation of the concrete mix. The extracted concrete
ameter was drilled and threaded at one end of the steel specimen. powder aqueous solutions are chemically analyzed to determine sodi-
Epoxy coating was applied on the surface of a steel specimen leaving um (Na+), potassium (K+), calcium (Ca++), chloride (Cl−) and sulfate
an exposed portion of 5 mm length at the opposite face of the drilled (SO2− +
4 ) ion concentrations. The concentrations of cations i.e. Na , Ca
++

end. The schematic diagram of a steel specimen is shown in Fig. 1.
2.2. Preparation of concrete powder aqueous solutions
The cubes prepared for obtaining concrete powder were crushed at
the age of 56 days from the day of preparation in the compression test-
ing machine and were further crushed in an abrasion testing machine.
The collected concrete powder was then sieved through a sieve of
Table 3
Mixture proportion of concrete for OPC and PPC.
and K+ ions in concrete powder aqueous solutions were determined by
using a flame photometer by preparing appropriate dilutions. Before
measuring the concentrations of Na+, Ca++ and K+ ions, the flame pho-
tometer was calibrated with standard solutions of Na+ (10 ppm), Ca++
(100 ppm) and K+ (10 ppm). The procedure to determine Na+, Ca++
and K+ ions by using the flame photometer was followed as mentioned
in the Standard Methods for the examination of water and wastewater
Table 5
Chemical composition of steel in wt%, determined by energy-dispersive X-ray (EDX)
analysis.

Ingredients Cement Water Fine aggregate Coarse aggregate Mn Si Ni Cr Cu S P C Fe

Quantity (kg/m3) 390 195 648 1152 1.2 0.6 0.2 0.2 0.1 0.2 0.1 b0.1 Balance

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
4 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx

Section Y-Y
Epoxy coating
Y 12 mm
70 mm

12 mm

3mm dia. threaded hole for

connecting to corrosion
5 mm exposed Y
monitoring instrument
length

Fig. 1. Schematic diagram of a steel specimen.

published by the American Public Health Association (APHA) [29]. The
free chloride (Cl−) ion concentration in the concrete powder aqueous
solution was determined by argentometric titration. The procedure of
argentometric titration to determine free Cl− ion concentration was
followed as described in Standard Methods for the examination of
water and wastewater published by APHA [29]. The turbidimetric meth-
od as mentioned in Standard Methods for the examination of water and
wastewater published by APHA [29] was used to determine the sulfate
ion (SO2−
4 ion) concentration in the concrete powder aqueous solution.
2.3.2. pH and conductivity measurement
The pH and conductivity of concrete powder aqueous solutions con-
taminated with chloride ions and chloride-sulfate ions were deter-
mined. The digital pH meter with pH range 0–14 and digital
conductivity meter were used to determine pH and conductivity respec-
tively of the concrete powder aqueous solutions.
2.3.3. Potentiodynamic polarization test
A potentiodynamic polarization test was carried out to evaluate the
electrochemical behaviour of steel specimens in electrolytic concrete
powder aqueous solutions. The electrochemical cell consists of a con-
crete powder aqueous solution, working electrode, auxiliary electrode
and reference electrode. The steel specimen immersed in the aqueous
solution was used as the working electrode. A saturated calomel
electrode (SCE) and a platinum electrode were used as the reference
electrode and auxiliary electrode respectively. The schematic represen-
tation of the test set-up is shown in Fig. 2.
The potentiodynamic polarization test was performed on steel
specimens using a corrosion monitoring instrument (make: ACM, Gill
AC serial no. 1542-sequencer). The guidelines for conducting a potenti-
odynamic polarization test are mentioned in ASTM G5-12 [30]. In the
present work, the potentiodynamic polarization test was conducted
on the steel specimen by applying the potential scan from 0 mV to
1500 mV with an offset from equilibrium potential at a sweep rate of
50 mV per minute. The anodic polarization curves obtained from the po-
tentiodynamic polarization test were analyzed to identify the potential
ranges of different zones of corrosion of the steel reinforcement. In this
investigation, two replicate steel specimens were tested for a given con-
crete powder aqueous solution to observe the reproducibility.
2.3.4. X-ray diffraction (XRD) analysis
X-ray diffraction was conducted on concrete powder samples to an-
alyze the changes in the phase composition of hardened concrete. The
analysis was performed on a Bruker D-8 Advance X-ray diffractometer
with Cu Kα radiation (λ = 1.5405 Å). Diffraction patterns were gener-
ated on a vertical goniometer attached to a board focus X-ray tube
with a copper target operating at 40 kV and 40 mÅ. The concrete pow-
der was filled into the sample holder and was scanned from 5° to 55°
(2θ) at a sampling interval of 0.05° 2θ per second. After obtaining the
XRD patterns, the phase identification process involves the calculation
of the most likely match score for a given phase based on peak intensity
and peak position, when compared with the database of standard
phases.
2.3.5. Fourier transform infrared (FTIR) spectroscopy
Fourier transform infrared (FTIR) spectroscopy was conducted to
identify different functional groups associated with different products
formed in concrete. The FTIR spectrum of a concrete powder sample

Fig. 2. Schematic illustration of an electrochemical cell.

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx 5

was collected in the transmission mode using a Thermo Fisher Scientific
Nicolet iS10 FTIR spectrometer. Sample pallets were prepared by mixing
250 mg of potassium bromide (KBr) with 3 mg of concrete powder sam-
ple. Fifteen scans were recorded over a range of 4000 cm−1 to 400 cm−1.
The background spectrum was collected at ambient atmosphere and then
the spectra of the samples were collected.
3. Results and discussion
3.1. Chemical composition of chloride contaminated concrete powder aque-
ous solution
The chemical composition of a concrete powder aqueous solution
prepared from the control mix and chloride contaminated concrete
mixes made with OPC and PPC are presented in Table 6. In addition in
this table, measured pH and conductivity values of solutions are also
presented. From Table 6, it is observed that the concentration of free
chloride ion i.e. Cl− ion increased with an increase in admixed NaCl dos-
age in both OPC and PPC. Further chloride ion concentration was lower
in OPC as compared to that in PPC in the presence of admixed NaCl. This
may be attributed to higher chloride binding with C3A in OPC as com-
pared to that in PPC as a result of higher C3A content in OPC. The concen-
tration of sulfate ion was higher in OPC as compared to that in PPC as
observed from Table 6. It may be noted that sulfate ion present in the
concrete powder solution (made from the control mix and chloride con-
taminated concrete mix) is due to the presence of gypsum added in the
manufacturing process to control the early setting and hardening be-
haviour of Portland cement. The higher concentration of sulfate ion in
OPC as compared to that in PPC may be due to the preferential reaction
of chloride ion than gypsum, with C3A in OPC. The conductivity of the
concrete powder aqueous solution made from the control mix was
higher in PPC as compared to that in OPC, which may be attributed to
higher concentration of cations Na+, Ca++ and K+ in PPC than that in
OPC as observed from Table 6. Further, the conductivity of a chloride
contaminated concrete powder aqueous solution made from PPC was
higher than that made from OPC, which may be due to the higher con-
centration of Cl− ion in PPC as compared that in OPC. In addition, the
concentrations of cations i.e. Ca++ and K+ were also higher in PPC as
compared to those made from OPC as observed from Table 6. The higher
concentration of Ca++ and K+ ions in PPC may be attributed to an alter-
ation in the extent of hydration of cement compounds due to the pozzo-
lanic reaction in PPC concrete and also due to a change in reactivity of
the alkali compounds. The concentration of Na+ ion was higher in
OPC as compared to that in PPC, which may be attributed to the reac-
tion of chloride ions with hydrated C3A to a greater extent in OPC in
the presence of admixed NaCl, thereby resulting in a higher concen-
tration of Na + ion in the concrete powder aqueous solution. The
presence of sodium chloride decreased the pH of the concrete pow-
der aqueous solution as observed from Table 6. However, there was
no significant difference in the pH value of the concrete powder
aqueous solution with different concentrations of admixed NaCl
and also between OPC and PPC.
3.2. Chemical composition of chloride-sulfate contaminated concrete pow-
der aqueous solution
The measured ionic concentration along with pH and conductivity of
concrete powder aqueous solutions prepared from OPC and PPC and
contaminated with conjoint chloride-sulfate salts are presented in
Table 7 for NaCl plus Na2SO4 and in Table 8 for NaCl plus MgSO4 contam-
inations. From these tables, it is observed that the concentration of Cl−
ion increased with an increase in admixed NaCl concentration for both
types of cement and at all admixed concentrations of Na2SO4 and
MgSO4. The Cl− ion concentration was higher whereas SO2− 4 ion con-
centration was lower in the concrete powder aqueous solution admixed
with NaCl plus MgSO4 as compared to that admixed with NaCl plus
Na2SO4 for both OPC and PPC as evident from Tables 7 and 8. This may
be attributed to reduced bound chloride and increased sulfate binding
with cement hydration products in the presence of MgSO4 in concrete.
From Table 7, it is observed that in the conjoint presence of NaCl plus
Na2SO4, the concentration of Cl− ion increased whereas that of SO2− 4 ion
decreased with an increase in Na2SO4 dosage in OPC. This may be due to
lower chloride binding as a result of the preferential reaction of sulfate
ions than chloride ions, with C3A hydrates resulting in higher Cl− ion
and lower SO24 − ion concentrations in the presence of NaCl plus
Na2SO4. In PPC the opposite behaviour was observed i.e. the concentra-
tion of Cl− ion decreased whereas that of SO2− 4 ion increased with an in-
crease in Na2SO4 dosage in the presence of NaCl plus Na2SO4. This may
be due to the preferential reaction of chloride ions than sulfate ions,
with C3A hydrates, thereby resulting in lower Cl− ion concentration
and higher SO2− 4 ion concentration in PPC in the conjoint presence of
NaCl plus Na2SO4.
From Table 8, it is observed that the concentration of SO2− 4 ion de-
creased whereas that of Cl− ion increased with an increase in MgSO4
dosage in both OPC and PPC in the conjoint presence of NaCl plus
MgSO4. This may be attributed to higher sulfate binding as compared
to chloride binding, with cement hydration products in the presence
of MgSO4 in concrete.
From Tables 7 and 8, it is observed that the conductivity of the con-
crete powder aqueous solution increased with an increase in admixed
NaCl concentration for OPC and PPC at all levels of admixed Na2SO4
and MgSO4, which may be attributed to an increase in Cl− concentra-
tion. The conductivity of the concrete powder aqueous solution was
higher in the conjoint presence of NaCl plus MgSO4 as compared to
that in the conjoint presence of NaCl plus Na2SO4. This indicates that
the presence of sulfate ion when associated with magnesium cation in-
creases the conductivity in the presence of NaCl. Further, the conductiv-
ity of the solution made from OPC increased with an increase in
admixed Na2SO4 and MgSO4 concentrations. In the case of PPC, the con-
ductivity increased with an increase in admixed MgSO4 concentration
whereas the conductivity mostly decreased with an increase in admixed
Na2SO4 concentration. These variations in the conductivity of the con-
crete powder aqueous solution made from OPC and PPC in the conjoint
presence of NaCl plus Na2SO4 and NaCl plus MgSO4 may be attributed to
the variations in both Cl− ion and SO2− 4 ion concentrations as observed
from Tables 7 and 8. The concentrations of cations i.e. Na+ and Ca++ in

Table 6
Chemical composition, pH and conductivity of a concrete powder aqueous solution prepared from control concrete and concrete mix admixed with NaCl for both OPC and PPC.

Cement Admixed salts concentration (% by weight of pH Conductivity Cl− SO2−

4 Na+ Ca++ K+
type cement) (mS/cm) (mmol/l) (mmol/l) (mmol/l) (mmol/l) (mmol/l)

OPC Control mix (without salt contamination) 13.4 5.5 2.8 0.22 12.8 25.2 11.2
PPC Control mix (without salt contamination) 13.2 6.6 5.6 0.3 17.1 88.6 349.1
OPC 3% NC 12.39 22.2 67.7 1.5 155.2 62.4 15.5
5% NC 12.36 27.3 138.2 1.7 174.6 94.7 16.6
7% NC 12.34 33.8 169.2 2.2 227.4 126 23.5
PPC 3% NC 12.36 24.4 73.3 1.3 113.7 514.6 33.9
5% NC 12.34 28.2 146.7 1.5 138.9 791.7 35.3
7% NC 12.32 34.6 172.1 1.7 184.2 1058.7 35.8

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
6 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx

Table 7
Chemical composition, pH and conductivity of a concrete powder aqueous solution prepared from concrete mix admixed with NaCl and Na2SO4 for both types of cement.

Cement Admixed salts concentration (% by weight of pH Conductivity Cl− SO2−

4 Na+ Ca++ K+
type cement) (mS/cm) (mmol/l) (mmol/l) (mmol/l) (mmol/l) (mmol/l)

OPC 3% NaCl + 3% Na2SO4 12.66 38.4 42 51.6 224.4 130.6 9.0

3% NaCl + 6% Na2SO4 12.6 41.6 54 40.7 233.7 134.4 9.9
3% NaCl + 12% Na2SO4 12.57 47.4 62 29.4 242.2 147.2 10.1
PPC 3% NaCl + 3% Na2SO4 12.48 40 71 40.1 150.4 1120.3 31.5
3% NaCl + 6% Na2SO4 12.64 38.7 65 44.8 194.8 872.4 28.6
3% NaCl + 12% Na2SO4 12.72 39.7 56 59.4 221.7 717.2 25.6
OPC 5% NaCl + 3% Na2SO4 12.62 39.7 124 30.5 230.7 160.6 11.1
5% NaCl + 6% Na2SO4 12.58 42.3 133 19.1 284.6 176.2 11.1
5% NaCl + 12% Na2SO4 12.55 49.2 135 18.7 285.9 196.9 11.3
PPC 5% NaCl + 3% Na2SO4 12.44 42.81 121 23.4 159.1 1033.0 38.8
5% NaCl + 6% Na2SO4 12.61 40.2 116 33.2 219.0 627.4 37.2
5% NaCl + 12% Na2SO4 12.68 40.4 113 44.8 269.6 504.5 36.2
OPC 7% NaCl + 3% Na2SO4 12.61 40.3 144 13.7 298.0 188.4 12.0
7% NaCl + 6% Na2SO4 12.56 45.7 158 7.0 349.1 199.1 12.3
7% NaCl + 12% Na2SO4 12.44 50.2 164 5.8 455.2 235.5 12.3
PPC 7% NaCl + 3% Na2SO4 12.18 47.4 138 13.2 192.2 908.2 48.0
7% NaCl + 6% Na2SO4 12.58 42.4 135 23.4 238.3 593.2 42.2
7% NaCl + 12% Na2SO4 12.65 41.6 118 40.6 314.4 492.2 40.5

the concrete powder aqueous solution varied significantly with concen-
trations of admixed NaCl, Na2SO4 and MgSO4. However, the variation in
concentration of K+ ion with an admixed concentration of these salts
was not significant. Further the concentrations of Ca++ and K+ ions in
the concrete powder aqueous solution made from PPC were higher
than that in the solution made from OPC in the conjoint presence of
NaCl plus Na2SO4 and NaCl plus MgSO4 as observed from Tables 7 and
8. The higher concentration of Ca++ and K+ ions in PPC may be due
to a change in the extent of the hydration reaction due to the pozzolanic
activity and also as a result of a change in reactivity of the alkali com-
pounds. The concentration of Na+ ion was higher in the concrete pow-
der aqueous solution contaminated with NaCl plus Na2SO4 in OPC than
that in PPC, whereas in NaCl plus MgSO4 contamination, the opposite
behaviour was observed, i.e. the Na+ ion concentration was higher in
PPC as compared to that in OPC. In NaCl plus Na2SO4 contamination,
the higher concentration of Na+ ion in OPC than that in PPC may be at-
tributed to the reaction of sodium sulfate with calcium hydroxide to a
greater extent, thereby resulting in a higher concentration of Na+ ion.
In PPC, the dominant effect of admixed NaCl has resulted in a higher
concentration of Na+ ion in the presence of MgSO4 as compared to OPC.
From Tables 7 and 8, it is observed that the concrete powder aqueous
solution contaminated with NaCl plus Na2SO4 showed a higher pH as
compared to that contaminated with NaCl plus MgSO4 for both OPC
and PPC. The higher pH in the presence of sodium sulfate may be
attributed to the formation of sodium hydroxide (as a result of the reac-
tion between calcium hydroxide and sodium sulfate), which increases
the pH value. In the presence of magnesium sulfate, magnesium hy-
droxide that is formed due to the reaction between calcium hydroxide
and magnesium sulfate has very low solubility and low pH value [3]
that has resulted in a reduction in pH value of the concrete powder
aqueous solution contaminated with NaCl plus MgSO4.
3.3. Different zones of corrosion
The anodic polarization curves for steel in electrolytic concrete pow-
der aqueous solutions made from different concrete mixes have been
obtained by conducting a potentiodynamic polarization test. The anodic
polarization curves of steel in concrete powder aqueous solutions made
from OPC and PPC at w/c ratio of 0.5 for the control mix are shown in Fig.
3. In these curves, different zones of corrosion of steel namely the active
zone, passive zone and transpassivity zone are shown. In the presence of
chloride ions, the transpassivity zone is termed as pitting zone.
From Fig. 3, it is observed that the range of the passive zone is higher
in OPC as compared to that in PPC, which may be attributed to more al-
kalinity due to the availability of more amounts of calcium hydroxide in
the OPC concrete. The corrosion potential (Ecorr), potential at the point
of transition from active to passive state i.e. act/pass zone boundary po-
tential and potential at the point of transition from passive to

Table 8
Chemical composition, pH and conductivity of a concrete powder aqueous solution prepared from concrete mix admixed with NaCl and MgSO4 for both types of cement.

Cement Admixed salts concentration (% by weight of pH Conductivity Cl− SO2−

4 Na+ Ca++ K+
type cement) (mS/cm) (mmol/l) (mmol/l) (mmol/l) (mmol/l) (mmol/l)

OPC 3% NaCl + 3% MgSO4 12.36 41.4 73 10.26 103.5 132.1 20.7

3% NaCl + 6% MgSO4 12.24 44.2 76 3.68 110.2 171.2 20.2
3% NaCl + 12% MgSO4 12.01 48.5 85 2.77 135.4 172.9 19.6
PPC 3% NaCl + 3% MgSO4 12.27 44.9 79 8.2 104.8 859.3 30.7
3% NaCl + 6% MgSO4 12.18 46.6 85 3.86 113.7 658.6 31.2
3% NaCl + 12% MgSO4 12.04 51.3 90 1.6 146.3 592.9 30.8
OPC 5% NaCl + 3% MgSO4 12.32 43.6 141 5.13 193.5 166.9 15.9
5% NaCl + 6% MgSO4 12.21 45.1 147 3.49 193.5 176.2 15.5
5% NaCl + 12% MgSO4 11.97 50.4 158 1.86 198.9 194.4 14.3
PPC 5% NaCl + 3% MgSO4 12.23 46.2 152 4.25 194.8 814.2 33.3
5% NaCl + 6% MgSO4 12.15 49.7 161 3.37 215.4 609.6 35.0
5% NaCl + 12% MgSO4 11.84 51.8 169 1.36 221.8 492.2 35.1
OPC 7% NaCl + 3% MgSO4 12.28 47.8 164 4.17 204.4 199.2 13.6
7% NaCl + 6% MgSO4 12.17 48.3 175 2.86 226.1 207.0 12.7
7% NaCl + 12% MgSO4 11.78 52.6 178 1.6 247.8 221.1 12.3
PPC 7% NaCl + 3% MgSO4 12.21 48.7 181 4.01 210.0 754.0 35.4
7% NaCl + 6% MgSO4 12.1 50.8 183 2.81 237.0 509.0 37.9
7% NaCl + 12% MgSO4 11.33 54.5 186 0.43 243.5 404.2 38.3

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx
Fig. 3. Anodic polarization curve showing zones of corrosion obtained for steel in the concrete powder aqueous solution made from OPC and PPC concrete (control mix).
transpassive state i.e. pass/transpass zone boundary potential are
shown in Fig. 3. In the presence of chloride ion, the potential at the
point of transition from passive to pitting state is termed as breakdown
potential or pitting potential.
3.3.1. Effect of chloride contamination on zones of corrosion
The anodic polarization curves of steel in concrete powder aqueous
solutions contaminated with 3%, 5% and 7% NaCl concentrations are
shown in Fig. 4 for both OPC and PPC. From these obtained polarization
curves, corrosion potential (Ecorr), act/pass boundary potential and
pass/pitt boundary potential (pitting potential) were obtained and are
presented in Table 9. In addition, the potential values for the control
mix (i.e. without any admixed salt) are also presented in this table. As
already stated, two replicate steel specimens were tested for a given
concrete powder aqueous solution to observe the reproducibility.
From the obtained polarization curves of replicates, it is observed that,
there is not much difference between the profiles of polarization curve
of both the replicates. The boundary potential values presented in
Fig. 4. Anodic polarization curves for steel in concrete powder aqueous solutions prepared
from OPC and PPC concrete admixed with 3% NaCl, 5% NaCl and 7% NaCl (added by weight
of cement).
Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
7
Table 9 are the average value of two replicate steel specimens for a
given concrete powder aqueous solution.
From Table 9, it is observed that the corrosion potential (Ecorr) be-
came more negative with an increase in admixed NaCl concentration
from 3% to 7% for both OPC and PPC. In addition, the range of a passive
zone (calculated from the difference of breakdown potential and act/
pass boundary potential) decreased with an increase in admixed chlo-
ride content in both OPC and PPC. The breakdown potential (pitting po-
tential) became more negative with an increase in admixed NaCl
dosage, which is attributed to an increase in Cl− ion concentration in
the aqueous solution as observed from Table 6. While analyzing the ef-
fect of binder type on pitting potential, it is observed that the pitting po-
tential of steel in PPC is more negative than that in OPC. This is
attributed to higher Cl− ion concentration in PPC as compared to that
in OPC. Further, the range of the passive zone of a steel reinforcement
was less in PPC than that in OPC at all levels of chloride contamination.
A typical plot showing the variations of boundary potentials with Cl−
ion concentration for OPC is presented in Fig. 5. From this figure, it is ob-
served that the range of the passive zone decreased with an increase in
Cl− ion concentration.
The XRD patterns obtained from concrete powder samples contam-
inated with 3%, 5% and 7% NaCl concentrations are shown in Fig. 6a, b
and c respectively, for both OPC and PPC. The XRD patterns in Fig.
6(a–c) indicate the peaks of gypsum (G), ettringite (E), calcium hydrox-
ide (CH), calcium carbonate (CC), quartz (Q), thaumasite (T) and calci-
um chloroaluminate (CCA), which are formed in concrete. The calcium
chloroaluminate peak was found at 11.2° 2θ and 23° 2θ. The peak inten-
sity of CCA was more in OPC as compared to that in PPC at all dosages of
admixed NaCl, as observed from Fig. 6(a–c), which is attributed to more
chloride binding with hydrated C3A in OPC than that in PPC. It may be
noted that the Cl− ion concentration was lower in OPC as compared to
that in PPC as observed from Table 6. Therefore, the steel reinforcement
in a chloride contaminated concrete powder aqueous solution made
from OPC showed a higher range of passivity as compared to that
made from PPC. Gypsum peaks were identified at 32.1° 2θ and 50.5°
2θ and the presence of this primary gypsum may be attributed to its ad-
dition to a Portland cement clinker during manufacturing, to prevent
flash setting of cement. Gypsum when combined with C3A, forms
ettringite. The peaks of ettringite were found at 8.8° 2θ, 15.75° 2θ,
25.6° 2θ, and 27.5° 2θ. It is observed that the peaks of ettringite in OPC
8 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx
Table 9
Corrosion potential and boundary potentials of steel reinforcement in a concrete powder aqueous solution prepared from control concrete and concrete admixed with NaCl for OPC and
PPC.
Cement type Admixed salts concentration Corrosion potential (mV/SCE)
(% by weight of cement)
OPC Control mix (without salt −346
contamination)
PPC Control mix (without salt −280
contamination)
OPC 3% NaCl −326
5% NaCl −349
7% NaCl −393
PPC 3% NaCl −338
5% NaCl −360
7% NaCl −363
concrete are less intense than that in PPC concrete at all levels of
admixed NaCl. This is due to the preferential reaction of chloride ions
with C3A to form more amounts of calcium chloroaluminate in OPC,
resulting in lesser availability of C3A to react with gypsum to form a
lower amount of ettringite. The OPC concrete showed the precipitation
of calcium hydroxide through well-defined peaks at 18.08° 2θ, 34.1° 2θ,
and 36.5° 2θ, whereas in PPC, the peaks of calcium hydroxide almost
disappeared at 18.08° 2θ and 34.1° 2θ. The peaks of calcium hydroxide
in PPC was found only at 36.5° 2θ with reduced intensity as compared
to that in OPC as evident from Fig. 6(a–c). The reduced peaks of calcium
hydroxide in PPC are due to its consumption in the pozzolanic reaction.
Further peaks of quartz were found at 20.85° 2θ, 26.65° 2θ, 39.45° 2θ,
42.5° 2θ and 50.1° 2θ, as shown in Fig. 6(a–c), which is mostly due to
the presence of aggregates in the concrete. Similarly, the peaks of
thaumasite and calcium carbonate were found at 27.9° 2θ and 29.4° 2θ
respectively.
As stated earlier, for the purpose of identifying different functional
groups associated with different products formed in concrete, Fourier
transform infrared (FTIR) spectroscopy was conducted. FTIR spectra of
concrete powder samples contaminated with 3%, 5% and 7% NaCl concen-
trations are shown in Fig. 7a–c respectively, for both OPC and PPC. From
Fig. 7(a–c), it is observed that the bands ranging from 3445 cm−1 to
3452 cm−1 cm and 1642 cm−1 to 1649 cm−1 for OPC and those at
3394 cm−1 and ranging from 1594 cm−1 to 1598 cm−1 for PPC at all
dosages of admixed chloride are caused by stretching and bending
bands of the O\\H group particularly contributed from gypsum
[31–33]. Further, the infrared spectra for OPC indicate an additional
stretching band of the O\\H group at 3663 cm−1 that is contributed by
the presence of more amounts of calcium hydroxide in the OPC concrete
[31,33]. The XRD patterns as shown in Fig. 6(a–c) indicate the presence
of calcium carbonate in concrete at 29.4° 2θ, which is substantiated by
infrared spectra showing CO23 − bands ranging from 1424 cm− 1 to
1432 cm−1 for OPC and ranging from 1388 cm−1 to 1399 cm−1 for PPC
Fig. 5. Potential vs. Cl− ion concentration in OPC concrete admixed with 3%, 5% and 7%
NaCl (added by weight of cement).
Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
Act/pass boundary potential Pass/transpass boundary potential (for control mix) and
(mV/SCE) Pass/pitt boundary potential (pitting potential) (mV/SCE)
−216 523
−211 430
−236 −34
−283 −105
−342 −178
−267 −83
−304 −145
−334 −186
[33–35] as shown in Fig. 7(a–c). The bands ranging from 996 cm−1 to
1004 cm−1 and 776 cm−1 to 778 cm−1 for OPC and at 940 cm−1 and
ranging from 725 cm−1 to 730 cm−1 for PPC represent ν1 and ν4
vibrations of SO2−
4 bands contributed by the presence of gypsum
[31–33]. The formation of ettringite as indicated by XRD patterns was
corroborated by the presence of Al\\O peak at 872 cm−1 for OPC and
824 cm−1 for PPC [33,35] as shown in Fig. 7(a–c) at all dosages of
admixed chloride.
3.3.2. Effect of conjoint chloride-sulfate contamination on zones of
corrosion
The anodic polarization curves of steel in concrete powder aqueous
solutions contaminated with all concentrations (shown in Table 4) of
NaCl plus Na2SO4 and NaCl plus MgSO4 were obtained and some typical
anodic polarization curves of steel in concrete powder aqueous solu-
tions contaminated with 3%NaCl + 3%Na2SO4, 5%NaCl + 6%Na2SO4,
and 7%NaCl + 12%Na2SO4 are shown in Figs. 8 and 9 for OPC and PPC re-
spectively. Similarly Figs. 10 and 11 show the typical anodic polarization
curves obtained from OPC and PPC respectively in concrete powder
aqueous solutions contaminated with 3%NaCl + 3%MgSO4, 5%NaCl +
6%MgSO4, and 7%NaCl + 12%MgSO4. From the anodic polarization
curves, the values of corrosion potential (Ecorr), act/pass boundary po-
tential and pass/pitt boundary potential (pitting potential) were obtain-
ed and are presented in Table 10 for NaCl plus Na2SO4 and NaCl plus
MgSO4 contaminations. The boundary potential values presented in
these tables are the average value of two replicate steel specimens for
a given concrete powder aqueous solution.
3.3.2.1. Effect of conjoint NaCl plus Na2SO4 contamination on passivity of
steel. From the boundary potential values presented in Table 10, it is ob-
served that the range of the passive zone decreased with an increase in
admixed NaCl concentration irrespective of admixed Na2SO4 concentra-
tion for both OPC and PPC. However the change in range of the active
zone with admixed NaCl concentration is not systematic in the presence
of sulfate ions for both types of cement. Further from Table 10, it is ob-
served that the range of the passive zone, which is calculated from the
difference of pass/pitt boundary potential and act/pass boundary poten-
tial is higher in OPC as compared to that in PPC at 3% Na2SO4 concentra-
tion whereas PPC showed higher passivity range at 6% and 12% Na2SO4
concentrations for all dosages of admixed NaCl. From the results pre-
sented in Table 7, it is observed that for 3% Na2SO4, the Cl− ion concen-
tration was significantly higher in PPC as compared to that in OPC at 3%
NaCl, whereas there was a minor difference in Cl− ion concentration be-
tween OPC and PPC at 5% and 7% NaCl concentrations. However at 6%
and 12% Na2SO4 concentrations, Cl− ion concentration was mostly
higher in the concrete powder aqueous solution made from OPC than
that in PPC at all dosages of NaCl. This indicates that the higher passivity
range in OPC at a lower Na2SO4 concentration (i.e. 3%) and that in PPC at
higher Na2SO4 concentrations (i.e. 6% and 12%) may be attributed to
higher chloride binding resulting in a lower Cl− ion concentration at
corresponding Na2SO4 concentrations in the presence of NaCl.
 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx 9

Fig. 7. a: FTIR spectra of OPC and PPC concrete admixed with 3% NaCl (added by weight of
cement). b: FTIR spectra of OPC and PPC concrete admixed with 5% NaCl (added by weight
of cement). c: FTIR spectra of OPC and PPC concrete admixed with 7% NaCl (added by
weight of cement).

From Table 10, it is observed that the passivity breakdown potential

Fig. 6. a: XRD patterns of OPC and PPC concrete admixed with 3% NaCl (added by weight of
cement). b: XRD patterns of OPC and PPC concrete admixed with 5% NaCl (added by
weight of cement). c: XRD patterns of OPC and PPC concrete admixed with 7% NaCl
(added by weight of cement).
or pitting potential of steel in aqueous solutions made from OPC con-
crete decreased (i.e. became more negative) with the increase in
Na2SO4 concentration at all dosages of NaCl. This may be attributed to

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
10 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx
Fig. 8. Typical anodic polarization curves obtained for steel in concrete powder aqueous
solutions prepared from OPC concrete admixed with different concentrations of NaCl
and Na2SO4 (added by weight of cement).
an increase in Cl− ion concentration and a decrease in pH of the solution
(Table 7) with an increase in Na2SO4 concentration in the presence of
NaCl. For steel in the concrete powder aqueous solution made from
PPC, the opposite behaviour was observed, i.e. the pitting potential in-
creased (i.e. became less negative) with the increase in concentration
of Na2SO4 at all dosages of NaCl as observed from Table 10. The increase
in pitting potential for PPC may be due to a decrease in Cl− ion concen-
tration and an increase in pH of the solution with an increase in Na2SO4
concentration in the presence of NaCl as observed from Table 7. This in-
dicates that the breakdown/pitting potential is a function of Cl− ion con-
centration in the solution, which in turn depends on the concentration
of Na2SO4 and is also influenced by a little change in pH value of the so-
lution. The minimum (more negative) pitting potential was observed in
the presence of higher Cl− ion concentration and lower SO2− 4 ion con-
centration (Tables 7 and 10) for both OPC and PPC in the concrete pow-
der aqueous solution contaminated with both NaCl and Na2SO4. The
reasons for variations in Cl− ion and SO2−4 ion concentrations for OPC
and PPC are already stated in Section 3.2.
The XRD patterns of concrete powder samples contaminated with
different concentrations of NaCl plus Na2SO4 were obtained and that
of a typical chloride-sulfate contamination is presented in Fig. 12 for
3%NaCl + 3%Na2SO4 for both OPC and PPC. It is to be noted that, the
compounds formed in concrete in the presence of composite chloride-
Fig. 9. Typical anodic polarization curves obtained for steel in concrete powder aqueous
solutions prepared from PPC concrete admixed with different concentrations of NaCl
and Na2SO4 (added by weight of cement).
Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
Fig. 10. Typical anodic polarization curves obtained for steel in concrete powder aqueous
solutions prepared from OPC concrete admixed with different concentrations of NaCl and
MgSO4 (added by weight of cement).
sulfate ions are identified in the XRD patterns at 2θ values the same as
that in the case of chloride contaminated concrete. In Fig. 12, the XRD
patterns show the peaks of gypsum and ettringite for both OPC and
PPC. The formation of gypsum and ettringite is also corroborated from
FTIR spectra shown in Fig. 13 for the above mentioned typical combina-
tion of NaCl plus Na2SO4 in both OPC and PPC. For OPC, the bands at
3447 cm−1 and 1641 cm−1 as shown in the FTIR spectra (Fig. 13) corre-
spond to stretching and bending modes of the O\\H group contributed
from gypsum. The bands at 1011 cm−1 and ranging from 649 cm−1 to
778 cm−1 are due to ν1 and ν4 vibrations of SO2− 4 associated with gyp-
sum. The presence of ettringite is confirmed by the stretching bands of
Al\\O at 874 cm−1 and 533 cm−1 in OPC concrete. For PPC concrete,
FTIR spectra shown in Fig. 13 indicate the stretching and bending
modes of the O\\H group at 3447 cm−1 and 1638 cm−1, which are con-
tributed from gypsum. Further, the bands at 1000 cm−1 and ranging
601 cm−1 to 776 cm−1 due to ν1 and ν4 vibrations of SO2− 4 are also as-
sociated with gypsum. The Al\\O stretching bands associated with
ettringite are found at 874 cm− 1 and 534 cm−1 for PPC as shown in
Fig. 13. Similar to 3% NaCl plus 3% Na2SO4 contamination, functional
groups associated with different products as shown by FTIR spectra
were also obtained for other levels of NaCl plus Na2SO4 contamination.
The peak intensity of calcium chloroaluminate was more in PPC than
that in OPC for 3% NaCl plus 3% Na2SO4 contamination as observed from
Fig. 12. In PPC the preferential reaction of chloride ions with C3A has led
Fig. 11. Typical anodic polarization curves obtained for steel in concrete powder aqueous
solutions prepared from PPC concrete admixed with different concentrations of NaCl and
MgSO4 (added by weight of cement).
 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx 11

Table 10
Corrosion potential and boundary potentials of steel reinforcement in a concrete powder aqueous solution prepared from concrete mix admixed with NaCl plus Na2SO4 and NaCl plus
MgSO4 for both types of cement.

Chloride-sulfate Cement Admixed salts concentration (% by Corrosion potential Act/pass boundary Pass/pitt boundary potential (pitting
contamination type weight of cement) (mV/SCE) potential (mV/SCE) potential) (mV/SCE)

Sodium chloride plus OPC 3% NaCl + 3% Na2SO4 −322 −202 369

sodium sulfate 3% NaCl + 6% Na2SO4 −328 −248 27
3% NaCl + 12% Na2SO4 −356 −305 −80
PPC 3% NaCl + 3% Na2SO4 −362 −284 −54
3% NaCl + 6% Na2SO4 −318 −265 59
3% NaCl + 12% Na2SO4 −354 −212 120
OPC 5% NaCl + 3% Na2SO4 −344 −306 −34
5% NaCl + 6% Na2SO4 −426 −363 −141
5% NaCl + 12% Na2SO4 −409 −379 −197
PPC 5% NaCl + 3% Na2SO4 −440 −408 −189
5% NaCl + 6% Na2SO4 −315 −289 −33
5% NaCl + 12% Na2SO4 −328 −250 18
OPC 7% NaCl + 3% Na2SO4 −333 −258 −83
7% NaCl + 6% Na2SO4 −381 −318 −167
7% NaCl + 12% Na2SO4 −346 −290 −168
PPC 7% NaCl + 3% Na2SO4 −361 −310 −152
7% NaCl + 6% Na2SO4 −356 −302 −83
7% NaCl + 12% Na2SO4 −324 −268 −42
Sodium chloride plus OPC 3% NaCl + 3% MgSO4 −204 −172 16
magnesium sulfate 3% NaCl + 6% MgSO4 −361 −269 −90
3% NaCl + 12% MgSO4 −396 −338 −179
PPC 3% NaCl + 3% MgSO4 −415 −380 −219
3% NaCl + 6% MgSO4 −266 −213 −76
3% NaCl + 12% MgSO4 −466 −407 −281
OPC 5% NaCl + 3% MgSO4 −320 −212 −36
5% NaCl + 6% MgSO4 −384 −294 −134
5% NaCl + 12% MgSO4 −396 −325 −181
PPC 5% NaCl + 3% MgSO4 −366 −289 −133
5% NaCl + 6% MgSO4 −285 −236 −90
5% NaCl + 12% MgSO4 −436 −338 −268
OPC 7% NaCl + 3% MgSO4 −286 −172 −9
7% NaCl + 6% MgSO4 −366 −291 −143
7% NaCl + 12% MgSO4 −436 −348 −230
PPC 7% NaCl + 3% MgSO4 −398 −344 −201
7% NaCl + 6% MgSO4 −418 −360 −229
7% NaCl + 12% MgSO4 −376 −340 −240

to higher chloride binding, thus resulting in the formation of more
amounts calcium chloroaluminate and a similar observation was
found for other levels of NaCl plus Na2SO4 contamination. The intensity
of a calcium hydroxide peak in XRD patterns is less in PPC as compared
to that in OPC at all levels of chloride-sulfate contaminations, which is
attributed to the consumption of Ca(OH)2 in pozzolanic reaction in
PPC concrete. Gypsum and ettringite peaks were more intense in OPC
as compared to that in PPC as observed from Fig. 12 and similar results
were found for other combinations of NaCl plus Na2SO4 concentrations.
The availability of a higher amount of Ca(OH)2 in OPC has resulted in the
formation of more amounts of gypsum in the presence of sulfate ions,
thus showing intense peaks of gypsum in OPC as compared to that in
PPC. Further in OPC, the preferential reaction of sulfate ions with C3A
has resulted in the formation of a higher amount of ettringite as com-
pared to that in PPC in the conjoint presence of Na2SO4 and NaCl, thus
showing intense peaks of ettringite in OPC. The reasons for the forma-
tion of lower amounts of gypsum and ettringite in PPC as compared to

Fig. 12. XRD patterns of OPC and PPC concrete admixed with 3% NaCl + 3% Na2SO4 (added Fig. 13. FTIR spectra of OPC and PPC concrete admixed with 3% NaCl + 3% Na2SO4 (added
by weight of cement). by weight of cement).

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
12 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx
OPC in the conjoint presence of Na2SO4 and NaCl are: a) in the first
stage, sodium sulfate reacts with calcium hydroxide liberated during
the hydration reaction and forms calcium sulfate and sodium hydrox-
ide. This stage is hindered in PPC due to less reserve of calcium hydrox-
ide leading to less formation of gypsum, thus showing its less intense
peaks in XRD patterns. In the second stage, gypsum produced (in the
first stage) reacts with C3A to form expansive ettringite. The amount
of ettringite formation is reduced in PPC due to a lesser availability of
gypsum and C3A (diluted due to the replacement of a part of the
Portland cement clinker by fly ash in PPC), thus showing less intense
peaks of ettringite in PPC. The XRD patterns (Fig. 12) show the peaks
of quartz, thaumasite and calcium carbonate for both OPC and PPC at
all levels of chloride-sulfate contaminations. Thaumasite may be formed
as a result of the reaction between C\\S\\H, calcium carbonate and cal-
cium sulfate in the presence of water. It may also be formed through a
woodfordite route due to the reaction between C\\S\\H, ettringite
and calcium carbonate in the presence of water [36,37]. The presence
of calcium carbonate is also substantiated by FTIR spectra showing
CO23 − bands at 1427 cm− 1 for OPC and at 1424 cm− 1 for PPC as ob-
served from Fig. 13.
3.3.2.2. Effect of conjoint NaCl plus MgSO4 contamination on passivity of
steel. From the boundary potential values presented in Table 10 for
NaCl plus MgSO4 contamination, it is observed that the passivity range
decreased with an increase in NaCl concentration for both OPC and
PPC at all levels of MgSO4 concentration. The variation in range of the ac-
tive zone with varying concentrations of NaCl is not systematic in the
presence of sulfate ions for both types of cement as observed from
boundary potential values presented in Table 10. Further the range of
the passive zone decreased with an increase in admixed MgSO4 concen-
tration at all levels of admixed NaCl for both types of cement as ob-
served from Table 10, which may be due to an increase in Cl− ion
concentration with an increase in the dosage of MgSO4. The increase
in Cl− ion concentration (presented in Table 8) with an increase in
added magnesium sulfate concentration may be due to lower chloride
binding as a result of the preferential reaction of sulfate ions as com-
pared to chloride ions, with hydrated C3A in concrete. It is also observed
that the range of passive zone of steel is higher in concrete powder
aqueous solutions made from OPC as compared to that made from
PPC at all levels of sodium chloride plus magnesium sulfate concentra-
tions, which indicates that OPC maintains the passivity of reinforcing
steel to a greater extent than PPC in the conjoint presence of NaCl and
MgSO4. This is attributed to lower Cl− ion concentration observed in
OPC as compared to that in PPC at all levels of admixed NaCl plus
MgSO4 concentrations. A further decrease in the passivity range of
steel in PPC in the conjoint presence of NaCl and MgSO4 can also be at-
tributed to its susceptibility to Mg-oriented attack. Magnesium sulfate
reacts with calcium hydroxide liberated in the hydration reaction of cal-
cium silicates (C3S and C2S) to form calcium sulfate (gypsum) and mag-
nesium hydroxide (brucite) [38]. In PPC due to less reserve of calcium
hydroxide, which acts as the first defensive material to react with mag-
nesium sulfate, the magnesium sulfate attack is therefore directed ex-
tensively towards C\\S\\H gel, ultimately forming more amounts of
gypsum and non-cementitious magnesium silicate hydrate (M\\S\\H)
[3]. Thus the passivity of steel in the concrete powder aqueous solution
made from PPC in the presence of NaCl plus MgSO4 is decreased due to
an increase in the conductivity of the concrete powder aqueous solution
as a result of more Cl− ion concentration and formation of more
amounts of non-cementitious magnesium silicate hydrate.
From the pitting potential values presented in Table 10, it is ob-
served that the pitting potential became more negative with an increase
in MgSO4 concentration for OPC at all dosages of NaCl. This is attributed
to a drop in pH of the solution and also due to an increase in Cl− ion con-
centration in the solution (Table 8) with an increase in MgSO4 concen-
tration in the conjoint presence of NaCl and MgSO4. For PPC, the pitting
potential increased (less negative) with an increase in MgSO4
Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
concentration up to 6% followed by a decrease (more negative) at 12%
MgSO4 concentration for 3% and 5% NaCl concentrations as observed
from Table 10. However at 7% NaCl, the pitting potential decreased
with an increase in MgSO4 concentration. Although, the variation in
pitting potential with MgSO4 concentration is not systematic in PPC,
the minimum pitting potential was observed at 12% MgSO4 concentra-
tion for all dosages of NaCl and this may be due to higher Cl− ion con-
centration and lower pH of the solution at 12% MgSO4 concentration
as observed from Table 8.
For both OPC and PPC, the XRD patterns of concrete samples con-
taminated with different concentrations of NaCl plus MgSO4 were ob-
tained and a typical plot is shown in Fig. 14 for 3%NaCl + 3%MgSO4.
The XRD patterns in Fig. 14 show the peaks of calcium hydroxide and
magnesium hydroxide (at 33.9° 2θ) for both OPC and PPC. From this fig-
ure, it is observed that peak intensities of both calcium hydroxide and
magnesium hydroxide (MH) are less in PPC as compared to that in
OPC. The similar results were obtained for other levels of NaCl plus
MgSO4 concentrations. The lower Ca(OH)2 reserve in PPC concrete is
due to its consumption in pozzolanic reaction, thus showing its less in-
tense peaks. The lower amount of Ca(OH)2 in PPC has resulted in the
formation of a lower amount of magnesium hydroxide in the presence
of magnesium sulfate, thus showing less intense peaks in PPC as com-
pared to that in OPC. Further, the XRD patterns show the peaks of gyp-
sum and ettringite for both types of cement at all levels of sodium
chloride plus magnesium sulfate contaminations. The peak intensities
of gypsum and ettringite are more in PPC as compared to that in OPC
in the conjoint presence of NaCl and MgSO4 as observed from the XRD
patterns. The formation of a higher amount of gypsum in PPC may be at-
tributed to a Mg-oriented attack on C\\S\\H because of less reserves of
calcium hydroxide in PPC, thus showing more intense peaks of gypsum.
The more intense peaks of ettringite in PPC as compared to that in OPC
may be due to the reaction of gypsum with hydrated aluminate phases
in concrete to a greater extent. The formation of gypsum and ettringite
is also confirmed from FTIR spectra shown in Fig. 15 for the typical com-
bination of 3% NaCl plus 3% MgSO4 in both OPC and PPC. For OPC, the
FTIR spectra shown in Fig. 15 indicate that the bands at 3446 cm−1
and 1641 cm−1 that correspond to stretching and bending modes of
the O\\H group contributed from gypsum and the bands at 1008 cm−1
and ranging from 649 cm−1 to 778 cm−1 are due to ν1 and ν4 vibrations
of SO2−
4 associated with gypsum. The presence of ettringite is confirmed
by the stretching bands of Al\\O at 874 cm−1 and 535 cm−1 for OPC
concrete. For PPC, the FTIR spectra show the stretching and bending
modes of the O\\H group at 3456 cm−1 and 1639 cm−1 that correspond
to gypsum. Further the bands at 965 cm−1 and ranging from 601 cm−1 to
773 cm−1 due to ν1 and ν4 vibrations of SO2− 4 are also associated with
Fig. 14. XRD patterns of OPC and PPC concrete admixed with 3% NaCl + 3% MgSO4 (added
by weight of cement).
 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx
Fig. 15. FTIR spectra of OPC and PPC concrete admixed with 3% NaCl + 3% MgSO4 (added
by weight of cement).
gypsum. The Al\\O stretching bands associated with ettringite
are found at 875 cm− 1 and 535 cm− 1 in PPC. Similarly, functional
groups associated with different products as shown by FTIR spectra
were also obtained for other concentrations of NaCl plus MgSO 4
contamination.
The reaction of chloride ions with C3A has led to the formation of cal-
cium chloroaluminate, as shown by peaks in both OPC and PPC as ob-
served from Fig. 14. The XRD patterns indicate the formation of higher
amount of calcium chloroaluminate in PPC in most of the cases as com-
pared to OPC for NaCl plus MgSO4 contaminations. The higher free Cl−
ion concentration in PPC than that in OPC for NaCl plus MgSO4 contam-
ination (as observed from Table 8) may be attributed to the dominant
effect of less physical binding of chloride ions with C\\S\\H, as C\\S\\H
converts to non-cementitious magnesium silicate hydrate (M\\S\\H)
in the presence of MgSO4 to a greater extent in PPC. The comparatively
higher physical chloride binding in OPC has resulted in lower Cl− ion
concentration, although there is less formation of calcium
chloroaluminate as indicated by its lower intense peaks in XRD patterns.
The peaks of quartz, calcium carbonate and thaumasite were also found
in XRD patterns shown in Fig. 14 for both OPC and PPC. The presence of
calcium carbonate is also substantiated by FTIR spectra shown in Fig. 15
−1
through the bands of CO2− 3 at 1424 cm for OPC and at 1478 cm−1 for
PPC.
3.3.3. Comparison between chloride contamination and conjoint chloride-
sulfate contamination on passivity
In both types of cement, the range of the passive zone of steel in con-
crete powder aqueous solutions contaminated with only sodium chlo-
ride is less as compared to that in concrete powder aqueous solutions
contaminated with sodium chloride plus sodium sulfate as observed
from Tables 9 and 10. This indicates that the presence of sodium sulfate
in a chloride environment has mitigated the effect of chloride ions on re-
ducing the passivity of reinforcing steel. The range of the passive zone of
reinforcing steel is more in concrete powder aqueous solutions contam-
inated with only sodium chloride as compared to that in the conjoint
presence of sodium chloride and magnesium sulfate as observed from
Tables 9 and 10. This indicates that the presence of magnesium sulfate
in a chloride environment has stimulated the effect of chloride ions on
reducing the passivity of steel reinforcement. It may also be noted that
a lower Cl− ion concentration was found in the concrete mixes contam-
inated with NaCl plus Na2SO4 whereas a higher Cl− ion concentration
was found in the concrete mixes contaminated with NaCl plus MgSO4
as compared to the concrete mixes contaminated with only NaCl. On
comparison of the effect of cation type (Na+ and Mg++) associated
with sulfate ions, it is observed that the range of the passive zone of
Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008
13
Fig. 16. Potential vs. Cl− ion concentration in OPC concrete admixed with different dosages
of NaCl with 6% Na2SO4 and 6% MgSO4 (added by weight of cement).
steel is more in a NaCl plus Na2SO4 environment as compared to that
in a NaCl plus MgSO4 environment for both types of cement as observed
from boundary potential values presented in Table 10. This is also evi-
dent from a typical plot shown in Fig. 16, which is showing the variation
in boundary potential values with Cl− ion concentration for Na2SO4 and
MgSO4 contaminations. This implies that Mg-oriented sulfate attack is
more aggressive in the presence of chloride ions in reducing the passiv-
ity of steel reinforcement as compared to Na-oriented sulfate attack.
Further, the range of the passive zone of steel is mostly higher in PPC
as compared to that in OPC in the conjoint presence of sodium chloride
and sodium sulfate whereas OPC showed a higher range of the passive
zone as compared to PPC in the conjoint presence of sodium chloride
plus magnesium sulfate. This indicates OPC performed better against
Mg-oriented sulfate attack whereas PPC performed better against Na-
oriented sulfate attack in the presence of chloride ions.
4. Conclusions
Following conclusions have been drawn from the results of the pres-
ent investigation.
i. The concrete powder aqueous solution contaminated with NaCl
plus Na2SO4 showed higher pH as compared to that contaminat-
ed with NaCl plus MgSO4 for both types of cement. Further, the
conductivity of the concrete powder aqueous solution was
lower in the conjoint presence of NaCl and Na2SO4 as compared
to that in the conjoint presence of NaCl and MgSO4.
ii. The passive zone decreased with an increase in admixed NaCl
concentration in all the concrete mixes.
iii. The passivity range of steel reinforcement in chloride contami-
nated concrete powder aqueous solutions is higher in OPC as
compared to that in PPC.
iv. The presence of sodium sulfate in a chloride environment has
mitigated the effect of chloride ions whereas the presence of
magnesium sulfate in a chloride environment has stimulated
the effect of chloride ions, on reducing the passivity of steel rein-
forcement.
v. The steel reinforcement in a concrete powder aqueous solution
made from PPC mostly showed a higher range of the passive
zone as compared to OPC in the conjoint presence of NaCl and
Na2SO4.
vi. In the concrete powder aqueous solutions contaminated with
NaCl and MgSO4, the range of the passive zone of the steel rein-
forcement was less in PPC as compared to that in OPC.
vii. The XRD patterns indicating the formation of different com-
pounds such as gypsum, calcium carbonate and ettringite in con-
crete were further substantiated with the FTIR spectra showing
the functional groups such O\\H, SO24 −, CO23 − and Al\\O
14 F. Shaheen, B. Pradhan / Cement and Concrete Research xxx (2016) xxx–xxx

associated with these compounds.
viii. For both NaCl plus Na2SO4 and NaCl plus MgSO4 contaminations,
the minimum (more negative) pitting potential was observed at
a higher Cl− ion concentration and lower SO2−
4 ion concentration
for both OPC and PPC.
ix. On evaluating the effect of cement type on the passivity of steel
reinforcement, it is observed that OPC performed better against
magnesium-oriented sulfate attack whereas PPC performed bet-
ter against sodium-oriented sulfate attack in a chloride
environment.
Acknowledgement
The authors express their gratitude to Department of Science and
Technology (DST), Government of India (SR/FTP/ETA-0072/2009) for
funding the corrosion monitoring instrument (used in this study)
through a project under the Fast Track scheme for Young Scientists.
References
[1] G.P. Gu, J.J. Beaudoin, V.S. Ramachandran, Techniques for corrosion investigation in
reinforced concrete, in: G.V.S. Ramachandran, J.J. Beaudoin (Eds.), Handbook of An-
alytical Techniques in Concrete Science and Technology, William Andrew/Noyes
Publications 2006, pp. 441–504.
[2] Performance of different types of Pakistani cements exposed to aggressive environ-
ments, in: A.R. Khan, Alexander, et al., (Eds.), Concrete Repair, Rehabilitation and
Retrofitting II, Taylor & Francis Group, London 2009, pp. 153–158.
[3] O.S.B. Al-Amoudi, Attack on plain and blended cements exposed to aggressive sul-
fate environments, Cem. Concr. Compos. 24 (2002) 305–316.
[4] B. Pradhan, B. Bhattacharjee, Role of steel and cement type on chloride-induced cor-
rosion in concrete, ACI Mater. J. 104 (2007) 612–619.
[5] A.M. Neville, J.J. Brooks, Concrete Technology, Pearson Education, 2004 Fourth Indi-
an reprint.
[6] O.S.B. Al-Amoudi, Influence of chloride ions on sulphate deterioration in plain and
blended cements, Mag. Concr. Res. 46 (1994) 113–123.
[7] O.S.B. Al-Amoudi, M. Maslehuddin, The effect of chloride and sulfate ions on rein-
forcement corrosion, Cem. Concr. Res. 23 (1993) 139–146.
[8] B. Pradhan, B. Bhattacharjee, Rebar corrosion in chloride environment, Constr. Build.
Mater. 25 (2011) 2565–2575.
[9] H.A.F. Dehwah, M. Maslehuddin, S.A. Austin, Effect of sulphate ions and associated
cation type on the pore solution chemistry in chloride-contaminated plain and
blended cements, Cem. Concr. Compos. 25 (2003) 513–525.
[10] N. Asrar, A.U. Malik, S. Ahmad, F.S. Mujahid, Corrosion protection performance of
microsilica added concretes in NaCl and seawater environments, Constr. Build.
Mater. 13 (1999) 213–219.
[11] K.M.A. Hossain, Resistance of scoria-based blended cement concrete against deteri-
oration and corrosion in mixed sulfate environment, J. Mater. Civ. Eng. ASCE 21
(2009) 299–308.
[12] J. Zuquan, S. Wei, Z. Yunsheng, J. Jinyang, L. Jianzhong, Interaction between sulfate
and chloride solution attack of concretes with and without fly ash, Cem. Concr.
Res. 37 (2007) 1223–1232.
[13] N.R. Jarrah, O.S.B. Al-Amoudi, M. Maslehuddin, O.A. Ashiru, A.I. Al-Mana, Electro-
chemical behaviour of steel in plain and blended cement concretes in sulphate
and/or chloride environments, Constr. Build. Mater. 9 (1995) 97–103.
[14] H.A.F. Dehwah, M. Maslehuddin, S.A. Austin, Long-term effect of sulfate ions and as-
sociated cation type on chloride-induced reinforcement corrosion in Portland ce-
ment concretes, Cem. Concr. Compos. 24 (2002) 17–25.
[15] A. Alhozaimy, R.R. Hussain, A. Al-Negheimish, R. Al-Zaid, D.D.N. Singh, Effect of sim-
ulated concrete pore solution chemistry, chloride ions, and temperature on passive
layer formed on steel reinforcement, ACI Mater. J. 111 (2014) 411–422.
[16] F. Zhang, J. Pan, C. Lin, Localized corrosion behaviour of reinforcement steel in sim-
ulated concrete pore solution, Corros. Sci. 51 (2009) 2130–2138.
[17] P. Ghods, O.B. Isgor, G. Mcrae, T. Miller, The effect of concrete pore solution compo-
sition on the quality of passive oxide films on black steel reinforcement, Cem. Concr.
Compos. 31 (2009) 2–11.
[18] W. Chen, R. Du, C. Ye, Y. Zhu, C. Lin, Study on the behaviour of reinforcing steel in
simulated concrete pore solutions using in situ Raman spectroscopy assisted by
electrochemical techniques, Electrochim. Acta 55 (2010) 5677–5682.
[19] V. Padilla, A. Alfantazi, Corrosion film breakdown of galvanized steel in sulphate-
chloride solutions, Constr. Build. Mater. 66 (2014) 447–457.
[20] B. Pradhan, B. Bhattacharjee, Corrosion zones of rebar in chloride contaminated con-
crete through potentiostatic study in concrete powder solution extracts, Corros. Sci.
49 (2007) 3935–3952.
[21] E.E.A. Aal, S.A. Wanees, A. Diab, S.M.A. Haleem, Environmental factors affecting the
corrosion behavior of reinforcing steel III. Measurement of pitting corrosion currents
of steel in Ca(OH)2 solutions under natural corrosion conditions, Corros. Sci. 51
(2009) 1611–1618.
[22] IS 12269–1987, Specifications for 53 Grade Ordinary Portland Cement, Bureau of In-
dian Standards, New Delhi, reaffirmed 2004.
[23] ASTM C150/C150M-12, Standard Specification for Portland Cement, ASTM Interna-
tional, West Conshohocken, PA, 2012.
[24] IS 1489–1991, Specifications for Portland Pozzolana Cement, Part 1: Fly Ash Based,
Bureau of Indian Standards, New Delhi, reaffirmed 2005.
[25] ASTM C595/C595M-12, Standard Specification for Blended Hydraulic Cements,
ASTM International, West Conshohocken, PA, 2012.
[26] IS: 383–1970, Specification for Coarse and Fine Aggregate from Natural Sources for
Concrete, Bureau of Indian Standard, New Delhi, reaffirmed 2002.
[27] ASTM C33/C33M-13, Standard Specification for Concrete Aggregates, ASTM Interna-
tional, West Conshohocken, PA, 2013.
[28] K. Sotiriadis, E. Nikolopoulou, S. Tsivilis, Sulfate resistance of limestone cement con-
crete exposed to combined chloride and sulfate environment at low temperature,
Cem. Concr. Compos. 34 (2012) 903–910.
[29] Standard Methods for the Examination of Water and Wastewater, 21st edition
American Public Health Association (APHA), Washington, 2005.
[30] ASTM G5-13, Standard Reference Test Method for Making Potentiodynamic Anodic
Polarization Measurements, ASTM International, West Conshohocken, PA, 2013.
[31] R. Ylmen, U. Jaglid, B. Steenari, I. Panas, Early hydration and setting of Portland ce-
ment monitored by IR, SEM, and vicat technique, Cem. Concr. Res. 39 (2009)
433–439.
[32] S. Wang, X. Peng, L. Tang, L. Zeng, C. Lan, Influence of inorganic admixtures on the
11 Å-tobermorite formation prepared from steel slags: XRD and FTIR analysis,
Constr. Build. Mater. 60 (2014) 42–47.
[33] T.L. Hughes, C.M. Methven, T.G.J. Jones, S.E. Pelham, P. Fletcher, C. Hall, Determining
cement composition by Fourier transform infrared, Adv. Cem. Based Mater. 2 (1995)
91–104.
[34] M.Y.A. Mollah, W. Yu, R. Schennach, D.L. Cocke, A Fourier transform infrared spec-
troscopic investigation of the early hydration of Portland cement and the influence
of sodium lignosulfonate, 30 (2000) 267–273.
[35] D.A. Silva, H.R. Roman, P.J.P. Gleize, Evidences of chemical interaction between EVA
and hydrating Portland cement, Cem. Concr. Res. 32 (2002) 1383–1390.
[36] A.H.M. Abdalkader, C.J. Lynsdale, J.C. Cripps, The effect of chloride on cement mortar
subjected to sulfate exposure at low temperature, Constr. Build. Mater. 78 (2015)
102–111.
[37] A.M. Ramezanianpour, R.D. Hooton, Thaumasite sulfate attack in Portland and
Portland-limestone cement mortars exposed to sulfate solution, Constr. Build.
Mater. 40 (2013) 162–173.
[38] O.S.B. Al-Amoudi, M. Maslehuddin, M.M. Saadi, Effect of magnesium sulfate and so-
dium sulfate on the durability performance of plain and blended cements, ACI
Mater. J. 92 (1995) 15–23.

Please cite this article as: F. Shaheen, B. Pradhan, Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete
powder aqueous solution in the pr..., Cem. Concr. Res. (2016), http://dx.doi.org/10.1016/j.cemconres.2016.10.008