Construction and Building Materials 258 (2020) 119589

Contents lists available at ScienceDirect

Construction and Building Materials

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

Effective use of micro-silica extracted from rice husk ash for the
production of high-performance and sustainable cement mortar
Kaffayatullah Khan a, Muhammad Fahad Ullah b, Khan Shahzada b, Muhammad Nasir Amin a,⇑,
Tayyaba Bibi b, Nauman Wahab c, Abdullah Aljaafari d
a
Department of Civil and Environmental Engineering, College of Engineering, King Faisal University (KFU), P. O. Box 380, Al-Hofuf, Al-Ahsa 31982, Saudi Arabia
b
Department of Civil Engineering, University of Engineering and Technology, Peshawar, Pakistan
c
Faculty of Engineering, Kasetsart University, Bangkok, Thailand
d
Department of Physics, College of Science, King Faisal University (KFU), P. O. Box 380, Al-Hofuf, Al-Ahsa 31982, Saudi Arabia

h i g h l i g h t s

Micro silica extracted from RHA (EMS) possessed very high fineness and reactivity.

Addition of EMS increases strength and decreases porosity of the mortar samples.

Incorporation of EMS to mortar bar samples showed better resistance to ASR.

EMS improved both micro and pore structure due to its high fineness and reactivity.

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

Article history: Utilization of high-performance and highly reactive sustainable materials in concrete are gaining popu-
Received 16 February 2020 larity nowadays for the development of strong, durable and sustainable infrastructures. Therefore, cur-
Received in revised form 13 May 2020 rent study focuses on viable use of highly reactive silica extracted from rice husk ash (RHA) for the
Accepted 14 May 2020
production of high-performance sustainable cement mortar. Mortar containing various percentages of
Available online 27 May 2020
extracted micro-silica (EMS) as a partial substitute of cement (5%, 15%, and 25%) were cast to test fresh
as well as hardened properties, and compare its results to that of control mortar. Test results showed that
Keywords:
the standard consistency increased with increasing percentage of EMS, whereas, a delay in the setting
Extracted micro silica
Strength and porosity
time was observed. The compressive and flexural strengths of all mortar mixes containing EMS were
Alkali–silica reactivity improved with aging and an effective role played by EMS in mitigating the expansion caused by the
SEM-EDS analysis alkali–silica reaction was observed. However, a slight reduction of strength at later ages was observed
Nitrogen adsorption in mortar having 25% EMS. At relatively low addition of EMS (5% and 15%), micro- and pore structural
FTIR analysis investigations revealed the formation of improved high-density C-S-H phases, which aid the formation
of refined and homogenous microstructures. The agglomeration was observed through micro- and pore
structural investigations in high dosage EMS mortars that occurred due to the oversaturation and poor
dispersion, which consequently affected the hydration products and increased the porosity of the paste
matrix. The current findings suggest that the reactive silica resource extracted from RHA can be used as a
potential revenue stream in concrete industry for the development of high-performance and sustainable
cement mortar.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction As a fundamental building material, concrete plays a significant

Concrete, a heterogeneous mixture of natural and synthetic
constituents, is one of the most vital, highly adaptable, and exten-
sively employed building construction materials around the world.
⇑ Corresponding author.
E-mail address: mgadir@kfu.edu.sa (M.N. Amin).
role in the construction and infrastructure development of a coun-
try, thus contributing toward its economic and social development.
Owing to the overwhelming growth of infrastructure development,
concrete is being increasingly used. Globally, the annual consump-
tion of concrete has surpassed 25 billion tons [1]. This increase in
concrete consumption places enormous pressure on the cement
industry to increase its yield, which is approximately 4.1 billion

https://doi.org/10.1016/j.conbuildmat.2020.119589
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
tons per year currently [2]. However, excessive consumption of
concrete has several adverse effects on the environment such as
the excessive utilization of natural resources, including the extrac-
tion of coarse and fine aggregates [3,4]. Furthermore, the cement
industry is one of the primary sources of greenhouse gas emissions,
especially CO2. Cement manufacturing is responsible for 5% of the
global anthropogenic CO2 emissions [5–7]. In the cement industry,
the calcination process (CO2 is released from calcium carbonate to
form calcium oxide) is mainly responsible for approximately 50%
of CO2 emissions, whereas the remaining half is linked with the
usage of energy during the production process [8].
There is an urgent need to preserve the natural environment by
reducing CO2 emissions to solve the problems of climate change
and global warming. Different methods and materials have been
employed to control excessive CO2 emissions in the cement indus-
try, such as shifting toward renewable energy sources, modifica-
tions in the manufacturing processes of clinkers, and partial or
full replacement of cement by supplementary cementing materials
(SCMs) [9,10]. According to Mehta and Ashish [11], the most
prominent and cost-effective strategies are the addition of alterna-
tive materials having cementitious properties during the manufac-
turing stage or a direct replacement of cement at the construction
site. Furthermore, the increase in CO2 emissions from the cement
industry could be reversed if cement is replaced by up to 30% with
SCMs [12]. For the last few decades, various industrial and agricul-
tural residual wastes have been used as secondary cementitious
(pozzolanic) materials for the partial substitution of cement. These
SCMs include fly ash [12–16], cement kiln dust [17,18], granulated
blast furnace slag [19–20], silica fume (SF) [11,21], volcanic ash
[22], sugarcane bagasse ash [23–25], wheat straw ash [26], and rice
husk ash (RHA) [27–31]. The addition of these pozzolanic materials
significantly enhanced the mechanical properties of concrete
[1,2,4,24,27,32,33]. Furthermore, it also improved the resistance
of concrete to sulfate and chloride attacks [16,34].
The utilization of these supplementary materials further helps
in providing a sustainable solution to the waste generated from
the industrial and agriculture sectors, especially in developing
countries where proper disposal of agro-wastes is a significant
issue. Among agricultural wastes, rice husk (RH) is considered
one of the most dominant crop residues. Its worldwide annual pro-
duction is expected to be higher than 150 million tons [35]. How-
ever, only 17% of this amount is utilized, whereas the remaining
83% is dumped as waste or burnt in open fields, causing water
and soil pollution [36]. Consequently, research and development
have been conducted in various industrial and agricultural sectors
to exploit RH as a source of energy—for instance, RH acts as a fuel
source in rice milling operations, producing steam in the power
generation units or electricity [28,35]. Burnt RH yields RHA, which
contains a high percentage of silica i.e., approximately 90%; how-
ever, this percentage varies with the burning conditions. They fur-
ther stated that burning RH at a control temperature yields high
silica contents, varying between 90% and 95% [37]. Before advance-
ments in the field of green technology, RHA was often dumped in
landfills or rivers, which resulted in the contamination of the nat-
ural environment [38]. Therefore, without proper treatment and
utilization, RHA cannot be termed eco-friendly [39].
Subsequently, the development of green materials has enabled
researchers to incorporate RHA as a partial replacement of cement.
Several studies have highlighted the effectiveness of RHA as a sub-
stituting cementitious material for the replacement of cement in
concrete and cement mortar [29–31,35,40–42]. Beside its positive
impact on improving the mechanical properties of concrete, RHA
can used in mitigating expansion due to alkali silica reaction
(ASR) [43]. According to Abbas et al. [44], alkali silica expansion
of cement paste containing 10 and 40% RHA as a substitute of
cement was reduced by 23 and 50%, respectively. Moreover, the
addition of RHA resulted in an elimination of cracks caused by
ASR expansion. Le et al. [45] found that the control and mitigation
of ASR is dependent on the particle size of the RH. Zerbino et al.
[31] investigated the effect of natural rice husk ash and grinded
rice husk ash as a partial substitute of cement in mortar and con-
crete. The addition of grinded rice husk ash exhibited better perfor-
mance, resulted in improved mechanical properties, and reduced
alkali silica expansion. Hasparyk et al. [46] replaced cement with
SF and RHA in different proportions in mortar bars containing reac-
tive aggregates and observed a significant reduction in the alkali
silica expansion, despite the presence of reactive aggregates.
Recently, high strength and high-performance concrete have
been utilized significantly throughout the world. To produce
high-performance concrete, SF is used all over globe due to its very
fine size and highly reactive silica particles. This is because it not
only increases strength, but also reduce permeability, and bleeding
[47–48]. In general, the SF is obtained as a by-product during the
production of silicon and ferrosilicon alloys at a very high temper-
ature around 2000 °C in the electric arc furnace [11]. Due to the
increasing demand of silica in concrete and other industries, many
studies have been conducted on the extraction of silica from differ-
ent sources such as silica sand, dourite sand and waste colored
glass and so on. However, silica extracted from these raw materials
required different complex processes such as crushing, high-
energy milling, purification from impurities and so on, while, in
other cases sintering at high temperatures [49–52]. On the other
hand, the silica extracted from organic sources such as RHA and
sugarcane bagasse ash was found as good quality and energy effi-
cient. Silica obtained from RHA exhibited high chemical reactivity
and amorphousness, and a high purity level [53–55]. Recently, the
sustainability assessment of different applications of RHA has been
conducted, including the extraction of micro-silica from RHA [56].
The EMS could be an economical and eco-friendly substitute of SF
[57].
Despite the high purity and chemical reactivity of silica
extracted from RHA, studies found a very limited research on its
potential use in mortar and concrete. Cavalcante et al. [58] evalu-
ated the effect of silica extracted from RHA on strength and
microstructure of cement paste. According to their findings, use
of a 16% silica extracted from RHA as a partial substitute of cement
enhanced the compressive strength significantly at all ages. At age
of 28 days, it resulted in greater compressive strength as compared
to control (100% cement) and those containing 40% metakaolin.
The improved compressive strength of paste containing silica
was attributed to high fineness and reactivity of silica extracted
from RHA, which ultimately led to increased pozzolanic reaction,
better filling ability and acceleration of hydration reaction. The
high pozzolanic reactivity of silica extracted from RHA and its
influence in better mechanical performance was confirmed by
microstructural investigation of paste samples. Lima et al. [54]
studied the performance of silica extracted from RHA through
hydrothermal process in cement paste. The modified Chapelli test
result showed high consumption of calcium hydroxide by
extracted silica, which confirmed the amorphous nature of silica
extracted from RHA. They further demonstrated that the cement
paste with 5% extracted silica as a partial substitute of cement
showed significantly improved compressive strength as compared
to control (100% cement) at all ages.
The existing studies are only focused on to evaluate the effect of
silica extracted from RHA on the chemical reactivity and
microstructural properties of cementitious matrix. Hence, it is very
important and necessary to further evaluate the effect of silica
extracted from RHA on the mechanical, durability and micro and
pore structural properties of cement mortar. Therefore, this study
aims to evaluate the effect of micro silica extracted from RHA as
a replacement of cement on macro and micro structural properties
 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
to produce high performance and sustainable mortar matrix. The
physical and chemical properties of cement, RHA, and EMS were
evaluated using X-ray diffraction (XRD), X-ray fluorescence (XRF),
and surface area analysis techniques. Mortar mixes, namely, con-
trol mortar (CM) having 100% cement and mortars containing var-
ious percentages of EMS (5%, 15%, and 25%) as a partial substitute
of cement, were prepared, and the consistency and setting behav-
ior of the fresh mortar mixes were examined. The compressive and
flexural strengths, porosity, and alkali–silica reactivity were also
investigated for the hardened mortar samples. Finally, the effect
of EMS on the micro- and pore structures of the paste samples
was investigated by performing scanning electron microscopy/
energy-dispersive X-ray spectroscopy (SEM-EDS), nitrogen adsorp-
tion, and Fourier-transform infrared spectroscopy (FTIR) analyses.
Pore and microstructure analyses were performed to understand
the formation of hydration products due to the addition of EMS
to the cement matrix.
2. Research significance
The demand of high strength and high-performance concrete is
increasing due to recent advancement in the development of
infrastructure. Silica based materials (micro and nano silica) from
natural and synthetic sources or as industrial by products, play
an important role in the production of these high strength and
high-performance concrete. Therefore, the purpose of current
research is to boost the scientific understanding and enhance the
available knowledge on impact of micro silica extracted from
RHA on mechanical and microstructural properties of mortar. The
unique aspect of current research is the identification and under-
standing of the dosage of micro silica extracted from RHA on the
strength, porosity, ASR and micro and pore structural properties
of mortar under conventional laboratory mixing environment.
The aim of this work is focused on the possible use of micro silica
extracted from RHA in the concrete industry to produce stronger,
durable, and sustainable concrete.
3. Materials and methods
3.1. Materials
In this study, a commercially available OPC Type I fulfilling the
requirements of ASTM C150 was used. A naturally available fine
aggregate, having a specific gravity of 2.57 and water absorption
of 2.98%, was used for the preparation of the mortar mixes. The
fineness modulus (FM) of the fine aggregate, calculated according
to ASTM C33, was 2.56 as shown in Table 1. In the initial phase,
RH was collected from different regions of Khyber Pakhtunkhwa
province, and subjected to different heating temperatures and
durations to optimize the process of obtaining an RHA sample with
high silica content. Several researchers highlighted the effect of soil
and climatic conditions, burning temperature, and duration on the
Table 1
Grain size distribution of fine aggregate (EN 196-1 and ISO 679:2009).
Sieve # Sieve Size (mm) Weight Retained (g)
3/8 in. 9.5 0 0
No. 4 4.75 0 0
No. 8 2.36 40
No. 16 1.18 65
No. 30 0.600 100
No. 50 0.300 205
No. 100 0.150 80
Pan - 10
Fineness Modulus (FM) = (0 + 0 + 0 + 8 + 21 + 41.1 + 82.2 + 98)/100 = 2.51
3
physical and chemical properties of RHA [59]. The initial investiga-
tion showed that the sample collected from Charsadda area, when
burned in a refractory kiln at 700 °C for 24 h, exhibited better
chemical and mineralogical properties. Subsequently, RHA was
subjected to different processes for extracting silica, which is the
main element responsible for the pozzolanic properties of these
materials. The chemical and physical properties of cement, RHA,
and EMS are shown in Table 2.
3.1.1. Extraction of silica from RHA
The silica extraction process was performed in 11 steps, as indi-
cated by the flow diagram in Fig. 1. This technique was previously
established by Kalapathy et al. [60,55], and adapted by Cavalcante
et al. [58] and Lima et al. [54].
The first phase includes the treatment of RHA with hydrochloric
acid to remove different impurities, especially the oxides of cal-
cium and potassium [49]. Subsequently, the sample was heated
until boiling, vigorously agitated for one hour using a hotplate with
a magnetic stirrer, and cooled under ambient temperature. Sample
filtration was then performed using a vacuum pump and Whatman
no. 41 filter paper, followed by a treatment of the ash with 1 M of
sodium hydroxide solution to solubilize the silica contents present
in the sample (treated ash), producing sodium silicate at stage 5
[54]. The chemical reaction is given in Eq. (1).
SiO2 + 2NaOH ! Na2 SiO3 + H2 O ð1Þ
The silicate was then boiled for two hours and cooled, similar to
steps 2 and 3. The solid residue was then removed by filtering the
sample using a vacuum pump and Whatman no. 41 filter paper.
The sodium silicate solution was then treated with hydrochloric
acid to reduce the pH to neutral, thus producing a gel, followed
by the addition of a dilute solution of sulfuric acid under constant
stirring to acidify the solution (pH 1–2). A glass rod was used to
disintegrate and disrupt the gel structure, followed by thorough
washing using distilled water to remove the remaining impurities.
Subsequently, the solution was vigorously agitated, forming gel
precipitation, and the water was discarded. This washing process
was performed five times until the sodium chloride, produced at
stage 9, was completely removed. Finally, the sample was oven-
dried for 25 h at 100 °C to obtain silica. Cavalcante et al. [58] stated
that complete drying is achieved by maintaining the sample at
100 °C for 25 h.
3.1.2. Mix proportions
In addition to control, three binary mixes by substituting
cement with various percentages of EMS were prepared. Table 3
shows the quantities of ingredients for mortar mixes used in this
study. The required quantities for different mixes were calculated
according to ASTM C109 [61]. For all mixes, a standard water to
cement ratio of 0.485 was selected, while, the sand to cement ratio
was 2.75. In this study, control mortar having 100% OPC is identi-
fied as CM, and mortar containing 5%, 15% and 25% EMS as a partial
Weight Retained (%) Cumulative Passing (%) Cumulative Retained (%)
100 0
100 0
8 92 8
13 79 21
20 59 41.1
41.1 18 82.2
16 2 98
10 – –
4 K. Khan et al. / Construction and Building Materials 258 (2020) 119589

Table 2 replacement of cement are identified as EMS-5, EMS-15 and EMS-

Physical and chemical properties of cement. RHA and EMS. 25, respectively.
C RHA EMS
Physical properties 3.2. Experimental methods
Specific gravity (g/cm3) 3.15 2.83 2.15
Fineness (m2/g) 0.360 (Blain) – 36.58 (BET)
3.2.1. Standard consistency and setting times
Chemical properties (oxides, % by weight)
SiO2 21 96.109 99.832
The measurement of the rheological properties of fresh paste
Al2O3 5.04 – – plays an important role in determining the water requirement of
Fe2O3 3.24 0.396 0.065 cement mortar and concrete to set their flow and workability
CaO 61.7 1.033 0.031 requirements, respectively. Moreover, it is important in determin-
MgO 2.56 – –
ing hydration behavior and hardened properties at a later stage.
SO3 1.51 0.206 –
K2O 0.62 1.159 0.045 The later-age strength and durability performance of mortar and
Na2O 0.13 – – concrete are largely dependent upon the degree of dispersion of
TiO2 – 0.032 0.017 cement particles in the water [62]. Therefore, in this study, the
CuO – 0.0013 0.010
effect of various percentages of EMS (5%, 15%, and 25%) on water
MnO – 0.061 –
LOI** 1.83 1.002 –
requirement and setting times (initial and final) were investigated
IR*** 0.54 – – by measuring the standard consistency of the pastes using the
Free lime 0.68 – – VICAT apparatus in accordance with ASTM C187 and ASTM C191,
Compounds (%) respectively [63,64].
C2S 52.1 – –
C3S 19.6 – –
C3A 8.17 – – 3.2.2. Strength and porosity
C4AF 8.81 – – In this study, 50 mm mortar cubes were prepared to investigate
*ASTM C618; ** LOI = loss on ignition; ***IR = Insoluble residue. the influence of various percentages of EMS on compressive
strength and porosity. For each mortar mix (Table 3), 18 identical
cubes specimens were cast at once to maintain uniformity among
1. Cleaning them, and later divided into two groups of nine samples each to
(RHA+HCl+H2O) investigate the development of compressive strength and to mea-
sure the porosity with respect to aging at 14, 28, and 56 days. The
2. Heating and Stirring for 1 hour
mixing of standard mortar and casting into steel mold were per-
formed according to ASTM C109 [61]. For flexural strength, nine
3. Cooling at room temperature rectangular beams of dimensions 150  50  50 mm
(length  height  thickness) were cast to test three identical spec-
4. Filtering and discarding liquid residue imens at the ages of 14, 28, and 56 days to investigate the influence
of EMS on flexural behavior. Immediately after casting, the rectan-
5. Extraction gular beam molds were filled with mortar following the methods
(Clean Ash +NaOH) specified by ASTM C348-14 [65]. After casting, all the specimens,
mortars cubes and rectangular beams, were stored in a laboratory
6. Heating and Stirring for 2 hours
under constant temperature and humidity conditions (T = 23 °C
and RH = 60%). All the specimens were demolded after 24 h of cast-
7. Cooling at room temperature. ing, and continuously moist-cured under the standard laboratory
conditions of temperature until the age of testing.
8. Filtering and discarding solid residue A universal testing machine (UTM) was used to perform the
compressive strength tests on the mortar cubes (ASTM C109),
9. Gelification and flexural tests on the rectangular beams using the four-point
(Sodium Silicate Solution + HCL + H2SO4).
loading method (ASTM C 348-14). In flexural tests, the length of
the span between the supports was equally divided into three parts
10. Gel disintegration and washing .
to ensure a uniform loading on the specimen. At each testing age
(14, 28, and 56 days), the compression and flexural tests were per-
111. Oven drying at 100 oC for 25 hours
formed on three identical specimens of each mix (CM, EMS-5, EMS-
15, and EMS-25) to calculate their average values.
Amorphous Silica Immediately after the compression tests, the porosity of the
mortar cubes was measured at the same ages (14, 28, and 56 days)
Fig. 1. Schematic flow diagram for the extraction of amorphous micro silica from to validate the compressive strength results indirectly. The poros-
RHA.
ity of the mortar cubes was determined by weighing the samples in
various moisture states. In their previous study, the authors pro-
vided the details of the method adopted to measure porosity

Table 3
Mixture proportions of mortar samples for compressive and flexural tests, porosity, and ASR expansion (w/cm = 0.485; cm:s = 1:2.75).

Mix ID Quantities (g)

Cement Replacement (%) Water Cement EMS Sand
Control Mortar (CM) 0 242.5 500 0 1375
Mortar containing 5% EMS (EMS-5) 5 242.5 475 25 1375
Mortar containing 15% EMS (EMS-15) 15 242.5 425 75 1375
Mortar containing 25% EMS (EMS-25) 25 242.5 375 125 1375
 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
[66]. After weighing, the porosity of the mortar samples was calcu-
lated as follows:
ðW ssd  W od Þ
q¼  100%
ðW ssd  W w Þ
where q is the porosity calculated as a percentage, Ww is the weight
of the sample in water, Wssd is the saturated surface dry weight of
the sample, and Wod is the oven-dried weight of the sample.
3.2.3. Alkali–silica reaction (ASR)
The effect of EMS on the mitigation of the expansion due to ASR
was measured according to the ASTM C1260 standard [67]. As per
the standard, two mortar bars (dimensions 25  25  285 mm)
were prepared for the control (100% cement) and the other mixes
having various percentages of EMS. Part of the natural sand was
replaced with crushed glass aggregates of sizes ranging 4.7–
1.18 mm to activate ASR [68]. After casting, the mortar bars were
cured under standard condition. After 24 h, the mortar bars were
demolded and the initial readings were measured using a com-
parator. After the initial readings, the samples were again cured
in an oven at 80 °C for the next 24 h. After the completion of oven
curing, the samples were removed, and the readings were consid-
ered as zero reading. Finally, the mortar bars were placed in 1 M
NaOH solution and maintained in an oven at 80 °C. The length
change of the mortar bars was measured at 16 days from the day
of casting.
3.2.4. Micro- and pore structure investigation
The micro- and pore structures of all the samples were investi-
gated by using XRF, FTIR, SEM-EDS analysis, and nitrogen adsorp-
tion. The equipment and parameters used for these experimental
techniques are described below:
3.2.4.1. Casting and curing of paste samples for micro- and pore
structure analysis. Samples of control cement paste (CP) and pastes
having various percentages of EMS as a partial substitute of cement
(by weight) were prepared. The pastes were mixed using a Hobart
mixer. The fresh pastes were poured in plastic containers of diam-
eter 20 mm and height 50 mm. Immediately after casting, the plas-
tic containers were caped, sealed, and cured in a laboratory under
standard room temperature. After 28 days of curing, the samples
were dried to stop the hydration process by using the solvent
exchange method. Accordingly, the thin slices and powder samples
were washed with isopropanol for 15 min [69]. After washing, the
samples were maintained in a laboratory oven for 30 min at 40 °C.
After the stoppage of hydration, the samples were stored in sealed
plastic bags until the time of testing.
3.2.4.1.1. X-Ray florescence (XRF) analysis. The elemental composi-
tions of cement, RHA, and EMS were measured by using
wavelength-dispersive (WD) XRF spectrometry. The chemical anal-
ysis was performed on the ground samples, and the results are
shown in Table 2. The RHA sample mainly consists of silica
(96.109%) and a few trace elements. The chemical composition of
the silica extracted from RHA demonstrates its high purity, which
is 99.832%.
3.2.4.1.2. SEM-EDS analysis. SEM-EDS analysis was performed on
thick slices of the hardened paste by using a JSM-IT100 scanning
electron microscope. The thick slices of hardened paste were dried
using the solvent exchange method with isopropanol as mentioned
above. The morphological and compositional variations of all the
samples were evaluated.
3.2.4.1.3. Nitrogen adsorption. Nitrogen adsorption analysis was
performed for the characterization of the surface area and pore
structure using the powder samples extracted from hardened paste
and a nitrogen sorption analyzer (NOVA2200e, Quanta chrome,
5
USA). A sample of approximately 0.2 g was used for each measure-
ment. The samples were first degassed to remove any contami-
nants absorbed due to their exposure to environment. The
ð2Þ nitrogen absorption of the samples was performed at a controlled
pressure and ambient temperature. The N2 sorptiometry study was
performed at 273 K.
3.2.4.1.4. FTIR analysis. Additional characterization of the phases
present in the paste samples was performed using FTIR with a Per-
kin Elmer Spectrum Two Fourier-Transform Infrared Spectrometer.
The dried powder samples were directly placed under an infrared
light source and infrared spectra were collected between
400 cm1 and 4000 cm1.
4. Results and discussion
4.1. Standard consistency
Table 4 shows the influence of the increase in the amount of
EMS on the standard consistency of the cement paste. It can be
observed that the requirement of water increased linearly with
the increase in the amount of EMS in the paste. The main reason
for this increased water requirement in the paste is the low specific
gravity and higher specific surface area of EMS as compared with
those of cement. The specific gravity and Brunauer–Emmett–Teller
(BET) specific surface area of the EMS used in this study are 2.15
and 36.6 m2/g, respectively. Thus, the porous structure and very
fine particles of EMS evidently need more water than the normal
cement particles to maintain the desired flow. The consistency
results of the current study coincide with the past findings of sev-
eral researchers. According to Rao [70], the water requirement of
cement pastes containing 20% to 30% SF was significantly increased
by as much as 40% compared with that of the control sample (100%
cement only). Qing et al. [71] investigated the influence of nano-
silica and observed very high consistency values compared with
those of the corresponding control samples with 100% cement. In
fact, the very fine particles of EMS can easily adjust their position
to occupy the empty spaces between cement particles. This leads
to a reduction in the size of flow channels, particularly when high
doses of EMS (15% and 25%) are used; thus, more water is eventu-
ally required to maintain a standard consistency.
4.2. Initial and final setting times
Table 4 shows the comparison of initial and final setting times
between the CM and the mortars containing different percentages
of EMS. It can be observed in Fig. 2 that both the initial and final
setting times increase with an increase in the percentage of EMS.
The initial and final setting times of the mortar containing a low
percentage of EMS (5%) were not affected much and increased by
only 4.1% compared with that of the CM. However, higher percent-
ages of EMS (15% and 25%) affected the setting times significantly,
which increased by 7.6% and 19.8%, respectively, compared with
that of the CM. These results coincide with the findings of previous
studies on adding SF as a partial substitute of cement. Alshamsi
Table 4
Standard consistency and setting time results of control and mortars containing
different percentages of EMS.
Mix ID Consistency Initial setting Final setting
(%) time (min) time (min)
CM 27 145 243
EMS-5 34 151 253
EMS-15 37 156 269
EMS-25 39.5 174 291
6 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
Fig. 2. Effect of EMS (5, 15 and 25%) on initial and final setting times.
et al. [69] reported an insignificant influence of adding a low per-
centage of micro-silica (10%) on the setting times and a 6%–20%
increase in the setting times when 20% micro-silica was used as
a replacement of cement. According to Lohtia and Joshi [72], the
setting time was delayed due to the addition of SF in concrete in
the absence of a water-reducing admixture compared with that
of a concrete of equal strength with no SF. Therefore, the increase
in the setting times of EMS mortars compared with that of the CM
may be due to the non-use of a water reducer in the current mixes.
4.3. Effect of EMS on the compressive strength of mortar with aging
Fig. 3 shows the comparison of compressive strength results of
the CM and the mortars containing different percentages of EMS
with aging. The results show that the mortars containing EMS
exhibited remarkably higher compressive strength compared with
the corresponding CM at all ages (14, 28, and 56 days), except for
25% EMS, which showed a slightly lower compressive strength
than the CM by only 1.10% at 56 days. Nevertheless, these results
indicate that the mortars containing EMS up to 25% easily satisfied
the ASTM C618 criteria of strength activity index (ASTM C311) for
cement-substituting pozzolanic materials. According to ASTM
Fig. 3. Comparison of compressive strength evolution between CM and mortars
having various percentages of EMS.
C618, the compressive strength of mixes containing cement-
substituting pozzolanic materials must be at least 75% that of the
corresponding CM at 28 days. According to ASTM C311, the
strength activity index values are mainly calculated to evaluate
the reactivity of mineral admixtures with cement.
From the comparison of results, it was observed that the com-
pressive strength values of mortars containing EMS were signifi-
cantly higher than that of the CM up to 28 days. For instance, the
compressive strength of the mortar containing 5% EMS was higher
than that of the CM by 37.6% and 64.2% at 14 and 28 days, respec-
tively (Table 5). The mortar containing 15% EMS exhibited higher
strength than the CM by 23.9% and 51.6% at 14 and 28 days, respec-
tively. Lima et al. [54] and Cavalcante et al. [58], respectively also
observed the increase in compressive strength of cement pastes
due to adding 5% and 16% silica extracted from RHA as a partial
substitute of cement. These results of increased strength can be
attributed to the presence of reactive amorphous SiO2 along with
high fineness in mortars containing EMS. According to the past
findings of several researchers, the presence of reactive amorphous
SiO2 in SF having pozzolanic nature and its high fineness lead to a
significant enhancement of the strength of cement mortar and con-
crete composites [73,74]. In this study, the high fineness and reac-
tivity of EMS resulted in the formation of more cementing gel (C-S-
H), eventually decreasing C–H in the matrix. This leads to the
remarkably high strength of EMS mixes (EMS-5, EMS-15, and
EMS-25) as demonstrated by the denser C-S-H phases in the
SEM-EDS analyses.
Unlike mortars containing low percentages of EMS (5% and
15%), the percentage increase in the strength of the mortar con-
taining 25% EMS is low. The strength of the mortar containing
25% EMS was only 8.01% and 10.6% higher than that of the CM at
14 and 28 days, respectively. The strength values of all the EMS
mixes were higher than that of the CM. However, the comparison
of the obtained results among the mortars containing EMS sug-
gests that the percentage increase in the strength compared with
that of the CM slightly decreased with an increase in the amount
of EMS from 5% to 15%, and reduced significantly with an increase
in the amount of EMS from 15% to 25%. At high percentages of EMS,
agglomeration occurs due to oversaturation and improper disper-
sion. This leads to reduced hydration and ultimately the formation
of a low-density and porous gel structure, as demonstrated by
micro- and pore structural investigations [75].
Moreover, the percentage increase in the strength compared
with that of the CM in all the EMS mixes increases with aging, par-
ticularly at the early ages from 14 to 28 days. The increase in
strength compared with that of the CM in the mortars with 5%,
15%, and 25% EMS was 37.6%, 23.9%, and 8.01%, respectively, at
14 days, and it increased to 64.2%, 51.6%, and 10.6%, respectively,
at 28 days. However, unlike at the early ages (14 to 28 days), the
percentage increase in the strength of all the EMS mixes compared
with that of the CM slightly reduced with aging at the later ages
(28 to 56 days). It was observed that the increase in strength of
the mortars with 5% and 15% EMS at 56 days is 53.7% and 48.5%
higher than that of the CM, respectively, at the corresponding
age. These values are slightly less than the corresponding increases
of 64.2% and 51.6% compared with that of the CM at 28 days,
respectively. Contrary to the above strength results of the mortars
with lower percentages of EMS (5% and 15%), the strength of the
mortar with 25% EMS was even lesser than that of the CM at
56 days. It was observed that the strength of the mortar containing
25% EMS was only less than that of the corresponding CM by 1.10%
at 56 days. As discussed earlier, when 25% EMS is used, poor dis-
persion leads to increased agglomeration, thus reducing the hydra-
tion reaction and causing the formation of weak products. This
resulted in lesser strength of the mortars containing relatively high
amounts of EMS [76].
 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
Table 5
Compressive strength, flexural strength and porosity of different mortar mixes with aging.
Mix ID Compressive strength (MPa) Flexural strength (MPa)
Age (days)
14 28 56 14
CM 15.0 16.9 20.3 3.39
EMS-5 20.6 27.8 31.2 4.25
EMS-15 18.6 25.6 30.2 3.93
EMS-25 16.2 18.7 20.1 3.55
4.4. Effect of EMS on the flexural strength of mortar with aging
Fig. 4 shows the comparison of flexural strength results of the
mortars containing different percentages of EMS with that of the
CM with aging. As with the compressive strength, the comparison
of results shows that the mortars containing EMS had significantly
higher flexural strength than the corresponding CM at all ages (14,
28, and 56 days), except for the reduction in the flexural strength of
the mortar containing 25% EMS compared with that of the CM by
6.9% at 56 days. As discussed in the preceding section, the com-
pressive strength of the mortar with 25% EMS was only lower than
that of the CM by 1.10% at the same age. All the other observations
discussed earlier for the compressive strength can be equivalently
applied to the results of flexural strength. The only difference
observed is in the percentage increase values of flexural strength
of the mixes containing EMS compared with that of the corre-
sponding CM. For instance, the increases in the flexural strength
of the EMS mixes compared with that of the CM are slightly lower
relative to their respective increases in compressive strength both
at early (14 and 28 days) and later ages (56 days). At the early age
of 14 days, the flexural strength values of the mixes with 5%, 15%,
and 25% EMS were higher than that of the CM by 25.3%, 15.8%, and
4.85%, respectively, whereas their percentage increases in the com-
pressive strength at the same age were quite high at 37.6%, 23.9%,
and 8.01%, respectively. A similar trend was observed at 28 days,
where the flexural strength values of the mixes with 5%, 15%,
and 25% EMS were higher than that of the CM by 46.8%, 24%, and
1.66%, respectively. These values are quite low compared with
their respective percentage increases in the compressive strength
(64.2%, 51.6%, and 10.6%, respectively), particularly for the mixes
containing high amounts of EMS (15% and 25%). At a later age
(56 days), the percentage increases in the flexural strength of the
mixes with 5% and 15% EMS were 35.5% and 21.2%, respectively,
Fig. 4. Comparison of flexural strength evolution between CM and mortars having
various percentages of EMS.
7
Porosity (%)
28 56 14 28 56
3.83 4.72 19.40 16.20 14.57
5.62 6.40 18.18 15.33 13.82
4.75 5.72 18.41 15.69 14.19
3.89 4.39 19.10 15.05 15.09
whereas their respective percentage increases in the compressive
strength were 53.7% and 48.5%. Similar to the decrease in the com-
pressive strength by 1.10% in the mix with 25% EMS at 56 days, an
even higher decrease in the flexural strength, i.e., by 6.9%, was
observed.
4.5. Effect of EMS on the porosity of cement mortars with aging
Fig. 5 shows the comparison of porosity between the CM and
the mortars containing different percentages of EMS with aging.
The porosity was measured mainly to validate the experimental
results of the compressive and flexural strengths of the studied
mortars indirectly. The porosity shown in Fig. 5 is an average value
for the three identical mortar cubes. These results indicate that the
porosity of the mortar decreased with aging for all the mortar
mixes, due to the consumption of water by the hydration reaction
and the generation of a solid gel in the matrix. The trend of
decreasing porosity with aging validates the results of the increase
in the strength with aging for all the mortars (control and those
containing EMS), which were discussed in the preceding sections.
Moreover, it can be observed from Fig. 5 that the porosity of the
mortars containing EMS decreased compared with that of the cor-
responding CM at all ages, except in the mortar with 25% EMS,
whose porosity exceeded that of the CM by 3.6% at 56 days. This
finding also supports the strength results, as the compressive and
flexural strengths of the mortars containing EMS were observed
to be higher than that of the corresponding CM at all ages, except
in the mortar with 25% EMS, whose compressive and flexural
strengths were lower than that of the CM by 1.10% and 6.84% at
56 days, respectively.
At any particular age (14, 28, or 56 days), the percentage
decrease in porosity compared with that of the CM decreases with
an increase in the amount of EMS from 5% to 25%. A similar trend
was observed for the percentage increases in the compressive and
Fig. 5. Porosity of mortars with and without EMS with aging.
8 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
flexural strengths at any particular age, which decreased with an
increase in the amount of EMS from 5% to 25%.
According to the porosity results (Table 5), the porosities of the
mortars containing 5%, 15%, and 25% EMS are lower than that of the
CM at 14 days by 6.3%, 5.1%, and 1.5%, respectively. With aging, the
difference of porosity between the CM and the mortars containing
EMS slightly decreased. At 28 days, the porosities of EMS-5, EMS-
15, and EMS-25 were 5.4%, 3.1%, and 0.93% lower than that of
the CM, respectively. With further aging, at 56 days, the trend of
porosities was almost similar to that at 28 days in the mixes with
relatively low amounts of EMS (5% and 15%). The porosities of the
mortar mixes with 5% and 15% EMS at 56 days were 5.1% and 2.6%
lower than that of the corresponding CM, respectively, whereas, in
25% EMS, the porosity was 3.6% higher. The above trends of the
percentage decrease or increase in the porosities of any mix at
any particular age are almost consistent with the trends of percent-
age increase or decrease in the strengths.
These results suggest that up to 15% of cement may be replaced
with EMS in its future application as a construction material. This
is because it has produced satisfactory strength results, which have
been validated through extensive porosity and micro- and pore
structural analyses. The use of higher percentages of EMS such as
25% is not recommended mainly due to the low increase in
strength up to 28 days followed by a slight reduction in both com-
pressive and flexural strengths at later ages.
4.6. Expansion due to alkali–silica reaction (ASR)
Fig. 6 shows the expansion of the CM and the mixes containing
different percentages of EMS due to ASR. According to ASTM
C1260, if the expansion of the mortar bar is between 0.1 and 0.2
at 16 days after casting, then the aggregate is regarded as reactive
and can cause deleterious expansion. The average expansion of CM
bars was 0.175, which shows the high reactivity of the aggregate
used in the study.
The ASR results show that the CM causes greater expansion
than the mortars containing EMS. This may be attributed to the for-
mation of more C-S-H because of the accelerated pozzolanic reac-
tivity of EMS. The high pozzolanic reactivity of EMS also helps in
the reduction of pore water and the fixation of alkali, thus decreas-
ing the tendency of promoting ASR gel expansion [77–79]. The ASR
results also demonstrate that mortar bars samples having 5% EMS
(0.043) showed better resistance to ASR expansion than those hav-
ing high percentages of EMS i.e., 15% (0.072) and 25% (0.083). The
high dosage of EMS causes dispersion-related issues in the mortar
Fig. 6. Comparison of ASR expansion results between CM and mortars containing
various percentages of EMS at age of 16 days.
mixes [75]. Therefore, the poor dispersion of EMS leads to the for-
mation of agglomerates with little or no cement hydration prod-
ucts, as observed in the SEM images. These agglomerates would
act as nucleation sites for the ASR gel and do not contribute toward
durability against ASR. Overall, all the percentage replacements of
EMS (5%, 15%, and 25%) showed ASR expansion values less than 0.1
at 16 days after casting, demonstrating the effectiveness of EMS in
mitigating ASR expansion.
4.7. SEM-EDS analysis of paste samples
The SEM micro scans and EDS elemental analysis results for the
control and the mixes containing various percentages of EMS are
shown in Fig. 7.
The visual observation of the digital micrograph demonstrates
that, compared with the control sample, both EMS-5 and EMS-15
samples showed a denser and compact matrix. This may be attrib-
uted to the high reactivity of EMS, which causes the formation of
dense hydration products and a more refined microstructure. How-
ever, as indicated in Fig. 7 for EMS-25, microstructure become rel-
atively less dense and porous due to an increased amount of EMS.
To identify the signs of unreacted particles and agglomeration of
silica particles, the location of accumulated particles and large
voids are marked on SEM image. These accumulated particles are
expectedly the unreacted cement and micro silica particles, which
can be attributed to oversaturation and insufficient mixing. More-
over, the large voids shown are a sign of partial agglomeration of
EMS particles, which could be due to oversaturation and poor dis-
persion of very fine silica particles in the matrix. According to
Nazari et al. [75] and Said et al. [76], agglomeration of fine silica
particles causes reduction in the cement hydration due to localized
dehydration, which leads to the formation of void with little or no
strength bearing structures and thus, ultimately responsible for
reduced mechanical resistance and durability performance.
The atomic ratio of Ca/Si of the cement paste matrix calculated
using EDS analysis was considered an important parameter from
the point of view of material chemistry in evaluating the role of
mineral admixtures in cement and concrete for the design of sus-
tainable concrete mixes with low carbon footprint [80]. The litera-
ture studies show that the chemistry of hydration products such as
C-S-H and C-H is mainly dependent on the activity of Ca and Si ions
present in the pore solution during the hydration process. The Ca/
Si atomic ratio of C-S-H generally varies from 0.67 to 2.0. Lower
values of Ca/Si ratio showed compacted and denser microstruc-
tures because of the formation of the denser C-S-H product. The
Ca/Si ratio values higher than 2.0 represent the presence of C-H
phase and the greater these values, the higher is the C-H content
[81,82].
The values of the Ca/Si atomic ratio for all the samples calcu-
lated via the EDS analysis are shown in Table 6. The EDS analysis
results show a reduction in the Ca/Si atomic ratio for all the mixes
having different percentages of EMS compared with that of the CM.
The result further demonstrates that the Ca/Si atomic ratio is low-
est for the EMS-5 mix, which is attributed to the accelerated reac-
tivity of EMS and the formation of high-density C-S-H and C-H. In
addition, the mixes with 5% and 15% EMS show lower values (both
1.54) of Ca/Si atomic ratio than the mix having 25% EMS (1.71) and
the control sample (1.91). This demonstrates the formation of
high-density C-S-H at the inclusion of 5% and 15% EMS. The Ca/Si
atomic ratio greater than 2.0 shows the formation of C-H phases
in the cement matrix [83,84]. The mixes having 5% and 15% EMS
showed lower values (2.03 and 2.27, respectively) of the Ca/Si
atomic ratio than both the mix with 25% EMS (2.54) and the con-
trol sample (2.73). These results indicate that the mixes with 5%
and 15% EMS cause a reduction in the overall formation of C-H,
and the density of the formed C-H is greater than those of the
 K. Khan et al. / Construction and Building Materials 258 (2020) 119589 9

CP EMS-5

EMS-15 EMS-25

Fig. 7. SEM images of CP and pastes containing EMS (EMS-5, EMS-15 and EMS-25) at age of 28 days.

Table 6 Table 7
Ca/Si atomic ratio from EDS analysis of control cement paste (CP) and pastes BET surface area and BJH total pore volume of CP and pastes containing different
containing different percentages of EMS at age of 28 days. percentages of EMS at age of 28 days.

Mix ID Ca/Si atomic ratio Mix ID BET Surface area (m2/g) BJH total pore volume (cm3/g)
EDS-001 EDS-002 CP 41.637 0.0200
EMS-5 52.552 0.0190
CP 1.91 2.73
EMS-15 50.875 0.0190
EMS-5 1.54 2.03
EMS-25 48.876 0.0193
EMS-15 1.54 2.27
EMS-25 1.71 2.54

show a significant increase in the BET surface area of the samples

mix having 25% EMS and the CM. Cavalcante et al. [58] also
observed reduction in C-H content having added silica as compared
to control cement paste sample through SEM analysis. Overall, the
addition of EMS plays a positive role in promoting the hydration
process and the development of a denser and refined microstruc-
ture; consequently, better mechanical properties and durability
can be achieved as shown earlier. In the future, advanced mixing
techniques for the dispersion of EMS in the cement matrix should
be studied for a better understanding of its optimum dosage and
performance.
4.8. N2 Adsorption
The BET results for the surface area and the Barrett–Joyner–H
alenda (BJH) results for the pore volume obtained by using the
nitrogen adsorption technique are listed in Table 7.
The BET surface areas show the characteristic of the cementi-
tious gel through the formation of C-S-H phases. An increase in
the BET surface indicates an increase in the degree of hydration
and the formation of more C-S-H phases [85,86]. The test results
having different percentages of EMS compared with that of the
control sample. This may be attributed to the high reactivity of
EMS, which facilitates the hydration process, thus forming denser
C-S-H phases, as demonstrated via SEM-EDS analysis. The EMS-5
sample showed a high BET surface area of 52.55 m2/g, whereas
the EMS-15 and EMS-25 samples showed BET surface areas of
50.88 m2/g and 48.89 m2/g, respectively. The slight decrease in
the BET surface area for both EMS-15 and EMS-25 compared with
that for EMS-5 may be due to the agglomeration caused by oversat-
uration and improper dispersion and the formation of low-density
C-S-H, as demonstrated via SEM-EDS analysis.
The total pore volume results calculated from the BJH pore size
distribution analysis for all the samples show that both EMS-5 and
EMS-15 exhibited less pore volume (0.0190 cm3/g) than the con-
trol (0.0200 cm3/g) and EMS-25 (0.0194 cm3/g). The increase in
the total pore volume for EMS-25 compared with those for EMS-
5 and EMS-15 may be due to the oversaturation of silica, as also
observed in the BET surface area analysis. The formation of high-
density C-S-H and C-H phases in the mixes having different per-
centages of EMS resulted in the improvement and densification
of the pore structure compared with that of the control sample.
10 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
Fig. 8. FTIR spectra of CP and pastes containing EMS (EMS-5, EMS-15 and EMS-25)
at age of 28 days.
4.9. Fourier-transform infrared spectroscopy (FTIR) analysis
The FTIR analysis results of the control cement paste and the
samples having different percentages of EMS are shown in Fig. 8.
All the samples show a complex group of bands in the region
between 4001 and 1200 cm1, which indicates the asymmetric
and symmetric stretching vibration of Si-O bands [87]. The peaks
between 450 cm1 and 500 cm1 show the Si-O-Si bending vibra-
tion of C-S-H. The main characteristic peaks of C-S-H are located
between 900 cm1 and 1100 cm1 [88,89]. A shift in the peak
occurs between these ranges, which indicates the process of poly-
merization of silica. For the control sample, the C-S-H peak is
observed at 971 cm1, which shows the asymmetric stretching
vibration of Si-O band. The replacement of cement with EMS at dif-
ferent percentages (5%, 15%, and 25%) caused a shift in the peak.
The peak shifts from 971 cm1 to 978 cm1, 981 cm1, and
981 cm1, respectively, for EMS-5, EMS-15, and EMS-25. These
shifts indicate a high degree of polymerization of silica with the
addition of EMS due to the formation of more SiO2 gel. The FTIR
spectra results are consistent with the EDS analysis results, which
indicate the formation of high-density C-S-H phases with low Ca/Si
atomic ratio in the samples having EMS compared with that of the
control. Furthermore, the peaks at 720 cm1, 875 cm1, and
1414 cm1 are associated with calcite formed due to carbonation
[89]. The sharp intense peak band at 3640 cm1 shows the pres-
ence of portlandite (Ca(OH)2) in the control sample [90]. A small
portlandite peak is observed for the EMS-5 sample, and it is further
reduced or even absent for the EMS-15 and EMS-25 samples.
Cavalcante et al. [58] also evidenced the reduction of Ca(OH)2 con-
tent with the increase of extracted silica amount in the cement
paste by performing thermal analysis. This increased in the con-
sumption of Ca(OH)2 with the addition of EMS is an indication of
the high pozzolanic reactivity of EMS.
5. Conclusion
This study focused on the development of high performance
and sustainable cement mortar, by partially substituting cement
with various percentages of micro-silica (5%, 15%, and 25%)
extracted from ground RHA. Influence of adding EMS on fresh (s-
tandard consistency and setting behavior) and hardened properties
(compressive and flexural strengths, porosity, ASR) of mortar were
evaluated, and compared to those of control mortar. Finally, paste
samples were prepared to examine the microstructure using SEM-
EDS and FTIR analyses, and the pore structure was assessed by
using nitrogen adsorption techniques to scientifically understand
the influence of EMS on the quality of the matrix.
The main findings of this study are summarized below:
The consistency of the cement paste increased with an increase
in the amount of EMS. This is because of the low specific gravity
(2.15) and very high specific surface area of EMS (36.6 m2/g) as
compared to OPC, which consequently, required more water to
achieve a standard flow. Also, the setting times (initial and final)
increased with an increase in the percentage of EMS. Mortars con-
taining 5, 15 and 25% resulted in increased setting times by 4.1, 7.6
and 19.8%, respectively, compared with that of the CM.
The compressive and flexural strength of the mortar containing
EMS up to 15% remarkably exceeded that of the CM at all ages by
23.9%–64.2% and 15.8%–46.8%, respectively. However, the percent-
age increase in strength compared with that of the CM decreased
with an increase in the percentage of EMS. This is probably due
to the agglomeration problem caused by the poor dispersion,
which ultimately affects the hydration progress and thus leads to
the formation of weak products. The strength results were indi-
rectly validated by porosity results as the porosity of mortar con-
taining EMS remained lower than that of the corresponding CM,
except for mortar containing 25% EMS. Like strength results, a sig-
nificant reduction of ASR expansion was observed in all the mixes
containing EMS. However, the mix having 25% EMS showed more
expansion than the mixes with 5% and 15% EMS, which is attribu-
ted to the formation of agglomerate acting as a nucleation site for
ASR gel.
The current results of improved strength and reduced ASR
expansion were scientifically validated by SEM-EDS analysis which
showed high reactivity of EMS that significantly improved the
microstructure of the paste matrix at lower dosages of EMS (5%
and 15%). The lower values of Ca/Si atomic ratio observed from
the EDS analysis for these dosages indicate the formation of
high-density C-S-H and C-H phases, which help in the formation
of more refined and homogenous microstructures. These results
are further strengthen by nitrogen adsorption that showed an
increase in the BET surface area of the samples having EMS, indi-
cating the high reactive nature of EMS, which consequently facili-
tates hydration and the formation of more C-S-H gel. Furthermore,
the FTIR results also demonstrate formation of high-density C-S-H
gels in EMS samples as indicated by a shift in the peak from
971 cm1 to 981 cm1. A sharp peak observed at 3640 cm1 indi-
cates the presence of portlandite phase in control samples was also
reduced or even absent for EMS samples, indicating the better poz-
zolanic reactivity of EMS.
Current study concluded that low dosages of EMS under low
energy mixing were more effective in improving the mechanical
and microstructural performance of mortar matrix. However, to
properly evaluate the applicability of this study, future research
is recommended by using high shear mixing or sonification tech-
niques for proper dispersion of EMS to minimize the agglomeration
problems at high dosage of EMS. This would help researchers to
decide on optimum dosage of EMS to achieve its best mechanical
performance in mortar matrix as well as other economic and envi-
ronmental benefits.
Author contributions
K.S., K.K., M.N.A. and T.B. contributed to the design of this
research project. M.F.U. and K.K. contributed to performing the
experiments started from collecting all materials, material prepa-
ration, mixing, casting, demolding, curing of paste samples, mortar
 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
cubes and bar samples. M.F.U and K.S. performed required strength
and porosity tests on mortar cubes and measured length compara-
tor readings for ASR analysis at the desired ages. M.F.U., K.K. and M.
N.A. supported in carrying out XRF, SEM-EDS, N2 adsorption and
FTIR analyses of materials and paste samples. N.W., K.K., M.N.A.
and M.F.U. contributed to writing the ‘Introduction’ and ‘Materials
and Method’ sections of the manuscript. M.N.A. and K.K. critically
analyzed and discussed the results of this research and prepared
an initial draft of this manuscript. K.S. and A.A. contributed to
acquisition of the financial support for the project and reviewed
the initial draft of manuscript. M.N.A. and K.K. edited and prepared
the final draft of this manuscript. At the revision stage, M.N.A., K.K.,
N.W. and M.F.U. contributed to the revision. M.N.A. prepared the
final revised manuscript and other files to submit to the journal.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors acknowledge the Deanship of Scientific Research
(DSR) at King Faisal University (KFU), Al-Ahsa, Saudi Arabia, for
the financial support under Nasher Track (Grant No. 186349).
The authors wish to express their gratitude for the financial sup-
port that has made this study possible. The authors also extend
their deep appreciation to Department of Civil Engineering at King
Faisal University, Saudia Arabia and Department of Civil Engineer-
ing at UET Peshawar, Pakistan for providing lab facilities to conduct
the desired experimental tasks.
References
[1] S.A. Zareei, F. Ameri, N. Bahrami, P. Shoaei, H.R. Moosaei, N. Salemi,
Performance of sustainable high strength concrete with basic oxygen steel-
making (BOS) slag and nano-silica, J. Build. Eng. 25 (2019).
[2] M. Koushkbaghi, M.J. Kazemi, H. Mosavi, E. Mohseni, Acid resistance and
durability properties of steel fiber-reinforced concrete incorporating rice husk
ash and recycled aggregate, Constr. Build. Mater. 202 (2019) 266–275.
[3] J.-P. Bravard, M. Goichot, S. Gaillot, Geography of sand and gravel mining in the
lower Mekong River, EchoGéo 26 (2013).
[4] A.M. Rashad, A preliminary study on the effect of fine aggregate replacement
with metakaolin on strength and abrasion resistance of concrete, Constr. Build.
Mater. 44 (2013) 487–495.
[5] D.N. Huntzinger, T.D. Eatmon, A life-cycle assessment of Portland cement
manufacturing: comparing the traditional process with alternative
technologies, J. Clean. Prod. 17 (2009) 668–675.
[6] S. Luhar, T.-W. Cheng, I. Luhar, Incorporation of natural waste from agricultural
and aquacultural farming as supplementary materials with green concrete: a
review, Compos. B Eng. 175 (2019).
[7] B. Suhendro, Toward green concrete for better sustainable environment,
Procedia Eng. 95 (2014) 305–320.
[8] C.A. Hendriks, W.E.D, deJager, K. Block, P. Riemer, Emission reduction of
greenhouse gases from the cement industry, IEA Greenhouse gas R&D
Programme, 2000.
[9] E. Gartner, Industrially interesting approaches to ‘‘low-CO2” cements, Cem.
Concr. Res. 34 (2004) 1489–1498.
[10] M.S. Imbabi, C. Carrigan, S. McKenna, Trends and developments in green
cement and concrete technology, Int. J. Sustain. Built Environ. 1 (2012) 194–
216.
[11] A. Mehta, D.K. Ashish, Silica fume and waste glass in cement concrete
production: a review, J. Build. Eng. (2019) (In press).
[12] M.M. Khotbehsara, E. Mohseni, M.A. Yazdi, P. Sarker, M.M. Ranjbar, Effect of
nano-CuO and fly ash on the properties of self-compacting mortar, Constr.
Build. Mater. 94 (2015) 758–766.
[13] R. Dandautiya, A.P. Singh, Utilization potential of fly ash and copper tailings in
concrete as partial replacement of cement along with life cycle assessment,
Waste Manag. 99 (2019) 90–101.
[14] Y. Hefni, Y.A.E. Zaher, M.A. Wahab, Influence of activation of fly ash on the
mechanical properties of concrete, Constr. Build. Mater. 172 (2018) 728–734.
[15] S. Hsu, M. Chi, R. Huang, Effect of fineness and replacement ratio of ground fly
ash on properties of blended cement mortar, Constr. Build. Mater. 176 (2018)
250–258.
11
[16] E.G. Moffatt, M.D.A. Thomas, A. Fahim, Performance of high-volume fly ash
concrete in marine environment, Cem. Concr. Res. 102 (2017) 127–135.
[17] N.T. Abdel-Ghani, H.A. El-Sayed, A.A. El-Habak, Utilization of by-pass cement
kiln dust and air-cooled blast-furnace steel slag in the production of some
‘‘green” cement products, H.B.R.C. J. 14 (2019) 408–414.
[18] D.M. Sadek, M.M. El-Attar, A.M. Ali, Physico-mechanical and durability
characteristics of concrete paving blocks incorporating cement kiln dust,
Constr. Build. Mater. 157 (2017) 300–312.
[19] H. Chol, J. Lee, B. Lee, J. Nam, Shrinkage properties of concretes using blast
furnace slag and frost-resistant accelerator, Constr. Build. Mater. 220 (2019)
1–9.
[20] R.P. Salvador, D.A.S. Rambo, R.M. Bueno, K.T. Silva, A.D.D. Figueiredo, On the
use of blast-furnace slag in sprayed concrete applications, Constr. Build. Mater.
218 (2019) 543–555.
[21] H. Sasanipour, F. Aslani, J. Taherinezhad, Effect of silica fume on durability of
self-compacting concrete made with waste recycled concrete aggregates,
Constr. Build. Mater. 227 (2019).
[22] K. Khan, M.N. Amin, Influence of fineness of volcanic ash and its blends with
quarry dust and slag on compressive strength of mortar under different curing
temperatures, Constr. Build. Mater. 154 (2017) 514–528.
[23] K. Ganesan, K. Rajagopal, K. Thangavel, Evaluation of bagasse ash as
supplementary cementitious material, Cem. Concr. Compos. 29 (2007) 515–
524.
[24] P. Jagadesh, A. Ramachandramurthy, R. Murugesan, Evaluation of mechanical
properties of Sugar Cane Bagasse Ash concrete, Constr. Build. Mater. 176
(2018) 608–617.
[25] A. Rajasekar, K. Arunachalam, M. Kottaisamy, V. Saraswathy, Durability
characteristics of Ultra High Strength Concrete with treated sugarcane
bagasse ash, Constr. Build. Mater. 171 (2018) 350–356.
[26] A. Qudoos, H.G. Kim, R. Attaur, J.-S. Ryou, Effect of mechanical processing on
the pozzolanic efficiency and the microstructure development of wheat straw
ash blended cement composites, Constr. Build. Mater. 193 (2018) 481–490.
[27] T.R. Praveenkumar, M.M. Vijayalakshmi, M.S. Meddah, Strengths and
durability performances of blended cement concrete with TiO2
nanoparticles and rice husk ash, Constr. Build. Mater. 217 (2019) 343–351.
[28] G. Rodríguez de Sensale, Strength development of concrete with rice-husk ash,
Cem. Concr. Compos. 28 (2006) 158–160.
[29] N. Van Tuan, G. Ye, K. van Breugel, A.L.A. Fraaij, D.D. Bui, The study of using rice
husk ash to produce ultra high performance concrete, Constr. Build. Mater. 25
(2011) 2030–2035.
[30] M.F.M. Zain, M.N. Islam, F. Mahmud, M. Jamil, Production of rice husk ash for
use in concrete as a supplementary cementitious material, Constr. Build.
Mater. 25 (2011) 798–805.
[31] R. Zerbino, G. Giaccio, G.C. Isaia, Concrete incorporating rice-husk ash without
processing, Constr. Build. Mater. 25 (2011) 371–378.
[32] M.M. Hossain, M.R. Karim, M. Hasan, M.K. Hossain, M.F.M. Zain, Durability of
mortar and concrete made up of pozzolans as a partial replacement of cement:
A review, Constr. Build. Mater. 116 (2016) 128–140.
[33] M.N.N. Khan, M. Jamil, M.R. Karim, M.F.M. Zain, A.B.M.A. Kaish, Utilization of
rice husk ash for sustainable construction: a review, Res. J. Appl. Sci. Eng. Tech.
9 (2015) 1119–1127.
[34] A. Karasßin, M. Doğruyol, An experimental study on strength and durability for
utilization of fly ash in concrete, Mix. Adv. Mat. Sci. Eng. (2014) 1–6.
[35] S.-H. Kang, S.-G. Hong, J. Moon, The use of rice husk ash as reactive filler in
ultra-high performance concrete, Cem. Concr. Res. 115 (2019) 389–400.
[36] E. Menya, P.W. Olupot, H. Storz, M. Lubwama, Y. Kiros, Production and
performance of activated carbon from rice husks for removal of natural
organic matter from water: a review, Chem. Eng. Res. Des. 129 (2018) 271–
296.
[37] M. Jamil, A.B.M.A. Kaish, S.N. Raman, M.F.M. Zain, Pozzolanic contribution of
rice husk ash in cementitious system, Constr. Build. Mater. 47 (2013) 588–593.
[38] R. Khan, A. Jabbar, I. Ahmad, W. Khan, A.N. Khan, J. Mirza, Reduction in
environmental problems using rice-husk ash in concrete, Constr. Build. Mater.
30 (2012) 360–365.
[39] G. Sua-iam, N. Makul, Utilization of high volumes of unprocessed lignite-coal
fly ash and rice husk ash in self-consolidating concrete, J. Clean. Prod. 78
(2014) 184–194.
[40] S.K. Antiohos, V.G. Papadakis, S. Tsimas, Rice husk ash (RHA) effectiveness in
cement and concrete as a function of reactive silica and fineness, Cem. Concr.
Res. 61–62 (2014) 20–27.
[41] S. Asavapisit, N. Ruengrit, The role of RHA-blended cement in stabilizing
metal-containing wastes, Cem. Concr. Compos. 27 (2005) 782–787.
[42] V.-T.-A. Van, C. Rößler, D.-D. Bui, H.-M. Ludwig, Mesoporous structure and
pozzolanic reactivity of rice husk ash in cementitious system, Constr. Build.
Mater. 43 (2013) 208–216.
[43] M.J. Munir, A.U. Qazi, S.M.S. Kazmi, A. Khitab, S.Z. Ashiq, I. Ahmed, A literature
review on alkali silica reactivity of concrete in Pakistan, Pak. J. Sci. 68 (2016)
53–62.
[44] S. Abbas, S.M.S. Kazmi, M.J. Munir, Potential of rice husk ash for mitigating the
alkali-silica reaction in mortar bars incorporating reactive aggregates, Constr.
Build. Mater. 132 (2017) 61–70.
[45] H.T. Le, K. Siewert, H.M. Ludwig, Alkali silica reaction in mortar formulated
from self-compacting high performance concrete containing rice husk ash,
Constr. Build. Mater. 88 (2015) 10–19.
[46] P.J.M. Nicole, P. Hasparyk, C. Helena, Effect of silica fume and rice husk ash on
alkali-silica reaction, ACI MATER. J. 97 (2000) 486–492.
12 K. Khan et al. / Construction and Building Materials 258 (2020) 119589
[47] M.J. Shannag, High strength concrete containing natural pozzolan and silica
fume, Cem. Concr. Compos. 22 (2000) 399–406.
[48] M. Mazloom, A.A. Ramezanianpour, J.J. Brooks, Effect of silica fume on
mechanical properties of high-strength concrete, Cem. Concr. Compos. 26
(2004) 347–357.
[49] S. Azat, Z. Sartova, K. Bekseitova, K. Askaruly, Extraction of high-purity silica
from rice husk via hydrochloric acid leachingtreatment, Turk. J. Chem. 43
(2019) 1258–1269.
[50] A. Tahir, M. Othman, A. Rafiq, Studying the effects of adding silica sand
nanoparticles on epoxy based composites, J. Nanomater. 5 (2013).
[51] M. Zainuri, Synthesis of SiO2 nanopowders containing quartz and cristobalite
phases from silica sands, Mater. Sci.-Poland 33 (2015) 47–55.
[52] H. Mori, Extraction of silicon dioxide from waste colored glasses by alkali
fusion using sodium hydroxide, J. Ceram. Soc. Jpn. 111 (2003) 376.
[53] S. Affandi, H. Setyawan, S. Winardi, A. Purwanto, R. Balgis, A facile method for
production of high-purity silica xerogels from bagasse ash, Adv. Powder
Technol. 20 (2009) 468–472.
[54] S.P.B.d. Lima, R.P.d. Vasconcelos, O.A. Paiva, G.C. Cordeiro, M.R.d.M. Chaves, R.
D. Toledo Filho, E.d.M.R. Fairbairn, Production of silica gel from residual rice
husk ash, Química Nova 34 (2011) 71–75.
[55] U. Kalapathy, A. Proctor, J. Shultz, An improved method for production of silica
from rice hull ash, Bioresour. Technol. 85 (2002) 285–289.
[56] S.N. Joglekar, R.A. Kharkar, S.A. Mandavgane, B.D. Kulkarni, Process
development of silica extraction from RHA: a cradle to gate environmental
impact approach, Environ. Sci. Pollut. Res. Int. 26 (2019) 492–500.
[57] J.L.G. Lim, S.N. Raman, F.-C. Lai, M.F.M. Zain, R. Hamid, Synthesis of nano
cementitious additives from agricultural wastes for the production of
sustainable concrete, J. Clean. Prod. 171 (2018) 1150–1160.
[58] D.G. Cavalcante, M.G.d.S. Marques, J.s.A. Melo Filho, R.P.d. Vasconcelos,
Influence of the levels of replacement of portland cement by metakaolin and
silica extracted from rice husk ash in the physical and mechanical
characteristics of cement pastes, Cem. Concr. Compos. 94 (2018) 296–306.
[59] H.C. Visvesvaraya, Recycling of agricultural wastes with special emphasis on
rice-husk ash, Use of vegetable plants and fibers as building materials. In
Proceedings of the Joint Symposium RILEM/CIB/NCCL, Baghdad, Iraq, 1–22,
1986.
[60] U. Kalapathy, A. Proctor, J. Shultz, Silica xerogels from rice hull ash: structure,
density and mechanical strength as affected by gelation pH and silica
concentration, J. Chem. Technol. Biotechnol. 75 (2000) 464–468.
[61] ASTM C109/C109M-16a, Standard Test Method for Compressive Strength of
Hydraulic Cement Mortars (Using 2-in. or [50-mm] Cube Specimens, ASTM
International, West Conshohocken, PA, 2016.
[62] R. Siddique, N. Chahal, Use of silicon and ferrosilicon industry by-products
(silica fume) in cement paste and mortar, Resour. Conserv. Recy. 55 (2011)
739–744.
[63] ASTM C187-16, Standard Test Method for Amount of Water Required for
Normal Consistency of Hydraulic Cement Paste, ASTM International, West
Conshohocken, PA, 2016.
[64] ASTM C191-19, Standard Test Methods for Time of Setting of Hydraulic
Cement by Vicat Needle, ASTM International, West Conshohocken, PA, 2019.
[65] ASTM C348-14, Standard Test Method for Flexural Strength of Hydraulic-
Cement Mortars, ASTM International, West Conshohocken, PA, 2014.
[66] M.N. Amin, T. Murtaza, K. Shahzada, K. Khan, K. Adil, Pozzolanic potential and
mechanical performance of wheat straw ash incorporated sustainable
concrete, Sustainability 11 (2019) 1–20.
[67] ASTM C1260-14, Standard Test Method for Potential Alkali Reactivity of
Aggregates (Mortar-Bar Method), ASTM International, West Conshohocken,
PA, 2014.
[68] H. Du, K.H. Tan, Effect of particle size on alkali–silica reaction in recycled glass
mortars, Constr. Build. Mater. 66 (2014) 275–285.
[69] A.M. Alshamsi, A.R. Sabouni, A.H. Bushlaibi, Influence of set retarding
superplasticizers and microsilica on setting time of pastes at various
temperatures, Cem. Concr. Res. 23 (1993) 592–598.
[70] G.A. Rao, Investigations on the performance of silica fume-incorporated
cement pastes and mortars, Cem. Concr Res. 33 (2003) 1765–1770.
[71] Y. Qing, Z. Zenan, K. Deyu, C. Rongshen, Influence of nano-SiO2 addition on
properties of hardened cement paste as compared with silica fume, Constr.
Build. Mater. 21 (2007) 539–545.
[72] Lohtia, R.P., Joshi, R.C., Mineral admixtures—concrete admixture handbook,
Noyes Publications, 2nd ed., USA, 1996.
[73] M. Fakhri, S.K. Farshad, The effect of waste rubber particles and silica fume on
the mechanical properties of Roller Compacted Concrete Pavement, J. Clean.
Prod. 129 (2016) 521–530.
[74] D. Pedroa, J.D. Brito, L. Evangelista, Mechanical characterization of high
performance concrete prepared with recycled aggregates and silica fume from
precast industry, J. Clean. Prod. 164 (2017) 939–949.
[75] A. Said, M. Zeidan, M. Bassuoni, Y. Tian, Properties of Concrete Incorporating
Nano-Silica, Constr. Build. Mater. 838–844 (2012).
[76] A. Nazari, S. Riahi, The effects of SiO2 nanoparticles on physical and mechanical
properties of high strength compacting concrete, Composites: Part B (2011)
570–578.
[77] D.A.M. Thomas, The effect of supplementary cement materials on alkali-silica
reaction: a review, Cem. Concr. Res. 41 (2011) 1224–1231.
[78] D.A.M. Thomas, Mitigating ASR in Maine Bridges – Reactive Solutions.
Department of Transportation – FHWA. 3 (2011) 1–3.
[79] CSA A23.2-27A, Use of Supplementary Materials for Counteracting Alkali-Silica
Reaction. CSA, 2000, www.csa.ca.
[80] W. Kunther, S. Ferreiro, J. Skibsted, Influence of the Ca/Si ratio on the
compressive strength of cementitious calcium–silicate–hydrate binders, J.
Mater. Chem. A 5 (2017) 17401–17412.
[81] L.P. Singh, A. Geol, S.K. Bhattacharya, U. Sharma, G. Mishra, Hydration studies
of cementitious material using silica nano particles, J. Adv. Concr. Technol. 13
(2015) 345–354.
[82] Q. Hu, M. Aboustait, T. Kim, M.T. Ley, J.C.J. Hanan, J. Bullard, R. Winarski, V.
Rosed, Direct three-dimensional observation of the microstructure and
chemistry of C3S hydration, Cem. Concr. Res. 88 (2016) 157–169.
[83] J.F. Young, W. Hansen, Volume Relationships for C-S-H Formation Based on
Hydration Stoichiometries Symposium M – Microstructural Development
During Hydration of Cement. 85 (1987) 313.
[84] H.G. Kurczyk, H.E. Schwiete, Concerning the Hydration Products of C3S and b-
C2S. Proc 4th International Symposium on Chemistry of Cement, Washington,
USA, 1962.
[85] Z. Zhang, G.W. Scherer, Supercritical drying of cementitious materials, Cem.
Concr. Res. 99 (2017) 137–154.
[86] Z. Zhang, G.W. Scherer, Evaluation of drying methods by nitrogen adsorption,
Cem. Concr Res. 120 (2019) 13–26.
[87] P. Yu, R.J. Kirkpatrick, B. Poe, P.F. McMillan, X. Cong, Structure of calcium
silicate hydrate (C-S-H): near-, mid-, and far-infrared spectroscopy, J. Am.
Ceram. Soc. 82 (1999) 742–748.
[88] F. Puertas, S. Goni, M.S. Hernandez, C. Varga, A. Guerrero, Comparative study of
accelerated decalcification process among C3S, grey and white cement pastes,
Cem. Concr. Compos. 35 (2012) 384–391.
[89] N.J. Saikia, P. Sengupta, P.K. Gogoi, P.C. Borthakur, Physicochemical and
cementitious properties of sludge from oil field effluent treatment plant, Cem.
Concr. Res. 31 (2001) 1221–1225.
[90] T.L. Hughes, C.M. Methven, T.G.J. Jones, S.E. Pelham, P. Fletcher, C. Hall,
Determining cement composition by Fourier Transform Infrared Spectroscopy,
Adv. Cem. Based Mater. 2 (1995) 91–104.