TECHNICAL PAPER
Efficient Production
of Alkali-activated
Geopolymers using
Low-calcium Fly ash
Abstract
An experimental investigation of fly ash activated with sodium-
based alkali-silicate activating solutions is presented. As the
first step a detailed characterization of the low-calcium fly ash
is performed. The reactive SiO2 and Al2O3 in fly ash are shown
to be smaller proportions of the total SiO2 and Al2O3 indicated
by the oxide analysis. In the experimental program, the roles of
reactive oxide ratios, and the molarity of sodium hydroxide in
influencing the compressive strength of alkali-activated fly ash
are evaluated. The reactive silica content in the alkali-activated
fly ash is taken as the sum of the reactive silica contributed by
the fly ash and the soluble silica from the activating solution.
The reactive alumina in the fly ash and the total sodium in the
activating solution are used in determining the reactive oxide
ratios. The ratio of reactive Al2O3/Na2O close to 2.5 produces
the highest compressive strength. The maximum ultimate
compressive strength is attained for a reactive SiO2/Al2O3 mass
ratio equal to 2.0 in the activated system. The minimum required
molarity of NaOH in the alkali-activated mixture is 3M. The
results presented in this paper indicate that the composition of
the activating solution for achieving the highest compressive
strength would depend on the reactive oxide composition
of the fly ash. Producing high strength geopolymers requires
optimizing the activating solution for the specific reactive oxide
ratios based on the reactive oxide content in the fly ash.
1. Introduction
Fly ash is most attractive source material to produce a cement-
free binder. Alkali-activation of low-calcium fly ash produces
geopolymers, which are primarily aluminosilicates. Typically,
sodium-based activators made of combinations of sodium
hydroxide (NaOH) and sodium silicate (Na2O.xSiO2) are used.
The sodium silicate is used to provide additional silica source in
the activated mixture [1]. Several factors, such as, reactive oxide
contents, fly ash particle size, temperature and duration of
curing time, mass ratio of alkaline activator to binder, molarity
of NaOH, and mass ratios of SiO2/Al2O3 and Al2O3/Na2O in
24 The Indian Concrete Journal | JULY 2020
G.V.P. BHAGATH SINGH
K.V.L. SUBRAMANIAM*
the alkali-activated fly ash mixture influence the strength
development of the geopolymers. As a general observation,
the ultimate compressive strength was found to increase with
increasing concentration of sodium hydroxide in the activating
solution [2]. For the production of geopolymers from fly ash,
activating solutions of varying compositions have been reported
in the literature. For instance, in one study, the mass ratio of
Na2O.xSiO2/NaOH in the activated solution equal to 2.5 was
reported to produce the highest strength [3]. In a different study
of fly ash based geopolymers, the highest strength was obtained
for the mass ratio of Na2O.xSiO2/NaOH close to 2.0 [4].
As a general observation, increasing the Al2O3/Na2O and
SiO2/Na2O mass ratios in the alkali-activated fly ash was
shown to increase the compressive strength of the resulting
geopolymers [5,6]. However, for producing highest strength from
the alkali-activated fly ash, different the ratios of SiO2/Al2O3
and Al2O3/Na2O, which vary over a wide range of values have
been reported. In one study, highest strength was achieved for
the SiO2/Na2O mass ratios in the activating solution equal to
0.69 [7]. In another study, the optimum oxide mass ratios of SiO2/
Na2O and of Al2O3/Na2O equal to 8.01 and 1.94, respectively
were shown to produce the highest compressive strength [8].
The optimum SiO2/Al2O3 and Al2O3/Na2O ratios to produce
highest compressive strength reported in another study are,
4.85 and 2.10, respectively [4]. It should be noted that in most
of the studies, the ratios of oxides are determined for the
activating solution and the contribution of fly ash is ignored.
Where the ratios are reported for the alkali-activated fly ash, the
contribution from fly ash is considered in the form of total oxide
present in fly ash.
Typical analysis of fly ash involves the analysis of its oxide
content. However, despite similarities in the total oxide contents,
the reactive content present in the different fly ashes were
found to vary significantly [9]. The reactive silica and the reactive
alumina are present in the amorphous glassy phase in the fly
ash. In an evaluation, which considered the reactive part of fly
ash, the compressive strength achieved after alkali activation
has been shown to depend on the vitreous oxide content of
*Corresponding author : K.V. L. Subramaniam, email : KVLS@iith.ac.in
 TECHNICAL PAPER

fly ash [2,10,11]. The results of these investigations reveal that only Table 2: Reactive SiO2 and Al2O3 contents and the
small portions of the total oxides in fly ash, the reactive oxides, total glassy content of fly ash (% by mass)
contribute to strength. Since there is a large variation in the
Reactive Al2O3 and SiO2 content
reactive oxide composition of fly ash, the oxide ratios reported (% mass) Total glassy
in the literature exhibit a very wide range. Consistent production content (% mass)
Al2O3 SiO2
of high strength geopolymers, therefore, requires consideration
of reactive content in the alkali-activated fly ash mixture. 16.2 23.4 55.5

The main focus of this paper is to establish the optimum reactive

oxide ratios on strength development in alkali activated low-
calcium fly ash. Role of different reactive ratios and molarity
of NaOH is investigated. The influence of the reactive SiO2/
Al2O3 ratio in the activated system on the reaction product
composition and the compressive strength achieved after
activation is investigated by varying the reactive SiO2 content
reactive to the reactive Al2O3 content. The influence of increasing
the Na2O content with respect to reactive Al2O3 content is
evaluated.
2. Materials and Methods
Siliceous fly ash as per the Indian Code of practice, IS: 3812 [12]
also meeting the requirement of Class F fly ash as per ASTM
C 618 [13] were used in this study. The fly ash was sourced from
a thermal power plant. The mass percentages of the different
oxides present in the fly ash determined using Energy Dispersive
X-ray Fluorescence spectroscopy (ED-XRF) are listed in Table 1.
The total glassy content, the reactive Al2O3, and the reactive SiO2
contents in the fly ash (determined according to the procedure
developed by Bhagath Singh and Subramaniam [9, 14, 15]) are given
in Table 2. Only 55.5% of the fly ash is in the glassy, reactive
form. While the SiO2 content is 55% by mass of fly ash, only
23.4% is available in the reactive form. Further, the reactive Al2O3
constitutes only 16.2% by mass of the fly ash while the total Al2O3
present in the fly ash is 27.1%. The remaining SiO2 and Al2O3 are
present in the crystalline forms as Quartz and Mullite, which are
non-reactive.
In the alkali-activated fly ash (AAF) mixture consisting of the
fly ash and the activating solution, the reactive SiO2 and the
reactive Al2O3 contribute to geopolymerization. The reactive
Al2O3 content in an AAF mixture is contributed only by the fly
ash. The fly ash used in the study has a low reactive SiO2 content.
Therefore, external additional of SiO2 is required to achieve
higher strength in the hardened geopolymer. Sodium silicate
was used to increase the soluble SiO2 content in the system.
The sodium silicate also contributes Na2O content to the AAF
mixture. The total sodium content in the AAF system, depends
on the quantities of sodium hydroxide and sodium silicate.
Finally, the molarity of NaOH is determined from the quantity of
water in the system.
In the mixture design, only the reactive oxides were used to
determine the oxide ratios. The total reactive oxide ratios in
the activated system were calculated using the primary oxides,
SiO2, Al2O3 and Na2O (the detailed procedure mentioned in
references [16,17]). The Al2O3 content was taken as the reactive Al2O3
content present in the fly ash. The reactive SiO2 content in the
AAF system was taken as the reactive SiO2 content in the fly ash
and the SiO2 from the sodium silicate. The sodium content was
adjusted relative the reactive silica and reactive alumina in the
system with addition of sodium hydroxide. The quantity of water
added to the mixture was adjusted to achieve a molarity of
NaOH higher than 3M.

Table 1: Oxide composition (% by mass) of fly ash Table 3: Different mixture proportions calculated
Composition Contents
based on the total reactive contents of the alkali
activated fly ash (mass ratios)
SiO2 55.4
Mass ratios of reactive Initial
Al2O3 27.1 contents w/b
Mix molarity
ratio
Fe2O3 7.3 SiO2/Al2O3 SiO2/Na2O Al2O3/Na2O (M)

CaO 2.5 A 2.0 5.0 2.5 5.0 0.19

TiO2 1.9 B 2.0 5.0 2.5 3.2 0.19

K2O 2.6 C 2.0 4.0 2.0 5.8 0.19

MgO 1.2 D 2.2 4.4 2.0 3.8 0.19

P2O5 0.9 E 2.3 4.1 1.8 3.2 0.19

SO3 0.6 F 1.8 3.5 1.9 7.9 0.19

The Indian Concrete Journal | JULY 2020 25

 TECHNICAL PAPER

The detailed experimental matrix showing the different mixes
used in the evaluation is given in Table 3. In the test matrix, all
the ratios are calculated using the reactive silica (silica content
from sodium silicate and the reactive silica content in fly ash)
and the reactive alumina (the reactive alumina content in fly ash)
in the activated system. The geopolymer binder (b) is defined
as sum of the solids in the whole system (mass of fly ash and
the Na2O and SiO2 contents contributed by sodium silicate).
The water to binder mass ratio (w/b) was kept fixed at 0.19 in all
the mixtures. The initial molarity of NaOH reported in the table
was determined using the water in the activated system. In the
test matrix, the Mixes A and B allow for studying the influence
of initial molarity. The influence of the other oxide ratios is
evaluated from the other mixes.
Sodium silicate solutions with two different compositions were
used for preparing activating solutions. For mix A, the sodium
silicate solution had a composition given by 10.8% Na2O, 30.5%
SiO2 and 41.3% H2O. In the remaining mixes, a sodium silicate
solution with a composition given by 15.35% Na2O, 33.65% SiO2
and 51% H2O composition was used. The sodium hydroxide
solution was prepared 24 hours prior to mixing with sodium
silicate solution using 99% reagent grade sodium hydroxide
pellets.
A paste of uniform consistency was prepared by mixing the fly
ash with alkali solution in a pan mixer. The paste mixtures were
poured in standard 7 cm cube moulds. All specimens were cured
at 60°C at a relative humidity equal to 95% till day of testing.
Compressive strength was measured from the cube samples at
1, 3, 7, 14 and 28 days of age. Small samples were collected from
the failed cube and ground to a smaller size (<60 µm. Powdered
samples were washed with iso-propanol o stop the further
reaction. The washed samples were dried at 40°C and stored in
a desiccator over silica gel for further evaluation.
The microstrucre of the reaction products was evaluated from
scanning electron microscopy (SEM) of samples collected from
failed compression specimens. The ‘as-fractured’ samples
collected from the crushed cubes were attached to a stainless
steel stub using a carbon tape. The elemental composition was
determined using energy dispersive X-ray analysis (EDS). An
acceleration voltage 15 kv was used for the EDS analysis.
3. Results and Discussion
The effect of initial NaOH molarity on the compressive
strength gain in the mixes are shown in Figure 1. To evaluate
the influence of molarity, mixes A and B are selected. The
compressive strength measured from both the mixtures shows a
rapid increase in the first 7 days, followed by a steady increment
in strength up to 14 days. There is a very small increase in
strength after 14 days. Results clearly indicate that increasing
the initial molarity of NaOH from 3.2M to 5M does not produce
any improvement in the strength. The values of compressive
strength at any age are comparable and the ultimate strength
achieved by both the mixes is nominally identical. Previous
results have shown that increasing the molarity form 3.2M does
not shown improvement in the ultimate strength [16,19].
The unreacted glassy content the reaction product content in
the mixes A and B are shown in Figure 2. The average values
from 5 different measurements are plotted and the range bars
correspond to the variation in the values. Results shows that
there is a steady decrease in the unreacted glassy content
with age in both the mixes. When compared to the initial
glassy content of raw fly ash, there is a substantial dissolution
of the glassy content by 1 day. The initial glassy content in
the fly ashes is approximately 55%. The mixes A and B, which
differ in the initial molarity of NaOH show an almost identical
decrease in the glassy content with age. The values of the glass
content in the two mixes at any age are nominally equal and
the observed differences are within the range of variability in
the measurement. The glassy content in the fly ash is nearly
depleted by 28 days. The amorphous reaction product contents
with age is shown in Figure 2(b). The amorphous reaction
product in the AAF mixtures is identified with alumino-silicate
gel (N-A-S-H) [16,17,20]. There is a rapid increase in the N-A-S-H
content up to 7 days following which the value is essentially
constant with increasing age. The N-A-S-H contents are
nominally identical in both the mixes at any particular age.

XRD measurements were performed using an automated

diffractometer. XRD signatures were measured in vertical
Bragg-Brentano (θ-θ) geometry between the 2θ angles of 10°
and 70° with a step size of 0.02°. Samples were rotated at 15
rpm during the acquisition. A 2 mm air scatter screen module
was positioned above the sample to reduce the air scatter. The
contents of the unreacted fly ash glassy and the amorphous
reaction products in the AAF samples were determined
using the direct decomposition method applied to the XRD Figure 1: Effect of Initial NaOH molarity on strength development.
signature [18]. compressive strength with age from mixes A and B.

26 The Indian Concrete Journal | JULY 2020


(a)
Figure 2: (a) Unreacted glassy content in mixes A and B with age; (b) Amorphous reaction product content in mixes A and B with age.
The results from the two mixes with different initial molarities
of NaOH further confirm previous findings on the requirement
of minimum initial molarity [15]. Increasing the molarity of NaOH
from 3.2M to 5M does not provide any improvement in the rate
and the extent of fly ash glassy phase dissolution. The strength
gain is also identical in these mixes. This suggests that for the
given fly ash, which has 55% glassy phase content, initial
molarity greater than 3.2M would result in the complete
dissolution of the glassy phase. Further, in mixes with initial
molarity greater than 3.2M, the influence of molarity can be
treated as providing a comparable effect and treated as a
constant for comparison.
The effect of Al2O3/Na2O ratio on strength development in
the AAF mixtures with age is shown in Figure 3. Mixes A and
C are considered for evaluating the influence of this ratio on
compressive strength. The results indicate that a decrease
in the ratio from 2.5 to 2.0 does not influence the strength.
Therefore, increasing the Na2O content with respect to the
reactive Al2O3 content below the mass ratio of 2.0 does not
Figure 3: Role of reactive Al2O3/Na2O mass ratio on strength
development in mixes B and C with age.
TECHNICAL PAPER
(b)
result in further increase in strength. Previous studies have
shown that maintaining the reactive Al2O3/Na2O close to 2.5
consistently produces the highest strength in alkali-activated
geopolymers [16,17].
The influence of the reactive SiO2/Al2O3 mass ratio on the
strength development is shown in Figure 4. Mixes C, D, E and
F are considered for evaluation. In all mixes, a rapid increase in
the strength is observed till 7 days. There is little further increase
in strength gain up to 28 days. On increasing the reactive SiO2/
Al2O3 mass ratio from 1.82 to 2.0 there is an increase in the
strength at any age. Increasing the reactive SiO2/Al2O3 ratio
beyond 2.0 results in no further improvement in the ultimate
compressive strength, while there is a reduction in compressive
strength at early ages. Based on these results, increasing in
the reactive SiO2/Al2O3 ratio beyond 2.0 does not produce any
additional gain in compressive strength. The maximum strength
is attained when the reactive SiO2/Al2O3 mass ratio is equal to
2.0. These results are consistent with previous findings where
Figure 4: Variation of SiO2/Al2O3 weight ratio on strength development of
AAF. C, D, E and F mixes with age.
The Indian Concrete Journal | JULY 2020 27
 TECHNICAL PAPER
the optimum ratio of the reactive SiO2/Al2O3 was equal to 2.0 for
achieving the highest strength in geopolymers produced from
AAF [16, 17].
The SEM image of the AAF mix C at the age of 7 days is shown
in Figure 5. It can be clearly seen that the microstructure
contains partially reacted cenospheres, along with a dense
reaction product. EDS analysis was performed on the dense
reaction product identified in all the mixes to determine the
individual elements present in the structure. The typical EDS
analysis performed on the dense reaction product of the mix C
is shown in Figure 5. The elemental composition of the dense
region of amorphous reaction products was primarily composed
of Si, Al and Na. In a few mixes only trace quantities of Ca and
Fe were identified. The dense reaction product is identified with
a ‘N-A-S-H’ type sodium aluminosilicate gel. The value obtained
from all the mixes were centered on a value of Si/Al equal to 3.0
with individual variations. The observed variation between the
different mixes was within the range of scatter. This correlates
with the very small variation in the strength with a variation in the
compressive strength on varying the reactive SiO2/Al2O3 in the
activated system.
5. Conclusions
The alkali-activation of low calcium fly ash in sodium-based
activating solutions is studied. As a first step the fly ash was
characterized to determine the reactive components. A smaller
proportion of the total Al2O3 and SiO2 indicated by the oxide
analysis are present in reactive forms. Alkali-activated mixtures
were proportioned for different oxide ratios and molarities
of NaOH. The following conclusions can be drawn from the
findings of the experimental program.
1. The total reactive oxide ratios in the alkali activated fly ash
mixture influence the final strength. The reactive oxide
ratios in the alkali-activated fly ash mixture depend on the
individual reactive contents in the fly ash.
Figure 5: Typical SEM image with EDS analysis of the reaction product identified in Mix C at the age of 7 days
28 The Indian Concrete Journal | JULY 2020
2. Reactive SiO2/Al2O3 ratio equal to 2.0 and reactive Al2O3/
Na2O ratio less than 2.5 in the alkali-activated fly ash
mixture produce the highest compressive strength.
3. Increasing the molarity of NaOH beyond 3.2M does not
produce an improvement to strength and dissolution of
glass for samples cured at 60°C.
4. The reaction products of alkali-activated fly ash contain the
sodium aluminosilicate gel. A high compressive strength
is obtained for a Si/Al ratio in the reaction product close
to 3.0. The dense reaction product with the Si/Al ratio of
3.0 is produced when the reactive SiO2/Al2O3 ratio in the
activated mixture is 2.0.
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G.V.P. Bhagath Singh is currently working as an Assistant Professor in the Department of Civil
Engineering at S.R.M. university, Andhra Pradesh. Prior to joining here, he was a Postdoctoral Fellow at The
École polytechnique fédérale de Lausanne (EPFL), Switzerland and Nanyang Technological University (NTU),
Singapore. He is a recipient of the prestigious Swiss Government Excellence Fellowship by Government of
Switzerland. His primary interests are material characterization, microstructure, low energy binders, fly ash
based geopolymers, nucleation seeding, carbonation, novel cements, 3D printing of concrete, properties and
durability of concrete.

K.V.L. Subramaniam is a Professor in the Department of Civil Engineering at Indian Institute

of Technology (IIT), Hyderabad. He has obtained his B.Tech. degree from IIT Delhi and Ph.D. degree from
Northwestern University, Illinois. Before joining IIT Hyderabad, he was a Professor in the Department of Civil
Engineering at the City University of New York. He was elected a Fellow of the American Concrete Institute
and is a life member of the Indian Concrete Institute (ICI). His research interests include alkali-activated
materials, rheology control and 3D printing, behavior of concrete and non destructive testing.

Cite this article: Bhagath Singh, G.V.P., Subramaniam, K.V.L. (2020). “Efficient Production of Alkali-activated Geopolymers using Low-
calcium Fly ash” The Indian Concrete Journal, Vol. 94, No. 7, pp. 24-29.

The Indian Concrete Journal | JULY 2020 29