Construction and Building Materials 70 (2014) 309–321

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Mechanical and durability properties of high volume fly ash (HVFA)

concrete containing calcium carbonate (CaCO3) nanoparticles
Faiz U.A. Shaikh ⇑, Steve W.M. Supit
Department of Civil Engineering, Curtin University, Perth, Australia

h i g h l i g h t s

 Nano-CaCO3 increased the early age and long-term compressive strength.

 Durability properties of HVFA concretes are improved due to nano-CaCO3 addition.
 Nano-CaCO3 effectively increases the consumption of Ca(OH)2 and calcium silicates.

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

Article history: The effects of CaCO3 nanoparticles on compressive strength and durability properties of high volume fly
Received 14 April 2014 ash (HVFA) concretes containing 40% and 60% fly ash as partial replacement of cement are evaluated in
Received in revised form 29 June 2014 this study. The experiment is completed in two phases. In the first phase, effects of different nano-CaCO3
Accepted 23 July 2014
contents ranged between 1% and 4% on the compressive strength of mortar and concrete are evaluated.
Available online 24 August 2014
The optimum nano-CaCO3 content that exhibited the highest compressive strength is selected to include
in high volume fly ash concretes and mortars to evaluate its effects on both early age and later age com-
Keywords:
pressive strengths. The second phase was designed to study the effect of optimum nano-CaCO3 (i.e. 1%)
CaCO3 nanoparticles
High volume fly ash
content obtained in the first phase on water sorptivity, volume of permeable voids, chloride permeability,
Compressive strength porosity and chloride diffusion of HVFA concretes containing 39% and 59% fly ash and cured at both 28
Durability and 90 days. Results show that 1% CaCO3 nanoparticles exhibited the highest compressive strength
Concrete among all nano-CaCO3 contents and about 22% higher than that of cement mortar. The results also
showed that, the HVFA concretes containing 1% CaCO3 nanoparticles have reasonably higher compressive
strength, lower volume of permeable voids, porosity, higher resistance to water sorptivity, chloride per-
meability and chloride ion diffusivity than the counterpart HVFA concretes. It is also found that 1% CaCO3
nanoparticles improves the microstructure by forming additional calcium silicate hydrate gels and
decreases the calcium hydroxide and calcium silicates of HVFA concretes. It is also revealed that the addi-
tion of CaCO3 nanoparticles not only led to much denser microstructure in HVFA matrix but also changed
the formation of hydration products, hence contributed to the improvement of early-age compressive
strength and durability properties of HVFA concretes.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
The use of fly ash as partial replacement of cement in concrete
is a common practice for many decades. During 2010–2012, the
utilisation of fly ash for construction application has achieved
approximately 55% and become a commercial product which is
available in bulk quantities [1]. As a by-product of industrial pro-
cess, the utilization of high volume fly ash in concrete addresses
the challenges of sustainable construction. Chemically, fly ash
has pozzolanic activity which is attributed to the presence of
⇑ Corresponding author.
SiO2 and Al2O3. It reacts with calcium hydroxide (CH) during
cement hydration, to form additional calcium silicate hydrate
(CSH) and calcium aluminate hydrate (CAH) which are effective
in forming denser matrix leading to higher strength and better
durability, for example, on sulphate attack and alkali silica reaction
resistance [2,3]. In practice, the quantity of fly ash to replace
cement is limited to 15–20% by mass of the total cementitious
material [4,5]. The use of nano particles has recently been intro-
duced and is being applied to meet the requirements of strength
development in many building materials applications. Nano mate-
rial is defined as a very small particle with size under a scale of
109 m, produced from the modification of atoms and molecules

http://dx.doi.org/10.1016/j.conbuildmat.2014.07.099
0950-0618/Ó 2014 Elsevier Ltd. All rights reserved.
310 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321

in order to produce large scale material [6]. Much of the works to metry (MIP), differential thermal analysis (DTA) and thermal gravi-
date with nanoparticles have been with nano silica (SiO2), nano metric analysis (TGA) to support the above mechanical and
iron (Fe2O3), nano titanium oxide (TiO2), nano alumina (Al2O3), durability properties.
and nano clay particles. It is suggested that nanoparticles act as a
nuclei for cement to accelerate cement hydration and densify the 2. Experimental details
microstructure and the interfacial transition zone (ITZ), thereby
reduce permeability [7]. The combination between fly ash and 2.1. Materials

nano materials can tightly bond the hydration product which is The cement used in this study was ordinary Portland cement Type I confirming
regarded as an important factor for accelerating the pozzolanic to ASTM C150 standard [20]. The fly ash used was class F fly ash in accordance with
reaction as it compensates for the increased early strength devel- ASTM C618 [21]. Commercially available dry nano-CaCO3 powder with size of about
opment [8–11]. Moreover, the addition of nano particles is found 40–50 nm and 97.8% Calcite (CaCO3) content was used (see Fig. 1). Fig. 2 shows the
X-ray diffraction (XRD) analysis of Portland cement (PC), fly ash (FA) and nano-
to be much more effective than micron size particles and increas-
CaCO3 (NC). Chemical composition and physical properties of cement, class F fly
ingly recognized as a means to improve the durability and mechan- ash and nano-CaCO3 are presented in Table 1.
ical properties of concrete or mortar.
In recent years nano-CaCO3 has also been introduced in con- 2.2. Mixture proportions
crete. In general, calcium carbonate can be found in limestone,
marble, chalk or produced artificially by combining calcium with The experiment is completed in two phases. In the first phase, effects of differ-
ent nano-CaCO3 contents on the compressive strength of mortar and concrete are
CO2 [12]. Although the use of calcium carbonate was first consid- evaluated. The optimum nano-CaCO3 content that exhibited the highest compres-
ered as filler to partially replace cement or gypsum, some studies sive strength is selected to include in high volume fly ash concretes and mortars
have shown advantages of using CaCO3 nanoparticles in terms of to evaluate its effects on both early age and later age compressive strengths. The
strength, accelerating effect and economic benefits as compared mixture proportions of mortars and concretes used in this phase are shown in
Tables 2a and 2b, respectively. The second phase was designed to study the effect
to cement and other supplementary cementitious materials.
of optimum nano-CaCO3 (i.e. 1%) on water sorptivity, volume of permeable voids,
Chemically, the presence of CaCO3 nanoparticles increase the rate chloride permeability, porosity and chloride diffusion of HVFA concretes containing
of reaction of tricalcium aluminate (C3A) to form carboaluminate 39% and 59% fly ash and cured at both 28 and 90 days.
complex thereby increase the total hydration products and conse-
quently strength [13,14]. In addition, it also reacts with tricalcium 2.3. Methods
silicate (C3S) and accelerates setting and early strength develop-
In the first phase of this study, six 50 mm cube mortar samples were cast and
ment [15]. As a consequence of the formation of a higher volume
demoulded after 24 h. The mortar specimens were tested to obtain the compressive
of hydrates, the increase in hydration degree compensates the dilu- strength of mortars after 7 and 28 days of water curing at room temperature
tion effect of the binding material thus develops higher initial according to ASTM C109 [22] standard. The water to binder ratio and binder to sand
strengths [16]. ratio of 0.4 and 2.75, respectively were kept constant in all mortar mixes. The flow
values of mortars were determined according to ASTM C1437 standard [23]. In
Some studies have suggested a potential benefit of physical
order to measure the compressive strength of concretes samples of
properties of CaCO3 on the development of cementitious system. 100  200 mm cylinder were cast and demoulded after 24 h. The compressive
Sato and Beaudoin [17] studied the incorporation of micro- and strength of concretes was determined at 3, 7, 28, 56 and 90 days after cured in
nano-CaCO3 in high volume of supplementary cementitious mate- water according to ASTM C39 [24] standard. For each age, three specimens were
rials. In that experiment, cement was replaced with 50% of fly ash tested and the mean value of these measurements is reported. The slump value
of each concrete mix was measured according to ASTM C143 standard [25].
(series one) and 50% of slag (series two) and incorporated with 10%
On the other hand, cement pastes corresponds to all different type of concrete
and 20% of micro- and nano-CaCO3 by weight of binders. It was mixes were also prepared with the same water/binder ratio of concretes and fol-
found that the replacement of cement with CaCO3 nanoparticle lowed similar curing condition to those of mortars and concretes. Small portions
accelerated the early hydration of cement and enhanced the early were cut from the 50 mm cube to perform scanning electron microscope (SEM),
development of modulus of elasticity as the amount of CaCO3 X-ray diffraction (XRD), mercury intrusion porosimetry (MIP), and thermal analysis
(DTA/TGA) of control paste and pastes containing fly ash, and combined fly ash and
nanoparticles was increased. In another study, Sato and Diallo nano-CaCO3.
[18] reported the seeding effect of CaCO3 nanoparticles where
rapid growth of CSH can be obtained by the access of CaCO3 nano- 2.4. Water sorptivity
particles on the surface of the C3S particles. This view is supported
by Kawashima et al. [19] who provided a basis for understanding The rate of water absorption (sorptivity) of 100 mm diameter and 50 mm thick
concrete specimens was determined at 28 and 90 days according to ASTM C1585
the mechanical properties of high volume fly ash when incorpo-
standard [26]. The principle of the method is that one flat surface of the specimen
rated with calcium carbonate nanoparticles. It was shown that
the 5% nano-CaCO3 with 30% fly ash–cement paste samples tested
at 1, 3 and 7 days improved the compressive strength compared to
typical fly ash–cement paste. It is also suggested that fly ash with
high aluminate content can introduce addition aluminates to the
system thereby decreased the SO3/Al2O3 ratio and amplified the
impact of the limestone powder on the hydration products [13].
While the above investigations evaluated the effects of nano-
CaCO3 on the hydration, setting, microstructure and compressive
strength of fly ash pastes, there has been limited progress on the
effect of nano-CaCO3 in HVFA mortars and concerts in terms of
early and long-term strength and durability properties. Therefore,
the objective of the present work is to study the effectiveness of
CaCO3 nanoparticles not only on strength development but also
its influence on the durability properties of including water sorp-
tivity, rapid chloride permeability, porosity and chloride ion diffu-
sion of HVFA mortars and concretes. Furthermore, the
microstructure and crystalline phases of paste samples are also
investigated by X-ray diffraction (XRD), mercury intrusion porosi- Fig. 1. SEM image of CaCO3 nanoparticles.
 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321 311

Fig. 2. X-ray diffractogram of cement, class F fly ash and CaCO3 nanoparticles [32].

Table 1 2.5. Volume of permeable voids

Chemical composition and physical properties of cementitious materials.
This test was conducted to estimate the percentage voids present in the con-
Chemical analysis Cement (wt%) Fly ash (wt%) Nano CaCO3 (wt%) crete specimens after curing at 28 and 90 days, based on ASTM C642 standard
SiO2 20.2 51.80 – [27]. Volume of permeable voids (VPV) is determined by boiling the 100 mm diam-
Al2O3 4.9 26.40 – eter and 50 mm thick concrete specimens for at least 5 h in a water tank at 105 °C,
Fe2O3 2.8 13.20 0.02 weighing the samples in water, then measuring the percentage of boiled specimen
CaO 63.9 1.61 97.8 with dried mass and mass in the water.
MgO 2.0 1.17 0.5
MnO – 0.10 –
2.6. Rapid chloride permeability
K2O – 0.68 –
Na2O – 0.31 –
The chloride ion penetration resistance of concrete popularly called the rapid
P2O5 – 1.39 –
chloride permeability test (RCPT) was conducted according to ASTM C1202 stan-
TiO2 – 1.44 –
dard [28]. The specimens from each series were tested at after 28 and 90 days of
SO3 2.4 0.21 –
water curing. Details procedure from preparation of specimens to test can be found
Physical properties
in [28].
Particle size 25–40% 6 7 lm 40% of 10 lm 40–50 nm
Specific gravity 2.7–3.2 2.6 –
Surface area (m2/g) – – 40 2.7. Chloride diffusion
Loss on ignition (%) 2.4 0.5 –
In order to evaluate the chloride content and chloride diffusion coefficient of
various concretes, 100  200 mm cylinder specimens were cast and cured. After
28 days of water curing, two specimens of 50 mm thick were sliced from each cyl-
inder and placed in the exposure container containing NaCl solution prepared with
is in contact with water (no more than 5 mm above the base of the specimen) while a concentration of 165 ± 1 g NaCl per L of solution. In this study, the specimens were
the other sides are sealed. This test determines the rate of absorption of water by remained in the NaCl solution for 60 days. Profile grinding was applied to collect
hydraulic cement by measuring the increase in mass of a specimen resulting from concrete powder samples at depth increments ranging between 1 mm and
absorption of water as a function of time. In this study, the mass of the specimen is 16 mm, according to ASTM C1556 standard [29]. Chloride contents of the powder
regularly measured to determine the initial absorption from 1 min to the first 6 h. samples were measured using CL-2000, Chloride Test System, James instruments.

Table 2a
Mix proportions of mortars.

Series Type of mixes Cement (kg/m3) Class F fly ash (kg/m3) Nano CaCO3 (kg/m3) Sand (kg/m3) Water (kg/m3)
1 PC 400 – – 1100 160
2 FA40 240 160 1100 160
FA50 200 200 – 1100 160
FA60 160 240 – 1100 160
3 NC1 396 – 4 1100 160
NC2 392 – 8 1100 160
NC3 388 – 12 1100 160
NC4 384 – 16 1100 160
4 FA39.NC1 240 156 4 1100 160
FA59.NC1 160 236 4 1100 160
312 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321

Table 2b
Mix proportions of concretes.

Series Type of mixes Cement (kg/m3) Class F fly ash (kg/m3) Nano CaCO3 (kg/m3) Sand (kg/m3) Coarse aggregate (kg/m3) Water (kg/m3)
1 PC 400 – – 674 1235 163
2 FA40 240 160 674 1235 163
FA60 160 240 – 674 1235 163
3 NC1 396 – 4 674 1235 163
NC2 392 – 8 674 1235 163
4 FA39.NC1 240 156 4 674 1235 163
FA59.NC1 160 236 4 674 1235 163

An accurately weighed 3 grams sample is dissolved in 20 ml of extraction liquid
consisting of a precisely measured concentration of acid. The chloride ions reacted
with the acid of the liquid in an electrochemical reaction. An electrode, with an
integral temperature sensor, is inserted into the liquid. The percentage of chlorides
is displayed directly on LCD readout of the apparatus. Chloride diffusion coefficient
of each sample is determined by fitting the data obtained from the chloride profile
analysis according to Fick’s second law of diffusion equation.
Fick’s second law of diffusion is a differential equation that describes how the
concentration of a diffusing species varies with time. For one-dimensional diffusion,
the differential equation is as follows:
@Cðx; tÞ @ 2 Cðx; tÞ
¼ Da
@t @x2
From a dimensional analysis, it can be shown that the diffusion coefficient, Da,
has unit of length2/time. The chloride penetration distance is measured in mm and
the exposure time is in terms of years.
If it is assumed that there is one-dimension diffusion and that the chloride ion
content at the surface is constant, a solution to Fick’s second law is as follows:
 
x
Cðx; tÞ ¼ C s  ðC s  C i Þ erf pffiffiffiffiffiffiffiffi
2 Da t
where
C(x, t) = the chloride ion concentration at a depth x in mm from the exposed sur-
face for an elapsed time t in years since the start of chloride exposure.
Cs = the chloride concentration at the surface, expressed as percentage (%) of
concrete mass.
Ci = the initial (or background) chloride concentration of the concrete,
expressed as a % of concrete mass.
erf = the error function (a special function related to the integral of a normal
probability function).
Da = the chloride diffusion coefficient in mm2/year.
2.8. X-ray diffraction (XRD) analysis
Small fragment of paste samples were grinded manually to prepare the powder
sample for XRD analysis. XRD patterns were acquired on a Bragg–Brentano Diffrac-
tometer. Operating conditions were set a 40 kV and 30 mA using a Cu Ka X-ray
source. An analysis from 5° to 70° (2h) is carried out at a speed of 0.5°/min.
2.9. Mercury intrusion porosimetry (MIP) analysis
This measurement was performed on a PoreMaster series – Quantachrome
instruments, with a pressure ranged between 0.0083 and 207 MPa, and the pore
diameter and intrusion mercury volume were recorded at each pressure point.
The pressures were converted to equivalent pore widths using the Washburn equa-
tion [30], as expressed in Eq. (3):
2c cos h
d¼
P
where d is the pore width (lm), c is the surface tension (mN/m), h is the contact
angle between mercury and the pore wall (°), and P is the net pressure across the
mercury meniscus at the time of the cumulative intrusion measurement (MPa).
2.10. Differential thermal analysis and thermogravimetric analysis (DTA/TGA)
DTA/TGA analysis measures both heat flow and weight changes in a material as
a function of temperature in a controlled atmosphere. DTA figures the thermal
decompositions of different phases in the paste, while TGA simultaneously mea-
sures the weight loss due to the decomposition of phases. About 50 mg of well-
powdered sample in a 110 ll platinum crucible was heated from ambient to
1000 °C at 20 °C per minute in a nitrogen atmosphere flowing at 100 ml per minute.
Mass and differential temperature data were acquired with respect to furnace
temperature.
3. Results and discussion
3.1. Effect of nano-CaCO3 on workability and compressive strength of
mortars and concretes
The effects of nano-CaCO3 on workability of cement mortar,
HVFA mortars and concretes are shown in Table 3. It can be seen
that the addition of nano-CaCO3 reduced the workability of mor-
tars and concretes and the workability decreased with increase
ð1Þ in percentage of cement replacement with CaCO3 nanoparticles.
The effects of nano-CaCO3 on compressive strengths of control
cement mortar and HVFA mortars are shown in Fig. 3. It can be
seen that 1% nano-CaCO3 exhibited highest compressive strength
at both 7 and 28 days among all four nano-CaCO3 contents and
the compressive strength is decreased gradually with increase in
nano-CaCO3 contents. The NC1 mortar exhibited about 22% and
ð2Þ 18% higher compressive strengths at 7 and 28 days, respectively
than control mortar (PC). The lower compressive strength of mor-
tars containing higher nano-CaCO3 contents can be attributed to
the poor dispersion due to agglomeration of nano-CaCO3 in wet
mix as its higher van der Waal’s forces are higher than cement.
It can be seen from Fig. 3 that the 7-day compressive strength of
mortar containing 40% fly ash is increased by about 21% due to
addition of 1% nano-CaCO3 and at 28 days this improvement is
ceased, indicating the effectiveness of nano-CaCO3 in compensat-
ing the low compressive strength at early age of HVFA system. A
similar increase (approximately 21%) in 7-days compressive
strength of paste containing 30% fly ash and 5% nano-CaCO3 is also
reported by Kawashima et al. [19]. The results also show significant
improvement of both 7 and 28 days compressive strengths of mor-
tar containing 59% of fly ash and 1% nano-CaCO3.
The effect of nano-CaCO3 on the compressive strength develop-
ment of HVFA concretes is shown in Fig. 4, which shows the effect
of 1% nano-CaCO3 on 3, 7, 28, 56 and 90 days compressive strength
of ordinary concrete. Similar to that observed in mortar, the con-
crete containing 1% nano-CaCO3 also exhibited higher compressive
strength at all ages than the ordinary concrete. It can also be seen
in Fig. 4 that 1% nano-CaCO3 significantly improved the 3 and
7 days compressive strength of HVFA concrete containing 39% fly
ash, where about 47% and 44% improvements are observed, respec-
ð3Þ
Table 3
Slump and flow values of different types of mixes.
Type of mixes Flow (mm) Slump (mm)
PC 135 140
FA40 140 160
FA60 175 200
NC1 132 135
NC2 130 120
NC3 125 –
NC4 120 –
FA39.NC1 135 150
FA59.NC1 160 170
 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321 313

Fig. 3. Compressive strength of control mortar containing nano-CaCO3 (NC) and HVFA mortars containing NC at 7 and 28 days.

Fig. 4. Compressive strength development of concrete containing nano-CaCO3 (NC) and HVFA concretes containing NC at 3, 7, 28, 56 and 90 days.

tively. At 28, 56 and 90 days the improvements are even higher
(between 53% and 58%) for the concrete containing 39% fly ash
and 1% nano-CaCO3. However, the improvement of compressive
strength of HVFA concrete containing 59% fly ash due to addition
of 1% nano-CaCO3 is not as great as that containing 39% fly ash
and 1% nano-CaCO3. Although due to limited published results
the above results on early age as well as later age compressive
strengths of HVFA concretes containing nano-CaCO3 cannot be
compared, the above trend, however, is very similar to that of
HVFA concretes containing fine limestone powder reported by
Tanesi et al. [31]. A detail discussion on the effect of nano CaCO3
on the compressive strength of concrete and HVFA concretes by
considering the XRD results can be found in authors’ recent
publication [32].
3.2. Effect of CaCO3 nanoparticles on sorptivity of cement concrete and
HVFA concretes
The effects of nano-CaCO3 on sorptivity of 28 and 90 days cured
ordinary cement concrete and HVFA concretes are shown in Fig. 5.
By comparing Fig. 5a and c, it can be seen that the addition of 1%
and 2% nano-CaCO3 reduced the rate of water absorption and 1%
nano-CaCO3 performed better than 2% at both ages. Water sorptiv-
ity of NC1 concrete is 19% and 60% lower than the control concrete
(PC) at 28 and 90 days, respectively (see Fig. 6). This result shows
that the rate of water absorption is reduced in concrete containing
nano-CaCO3 due to formation of CSH gels which filled the water-
filled spaced and reduced the concrete capillary pores. The reduc-
tion of pore volumes of NC1 and NC2 concretes is also evidenced in
314 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321
Fig. 5. Rate of absorption of concrete containing nano-CaCO3 (NC) and HVFA concretes containing NC at 28 and 90 days.
this study through mercury porosimetry test results as discussed in
the following section.
The sorptivity test results also show that the use of 1% CaCO3
nanoparticles in HVFA concretes significantly reduced the rate of
water absorption (See Fig. 5b and d). As can be seen in Fig. 6 that
the water sorptivity of FA39.NC1 concrete at 28 and 90 days are
52 and 46 (104 mm/sec1/2), respectively, which is lower than
concrete containing 40% fly ash (FA40). It can also be seen that at
longer curing time (90 days) the water sorptivity of FA30.NC1 con-
crete is lower than 28 days curing. The effect of longer curing can
Fig. 6. Sorptivity values of various concretes measured after 28 and 90 days of
curing.
also be seen in FA59.NC1 concrete where the sorptivity value is
reduced from 82 to 57 (104 mm/sec1/2) due to 90 days wet cur-
ing. This is an indication that the addition of 1% CaCO3 nanoparti-
cles in HVFA paste forms a finer pore structure than HVFA paste
alone in longer term. Based on the above results, it can be com-
mented that by combining nano-CaCO3 in HVFA concrete, the
acceleration of the hydration process can be intensified due to
the consuming of CH and formation of new CSH gels. In addition,
the nano-CaCO3 densified the microstructure and refine the pores
and increased the density of concrete, which is confirmed by the
results in mercury intrusion porosimetry tests.
3.3. Effect of CaCO3 nanoparticles on volume of permeable voids of
cement concrete and HVFA concretes
The volume of permeable voids (VPV) of concrete gives an indi-
cation of its durability related to permeability, absorption, etc. It
can be observed form the VPV results shown in Fig. 7 that the per-
centage of voids in concrete is reduced due to addition of nano-
CaCO3 irrespective of curing ages. For example, the concrete con-
taining 1% CaCO3 nanoparticles decreased the VPV significantly
up to 46% at 28 days in relation to ordinary cement concrete. As
expected, the volume of permeable voids are decreased with
increase in curing time of concretes.
The effect of 1% CaCO3 nanoparticles on VPV of high volume fly
ash concretes is also shown in Fig. 7. It can be seen that the addi-
tion of 1% nano-CaCO3 significantly reduced the VPV of HVFA con-
cretes containing 40% fly ash by 30% and 46% at 28 and 90 days
 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321
Fig. 7. Volume of permeable voids of different concretes measured after 28 and
90 days of curing.
curing, respectively. However, the reduction of VPV was only 7%
and 21% at 28 and 90 days curing, respectively in FA59.NC1 con-
crete. Consisted with sorptivity and compressive strength results,
the NC1 concrete performed better than the NC2 concrete, presum-
ably due to better dispersion of CaCO3 nanoparticles in the former
than the later.
3.4. Effect of CaCO3 nanoparticles on rapid chloride permeability of
cement concrete and HVFA concretes
Rapid chloride permeability test (RCPT) was conducted to
investigate the performance of concrete against chloride ingress.
The lower the total charge passed through the concrete, the higher
the resistance to chloride penetration. ASTM C1202 [28] specifies
the rating of chloride permeability of concrete based on the total
charge passed through the specimen during 6 h of testing period.
A charge value of less than 2000 coulombs is characterized as
low chloride permeability, between 2000 and 4000 coulombs is
Fig. 8. Chloride ion permeability resistance of different concretes measured after 28 and 90 days of curing.
315
in medium level while higher than 4000 coulombs is defined as
high chloride permeability.
Fig. 8 shows the resistance against chloride ions penetration of
ordinary concrete and HVFA concretes containing nano-CaCO3.
Based on the obtained results, it can be seen that a replacement
of 1% Portland cement with CaCO3 nanoparticles increased the
resistance against chloride ion penetration of ordinary cement con-
crete by 20% and 50% at 28 and 90 days, respectively. At 90 days,
the charge decreased from 2916 Coulombs to 1475 Coulombs
(i.e. changed from moderate to low chloride permeability rating).
When the replacement of cement was increased to 2% nano-CaCO3,
the Coulombs values were not significantly different from 28 days
values and decreased by only 20% at 90 days.
With regard to the effect of 1% CaCO3 nanoparticles on chloride
permeability of HVFA concretes, it is observed that the charge
passed at 28 days decreased from 4995 Coulombs to 4057 Cou-
lombs (approximately 18%) in FA39.NC1 concrete and from 6075
to 5360 Coulombs (approximately 11%) in FA59.NC1 concrete. Con-
sidering specimens cured at 90 days, the total charge passed of
high volume fly ash concrete containing 1% CaCo3 nanoparticles
ranged from 3465 to 4556 Coulombs. For all concrete specimens
tested, the total charge passed decreased with increase in curing
age. It can be concluded that the extension of the curing period
from 28 to 90 days resulted in a reduction of the total charge
passed through the concrete specimens due to hydration and poz-
zolanic reactions.
3.5. Effect of CaCO3 nanoparticles on chloride diffusion of cement
concrete and HVFA concretes
The chloride content profile of different mixes of 28 days cured
concretes subjected to 60 days exposure to NaCl solution is pre-
sented in Fig. 9. The figure shows the measured chloride concentra-
tion at different depths, where the chloride concentration inside
the concrete is measured by percent of concrete’s weight. In the
chloride content profile, the rate of chloride diffusion can be deter-
mined from the steepness of the curve. A less steep curve indicates
that the concentration of chloride inside the concrete equals to the
concentration on the concrete’s surface. On the other hand, the
steep curve indicates the slow chloride ion diffusion inside the
concrete due to very slow chloride penetration from the concrete’s
surface.
316 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321

In Fig. 9, it is clearly seen than the steepness of the curves is

higher in concrete and HVFA concretes containing 1% CaCO3 nano-
particles indicating the influence of CaCO3 nanoparticles on the
reduction of chloride diffusivity. In order to quantify the durability
performance of the concretes, the surface chloride concentration
(Cs) and the effective diffusion coefficient (Da) are calculated for
each type of concrete. The procedure used a least-square best-fit
analysis for Crank’s solution to Fick’s law as mentioned earlier.
The chloride diffusion coefficient of the variation of concrete mixes
is presented in Fig. 10. For the ordinary concrete, the calculated
chloride diffusion coefficient is 4.1  1012 m2/sec whilst for con-
crete containing 1% CaCO3 nanoparticles (NC1), the diffusion coef-
ficient is 1.07  1012 m2/sec, which is about 73% reduction from
the ordinary concrete. The chloride diffusion coefficient of the
HVFA concretes is also reduced by about 60% and 32% when 1%
nano-CaCO3 is added (see Fig. 10). It indicates that the CaCO3 nano-
particles are very effective in reducing the pore space and its con-
nectivity inside the concrete and therefore the penetration of
chloride ions.

3.6. Effect of CaCO3 nano particles on porosity of cement and HVFA

pastes

Mercury intrusion porosimetry (MIP) analysis is widely used to

evaluate total porosity and size distributions of pores in cement
pastes and concretes. The MIP results of the paste samples after

Fig. 9. Chloride content profile of different concretes after 60 days exposure in NaCl
solution.

Fig. 10. Chloride diffusion coefficient of various concrete mixes measured after Fig. 11. Cumulative pore volume of (a) pastes containing nano-CaCO3 (NC) and (b)
60 days exposure in NaCl solution. HVFA pastes containing NC measured after 28 days of curing.
 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321 317

28 days of curing are shown in Fig. 11. It shows the relationship

between cumulative pore volume and pore diameter in the range
of 0.01–100 lm. Zhang and Islam [33] classified the pores from
10 to 0.05 lm as large capillary pores, from 0.05 to 0.01 lm as
medium capillary pores and <0.01 lm as gel pores.
From Fig. 11 it can be seen that the pore size distributions of
control cement paste has the same general shape as those of
cement paste with CaCO3 nanoparticle. However, the cement paste
is more porous than the corresponding cement pastes containing
CaCO3 nanoparticles. It is clearly seen that the total porosity of
pastes containing 1% and 2% CaCO3 nanoparticle is about 0.18 cc/
g and 0.27 cc/g, respectively (see Fig. 11a), where there is no dis-
tinct difference on the initial pore entry diameter between paste
with 1 wt% and 2 wt% of CaCO3 nanoparticles. The initial pore entry
diameter indicates the minimum diameter of pores that are contin-
uous through the paste [34]. In addition, it is also observed that the
large capillary pores of pastes containing CaCO3 nanoparticle are
decreased significantly, while the medium capillary pores are
slightly decreased. In this case, the use of CaCO3 nanoparticles
leads to a more compact paste with a significant reduction of pores
between 0.1 and 100 lm. In the case of HVFA pastes with 1% CaCO3
nanoparticles addition, there is a notable reduction in pore concen-
tration indicating the presence of CaCO3 nanoparticles is advanta-
geous in pores modification. With regard to FA40 paste sample, the
result shows that the cumulative pore volume is reduced signifi-
cantly after adding 1% nano-CaCO3. While the total porosity of
FA40 and FA60 are 0.39 and 0.61 cc/g, the FA39.NC1 and FA59.NC1
paste samples have total porosity of 0.20 and 0.32 cc/g, respec-
tively. Both large and medium capillary pores are reduced signifi-
cantly by the addition of nano-CaCO3 in HVFA system.
Fig. 12 shows the effect of 1% nano-CaCO3 addition on pore size
distribution of control paste and HVFA pastes. The region under the
curve represents the concentration of the pores. The value of crit-
ical diameter corresponds to the peak point of log differential curve
Fig. 12. Change in intruded pore volume of (a) pastes containing nano-CaCO3 (NC)
from MIP results. Fig. 12a shows that the maximum concentration
and (b) HVFA pastes containing NC measured after 28 days of curing.
of pores in paste containing 1% CaCO3 nanoparticle tend to be
around medium capillary pore sizes. The porosity of pastes con-
taining 1 wt% and 2 wt% CaCO3 nanoparticles are concentrated
around 0.04–0.05 lm, respectively. The graph in Fig. 12b presents under endothermic process [36]. In Fig. 13, the DTA curve shows
that the porosity of FA39.NC1 is concentrated around 0.05 lm two major endothermic peaks at 103 °C and 462 °C, corresponding
which is lower than the concentration of the pores in FA40 paste. to the dehydration of calcium silicate hydrate (CSH)/ettringite
Similar trend is also observed in FA59.NC1 paste. It is noted that (AFt) and calcium hydroxide (CH), respectively. In Fig. 13a and c,
CaCO3 nanoparticles due to the pozzolanic reaction and the filler lower peak of CH within the temperature range of 428–495 °C in
effect has a significant influence in decreasing the total capillary HVFA pastes with CaCO3 nanoparticles can be seen than the refer-
porosities of HVFA pastes. ence FA40 and FA60 pastes, indicating the consumption of CH by
the pozzolanic reaction at 7 days. In addition, increase in AFt/CSH
3.7. Thermogravimetric analysis (TGA) and differential thermal phases can also be identified within the temperature range of
analysis (DTA) of control paste and HVFA pastes containing CaCO3 about 62–157 °C, which is an indication of decomposition of more
nanoparticles hydration products in HVFA pastes containing 1% nano-CaCO3 than
reference fly ash pastes. After 28 days of curing, the FA39.NC1 and
The thermogravimetric analysis (TGA) and differential thermal FA59.NC1 paste samples also exhibited smaller broad peak of CH
analysis (DTA) results of HVFA pastes containing CaCO3 nanoparti- than reference FA40 and FA60 pastes, indicating the mass loss
cles are shown in Fig. 13. It shows the normalized mass loss in per- and the reduction of CH content due to the presence of 1 wt%
cent (current mass divided by initial mass) versus temperature and CaCO3 nanoparticles (see Fig. 13b and d).
the temperature difference divided by initial mass versus temper- TGA is defined as the technique whereby the mass of a sub-
ature. In order to investigate the effectiveness of CaCO3 nanoparti- stance in a heated environment is recorded at a controlled rate
cles in reducing the CH at early age, the DTA/TGA measurements as a function of time or temperature. This analysis allows the esti-
have been performed on 7 and 28 days hydrated HVFA pastes mation of the content of CH from the weight losses. Fig. 13 shows
blended mixture with and without 1% CaCO3 nanoparticles. Mass the TGA curves which indicate the changes in mass of pastes due to
loss between 105 °C and 420 °C represents the loss of combined heating from room temperature to about 1000 °C. It demonstrates
water due to dehydration of calcium silicate hydrate, aluminate the weight loss of all paste samples. Based on Fig. 13, the weight
hydrate and ferroaluminate hydrate, between 420 °C and 540 °C loss due to the dehydroxylation of CH can be observed at temper-
corresponds to the dehydration of calcium hydroxide and de-car- ature range between 400 and 500 °C. As expected, the weight loss
bonation of well-crystalline calcium carbonate occurs at tempera- of CH in HVFA containing 1% CaCO3 nanoparticles pastes is
ture between 720 °C and 950 °C [35]. The U-shaped DTA curve decreased at 7 days indicating that the CH is turned into CSH.
refers to rapid loss of weight followed by rapid gain in the weight The same trend can also be seen in Fig. 13 where the results from
318 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321
Fig. 13. TGA/DTA analysis of HVFA cement pastes containing 1% CaCO3 nanoparticles at 7 and 28 days.
Fig. 14. Calcium hydroxide content in paste containing 1% CaCO3 nanoparticles at
28 days and HVFA pastes containing 1% CaCO3 nanoparticles at 7 and 28 days.
DTA/TGA analysis of HVFA cement pastes containing 1 wt% CaCO3
nanoparticles at 28 days is presented. In addition, the calcium
hydroxide (CH) content can be calculated according to Taylor’s for-
mula [37]:
MWCH
CH ð%Þ ¼ WLCH ð%Þ  ð4Þ
MWH2 O
where WLCH is the weight loss during the dehydration of CH as per-
centage of the ignited weight (%); MWCH is the molecular weight of
CH; MWHO is the molecular weight of H2O.
From Fig. 14, it can be seen that the amount of CH is decreased
in both HVFA pastes and those containing 1 wt% CaCO3 nanoparti-
cles. It is also be seen that the presence of 1% CaCO3 nanoparticles
reduced the CH content in FA39.NC1 and FA59.NC1 pastes com-
pared FA40 and FA60, respectively. This could be due to the reac-
tivity of CaCO3 nanoparticles in HVFA and the consumption of CH
by the pozzolanic reaction. The addition of 1% CaCO3 nanoparticles
combined with 39% and 59% of fly ash lead to a reduction of CH by
10% and 15% (at 7 days) and 15% and 59% (at 28 days), respectively.
This explains the difference in strength between typical HVFA and
HVFA with CaCO3 nanoparticles addition. The TGA results also con-
firmed the XRD results showing the reactivity of 1 wt% CaCO3
nanoparticles with HVFA in reducing the CH content.
3.8. X-ray diffraction analysis of cement paste and HVFA pastes
containing CaCO3 nanoparticles
Figs. 15 and 16 show the XRD patterns of HVFA cement pastes
containing nano-CaCO3. The horizontal scale (diffraction angle) of
a typical XRD pattern gives the crystal lattice spacing, measured
 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321
Fig. 15. XRD analysis of HVFA pastes with and without nano-CaCO3 at 7 days.
in degrees, and the vertical scale (peak height) gives the intensity
of the diffracted ray, measured in pulses/s. The diffraction spectra
analysis in cement and HVFA pastes indicated the predominance of
Portlandite (CH), calcium silicate (C2S/C3S) and Quartz (SiO2).
Changes in the mineral phases during hydration were found since
ettringite and calcite were present in pastes containing CaCO3
nanoparticles. It is also noticed in XRD patterns the presence of
unnamed peaks with high intensity. It is identified as internal stan-
dard (corundum phase) which has not been included in the phase
abundance calculations. In this study, the CH peak was considered
to be the main indicator of performance in cement paste samples.
On the XRD scale, the CH has a strong peak located at 2-theta angle
of 18.05 and 34.09°.
In cement blended pastes containing HVFA and 1% CaCO3 nano-
particles, the XRD results show reduction of the CH peak intensity
compared to that of HVFA pastes (see Figs. 15 and 16). For instance,
after 7 days curing, the intensity peak of CH decreased from 4481
to 4218 at 2h = 18.05° while at 28 days, the reduction of CH inten-
sity was appeared at 2h = 34.09°. The same trend was also found in
paste with 60% replacement of cement with fly ash, where the
319
addition of 1% nano-CaCO3 decreased the intensity of CH from
4840 to 3698 and 5485 to 4057 at 7 and 28 days, respectively.
When combining CaCO3 nanoparticles and high volume fly ash,
the fly ash with high silicate and aluminate content reacts with
CaCO3 nanoparticles to produce additional hydration products in
the system. It is reported that CaCO3 performs as nucleation sur-
face for CH and CSH precipitation [18]. The XRD results in Figs. 15
and 16 also showed reduction of calcium silicate (CS) peaks for
both HVFA pastes at both curing ages due to addition of 1%
nano-CaCO3. The reduction of CS is a clear indication of formation
of hydration products (e.g. CSH) in the system. On the other hand,
new peaks of ettringite were present at 7 days sample of HVFA and
CaCO3 nanoparticle pastes. Over time, the ettringite (Aft) was
transformed to monosulfate (AFm) and other products, therefore
the ettringite peaks were found decreased at 28 days. This phe-
nomenon is also found in DTA/TGA analysis as discussed in previ-
ous section. Furthermore, the results indicate that the
consumption of CH and CS and the formation of ettringite contrib-
uted to the strength development of HVFA pastes containing CaCO3
nanoparticles.
320 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321
Fig. 16. XRD analysis of HVFA pastes with and without nano-CaCO3 at 28 days.
4. Conclusions
The following conclusion can be drawn from the obtained
experimental results:
1. The concrete containing 1 wt% CaCO3 nanoparticles yielded the
highest compressive strength at all ages. The early age compres-
sive strength of concrete containing 1% nano-CaCO3 is about
146–148% higher than the ordinary concrete. The early age
compressive strength of HVFA concretes is also improved due
to addition of 1% nano-CaCO3. Most significant improvement
of about 46–48% is observed in HVFA concrete containing 39%
fly ash and 1% nano-CaCO3.
2. The addition of 1% nano-CaCO3, also improved the long term
(90 days) compressive strength of ordinary concrete by about
40% and that of HVFA concrete containing 39% and 59% fly
ash by about 57% and 8%, respectively.
3. Water sorptivity of ordinary concrete containing 1% CaCO3
nanoparticles was about 17% and 30% lower at 28 and 90 days,
respectively than the ordinary concrete. In addition, the use of
1% CaCO3 nanoparticles in HVFA concrete was found to be sig-
nificantly effective in reducing the water sorptivity when com-
bined with 39% of fly ash as partial replacement of cement in
concrete. This is an indication that the 1% CaCO3 nanoparticles
addition in HVFA system forms a finer pore structure than HVFA
paste alone.
4. The volume of permeable voids of concrete containing 1% CaCO3
nanoparticles is decreased significantly up to 46% at 28 days in
relation to Portland cement concrete. On the other hand, the
addition of 1% CaCO3 nanoparticles in HVFA concrete containing
39% fly ash reduced the VPV by about 30% compared to the
FA40 concrete. The improvement further confirmed that the
1% CaCO3 nanoparticles improved the microstructure of HVFA
concretes and thus affected the concrete performance including
the improved strength and reduced VPV.
5. It was also found that a replacement of 1% Portland cement
with CaCO3 nanoparticles decreased the chloride ion perme-
ability of Portland cement concrete by approximately 20%
and 50% at 28 and 90 days, respectively. Additionally, the ben-
efits of adding CaCO3 nanoparticles were also observed in
HVFA concretes, where about 19% and 12% reductions in chlo-
ride ion penetration of HVFA concretes containing 40% and 60%
fly ash, respectively were measured due to addition of 1%
nano-CaCO3 after 28 days of curing. However, no significant
improvement in above concretes was observed for 90 days
curing.
 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 70 (2014) 309–321
6. The chloride diffusion coefficient of cement concrete is reduced
by about 73% due to addition of 1% nano-CaCO3. The chloride
diffusion coefficient of the high volume fly ash concretes con-
taining 1% CaCO3 nanoparticles were about 60% and 32% lower
than FA40 and FA60 concretes, respectively. It indicates that
CaCO3 nanoparticles due to its reactivity and filler effect are
very effective in reducing the pore space and its connectivity
inside the concrete and therefore the penetration of chloride
ions.
7. The mercury intrusion porosimetry (MIP) analysis results
showed that the presence of 1 wt% CaCO3 nanoparticles in
ordinary concrete and HVFA concretes decreased the total cap-
illary porosities and pores refinement.
8. The XRD analysis results showed that the nano-CaCO3 replace-
ment of cement is effective in reducing the CH and CS in HVFA
pastes and hence the formation of additional CSH gels. New
peaks of Ettringite are also noticed in HVFA pastes due to addi-
tion of 1% nano-CaCO3. The TGA results are also confirmed the
XRD results showing the reactivity of 1% CaCO3 nanoparticles
with HVFA in reducing the CH content.
9. In high volume fly ash in concrete containing CaCO3 nanoparti-
cles, the fly ash with high silicate and aluminate content reacted
with CaCO3 nanoparticles to produce additional hydration
products in the system, hence, contributed to the improvement
of early-age and later-age compressive strengths and durability
properties of HVFA concretes.
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