Flyash Geopolymer Concrete As Future Concrete: Authors:-Rachit Ghosh, Anil Kumar and Sanjay Kumar

International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec.
2013
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954
Flyash Geopolymer Concrete as Future Concrete

Authors:- Rachit Ghosh 1, Anil Kumar 2 and Sanjay Kumar 1
CSIR-National Metallurgical Laboratory,Jamshedpur
National Institute of Foundry and Forge Technology, Hatia, Ranchi
Abstract
Demand for concrete as construction material is on the increase so as the

production of cement. It is estimated that ~6-8% of total CO2 is generated from construction
industry. To reduce the concrete industry‟s carbon footprint, blended cements are in use in the
market. The research trend is directed towards more eco-friendly concrete such as
geopolymer. Recently the focus of research has been shifted on use of fly ash for
geopolymerisation. This is based on the alumino-silicate composition of fly ash, it‟s easy
availability, better flow ability and improved durability.
The chemical composition of geopolymer is similar to that of zeolite, but amorphous

in microstructure. Flyash-based geopolymer concrete show excellent short and long-term
properties. The properties and uses of geopolymers are being explored in many scientific and
industrial disciplines like modern inorganic chemistry, physical chemistry, colloid chemistry,
mineralogy, geology, and in all types of engineering process technologies. The current paper
presents scope of flyash based geopolymer concrete as future concrete, summarizes and
critically analyses the most important research findings.
Keywords: Geopolymers; Zeolites; Microstructure; Compressive strength
Contents:
1. Introduction
2. Raw materials for Future Concrete
3. Focus for use of flyash as principal ingredient
4. Mechanisms – Chemical Aspects
5. Characterization and other analytical techniques
6. Factors affecting compressive strength
7. Long term performance
8. Conclusions
9. Acknowledgement
10. References
R S. Publication (http://rspublication.com), [email protected]. Page 260

International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec. 2013
1.Introduction
Many concrete structures, especially those built in corrosive environments, start to
deteriorate after 20 to 30 years, even though they have been designed for more than 50 years
of service life (Mehta.P.K,2001)1.
The search for environment friendly construction materials is imperative, as the world
is facing serious problems due to environmental degradation. There is a significant
expectation on the industry to reduce carbon dioxide (CO2) emissions to the atmosphere. In
view of this, one of the efforts to produce environmentally friendly concrete is to reduce the
use of Portland cement by using by-product materials, such as fly ash. It is known that
production of one ton of Portland cement accounts for about one ton of carbon dioxide
released to the atmosphere, as the result of de-carbonation of limestone in the kiln during
manufacturing of cement, i.e.:
5 CaCO3 + 2 SiO2 → 3 CaO.SiO2 + 2 CaO.SiO2 + 5 CO2 (1)
Alkali Activated systems was first introduced by Victor Glukhovsky and subsequently
Pavel Krivenko developed in the 1950s in Ukraine. The alkaline alumino-silicate cementitious
systems were first called „„soil silicates‟‟ (Glukhovsky,19592,19653,19894; Krivenko and
Kovalchuk, 20075). The term „„geopolymers‟‟ was first introduced to the chemical world by
Davidovits in the mid 1970‟s (Davidovits, 19936). The main barrier that geopolymerisation
has to overcome and become accepted by the industry is mainly related with the entrenched
position of OPC.
2. Raw materials for future concrete

The production of consistent geopolymer concrete from heterogeneous industrial
waste sources is a challenging issue for the minerals industry, since raw material suitability
cannot be fully guaranteed by elemental composition analysis (Fernańdez-Jimeńez and
Palomo, 20037). As far as flyash based geopolymer concrete are concerned, the mechanical
strength increases due to the formation of an Al-rich alumino-silicate gel during the first stage
of alkaline activation of ash particles, and may further increase as a result of the Si enrichment
of the material (Fernańdez-Jimeńez et al.,20068). Therefore, it is critical to manipulate Al
and Si dissolution from the raw materials, through pre-processing and/or use of combinations
of raw materials with different reactivity (Duxson et al., 2007c9).
The manufacture of lightweight geopolymer based building materials (pre-formed
blocks) can be effectively manufactured at 250C starting from fly ash (S. Andini et. Al.). The

properties of the final products depend on a number of variables such as composition of the
starting mixture, nature of the alkali metal silicate and polycondensation conditions
(temperature and time).The original quantitative method for the determination of reacted
water and alkali metal silicate previously developed for a metakaolinite-based system has
been successfully applied to the systems investigated for flyash based systems.The results
have shown that the kinetics of the polycondensation reaction is less favoured at 40 and 60 0C
in respect to 250C and that a strong enhancement occurs at 850C.
Another important issue that has to be considered during geopolymerisation is the
assessment of the effect of contaminants present in the raw materials that add reaction
pathways and affect the properties of the final product as a result of changes in setting times,
slump, strength and shrinkage. This issue is very well covered for flyash geopolymers in a
recent publication (Duxson et al., 2007c9).
3. Focus for use of flyash as principal ingredient
According to the American Concrete Institute (ACI) Committee 116R, fly ash is
defined as “the finely divided residue that results from the combustion of ground or powdered
coal and that is transported by flue gasses from the
combustion zone to the particle removal system”. Fly ash
particles are typically spherical, finer than Portland cement
and lime, ranging in diameter from less than 1 µm to no more
than 150 µm. The chemical composition is mainly composed
of the oxides of silicon (SiO2), aluminium (Al2O3), iron
(Fe2O3), and calcium (CaO), whereas magnesium, potassium,
sodium, titanium, and sulphur are also present in a lesser
amount. The characteristics of fly ash that generally
considered are loss on ignition (LOI), fineness and
uniformity. LOI is a measurement of un-burnt carbon
remaining in the ash. Fineness of fly ash mostly depends on the operating conditions of coal
crushers and the grinding process of the coal itself. Finer gradation generally results in a more
reactive ash and contains less carbon.
A series of tests were performed on geopolymer concrete made using fly ash as the
source material (D. Hardjito,et.al, 200410). Based on the results of his tests the following
conclusions are drawn:

1. The H2O-to-Na2O molar ratio or the water-to-geopolymer solids ratio by mass

influences the compressive strength of fly ash-based geopolymer concrete. As these
ratios increased, the compressive strength decreased.
2. The Na2O-to-SiO2 molar ratio of the geopolymer mixture does not have any
significant effect on the compressive strength of fly ash-based geopolymer concrete
for the range of values of this ratio between 0.095 and 0.120.
3. Extra water improved the workability of the concrete mixture. However, water
content alone did not have any significant influence on the compressive strength,
provided that either the H2O-to-Na2O molar ratio or the water-to-geopolymer solids
ratio by mass remained constant.
4. Mechanisms – Chemical Aspects
The polymerisation process yields polymeric Si-O-Al-O bonds, as described by:

Mn [ – (Si – O2 ) z – Al – O ] n . wH2O (2)
where M is the alkaline element, the symbol – indicates the presence of a bond, z is 1, 2, or 3,
and n is the degree of polymerisation.
Geopolymerisation (Hua Xu et.al,200011) also involves a chemical reaction between
various alumino-silicate oxides Al in IV–V fold coordination with silicates under highly
alkaline conditions, yielding polymeric Si–O–Al–O bonds, which can be presented
schematically as follows:
The above two reaction paths indicate that any Si–Al materials might become sources
of geopolymerisation (Van Jaarsveld et al., 199712). According to (Davidovits 199413),
geopolymeric binders are the amorphous analogues of zeolites and require similar
hydrothermal synthesis conditions. Reaction times, however, are substantially faster, which

results in amorphous to semi-crystalline matrices compared with the highly crystalline and
regular zeolitic structures. The electron diffraction analysis conducted by (Van Jaarsveld et al.
199914) showed that the structure of geopolymers is amorphous to semi-amorphous. In
alumino-silicate structures silicon is always 4 co-ordinated, while aluminium ions can be 4 or
6 co-ordinated. It is possible that the coordination number of aluminium in the starting
materials will have an effect on its eventual bonding in the matrix.
5. Characterization and other analytical techniques
A number of relatively simple or advanced techniques may be used to obtain

maximum information and elucidate geopolymerisation mechanisms. The ability of Al–Si
minerals to undergo geopolymerisation may be predicted by specific surface area
measurements, which provide an indication of how much surface area participates in
heterogeneous reactions within a solid–fluid system (Van Jaarsveld,200015).
The XRD patterns (E. Álvarez-Ayuso a, X. Querol, et.al.,200816) of flyash samples as

well as those of geopolymers synthesised from them. The XRD patterns of flyashes displayed
peaks in Fig.3 due to quartz, mullite and
iron oxides either magnetite or hematite
or both, also other crystalline phases such
as anhydrite, calcite, anorthite-albite,
illite and microcline were also detected
in some samples, but always at trace
level. In addition to these crystalline
components, abroad peak in the region
20–3202θ arising from the glassy phase
of flyashes could be observed in all the
patterns. For all the studied flyashes the
intensity of this peak was progressively
decreased after the geoplymerisation
processes with the activation medium
concentration increase. This decrease is
related to the high glassy phase content
of flyashes.

The morphological features (E. Álvarez-Ayuso a, X. Querol,et.al.,200816) of the

original fly ashes and derived geopolymers in Fig.4 shows different degree of reaction was
observed at the different concentrations of activation medium for the different fly ashes is
subject of study. When the least concentrated alkaline solution (5M NaOH) was employed in
the activation process this always yielded the lowest degree of reaction, although great
differences between fly ashes were apparent, with the FA-1 and FA-3 samples being the most
extreme examples.
Fourier transform infrared spectroscopy (FTIR) analysis in Fig. 5 shows the infrared
spectra of the original fly ashes and geopolymer samples synthesised from them. Original fly
ash samples (E. Álvarez-Ayuso a, X. Querol,et.al,200816) showed two main spectral peaks at
about 480 and 1110 cm−1, the former has been assigned to Si–O–Si and O–Si–O bending,
and the latter to Si–O–Si and Al–O–Si
asymmetric stretching. In addition to
these two bands, the spectra of untreated
fly ashes showed three other peaks
associated with their Al–Si framework,
generally of much lesser intensity, at
about 810, 750 and 590 cm−1, being
attributed to Si–O–Si and Al–O–Si
symmetric stretching[Farmer.V.C,197417
and J.A. Gadsden,197518] was generally manifested. After the fly ash activation, besides
spectral changes related to the Si–Al framework, also broad bands at about 3485 and 1655
cm−1 were present in the spectra of geopolymer samples, these bands are associated to –OH
stretching and H–O–H bending, respectively, being characteristic of weakly bound molecules
of water either surface adsorbed or trapped in large cavities.
6. Factors affecting compressive strength
Compressive strength development is a primary measure of the utility of materials

used in different applications of the construction industry (Hardjito,200419).
Compressive Strength at Different Ages

The effect of age of concrete on the compressive strength

is show below in Fig. 6. The chemical reaction of the geopolymer
gel is due to substantially fast polymerisation process, the
compressive strength does not vary with the age of concrete. This
Fig. 6 Compressive Strength of observation is in contrast to the well-known behaviour of OPC
Different Ages.
concrete, which undergoes hydration process and hence gains
strength over the time.
Effect of Curing Time

The influence of curing time on the compressive strength is
shown in Fig. 7. Longer curing time improves the polymerisation
process resulting in higher compressive strength. The results
shown indicate that longer curing time does not produce weaker
Fig. 7 Influence of Curing time on material as claimed by van Jaarsveld18 et al. However, the increase
Compressive Strength.
in strength after curing for 48 hours is not significant.
Effect of Superplasticizer
In the fresh state, the geopolymer concrete has a stiff consistency. Although adequate
compaction was achievable, an improvement in the workability
was considered as desirable. Tests were therefore performed to
study the effect of adding commercially available naphthalene-
based superplasticizer. The results of these tests are shown in
Fig. 8 Effect of Super plasticizer on Figure 8. The addition of superplasticizer improved the
the Compressive Strength
workability of the fresh concrete but had very little effect on the
compressive strength up to about two percent of this admixture to the mass of fly ash. Beyond
this value, there is some degradation of the compressive strength.
Effect of Water Content in the Mix
Previous research by Barbosa et.al,200020 on geopolymer pastes showed that the water
content in the mix played an important role on the properties of
geopolymer binders. The addition of water improved the
workability of the mixtures. The results shown in Figure 9 clearly
demonstrate the effect of the molar ratio of H2O-to-Na2O on the
Fig. 9 Effect of the molar H2O to-
Na2O on Compressive Strength compressive strength of geopolymer concrete. The trends of
these test results by Hardjito,200418 are similar to those observed
by Barbosa et. al,200019 for their tests on geopolymer pastes.

The test data shown in Figure 10 demonstrate that the

compressive strength of geopolymer concrete decreases as the
ratio of water-to-geopolymer solids by mass increases. The test
trends shown in Figure 10 are somewhat analogous to the well-
known effect of water-to-cement ratio on the compressive strength
Fig. 10 Effect of water-to-
of OPC concrete, although the chemical processes involved in the geopolymer solids ratio on
Compressive Strength
formation of the binders of both these types of concretes are
entirely different.
7. Long term performance
The long term behaviour of geopolymer concrete by D. Hardjito et.al. 200421 were
being showed by the test results that the drying shrinkage strains of fly ash-based geopolymer
concretes were found to be insignificant. The ratio of creep strain to-elastic strain (called
creep factor) reached a value of 0.30 in approximately 6 weeks after loading on the 7th day
with a sustained stress of 40% of the compressive strength. Beyond this time, the creep factor
increased only marginally (Hardjito.D et.al. 200322).
A series of tests were performed on the resistance of fly ash-based geopolymer

concrete to sulfate attack. After soaking the specimens in a 5% sodium sulfate (Na2SO4)
solution for 12 weeks, there were no significant changes in the compressive strength, the
mass, and the length of the test specimens (Wallah, S.E. et.al. 200323). These series of tests on
the long-term behaviour of the fly ash based geopolymer concrete are continuing for a period
of one year. Davidovits,199924 has reported earlier that geopolymer cement is acid resistant.
He also reported that geopolymer materials do not generate any dangerous alkali-aggregate
reaction, even in the presence of high alkali content.
Phair et al. (200325) investigated alumino-silicate geopolymer and hydrogel

microstructure by differential scanning calorimetry (DSC). This technique was used to
determine the glass transition temperature of precursor sodium silicate and sodium aluminate
solutions. The use of DSC is also very useful for optimisation purposes, due to its ability to
assess the reactivity of the products obtained under different calcination conditions (Cioffi et
al., 200326).
Leaching tests are a very powerful tool to determine the degree of ion immobilisation
within a geopolymeric system.Yunsheng et al.(200727) conducted leaching tests which

revealed that geopolymers can effectively immobilise Cu and Pb. Zaharaki et al. (200628)
conducted durability and structural integrity studies for geopolymers made of slag and
kaolinite. The specimens were almost unaffected when immersed in distilled- and seawater
over a period of one year, whereas noticeable loss of strength was seen when immersed in 1N
HCl or simulated acid rain solutions.
Alkali-activated fly ash cement exhibited good durability when exposed to sulphates

and seawater. However, in highly acidic media loss of mass due to dealumination and poorer
mechanical strength was seen(Fernańdez-Jimeńezetal.,200729).Geopolymers derived from
various combinations of granulated blast-furnace slag, Class C fly ash,clay, sand, and basalt
were tested for resistance to solid particle erosion. The geopolymer that did not contain flyash
eroded most rapidly. Fly ash promoted dissolution of slag and sand aggregates, but the
mechanism involved in improved erosion resistance has yet to be identified (Goretta et al.,
200730).
8. Conclusions
Geopolymer concrete shows significant potential to be a material for the future,

because it is not only environmentally friendly but also possesses excellent mechanical
properties, both in short term and long term, and durability. Significant information is already
available in the literature to utilise geopolymer concrete technology in practical applications
such as precast concrete products and waste encapsulation.
Due to the involvement of very strong research groups considerable progress has been
made in this field over the last years and it is believed that relatively soon the
geopolymerisation potential for large scale applications in the construction and minerals
industry will be well established. The knowledge gained will enable broad exploitation of the
technological potential of these materials and the production of tailored geopolymers.
Future study in the field of the application of geopolymer is required for its
commercial uses. Establishment of geopolymerisation as a feasible technology for the
management of industrial wastes will contribute to considerable savings in disposal costs,
recycling of wastes, and substantial reduction of greenhouse gas emissions and enhanced
social acceptance of the industry.

9. Acknowledgement
The authors acknowledges the infrastructure support and guidance of the two
Institutes CSIR-National Metallurgical Laboratory,Jamshedpur and National Institute of
Foundry and Forge Technology, Hatia, Ranchi.
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International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec.

Flyash Geopolymer Concrete as Future Concrete

CSIR-National Metallurgical Laboratory,Jamshedpur

National Institute of Foundry and Forge Technology, Hatia, Ranchi

Demand for concrete as construction material is on the increase so as the

The chemical composition of geopolymer is similar to that of zeolite, but amorphous

Keywords: Geopolymers; Zeolites; Microstructure; Compressive strength

R S. Publication (http://rspublication.com), [email protected]. Page 260

5 CaCO3 + 2 SiO2 → 3 CaO.SiO2 + 2 CaO.SiO2 + 5 CO2 (1)

2. Raw materials for future concrete

R S. Publication (http://rspublication.com), [email protected]. Page 261

3. Focus for use of flyash as principal ingredient

R S. Publication (http://rspublication.com), [email protected]. Page 262

1. The H2O-to-Na2O molar ratio or the water-to-geopolymer solids ratio by mass

4. Mechanisms – Chemical Aspects

The polymerisation process yields polymeric Si-O-Al-O bonds, as described by:

R S. Publication (http://rspublication.com), [email protected]. Page 263

5. Characterization and other analytical techniques

A number of relatively simple or advanced techniques may be used to obtain

The XRD patterns (E. ´Alvarez-Ayuso a, X. Querol, et.al.,200816) of ﬂyash samples as

R S. Publication (http://rspublication.com), [email protected]. Page 264

The morphological features (E. ´Alvarez-Ayuso a, X. Querol,et.al.,200816) of the

6. Factors affecting compressive strength

Compressive strength development is a primary measure of the utility of materials

Compressive Strength at Different Ages

R S. Publication (http://rspublication.com), [email protected]. Page 265

The effect of age of concrete on the compressive strength

Effect of Curing Time

R S. Publication (http://rspublication.com), [email protected]. Page 266

The test data shown in Figure 10 demonstrate that the

7. Long term performance

A series of tests were performed on the resistance of fly ash-based geopolymer

Phair et al. (200325) investigated alumino-silicate geopolymer and hydrogel

R S. Publication (http://rspublication.com), [email protected]. Page 267

Alkali-activated ﬂy ash cement exhibited good durability when exposed to sulphates

Geopolymer concrete shows significant potential to be a material for the future,

R S. Publication (http://rspublication.com), [email protected]. Page 268

1. Mehta, P. K., Reducing the Environmental Impact of Concrete, Concrete

R S. Publication (http://rspublication.com), [email protected]. Page 269

R S. Publication (http://rspublication.com), [email protected]. Page 270

29. Fernańdez-Jimeńez, A., Garcıá-Lodeiro, I., Palomo, A., 2007. Durability of

R S. Publication (http://rspublication.com), [email protected]. Page 271

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