Construction and Building Materials 201 (2019) 186–195

Contents lists available at ScienceDirect

Construction and Building Materials

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

Influence of composition and concentration of alkaline activator on the

properties of natural-pozzolan based green concrete
Mohammed Ibrahim a,b,⇑, Megat Azmi Megat Johari a, Mohammed Maslehuddin b,
Muhammed Kalimur Rahman b, Babatunde Abiodun Salami c, Hatim Dafalla Mohamed b
a
School of Civil Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Pulau Penang, Malaysia
b
Center for Engineering Research, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
c
Projects Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

h i g h l i g h t s

 Natural pozzolan (NP) was activated using sodium silicate and varying molarity of sodium hydroxide.
 Increase in the molarity of sodium hydroxide from 8 to 14 M increased strength by 24%.
 Silica modulus of 1.351 of combined activator was suitable to achieve better strength.
 14 M sodium hydroxide resulted in dense and uniform microstructure compared with milder solutions.
 EDS revealed that the higher concentration of NaOH lead to the enhanced formation of C-A-S-H.

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

Article history: The chemical constituents of precursor materials, the composition and concentration of alkaline activa-
Received 13 August 2018 tors, volume of free water, and curing conditions are some of the mix design variables that influence the
Received in revised form 10 December 2018 fresh and hardened properties of alkali-activated binders (AABs). To achieve desirable engineering prop-
Accepted 20 December 2018
erties and long-term performance of an AAB under various exposure conditions, each of these variables
has to be carefully controlled. The reported research focused on the influence of concentration and com-
position of alkaline activators on the properties of natural pozzolan (NP)-based AAB. Since the molarity of
Keywords:
sodium hydroxide (SH) and the ratio of sodium silicate (SS) to sodium hydroxide (SH) influence the prop-
Natural pozzolan
Alkali-activated binder
erties of an AAB, the NP-based AABs were prepared by varying the SS to SH ratio from 2.0 to 2.75, at an
Strength development increment of 0.25, and the molarity of SH from 8 to 14. The developed AAC specimens were tested to eval-
Morphology uate the strength development and the binder was characterized using SEM, XRD and FTIR techniques. A
Mineralogical composition SS/SH ratio of 2.5 and 14 M SH solution were required to obtain maximum strength and dense
Molarity of sodium hydroxide microstructure. In addition, it was established that there exists an optimum silica modulus of the com-
Silica modulus bined activator that results in faster polymerization of the precursor material.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction this pursuit, alternative binders, such as calcium sulfoaluminate

Globally, the focus of building materials research has recently
shifted towards the development of cementitious binders that can
be used in lieu of ordinary Portland cement (OPC). This is due to
the unfavorable consequences that OPC production has on the envi-
ronment which contributes significantly to the greenhouse gases. In
⇑ Corresponding author at: School of Civil Engineering, Universiti Sains Malaysia,
Engineering Campus, 14300 Nibong Tebal, Pulau Penang, Malaysia.
E-mail addresses: ibrahim@kfupm.edu.sa, mibrahim@student.usm.my
(M. Ibrahim), cemamj@usm.my (M.A. Megat Johari), muddin@kfupm.edu.sa
(M. Maslehuddin), mkrahman@kfupm.edu.sa (M.K. Rahman), salami@kfupm.edu.
sa (B.A. Salami), dmhatim@kfupm.edu.sa (H.D. Mohamed).
cement [1], magnesium-based-cement [2] and alkali activated bin-
ders (AABs) [3] have been explored. Among these, AABs have a
promising future as they can be synthesized using industrial by-
products and natural materials, which will promote their effective
utilization in developing more sustainable green binders [4–6]. Con-
sequently, the greenhouse gas emissions from OPC manufacturing
and accumulation of industrial waste problems can be efficiently
managed. However, there are several mix design variables that
influence primarily the fresh properties of these binders and then
on the hardened characteristics apart from the effect of curing con-
ditions on the strength gain [7–10]. In order to achieve the desired
engineering properties of these binders and to ensure their ade-

https://doi.org/10.1016/j.conbuildmat.2018.12.117
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195
quate performance under the expected exposure conditions, each of
these mix design variables has to be appropriately controlled.
Industrial by-products such as fly ash, ground granulated blast
furnace slag (GGBFS) and palm oil fuel ash (POFA) have been exten-
sively utilized to synthesize AABs [11–13]. The factors affecting the
properties of these binders, such as composition and concentration
of the alkaline activator, curing conditions and duration as well as
incorporation of mineral additives like aluminum hydroxide, lime,
and silica fume have been studied [14–16]. Most of the AABs devel-
oped so far have mostly used fly ash as the precursor material
which was cured at temperatures ranging from 40 °C to 80 °C
[10,17]. The composition and concentration of the alkaline activa-
tors are the key components of the liquid portion of the alkali acti-
vated mix. Wide range of alkali activating materials have been used
in the past, most common being SS and SH either individually or in
combination with varying results [18]. However, alkaline activator
sourced from combination of SS and SH resulted in better outcomes
[19]. A review of the literature indicates that the SS/SH ratio ranged
between 0.25 [20] and 3.0 [21], while, molarity of NaOH was as low
as 4 [22] and as high as 20 [18] in the alkaline activators. Hardjito
and Rangan [23] reported that the higher SS/SH ratio results in
higher strength due to the availability of more Si in the system,
however, beyond certain value the strength tends to decrease.
The recommended ratio of SS/SH of 2.5 was suitable for fly ash in
achieving better fresh and hardened properties of these binders.
As far as concentration of SH is concerned, the results of most of
the previous studies have shown that as the concentration
increases so does the strength [24,25]. However, beyond a certain
molarity of SH, for a particular precursor material, there was a neg-
ative influence on the fresh properties of these binders as well as on
their strength development [26,27]. Moreover, the strength gain in
the AAB is primarily governed by the presence of SH in the alkaline
activators [28]. In one of the study conducted earlier [4], it was
established that the quantity of Na2O, which determines the silica
modulus of alkaline activators, had profound effect on the mechan-
ical properties and durability of slag-based AAB.
Phoo-ngernkham et al. [28] concluded that a combination of SH
and SS in the alkaline activator significantly improves the strength
of AAB. In their study, binary blends of fly ash and GGBFS were
activated with two different types of alkaline activators. One hav-
ing a combination of 10 M SH and SS and the other with only SS. It
was reported that there was more than 100% increase in the
strength in the former compared to the latter after 28 days of cur-
ing. In another study, Juhyuk et al. [20] synthesized two mixes, one
containing only 10 M sodium hydroxide and the other utilized a
combination of sodium silicate and sodium hydroxide at a mass
ratio of 0.25, and all the samples were cured at 80 °C. It was
reported that the combination of SH and SS in the alkaline activa-
tors not only improved the strength of AAB by more than 40% but it
also yielded additional C-S-H and zeolite Y, which consequently
improved its microstructure. Hanjitsuwan et al. [29] also high-
lighted the importance of Na2O in the alkaline activators in obtain-
ing the desired properties of AABs. The results of their study
revealed that higher molarity of SH had a positive influence on
the strength and other properties of AAB because of the fact that
the higher concentration of SH activates higher leaching of Si and
Al from the precursor material. The quantity of Na2O in the alkaline
activator has a direct relation with the concentration of SH [30]. To
this end, the concentration of SH has a significant effect on the
strength development even more than the curing regime [31,32].
Natural pozzolan (NP) is an alumino-silicate material and its use
as a partial replacement of OPC has been reported to be beneficial in
improving the fresh and hardened properties of Portland cement
concrete due to the formation of secondary C-S-H [33–35]. Though
it is available in many regions of the world, its usage as precursor
material in developing AAB is limited to only few sources. The NP
187
from Iran and Colombia has been used for this purpose [36,37].
However, the NP from these mentioned sources is rich in Si
(>60%) and Al (>15%) which facilitated its development in to AAB.
As stated earlier, the composition and concentration of alkaline
activator including the presence of SH has a significant influence
on the fresh and hardened properties of an AAB, including its
long-term performance under various exposure conditions. Conse-
quently, the composition and concentration of the alkaline activa-
tor for a particular precursor material may not be suitable for the
other due to the significant differences in their chemical composi-
tion. The chemical composition of the NP varies significantly from
one region to the other. It is also available in significant quantities
on the western region of Saudi Arabia. However, its usage as a pre-
cursor material in developing AAB has not been studied adequately
as compared to other alumino-silicate materials. The quantity of Si
and Al of the selected NP for developing AAB in this study were rel-
atively low as compared to the other sources [38], which may
require different composition and concentration of alkaline activa-
tors to obtain a binder with better fresh and hardened properties.
Therefore, this study was conducted to assess the suitable propor-
tions of the activators for developing NP-based AAB. It is envisaged
that the Saudi-NP posesses great potential to be used as a precursor
material in the development of AAB. The effect of SH concentration,
SS to SH ratio and silica modulus on the compressive strength and
microstructure of the developed NP-based AAB has been evaluated.
Thus, this study avails the opportunity of utilizing natural material
in an efficient way by developing a sustainable binder as alternative
to OPC which could be potentially used in structural applications.
2. Materials and methods
2.1. Precursor material and alkaline activators
The chemical composition of the NP, obtained by XRF is shown in
Table 1. The NP is the ground form of volcanic rock from the red sea
coast of Saudi Arabia. The sustainability of the source material is
good as it is abundantly available covering at least 100,000 km2 in
the western region of Saudi Arabia [39]. The locally acquired NP con-
forms to the physical and chemical requirements of ASTM C618 [40].
The specific surface area, density and average particle size of NP used
are 442 m2/kg, 2.98 gr/cc and 30 mm, respectively. The alkaline acti-
vators used were a combination of aqueous industrial grade sodium
silicate (SS) solution in combination with 8 M, 12 M and 14 M SH
solution. The silica modulus of sodium silicate was 3.3 and its com-
position includes H2O: 62.50%, SiO2: 28.75% and Na2O: 8.75%.
2.2. Experimental design
In order to assess the suitable composition of alkaline activator,
concrete mixes were prepared with SS/SH of 2.0, 2.25, 2.5 and 2.75
with a constant 14 M SH solution. Table 2 gives the quantities of
constituent materials used to prepare these concrete specimens.
Subsequently, a suitable SS/SH ratio was selected which resulted
in better strength in the first stage of the experimental design
and two different concrete mixes were prepared, one with 8 M
and another with 12 M sodium hydroxide solution in the alkaline
activator to determine the effect of SH concentration on the
strength and microstructure of the developed binder. Table 3
shows the quantities of constituent materials used for preparing
the AAC specimens with varying SH molarity. The coarse and fine
aggregates constituted 65% and 35%, respectively, of the total
aggregate. Crushed limestone aggregate was used as the coarse
aggregate, while desert sand was used as the fine aggregate.
Alkali-activated paste (AAP) specimens were prepared with NP
and varying molarity of SH to investigate the morphology and
188 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195

Table 1
Chemical compositions of NP.

Oxides SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O P2O5 LOI
Weight, % 40.48 12.90 17.62 11.83 8.33 1.67 3.60 1.37 1.6

Table 2
Constituent materials used to prepare the AAC mixes.

Trial Binder Sodium Silicate Sodium Hydroxide Total Water, Total Alkaline SS/SH Fine Aggregate Coarse Aggregate
mix# Content, kg/m3 (SS), kg/m3 (SH), kg/m3 kg/m3 Activator, kg/m3 Ratio (FA), kg/m3 (CA), kg/m3
M1 400 140 70 139.22 210 2.00 650 1206
M2 400 145 65 139.37 210 2.25 649 1207
M3 400 150 60 139.51 210 2.50 650 1206
M4 400 154 56 139.63 210 2.75 650 1207

Table 3
Mix proportion of AAC with varying molarity of NaOH solution.

Mix# Natural pozzolan Sodium Silicate Sodium Hydroxide Total Water, Total Alkaline SS/SH, Fine Aggregate Coarse Aggregate
(NP), kg/m3 (SS), kg/m3 (SH), kg/m3 kg/m3 Activator, kg/m3 Ratio (FA), kg/m3 (CA), kg/m3
M0-8M 400 150 60 140 210 2.50 643 1195
M0-12M 400 150 60 140 210 2.50 645 1198
M0-14M 400 150 60 140 210 2.50 650 1206

minerological composition of the binder. The AAP and AAC speci- binder content ranging from 180 to 225 kg/m3 and 350 to
mens were demolded after 24 h of casting, placed in plastic bags 450 kg/m3, respectively. It was found that the total alkaline activa-
to avoid excessive evaporation of moisture and placed in an oven tor content of 210 kg/m3 was suitable in obtaining a workable mix
maintained at 60 °C for curing. at a binder content of 400 kg/m3. The workability of the mixes with
a low alkaline activator content was observed to be very poor [38].
2.3. Methods The compressive strength development of concrete prepared by
varying SS/SH ratio from 2.0 to 2.75 with an increment of 0.25 is
2.3.1. Compressive strength depicted in Fig. 1. Generally, there was a steady increase in the
The compressive strength of AAC was determined on 50 mm compressive strength with the duration of curing up to 7 days in
cube specimens. The compressive strength was measured after all the mixes. Since the onset of curing, higher strength was
½, 1, 3, 7, 14 and 28 days of curing. Three specimens from each recorded in the concrete mix synthesized with a SS/SH ratio of
mix were tested under compression at each curing period and 2.5. For instance, after 12 h of curing it was 9.59, 11.17, 12.57
the average values are reported. and 9.68 MPa, in the mixes prepared with SS/SH ratio of 2.0,
2.25, 2.5 and 2.75, respectively. The compressive strength develop-
2.3.2. Morphology and mineralogical composition ment was continuously higher, as the curing continued in the con-
After 7 days of curing, 25 mm cube specimens of AAP were care- crete mix prepared with a SS/SH ratio of 2.5 in comparison to other
fully broken and the core portions were retrieved to assess the mixes. There was a remarkable increase in strength recorded just
morphology and minerelogical composition. The prepared speci- after 24 h of curing in this particular mix, which was about 64%
men was dried and a layer of gold coating was applied on it. A JEOL of the ultimate strength and more than 90% compared to the
scanning electron microscope fitted with energy dispersive spec-
troscope (SEM + EDS) model 5800 LV was used to evaluate the
morphology and elemental compositions of the binder. For
microstructural examination, micrographs were collected at
20 kV using backscattered mode, while, the elemental composition
was determined utilizing the secondary mode. The mineralogical
composition was determined using a Bruker instrument model
d2-Phaser. The X-ray patterns were collected at a scan rate of
2.5°/min using Cu-Ka radiation (40 kV, 40 mA) through continuous
scanning within the 2-theta angle in the range of 0–80°. The Four-
ier transform infrared (FTIR) analysis was performed using Perkin
Elmer 880 spectrometer by KBr pellet technique utilizing pulver-
ized AAP retrieved from the core of the 25 mm cube specimens
such that specimen/kBr powder mass ratio was 1:9.

3. Results and discussion

3.1. Compressive strength

3.1.1. Effect of alkaline activator composition on the compressive

strength
Earlier the authors carried out extensive trials utilizing NP as
the precursor material by varying the total alkaline activator and Fig. 1. Compressive strength of concrete prepared with varying SS/SH ratio.
 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195
strength after 12 h of curing. The magnitude of compressive
strength after 12 and 24 h of curing in the AAC with SS/SH ratio
of 2.5 indicates the fact that it is suitable to be widely utilized in
the precast industry where shorter demolding time is beneficial.
Further, after seven days of curing, the compressive strength of
mixes prepared with SS/SH ratio of 2.0, 2.25, 2.5 and 2.75 was
35.22, 36.72, 37.52 and 36.48 MPa, respectively. Noticeably, in
most of the AAC mixes investigated in this study, there was greater
strength development in the initial stages of curing. However,
beyond these early stages, the increase in strength was not that
significant. These results are consistent with the outcome of an
earlier research [41]. After seven days of curing, there was a reduc-
tion in the compressive strength in all the mixes. This reduction
was in the range of about 7% to 13%. Hardjito et al. [42] and Ward-
honoa et al. [43] reported similar trend and it was attributed to the
weakening of the microstructure. A higher reduction was noted in
the AAC mixes prepared with lower SS/SH ratio probably due to
continued curing which resulted in the development of micro
cracks after the completion of hydration in these mixes.
The AAC mixes prepared with a SS/SH ratio of 2.00, 2.25, 2.50
and 2.75 resulting in a combined activator silica modulus of
1.178, 1.262, 1.351 and 1.425, respectively. These mixes were hav-
ing alkali content ranging from 7.752% to 8.542% of the binder con-
tent. According to the compressive strength results, it is evident
that there exists a suitable composition of alkaline activator and
combined silica modulus, which results in better strength for a
given precursor material, as illustrated in Fig. 2. The compressive
strength increased with an increase in the combined silica modu-
lus. However, a combined silica modulus of alkaline activator of
about 1.351 in developing NP-based AAC appears to be suitable;
beyond this value there could be reduction in the compressive
strength. An increase in the SS/SH ratio beyond 2.5 slowed down
the strength development and took longer period of curing to
achieve the ultimate strength. This is largely due to the excessive
silica modulus for a given binder content, which delayed the poly-
merization process [44]. Therefore, a SS/SH ratio of 2.5 by weight
and seven days of curing was found to be suitable for achieving
higher strength for the developed NP-based AAC.
3.1.2. Effect of molarity of NaOH on the compressive strength
Fig. 3 shows the compressive strength development in the con-
crete specimens prepared with varying concentration of SH, but
Fig. 2. Variation in compressive strength of concrete prepared with varying silica
modulus (Mixes M1 to M4 in Table 2).
189
with a SS/SH ratio of 2.5. The compressive strength development
was steady as the curing progressed up to seven days of curing
in all the concrete mixes. The strength gain at the onset of curing
in the lower concentration of SH (8 M) mix was lower than that
in higher ones. A more or less similar strength was noted in the
mixes prepared with 12 M and 14 M SH at the primary stages of
curing. However, as the curing continued, the strength develop-
ment was more in the specimens prepared with higher molarity
of SH solution compared to the lower ones. For instance, at the
completion of seven days of curing, the compressive strength of
the mix prepared with 14 M SH solution was 37.52 MPa compared
to 30.45 MPa in specimens with 8 M molar which is about 23%
more. The increase in the compressive strength due to an increase
in the molarity may be attributed to the fact that stronger SH solu-
tion increases the solubility of Si from the precursor materials due
to the presence of higher hydroxyl ions for a given binder content
in the solution. In addition, it is expected that the solubility of Al in
a four-fold reaction that was required to accommodate Si would
have accelerated thereby permitting the formation of Si-O-Al
phase, which perhaps resulted in an increase in the strength at
higher SH concentration due to the formation of C-A-S-H phase
together with the pure polymeric gel as the reaction products
[45–47]. Therefore, to summarize a 14 M SH and SS/SH ratio of
2.5 appeared to be suitable for achieving a higher compressive
strength of the NP-based AAC.
3.2. Morphology
Figs. 4–6 show the SEM micrographs (lower and higher magni-
fication) of AAP prepared with 8 M, 12 M and 14 M SH, respec-
tively, while the EDS spectra is depicted in Figs. 7 through 9. The
microstructure of specimens with 14 M SH, as seen in the Fig. 6,
was homogenous, relatively compact and dense compared to the
ones prepared with lower concentrations of SH solution. The
microstructure of the specimen prepared with 8 M SH was coarser
and non-homogenous because of unreacted and partially reacted
binder particles in the matrix. Because of incomplete polymeriza-
tion, larger voids and pores are evident in the micrograph. How-
ever, the microstructure of AAP prepared with 12 M SH was
moderately compact without excessive unreacted binder particles,
which corroborates the fact that higher degree of polymerization
occurs in higher concentration of alkali activators than the weaker
solution [47].
Fig. 3. Evolution of compressive strength of AAC with varying SH molarity.
190 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195

Fig. 4. Scanning electron micrograph of AAP prepared with 8 M SH.

Fig. 5. Scanning electron micrograph of AAP prepared with 12 M SH.

Fig. 6. Scanning electron micrograph of AAP prepared with 14 M SH.

 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195
Fig. 7. EDS of specimens prepared with 8 M SH.
The EDS showed the presence of Al and greater proportions of
Ca and Si in the AAP prepared with 12 and 14 M SH, as shown in
Figs. 8 and 9, respectively, compared to 8 M. This indicates an
improved dissolution of precursor material with the higher SH con-
centration. The presence of these elements has a very prominent
influence on the properties of the alkali-activated products whose
gel structure consists of C-A-S-H or C/N-A-S-H [48]. However, in
the AAP with 8 M SH, Si and Ca were found to be relatively mar-
ginal, as shown in Fig. 7, which points to the minimal formation
of C-S-H products. Apart from this, Ca/Si and Ca/Na ratios were
high in the pastes prepared with 12 M (Fig. 8) and 14 M (Fig. 9)
SH solutions, which enhanced the formation of Si-O bonds [49].
Therefore, to summarize in the AAP synthesized using higher SH
concentration the framework consisted of C-S-H as well as C/N-
A-S-H, whereas, in 8 M binder C-S-H appeared to be absent due
to which the strength of the former was more than that of the
latter.
Fig. 10 shows the XRD patterns of AAP prepared with varying
concentration of SH solution. NP activated with various concen-
tration of SH in the alkaline solution exhibited similar pattern
with more or less the same degree of crystallinity, however, there
was a transition towards increased crystallinity as the SH concen-
tration was increased. Alkali activated NP has shown phases of
quartz, philipsite as well as calcite were noted in the pattern in
the range of 20°–28° 2h. In addition, a phase of C-S-H, which is
crucial in matrix strength development, is seen at 30° 2h [50].
Traces of hematite and zeolite-Y were also detected between
50° and 60° 2h. The XRD results obtained in this investigation
191
are consistent with the findings of a similar study undertaken
with NP as a precursor material and activated with a combination
of SS and SH [20]. However, the composition of alkaline activating
solution used earlier [20] composed of one part of SH to 0.25 parts
of SS, which was quite different from what was utilized in this
study.
A careful examination of the XRD pattern revealed the exis-
tence of increased crystallinity between 25° and 32° degrees 2h
for the NP activated with 14 M SH solution in the alkaline acti-
vator, which implies that there was transition from a certain
level of amorphosity to crystallinity of paste compared to AAP
prepared with low concentration of alkaline activator. In addi-
tion, a moderate peak at 28.4° 2h associated with anorthite, a
calcium aluminosilicate hydrate (C-A-S-H) was noted in the
AAP prepared with 12 and 14 M SH solution, which was not evi-
dent in the specimen prepared with 8 M SH. It can thus be con-
cluded that C-S-H was existent together with polymeric
compounds in the binder structure of AAP, which positively
influenced the strength of the developed AAP [51–53]. This
was more evident in the AAP with 14 M SH due to the highly
concentrated alkaline solution either reacted with the precursor
material to produce C-S-H in which Ca might have been
replaced with Na and Al to form N-A-S-H or combined with
either Na or Al to produce C-A-S-H with Na in the framework
[54]. To summarize, it can be stated that the structural organiza-
tion of bonds in raw NP and its degree of polymerization were
enhanced by increasing the molarity of the SH solution, which
consequently improved the strength of AAC.
192 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195
Fig. 8. EDS of specimens prepared with 12 M SH.
3.3. FTIR of AAP with varying molarity of SH
Fig. 11 depicts the FTIR spectra of raw NP as well as the ones
activated with 8, 12 and 14 M SH. Notably, the FTIR transmittance
spectra of raw NP and those activated with the alkaline solution
are seemingly different. Stretching vibration between 3600 cm 1
and 3000 cm 1 was not present and also bending in the range of
1700 cm 1 to 800 cm 1 wave numbers in the raw NP was not sim-
ilar to that in the AAP. These changes in the transmittance spectra
of AAP compared to raw NP is indicative of the fact that new bonds
are formed due to the alkali activation [55,56]. Moreover, the
transmittance spectra of alkali-activated NP with different concen-
trations of SH, however, exhibited more or less similar pattern with
the formation of identical bonds with minor changes.
Noticeably, the FTIR transmittance spectra of NP activated with
different concentrations of SH solution demonstrated a stretching
vibration between the wave numbers of 3700 cm 1 to 2900 cm 1
related to O–H bond [57]. The peak in this region for AAP prepared
with 8, 12 and 14 M were noticed at 3229, 3203 and 3201 cm 1,
respectively, indicating that there was a shift in the peak from
higher to the lower wavenumber as the concentration increased.
Similarly, a bending vibration in the range of wave numbers
1640 cm 1 and 1550 cm 1 was seen associated to HOH indicating
the presence of water perhaps in the form of C-S-H gel in the bin-
der structure [57–59]. In addition, there were absorption peaks
attributed to Si-O-Si(Al) noted at 973 cm 1, 969 cm 1 and
966 cm 1, in the AAP produced with 8, 12 and 14 M SH solutions,
respectively [56]. A stronger, broader and shifted peak towards
lower frequency was associated with higher concentration of SH
compared to the weaker one because of attachment of Ca2+ with
Si-O-Si bond to form C-A-S-H with Na embedded in the structure
[20]. In addition, there was an asymmetric stretching vibration
around 780 cm 1 wavenumber. Furthermore, the intense bending
vibration between wavenumber 1640 cm 1 and 1550 cm 1 and
stronger and broader low frequency absorption peak around
960 cm 1 in the AAP synthesized using higher concentrations of
SH certainly indicates the formation of more crystalline nature of
binder compared to the one in lower molar SH solution. This also
implies that the highly concentrated nature of the solution, in
the case of NP used in this study, prompts higher leaching of Si
and Al species from the precursor material to allow the formation
of more polymeric compounds. These findings lead to the conclu-
sion that the concentrated alkaline solutions contributed towards
more crystalline nature of the binder, which consequently
increased the strength of the AAC particularly those prepared with
12 and 14 M SH solution.
4. Conclusions
The objective of the reported study was to find the suitable
alkaline activator composition and SH concentration for the syn-
thesis of NP-based AAC in achieving superior mechanical and
microstructural properties. The SS/SH ratio and concentration of
SH were varied to synthesize optimum NP-based AAC. The follow-
ing conclusions are made from the experimental data:
 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195 193

Fig. 9. EDS of specimens prepared with 14 M SH.

Fig. 10. XRD pattern of alkali activated NP with varying SH concentration. (Q:Quartz, CSH: Calcium Silicate Hydrate, P: Philipsite, C: Calcite, Z: Zeolite Y, A: Aluminosilicate, H:
Hematite).

 The maximum compressive strength was obtained in the NP-
based AAC prepared with SH concentration of 14 M and SS/SH
ratio of 2.5 resulting in a silica modulus of 1.351.
 The compressive strength of NP-based AAC increased with an
increase in the concentration of SH. There was about 24%
increase in the compressive strength of AAC as the molarity of
the SH was increased from 8 M to 14 M.
 More than 88% of the maximum strength was achieved in
3 days of curing in the AAC with 14 M SH solution due to the
greater dissolution of the precursor material.
 The morphology of AAB prepared with 14 M SH solution was
dense and homogenous compared to the AABs prepared with
lower concentration of SH. The dense morphology of the former
can be attributed to the greater formation of the polymeric
compounds compared to the latter ones.
 EDS results confirmed the increased leaching of Si and Al with
an increase in the molarity of the SH solution. The higher con-
centration of the SH resulted in the enhanced transformation
of precursor material to form C-A-S-H with Na in the framework
as a result of which the strength and microstructural character-
194 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195
Fig. 11. FTIR of raw and alkali activated NP with varying SH concentration.
istics of the binder improved compared to NP activated with
milder SH solution in the alkaline activator.
Conflict of interest
The authors declare that there is no conflict of interest in this
research work.
Acknowledgement
The authors gratefully acknowledge the support provided by
the School of Civil Engineering, Universiti Sains Malaysia, Pulau
Penang, Malaysia, and Center for Engineering Research, Research
Institute, King Fahd University of Petroleum and Minerals, Dhah-
ran, Saudi Arabia, for the reported work
References
[1] M.M. AIi, S. Gopal, S.K. Handoo, Studies on the formation kinetics of calcium
sulphoaluminate, Cem. Concr. Res. 24 (4) (1994) 715–720.
[2] N. Yang, H.M. Tran, A. Scott, R.P. Dhakal, M. Watson, C.J. Shi (12–14 October
2017). ‘‘Properties of megnesium based cemenets, The Newzealand concrete
industry.” Conference 2017, Creative solutions, Te Papa, Wellington, vol. 24,
(4), pp. 715–720.
[3] G.S. Ryu, Y.B. Lee, K.T. Koh, Y.S. Chung, The mechanical properties of fly
ashbased geopolymer concrete with alkaline activators, Constr. Build. Mater.
47 (2013) 409–418.
[4] M. Chi, Effects of dosage of alkali-activated solution and curing conditions on
the properties and durability of alkali-activated slag concrete, Constr. Build.
Mater. 35 (2012) 240–245.
[5] M.O. Yusuf, Johari M.A. Megat, Z.A. Ahmad, M. Maslehuddin, Strength and
microstructure of alkali-activated binary blended binder containing palm oil
fuel ash and ground blast-furnace slag, Construct. Build. Mater. 52 (2014) 504–
510.
[6] I. Lancellotti, M. Catauro, C. Ponzoni, F. Bollino, C. Leonelli, Inorganic polymers
from alkali activation of metakaolin: effect of setting and curing on structure, J.
Solid State Chem. 200 (2013) 341–348.
[7] E.I. Diaz, E.N. Allouche, S. Eklund, Factors affecting the suitability of fly ash as
source material for geopolymers, Fuel 89 (5) (2010) 992–996.
[8] S. Aydın, B. Baradan, Effect of activator type and content on properties of
alkaliactivated slag mortars, Compos. B Eng. 57 (2014) 166–172.
[9] D. Khale, R. Chaudhary, Mechanism of geopolymerization and factors
influencing its development: a review, J. Mater. Sci. 47 (3) (2007) 729–746.
[10] S. Pangdaeng, T. Phoo-ngernkham, V. Sata, P. Chindaprasirt, Influence of curing
conditions on properties of high calcium fly ash geopolymer containing
Portland cement as additive, Mater Des. 53 (2014) 269–274.
[11] M. Ankur, S. Rafat, An overview of geopolymers derived from industrial by-
products, Constr. Build. Mater 127 (2016) 183–198.
[12] S. Kumar, R. Kumar, S.P. Mehrotra, Influence of granulated blast furnace slag on
the reaction, structure and properties of fly ash based geopolymer, J. Mater.
Sci. 45 (3) (2010) 607–615.
[13] A.S. Babatnde, B.A. Salami, Johari M.A. Megat, Z.A. Ahmad, M. Maslehuddin,
Impact of added water and superplasticizer on early compressive strength of
selected mixes of palm oil fuel ash-based engineered geopolymer composites,
Constr. Build. Mater. 109 (2016) 198–206.
[14] S.S. Jamkar, Y.M. Ghugal, S.V. Patankar, Effect of fly ash fineness on workability
and compressive strength of geopolymer concrete, Indian Concr. J. (2013) 57–
62.
[15] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, A.A. Ramezanianpour,
Effect of adding mineral additives to alkali-activated natural pozzolan paste,
Constr. Build. Mater. 25 (2011) 2906–2910.
[16] H.M. Khater, Effect of silica fume on the characterization of the geopolymer
materials, Int. J. Adv. Struct. Eng. 5 (12) (2013) 1–10.
[17] P. Chindaprasirt, P. De Silva, K. Sagoe-Crenstil, S. Hanjitsuwan, Effect of SiO2
and Al2O3 on the setting and hardening of high calcium fly ash-based
geopolymer systems, Mater. Sci. 47 (2012) 4876–4883.
[18] F. Pacheco-Torgal, J. Castro-Gomes, S. Jalali, Alkali-activated bases: a review.
Part 2. About materials and bases manufacture, Constr. Build. Mater. 22 (2008)
1315–1322.
[19] A. Palomo, M.W. Grutzeck, M.T. Blanco, Alkali-activated fly ashes, a cement for
the future, Cem. Concr. Res. 29 (1999) 1323–1329.
[20] M.A. Juhyuk, B.B. Sungchul, K.B. Celik, S.B. Yoon, K.B. Ki-Hyun, S.K.C. Kang, J.M.
Paulo, B. Monteiro, Characterization of natural pozzolan-based geopolymeric
binders, Cem. Concr. Compos. 53 (2014) 97–104.
[21] Y. Zarina, A. Mustafa Al Bakri, H. Kamarudin, I. Khairul Nizar, Rafiza Abd Razak,
V.S. Andrei, Effect of solids-to-liquids”. Na2SiO3-To-NaOH and curing
temperature on the palm oil boiler ash (Si + Ca) geopolymerisation system,
Materials 8 (2015) 2227–2242.
[22] M.O. Yusuf, M.A. Megat Johari, Z.A. Ahmad, M. Maslehuddin, Influence of
curing methods and concentration of NaOH on strength of the synthesized
alkaline activated ground slag-ultrafine palm oil fuel ash mortar/concrete,
Constr. Build. Mater. 66 (2014) 541–548.
[23] D. Hardjito, B.V. Rangan, ‘‘Development and properties of low-calcium fly ash-
based geopolymer concrete”. Research Report. GCI, Faculty of Engineering,
Curtin University of Technology, Australia, 2005.
[24] J. Wongpa, K. Kiattikomol, C. Jaturapitakkul, P. Chindapraisirt, Compressive
strength, modulus of elasticity, and water permeability of inorganic polymer
concrete, Mater. Des. 31 (2010) 4748–4754.
[25] A. Nazari, A. Bagheri, S. Riahi, Properties of geopolymer with seeded fly ash and
rice husk bark ash, Mater. Sci. Eng. A 528 (24) (2011) 7395–7401.
[26] P. Chindaprasirt, T. Cheerat, V. Sircicatnanon, Workability and strength of
coarse high calcium fly ash geopolymer, Cem. Concr. Compos. 29 (2007) 224–
229.
[27] K. Somna, C. Jatuarapitakkul, P. Kajitvichyanukul, P. Chindaprasirt, NaOH-
activated ground fly ash geopolymer cured at ambient temperature, Fuel 90
(6) (2011) 2118–2124.
[28] Tanakorn Phoo-ngernkhama, M. Akihiro, M. Naoki, H. Shigemitsu, Prinya
Chindaprasirtd, Effects of sodium hydroxide and sodium silicate solutions on
compressive and shear bond strengths of FA–GBFS geopolymer, Constr. Build.
Mater. 91 (2015) 1–8.
[29] S. Hanjitsuwan, S. Hunptratub, P. Thongbai, S. Maensiri, V. Sata, P.
Chindaprasirt, Effects of NaOH concentrations on physical and electrical
properties of high calcium fly ash geopolymer paste, Cem. Concr. Compos. 45
(2014) 9–14.
[30] G. Görhan, G. Kürklü, The influence of the NaOH solution on the properties of
the fly ash-based geopolymer mortar cured at different temperatures,
Composite Part B 58 (2014) 371–377.
[31] A.S. deVargas, D.C.C. Dal Molin, A.C.F. Vilela, F.J. daSilva, B. Pavão, H. Veit, The
effects of Na2O/SiO2 molar ratio, curing temperature and age on compressive
strength, morphology and microstructure of alkali-activated fly ash-based
geopolymers, Cem. Concr. Compos. 33 (2011) 653–660.
[32] T. Bakharev, Geopolymeric materials prepared using class F fly ash elevated
temperature curing, Cem. Concr. Res. 35 (2005) 1224–1232.
[33] V. Papadakis, S. Tsimas, Supplementary cementing materials in concrete: part
I: efficiency and design, Cem. Concr. Res. 32 (10) (2002) 1525–1532.
[34] R. Rodrı́guez-Camacho, R. Uribe-Afif, Importance of using the natural
pozzolans on concrete durability, Cem. Concr. Res. 32 (12) (2002) 1851–1858.
[35] M. Khan, A. Alhozaimy, Properties of natural pozzolan and its potential
utilization in environmental friendly concrete, Can. J. Civ. Eng. 38 (1) (2010)
71–78.
[36] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, A.A. Ramezanianpour,
Engineering properties of alkali-activated natural pozzolan concrete, ACI
Mater. J. 108 (1) (2011) 64–72.
[37] R.A. Robayoa, R. Mejía de Gutiérreza, M. Gordillob, Natural pozzolan-and
granulated blast furnace slag-based binary geopolymers, Mater. Construct. 66
(321) (2016) 1–8.
[38] M. Ibrahim, M.A. Megat Johari, M.K. Rahman, M. Maslehuddin, Effect of
alkaline activators and binder content on the properties of natural pozzolan-
based alkali activated concrete, Constr. Build. Mater. 147 (2017) 648–660.
[39] A. Mouftu, A. Sabtan, O. El-Mahdy, W. Shehata, Assessment of the industrial
utilization of scoria materials in central Harrat Rahat, Saudi Arabia, Eng. Geol.
57 (2002) 155–162.
[40] ASTM C618-10, Standard Specification for Coal Fly Ash and Raw or Calcined
Natural Pozzolan for Use in Concrete, ASTM International, West
Conshohocken, PA, 2010.
[41] A.B. Malkawia, M.F. Nuruddina, A.C. Fauzia, H. Almattarnehb, S.M. Bashar,
Effects of Alkaline Solution on Properties of the HCFA Geopolymer Mortars.”
4th International Conference on Process Engineering and Advanced Materials,
Proced. Eng. 148 (2016) 710–717.
 M. Ibrahim et al. / Construction and Building Materials 201 (2019) 186–195
[42] D. Hardjito, S.E. Wallah, D.M.J. Sumajouw, B.V. Rangan, Fly ash-based
geopolymer concrete, Aust. J. Struct. Eng. 6 (1) (2005) 77–85.
[43] A. Wardhonoa, W.L. David, S. Anthony, The strength of alkali-activated slag/fly
ash mortar blends at ambient temperature. The 5th International Conference
of Euro Asia Civil Engineering Forum (EACEF-5), Procedia Eng. 125 (2015) 650–
656.
[44] C. Villa, E.T. Pecina, R. Torres, L. Gomez, Geopolymer synthesis using alkaline
activation of natural zeolite, Constr. Build. Mater 24 (2004) 2084–2090.
[45] S. Song, D. Sohn, H.M. Jennings, T.O. Mason, Hydration of alkali activated
ground granulated blast furnace slag, Mater. Sci. 35 (2004) 249–257.
[46] J.L. Provis, J.S.J. Van Deventer, Geopolymers: Structure, Processing, Properties
and Industrial Applications, Woodhead Publishing Limited, 2009.
[47] Z. Zuhua, Y. Xiao, Z. Huajun, C. Yue, Role of water in the synthesis of calcined
kaolin-based geopolymer, Appl. Clay Sci. 43 (2009) 218–223.
[48] C.K. Yip, G.C. Lukey, J.S.J. Van Deventer, Coexistence of geopolymeric gel and
calcium silicate hydrate at the early stage of alkali activation, Cem. Concr. Res.
35 (2005) 1688–1697.
[49] T.O. Yusuf, M. Ismail, J. Usman, A.H. Noruzman, Impact of blending on strength
distribution of ambient cured metakaolin and palm oil fuel ash based
geopolymer mortar, Adv. Civ. Eng. (2014) 1–8.
[50] I. Lecomite, C. Henrist, M. Liegeois, F. Maseri, A. Rulmont, R. Cloots,
Microstructural comparison between geopolymers alkali activated slag
cement and Portland cement, J. Eur. Ceram. Soc. 26 (2006) 3789–3797.
[51] H. Xu, J. Van Deventer, The geopolymerisation of alumino-silicate minerals,
Int. J. Miner. Process 59 (3) (2000) 247–266.
195
[52] J.E. Oh, P.J. Monteiro, S.S. Jun, S. Choi, S.M. Clark, The evolution of strength and
crystalline phases for alkali-activated ground blast furnace slag and fly
ashbased geopolymers, Cem. Concr. Res 40 (2) (2010) 189–196.
[53] K. Somna, C. Laturapitakkul, P. Kajitvichyanukul, P. Chindraprasirt, NaOH
activated ground fly ash geololymer cured at ambient temperature, Fuel 90
(2011) 2118–2124.
[54] I. Ismail, S.A. Bernal, J.L. Provis, R.S. Nicolas, S. Hamdan, J.S. van Deventer,
Modification of phase evolution in alkali-activated blast furnace slag by the
incorporation of fly ash, Cem. Concr. Compos. 45 (2014) 125–135.
[55] J. Davidovits, Geopolymer Chemistry and Applications, 3rd ed, Institute
Geopolymer, Saint Quentin France, 2011.
[56] M.A. Salih, Ali A.A. Abang, N. Farzadnia, Characterization of mechanical and
microstructural properties of palm oil fuel ash geopolymer cement paste,
Constr. Build. Mater 65 (2014) 592–603.
[57] K. Boonserm, V. Sata, K. Pimraksa, P. Chindaprasirt, ‘‘Improved
geopolymerization of bottom ash by incorporating fly ash and using waste
gypsum as additive, Cem. Concr. Compos. 34 (2012) 819–824.
[58] S. Ahmari, X. Ren, V. Toufigh, L. Zhang, Production of geopolymeric binder from
blended waste concrete powder and fly ash, Constr. Build. Mater. 35 (2012)
718–729.
[59] A. Buchwald, H. Hilbig, C. Kaps, Alkali-activated metakaolin-slag blends—
performance and structure in dependence of their composition, J. Mater. Sci.
42 (9) (2007) 3024–3032.