148 The Masterbuilder - April 2012 www.masterbuilder.co.

in
Geopolymer Concrete
Literature Survey on Geopolymer
Concretes and a Research
Plan in Indian Context
A comprehensive literature survey on various aspects of Geopolymer Concretes (GPCs) has been provided in this paper to under-
stand the nature of GPCs from engineering applications point of view so that a rational technical plan for development of GPCs with
given aluminosilicate sources (such as fly ash, blast furnace slag powder etc) can be formulated. The literature survey indicates that
geopolymer (GP) is only one of the many names used for describing the binder formed with alumino-silicate gel structure. Com-
paratively, more papers are published on science of geopolymerisation where often paste is utilised. Concretes and mortars based
on GPs are also reported, but, lesser in numbers. The science of GP has not yet reached the stage where GPC mix can be made by
user by just adding water as it has happened in case of Portland cement technology. This requires the actual engineer on site to be
aware of chemical nature of the GP binding action involved. However, enough qualitative information is available on the mechanical
strength so that GPC mixes can be developed to achieve the desired level of strength for use in structures. The second part of this
paper would concentrate on the typical research plan to develop engineering properties of GPCs based on the information available
in the literature.
Portland Cement Based Concretes
Cement concrete is often considered as an artificial
stone which is made by mixing Portland cement (P-C),
water, sand, and crushed stone aggregate to produce a
mouldable mixture. This concrete, during the last century,
has developed into the most important building material
in the world; the beginning was made by August Perret,
in 1902, by designing and building an apartment building
in Paris employing a system for reinforced concrete
(columns, beams, and slabs, but with no load-bearing
walls) [URLa]. Concrete is, now, an essential product
used in a variety of constructions including infrastructure
and industrial sectors. This is partly due to the fact that
concrete is produced from natural materials available in all
parts of the globe, and partly due to the fact that concrete is
a versatile material, giving architectural freedom. Concrete
is used more than any other man-made material in the
world [Bjorn Lomborg, 2001]. More than a ton of concrete
is produced every year for each human on the earth planet,
making the concrete as the second most widely consumed
substance on the earth after water [Sara Hart, 2008]. But,
the environmental aspects of concrete are now being
discussed with a view to develop an eco-friendly material
of construction. In this regard, it would be interesting to
note that the embodied carbon dioxide (ECO
2
) of a tonne
of concrete was reported to be in the range of 75176
kg CO
2
/tonne, depending upon the type and method of
mix design [URLb]. The embodied energy (EE) content
of concrete is also very high which could vary from 400
to 600 kWH/m3 of concrete. Therefore, there is an urgent
need for making the concretes more eco-friendly so that
both ECO
2
and EE of concrete are reduced. It has been
well established that any developmental activities aimed
towards improvement of quality of life of human beings
involves always a large amount of construction activities
which in turn require production of varieties of concretes.
Therefore, development of concretes with more eco-friendly
characteristics has become tasks of many scientists all
over the world.
Need for Alternate Concretes
Continuous technological upgrading and assimilation of
Rajamane N. P.
1
, Nataraja M. C.
2
, Lakshmanan N
3
,
and Ambily P S
4
1
Head, CACR, SRM University,
2
Professor, Dept. of Civil Engg, SJCE,
3
Former Director, CSIR-SERC,
4
Scientist, CSIR-SERC
www.masterbuilder.co.in The Masterbuilder - April 2012 149
latest technology has been going on in the cement industry.
Presently, 93% of the total capacity in the industry in India
is based on modern and environment-friendly dry process
technology and only 7% of the capacity is based on old
wet and semi-dry process technology. There is a scope
for waste heat recovery in cement plants and thereby
reduction in emission level.
The cement production is highly energy intensive next
only to steel and aluminium (also consumes significant
amount of non-renewable natural resources such as lime
stone deposits, coal, etc.). The EE of P-C being about 1.3
kWh / kg, is a very high quantity. A tonne of P-C production
involves emission of about a tonne of CO
2
, which is a
greenhouse gas causing global warming. More than 7%
of world CO
2
production is attributed towards production
of P-C. Moreover, among the greenhouse gases, CO
2

contributes about 65% of global warming [McCaffery,
2002]. Therefore, the Portland cement industry does not
fit the contemporary desirable picture of a sustainable
industry. There is an urgent need to find an alternate to P-
C in order to make the construction industry eco-friendly.
However, the new binder material should also possess
satisfactory strength and durability characteristics which
are comparable, preferably superior to those conventional
concretes (CCs) based on P-C.
Geopolymer as Alternate to Portland Cement
A new binder material, known as geopolymer was first
introduced by Davidovits in 1978 to describe a family of
mineral binders with chemical composition similar to
zeolites but with an amorphous microstructure [Davidovits,
1994]. He utilised silica (SiO
2
) and alumina (Al
2
O
3
)
available in the specially processed clay (metakaolin) to
get inorganic polymeric system of alumino-silicates. Unlike
ordinary Portlandcement (P-C), geopolymers do not need
calcium-silicate-hydrate(C-S-H) gel for matrix formation
and strength, but utilise the polycondensation of silica and
alumina precursors to achieve required strength level. Two
main constituents of geopolymers are: geopolymer source
materials (GSMs) and alkaline activator liquids. The GSMs
should be alumino-silicate based and rich in both silicon
(Si) and aluminium (Al) and thus, by-product materials
such as fly ash, silica fume, slag, rice-husk ash, red mud,
etc. can form GSMs.
Recently, Rangan and Hardijto, [2005] exploited silica and
alumina of fly ash to produce three-dimensional polymeric
chain and ring structure consisting of Si-O-. Geopolymers
are unique in comparison to other aluminosilicate materials
(e.g. aluminosilicate gels, glasses, and zeolites). The
concentration of solids during geopolymerisation reactions
is higher than that in aluminosilicate gel or zeolite synthesis
[Rangan, 2005; Rajamane, 2011a and 2011b, Sindhunata,
2006]. Al-O bonds of geopolymeric binder are useful to
prepare structural grade concretes.
From above, it is clear that any of the minerals containing
reactive oxides of silicon and aluminium can be activated
by suitably formulated highly alkaline liquid to obtain
inorganic polymeric binding material [Sindhunata, 2006].
Preliminary studies in this regard, were carried out at SERC
in early 2000s; both fly ash and Ground Granulated Blast
Furnace Slag (GGBS), (either individually or combined in
certain proportions) from indigenous sources were found to
be suitable to produce geopolymeric systems to achieve
sufficient strength levels in geopolymer concretes (GPCs)
[Rajamane and Sabitha, 2005]. It was observed that the
activation of FA and GGBS involved use of hydroxides and
silicates of alkali (such as sodium, potassium) which are
commonly available in India; the processing conditions for
GPCs were almost similar to Conventional Concretes (CCs)
except that during mixing operations of GPCs, instead of
water, a premixed alkaline solution, known as Alkaline
Activator Solution (AAS), was added. Following materials
were used to produce GPCs [Rajamane, 2009a]:
- Fly ash,
- Ground Granulated Blast Furnace Slag(GGBS),
- Fine aggregates (in the form of river sand),
- Coarse aggregates (in the form of crushed granite
stone),
- Alkaline Activator Solution (AAS):
(It is a combination of solutions of alkali silicates and
hydroxides, besides distilled water. The role of AAS is to
activate the GSMs, containing Si and Al, such as FA and
GGBS).
Besides above mentioned materials, synthetically produced
alumina and silica, metakaolin, rice husk ash, silica fume,
etc. can also be used appropriately keeping considering
that both aluminium and silicon elements are required
beside small amount of alkali elements (such as Sodium,
Potassium, etc.) to form alumino-silicate geopolymers.
GPCs, being a new class of materials (with complete
absence of Portland cement), conventional concrete mix
design approaches are not generally directly applicable. The
formulation of GPC mixtures requires systematic numerous
investigations on the materials available [Rajamane, 2005].
However, basic concepts related to particle packing,
rheology of fresh mixes, etc, can be judiciously utilised in
developing GPC mixes which require AAS consisting of
hydroxides and silicates of sodium whose concentration
plays a major role in determining the geo polymerization
ratio of alumina and silica of geo polymeric source material
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150 The Masterbuilder - April 2012 www.masterbuilder.co.in
(GSM) such as fly ash, metakaolin, GGBS etc., of GPC.
Desirable Properties of GPCs
It was recognised that any new binder material to be
developed for use in concretes should be eco-friendly and
it would be acceptable if it has following characteristics:
- It should be preferably produced from widely available
waste by-products from industries
- Internal Energy Content (Embodied Energy) should be
less
- Chemical activators for generating binding system
should be commonly available
- The new binder based concretes should be similar or
superior to that of P-C based concretes in respect of :
- processing conditions for production of fresh mixes
- time required for demoulding or formwork removal
- curing regimes and periods
- rate of strength developments with age
- mechanical properties such as
- compressive strength
- tensile strength
- flexural strength
- modulus of elasticity
- durability related properties such as
- protection to embedded steel reinforcement
- diffusion of
- chloride ions
- moisture/water, etc
- resistance against attack by
- sulphates
- acidic solutions, etc
- cost per unit volume
- long term chemical stability of the binding system
formed
- capable of accepting common filler aggregate systems
such as sand, crushed natural stones, etc
Literature Review
Origin of Term Geopolymer
The term geopolymers was first introduced to the
world by Davidovits of France resulting in a new field
of research and technology. Davidovits explained that
geosynthesis is the science of manufacturing artificial rock
at a temperature below 100C in order to obtain natural
characteristics (hardness, longevity and heat stability) of
rock. Geopolymers can be thus viewed as mineral polymers
resulting from geochemistry or geosynthesis. However
for the purpose of this literature survey, geopolymer (GP)
means any aluminosilicate based binder.
History of Geopolymers
Davidovits coined the term geopolymer in 1978 to represent
a broad range of materials characterised by chains or
networks of inorganic molecules [Davidovits, 1979, 1993,
2008], and explained in many of his publications about the
possibility of GPs being used by Egyptians construction of
pyramids, based on microscopy, IR and NMR spectroscopy
of sparse specimens from ancient Egyptian constructions
[Davidovits and Morris, 1988; Davidovits, 1999]. Demortier
observed the noticeable differences in porosities in the top
and bottom sections of pyramid blocks which were also
subjected to X-ray and NMR analyses to conclude that
pyramids could be made from concreting operations
[Demortier, 2004]. Use of slurry to form bearing courses
of horizontal joints and vertical joints between the blocks
including presence of hair in the joints of pyramids did
indicate the possibility of concrete like technology for
pyramid constructions [kvra et al, 2008].
But, the actual modern alumino-silicate based work could
be traced to 1930s when alkali oxides were used for
reaction with slags to test their suitability for use in Portland
cement. A rapid hardening binder by slag activation was
reported in 1940 by Belgian scientist [Purdon, 1940]. US
Army used, in 1950s, NaCl and NaOH to activate slag to
produce binder for use in Military applications [Malone et al,
1986]. Glukhovsky in 1965 observed that alumino-silicate
hydrates as solid binder products are formed during alkali
activation of slag and these are also noticed during alkali
treatment of rock and clay minerals, prompting him to call
the binder as soil cements and concrete as soil silicate
concretes [Glukhovsky, 1965]. In 1974, Davidovits and
Legrand filed a patent on Siliface process which involved
use of NaOH, Quartz, kaolinite, and water. It is interesting
to note here that alkali activated slag (AAS) would basically
consist of silicon element in mainly one dimensional chains
whereas, GPs would have a 3-dimensional alkali-alumino-
silicate framework [Duxon et al, 2007].
However, after Davidovits (1991) described his new breed
of aluminosilicate binders (synthesised by activating
calcined kaolinitic clay with sodium silicate solution at
low temperature) as geopolymer for the first time, the
real impetus to the field of GP technology started. The
Geopolymer was an aluminosilicate gel, where the silicon
and aluminium are tetrahedrally-bonded through sharing
oxygen atoms forming the basic monomer unit is a sialate
(O-Si-O--Al-O) carrying excess negative charge which
occurs when the Al3+(of the source material such as clay)
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is substituted by Si4+.The polysialate structure is charge-
balanced by alkali metal cations (K+ or Na+).
The field of geopolymers saw major contributions from
authors such as Alonso (2001), Bakharev (2005), Sanjayan
(1999), Bankowski (2004), Cheng (2003), Duxson (2005),
Fernandez-Jimenez (2006a), Iler (1979), Katz (1998),
Khalil (1994), Kriven (2003), Krivenko (2002), Lee and Van
Deventer (2002a), Li (2006), Palomo (2004), Phair (2001),
Provis (2005b), Shi (1996), Sindhunata (2006), Xu (2004),
Talling (1989), Van Jaarsveld (2000), Wang (1995), Xu
(2000b), Yip (2003), Hardjito, Wallah, Sumajouw, Rangan
(2001). Meantime, a few books having comprehensive
information on geopolymer based on the vast literature
were also published [Davidovits, 2011; Shi, 2006; Provis,
2009].
Though the term, geopolymer has become now more
common to represent the synthetic alkali aluminosilicate
material (produced by reaction of a solid aluminosilicate
with a highly concentrated aqueous alkali hydroxide or
silicate solution), it is worthwhile to note that the following
nomenclatures are also reported to describe similar
materials:
- Inorganic polymer [Van Wazer, 1970]
- Low-temperature aluminosilicate glass[Rahier, 1996]
- Alkali-activated cement [Roy, 1999; Palomo, 2003; ]
- Alkali-activated binders [Torgal, Gomes, and Jalali,
2008]
- Geocement [Krivenko, 1994]
- Alkali-bonded ceramic [Mallicoat, 2005]
- Inorganic polymer concrete [Sofi, 2006]
- Hydroceramic [Bao, 2005]
- Mineral Polymers[Davidovits, 1980]
- Inorganic polymer glasses[Rahier, 2003]
- Alkali ash material[Rostami, 2003]
- Soil cements [Glukhovsky, 1965]
- Alkali Activated Binder [Provis and Deventer, 2009],
It is seen that GP is a versatile binder being studied by
scientists of various backgrounds and expertise, but, having
good potential to become eco-friendly alternate to P-C for
use in civil engineering applications. But, to understand
various aspects of this new material from, it is necessary
to consider the above nomenclatures also so that the
information available in various forums is readily utilised. In
the present paper, more widely used term, geopolymer is
adopted for presentation of data and discussions.
Basics of Typical Geopolymer Concretes
Major ingredients of geopolymer concretes (GPCs) having
geopolymer (GP) as the binder, are:
- Geopolymeric source materials (GSMs) such as fly ash,
GGBS, etc
- Aggregate system consisting of fine and coarse
aggregates
- Alkaline Activator Solution (AAS)
It is seen that GPCs are almost similar to conventional
concretes (CCs) (which are P-C based), consisting of
binder made from fine powdery materials, bulk volume
filling granular particles made of aggregates, and liquid
component of the mix made of alkaline chemicals. Thus,
the powdery P-C of CCs is replaced by mineral materials
(usually referred as mineral or pozzolanic admixtures in
CC technology), and liquid component of water of CCs is
replaced by viscous, alkaline activator solution made of
hydroxides and silicates of alkali metals such as sodium
and potassium. The aggregate filler component of CCs is
retained in GPCs.
Besides above mentioned materials, synthetically produced
alumina and silica, metakaolin, rice husk ash, silica fume,
etc. can also be used appropriately keeping in view that
both aluminium (Al) and silicon (Si) elements are both
required beside small amount of alkali elements such as
Sodium (Na), Potassium (K), etc to form alumino-silicate
geopolymers.
GPCs being a new class of materials (with complete absence
of Portland cement), traditional CC mix design approaches
cannot generally be directly applied. The formulation of the
GPC mixtures requires systematic numerous investigations
on the materials available [Rajamane, 2005]. However,
basic concepts related to particle packing, rheology of
fresh mixes, etc can be judiciously utilised in developing
GPC mixes.
To prepare a typical AAS consisting of hydroxide and
silicate of sodium, Sodium Hydroxide flakes (SHf), a highly
hygroscopic granular material are first dissolved carefully
in Distilled Water (DW), to get sodium hydroxide solution
(SHS). After allowing the SHS to cool to room temperature,
Sodium Silicate Solution (SSS) is added to it, the resulting
liquid is termed as AAS which is used to prepare the GPC
mix. Mixing of GSMs, aggregates, and AAS is done using
the conventional tools (such as mixer machine) adopted
for producing of CCs, however, with due considerations
for viscosity and chemical nature of the AAS. The rates
of hardening and chemical reactions in GPCs are quite
different from the concretes based on Portland cement.
Handling of some ingredients, especially, the constituents
of AAS would require specific precautions. It is to be noted
here the exactly required liquid component of GPCs is
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152 The Masterbuilder - April 2012 www.masterbuilder.co.in
not readily available in the market, unlike water in case
of conventional concrete (CC), and it has to be prepared
carefully much before the actual mixing of GPCs is started.
It may be worth noting here that specifically formulated
chemical additives to function reliably as setting time
changing admixtures such as retarders, accelerators, etc
are not yet readily available for geopolymers. Hence, field
adjustments for changed ambient temperature conditions
and changes in properties of ingredients would not be easy,
even though conventional methods of mixing, compaction,
moulding, and demoulding can be still adopted for GPCs
also. However, for some mixes, ambient conditions may
not be adequate for demoulding within 24 hours of casting
and some higher temperature exposure may have to be
created for effecting the setting of the GPC mixes.
Many of the geopolymeric systems reported in the literature
are involving use of high temperature curing in the form of
storing the moulds containing GPC mixes in hot air oven or
steam chambers [Rangan, 2005]. However, the works at
CSIR-SERC has shown that it is now possible to formulate
the GPC mixes for self-curing so that ambient conditions
would be sufficient for setting as well as for gaining
mechanical strengths [Rajamane, 2009b].Curing of GPCs
may involve application of steam and hot air, in contrast to
water curing of CCs. With special formulations, GPCs can
get cured at ambient conditions after demoulding, thereby
they can be considered as self-curing. For visual inspection,
GPCs and CCs would look similar, but, chemical natures of
microstructures are quite different.
Literature on Geopolymer Science
Ingredients of GP and Geopolymeric Source Materials
Geopolymer concretes (GPCs) have geopolymer (GP) as
the binder to bind the aggregate system consisting of fine
and coarse aggregates. Two main ingredients required for
creation of geopolymer binders are:
- Geopolymeric source materials (GSMs) rich in silica
and alumina, which could be natural minerals (such as
kaolinite, clays, etc) or industrial by-products (such as
fly ash, silica fume, slag, rice-husk ash etc).
- Alkaline Activator Solution (AAS) based on alkali metals
(commonly Sodium or Potassium) based. The most
common AAS is a combination of alkali hydroxide
(NaOH, KOH) and alkali silicate (Sodium or potassium
silicate).
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 (Xu & van Deventer 2002).
Geopolymerisation Reactions
The mechanism of geopolymerisation may be considered
to occur in three stages (Xu & van Deventer 2000) :
- dissolution,
- transportation or orientation, and
- polycondensation
The reactions of geopolymerisation take place through
a series of exothermic processes (Palomo, Grutzeck &
Blanco 1999; Davidovits 1999).
Cheng and Chiu (2003) had observed that unlike
conventional organic polymers, glass, ceramic, or cement,
the geopolymers are formed at low temperatures and
they are non-combustible, heat-resistant, and fire/acid
resistant. It was recognised that three sources essentially
are needed for synthesis of geopolymer: (i) raw materials
(such as fly ash, GGBS, MK, etc), (ii) inactive filler (such as
sand and crushed granite aggregate), and (iii) geopolymer
liquor (Alkali Activator Solution (AAS). Raw materials (or
geopolymer source materials) can be industrial wastes,
such as fly ash, blast furnace slag, red mud, waste glasses,
or some natural minerals and rocks. The active powdery
fine material, containing mainly geo-synthesis supporting
Al+3 ions, can be kaolinite or metakaolinite. Geopolymer
liquor (AAS) consists of sodium silicate solution acting as
binder, and alkali hydroxide solution for the dissolution of
raw materials. The authors noted that the chemical process
to form geopolymers involves two steps: (i) dissolution of
raw materials in alkaline solution to form Si and Al gel on the
materials surface, (ii) polycondensation to form networked
polymeric oxide structures. However, the exact mechanism
of geopolymer setting and how hardening occurs was felt
to be still not fully understood
Xu and Van Deventer (2000) investigated the
geopolymerisation of 15 natural Al Si minerals. It was
found that the minerals with a higher extent of dissolution
demonstrated better compressive strength after
polymerisation. The percentage of calcium oxide (CaO),
potassium oxide (K2O), the molar ratio of Si-Al in the
source material, the type of alkali and the molar ratio of
Si/Al in the solution during dissolution had significant effect
on the compressive strength.
In the synthesis of geopolymers, there are essentially two
types of raw materials, the aluminosilicate-containing solids
and alkali-silicate solutions. The aluminosilicate solids
function as sols in the alkali-silicate liquid medium. The
sol-liquid combination will turn into a sol-gel matrix, as is
usually done in the sol-gel methodology. The aluminosilicate
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Consultants Pvt Ltd.
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sources include the commonly used kaolinite, especially,
calcined kaolinite, or metakaolinite (Barbosa et al., 2000;
Davidovits, 1991; 1999; Davidovits and Davidovics, 1998;
Palomo and Glasser, 1992; Rahier et al., 1996a; b; 1997)
and other natural aluminosilicate minerals (Xu and Van
Deventer, 2000b; 2002a) and industrial waste-based
materials, such as GGBS (Cheng and Chiu, 2003; Yip and
Van Deventer, 2003) and FA(Lee and Van Deventer, 2002a;
b; Palomo et al., 1999b; Phair and Van Deventer, 2001).
Van Jaarsveld, Van Deventer and Lukey (2002) studied the
interrelationship of parameters that affected the properties
of FA-based geopolymer and reported that the properties of
geopolymer were influenced by the incomplete dissolution
of the materials involved in geopolymerisation. The water
content, curing time and curing temperature affected the
properties of geopolymer; specifically the curing condition
and calcining temperature influenced the compressive
strength. When the samples were cured at 700C for 24
hours a substantial increase in the compressive strength
was observed. Curing for a longer period of time reduced
the compressive strength.
Wang Bao-min and Wang Li-jiu (2005) studied the
applications of geopolymeric activation techniques of FA
in conventional cement concretes. The research showed
that when weight of FA reaches 20%-80% of 32.5 grade
cement, M40 concrete with satisfactory properties can
be prepared through using activating techniques such as
adding some high-efficiency FA activating admixture.
[3] Fresh Geopolymer concrete mixes
Hardjito et al, (2002) observed that fresh geopolymer
concrete is highly viscous, and cohesive with low workability
when the calcined kaolin was the source material.
Structural Usages
Davidovits and Sawyer (1985) used ground blast furnace
slag to produce geopolymer binders. This type of binders
patented in the USA under the title Early High-Strength
Mineral Polymer, was used as a supplementary cementing
material in the production of precast concrete products.
Activating Medium
A combination of sodium or potassium silicate and sodium
or potassium hydroxide has been widely used as the alkaline
activator (Palomo et al, 1999; van Jaarsveld, van Deventer
& Lukey 2002; Xu & van Deventer, 2000; Swanepoel &
Strydom, 2002), with the activator liquid-to-source material
ratio by mass in the range of 0.25-0.30 (Palomo, Grutzeck
& Blanco 1999; Swanepoel & Strydom 2002).
Anurag Mishra (2008, 2009) conducted experiments on
FA based GPC by varying the concentration of NaOH and
curing time. Total nine mixes were prepared with NaOH
concentration as 8M, 12M, 16M and curing time as 24hrs,
48hrs, and 72hrs. The investigation indicated: an increase in
compressive strength with increase in NaOH concentration
and curing time, increase in compressive strength after
48hrs curing time not significant. Compressive strength
up to 46 MPa was obtained with curing at 60C. Water
absorption decreased with increase in NaOH concentration
and curing time.
Swanepoel and Strydom (2002) conducted a study on
geopolymers produced by mixing FA, kaolinite, sodium
silica solution, NaOH and water. Both the curing time and
the curing temperature affected the compressive strength,
and the optimum strength occurred when specimens were
cured at 600C for a period of 48 hours
Palomo, Grutzeck, and Blanco (1999) studied the influence
of curing temperature, curing time and alkaline solution-to-FA
ratio on the compressive strength. It was reported that both
the curing temperature and the curing time influenced the
compressive strength. The utilization of sodium hydroxide
(NaOH) combined with sodium silicate (Na2SiO3) solution
produced the highest strength. Compressive strength up
to 60 MPa was obtained when cured at 85C for 5 hours.
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 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.
Curing
Because heat is a reaction accelerator, curing of fresh
geopolymer is carried out mostly at an elevated temperature
(Palomo et al,1999). When curing at elevated temperatures,
care must be taken to minimize the loss of water.
Swanepoel and Strydom,(2002), described the effects of
curing at 40, 50, 60 and 70C for different durations (6, 24,
48 and 72 h) and the optimum condition was noted to be
60C for a period of 48 hours.
Curing at room temperature has successfully been carried
out by using calcined source material of pure geological
origin, such as metakaolin (Davidovits 1999; Barbosa,
MacKenzie & Thaumaturgo 2000).
Cheng and Chiu (2003) found that the setting
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time of geopolymer paste made with GGBS as
the source material along with metakaolinite, was
affected by the curing temperature, type of alkaline
activator, and the actual composition of the source
material. The setting time of geopolymer paste
was observed to range from 15 to 45 minutes at
60
o
C.
Van Jaarsveld et al. (2002) observed that curing at elevated
temperature for long periods of time may weaken the
structure of hardened material. The test data showed that
curing temperature and its duration significantly influences
the compressive strength. Longer curing time and higher
curing temperature increased the compressive strength,
although the increase in strength may not be significant
for curing at more than 60oC and curing for periods longer
than 48 hours. The compressive strength of fly ash-based
geopolymer concrete cured at 60oC for 24 hours did not
vary with the age and remained constant at approximately
60 MPa.
Chindaprasirt (2006) conducted the compression strength
test on GPC specimens prepared by using the NaOH of
10M concentration. He concluded that the GPC specimens
prepared by using above concentration can achieve high
strength (70MPa) when cured in oven at a temperature of
75C for two days.
GPC Mix Design
Djwantoro Hardjito, et al (2004), showed that the geopolymer
paste binds the coarse aggregates, fine aggregates and
other un-reacted materials together to form the GPC, and
usual concrete technology methods to produce GPC mixes
can be often employed. As in the Portland cement concrete,
the aggregates occupy the largest volume, (about 75-80 %
by mass) in GPCs. The silicon and the aluminium in the fly
ash are activated by a combination of sodium hydroxide
and sodium silicate.
Rangan and Hardjito (2005) have noted that unlike
conventional cement concretes GPCs are a new class of
construction materials and therefore no standard mix design
approaches are yet available for GPCs. While GPC involves
more constituents in its binder (viz., FA, GGBS, sodium
silicate, sodium hydroxide and water), whose interactions
and final structure and chemical composition are under
intense research whereas the chemistry of Portland
cement and its structure and chemical composition (before
and after hydration) are well established due to extensive
research carried out over more than century. While the
strength of cement concrete is known to be well related to
its water-cement ratio, such a simplistic formulation may
not hold good for GPCs. Therefore, the formulation of the
GPC has to be done by trial and error basis.
Rajmane (2006) studied the effect of geopolymeric binders
such as GGBS and FA by activating silicon dioxide and
aluminium oxide present in the binders, to form inorganic
polymer binder system. This binder system can be used to
produce concretes containing river sand as fine aggregate
and coarse aggregate in the form of either sintered FA
aggregates (SFFA) or crushed granite aggregates (CGA).
It was concluded that the lightweight aggregate based
geopolymer concrete have one day compressive strength
of about 35 MPa and a 28 days strength of more than
50 MPa. CGA based geopolymer concretes produced
marginally higher compressive strength of about 45 MPa
at one day and 65 MPa at 28 days
Frantiek kvra et al (2005) showed that the structure of
the geopolymers prepared on the basis of fly ashes (cured
at 60-80C 6-12 hours ) is predominantly of the AlQ4(4Si)
type and SiQ4 (4Al), SiQ4 (2-3Al). The strength range was
15 to 70 MPa and is affected substantially by macro-pores
(103 nm and more) formed in result of the air entrained into
the geopolymers. There are fly ash particles that underwent
only partial reaction. The presence of Ca-containing
additives (slag, gypsum) reduces considerably the porosity.
There was no transition phase of different composition
between the geopolymers and the aggregate.
Geopolymers and Zeolites
Geopolymers are unique in comparison to any other
aluminosilicate materials (e.g. aluminosilicate gels,
glasses, and zeolites). The concentration of solids in
geopolymerisation is higher than in aluminosilicate gel
or zeolite synthesis. Geopolymers are believed to be an
amorphous metastable phase of zeolites (i.e., zeolitic
precursors) that can be converted to a more well-
defined crystalline phase (zeolites) provided that the right
conditions and reactant concentrations are used (Xu and
Van Deventer, 2002b).
A recent review by Provis et al. (2005c) suggested that that
geopolymer is constituted from agglomerates of zeolitic
nanocrystals bound by an amorphous gel phase. The
degree of Crystallinity is affected by reaction conditions
and starting reactant concentration, particularly silicate
and alkali concentrations.
Geopolymerisation Modelling
Sindhunata (2006) studied the conceptual model of
geopolymerisation. He conducted studies under controlled
conditions typically used for geopolymerisation, thus leading
to findings, which improved the understanding of reaction
steps. Various influencing parameters investigated, were the
concentration of reactants (silicate concentration, alkalinity,
and water content) and the curing conditions (temperature,
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156 The Masterbuilder - April 2012 www.masterbuilder.co.in
time, humidity). A conceptual model of geopolymerisation
was developed by incorporating the above mentioned
factors. Three key aspects of GPC studied were: firstly,
an investigation on the development of pore structure in
geopolymers; secondly, an investigation on the competition
between dissolution, polymerization, and crystallization of
aluminosilicate gels during geopolymerisation and finally,
an investigation on the ageing of geopolymers in alkali and
carbonate solutions. The occurrence of different reaction
mechanisms is influenced by the alkali-silicate concentration
and the type of alkali metal cation used. The investigation
of ageing provides insight into the reaction mechanisms of
late geopolymerisation (i.e. post- set processes).
Reinforced GPCs
Past studies on reinforced fly ash-based geopolymer
concrete members are extremely limited. Palomo et.al
(2004) investigated the mechanical characteristics of fly
ash based geopolymer concrete. It was found that the
characteristics of the material were mostly determined
by curing methods especially the curing time and curing
temperature. Their study also reported some limited
number of tests carried out on reinforced geopolymer
concrete sleeper specimens. Another study related to the
application of geopolymer concrete to structural members
was conducted by Brookeet al. al (2005). It was reported
that the behaviour of geopolymer concrete beam column
joints was similar to that of members made of Portland
cement concrete.
Shuguang Hu and Hongxi Wang (2008) investigated the
mechanical properties of geopolymeric materials (steel slag
based) and other conventional materials. The compressive
strength, bond strength and abrasion resistances were
experimentally studied. It was found that the bond strength
of geopolymeric material with steel slag was 2.6% higher
than those of other materials. It was also concluded that
the steel slag was almost fully absorbed to take part in
the alkali activated reaction and incorporated into the
amorphous aluminosilicate geopolymer matrix.
Palomo et.al (2004) investigated the mechanical
characteristics of FA based GPC concrete. It was found that
the characteristics of the material were mostly determined
by curing methods especially the curing time and curing
temperature. Their study also reported some limited number
of tests carried out on possible use of GPC concrete for the
production of prestressed sleeper specimens.
Brooke et al. al (2005) studied the application of GPC
concrete to structural members. It was reported that the
behaviour of GPC concrete beam column joints was similar
to that of members made of Portland cement concrete.
Sumajouw and Rangan (2006) conducted extensive studies
on low-calcium FA based reinforced GPC concrete beams
and columns. The behavior and failure modes of reinforced
GPC concrete columns and beams were similar to those
observed in the case of reinforced Portland cement concrete
columns. The results demonstrated that the methods
of calculations used in the case of reinforced Portland
cement concrete beams and columns are applicable for
reinforced GPC concrete beams and columns. The results
demonstrated that reinforced low-calcium (ASTM Class
F) FA based GPC concrete structural members can be
designed using the design provisions currently used in the
case of reinforced Portland cement concrete members.
Excellent correlation between experimental and analytical
results is found.
Prabir Kumar Sarker (2008) reports study on analysis on
GPC columns. It is found that the equation of Popovics
(proposed for OPC concrete) can be used for geopolymer
concrete with minor modification to the expression for the
curve fitting factor, to better fit with the post peak parts of
the experimental stressstrain curves. A good correlation
is achieved between the predicted and measured ultimate
loads, loaddeflection curves and deflected shapes for 12
slender test columns
Durability
(i) Corrosion of Embedded Steel
Miranda et al (2005) gave details of corrosion potential and
polarisation resistances for steel electrodes embedded
in Portland cement mortar and two fly ash mortars
(respectively activated with NaOH and waterglass+NaOH
solutions). Chloride-free activated fly ash mortars were
found to passivate steel reinforcement as speedily and
effectively as Portland cement mortars. The polarization
curves and the response to short-term anodic current
pulses (galvanostatic pulse technique) corroborated the
full and stable passivation of the steel. They concluded that
the icorr value for both OPC and GPC mortar are similar
(0.1 A/cm
2
).
Yodmuneeand Yodsudjai (2006) studied the corrosion
of steel bar located inside in fly ash-based geopolymer
concrete in an accelerated corrosion test. All the GPC
mixes had higher compressive strength than conventional
concrete (10 to 16 MPa). The test results included the half-
cell potential and cross sectional loss of steel bar and in
both the respects GPCs performed better. He conclude that
at 72 hrs, the GPC specimens gives the Half cell potential
value of -175mV which is mostly equal to the OPC value
(-200 mV).
Holloway and Sykes (2005) studied the Corrosion of mild
steel reinforcement in an alkali-activated slag (AAS) cement
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158 The Masterbuilder - April 2012 www.masterbuilder.co.in
mortar containing NaCl admixtures using an improved
galvanostatic pulse technique. He concluded that, at initial
stage highest corrosion rates are seen with the lowest
chloride levels(0% and 2%), but over time(107days) the
corrosion rate decrease to 1 Acm-2 even when the NaCl
level increase to 8%.
Shi 2003a reported that the Alkali activated slag showed
much less corroded depth (<4mm) then OPC specimens
(>14mm) which are immersed in nitric acid even after
90days continuous exposure.
Davidovits (1994) noted that unlike conventional Portland
cement, geopolymeric cements do not rely on lime and are
not dissolved by acidic solutions. Geopolymeric cements,
Potassium-Poly (sialatesiloxo) type, remain stable with a
loss in the 5-8 % range.
(ii) Acid Resistance
Bakharev et al (2003) investigated the durability of alkali-
activated slag (AAS) concrete exposed to acetic acid
solution of pH = 4. It was found that AAS concrete of Grade
40 had a high resistance in acid environment, superior to
the durability of OPC concrete of similar grade.
Songa (2005) investigated the durability property of
geopolymer concrete exposed to sulphuric acid corrosion.
It was concluded that GPC is highly resistant to sulphuric
acid; in terms of a very low mass loss, less than 3%.
Moreover, Geopolymer cubes were structurally intact and
still had substantial load capacity even though the entire
section had been neutralized by sulphuric acid.
(iii) Fire Resistance
Van Jaarsveld, Van Deventer, and Schwartzman (1999)
carried out experiments on geopolymers using FA and
found them to be fire resistant with compressive strengths of
5 to 51 MPa. The factors affecting the compressive strength
were the mixing process and the chemical composition of
the FA. A higher CaO content decreased the microstructure
porosity and, in turn, increased the compressive strength.
Besides, the water-to-FA ratio also influenced the strength.
It was found that as the water-to-FA ratio decreased, the
compressive strength of the binder increased.
Lyon et al (1996) discussed the fire response of a potassium
aluminosilicate (Geopolymer) matrix carbon fiber composite.
At irradiance levels of 50 kW/m2(typical of the heat flux in a
well developed fire), glass- or carbon-reinforced polyester,
vinyl ester, epoxy, bismaleimde, cyanate ester, polyimide,
phenolic, and engineering thermoplastic laminates ignited
readily and released appreciable heat and smoke, while
carbon-fiber reinforced Geopolymer composites did not
ignite, burn, or release any smoke even after extended
heat flux exposure. The Geopolymer matrix carbon fiber
composite retained 67% of its original flexural strength after
a simulated large fire exposure
(iv) Sulphate Attack
Hardjito and Rangan (2005) studied the development and
properties of low-calcium FA based geopolymer concrete.
The research report described the development, the
mixture proportions, and the short-term properties of low-
calcium FA based GPC concrete. It was concluded that
low-calcium FA-based geopolymer concrete had excellent
compressive strength, suffer very little drying shrinkage
and low creep, had excellent resistance to sulfate attack,
and good acid resistance.
Test results showed that heat-cured low-calcium fly ash-
based geopolymer concrete has an excellent resistance to
sulphate attack. Research data shows that geopolymeric
materials performed significantly better in acid resistance
compared to Portland cement (Davidovits, 1994; Gourley
and Johnson, 2005).
Bakharev (2003) investigated the durability of alkali-
activated slag (AAS) concrete exposed to sulphate attack.
AAS concrete was immersed in 5% sodium, 5%magnesium
and5% sodium + magnesium sulphate solution. The
main parameters studied were the compressive strength,
products of degradation, and micro structural changes.
It was found that in AAS concrete the material prepared
using sodium hydroxide had the best performance due to
its stable cross-linked aluminosilicate polymer structure.
Douglas (1992) reported that the changes in dynamic
modulus of elasticity, pulse velocity, weight and length of
sodium silicate-activated slag cement concrete after 120
days of immersion in 5% sodium sulphate solutions. They
noticed that the changes are even smaller than those in the
controlled specimens immersed in lime-saturated water.
(v) Salt Environment
Nguyen Van Chanh et al [2008] found that compressive
strength of heat-cured fly ash-based geopolymer concrete
does not depend on age. Longer curing time (24 to
72 hours) produces higher strength, but, increase in
strength beyond 48 hours is not significant. Geopolymer
concrete has excellent properties within both acid and
salt environments. Comparing to Portland cement, the
geopolymers have a relative higher strength, excellent
volume stability, better durability.
Gailius and Kazberuk (1998) monitored the long-term
behaviour of concretes in a chloride exposure regime under
influence of cyclic wetting and drying as well as freezing
and thawing with chlorides. They concluded that the
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resistivity of concrete was closely connected with cement
type and mineral addition content, cement mass as well as
the time of storage. The resistance to chloride penetration
was found to increase with time but the value of diffusion
coefficient from migration test depended on cement type.
Yang and Cho (2001) Huang stated that the accelerated
chloride migration test indicated a good correlation between
the charge passed and the steady-state chloride flux.
2.4.3 Applications
(a) Hazardous Waste Encapsulation
Davidovits [2002] informs about zeolitic materials abilities
to adsorb toxic chemical wastes. Geopolymers behave
similarly to zeolites and feldspathoids. They immobilise
hazardous elemental wastes within the geopolymeric
matrix, as well as act as a binder to convert semi-solid
waste into an adhesive solid. Hazardous elements of
waste materials mixed with geopolymer get locked into the
three dimensional framework of the geopolymeric/zeolitic
matrix.
Davidovits (1999) suggested that the atomic ratio of Si-to-
Al of should be about 2 for making geopolymeric binder
based pastes, mortars and concretes. Geopolymer can
also be used for waste encapsulation to immobilise toxic
metals (van Jaarsveld, van Deventer & Lorenzen 1997).
Palomo and Palacios (2003), described the stabilisation/
solidification capacity of a matrix made using alkali
activation of fly ash, in the presence of toxic elements
chromium and lead. Leaching tests proved that the matrix
is able to stabilise and solidify lead efficiently (analysed
lead concentrations from leaching were in parts per billion).
However, geopolymer was not efficient for chromium
fixation since this element strongly disturbed the alkali-
activation mechanism of the ash
(b) Precast Products
Gourley and Johnson (2005) have reported commercial
production of geopolymer precast concrete products.
Reinforced GPC sewer pipes outperformed comparable
Portland cement concrete pipes. Good performance of
reinforced GPC railway sleepers on mainline tracks and
excellent fire resistance of GP mortar wall panels were also
reported.
Siddiqui (2007) demonstrated the successful commercial
scale manufacture of reinforced geopolymer concrete culverts.
Davidovits and Sawyer (1985) used ground blast furnace
slag to produce geopolymer binders. This type of binders was
patented in the USA under the title Early High-Strength
Mineral Polymer was used as a supplementary cementing
material in the production of precast concrete products.
(c) Structural Concretes
Zongjin Li et al (2004) terming the geopolymers as
sustainable composites and found that they are a type
of amorphous alumino-silicate product and can be
synthesized by polycondensation reaction of geopolymeric
precursor and alkali polysilicates. Geopolymers are energy
efficient and environment friendly sustainable cementitious
materials with superior properties compared to the Portland
cement, such as high early strength, excellent volume
stability, better durability, good fire resistance, and easy
manufacturing process.
.Djwantoro Hardjito et al (2004) investigated geopolymer
as the binder (in place of Portland cement) where binding
action is achieved in fly ash by hydroxide-silicate based
chemicals (as an initiators or catalysts for polymeric
reaction) to produce concrete using the usual concrete
technology methods.
Davidovits and Sawyer (1985) had used ground blast
furnace slag to produce geopolymer binders. This type
of binders patented in the USA under the title Early High-
Strength Mineral Polymer for used as a supplementary
cementing material in the production of precast concrete
products. In addition, a ready-made mortar package that
required only the addition of mixing water to produce
a durable and very rapid strength gaining material was
produced and utilised in restoration of concrete airport
runways, aprons and taxiways, highway and bridge decks,
and for several new constructions when high early strength
was needed.
Concluding Remarks
The literature survey indicates that geopolymer word is one
of the many names used for describing the binder formed
with alumino-silicate gel structure which according to
some researchers need not be in polymeric form. However,
Davidovits has data to show that polymer is indeed formed.
Commonly, Metakaolin (MK) is often used by some authors
to produce so called pure geopolymers since MK, mostly
consist of alumina and silica. However, much literature
exists on activation of MK in combination with FA, GGBS,
etc. works on only FA based GPs were also reported, and
notable among them is Prof. Rangan, of Curtin University.
Davidovits advocates use of slag in combination with other
GSMs such as MK and fly ash and he emphasizes on
development with lower activation temperatures and lower
alkali levels in AAS.
Comparatively, more papers are available in science of
geopolymer where often paste is prepared for making test
specimens. Concretes and mortars formulation are also
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160 The Masterbuilder - April 2012 www.masterbuilder.co.in
reported, but, lesser in numbers. GP science has not yet
came up with a unique way of describing the matrix of GP
and the AAS has to be developed for each set GSMs used
in any particular experiment.
About the mechanical strengths, only qualitative information
is available which can be used to decide about any
particular combination of GP mixes to achieve the desired
level of strength.
Works on reinforced GPC are not many and however, the
existing test results shows that structural behaviour of
GPCs and CCs are essential and similar in nature, except
that sometime at the same strength level, GPCs may tend
to have lower modulus of elasticity.
Contrastingly, GP composites have performed better
than P-C composites in durability related tests such as
Sulphate, acid and corrosion resistance. This is mainly due
to polymeric nature of GP matrix without presence of free
lime.
Numerous studies on GPs indicated that though exact
nature of GP microstructure is still to be decided, it is
still possible to formulate the GP composites to achieve
consistently the desired level of strengths for structural
usages by suitable selection of GSMs, AAS, besides curing
regimes.
Abbreviations/Notations
AAS = Alkaline Activator Solution
Alumina = Al
2
O
3

CCs = Conventional concretes
CGA = Crushed granite aggregates
C-S-H = Calcium-silicate-hydrate
DW = Distilled Water
ECO
2
= Embodied carbon dioxide
EE = Embodied energy
FA = Fly ash
FAA = Fly Ash Aggregates
GGBS = Ground Granulated Blast Furnace Slag
GP = Geopolymer
GPC = Geopolymer concrete
HVFA = High volume fly ash
IR = Infrared
MK = Metakaolin
MR = Molar ratios
NMR = Nuclear Magnetic Resonance
OPC = Ordinary Portland Cement
P-C = Portland Cement
SHf = Sodium Hydroxide flakes
SHS = Sodium hydroxide solution
SiO
2
= Silica
SSD = Saturated surface dry
SSS = Sodium Silicate Solution
W/C= Water-cement ratio
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For a complete list of the references please visit:
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Publishers Note: Part - 2 to be features in May 2012 edition.
Geopolymer Concrete