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CERAMICS
INTERNATIONAL
Ceramics International 42 (2016) 3000–3006
www.elsevier.com/locate/ceramint

Effect of silica fume on the mechanical properties of fly ash

based-geopolymer concrete
F.N. Okoyea, J. Durgaprasada, N.B. Singhb,n
a
Department of Civil Engineering, Sharda University, Greater Noida, India
b
Research and Technology Development Centre, Sharda University, Greater Noida, India
Received 22 August 2015; received in revised form 14 October 2015; accepted 15 October 2015
Available online 21 October 2015

Abstract

In this paper fly ash based geopolymer concretes with different percentages of silica fume were made by using NaOH/sodium silicate and cured
in an oven at 100 1C. Workability, compressive strength, flexural and tensile strengths were determined. Portland cement concrete was used as a
reference. Sodium hydroxide (14 M) and sodium silicate were used as alkali activators. The results have shown that addition of silica fume
improved the compressive strength of the produced geopolymer concretes. Tensile and flexural strengths also increased as the silica fume content
increased. The geopolymer concretes were found quite durable in the presence of 2% H2SO4, 5% Na2SO4 and 5% NaCl.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Geopolymer; Silica fume; Fly ash; Compressive strength; Flexural strength

1. Introduction achieve the required strength level. In recent years consider-

able amount of research work on geopolymer cement and
The global use of concrete is second only to water. As the concrete is being carried out to elucidate the mechanism of
demand for concrete as construction material increases, so also formation, strength development and durability [5]. In our
the demand for Portland cement. The cement manufacture is earlier publication we reported the effect of metakaoline on the
highly energy intensive and each tonne emits about a tonne of properties of fly ash based geopolymer concrete [19]. In this
CO2, which is a greenhouse gas causing global warming [1–3]. paper we have studied the effect of silica fume on the
Thus, there is an urgent need to produce an alternative to mechanical properties of fly ash based geopolymer concrete.
cement material with adequate strength and durability in order
to make cement industry more eco-friendly and sustainable.
A new binding material known as ‘geopolymer’ was first 2. Experimental
introduced by Davidovits in 1978 [4]. The reaction of
aluminosilicate materials such as fly ash [5–8], metakaoline 2.1. Materials
[9–12], silica fume [13,14], slag [15,16], rice-husk ash [17],
red mud [18], etc. with highly alkaline solutions (hydroxides, Low calcium fly ash (Class F) (ASTM C618) was used in
silicates) produces geopolymers. Unlike ordinary Portland this investigation. The fly ash used was obtained from National
cement (OPC), geopolymers do not require calcium-silicate- Power station, Dadri, Uttar Pradesh, India. Silica fume was
hydrate (C-S-H) gel for matrix formation and strength, but obtained from Counto microfine products Pvt. Ltd., Pissurlem
utilise the polycondensation of silica and alumina precursors to industrial estate, Pissurlem, Sattari, Goa, India, (BS EN 13263-
1 (2005)). OPC-43 was used for making reference concrete.
n
Corresponding author. The chemical compositions of OPC, fly ash and silica fume are
E-mail address: [email protected] (N.B. Singh). given in Table 1.

http://dx.doi.org/10.1016/j.ceramint.2015.10.084
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 F.N. Okoye et al. / Ceramics International 42 (2016) 3000–3006 3001

Table 1 Table 2
Chemical composition of binders. Physical properties of gravels and sand.

Constituents Composition (%) Sample Specific gravity Water absorption (%) Fineness modulus

OPC Fly ash Silica fume 20 mm aggregate 2.5 0.17 2.7

10 mm aggregate 2.4 0.87 2.8
SiO2 19.01 50.70 93.67 Sand 2.6 – 2.1
CaO 66.89 2.38 0.31
MgO 0.81 1.39 0.84
P2O5 0.08 – –
Na2O 0.09 0.84 0.40 2.3. Mix proportion of geopolymer concrete
K2O 1.17 2.40 1.10
MnO 0.19 – 0.84
Al2O3 4.68 28.80 0.83
The designs of geopolymer concretes with fly ash were
Fe2O3 3.20 8.80 1.30 similar to that of OPC concrete. Coarse and fine aggregates
SO3 3.00 0.30 0.16 were taken as 77% by mass of the entire mixture. The
Loss of ignition 2.48 3.79 2.10 concentration of NaOH solution was 14 M as this concentra-
tion gave the highest strength [19]. 1% Naphthalene sulpho-
nate based superplasticiser was used to improve the
workability of fresh geopolymer mix. Higher W/S ratio
improved the workability but the compressive strength was
reduced. So a fixed W/S ratio (0.2) was used in order to have
higher compressive strength. The detailed mix design of
geopolymer concrete mixes are given in Table 3. Geopolymer
mixes with different amount of silica fume (5%, 10%, 15%,
20%, 30% and 40%) were also made. A control mix was cast
as M40 with Portland cement concrete to compare the
performance of geopolymer concrete.

2.4. Workability test

The workability of the fresh concretes was determined by

using slump cone test in compliance with BS EN 12350-
2:2000 standard.
Fig. 1. Grading curve of 20 mm and 10 mm coarse aggregates and sand.
2.5. Casting of geopolymer concrete

Casting of geopolymer concrete was done at room tempera-

Coarse aggregates of sizes 20 mm and 10 mm were used. ture in the laboratory in a similar way as described earlier [19].
Sieve analyses were performed to determine the particle size After mixing, the concrete mixture was cast in a
distribution as prescribed in BS 812, Part1, 1975 while fine 100 mm  100mm steel mould in three layers, and each layer
aggregate used was river sand and graded as prescribed in BS was given 60 strokes with 20 mm compacting rod. Six
812, Part1, 1975 (Fig. 1). concrete cubes were cast for each mix beside the trial mixes
The physical properties of coarse and fine aggregates are for compressive strength. The split tensile and flexural tests
given in Table 2. were performed with cylindrical moulds of 150 mm diameter
Sodium hydroxide in the form of pellets with 98% purity and 300 mm height as per ASTM C 496-90 requirement and
and commercially available sodium silicate solution were used. beam mould of 100 mm  100 mm  500 mm in compliance
The sodium silicate solution used had a silicon dioxide to with EN 12390-51997 requirement respectively.
sodium oxide ratio (SiO2/Na2O) of 2.0 with 60% water by the
total weight. 2.6. Curing and testing of geopolymer specimens

The concrete cubes were demoulded after 48 h and cured in

an oven at 100 1C for 72 h since at this temperature, strength
2.2. Preparation of alkali was found maximum [19]. The specimens were left at room
temperature until the day of testing. The compressive strength
Solution of sodium hydroxide (14 M) was prepared and left of the cubes was determined after 3, 7, 14, 21 and 28 days
for 24 h before mixing with sodium silicate. The mixture of while the specimens in cylindrical forms for tensile and
sodium hydroxide and sodium silicate solutions was left for flexural strengths were left at room temperature for 28 days
one day and then used for a geopolymerisation process. before testing.
3002 F.N. Okoye et al. / Ceramics International 42 (2016) 3000–3006

Table 3
Mix proportion of geopolymer concrete.

MIX NO Quantity of ingredients (kg/m3)

Coarse aggregate Fine sand Fly ash Silica fume OPC SS NaOH (14 M) SP ALK/ FA W/S

20 mm 10 mm

GPF 862 431 554 400 0 0 113 45 4.0 0.4 0.2

GP1 862 431 554 380 20 0 113 45 4.0 0.4 0.2
GP2 862 431 554 360 40 0 113 45 4.0 0.4 0.2
GP3 862 431 554 340 60 0 113 45 4.0 0.4 0.2
GP4 862 431 554 320 80 0 113 45 4.0 0.4 0.2
GP5 862 431 554 280 120 0 113 45 4.0 0.4 0.2
GP6 862 431 554 240 160 0 113 45 4.0 0.4 0.2
M40 862 431 554 0 0 400 N.A N.A 4.0 N.A 0.3

FA – Fly ash, SS – Sodium silicate, SP – Superplasticisers, ALK – Alkaline, W/S – Water/solid ratio.

Fig. 3. Compressive strength of fly ash based geopolymer concrete in presence

of silica fume in relation to control.

Fig. 2. Slump of fly ash based geopolymer concrete with various amounts of

3. Results and discussions
silica fume in relation to control.

3.1. Workability

2.7. SEM studies Workability of geopolymer concrete was studied using

slump cone test. It was observed that the workability of
SEM pictures of GPF and GP4 hydrated for 28 days were geopolymer was low as compared to that of control (Fig. 2).
recorded with Quanta FEG 250 ESEM instrument. The fresh geopolymer concrete formed pellets when mixed
properly in a drum concrete mixer. Although the mixes were
highly viscous, even then adequate compaction could be
achieved. To improve the workability of fresh geopolymer
2.8. Durability tests mix, Naphthalene sulphonate based superplasticizer was used.
The slump of M40 concrete with 100% OPC was higher than
After curing, the concrete cubes (M40 and GP4) were those of geopolymer concretes with fly ash and silica fume.
immersed in 2% sulphuric acid, 5% sodium sulphate and 5% It was found that the slump of geopolymer concretes
sodium chloride solutions separately. The compressive decreased with the increase of silica fume content. The poor
strength of each cube was determined after 3, 28, 56 and 90 workability of geopolymer concretes could be attributed due to
days. SEM picture of GP4 exposed to 2% H2SO4 was also high viscosity of the mixes. The geopolymer mixes were more
recorded. For each test three cubes were immersed in the viscous than the OPC concrete due to cohesiveness of the
solutions and the strength measured. The values plotted were system [20,21]. When sodium silicate solution was added in
the average values which deviated within a limit of 5%. the mixes, the binding of the fine and aggregates occurred and
 F.N. Okoye et al. / Ceramics International 42 (2016) 3000–3006 3003

Table 4
Percentage increase in compressive strength at different time interval with
reference to control (M40).

Mix Increase in compressive strength in relation to control (%) at different

days

3 days 7 days 14 days 21 days 28 days

M40
GPF 0 2.9 14.6 5.9 0
GP1 46.5 26.6 26.4 19.6 1.5
GP2 22.9 40.6 39.9 32.3 9.3
GP3 46.5 26.3 27.3 23.8 12.4
GP4 110.0 82.9 90.5 79.9 51.2

the system became sticky. As a result of this the slump was

reduced.
Fig. 4. Effect of silica fume on compressive strength.

3.2. Compressive strength

and enhance the compactness. As a result of this, the porosity
The variation of compressive strength of different mixes may decrease. These significant variations in the geopolymer
with time is shown in Fig. 3. The compressive strength specimens may affect their mechanical properties. Porosity has
increased continuously with time in the following sequence been reported to be the main microstructural variable limiting
and the minimum value was for M40. the mechanical properties of geopolymers [24]. Adak et al.
[14] studied the effect of colloidal nanosilica on the compres-
M40 o GP1 o GP2 o GP3 oGP4 sive strength of geopolymer mortars and found that 6%
The relative percentage increase in compressive strength additions increased the strength but beyond that there was
with reference to control (M40) is given in Table 4. From the detrimental effect. However, in the present case the effect of
table it is quite clear that the percentage increase is maximum silica fume on compressive strength of geopolymer concrete
(almost double) in the case of GP4 containing 40% SF for was studied. It was found that the strength increased con-
3 days. The variation of compressive strength with silica fume tinuously upto 40% silica fume addition (maximum silica fume
at 28 days is shown in Fig. 4. The compressive strength added in the present experiment). Since the concrete has a
increased with the increase of silica fume. porous structure, silica fume which consists of spherical fine
The parameters that affect compressive strength of geopo- particles of amorphous silicon dioxide (may be of nanodimen-
lymer concretes are: type and concentration of alkaline sion) enters the pores making the structure more compact. Due
activator, the curing temperature, the curing time, relative to additional amount of amorphous silica, larger quantity of
amounts of Si, Al, K, Na and molar ratio of Si to Al present in aluminosilicate gels might be formed in the geopolymer
solution [22]. The presence of silicate ions in the alkaline matrix. To some extent it can be detected by XRD pattern.
solution substantially improved the mechanical strength and Thus both the effects may generate dense geopolymer structure
modulus of elasticity values. It is also reported that the H2O/ with increased compressive strength.
M2O molar ratio in the mixture significantly affected the SEM pictures of GPF and GP4 hydrated for 28 days were
compressive strength [22]. Skvara et al. [23] found that the recorded and are given in Fig. 5. Morphology of GPF shows
Na2O content and SiO2/Na2O ratio of geopolymer mix fractured surfaces whereas GP4 shows compact and smooth
significantly affect pore characteristics and compressive surface. These morphological differences may also be respon-
strength. Dutta et al. [13] studied the effect of 5% silica fume sible for compressive strength differences.
on porosity and compressive strength of geopolymer paste and
mortar. They found that the compressive strength of paste
decreased with the addition of silica fume because of increase 3.3. Flexural and tensile strength
of porosity. On the other hand the compressive strength of
mortar increased due to decrease of porosity. Addition of silica Flexural test is the most common test conducted on
fume which has a high percentage of SiO2 could have hindered hardened concrete. The flexural strength increased continu-
the process of geopolymerisation. This should be attributed to ously as the percentage replacement of fly ash with silica fume
the fact that with increased silica fume content, Na2O required increased (Fig. 6). Tensile strength of concrete determines the
for complete dissolution is not available in the activator load at which the concrete cracks. The tensile strength also
solution. Due to this, a part of silica fume remained unreacted increased as the percentage replacement of fly ash with silica
in the produced geopolymer gel. However, in case of mortars, fume increased, first slowly and then rapidly (Fig. 7). In
these excess fine silica fume particles may enter in the voids general both the flexural and tensile strength of fly ash based
3004 F.N. Okoye et al. / Ceramics International 42 (2016) 3000–3006

Fig. 5. SEM picture of GPF and GP4 hydrated for 28 days.

Fig. 6. Flexural strength of fly ash geopolymer concrete with different Fig. 7. Tensile strength of fly ash based geopolymer concrete with different
proportions of silica fume. proportions of silica fume.

compressive strength in the case of M40. It appears that due to

geopolymer concretes containing silica fume followed the porous nature of concrete, Cl ions enter and accelerate the
same pattern as compressive strength. All the mix proportions hydration upto certain period of time causing an increase in the
containing silica fume performed better than the control mix. strength and after that there is detrimental effect. In the case of
GP4, there is a very little loss in compressive strength. It is seen
3.4. Durability that there is slight increase in strength in the case of GP4 in 5%
NaCl after 56 days. This may be due to some passivation effect.
The variation of compressive strength (average of 3 samples) The small loss occurred may be due to some depolymerisation of
after immersion in different chemical environments is shown in aluminosilicate. SEM picture (Fig. 9) of GP4 kept for 90 days in
Fig. 8. From the figure, it is quite obvious that there is a rapid loss 2% H2SO4 indicates some morphological change supporting
in compressive strength in the concrete made from OPC (M40). some deterioration.
Compressive strength at different intervals of time in different Both physical and chemical interactions occur within con-
chemical environment is given in Table 5. M40 sample was crete when it is exposed to aggressive chemical environment.
severely deteriorated on exposure to sulphuric acid and Na2SO4 The movement of deteriorating ions in concrete is a function of
for 90 days. Strength losses in M40 are possibly connected to the several variables. These include the concentration of aggres-
decomposition of hydration products and migration of alkalis sive chemical at the concrete surface, pore size and spacing,
from the specimens into the solution imposed by the acid attack. pore volume fraction, changes in pore size with respect to
However, in the presence of 5% NaCl, there is some increase in location within the cement paste, and chemical composition of
 F.N. Okoye et al. / Ceramics International 42 (2016) 3000–3006 3005

Fig. 9. SEM picture of GP4 stored in 2% H2SO4 for 90 days.

Fig. 8. Durability properties of fly ash based geopolymer concrete blended

concrete [27]. Probably both the anions consume some of the
with silica fume. available alkali activators hindering geopolymerisation
reactions.
Table 5
Compressive strengths. 4. Conclusions

Mix Comr. strength Compressive strength exposed in different chemical The effect of different concentration of silica fume on
unexposed environment (N/mm2) mechanical properties of fly ash based geopolymer concrete
(N/mm2)
28d 3d 28d 56d 90d
was studied and results are discussed. It is found that in the
presence of silica fume, the workability of the paste decreases.
M40 48.5 43.8 41.2 33.1 32.6 The geopolymer concrete containing silica fume showed
(2% (2% (2% (2% higher compressive, tensile and flexural strengths as compared
H2SO4) H2SO4) H2SO4) H2SO4)
to that of control and these values increased with the increase
38.3 35.3 34.0 33.0
(5% (5% (5% (5% of silica fume content. This was due to an increase in
Na2SO4) Na2SO4) Na2SO4) Na2SO4) compactness and denser microstructure. Geopolymer concretes
51.4 50.4 44.0 42.0 were found to be more durable in 2% H2SO4, 5% NaCl and
(5% NaCl) (5% NaCl) (5% NaCl) (5% NaCl) 5% Na2SO4 solutions. Still there is a significant gap of
GP4 69.7 59.9 59.8 58.3 58.0
(2% (2% (2% (2%
knowledge related to the geopolymerization reaction, strength
H2SO4) H2SO4) H2SO4) H2SO4) development and durability issues. Thus there is a need to
58.3 60.8 63.2 57.6 investigate all these problems in detail.
(5% (5% (5% (5%
Na2SO4) Na2SO4) Na2SO4) Na2SO4)
Acknowledgement
61.2 61.52 59.9 63.1
(5% NaCl) (5% NaCl) (5% NaCl) (5% NaCl)
One of us (FNO) wishes to express his profound gratitude to
Federal government of Nigeria through the TET FUND for
their financial support, without which, it wouldn not have been
phases present in the hydrated cement paste. During hydration possible to carry out this research work. We are also thankful
reaction OPC yields C-S-H gels while during polymerisation, to Federal Polytechnic Oko, Nigeria for their moral support.
geopolymer binders yield N-A-S-H, C-A-S-H or C-S-H gels.
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