Construction and Building Materials 101 (2015) 675683

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Construction and Building Materials

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Effects of nano-silica on the strength development of geopolymer cured

at room temperature
Partha Sarathi Deb , Prabir Kumar Sarker, Salim Barbhuiya
Department of Civil Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia

h i g h l i g h t s
 Effects of nano-silica on strength and microstructure of geopolymers were studied.
 Early-age strength of ambient-cured fly ash geopolymers increased by nano-silica.
 Dense microstructure with better interlocking morphology was resulted by nano-silica.
 Use of OPC or GGBFS with nano-silica and fly ash yielded CSH or CASH and NASH.

a r t i c l e

i n f o

Article history:
Received 24 March 2015
Received in revised form 16 August 2015
Accepted 14 October 2015

Keywords:
Blended fly ash
Compressive strength
Geopolymer
Microstructure
Nano-silica

a b s t r a c t
Use of nano-silica is gaining wider attention due to its significant effect on the microstructural and
mechanical properties of Portland cement based binders. Effects of the incorporation of nano-silica in
fly ash based geopolymer binders have been investigated in this study. Low-calcium fly ash was used
as the principal source of aluminosilicate and it was blended with either blast furnace slag or Portland
cement at small percentages in order to accelerate the curing at room temperature. Nano-silica was used
at a rate up to 3% of the total binder in order to understand its effect on the strength and microstructural
development. The experimental results show that the strength and microstructural properties could be
further developed with inclusion of nano-silica in geopolymer mixes. Compressive strength increased
with the increase of nano-silica content up to 2%. Scanning electron microscopy (SEM) images showed
denser microstructures with well-connected interlocking morphology for the optimum nano-silica
dosage. The strength increase is contributed by densification of the microstructure with the addition
of nano-silica.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Geopolymerization is a process where a large amount of amorphous aluminosilicate phase is transformed into compact cement
by hydrothermal polycondensation [1,2]. Previous researchers
revealed that geopolymer binder may be viewed as an amorphous
analogue of zeolites or zeolitic precursors [3,4] that follows the
same formation process as in zeolites [5,6].
The main reaction product in geopolymers is an aluminosilicate
gel where tetrahedral Al3+ sites charge-balanced by alkali metal
cations. Fly ash, ground granulated blast furnace slag, calcined
clay and metakaolin are the common source materials used for
geopolymers [7,8]. Most commonly used activators are alkali
silicates, hydroxides, carbonates or combinations of these chemi Corresponding author.
E-mail address: partha.deb@postgrad.curtin.edu.au (P.S. Deb).
http://dx.doi.org/10.1016/j.conbuildmat.2015.10.044
0950-0618/ 2015 Elsevier Ltd. All rights reserved.

cals selected based on the chemical compositions of the source

material [9,10].
Fernandez and Palomo [3] studied the reactivity of fly ash in
alkali solutions where reactive silica, alumina content and amorphous phase content played a vital role in the geoploymerization
process. Other researchers [2,11] showed that higher amount of
reactive silica resulted in the formation of higher amount of
geopolymeric gel and consequently developed higher mechanical
strength. Criado et al. [11] found that products of higher strengths
consisted of higher soluble silica content when compared the reaction of fly ash with pure NaOH and sodium silicates with moduli up
to 1.27.
Other researchers indicate that particle size distribution has a
significant impact on the reactivity of fly ash. Higher amount of
fine particles will result in higher surface area, and therefore higher
reactivity, resulting in higher compressive strength [12]. The roles
of other factors such as molarity of NaOH, alkaline content, curing

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P.S. Deb et al. / Construction and Building Materials 101 (2015) 675683

conditions, composition of binder materials [1316] and postcuring chemical treatments [11] were also investigated by other
researchers. Results indicated that higher molarity with low alkaline content and elevated curing temperature at early ages
enhanced the high early strength of geopolymer systems. The presence of calcium compound in the source material plays a vital role
because the Ca2+ is capable of acting as a charge-balancing cation
within the geopolymeric binder [17] and forms CaAlSi amorphous structures [18]. The Ca2+ available in blast furnace slag
and OPC are able to create a coexistence of geopolymeric gel and
CSH that leads to the increase of mechanical strength [19,20]
of geopolymer materials.
The microstructural analysis of geopolymer paste has been highlighted to a microporous framework with the high amount of aluminosilicate gel in the matrix. The characterizations of the micro and
nanostructures of geopolymer pastes are complex and generally
consist of amorphous gels and different unreacted crystalline phases
in the activated systems [1,2,11]. It was shown that the water
released during geopolymer formation causes discontinuous nanopores throughout the hydrated geopolymer matrix [18]. Moreover,
Bakharev [20] found that the micrographs of geopolymer materials
are heterogeneous and contain a large proportion of unreacted fly
ash surrounded by aluminosilicate gel. The XRD patterns of
alkali-activated fly ashes show that the original crystalline phases
are not changed by the activation reactions [21]. However, the
formation of hydration products depends on the source materials
such as fly-ash, metakaolin, OPC and slag [2224,34,37].
The ingress of fluid to the interior of geopolymer paste primarily takes place through its pore systems. It was observed that the
amount of small pores proportionately increases with the higher
molarity of the alkaline activator solution [25]. However, KOH
based geopolymer mortars were shown to have lower amount of
total porosity than NaOH based geopolymer mortars [26].
Despite the fact that geopolymer mechanism was developed
over a couple of decades ago and has many advantageous characteristics, it has not yet been used in concrete as extensively as Portland cement. Widespread use of low calcium fly-ash geopolymers
is hindered due to some of its limitations such as slow setting, high
porosity and subsequent slow strength development. Improvement of these properties is essential in order to increase the use
of geopolymers in concrete as an alternative to energy-intensive
OPC binders. The effects of nano-silica in OPC systems are widely
investigated and it was found as an effective additive towards
the mechanical and microstructural development [32]. However,
research on the effects of nano-silica on the properties of geopolymers is scarce in literature. Therefore, this study aimed to
investigate the effect of nano-silica on the properties of fly ash
geopolymers. In order to determine the optimum quantity of
nano-silica in the different types of geopolymers, experimental
work was carried out on OPC and GGBFS blended fly ash based
geopolymer binders with 03% nano-silica contents. The strength
and microstructural development of geopolymer paste samples
containing different proportions of nano-silica and subjected to
room temperature curing were studied.
2. Experimental work
2.1. Materials
Class F fly ash (FA), nano-silica (NS), ground granulated blast-furnace slag
(GGBFS) and ordinary Portland cement Type I (OPC) were used in this study.
Nano-silica with average particle diameter of 15 nm was obtained from a commercial supplier. The chemical composition and physical properties of the fly- ash, OPC,
GGBFS and nano-silica are presented in Table. 1. The alkaline activator was a
combination of sodium hydroxide and sodium silicate solutions. Sodium hydroxide
solution of 8 M concentration was prepared by mixing 9798% pure pallets with tap
water. The mass ratio of SiO2 to Na2O of the sodium silicate solution was 2.61
(SiO2 = 30.0%, Na2O = 11.5% and water = 58.5%).

Table 1
Chemical composition and physical properties of fly ash, OPC, GGBFS and Nano-silica.

a
b

Chemical analysis

Class F flya
(wt.%)

OPC
(wt.%)

GGBFS
(wt.%)

Nano-silica
(wt.%)

SiO2
Al2O3
Fe2O3
CaO
MgO
MnO
K2O
Na2O
P2O5
TiO2
SO3
Specific gravity
LOIb

46.69
29.14
13.81
3.29
1.4
0.16
0.72
0.86
1.63
1.34
0.43
2.40
0.68

21.1
4.7
2.7
63.6
2.6

2.5
3.15
2.0

29.96
12.25
0.52
45.45

0.38
0.31
0.04
0.46
3.62
2.9
2.39

99.5
0.001
0.001

ASTM C 618.
Loss on ignition.

2.2. Geopolymer mixes containing nano-silica

The binder compositions of the geopolymer paste mixes were proportioned
based on the previous works on geopolymers cured at room temperature [14,16].
Twenty-one geopolymer paste mixes in 3 series (fly ash only, GGBFS blended fly
ash and OPC blended fly ash) were mixed in the laboratory. The mix proportions
are given in Table. 2. In the fly ash only series, fly ash was used as the main binder
with 03% nano-silica. In the GGBFS blended fly ash series, 03% nano-silica was
included with 15% GGBFS and 8285% fly ash. The binder composition of the OPC
blended fly ash series was 03% nano-silica, 10% OPC and 8790% fly ash. The
GGBFS and OPC contents of 15% and 10% respectively were used since these proportions were found in previous studies [14,16,24] as the optimum blending with
low-calcium fly ash for reasonable setting times. The alkaline liquid content of each
mix consisted of the same proportion of alkaline solution (40%) with a sodium
silicate to sodium hydroxide ratio of 2.0. The concentration of the NaOH solution
was 8 M. The samples containing different binders were named according to the
type of binder used in the mix. For example, FA-PC-NS3 represents a geopolymer
paste mix having 3% nano-silica (NS) in the Portland cement (PC) blended fly ash
based geopolymer paste. Similarly, the mix designations of FA-NS and FA-S-NS
represent the fly ash only and GGBFS blended fly ash series respectively.

2.3. Preparation, casting and curing of test specimens

The alkaline solution was prepared in the laboratory by mixing sodium silicate
and sodium hydroxide solutions at the required ratio. Usually, nano-silica may not
get dispersed well after wetting and add microbubbles to the mix during mixing. A
uniform dispersion of the nanoparticles is essential to avoid agglomeration and

Table 2
Mix proportions of geopolymer pastes.
Mix id

NS (wt.%)

Si/Al

FA-NS0.0
FA-NS0.5
FA-NS1.0
FA-NS1.5
FA-NS2.0
FA-NS2.5
FA-NS3.0
FA-PC-NS0.0
FA-PC-NS0.5
FA-PC-NS1.0
FA-PC-NS1.5
FA-PC-NS2.0
FA-PC-NS2.5
FA-PC-NS3.0
FA-S-NS0.0
FA-S-NS0.5
FA-S-NS1.0
FA-S-NS1.5
FA-S-NS2.0
FA-S-NS2.5
FA-S-NS3.0

0.0
0.5
1.0
1.5
2.0
2.5
3.0
0.0
0.5
0.5
1.5
2.0
2.5
3.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0

1.29
1.30
1.31
1.32
1.34
1.35
1.36
1.34
1.35
1.37
1.38
1.40
1.41
1.43
1.34
1.36
1.37
1.39
1.40
1.42
1.43

Mix components (kg/m3)

Fly-ash

OPC

GGBFS

NS

400
398
396
394
392
390
388
360
358
356
354
352
350
348
340
338
336
334
332
330
328

40
40
40
40
40
40
40

60
60
60
60
60
60
60

0
2
4
6
8
10
12
0
2
4
6
8
10
12
0
2
4
6
8
10
12

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677

promote the reaction. Ultrasonic processing was found to be the most effective way
of dispersion of nano-silica particles. Therefore, ultra-sonication was used to disperse the nano-silica particles in the alkaline solution to avoid the agglomeration
during wetting and mixing. Operating conditions of the UP400S (400 W, 24 kHz)
ultrasonic device were set at 24 kHz and amplitude 100% with 80% pulse range
for 30 min. The nano-silica particles were found evenly distributed in the alkaline
liquid after ultra-sonication, as shown in Fig. 1.
All dry ingredients were first added in a Hobart mixer following by addition of
the activator solutions to the dry materials and mixing it further for 35 min. The
geopolymer paste specimens of size 50  50  50 mm cube were cast in accordance
with the ASTM C109 standard [56]. The specimens were demolded 24 h after
casting. The specimens were compacted by using a table vibrator during casting.
The paste specimens were cured in room temperature (20 2 C) and at a relative
humidity of 70 10%. Compressive strength of the paste specimens was tested at
7, 14 and 28 days in accordance with the ASTM: C109 standard using a loading rate
of 0.33 MPa/s.

the long-chain silicate oligomers in the geopolymer matrix and

eventually increased the mechanical strength. Fernandez and
Palomo [3] showed that the extent of the soluble silicon concentration is a critical variable controlling the geopolymerization process.
The highest 28-day compressive strength in this series was
observed in mix FA-NS2.0. The strength increase declined for
nano-silica contents in excess of 2%. This is mainly because the
nano-silica content of 2% was sufficient for reaction to its entirety
due to its high surface area. An addition of nano-silica in excess of
2% did not participate in the reaction process and hence did not
increase the strength any further. The effect of nano-silica is found
to follow the same trend on the compressive strengths at 7, 14 and
28 days of age, as shown in Fig. 2.

2.4. SEM and EDX analysis

3.2.2. OPC blended fly ash geopolymers

Fig. 3 presents the effect of nano-silica on the compressive
strengths of the 10% OPC blended fly ash based geopolymer mixes.
It is noted from the figure that compressive strengths of the mixes
with nano-silica are significantly higher than that of the control
mix at 28th day.
The addition of the nano-silica significantly increased the
strength of the mixes. The compressive strength continuously
increased with the increase of nano-silica dosage from 0.5% to 2%
and then reduced with further increase in the percentage of
nano-silica. For example, FA-PC-NS1 exhibited 75% higher strength
than the control mix (FA-PC-NS0). The highest 28-day compressive
strength in this series was 65.0 MPa obtained for the mix FA-PCNS2. This strength is significantly higher than that of the control
mix (28.5 MPa). It is observed from the results (Fig. 3) that the rate
of strength development can be controlled by the addition of nanosilica in the mixes. However, increasing the dosage of nano-silica
above 2% did not further increase strength. Mix FA-PC-NS3 with
3% nano-silica showed 35% higher strength than the mix FA-PCNS0 but 90% less than the mix FA-PC-NS2. These results indicate
that the optimal content of nano-silica for reinforcing the geopolymer paste is 2% for the fly ash only and OPC-blended fly ash mixes.

Scanning electron micrographs (SEM) and energy dispersive X-ray (EDX)

spectroscopy were conducted to examine the localized morphology and elemental
distributions at the microscopic scale for small cut paste samples using the MIRA3
TESCAN from platinum coated exposed surfaces. The samples were coated with
carbon before putting the samples for SEM and EDX.

3. Results and discussion

3.1. Properties fresh geopolymer mixtures
All the geopolymer mixtures were workable as they were
flowing easily after mixing. The mixtures could be handled with
adequate ease to pour into the moulds and casting of the test specimens. The initial and final setting times of the geopolymer mixes
were determined by the Vicat apparatus. Geopolymers based on fly
ash alone generally takes a long time (>24 h) to set because of its
slow rate of chemical reaction when cured at room temperature
[13,24,35]. Van Jaarsveld et al. [27] reported that the surface
charge on the fly ash particle affects the initial setting properties
of a geopolymeric mix. The initial setting times of the fly
ash-only geopolymers containing 1%, 2% and 3% nano-silica were
13 h, 11 h and 10 h respectively. The final setting of these mixtures
were 19 h, 18 h, and 16 h respectively. Larger reductions in setting
times were achieved by blending of the fly ash with OPC and
GGBFS. For example, use of 3% nano-silica in the slag blended fly
ash geopolymer reduced the initial and final setting times from
2.5 h to 1.3 h and 5.8 h to 4.0 h respectively. The setting times of
the OPC blended fly ash were relatively short. Addition of 3%
nano-silica reduced the initial and final setting times of the OPC
blended fly ash geopolymers from 110 min to 60 min and from
70 min to 35 min respectively. Thus, it can be seen that the desired
setting time for an application can be achieved by changing the
percentage of GGBFS, OPC and nano-silica in the geopolymer
mixture.
3.2. Effect of nano-silica on compressive strength
3.2.1. Fly ash only geopolymers
The compressive strengths of fly ash only geopolymer pastes
with 03% nano-silica are plotted in Fig. 2. The 28-day compressive
strength of the control mix was 29.0 MPa which increased up to
67 MPa by the inclusion of nano-silica. It can be seen from the figure that compressive strengths of the mixes containing 0.53%
nano-silica were significantly higher than that of the control mix.
Mixes FA-NS1.0, FA-NS2.0 and FA-NS3.0 exhibited 87%, 129% and
93% higher 28-day compressive strength values than the mix
FA-NS0.0. This shows that the binder became stronger with the
increase of soluble silica or silica concentration in the mixes. Similar behavior was also observed by other researchers [11,21,50]. Xu
and Deventer [28] showed that the addition of soluble silicates
accelerated the reaction process at a higher rate and helped build

3.2.3. GGBFS blended fly ash geopolymers

The variations in compressive strength with addition of nanosilica in the 15% GGBFS blended fly ash based geopolymers are presented in Fig. 4. Addition of higher amount of GGBFS content (20%)
with the lower SS/SH ratio (1.5) along with higher molarity of
NaOH (14 M) in the fly ash based system generally exhibited
higher strength [14,15]. However, it can be seen from the current
experimental results (Fig. 4) that the strength can be further
increased with the addition of nano-silica in the mixes even with
lower molarity (8 M) of NaOH and GGBFS content of 15% in the
mixes.
At 28 days, mix FA-S-NS1 containing 1% nano-silica achieved
45% higher compressive strength than the control mix (FA-SNS0). The effect of nano-silica addition on the strength development is shown to be maximized at 2% that was also observed in
the other two series. The increase in strength is seen to decline
for the nano-silica dosage exceeding 2%. The strength of the mix
containing 2% nano-silica reached at 73.0 MPa which is 88% higher
than that of the control mix (39.0 MPa). However, the compressive
strength for 3% nano-silica (mix FA-S-NS3) addition was observed
only 24% higher than that of the control mix (FA-S-NS0) but 51%
less than the strength for 2% nano-silica (mix FA-S-NS2). The lower
strength of the mix containing 3% nano-silica than that containing
2% nano-silica is attributed to the presence of excess unreacted
particles in the geopolymer matrix. It is believed that the unreacted particles caused excessive self-desiccation and cracking in
the matrix that eventually reduced the strength [45]. This implies
that 2% nano-silica in GGBFS blended fly ash based geopolymer
reacted almost entirely and further increase in nano-silica was

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P.S. Deb et al. / Construction and Building Materials 101 (2015) 675683

Fig. 1. Alkaline solution with nano-silica (a) before ultra-sonication (b) after ultra-sonication.

7 day

80

14 day

28 day

Compressive strength (MPa)

70
60
50
40
30
20
10
0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Percentage of Nano-silica
Fig. 2. Compressive strength development of fly ash-only based geopolymer with
nano-silica.

not effective in the improvement of strength. This finding is similar

to the effect of nano-silica on the strength of ordinary Portland
cement binders [48,30,54]. It was shown that there is an optimum
dosage of nano-silica for the strength improvement of cement
mortar and concrete [2931,33]. The higher strength of the GGBFS
blended geopolymer mixes is attributed to the its lower binding
energy as compared to that of fly ash at molecular level. The binding energies of Si and Al in GGBFS are 101.92 eV and 74.23 eV
respectively [51], while those in fly ash are 102.55 eV and
74.52 eV respectively [51]. It is known that the reactivity is higher
for lower binding energies. Thus, the inclusion of GGBFS resulted in
increased reactivity of the source material and higher strength.
7 day

80

14 day

3.2.4. Strengths of the mixes containing the optimum nano-silica

Nano-silica, with its high surface area to volume ratio strongly
influenced the compressive strengths of all types of geopolymer
mixes. All the geopolymer paste samples showed increased
compressive strength at higher nano-silica content up to 2%. A
comparison of the 28-day compressive strengths with 2% nanosilica for three geopolymer series of this study is displayed in
Fig. 5. Previous research showed that higher amount of OPC
(>12%) [24] and GGBFS (>20%) [14,16] in fly ash geopolymer mixes
cause rapid setting and rapid loss of workability during the casting
process. Hence, the amount of OPC and GGBFS content were kept at
10% and 15% respectively in this study to avoid the undesirable
consequences.
It is noted from Fig. 5 that the addition of 2% nano-silica
resulted in similar compressive strengths in the mixes of each
series at a given age between 7 and 28 days when cured at room
temperature. As explained in Section 3.2.3, the reduced binding
energy at molecular level by the inclusion of GGBFS has resulted
in increased strength. Also, the binding energy of Si of the nanosilica is 102.1 eV, which is smaller than that of fly ash [48,51]. Thus,
the combined reduction in the binding energy by GGBFS and nanosilica has resulted in the highest strength of this mix.
3.2.5. Role of the Si/Al and Na/Al ratios on strength of geopolymers
The binding energies of Si, Al and Na based on the previous
works [48,49,5153] for different materials were used to calculate
the Si/Al and Na/Al ratios of the geopolymer mixes. The Si/Al ratios
of the mixes are given in Table. 2. Fig. 6 presents the variation of
compressive strengths with Si/Al ratio for different types of
nano-silica blended fly ash based geopolymers. Nano-silica used

28 day

14 day

28 day

70

Compressive strength (MPa)

70

Compressive strength (MPa)

7 day

80

60
50
40
30
20

60
50
40
30
20
10

10

0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Percentage of Nano-silica
Fig. 3. Compressive strength development of OPC blended fly ash based geopolymer with nano-silica.

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Percentage of Nano-silica
Fig. 4. Compressive strength development of GGBFS blended fly ash based
geopolymer with nano-silica.

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Compressive strength (MPa)

P.S. Deb et al. / Construction and Building Materials 101 (2015) 675683

80

GGBFS blended fly-ash

70

Fly-ash only

60

OPC blended fly-ash

50
40
30
20
10
0
7 day

14 day

28 day

Age
Fig. 5. Compressive strength Development with age of the geopolymer mixes
containing 2% nano-silica.

3.3. Microstructural development

3.3.1. SEM and EDX analysis
Fig. 8 shows the SEM images of the fly ash only geopolymer
samples after 28 days. Incorporation of nano-silica was noticed to
influence the microstructure of the hardened geopolymer paste
samples. In Fig. 8, formation of sodium aluminosilicate gel was
noticed which was also found by other researchers [19,23,26]. A
key difference between the microstructures of FA-NS2 (2% NS)
and FA-NS0 (0% NS) is that FA-NS2 is denser than FA-NS0 with less
number of unreacted particles. The zone surrounding the unreacted particles appears compact, although few micro cracks were
detected in the vicinity of the particles. It is also observed that
nano-silica acted as a filler material in this case to fill the spaces
inside the skeleton of hardened microstructure of geopolymer

80

80

70

70

60

60

Compressive strength

Compressive Strength

in this study as a small percentage replacement of fly ash altered

the overall Si/Al ratio in the mixes. Hajimohammadi et al. [36]
showed that the geopolymer chemistry can be controlled as a
function of silica availability in the initial stages of the reaction.
Moreover, other researchers [48,53,30,54] noted that the dissolution rate of nano-silica was faster than that of fly ash due to its
higher surface area and smaller binding energy. Mechanical
strength was shown to increase with the increase in the Si/Al ratio.
Fig. 6 indicate that the ratio of Si/Al greater than 1.338 exhibited
declined strength. Xu and Deventer [28] showed in their study that
the ratio of Si/Al in the original mineral presents a correlation with
mechanical strength and the microstructural development process.
In this study, addition of nano-silica beyond the optimum level
(>2%) caused less amount of aluminium available to react and create additional sodium aluminosilicate gel. Duxson et al. [46]
reported that the decrease in strength with higher silica content
than the optimum has been linked to the amount of unreacted
material in the specimens, which act as defect sites. With the right
percentage of nano-silica (2%), the high density product contributes to strength enhancement due to the reduced porosity.
When added at higher percentages, the additional nano-silica
remains as defect sites to cause decline of strength. It was also
shown by other researchers [38,8] that a certain amount of
aluminium is required to be available throughout the reaction to
accelerate and attain the final compressive strength. In the OPC
and GGBFS blended fly ash geopolymers with 2% nano-silica, the
optimum levels of Si/Al ratio were found to be 1.396 and 1.402
respectively. This is in good agreement with the other researchers
[21,22] who reported that an optimized Si/Al ratio exhibits higher
mechanical strength with dense microstructure.
It was shown by Fernandez-Jimenez et al. [55] that the amount
of Al2O3 plays an important role in the kinetics of geopolymerisa-

tion. The effect of Na/Al ratio in the geopolymerization process

was studied by several authors [3941]. Rowles [39] and Stevenson
[40] found that compressive strength increased with the increase
of Na/Al molar ratio up to a certain value and then strength
declined with further increase in the Na/Al ratio. The effects of
Na/Al ratio on the strength development of the mixes of this study
are shown in Fig. 7. It is noted from the Fig. 7 that the strength of
nano-silica blended fly ash geopolymers increased with the
increase of Na/Al ratio from 3.22 up to 3.27. The strength declined
with the increase of Na/Al ratio beyond the value of 3.27. Similarly,
the maximum strengths in the OPC and GGBFS blended fly ash
based geopolymers with 2% nano-silica were observed at the Na/
Al ratio of 3.53 and 3.55 respectively. Xu and Deventer [44]
concluded that increasing the sodium content leads to increasing
dissolution of silica and aluminium rate in the geopolymeric
systems. Fernandez and Palomo [21] pointed out that the amount
of OH ion in the alkaline solution contributes towards the dissolution of Si4+ and Al3+ from fly ash, while the Na+ ion contributes
to the crystallization process. However, it was shown by Jaarsveld
[47] that excess alkali serves to weaken the structure causing a
negative impact on most physical properties. Thus, the trends
shown by the Na/Al ratio on the strengths of the mixes of this
study are consistent with those shown by the previous studies.
As the other parameters remained constant, the addition of
nano-silica contributed to higher strength up to a certain value
of Na/Al ratio. Bjornstrom et al. [42] found that the nano-silica
particles with high specific surface area constituted a highly reactive siliceous media in the alkaline environment. The reactive silica
involves in the formation of aluminosilicate gel resulting in a
higher mechanical strength of the product [13]. The results of the
present study support the findings of Catherine et al. [41] that
the formation of geopolymer product decreases beyond an
optimum value of the Na/Al ratio.

50
40
30
Fly ash only

20

50
40
30
20

OPC blended fly ash

10
0
1.260

GGBFS blended fly ash

1.280

1.300

1.320

1.340

1.360

1.380

1.400

1.420

1.440

Si/Al ratio
Fig. 6. Effects of Si/Al ratio in different types of geopolymer paste mixes.

10
0
3.15

3.2

3.25

3.3

3.35

3.4

3.45

3.5

3.55

3.6

Na/Al ratio
Fig. 7. Effects of Na/Al ratio in different types of geopolymer paste mixes.

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P.S. Deb et al. / Construction and Building Materials 101 (2015) 675683

Fig. 8. SEM images of fly-ash only geopolymer containing nano-silica: (a) 0 wt.% (FA-NS0), (b) 2 wt.% (FA-NS2) and (c) 3 wt.% (FA-NS3).

paste to increase its compactness. This agrees with the observations on fly ash based geopolymers by Shih et al. [43].
The SEM micrographs of OPC blended fly ash based geopolymers with different amount of nano-silica are presented in Fig. 9.
Significant differences in microstructure were observed with the
addition of nano-silica in OPC blended fly-ash based geopolymers.
In mix FA-PC-NS0, a large amount of unreacted particles (point 1 of
Fig. 9a) with a large amount of small pores (point 3 of Fig. 9a) was
observed. Fernandez and Palomo [3] pointed out that the considerable amount of unreacted or not totally consumed spheres indicate
a moderate degree of reaction in the system. Fig. 9 shows that the
addition of 2% nano-silica particles (FA-PC-NS2) in the OPC
blended fly ash geopolymer, the voids between the unreacted particles and pores in the hydrated matrix were filled with amorphous
hydrated gel and resulted in denser microstructure. No portlandite
(calcium hydroxide) was observed and can be considered to have
been fully converted into CSH by the pozzolanic reaction.
However, the structure of the FA-PC-NS3 (3% NS) was observed less
dense than FA-PC-NS2 (2% nano-silica) and a loose connection of
unreacted fly ash particles was noticed in this case. It is noteworthy
that the increase in nano-silica form 2% to 3% in the mixes lead to an
increase in the amount of partially hydrated gel (Fig. 9c) and are not
well connected in the geopolymer matrix due to its excess amount
in the mixes.
The SEM images of the GGBFS blended fly ash geopolymers are
shown in Fig. 10. The microstructure of the GGBFS blended fly ash
geopolymer with 2% nano-silica (Fig. 10b) is seen to be much more
compacted and dense with almost less pores as compared to the
other two mixes. The microstructures of mixes FA-S-NS0 and
FA-S-NS3 are similar to those of mixes FA-PC-NS0 and FA-PC-NS3.
From the above comparison of the microstructures, it can be
seen that the mixes with 2% nano-silica resulted in more compact
and dense product as compared to those with no or 3% nano-silica.

This more compact microstructure resulted in the highest

compressive strength of the mixes containing 2% nano-silica as
presented in Figs. 24. Also, the most compact microstructure with
least amount of pores observed in the GGBFS blended fly ash mix
with 2% nano-silica (Fig. 10(b)) resulted in the highest compressive
strength (72 MPa) among all the mixes of this study.
Fig. 11, shows the EDX spectra with identified elements in
the hydrated geopolymer paste. The spectrum of EDX provided
valuable information on the change of the phase composition
of the geopolymer pastes. High concentrations of silicon, oxygen
and aluminium can be observed in all the geopolymer paste
samples indicating formation of aluminosilicate gels. Relatively
high concentrations of calcium and sodium are also observed
in the EDX spectra of the OPC and GGBFS blended fly ash
geopolymers (Fig. 11b and c). These high concentrations of calcium and sodium in addition to silicon, oxygen and aluminium
are attributed to the formation of additional calcium silicate
(CSH) or calcium aluminosilicate (CASH) and sodium aluminosilicate (NASH) hydrates in these two mixes. Formations of these
additional products have resulted in the more compact and
dense microstructures. Thus, the unreacted particles of these
mixes are seen to be well connected by the reaction products
as shown in Fig. 11b and c.
Mechanical strength and microstructural development for all
types of geopolymer mixes differed greatly with the amount of
nano-silica used in this study. The microstructural characterisation
of the geopolymer pastes generated with 2% nano-silica showed a
complex mix of amorphous gels (aluminosilicate and CSH gel) as
the final hydrated products for GGBFS and OPC blended fly ash
based systems with fewer amounts of pores and unreacted particles in the matrix. It means the inter-locking morphology of the
hydrated gel with the remaining unreacted particles lead to dense
the microstructure and resulted in higher mechanical strength of

P.S. Deb et al. / Construction and Building Materials 101 (2015) 675683

681

Fig. 9. SEM image of OPC blended fly-ash based geopolymer paste containing different amounts of nano-silica particles (a) 0 wt.% (b) 2 wt.% and (c) 3 wt.%.

Fig. 10. SEM image of GGBFS blended fly-ash geopolymers containing nano-silica: (a) 0 wt.% (b) 2 wt.% and (c) 3 wt.%.

the GGBFS and OPC blended fly ash based geopolymer pastes. The
strength values at 28 days for these cases were found to be 72 MPa
and 66 MPa respectively. However, it is noted that excessive
amount of nano-silica (3%) in the abovementioned systems created

lower strength values with relatively loose interlocking morphology and higher amount of unreacted particles and pores in the system. This means that the optimum level of nano-silica in the fly ash
only and GGBFS and OPC blended fly ash based systems is 2% and

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P.S. Deb et al. / Construction and Building Materials 101 (2015) 675683

a
Spectrum

Spectrum

Spectrum

Fig. 11. EDX spectra of geopolymers with 2% nano-silica (a) fly-ash only (b) OPC blended fly-ash and (c) GGBFS blended fly-ash.

beyond this value will result in lower strength with relatively loose
microstructures.
4. Conclusions
The influence of nano-silica on the strength development in different types of geopolymer pastes has been investigated for the
room temperature curing condition. Nano-silica was added at rates
of 03% in the geopolymer pastes based on fly ash only, fly ash
blended with 10% OPC and fly ash blended with 15% GGBFS. The
strength and microstructural developments were studied up to
the age of 28 days.
 Compressive strength of ambient-cured geopolymers was found
to increase with the addition of nano-silica at early ages. The 7day strength increased by blending of low calcium fly ash with
OPC or GGBFS and it increased further with the addition of
nano-silica. Strength increased with the addition of nano-silica
up to a dosage of 2% and then it declined with further addition.
The maximum 28-day compressive strength among all the mixes
was 72 MPa which was obtained for the geopolymer paste containing 83% fly ash, 15% GGBFS, and 2% nano-silica. The strengths
of this mix were 39 MPa and 53 MPa at 7 and 14 days respectively. The Si/Al ratio of the mixes containing 2% nano-silica
resulting in maximum strength varied between 1.33 and 1.40.

 The SEM images showed that the addition of nano-silica

improved the compactness of the reaction product. The contribution of nano-silica to the formation of a more compact and
dense microstructure with better interlocking morphology has
resulted in the increase of compressive strength. The EDX spectra showed that additional reaction products such as CSH or
CASH and NASH are produced in the mixes containing OPC
and GGBFS. Formation of these additional reaction products further improved the microstructure of the geopolymer pastes
increasing the compressive strength.
Acknowledgments
The authors wish to gratefully acknowledge the support of Coogee Chemicals for supplying the chemicals used in this study. The
use of equipment, scientific and technical assistance of the Curtin
University Electron Microscope facility, which has been partially
funded by the university, State and Commonwealth Governments
is also gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.conbuildmat.
2015.10.044.

P.S. Deb et al. / Construction and Building Materials 101 (2015) 675683

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