ACI MATERIALS JOURNAL TECHNICAL PAPER

Title no. 101-M52

On the Development of Fly Ash-Based

Geopolymer Concrete
by Djwantoro Hardjito, Steenie E. Wallah, Dody M. J. Sumajouw, and B.Vijaya Rangan

To reduce greenhouse gas emissions, efforts are needed to develop to date is limited. From the 1998 estimation, the global coal
environmentally friendly construction materials. This paper presents ash production was more than 390 million tonnes annually,
the development of fly ash-based geopolymer concrete. In geopolymer but its use was less than 15%.7 In the future, fly ash produc-
concrete, a by-product material rich in silicon and aluminum, such as tion will increase, especially in countries such as China and
low-calcium (ASTM C 618 Class F) fly ash, is chemically activated
India. From these two countries alone, it is estimated that by
by a high-alkaline solution to form a paste that binds the loose coarse
and fine aggregates, and other unreacted materials in the mixture. the year 2010 the amount of the fly ash produced will be 780
The test results presented in this paper show the effects of various million tonnes annually.5 Accordingly, efforts to use this by-
parameters on the properties of geopolymer concrete. The application product material in concrete manufacture are important to
of geopolymer concrete and future research needs are also identified. make concrete more environmentally friendly.
This paper presents the technology of making geopolymer
Keywords: compressive strength; creep; fly ash; shrinkage; sulfate resistance. concrete using low-calcium (Class F)8 dry fly ash as its
source material and presents the results of laboratory tests
INTRODUCTION conducted on this material.
The contribution of ordinary portland cement (OPC)
production worldwide to greenhouse gas emissions is estimated RESEARCH SIGNIFICANCE
to be approximately 1.35 billion tons annually or approximately Most of the published research on geopolymer studied the
7% of the total greenhouse gas emissions to the earths behavior of pastes. The present study deals with the
atmosphere.1 Also, it has been reported that many concrete manufacture of geopolymer concrete and the influence of
structures, especially those built in corrosive environments, several parameters on the compressive strength. The research
start to deteriorate after 20 to 30 years, even though they data presented in this paper are useful to understand the
have been designed for more than 50 years of service life.2 behavior of geopolymer concrete.
The concrete industry has recognized these issues. For
example, the U.S. Concrete Industry has developed plans to PAST RESEARCH ON GEOPOLYMER
address these issues in Vision 2030: A Vision for the U.S. PASTE OR MORTAR
Concrete Industry. In this document, strategies to retain The chemical compositions of geopolymer materials are
concrete as a construction material of choice for infrastructure similar to zeolite, but they reveal an amorphous micro-
development, and at the same time to make it an environ- structure.6 High-alkaline solutions are used to induce the
mentally friendly material for the future, have been outlined.3 silicon and aluminum atoms in the source materials to
To produce environmentally friendly concrete, Mehta4 dissolve and form the geopolymer paste. The polymerization
suggested the use of fewer natural resources, less energy, and process may be assisted by applied heat, followed by
to minimize carbon dioxide emissions. He categorized these drying. The chemical reaction period is fast, and the required
short-term efforts as industrial ecology. The long-term goal of curing period may be within 24 to 48 h. Davidovits6 reported
reducing the impact of unwanted by-products of industry can that this material possesses excellent mechanical properties,
be attained by lowering the rate of material consumption. does not dissolve in acidic solutions, and does not generate
In line with the above view, one of the efforts to produce any deleterious alkali-aggregate reaction even in the presence
more environmentally friendly concrete is to partially of high alkalinity.
replace the amount of OPC in concrete with by-product Very limited research data are available in the literature.
materials such as fly ash. An important achievement in this Most of the past research on the behavior of geopolymeric
regard is the development of high-volume fly ash (HVFA) material was based on the binder paste or mortar using small
concrete that uses only approximately 40% of OPC, and yet size samples. In addition, some of the conclusions are
possesses excellent mechanical properties with enhanced contradictory. Based on the laboratory tests on fly ash-based
durability performance. The test results show that HVFA geopolymer binder, Palomo, Grutzeck, and Blanco9 have
concrete is more durable than OPC concrete.5 shown that the curing temperature, the curing time, and the
Another effort in this regard is the development of inor- type of activator affected the compressive strength, while the
ganic alumino-silicate polymer, called geopolymer, synthe- solution-to-fly ash ratio was not a relevant parameter.
sized from materials of geological origin or by-product Increase in the curing temperature increased the compressive
materials such as fly ash that are rich in silicon and
aluminum.6 The geopolymer paste can be used as a binder to ACI Materials Journal, V. 101, No. 6, November-December 2004.
produce concrete, instead of the cement paste. MS No. 03-367 received August 28, 2003, and reviewed under Institute publication
policies. Copyright 2004, American Concrete Institute. All rights reserved, including
Fly ash, one of the source materials for geopolymer the making of copies unless permission is obtained from the copyright proprietors.
Pertinent discussion including authors closure, if any, will be published in the September-
binders, is available abundantly worldwide, and yet its use October 2005 ACI Materials Journal if the discussion is received by June 1, 2005.

ACI Materials Journal/November-December 2004 467

Djwantoro Hardjito is affiliated with the Civil Engineering Department at Widya Table 1Composition of fly ash as determined by
Mandira Catholic University, Kupang, Indonesia, and is pursuing a PhD at Curtin XRF (mass %)
University of Technology, Perth, Australia. He received his bachelors degree at Petra
Christian University, Surabaya, Indonesia, and MEng in structural engineering at the SiO2 Al2O3 Fe2O3 CaO Na2O K2O TiO2 MgO P2O5 SO3 LOI*
Asian Institute of Technology, Bangkok, Thailand.
53.36 26.49 10.86 1.34 0.37 0.80 1.47 0.77 1.43 1.70 1.39
Steenie E. Wallah is a PhD student at Curtin University of Technology. He *
Loss on ignition.
received his bachelors degree in civil engineering from Sam Ratulangi University of
Manado, Indonesia, and his masters degree in structural engineering from the
University of Illinois at Urbana-Champaign, Urbana, Ill. dry condition, were mixed together. The grading of this
Dody M. J. Sumajouw is a PhD student at Curtin University of Technology. He combined aggregate had a fineness modulus of 5.0.
received his bachelors degree in civil engineering from Sam Ratulangi University of The aggregates and the fly ash were mixed dry in a pan
Manado, Indonesia, and completed his masters in the Department of Civil and mixer for 3 min. The alkaline solutions and the high-range
Environmental Engineering, Carleton University, Ottawa, Ontario, Canada.
water-reducing admixture were mixed together, then added
B. Vijaya Rangan, FACI, is the Dean of the Faculty of Engineering & Computing, to the solid particles and mixed for another 3 to 5 min. The
Curtin University of Technology. He is a member of ACI Committee 435, Deflection of fresh concrete had a stiff consistency and was glossy in
Concrete Building Structures; and Joint ACI-ASCE Committees 441, Reinforced
Concrete Columns; and 445, Shear and Torsion. His current interests include appearance. The mixture was cast in 100 x 200 mm cylinder
geopolymer concrete. steel molds in three layers. Each layer received 60 manual
strokes and vibrated for 10 s on a vibrating table. Five cylinders
were prepared for each test variable.
strength. The type of alkaline activator that contained Immediately after casting, the samples were covered by a
soluble silicates resulted in a higher reaction rate than when film to avoid the loss of water due to evaporation during
hydroxides were used as the only activator. curing at an elevated temperature. After being left in room
While van Jaarsveld, van Deventer, and Lukey10 confirmed temperature for 30 to 60 min, specimens were cured in an
the importance of curing at elevated temperature for fly ash- oven at a specified temperature for a period of time in
based geopolymeric material, they found that curing for a accordance with the test variables selected.
longer period of time at elevated temperature weakened the At the end of the curing period, the 100 x 200 mm test
microstructure. Barbosa, MacKenzie, and Thaumaturgo11 cylinders were removed from the molds and kept in the
stated that the water content played an important role on the plastic bag for 6 h to avoid a drastic change of the environ-
properties of geopolymer binders, besides the chemical mental conditions. The specimens were then left to air dry at
composition of the oxides used as activators. 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
WHAT IS GEOPOLYMER CONCRETE? loading rate and other test procedures used were in accordance
In the authors experimental work, geopolymer is used as with the details specified in the relevant Australian Standard
the binder, instead of cement paste, to produce concrete. for testing OPC concrete.12
The geopolymer paste binds the loose coarse aggregates, Numerous trial mixtures of geopolymer concrete were
fine aggregates and other unreacted materials together to made and tested in the laboratory. The data collected from
form the geopolymer concrete. The manufacture of these studies indicated that the salient parameters affecting
geopolymer concrete is carried out using the usual concrete the compressive strength of geopolymer concrete are as
technology methods. listed below:
As in the portland cement concrete, the aggregates occupy Silicon oxide (SiO2)-to-aluminum oxide (Al2O3) ratio
the largest volume, that is, approximately 75 to 80% by mass, by mass of the source material (fly ash); this ratio
in geopolymer concrete. The silicon and the aluminum in the should preferably be in the range of 2.0 to 3.5 to make
fly ash are activated by a combination of sodium hydroxide good concrete (Table 1);
and sodium silicate solutions to form the geopolymer paste Activator liquids-to-source material (fly ash) ratio by mass;
that binds the aggregates and other unreacted materials. Concentration of sodium hydroxide (NaOH) liquid mea-
sured in terms of Molarity (M), in the range of 8 to 16 M;
EXPERIMENTAL WORK Sodium silicate-to-sodium hydroxide liquid ratio by
mass; the effect of this parameter depends on the com-
In the present experimental work, low-calcium (Class F)8
position of the sodium silicate solution;
dry fly ash obtained from the silos at a local power station
Curing temperature in the range of 30 to 90 C;
was used as the base material. The chemical composition of
Curing time in the range of 6 to 96 h; and
the fly ash, as determined by x-ray fluorescence (XRF) Water content in the mixture.
analysis, is given in Table 1. It must be noted that only the binder (which usually
Analytical grade sodium hydroxide in flake form (NaOH occupy approximately 20 to 25% of the total mass) is
with 98% purity) and sodium silicate solutions (Na2O = 14.7%, different in geopolymer concrete when compared to OPC
SiO2 = 29.4% and water = 55.9% by mass), were used as concrete. Therefore, the effects of properties and grading of
the alkaline activators. To avoid the effect of unknown aggregates were not investigated in this study.
contaminants in the mixing water, the sodium hydroxide
flakes were dissolved in distilled water. The activator solution EFFECT OF PARAMETERS
was prepared at least one day prior to its use. To improve the In this section, we present the influence of various parameters
workability of fresh concrete, a commercially available on the compressive strength of geopolymer concrete as
naphthalene-based high-range water-reducing admixture was observed in the laboratory tests. In the later part of the paper,
used. Four types of locally available aggregates, that is, 20, the test results on drying shrinkage, creep, and sulfate
14, and 7 mm aggregate, and fine sand, in saturated surface resistance are presented. Each of the test data points plotted

468 ACI Materials Journal/November-December 2004

in various graphs corresponds to the mean value of the Table 2Effect of parameters on
compressive strengths of five test cylinders in a series. The compressive strength
standard deviations are plotted on the test data points as the 7-day compressive
error bar. Concentration of strength after curing
NaOH liquid in Sodium silicate/NaOH at 60 C for 24 h,
In the experimental work, the activator liquids-to-fly ash Mixture molarity (M) liquids ratio by mass MPa
ratio by mass was kept constant at approximately 0.35. The A-1 8M 0.4 17.3
coarse and fine aggregates constituted approximately 77% A-2 8M 2.5 56.8
by mass in all mixtures.
A-3 14M 0.4 47.9
Table 2 gives the composition of four different mixtures
A-4 14M 2.5 67.6
and the 7-day compressive strengths of 100 x 200 mm test
cylinders cured at 60 C for 24 h. In Table 2, the second
column gives the concentration of NaOH liquid in terms
of molarity (M). The third column is the ratio of sodium
silicate/NaOH by mass in liquid form. The last column
gives the mean 7-day compressive strengths of test cylinders.

Concentration of sodium hydroxide

In Table 2, the only difference between the Mixtures A-1
and A-3 is the concentration of sodium hydroxide as
measured by Molarity (second column). Mixture A-3 with
higher concentration of NaOH yielded higher compressive
strength than Mixture A-1. A similar trend is also observed
for the Mixtures A-2 and A-4.

Sodium silicate-to-sodium hydroxide liquid ratio Fig. 1Effect of curing temperature on compressive strength.
The effect of sodium silicate-to-NaOH ratio in liquid form
on compressive strength can be seen by comparing the
compressive strengths of Mixtures A-1 and A-2 as well as
A-3 and A-4 (Table 2). For Mixtures A-1 and A-2, although
the concentration of NaOH liquid (in terms of molarity) is
the same, in Mixture A-2 the sodium silicate/NaOH ratio is
higher than that of Mixture A-1. This produced a higher
compressive strength in Mixture A-2 than Mixture A-1. A
similar trend is also observed in the results of Mixtures A-3
and A-4.
The results given in Table 2 reveal that the interrelation of
various oxides contained in the mixture composition affects
the compressive strength.

Curing temperature
Figure 1 shows the effect of curing temperature on the
compressive strength for Mixtures A-2 and A-4. All other Fig. 2Influence of curing time on compressive strength for
test variables were held constant. Higher curing temperature Mixture A-2.
resulted in larger compressive strength, even though an
increase in the curing temperature beyond 60 C did not The results of these tests are shown in Fig. 3. The addition of
increase the compressive strength substantially. high-range water-reducing admixture improved the work-
ability of the fresh concrete, but has very little effect on the
Curing time compressive strength up to approximately 2% of this admixture
Figure 2 shows the influence of curing time on the to the amount of fly ash by mass. Beyond this value, the
compressive strength for Mixture A-2. Longer curing time compressive strength decreased from 56.5 MPa for 2% of
improved the polymerization process resulting in higher high-range water-reducing admixture to 46 MPa for 3.5% of
compressive strength. The results indicate that a longer this admixture.
curing time at 60 C does not produce weaker material as Figure 3 shows two sets of data. In one set, the test
claimed by van Jaarsveld, van Deventer, and Lukey.10 cylinders were allowed to rest for 60 min after casting and
However, the increase in strength for curing periods then placed in the oven for curing at 60 C for 24 h. In the
beyond 48 h is not significant. other set, there was no rest period and the test cylinders were
placed in the oven immediately after casting.
High-range water-reducing admixture The results plotted in Fig. 3 show very little difference
In fresh state, the geopolymer concrete has a stiff consis- between the strengths of the two sets of specimens. This is an
tency. Although adequate compaction was achievable, an important outcome in practical applications of geopolymer
improvement in the workability was considered as desirable. concrete. For instance, when geopolymer concrete is used in
A series of tests were therefore performed on Mixture A-2 precast concrete industry, the results in Fig. 3 indicate that
(Table 2) to study the effect of adding commercially available there is sufficient time available between casting of products
naphthalene-based high-range water-reducing admixture. and sending them to the curing room.

ACI Materials Journal/November-December 2004 469

 To obtain the data plotted in Fig. 4, the fresh concrete
was allowed to stand at room temperature after mixing and
prior to being placed in molds for a certain period of time.
This time is referred to as the delay time in Fig. 4. For
instance, a delay time of 60 min means that the fresh
concrete was cast in the molds 60 min after mixing, and a
zero delay time indicates that casting took place immediately
after mixing. The slight variation in the compressive
strengths plotted in Fig. 4 is probably due to minor changes
in the laboratory room temperature and humidity.

Water content in the mixture

Previous research by Barbosa, MacKenzie, and
Thaumaturgo11 on geopolymer pastes showed that the
water content in the mixture played an important role on the
properties of geopolymer binders. To study the effect of water
Fig. 3Effect of high-range water-reducing admixture content on the compressive strength of geopolymer concrete,
addition on compressive strength for Mixture A-2. several tests were performed. The basic mixture used in this
series of tests was Mixture A-4 (Table 2). The other details of
the mixtures were the same as those used in the earlier part of
this paper. The percentage of the high-range water-reducing
admixture to the mass of fly ash was 1.5%, the delay time was
30 min, and there was no rest period.
The effect of water content is illustrated in Fig. 5 by plotting
the compressive strength versus water-to-geopolymer solids
ratio by mass. 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 (that is, the mass of Na2O
and SiO2 in sodium silicate solution).
To vary the water-to-geopolymer solids ratio, water was
added to Mixture A-4 (Table 2). The water-to-geopolymer
Fig. 4Influence of delay time on compressive strength for solids ratio of Mixture A-4 was 0.174. By adding extra water
Mixture A-2. of 10.6 kg/m3, the water-to-geopolymer solids ratio became
0.197, and by adding extra water of 21.2 kg/m3, this ratio
was 0.220. The 7-day compressive strengths of geopolymer
concrete cylinders produced from these mixtures are plotted in
Fig. 5 for different curing temperatures.
As expected, the addition of water improved the work-
ability of the mixtures. The test data shown in Fig. 5
demonstrate that the compressive strength of geopolymer
concrete decreases as the ratio of water-to-geopolymer
solids by mass increases. The trends of these test results are
similar to those observed by Barbosa, MacKenzie, and
Thaumaturgo11 for their tests on geopolymer pastes. The test
trends are somewhat analogous to the well-known effect of
water-to-cement ratio on the compressive strength of OPC
concrete, although the chemical processes involved in the
formation of the binders of both these types of concretes are
entirely different.
Fig. 5Effect of the water-to-geopolymer solids ratio on
The results shown in Fig. 5 also confirm that an increase
compressive strength.
in the curing temperature increased the concrete compressive
strength. However, increasing the curing temperature from
Handling time 75 to 90 C did not show any significant gain in the
Due to lack of a suitable method to determine the initial compressive strength. Similar results were reported by
setting time of geopolymer concrete, the setting time of the previous researchers working on geopolymer binders9,10
fresh concrete could not be measured. The laboratory using various source materials.
experience by the authors, however, showed that the fresh
concrete could be handled up to 120 min after mixing Age of concrete
without any sign of setting and without any degradation in the Figure 6 shows the effect of age of concrete on the
compressive strength (Fig. 4). compressive strength. The concrete specimens for this purpose

470 ACI Materials Journal/November-December 2004

were prepared without adding any high-range water-reducing
admixture, and there was no delay time and rest period.
Because the chemical reaction of the geopolymer paste is
a fast polymerization process, the compressive strength does
not vary with the age of concrete, when cured for 24 h. This
observation is in contrast to the well-known behavior of
OPC concrete, which undergoes a hydration process and
hence gains strength over time.13

Unit weight
The unit weight of concrete primarily depends on the unit
weights of aggregates used in the mixture. Because the type of
aggregates in all mixtures did not vary, the unit weight of the
concrete varied only marginally between 2330 to 2430 kg/m3.

DRYING SHRINKAGE, CREEP, AND Fig. 6Compressive strength at different ages for Mixture A-2.
SULFATE RESISTANCE
Figure 7 shows the measured drying shrinkage and creep
strains of geopolymer concrete produced using Mixture A-2.
The test specimens were cured for 24 h at 60 C. The
percentage of high-range water-reducing admixture by mass
of fly ash was 1.5%. There was no rest period before casting,
and the delay time after mixing was 30 min. The 7-day
compressive strength was 53.7 MPa. The creep specimens
were loaded on the seventh day to produce a sustained stress
of 22 MPa (approximately 40% of the compressive strength).
The details of test specimens and test procedure for creep
tests were in accordance with the relevant Australian Standard
for OPC concrete.
Figure 7 shows that the drying shrinkage strains are
extremely small indeed. The ratio of creep strain-to-elastic
strain (that is, creep factor) reached a value of approximately
Fig. 7Drying shrinkage and creep strains for Mixture A-2.
0.30 in approximately 6 weeks. Beyond this time, the creep
factor increased only marginally.
To evaluate the resistance of geopolymer concrete to reinforced and prestressed) elements and other products
sulfate attack, a series of tests were performed. The test needed for infrastructures.
specimens were soaked in a 5% sodium sulfate (Na2SO4) Based on their laboratory experience, the authors found
solution for periods of time. The test results reported that the cost of geopolymer concrete per cubic meter is
elsewhere14 showed that after 12 weeks of exposure, there approximately the same as that of portland-cement concrete.
were no significant changes in the compressive strength, the If one considers the impact of the possible carbon dioxide tax
mass, and the length of test specimens. on the price of cement and the environmental advantage of
utilization of fly ash, the geopolymer concrete may prove to be
APPLICATIONS AND ECONOMICS OF economically advantageous.
GEOPOLYMER CONCRETE
The authors have used conventional methods, similar to FUTURE RESEARCH NEEDS
those used in the case of portland cement concrete, for As in the case of portland cement concrete, the properties of
mixing and placing of geopolymer concrete. For a specified constituent materials in the geopolymer concrete mixture will
compressive strength, the required workability of the influence the physical properties of the hardened concrete. It
concrete, in terms of slump, can be obtained by adjusting the is therefore necessary to collect experimental data on various
water content and the concentration (in terms of molar) of properties and use these data to formulate appropriate codes of
sodium hydroxide in the mixture. For instance, the authors practice. Future research should also focus on the fundamental
have successfully manufactured many mixtures with a science of geopolymers to determine the mechanism of
compressive strength in the range of 30 to 80 MPa and the chemical reaction during setting and hardening.
slump of concrete varying from 100 to 250 mm depending
on the molar of sodium hydroxide and the mass of extra CONCLUSIONS
water added to the mixture. This paper presented the development of geopolymer
A series of 175 x 175 x 1500 mm reinforced geopolymer concrete. The binder in this concrete, the geopolymer paste, is
concrete columns were also manufactured and tested in the formed by activating by-product materials, such as low-calcium
laboratory. The compressive strength of the concrete in these (Class F) fly ash, that are rich in silicon and aluminum.
structural columns ranged between 42 to 66 MPa, and the In the experimental work, the fly ash (Table 1) from a local
slump was approximately 240 mm. The details of this research power generation plant was used as the source material. A
will be presented in forthcoming papers. With the current state combination of sodium silicate solution and sodium
of knowledge, the authors believe that geopolymer concrete is hydroxide solution was used as the activator. The
ideally suitable for the manufacture of precast concrete (both geopolymer paste binds the loose coarse and fine aggregates

ACI Materials Journal/November-December 2004 471

and any unreacted materials to form the geopolymer This paper also identified the applications of geopolymer
concrete. Based on the experimental work reported in this concrete and future research needs.
paper, the following conclusions are drawn:
1. Higher concentration (in terms of molar) of sodium REFERENCES
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472 ACI Materials Journal/November-December 2004

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