International Journal of Emerging Technology and Advanced Engineering

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ALKALI Activated FLY-ASH Based Geopolymer Concrete

Ammar Motorwala1, Vineet Shah2, Ravishankar Kammula3, Praveena Nannapaneni4, Prof. D. B. Raijiwala5
1
Department of Applied Mechanics, SVNIT-Surat, Gujarat-395007
2
Department of Civil Engineering, IIT-Delhi
3,4
Department of Civil Engineering, SVNIT-Surat, Gujarat-395007
5
Associate Professor, Department of Applied Mechanics, SVNIT-Surat, Gujarat-395007
Palomo et al (1999)
more often applied to the
Abstract- Considering the increasing demand for
description of soils which
suggested
that
pozzolans
developing alternative construction materials, due to the
are consolidated with a
such
as
blast
furnace
slag
growing environmental concerns, this paper discusses the
small amount of Portland
feasibility of alkali activated geo-polymer concrete, as a might be activated using
cement
to
enhance
alkaline
liquids
to
form
a
future construction material. The main objective of this study
strength
and
stability.
binder
and
hence
totally
involves observation of structural behaviours of the fresh fly
Geo-polymer cements are
ash-based geo-polymer concrete, understanding the basicreplace the use of OPC in
an example of the broader
concrete.
Hence,
in
this
mixture proportioning of fly ash-based geo-polymer concrete
binders,
which
also
paper an effort is made to
and evaluating various economic considerations.
identify and study the
activated metallurgical
of
salient
slags and other related
Keywords- Alkali activated fly-ash based geo-polymer,effect
construction material for green building, geo-polymer parameters that affects
materials
concrete, eco-friendly construction material, low calciumthe properties of lowbased geo-polymer concrete.
A. Constituents of geocalcium fly ash-based
polymer concrete
geo-polymer concrete and
9. INTRODUCTION
the properties of concrete
There are two main
at varied concentrations
constituents of geoConcrete usage around the world is second only to of alkali solutions and
polymers, namely the
water and Ordinary Portland Cement (OPC) is
how the change in
source materials and the
conventionally used as the primary binder to produce
concrete. The environmental issues associated with the temperature affects the
alkaline liquids. The
production of OPC are too many. The cement industry is strength characteristics.
source materials for geoheld responsible for some of the CO2 emissions. The
polymers
based
on
35. GE
amount of the carbon dioxide released during the
alumina-silicate should
OP
manufacturing of OPC due to the calcination of limestone
be rich in silicon (Si)
OL
and combustion of fossil fuel is in the order of one ton for
and aluminium (Al).
YM
every ton of OPC produced. In addition, the extent of
These could be natural
ER
energy required to produce OPC is only next to steel and
minerals
such
as
aluminium.
Geo-polymer is a term
kaolinite,
clays,
etc.
The demand for Portland cement is increasing day by covering a class of
Alternatively,
byalumino-silicate
day and hence, efforts are being made in the constructionsynthetic
materials with potential
product materials such
industry to address this by utilising supplementaryuse in
as fly ash, silica fume,
materials and developing alternative binders in concrete; a number
of areas, essentially
a replacement
slag,asrice-husk
ash, red
the application of geo-polymer technology is one such for Portland
cement and for mud,
advanced
high-tech
etc. could
be used
alternative. The abundant availability of fly ash worldwide
composites,
ceramic
as
source
materials.
The
creates opportunity to utilise this by-product of burningapplications or as a form
choice
of
the
source
coal, as a substitute for OPC to manufacture concrete. of cast stone. The name
materials for making
When used as a partial replacement of OPC, in theGeo-polymer was first
geo-polymers depends
presence of water and in ambient temperature, fly ash applied to these
reacts with the calcium hydroxide during the hydration materials by Joseph Davidovits inon factors such as
process of OPC to form the calcium silicate hydrate (C-S-similar materials had been availability, cost, type of
application, and specific
former Soviet Union
H) gel.
the
1950s,
demand of the end users.
In 1978, Davidovits (1999) proposed that binders could since
originally
under
the
name
be produced by a polymeric reaction of alkaline liquids
with the silicon and the aluminium in source materials of "soil cements". However,
geological origin or by-product materials such as fly ash this name never found
and rice husk ash. He termed these binders as geo-widespread usage in the
English language, as it is
polymers.

159

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The characteristics of
fly ash that generally
According to the American Concrete Institute (ACI) considered are loss on
Committee 116R, fly ash is defined as the finely divided ignition (LOI), fineness
residue that results from the combustion of ground or and uniformity. LOI is a
powdered coal and that is transported by flue gasses frommeasurement of un-burnt
the combustion zone to the particle removal systemcarbon remaining in the
(ACI Committee 232 2004). Fly ash is removed from the ash. Fineness of fly ash
combustion gases by the dust collection system, either mostly depends on the
mechanically or by using electrostatic precipitators, operating conditions of
before they are discharged to the atmosphere. Fly ash coal crushers and the
particles are typically spherical, finer than Portland grinding process of the
itself.
Finer
cement and lime, ranging in diameter from less than 1 coal
gradation
generally
m to no more than 150 m.
results in a more reactive
The chemical composition is mainly composed of the ash and contains less
oxides of silicon (SiO2), aluminium (Al2O3), ironcarbon.
(Fe2O3), and calcium (CaO), whereas magnesium,
potassium, sodium, titanium, and sulphur are also presentC. Use of Fly Ash in
Concrete
in a lesser amount.
B. Fly Ash

Figure 1 Ungraded fly-ash

Fly ash plays the role

of an artificial pozzolan,
where its silicon dioxide
content reacts with the
calcium hydroxide from
the cement hydration
process to form the
calcium silicate hydrate
(C- S-H) gel. The
spherical shape of fly
ash often helps to
improve the workability
of the fresh concrete,
while its small particle
size also plays as filler
of voids in the concrete,
hence to produce dense
and durable concrete.
An
important
achievement in the use
of fly ash in concrete is
the development of high
volume fly ash (HVFA)
concrete
that
successfully replaces the
use of OPC in concrete
up to 60% and yet
possesses
excellent
mechanical
properties
with enhanced durability
performance.
D. Alkaline Liquids

Figure 2 Graded fly-ash

The most common

alkaline liquid used in
geo-polymerisation is a
combination of sodium
hydroxide (NaOH) or

potassium
hydroxide
(KOH)
and
sodium
silicate or potassium
silicate
(Davidovits
1999; Palomo et al. 1999;
Barbosa et al. 2000; Xu
and van Deventer 2000;
Swanepoel and Strydom
2002; Xu and van
Deventer 2002). The use
of a single alkaline
activator
has
been
reported (Palomo et al.
1999; Teixeira- Pinto et
al. 2002),
Palomo et al (1999)
concluded that the type
of alkaline liquid plays
an important role in the
polymerisation process.
Reactions occur at a high
rate when the alkaline
liquid contains soluble
silicate, either sodium or
potassium
silicate,
compared to the use of
only alkaline hydroxides.
Xu and van Deventer
(2000) confirmed that the
addition
of
sodium
silicate solution to the
sodium
hydroxide
solution as the alkaline
liquid enhanced the
reaction between the
source material and the
solution.
Furthermore,
after a study of the geopolymerisation of sixteen
natural Al-Si minerals,
they found that generally
the
NaOH
solution
caused a higher extent of
dissolution of minerals
than the KOH solution.
E. Super Plasticisers:
In order to improve
the workability of fresh
concrete,
high-range
water-reducing
naphthalene based super
plasticiser was added to
the mixture. The dosage
of super plasticizer also
has an effect on the
compressive strength of
the concrete.

160

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F. Polymerisation
The specific super plasticizer used in the mixture Process
made for the project is Sikament-581.As a super
are
plasticizer it substantially improved the workability Geo-polymers
without increasing the amount of water and hence members of the family of
reducing the risk of segregation. It results in normal set inorganic polymers. The
even when overdosed. It gives a good surface finish andchemical composition of
as it is chloride free it doesnt attack reinforcement or the geopolymer material
pre-stressed cables if any. Apart from this, various other is similar to natural
super plasticisers, which can be used, are categorized as zeolitic materials, but the
is
Plasticiser
A
(Naphthalene microstructure
amorphous.
The
Formaldehyde Condensate)
process
2Super Plasticiser B (Sulphonated Melamine polymerization
involves a substantially
Formaldehyde Condensate)
fast chemical reaction
3Super Plasticizer C (Aqueous De under alkaline condition
Policarboxilato)
on Si- Al minerals, which
4Super Plasticizer D (Aqueous Solution of results in a threeLigno Sulphonate)

1Super

dimensional

polymeric

The main chemical base is Modified Naphthalenechain and ring structure

Formaldehyde and the dosage varies from 0.6-2% of the consisting of Si-O- Al-O
weight of fly ash.
bonds

M n [(SiO2) z
AlO2] n .
wH 2O
Where: M = the
alkaline element or
cation such as potassium,
sodium or calcium;
The symbol
indicates
the
presence of a
bond, n is the
degree of polycondensation
or
polymerisation;
z is 1, 2,3, or
higher, up to 32.
The schematic
formation of geopolymer
material can be shown as
described by

Al

n(OH)3-Si-On(Si2O5,Al2O2)+2nSiO2+4nH2O+
materials)
+ NaOH or KOH
(Na+,K+)-( + +
(OH)
NaOH or KOH Na ,K +
Al
-O-Si-(OH)
3
Si-O-Al -O-Si-O-) + 4nH2O (OH)2
n(OH)3-Si-O-Al -O-Si-(OH)3 (Siment on
that occurs
polymer
O
O
the surface
in
the
mixture,
of the fly
O
ash
formation
therefore,
particle
of
geoplays noG. Chemical
The chemical reaction may polymers.
role in the
The
composition of the geocomprise the following steps
This water,
chemical
band
correspond
reaction polymers
1 Dissolution of Siexpelled
ing to Si-O
from
the
that
takes
Differences
due
to
and Al atoms from
and Al-O
various
conditions
of
the
place;
it
the source materialgeoalkaline activation may vibrations
through the actionpolymer
merely
be
of hydroxide ions. matrix
found on the FTIR can
provides be
observed
spectra.
in the
2 Transportation or during the
the
orientation
or curing and
original fly
workabilit
condensation of
ash at
further
y
to
the
precursor
ions
1,080drying
mixture
into monomers.
1,090
periods,
during
3 Setting or poly- leaves
-1
handling.
condensation/poly
cm but
this
band
This is in
merisation
of behind
is
monomers
into discontinu
contrast to
displaced
polymeric
towards
ous Nanothe
lower
structures.
values in
pores
in
chemical
the geoHowever, these three stepsthe matrix,
reaction of
polymers.
can overlap with each otherwhich
water in a
and
occur
almostprovide
Portland
simultaneously, thus makingbenefits to
cement
it difficult to isolate andthe
mixture
examine each of them
performan
during the
separately (Palomo et al.
ce
of
geohydration
1999).
Figure 3 Beginning of the
polymers.
process.
geoThe last term in EquationThe water
polymer
reveals that water is releasedin a geos phase
develop
during the chemical reaction

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A prevailing part of
The shift is interpreted as a consequence of the Al water gets lost during
penetration into the original structure of the Si-O-S the heating
skeleton (an analogous phenomenon was observed in
of 150zeolites). The more pronounced the shift, the greater the at a temperature
o
extent of the Al penetration from the glassy parts of the 200 C. No crystalline
hydrates
could
be
4detected in the geofly ash into the [SiO4] skeleton.
polymers microstructure.
The geo-polymerization process (alkaline activation of Therefore, the geocan
be
fly ashes in the aqueous environment at pH>12) polymer
accompanied by the hardening of the material is different characterized as threedimensional
inorganic
from the hydration processes of inorganic binders (e.g. polymer with a summary
Portland cement). This process obviously takes place formula:
predominantly via solution when, first, the fly ash
Mn [-(Si-O)z
particles are dissolved and a new geo-polymers structure
Al-O]n .
is then formed starting from the solution (Fig 3).
w(H2O).
In addition to the preparation conditions also the
presence of Ca atoms entering the Si- O-Al-O skeleton
and compensating the charge on Al atoms plays an
important role.

61. EXPERIME
NTAL
DEDUCTIO
NS

1. Mixture Proportions:
The
mixture
proportion
of
concrete
contains
coarse
aggregate, fine aggregate,
fly ash, Sodium silicate
solution
and
NaOH
solution. Three different
mixtures with 8M, 10M,
12M and 14M were
prepared
and
compressive strengths of
these sample cubes were
Figure 4 Detailed character of the geo-polymers (the paste w = measured.
0.27, fracture surface, after 28 days)
The sodium hydroxide
These charges are usually compensated by Na+ ions. (NaOH) solids were
Nevertheless Ca+2 ions may probably interconnect dissolved in water to
individual Si-O-Al-O chains thus giving rise to a make the solution. The
stronger structure characterized by higher strength values mass of NaOH solids in a
varied
resulting from the alkaline activation of fly ashes in solution
depending
on
the
presence of Ca-containing materials.
concentration
of
the
Water is present in the geo-polymers structure as this
is revealed by the GTA curves. Water obviously occurs in solution expressed in
the form of free water but water molecules also exist terms of molar, M.
For instance, NaOH
with
a
inside the structure; furthermore, OH groups are also solution
present.

concentration of 8M
consisted of 8x40 = 320
grams of NaOH solids
(in flake or pellet form)
per litre of the solution,
where
40
is
the
molecular weight of
NaOH. Similarly, the
mass of NaOH solids
per kg of the solution for
14M concentration was
measured as 404 grams.
The sodium silicate
solution and the sodium
hydroxide solution were
mixed together at least
one day prior to use to
prepare the alkaline
liquid. On the day of
casting of the specimens,
the alkaline liquid was
mixed together with the
super plasticizer and the
extra water (if any) to
prepare
the
liquid
component
of
the
mixture.

Figure 5 Schematic
diagrams for mixing
process

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Table 1
Mixture proportions

Aggregates (kg)
Mixture No.

20mm

10mm

4.75mm

Fly-ash
(kg)

1
2
3
4
5
6
7
8

5
5
10.2
12
12
12
12
12

12
12
6.8
5
5
5
5
5

7.3
7.3
7.3
7.3
7.3
7.3
7.3
7.3

6
6
4
4.8
4.8
4.5
4.8
4.5

Water
content
2
2.25
2.1
2.3
2
2.1
2.2
2

Strength
(N/mm2)

(litres)

1.09
3.48
30.95
24.4
15.26
3.7
2.18
1.74

Table 2
Mixture proportion

Mixture
No.
1
2
3
4
5
6
7
8

Molarities
10 M
12 M
14 M
14 M
16 M
16 M

IV.

Sodium

Potassium

Hydroxide
(kg)
0.173
0.238
0.267
0.267
0.293
0.293

Hydroxide
(kg)
0
0
0
0
0
0
0.314
0.314

EFFECT OF SALIENT PARAMETERS

A. Ratio of Alkaline Liquid-to-Fly Ash

The ratio of alkaline liquid-to-fly ash, by mass, was
not varied. This ratio was taken as 0.4.

Strength
40

0
N/mm2

compressive
strength

20

4
Flyash
(Kg)

4.
8

Sodium
(kg)
1.657
1.657
1.657
1.657
1.657
1.657
1.657
1.657

Silicate plasticizer Strength

(ml)
(N/mm2)
90
48
60
50
50
50
50
50

1.09
3.48
30.95
24.4
15.26
3.7
2.18
1.74
B. Concentration of
Sodium Hydroxide
(NaOH) Solution
Mixtures were made to
study the effect of
concentration of sodium
hydroxide solution on the
compressive strength of
concrete.
Complete
details of these mixtures
and their properties are
given in Table. The test
cubes were left at
ambient conditions for
about 30 minutes prior to
start of dry curing in an
oven. The curing time
was 24 hours at various
temperatures.
The
measured
7th
day
compressive strengths of
test cubes are given in
Table.

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Sodium Hydroxide
(Kg)

D. Curing Temperature

strengthcompressive
N/mm2

Higher
curing
temperature resulted in
larger
compressive
strength, although an
40
increase in the curing
30
temperature beyond 80
20
degrees Centigrade did
10
Sodiu not
increase
the
0
m compressive
strength
substantially.
Three
different
curing
temperatures were used,
i.e. 25, 80 and 100
NaO
degrees
Centigrade.
H
Curing was performed in
an oven for 24 hours.
The results shown in
C. Effect of Molarity of Alkaline Solutions
Table confirm that higher
temperature
Mixture Concentration
Ratio of Compressive curing
in
higher
th resulted
of
NaOH Sodium strength at 7 compressive strength.
solution
Silicate
day in Mpa
(In molars)
to
(Cured at 80
Curing
0
C)
NaOH
Mixture
Temperature
in
solution
O
C
1
10 M
2.5
1.5
1
25
2
12 M
2.5
2.6
2
60
14 M

2.5

26.67

16 M

2.5

25.28

compressive strength
N/mm2

35
30

25
20
15
10
5
0
1
0 12 14 16
M M M M
Molari
ty

80

E. Addition of Super
plasticizer

In fresh state, the geopolymer concrete has a

stiff
consistency.
Although
adequate
compaction
was
achievable,
an
improvement in the
workability
was
Strengt considered as desirable.
h As the concentration of
Super
plasticizer
increases the amount of
water required decreases.
Series
of
tests,
performed to study the
effect of super plasticizer
on
fly-ash
concrete
indicated that super
plasticizer improved the
workability of the fresh
concrete but had very
little effect on the

compressive strength up
to 2% of this admixture
to the amount of fly ash
by mass.
F. Water Content of
Mixture
In ordinary Portland
cement (OPC) concrete,
water in the mixture
chemically reacts with
the cement to produce a
paste that binds the
aggregates. In contrast,
the water in a lowcalcium fly ash-based
geo-polymer
concrete
mixture does not cause a
chemical reaction. In
fact,
the
chemical
reaction that occurs in
geo-polymers produces
water that is eventually
expelled from the binder.
G. Density
The
density
of
concrete
primarily
depends on the unit mass
of aggregates used in the
mixture. Because the
type of aggregates in all
the mixtures did not
vary, the density of the
low-calcium fly ashbased
geo-polymer
concrete varied only
marginally
between
2330 to 2430 kg/m3.

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Higher concentration
(in terms of molar) of
sodium
hydroxide
1. Cement Concrete (Grade M20)
solution results in higher
compressive strength of
Quantity
Amount
Particulars
Rate
fly-ash
based
geo(in Kg)
(Rs.)
polymer concrete and
Cement
400
5.2
2080
higher the ratio of sodium
silicate-to-sodium
Fine
640
1000
420
hydroxide ratio by mass,
Aggregate
higher is the compressive
Coarse
strength of fly ash based
1280
1200
1008
geo-polymer concrete, as
Aggregate
the curing temperature in
Super
the range of 30C to 90C
0.0044
75000
330
plasticizer
increases,
the
compressive strength of
Total
3838
fly
ash-based
geo
Note: All the rates are as per the standard rates in the polymer concrete also
prevalent Indian market during the year 2012.
increases, longer curing
time, in the range of 4 to
B. Geo-polymer Concrete (Grade M20)
96 hours (4 days),
Quantity
Amount
produces
higher
Particulars
Rate
(in Kg)
(Rs.) compressive strength of
fly
ash-based
geoFine
640
1000
420 polymer concrete.
Aggregate
With
the
main
Coarse
1280
1200
1008 objective of finding the
Aggregate
effect
of
varied
concentrations of alkaline
Super
0.0044
75
330 solutions on the strength
plasticizer
characteristics of the
the
test
NaOH
19.77
40
791 concrete,
conducted, yielded certain
important findings from
Na2SiO3
49.4
25
1235 the material collected
from local vendors.
Fly Ash
500
3.3
1650
1 In the process of
conducting the test
Total
5434
fly
ash
were
procured from two
different
vendors
Note: All the rates are as per the standard rates in the
which also led to
prevalent Indian market during the year 2012.
contrasting variation
in the results. Thus,
VI.
DISCUSSION
highlighting
the
importance of choice
The main objective of this study was to find the
of fly ash.
effect of varied concentrations of alkaline solutions on
2
Selection
and
the strength characteristics of the concrete. We expect
grading of
fine
that the combined use of KOH and NaOH would help
aggregate
also
in achieving a more rigid structure and hence improve
played
the strength characteristics.
a major role. For a
Based on the general finding, the following
conclusions were drawn:
ratio of 0.67 (10mm:
20mm) compressive
strength of 26.67
N/mm2, and for the
same molarity with a
ratio
of
0.42
comparatively very
low
compressive
strength
was

22. RATE ANALYSIS

measured,
highlighting
how
important it is to
select a proper ratio
for grading.

3 A

general
increase in the
compressive
strength
with
increase in the
molarity was seen.
4 Importance of
curing temperature
also was clearly
seen in the tests
conducted. For test
conducted at 25C,
strength
obtained
was 0.872 N/mm2,
while,
on
the
contrary, for 80C2 it
was 30.95 N/mm .
5 Another
important
observation
was
that curing
under
normal
sunlight
yielded
strength
of
16
N/mm2. This test
was done in the
month of February
2012 in Sardar
Vallabhbhai
National
Institute
of
Technology,
Surat(Gujarat)
in
India, where the
ambient
temperature
was
0
around
25
C,
hence, similar test
when conducted in
hotter months can
yield still better
results.
Thus,
making insitu use of
fly ash concrete a
future possibility.

6 Curing

when
done by wrapping
with plastic bag
gave
better
compressive
strength
as
it
preserves
the
moisture.

7 In

the
rate
analysis carried, it
came out clearly
with the available
resources fly ash
based concrete is
expensive
than
cement
concrete
and
hence
not

economical. However in the broader picture

considering carbon credit, waste disposal and
limited availability of non-renewable resources,

geo-polymer
concrete is sure to
play major role in

construction
industry.

165

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REFERENCES

[9]

Malhotra V. M, High
performance high volume
fly-ash concrete, ACI
concrete
international
24(7): 1-5, 2002.

[1]

Davidovits, J. "Geopolymers: Inorganic Polymeric New

Materials" Journal of Thermal Analysis 37: 1633-1656, 1991.

[2]

Davidovits, J. Chemistry of Geopolymeric Systems, [10]

Malhotra V. M.,
Terminology. Geopolymer 99 International Conference, France,
Role of supplementary
(1999).
cementing materials and
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