This document summarizes literature on geopolymer binders as an alternative to ordinary portland cement. It discusses that the major factors affecting geopolymerization are the type and properties of raw materials used, the alkaline activators, and curing conditions. Raw materials rich in reactive silica and alumina such as fly ash, slag, and clay are commonly used. The concentration of the alkaline activator solution, the ratio of activator to raw materials, and the ratio of sodium silicate to sodium hydroxide in the activator affect the geopolymerization process. Different optimized conditions are required for different raw material and activator combinations.

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GEOPOLYMER BINDER FROM INDUSTRIAL WASTES:
A REVIEW
S Usha1
, Deepa G. Nair2
, Subha Vishnudas2
1
Research Scholar, Division of Civil Engineering, School of Engineering, CUSAT, Kochi, India
2
Faculty, Division of Civil Engineering, School of Engineering, CUSAT, Kochi, India
ABSTRACT
This paper summarizes the review of literature on geopolymer binders as alternative to ordinary portland
cement. The major factors affecting geopolymerization are identified as type and nature of raw materials, alkaline
activators and curing conditions. Raw materials rich in reactive silica and alumina are commonly used. Alkali
concentration is a significant factor in controlling the leaching of alumina and silica from raw material. Silicate activation
increases the dissolution of raw materials and gives rise to favourable mechanical properties. For different raw materials
the optimum alkaline concentration, activator liquid to raw material mass ratio and sodium silicate/sodium hydroxide
solution ratio would be different. Different curing conditions are reported for different raw materials and different
activators. Area for future research is also suggested.
Key words: Alkaline Activator, Aluminosilicate, Eco-Friendly Binder Material, Geopolymer, Molarity.
1. INTRODUCTION
The world is facing the challenges of global warming and climate changes due to increase in CO2 and
greenhouse gases and also disposal problems of industrial wastes. Sustainable and environment friendly technology
developments ensure low energy consumptions and minimal CO2 emissions. Geopolymer technology can be a viable
solution towards this aim. 80% to 90% reduction in CO2 emission can be achieved by the replacement of ordinary
portland cement (OPC) with geopolymer cement. Alkali-activated binders have emerged as an alternative to OPC
binders, which seem to have superior durability and environmental impact [1, 2].
In 1979 Davidovits defined the geopolymer as an amorphous to semi crystalline aluminosilicate polymer
originated by inorganic poly condensation reaction of a solid aluminosilicate with highly concentrated alkali hydroxide
or silicate solution. A three-dimensional alumino-silicate network characterized by the empirical formula.
Mn{-(Si-O)z –Al-O}n .wH2O (1)
where, M is K, Na or Ca atom, n is the degree of poly-condensation, z is 1, 2, 3 or more than 3 is formed during
polymerization. Hardened geopolymer cements are referred as zeolite precursors rather than actual zeolites. The final
product of geopolymerization is an amorphous, semi- crystalline cementitious material [3].
2. GEOPOLYMERIZATION
The geopolymerization involves a chemical reaction between various alumino silicate oxides with silicates
under highly alkaline condition, yielding polymeric Si-O-Al-O bonds [1]. The two reactions are as follows [4]:
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(2)
(3)
The reaction path indicates that Si-Al materials might become raw material for geopolymers. For the optimal
reaction, alkali activator (alkali solution and sodium silicate) and the favorable environment for reaction (curing
condition) are required. The main factors affecting geopolymerization are identified as type and nature of raw materials,
alkaline activators and curing conditions [2].
2. 1. Raw materials for Geopolymer
The raw materials play a significant role in the geopolymer reaction and affect the mechanical properties and
microstructure of the final geopolymeric products. Generally, materials containing mostly amorphous silica (SiO2) and
alumina (Al2O3) are a possible source for geopolymer production. Naturally available materials like kaolin [5,6], natural
puzzolana [7, 8] and Malaysian marine clay [9], treated minerals like metakaoline and waste materials like fly ash
[10,11,12, 13, 14, 15, 16, 17, 18], Construction waste [19], red clay brick waste [20], fly ash and rice husk-bark ash[21],
fly ash and blast furnace slag[22] etc can be used. The chemical composition and particle size of these materials are
important factors affecting the geopolymer reaction.
2.1.1. Chemical composition
Xu and Deventer [4] studied the alkali activation of a large number of natural alumino silicate minerals and
confirmed that source materials with a high reactivity are required in order to synthesize a geopolymer with high
compressive strength. They also concluded that Si/Al ratio in the original mineral presents a correlation with mechanical
strength of the geopolymer. Fernandez et al. [23] also agreed with the above finding by studying three types of fly ashes
having Si/Al molar ratio of the reactive phase as 1.42, 1.64 and 2.38 and concluded that fly ash F with high reactive SiO2
and Al2O3 contents and (Si/Al)reactive ratio below 2 is suitable to produce good cementitious property alkaline cement on
alkali activation. Also alkali activated fly ash with calcium content show higher mechanical strength [24]. An increase in
the rate of hardening is observed with the addition of slag to fly ash. The free calcium ions present in the slag prolong fly
ash dissolution and enhances geopolymer gel formation [25]. Deventer et al [10] in their study proved that fly ash based
geopolymers are more durable and stronger than metakaolin based geopolymers. Silva et al. [26] concluded that minor
changes in the oxide (SiO2, Na2O, and Al2O3) ratios of initial mix formulations can dramatically change the chemistry of
the geopolymer system. Geopolymer materials produced by alkali activation of fly ashes with a high content of loss of
ignition were resistant against solutions of NaCl and Na2SO4 or H2SO4 [27].
2.1.2. Particle size and reactivity of raw material
Mechanical activation (MA) by milling enhanced the reactivity due to the combined effect of lower particle
size, angular shape, increase in surface area and change in bulk and surface reactivity. Microstuctural features such as
increase in compactness, formation of more reaction product and changes in nature of gel are also associated with
mechanical activation [28]. 80% increase in compressive strength of the geopolymer was observed by Temuujin et al.
[29] which attributes to reduction of particle size and change in morphology allowing a higher dissolution rate of fly ash
particles. Kiatsuda Somna et al. [30] in their study obtained reasonable strength for geopolymer made from ground fine
fly ash (median particle size 10.5 µm) at ambient temperature curing. The higher reactivity of the raw material through
MA has been again confirmed by Sanjay Kumar et al. [31] during the development of geopolymer from Silico Manganes
(Si Mn) slag. Bajare et al. [32] also agreed with the above findings in their geopolymer study with ground glass waste.
According to VanchaiSata et al. [33], fine bottom ash was more reactive than those of the coarser fly ashes, which
exhibited higher compressive strength. As a result of the investigation done by Gabor Mucsi et al. [34], it was found that
the geopolymer strength increased as function of fly ash fineness. Differences in the network modifying element content,
the amorphous phase content, and the particle size lead to large differences in compressive strength [35].

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2.2. Alkaline activators
The alkaline activator plays a crucial role in the polymerization reaction [36]. The type and concentration of
alkali solution affect the dissolution of raw material (fly ash). Leaching of Al3+
and Si4+
ions are generally high with
sodium hydroxide solution compared to pottassium hydroxide solution. Alkali concentration is a significant factor in
controlling the leaching of alumina and silica from fly ash particles in geopolymerization [37]. It has been shown that
silicate activation increases the dissolution of the raw materials and gives rise to favorable mechanical properties [38].
Geopolymerization reactions occur at a high rate when the alkaline activator contains soluble silicate, compared to the
use of only alkaline hydroxides [36]. Concentration of alkali, activator liquid to binder material mass ratio and sodium
silicate to sodium hydroxide solution mass ratio are the main factors affecting geopolymerization in connection with
alkaline activator.
2.2.1. Concentration
Sodium hydroxide concentration is different for different raw materials [1,2]. Hardjito et al. [39] confirmed that
alkali concentration is the most significant factor for geopolymerization and stated that a higher concentration of NaOH
yields a higher compressive strength. The compressive strength of fly ash based geopolymer with 10M NaOH was
observed as 35 MPa where as 18MPa was observed with bottom ash based geopolymer prepared using 15M NaOH
solution [40]. Concentration of sodium hydroxide play an important role in the compressive strength and microstructure
of fly ash based geopolymer paste [30]. Mustafa Al Bakri et al. [13] studied the factors influencing early age compressive
strength of fly ash based polymer with different molarities of sodium hydroxide and concluded that the geopolymer paste
with NaOH concentration of 12M produced maximum compressive strength. Joshi and Kadu [41], in their study
observed the same 12M NaOH concentration for the optimum geopolymer concrete from fly ash. A greater amount of
alumino-silicate gel would be produced when the Na2O/SiO2 molar ratio increased (greater concentration of NaOH)
which enabled the solubilization of fly ash particle [42]. Improvement in the compressive strength and stiffness of the
final geopolymeric products were observed with a higher alkalinity [43]. NaOH concentration had significant effect on
compressive strength of kaolin based geopolymer also [5]. Alkaline concentration 8M showed optimal compressive
strength for kaolin based geopolymer [6]. Reig et al. [20] studied the geopolymerization of red clay brick waste and
concluded that the optimum mix was obtained at 7M NaOH.
2.2.2. Activator liquid to binder material mass ratio
Change in activator liquid to raw material mass ratio changes the quantity of activator solution taking part in the
dissolution of the raw materials. Liew et al. [44] claimed that with solid to liquid ratio as 0.8 and Na2SiO3/NaOH ratio as
0.2, the calcined Kaolin based geopolymer resulted in high compressive strength. According to Joshi and Kadu [41], the
optimum combination of mix for development of geopolymer concrete from fly ash is with alkaline liquid to fly ash mass
ratio 0.35, keeping water to binder ratio as 0.26 for workability. Kaolin based geopolymer was optimised with solid to
alkaline solution ratio as 1[6].
2.2.3. Sodium silicate to sodium hydroxide solution mass ratio
Fly ash when activated with soluble silicates (sodium or potassium silicate), the reaction rates would be higher
than that activated with hydroxides only and quicker development of mechanical strength would be the result [36].
Fernandez-Jimeneza et al. [45] carried out a factorial experimental design with alkaline-activated slag cement mortars
and found that the most significant factor on the geopolymerization response as the alkaline activator nature. The
optimum mechanical strength was obtained with combination of Na2SiO3 and NaOH as activator. The addition of sodium
silicate solution to the sodium hydroxide solution as the alkaline activator enhanced the reaction between the raw
material and the solution [4]. The most common alkaline activator used in geopolymerization is a combination of
sodiumhydroxide (NaOH) or potassium hydroxide (KOH) and sodium silicate or potassium silicate [17]. The sodium
silicate to sodium hydroxide ratio are different for different raw materials [2]. Hardjito et al. [39] observed that the
compressive strength of geopolymer concrete increases with increase in sodium silicate to sodium hydroxide ratio.
According to Bakharev [46] geopolymers formed with sodium hydroxide activator showed more stable strength
properties than geopolymers formed with sodium silicate activator. Joshi and Kadu [41], arrived sodium silicate to
sodium hydroxide solution mass ratio as 2.5 for maximum compressive strength for fly ash based geopolymer concrete.
2.3. Curing Condition
Water serves as a carrier of the alkali activating agent during the geopolymer hardening [3]. To avoid water
evaporation from moulded geopolymer samples which was necessary for the reactions of geopolymerization, the samples
were covered with plastic film during curing [42]. Different curing conditions have been reported with different
geopolymers created from different raw materials and different activators [36]. The geopolymerization reaction of non
milled fly ash obtained from industry was extremely slow at ambient temperature [22] which can be enhanced by curing

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at elevated temperature to get the optimum compressive strength from geopolymer concrete based on raw Class F fly ash
[39].
2.3.1. Ambient Temperature Cure
In practical application, curing at ambient temperature is more convenient. But at ambient temperature,
geopolymerization reaction of the raw fly ash is extremely slow [22] which can be enhanced by mechanical activation or
addition of ground granular blast furnace slag to fly ash [29, 47, 48]. For alkali activated Kaolin, curing at ambient
temperature is unfeasible due to delay in the beginning of setting [6]. Temuujin et al. [29] obtained increased
compressive strength for geopolymer with mechanically activated fly ash, cured at ambient temperature. Compressive
strength of ambient cured geopolymer mortar with fly ash increases with increase in ground granular blast furnace
content and molarity of alkaline solution [47]. The geopolymer made with 70% fly ash and 30% GGBS produced the
maxium strength for sodium silicate to sodium hydroxide ratio 2.5, under ambient curing [48]. Fly ash partially dissolved
and involved in the reactive process when 50% fly ash and 50% slag in combination was used [22]. Reasonable strength
was obtained with sodium hydroxide activated ground fine fly ash, cured at ambient temperature [30].
2.3.2. Elevated Temperature Cure
From the experimental results Palomo et al. [36], concluded that if all the factors remain constant, the increase
in temperature tends to result in a gain of mechanical strength for geopolymers. But blast furnace slag based geopolymer
decreased its compressive strength with increase of curing temperature, when activated with the solution of sodium
silicate and sodium hydroxide. However strength increases without sodium silicate [45]. The curing temperature had a
positive effect in the strength increase at the first days of reaction [22]. Hardjito et al. [39] reported that curing
temperature in the range of 30 to 90 °C and longer curing time (48 h) will increase the compressive strength of fly ash
based geopolymer concrete. Bakharev [46] in his study confirmed that long precuring (24hr) at room temperature is
beneficial for strength development of geopolymeric materials utilizing fly ash and cured at elevated temperature as it
allows shortening the time of heat treatment for achievement of high strength. Najafi Kani and Allahverdi [49] studied
the influence of curing condition on geopolymer prepared from natural pozzolan and claimed higher strength
development with longer (7days) precuring at an ambient of more than 95% relative humidity at room temperature,
before the application of heat. Klabprasit et al [21] studied the effect of curing temperature on both compressive strength
and rate of reaction of fly ash and rice husk-bark ash based geopolymer paste and observed that curing at 60 o
C enhanced
the higher compressive strength within early ages. Relatively long precuring (1-7days) in humid atmosphere (95%
relative humidity) before the application of heat showed higher compressive strength development of geopolymer based
on natural puzzolan [19]. The geopolymerization process of an alkali-metakaolin system at different curing temperatures
was studied by Muniz-Villarreal et al. [50] and observed that geopolymer cured at 60°C for 24 hrs exhibits the best
physical and mechanical properties. The maximum compressive strength of fly ash based geopolymer was obtained at
60o
C curing for 24 hours, but the compressive strength decreased with further increase in temperature for curing [51].
Joshi and Kadu [41] investigated that low calcium fly ash is suitable for optimum mix development of geopolymer
concrete under oven dry curing at 75o
C for 24 hrs. The maximum compressive strength was observed by Arioz et al. [52]
with F class fly ash based geopolymer synthesized using sodium silicate and 8 M sodium hydroxide solutions, cured at
80o
C for 24hours, followed by curing at room temperature till testing. But there was no significant effect of curing
conditions on the microstructure of the samples. Highest strength was obtained with alkali activated Kaolin, cured at
60o
C for 3days [6]. However curing at more than 60o
C for a long period of time caused failure of the sample at a later
age. Bajare et al.[32], during their investigations with six different Geopolymers made from Barley ash, wood ash,
combination of calcined clay with Orginal roughly ground glass, Additionally ground waste glass, Barley ash and wood
ash, concluded that specimens cured at elevated temperature showed significant increase of compressive strength than
ambient temperature cured ones.
3. CONCLUSION
Raw material commonly used for geopolymer formation includes metakaolin, GGBFS, and fly ash, rich in
reactive silica and alumina. Recent researchers concluded that several other locally available alumino silicate minerals
can be used as raw material for the formation of geopolymer binder. The mixture of two or more raw materials could also
be used for better curing condition and strength requirement.
Alkali concentration is a significant factor in controlling the leaching of alumina and silica from fly ash particles
in geopolymerization. The available quantity of activator solution will be affected by activator liquid to raw material
mass ratio for geopolymerization. Most widely used alkaline activator is a mixture of sodium silicate and NaOH solution.
Silicate activation increases the dissolution of the raw materials and gives rise to favourable mechanical properties. For
different raw materials the optimum alkaline concentration, activator liquid to raw material mass ratio and sodium
silicate to sodium hydroxide solution ratio would be different.
Different curing conditions are required for different raw materials and different activators. Majority of the
authors observed that early strength could be achieved by curing at elevated temperature for 24-48 hrs. Finely ground

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raw material can produce a geopolymer with reasonable strength under ambient curing, which is suitable for practical
application. The geopolymerization reaction rate can be increased under ambient temperature by the addition of ground
granular blast furnace to the raw material in certain percentage. Literatures lack in research in the area of geopolymer
from locally available material as an eco- friendly binder material. Hence there is ample scope for future research in this
area.
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