Geopolymer: green chemistry and sustainable development solutions

133
I ntroducti on
Concrete is the most commonly used construction
material; its usage by the communities across the globe is
second only to water. Customarily, concrete is produced
by using the Ordinary Portland Cement (OPC) as the
binder. The usage of OPC is on the increase to meet
infrastructure developments. The world-wide demand for
OPC would increase further in the future. It is well-known
that cement production depletes significant amount of
natural resources and releases large volumes of carbon-di-
oxide. Cement production is also highly energy-intensive,
after steel and aluminium. On the other hand, coal-
burning power generation plants produce huge quantities
of fly ash. The volume of fly ash would increase as the
demand for power increases. Most of the fly ash is
considered as waste and dumped in landfills.
In order to address the issues mentioned above, it is
essential that other forms of binders must be developed to
make concrete. The geopolymer technology developed by
Davidovits in the 1980s offers an attractive solution (1, 2).
In 2001, the authors embraced Davidovits original
concept of geopolymers to make fly ash-based
geopolymer concrete. This paper presents a summary of
the results of this on-going research.
Past research on geopol ymer mat eri al
In geopolymers, the polymerisation process involves a
chemical reaction under highly alkaline conditions on Al-
Si minerals, yielding polymeric Si-O-Al-O bonds as
proposed by Davidovits (1, 2).
The chemical composition of geopolymers is similar to
zeolite, but shows an amorphous microstructure (3). The
structural model of geopolymer material is still under
investigation; hence the exact mechanism by which
geopolymer setting and hardening occur is not yet clear
(4). The mechanism of geopolymerisation may consist of
dissolution, transportation or orientation, and
polycondensation, and takes place through an exothermic
process (1, 2).
The strength of geopolymer depends on the nature of
source materials. Geopolymers made from calcined source
materials, such as metakaolin (calcined kaolin), fly ash,
slag etc., yield higher compressive strength when
compared to those synthesised from non-calcined
materials, such as kaolin clay. The source material used for
geopolymerisation can be a single material or a
combination of several types of materials (5). A
combination of sodium or potassium silicate and sodium or
potassium hydroxide has been widely used as the alkaline
activator, with the activator liquid-to-source material ratio
by mass in the range of 0.25-0.30 (1-7).
Because heat is a reaction accelerator, curing of fresh
geopolymer is carried out mostly at an elevated
temperature. When curing at elevated temperatures, care
must be taken to minimize the loss of water. However,
curing at room temperature has successfully been carried
out by using calcined source material of pure geological
origin, such as metakaolin (1-7).
The geopolymer material can be used in various
applications, such as fire and heat resistant fibre
composites, sealants, concretes, ceramics, etc., depending
on the chemical composition of the source materials and
the activators. Davidovits (1, 2) suggested that the atomic
Studi es on fl y ash-based geopol ymer concret e
tudes sur le bton gopolymre base de cendres volantes








B. Vijaya Rangan, Djwantoro Hardjito, Steenie E. Wallah, and Dody M.J. Sumajouw
Faculty of Engineering and Computing, Curtin University of Technology, GPO Box U 1987, Perth 6845, Australia
Abstract:
This paper presents test data on fly ash-based geopolymer concrete. The paper covers the material and the mixture
proportions, the manufacturing process, the fresh and hardened state characteristics, the influence of various parameters
on the fresh and hardened state concrete, the utilisation of the material in structural members, and the long-term
behaviour.

Cet article prsente les rsultats des essais sur le bton gopolymre base de cendres volantes, raliss Curtin
University, Perth, Australie. Il couvre le matriau en soit, les proportions des mlange, le processus de fabrication, les
caractristiques du bton frais et durci, l'influence de divers paramtres sur le bton frais et durci, l'utilisation du
matriau dans les pices de structure, et son comportement long terme.
134
ratio of Si-to-Al of about 2 for making cement and
concrete. Geopolymer can also be used as waste
encapsulation to immobilise toxic metals (8).
Fl y ash-based geopol ymer concrete
In the authors experimental work, geopolymer is used as
the binder, instead of cement paste, to produce concrete.
The geopolymer paste binds the loose coarse aggregates,
fine aggregates and other un-reacted materials together to
form the geopolymer concrete. The manufacture of
geopolymer concrete is carried out using the usual
concrete technology methods.
As in the Portland cement concrete, the aggregates occupy
the largest volume, i.e. about 75-80 % by mass, in
geopolymer concrete. The silicon and the aluminium in
the low-calcium fly ash are activated by a combination of
sodium hydroxide and sodium silicate solutions to form
the geopolymer paste that binds the aggregates and other
un-reacted materials.
Materi al s, mi xture composi ti ons, and
test speci mens
In the authors experimental work (9-16), low-calcium
ASTM Class F dry fly ash obtained from a local power
station was used as the source material. Most of the fly
ash comprised oxides of silicon (about 50% by mass),
aluminium (about 25% by mass), and iron (about 10 to
18% by mass). The calcium content of the fly ash was
about 2% by mass. About 80% of the fly ash had particles
of less than 38 to 55 micrometer in size. The details of the
chemical composition of various batches of the fly ash, as
determined by X-Ray Fluorescence (XRF) analysis, are
given elsewhere (9-16).
Analytical grade sodium hydroxide (NaOH with 98%
purity) flakes dissolved in water and sodium silicate
solution (Na
2
O=14.7%, SiO
2
=29.4% and water=55.9% by
mass) were used. Both the liquids were mixed together
and the activator solution was prepared at least one day
prior to its use. To improve the workability of fresh
concrete, a commercially available naphthalene based
superplasticiser was used. A combination of locally
available aggregates, i.e. granite-type coarse aggregates
and fine sand, in saturated surface dry condition, were
mixed together. The grading of the combined aggregates
had a fineness modulus of approximately 4.5. The details
of some of the Mixtures used in authors studies are given
in Table 1. Complete details are given in References 9 to
16.
The aggregates and the fly ash were mixed dry in a pan
mixer for about 3 minutes. At the end of this dry mixing,
the activator solution, the super plasticiser, and the extra
water (if any) were mixed together, and then added to the
solid particles and the mixing continued for another 3 to 5
minutes. The fresh concrete had a stiff consistency and
was glossy in appearance. The fresh concrete mixture was
then cast in 100x200 mm cylinder steel moulds in three
layers. Each layer received 60 manual strokes and
vibrated for 10 seconds on a vibrating table. Five
cylinders were prepared for each test variable.





Table 1: Details of the mixtures
A
g
g
r
e
g
a
t
e
s

F
l
y

A
s
h

S
o
d
i
u
m

S
i
l
i
c
a
t
e

s
o
l
u
t
i
o
n

S
o
d
i
u
m

H
y
d
r
o
x
i
d
e

s
o
l
u
t
i
o
n

S
u
p
e
r
-
p
l
a
s
t
i
c
i
s
e
r

A
d
d
e
d

W
a
t
e
r

M
i
x
t
u
r
e

N
o
.

[ kg / m
3
]
C
u
r
i
n
g

1 1848 408 103
41
(8M)
6 -
60
o
C
Oven
2 1848 408 103
41
(10M)
6 7.5
60
o
C
Oven
3 1848 408 103
41
(12M)
6 14.4
60
o
C
Oven
4 1848 408 103
41
(14M)
6 20.7
60
o
C
Oven
5 1848 408 103
41
(16M)
6 26.5
60
o
C
Oven
6 1848 408 103
41
(14M)
8 -
Varied
Oven
7 1848 408 103
41
(14M)
8 10.6
Varied
Oven
8 1848 408 103
41
(14M)
8 21.3
Varied
Oven
9 1756 476 120
48
(8M)
- -
60
o
C
Oven
10 1756 476 120
48
(14M)
- -
60
o
C
Oven
11 1848 408 103
41
(14M)
8 -
90
o
C
Oven
12 1848 408 103
41
(8M)
6 -
90
o
C
Oven
13 1848 408 103
55.4
(8M)
6 -
60
o
C
Oven
14 1848 408 103
55.4
(8M)
6 -
60
o
C
Steam
Immediately after casting, the samples were covered by a
film to avoid the loss of water due to evaporation during
curing at an elevated temperature. The specimens were
cured in an oven or steamed chamber at a specified
temperature for a period of time in accordance with the test
variables selected. The details of the authors research
have been reported elsewhere (9-12).
At the end of the curing period, the 100x200 mm test
cylinders were removed from the curing chamber, and
were left in the moulds for six hours in order to avoid a
drastic change of the environmental conditions. The
specimens were then removed from the moulds, and left to
air dry at room temperature until loaded in compression at
the specified age in a universal test machine. Before
testing, the specimens were weighed to determine the
density of the material. The loading rate and other test
procedures used were in accordance with the details
specified in the relevant Australian Standard for testing
Portland cement concrete. Each of the compressive
strength test data points plotted in various graphs
corresponds to the mean value of the compressive
strengths of five test cylinders in a series. The standard
deviations are plotted on the test data points as the error
bar.
Parameters aff ecti ng fresh and hardened
concrete
The fresh fly ash-based geopolymer concrete has a stiff
consistency and is glossy in appearance.
As in the case of Portland cement concrete, water content
of the mixture influences the workability of geopolymer
Geopolymer: green chemistry and sustainable development solutions
135
concrete, as measured by the conventional slump test.
This is demonstrated in Figure 1.

Figure 1: Slump values for mixtures 1 to 5
In Figure 1, the slumps of various mixtures are plotted. In
order to maintain the molar ratio of H
2
O-to-Na
2
O
constant, the concentration of sodium hydroxide (NaOH)
was increased in the mixtures that were added with extra
water. The net effect is that higher the water content of the
mixture higher is also the Na
2
O-to-SiO
2
molar ratio. It is
interesting to note that an increase in the Na
2
O-to-SiO
2

ratio has insignificant effect on the compressive strength
of hardened concrete (Figure 2).

Figure 2: Effect of molar NaO
2
-to-SiO
2
ratio on compressive strength
Another important characteristic of fresh concrete state is
the setting time. Our laboratory experience showed that
fresh fly ash-based geopolymer concrete could be handled
at least up to 120 minutes after mixing, without any sign
of setting, and without any degradation in compressive
strength (11).

Figure 3: Effect of the H
2
O-to-Na
2
O molar ratio on compressive
strength

Figure 4: Effect of Water-to-Geopolymer Solids ratio by mass on
compressive strength
With regard to hardened concrete, the molar ratio of H
2
O-
to-Na
2
O significantly influences the compressive strength
of fly ash-based geopolymer concrete. An increase in this
ratio decreases the compressive strength (Figure 3). The
test results plotted in Figure 3 are recast in Figure 4 in
terms of geopolymer solids-to-water ratio by mass versus
compressive strength. For a given geopolymer concrete,
the total mass of water in the mixture is taken as the sum
of the mass of water in the sodium silicate solution, the
mass of water in the sodium hydroxide solution, and the
mass of extra water, if any, added to the mixture. The mass
of geopolymer solids is the sum of the mass of fly ash, the
mass of sodium hydroxide flakes, and the mass of sodium
silicate solids (i.e. the mass of Na
2
O and SiO
2
in sodium
silicate solution). Again, this relation is similar to the
relationship between the water-to-cement ratio and the
compressive strength of Portland cement concrete.
Other important factors that influence the properties of
hardened fly ash-based geopolymer concrete are the curing
temperature and the curing time. Higher the curing
temperature higher is the compressive strength (Figure 5).
On the influence of curing time, fly ash-based geopolymer
concrete cured for longer periods of time, shows an
increase in its compressive strength, at least up to 48 hours
(Figure 6).

Figure 5: Effect of curing temperature on compressive strength

Figure 6: Influence of curing time on compressive strength

Figure 7: Compressive strength at different ages
In fly ash-based geopolymer concrete, we believe that the
curing temperature and the curing time play significant
136
roles not only as accelerators of chemical reaction, but
also determine the extent of that reaction. Therefore, we
found that geopolymer concrete samples cured at 60
o
C for
a period of 24 hours showed very little strength gain after
curing (Figure 7).
El asti c constants and stress-strai n
rel ati ons
To measure the elastic constants and to investigate the
stress-strain relations of fly ash based geopolymer
concrete, four different mixtures were prepared to obtain
four different compressive strengths in the range of 40 to
90 MPa (12). The elastic properties, Youngs modulus
and Poissons ratio, were measured in accordance with the
relevant Australian Standard. The Youngs modulus was
determined as the secant modulus, measured at a stress
level equal to 40 percent of the compressive strength of
concrete.

Table 2: Youngs Modulus (E
c
) and Poissons Ratio (!) of fly ash-based
geopolymer concrete
Mixture
No.
f
cm

(MPa)
E
c

(GPa)
!
11 89 30.84 0.16
12 68 27.29 0.12
13 55 26.05 0.14
14 44 22.95 0.13

The values of Youngs modulus of fly ash- based
geopolymer concrete shown in Table 2 are similar to
those of Portland cement concrete using the same coarse
aggregate type. These values are at the lower end of the
values predicted by the empirical expression given in the
Australian Standard for Concrete Structures, AS3600.
The Poissons ratio falls between 0.12 and 0.16, and is
within the range observed for Portland cement concrete.
The stress-strain relation in compression of fly ash-based
geopolymer concrete is also similar to that of Portland
cement concrete (12).
Structuural appl i cati ons
Studies on the utilisation of fly ash-based geopolymer
concrete in structural members have been carried out.
Twelve 175x175x1500 mm reinforced columns were
manufactured and tested. The primary variables of the
experimental work were longitudinal reinforcement, load
eccentricity, and concrete compressive strength in the
range of 40 and 60 MPa to represent concrete with normal
and high strength. The authors have also conducted tests
on twelve 200x300x3300 mm reinforced geopolymer
concrete beams. The test variables were the longitudinal
tensile reinforcement ratio and the compressive strength
of concrete. The behaviour of these reinforced columns
and beams was similar to that of members made of
Portland cement concrete. The test results have also
shown that the design provisions of the current codes and
standards are applicable to reinforced fly ash-based
geopolymer concrete members. The details of these works
are described elsewhere (13, 14).
Long-term properti es
On the long-term properties, our laboratory experiments
have shown that the fly ash-based geopolymer concrete
undergoes low creep and very little drying shrinkage.
After 52 weeks under sustained load of 40 % of the
compressive strength, the drying shrinkage strain
measured was approximately 100 x 10
-6
and the creep
factor (the ratio of creep strain to elastic strain) was found
to vary between 0.44 and 0.63 when the compressive
strength of concrete was approximately 60 MPa (15).
In order to study the effect of chemical attack, specimens
of fly ash-based geopolymer concrete were soaked in 5%
concentration of sodium sulfate solution (Na
2
SO
4
). The
variations in the compressive strength, the unit mass, the
length change, as well as the physical appearance, were
measured. It was found that after 52 weeks exposure, the
geopolymer concrete did not show any sign of sulfate
attack or degradation in properties. However, the
compressive strength significantly decreased when the fly
ash-based geopolymer concrete was immersed in 2%
concentration of sulfuric acid solution (16).
Manufacture of fl y ash-based
geopol ymer concrete i n ambi ent
condi ti ons
In most of our work, we have used heat curing (either
steam curing or dry curing) to make the test specimens.
However, we have also manufactured fly ash-based
geopolymer concrete test specimens and cured them in
ambient conditions at room temperature.
For instance, the mixture given in Table 3 was used to cast
100mm by 200mm test cylinders. The slump of the fresh
concrete was approximately 150 mm. The granite-type
coarse aggregates were a combination of three different
grades with maximum sizes of 20mm, 14mm, and 7mm.
Both coarse and fine aggregates were in a saturated-
surface dry condition.

Table 3: Mixture proportion of geopolymer concrete cured in ambient
conditions
Material Mass, kg/m
3

20mm 277
14mm 370
Coarse
aggregates
7mm 647
Fine sand 554
Fly ash
(low-calcium ASTM Class F)
408
Sodium silicate solution
( SiO
2
/Na
2
O=2)
103
Sodium hydroxide solution
(8 Molar)
41
Super Plasticiser 6

The cylinders were left in ambient conditions of the
laboratory when the room temperature varied between 20
and 25 degree C. The test specimens hardened within 24
hours, and were removed from the moulds three days after
casting.
The cylinders were tested in compression at various ages.
Four cylinders were tested at each age. The mean
compressive strength was 35 MPa on the 7
th
day and 47
MPa on the 28
th
day, after casting.
It must be noted that the mean 7
th
day compressive
strength of test cylinders manufactured using the same
mixture and, cured immediately after casting at 60 degree
C for 24 hours, ranged between 55 MPa (steam curing)
and 65 MPa (dry curing). These heat-cured specimens did
not gain strength with age (Figure 7).
Geopolymer: green chemistry and sustainable development solutions
137
Economi c benef i ts
Fly ash-based geopolymer concrete offers several
economic benefits over Portland cement concrete.
The cost of one ton of fly ash is only a small fraction, if
not free in some parts of the world, of the cost of one ton
of Portland cement. Therefore, after allowing for the cost
of activator liquids needed to the make the geopolymer
concrete, we have estimated that the cost of fly ash-based
geopolymer concrete may be about 10 to 30 percent
cheaper than that of Portland cement concrete.
In addition, we have learnt that the appropriate usage of
one ton of fly ash earns one carbon-credit that has a
redemption value of about 10 to 20 Euros. Based on the
data given in this paper, one ton low-calcium fly ash can
be utilised to manufacture approximately 2.5 cubic metres
of fly ash-based geopolymer concrete, and hence earn
monetary benefits through carbon-credit trade.
Furthermore, the very little drying shrinkage, the low
creep, and the excellent resistance to sulfate attack offered
by the fly ash-based geopolymer concrete may yield
additional economic benefits when it is utilised in
infrastructure applications.
Concl udi ng remarks
The paper presented a summary of the extensive studies
carried out by the authors on the fly ash-based
geopolymer concrete. Low-calcium fly ash is used as the
source material, instead of the Portland cement, to make
concrete.
Fly ash-based geopolymer concrete has excellent
compressive strength and is suitable for structural
applications. The salient factors that influence the
properties of the fresh concrete and the hardened concrete
have been identified. The elastic properties of hardened
concrete and the behaviour and strength of reinforced
structural members are similar to those of Portland cement
concrete. Therefore, the design provisions contained in
the current standards and codes can be used to design
reinforced fly ash-based geopolymer concrete structural
members.
The fly ash-based geopolymer concrete also shows
excellent resistance to sulfate attack, undergoes low creep,
and suffers very little drying shrinkage. The paper has
identified several economic benefits of using fly ash-
based geopolymer concrete.
References
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policy
138