A : STRUCTURE AND MATERIAL / 39

International Conference on Sustainable Infrastructure and Built Environment in Developing Countries

November, 2-3, 2009, Bandung, West Java, Indonesia
ISBN 978-979-98278-2-1

TheEffectofDosageandModulusofActivatorontheStrengthof
AlkaliActivatedSlagandFlyAshBasedGeopolymerMortar


Andi Arham Adam
1,*
, Tom Molyneaux
2
, Indubhushan Patnaikuni
2
, David Law
3

1
Universitas Tadulako, Palu , Indonesia
2
RMIT University, Melbourne, Australia
3
Herriot Watt University, Edinburgh, Scotland, UK
*Corresponding author: adam.arham@gmail.com

Abstract
The use of industrial by-products to partly substitute ordinary Portland cement (OPC) has
become common practice. However, the total replacement of OPC has only recently become
a focus of research due to the environmental impact, as the production of OPC greatly
contributes to the production of CO
2
to the atmosphere. Research has shown that alkali
activated binders can achieve similar strengths to both ordinary Portland cement and blended
cements. The aim of the work reported in this paper is to compare the strength of two different
alkali activated cementitious materials; an alkali activated slag (AAS), and a fly ash based
geopolymer mortar. To achieve this purpose, one set of mortars has been prepared with slag
activated by a low dosage of alkaline solution and another set with fly ash activated by high
alkaline solution. Variable alkali moduli were employed for both types of alkaline solution.
The study shows that dosage of activator has a significant influence on the strength of both
AAS and fly ash based geopolymer mortars. However, there is a limit for increasing the
strength by increasing the alkali modulus (M
s
), beyond this limit, a reduction of strength is
likely to occur. Given the alkali modulus and activator dosage, it was found that M
s
=1 in 5%
Na
2
O for AAS and M
s
=1.25 in 15% Na
2
O for fly ash based geopolymer were the optimum
mix composition providing the highest compressive strength for the mortars.

Keywords: alkali, activator, geopolymer, modulus.


1. Introduction
It is widely known that the production of Portland cement has a high energy requirement
and contributes large quantities of CO
2
to the atmosphere. However, at present Portland
cement is still the main binder in concrete construction and the search for more
environmentally friendly materials is essential.
One possible alternative is the use of alkali-activated binder using industrial by-products
containing silicate materials (Gjorv, 1989, Philleo, 1989). The most common industrial
by-products used as binder materials are fly ash and ground granulated blast-furnace slag
(GGBS). The GGBS has been widely used as a cement replacement material due to its latent
hydraulic properties, while fly ash has been used as a pozzolanic material to enhance
physical, chemical and mechanical properties of cements and concretes (Swamy, 1986).
The GGBS reacts directly with water, but requires an alkali activator. In concrete, this
activator is the Ca(OH)
2
released from the hydration of Portland cement. By contrast fly ash is
a pozzolanic material which reacts with Ca(OH)
2
from Portland cement hydration forming
calcium silicate hydrate (C-S-H) as the hydration product of Portland cement. Thus, when
used with Portland cement, GGBS or fly ash will not start to react until some Portland cement
hydration has taken place.
Recent research has shown that it is possible to use fly ash or slag as a sole binder in
40 / A : STRUCTURE AND MATERIAL
mortar by activating them with an alkali component, such as; caustic alkalis, silicate salts, and
non silicate salts of weak acids (Talling and Brandstetr, 1989). There are two models of alkali
activation. Activation by low to mild alkali of a material containing primarily silicate and
calcium will produce calcium silicate hydrate gel (C-S-H), similar to that formed in Portland
cements, but with a lower Ca to Si ratio (Bakharev and Patnaikuni, 1997, Brough and
Atkinson, 2002). The second mechanism involves the activation of material containing
primarily silicate and aluminates using a highly alkaline solution. This reaction will form an
inorganic binder through a polymerization process (Xu, 2002, Sindhunata, 2006). The term
Geopolymeric is used to characterize this reaction, and accordingly, the name
geopolymer has been adopted for this type of binder (Davidovits, 1991). The geopolymeric
reaction differentiates geopolymer from other types of alkali activated materials (eg. alkali
activated slag) since the product is polymer rather than a C-S-H gel.
In order to investigate the effect of dosage and modulus of activator on the strength of
alkaliactivatedslagandflyashbasedgeopolymer,mortars have been prepared with GGBS
activated by a low dosage of alkaline solution while others prepared with fly ash activated by
high alkaline solution. Variable alkali moduli were employed for both type of alkaline
solution.

2. Materials and Methods
The ground granulated blast-furnace slag (GGBS) supplied conformed to Australian
Standard AS 3582.2-2001. The fly ash was a low calcium fly ash from Gladstone power
station conforming to AS 3582.1-1998. The chemical analysis of these materials is given in
Table 1.
Sodium silicate solution (Na
2
SiO
3
) of 1.53g/cc density with an alkali modulus (M
s
) of 2
(Na
2
O = 14.7% and SiO
2
= 29.4%) was used. Sodium hydroxide solution (NaOH) was prepared
by dissolving sodium hydroxide pellets in deionised water.

Table 1 Composition of cementitious materials (%)
Component Slag Fly ash
SiO
2
33.45 49.45
Al
2
O
3
13.46 29.61
Fe
2
O
3
0.31 10.72
CaO 41.74 3.47
MgO 5.99 1.3
K
2
O 0.29 0.54
Na
2
O 0.16 0.31
TiO
2
0.84 1.76
P
2
O
5
0.53
Mn
2
O
3
0.40 0.17
SO
3
2.74 0.27
S
2-
0.58 0.21

A water to binder ratio of 0.5 was used to prepare all AAS mortars. In the case of the fly
ash based geopolymer mortars, the water to solid ratio of 0.37 was used instead of the water
to binder ratio. The amount of water in the mix was the sum of the water contained in the
sodium silicate, sodium hydroxide and the added water, while the amount of solid was the
sum of the weight of fly ash, and the solid contained in the activator solution. The sand to
binder ratio was 2.75
Table 2 summarizes the composition of the alkaline activators. Liquid sodium silicate and
sodium hydroxide were blended in different proportions, providing the alkali modulus in
solution (mass ratio of SiO
2
to Na
2
O) ranging from 0.75 to 1.25 for AAS mix and 1 to 1.5 for
fly ash based geopolymer mix. Two dosages of Na
2
O by slag mass in the solution, 3% and 5%
A : STRUCTURE AND MATERIAL / 41
were investigated for the AAS mix. For the Geopolymer mix, activator dosages of 10% and
15% by fly ash weight were used.

Table 2 Details of the proportions of the alkaline solution

Mortar

binder
Alkaline solution
Na
2
O (% by binder
weight)
M
s

(SiO
2
/Na
2
O)
AAS3-0.75 Slag 3 0.75
AAS3-1 Slag 3 1
AAS3-1.25 Slag 3 1.25
AAS5-0.75 Slag 5 0.75
AAS5-1 Slag 5 1
AAS5-1.25 Slag 5 1.25
G10-1 Fly ash 10 1
G10-1.25 Fly ash 10 1.25
G10-1.5 Fly ash 10 1.5
G15-1 Fly ash 15 1
G15-1.25 Fly ash 15 1.25
G15-1.5 Fly ash 15 1.5

The mixing was performed using a 5-liters Hobart mixer, the mix was then poured into 5
cm cubic moulds and vibrated for 1 minute. One set of the AAS specimens was left for 24
hours at room temperature and demoulded before being subjected to 80C steam curing for a
further 24 hours and then allowed to cool in a humidity cabinet at 20 C and 90% relative
humidity (RH) for a further 24 hours and subsequently stored at room temperature before
testing. Another set of the specimens was cured at 20C water for 6 days after demoulding and
then left at room temperature prior to testing
The structural integrity of the geopolymer specimens left at room temperature was not
good enough to allow the specimens to be demoulded before three days, therefore a different
curing regime was applied. After leaving for 24 hours at room temperature, the specimens
were wrapped with cling film and left in the oven for 24 hours at 90C and cooled before they
were demoulded. The specimens were then left at room temperature until testing.
Compressive strength measurements of mortars were performed on an MTS machine
under a load control regime with a loading rate of 20 MPa/min. Three to five cubes were
tested for each data point. The specimens were tested at 3, 7, and 28 days after casting.

3. Results and Discussions
3.1.EffectofmodulusanddosageofalkalineactivatoronthestrengthofAASmortar
Alkali modulus which is defined as the ratio of Na
2
O to SiO
2
in the activator has a
significant influence on the strength of AAS mortars as seen in Figure 1 and 2. However the
strength improvement due to the increase in alkali modulus was only observed up to M
s
=1 for
both 3% and 5%Na
2
O AAS mortars.
Increasing the activator dosage (%Na
2
O by slag weight) also increased the strength
significantly. However it is recommended that the maximum activator dosage of 5% by slag
weight is used. Higher values can result in efflorescence and brittleness problems depending
on slag type, activator nature, and curing temperature. Additionally, a very high activator
dosage would be uneconomical.
AAS mortar was found to be very sensitive to heat curing. As can be seen from Figure
1and 2, heat cured AAS mortars developed rapidly at an early age compared to normal cured
specimens.
The 3-days strength of heat cured 3%Na
2
O specimens were more than 85% of its 28-days
strength, while the normal cured specimens had the 3-days strength approximately 60% of the
28-days strength.
42 / A : STRUCTURE AND MATERIAL
Similar trends were also found with 5%Na
2
O AAS mortars, the heat curing specimens
gained approximately 90% of the 28-days strength within 3 days. The 3-days strength of heat
cured specimens even exceeded the 28-days strength of normal cured specimens. The 28-days
strength of heat cured specimens was approximately 8-20% higher than that of normal cured
specimens.
Given the alkali modulus and activator dosage it was found that M
s
=1 in 5% Na
2
O is the
optimum mix composition providing the highest compressive strength for AAS mortar.

0
10
20
30
40
50
60
70
A
A
S
3
-
0
.
7
5
A
A
S
3
-
1
A
A
S
3
-
1
.
2
5
A
A
S
5
-
0
.
7
5
A
A
S
5
-
1
A
A
S
5
-
1
.
2
5
C
o
m
p
r
e
s
s
i
v
e

s
t
r
e
n
g
t
h

(
M
P
a
)
3 days
7 days
28 days

Figure 1 Strength of alkali activated slag mortars with different alkali dosage and modulus
subjected to heat curing



0
10
20
30
40
50
60
70
A
A
S
3
-
0
.
7
5
A
A
S
3
-
1
.
0
0
A
A
S
3
-
1
.
2
5
A
A
S
5
-
0
.
7
5
A
A
S
5
-
1
.
0
0
A
A
S
5
-
1
.
2
5
c
o
m
p
r
e
s
s
i
v
e

s
t
r
e
n
g
t
h

(
M
P
a
)
3 days
7 days
14 days
28 days

Figure 2 Strength of alkali activated slag mortars with different alkali dosage and modulus
subjected to normal curing

3.2. Effect modulus and dosage of alkaline activator on strength of fly ash based
geopolymermortar
The alkali modulus of the activator has a marginal influence on the strength of the fly ash
based geopolymer mortar, and at higher dosage, the increase in strength was only observed up
to M
s
=1.25 (as seen from Figure 3). In this study, increasing the alkali modulus means an
A : STRUCTURE AND MATERIAL / 43
increase in soluble silicates and consequently an increase in the reaction rate (a higher dosage
of reactants induces a higher reaction rate). However increasing alkali modulus (for the same
alkali dosage) also means reducing the amount of hydroxide which is needed to dissolve
silicate and aluminate monomer from the fly ash grain. Strength development does not seem
to show a clear correlation with the age, as can be seen from Figure 3. A small reduction was
observed in certain mixtures as well as some increase in others at 7 days age. Although all
mixtures showed a small increase in strength at 28 days, the differences appear to be caused
by the variability in the batch of the mix and the effect of micro cracking due to drying at high
temperature in the oven.
It can also be seen from Figure 3 that the optimum mix composition is with M
s
=1.25 in
15% Na
2
O which gives the highest compressive strength for a fly ash based geopolymer
mortar.

0
10
20
30
40
50
60
70
80
90
G10-1.00 G10-1.25 G10-1.5 G15-1.00 G15-1.25 G15-1.5
C
o
m
p
r
e
s
s
i
v
e

S
t
r
e
n
g
t
h

(
M
P
a
)
3 days 7 days 28 days

Figure 3 Strength of fly ash based geopolymer mortars with different alkali dosage and
modulus subjected to heat curing

4. Conclusions
Slag and fly ash are two industrial by products which can be used to produce alkali
activated binders for concrete.
The alkali activated binders produced using slag and fly ash are not only environmentally
friendly but also have additional benefits such as high early and ultimate strength
depending on the mix composition.
Activator dosage has significant influence on the strength of both AAS and fly ash based
geopolymer mortars.
There is a limit to the increase of the alkali modulus, i.e 1 for AAS and 1.25 for
geopolymer mortar, beyond this limit, a reduction of strength is likely to occur due to a
reduction of hydroxide while the excess silicate will not contribute to the strength
Given the alkali modulus and activator dosage, it was found that M
s
=1 in 5% Na
2
O for
AAS and M
s
=1.25 in 15% Na
2
O for fly ash based geopolymer is the optimum mix
composition providing the highest compressive strength on the mortars.

5. References
Bakharev, T. & Patnaikuni, I. (1997) Microstructure and durability of alkali activated
cementitious pastes. In: Ong, K. C. G. (Ed.) the Fifth International Conference on
Structural Failure, Durability and Retrofitting. Singapore, Singapore Concrete Institute.
Brough, A. R. & Atkinson, A. (2002) Sodium silicate-based, alkali-activated slag mortars:
Part I. Strength, hydration and microstructure. Cement and Concrete Research, 32,
865-879.
44 / A : STRUCTURE AND MATERIAL
Davidovits, J. (1991) Geopolymers: Inorganic Polymeric New Materials. Journal of Thermal
Analysis, 37, 1633-1656.
Gjorv, O. E. (1989) Alkali Activation of a Norwegian Granulated Blast Furnace Slag. In:
Malhotra, V. M. (Ed.) third international conference on fly ash, silica fume, slag, and
natural pozzolans in concrete. Trondheim, Norway, American Concrete Institute.
Philleo, R. E. (1989) Slag or other supplementary materials? In: Malhotra, V. M. (Ed.) third
international conference on the use of fly ash, silica fume, slag and natural pozzolan in
concrete. Trondheim, Norway, American Concrete Institute.
Sindhunata (2006) A Conceptual Model of Geopolymerisation. Department of Chemical and
Biomolecular Engineering. Melbourne, The University of Melbourne.
Swamy, R. N. (1986) Cement replacement materials, Glasgow, Surrey University Press.
Talling, B. & Brandstetr, J. (1989) Present State and Future of Alkali-Activated Slag
Concretes. In: Malhotra, V. M. (Ed.) third international conference on fly ash, silica fume,
slag, and natural pozzolans in concrete. Trondheim, Norway, American Concrete Institute.
Xu, H. (2002) Geopolymerisation of Aluminosilicate Minerals. Department of Chemical
Engineering. Melbourne, The University of Melbourne.