CHAPTER 1

INTRODUCTION

1.1 General
“Concrete Utilization” is one of the important factor to determine the development of the
country. Concrete is the product of cement (binder), water and aggregate, production of
cement is the energy intensive activity and has tremendous environmental degradative
effect. The amount of the carbon dioxide (CO2) released during the manufacture of OPC due
to the calcination of limestone and combustion of fossil fuel is in the order of one ton for
every ton of OPC produced. In addition, the amount of energy required to produce OPC is
only next to Steel and Aluminum. According to India Brand Equity Foundation (IBEF)
Cement production in India increased from 230.49 million tonnes in 2011-12 to 297.56
million tonnes in 2017-18. Among the greenhouse gases, CO2 contributes about 65% of
global warming. India is the developing nation and also it is the second most populous
country of the world, with the surging demand of cement continuously, leads to numerous
problem and main and most dangerous problem is the hazardous impact on our
Environment, Ecosystem and mother Earth, which has to be curb. The second issue is the
generation of large heaps of industrial waste like Flyash, Silica fume, Granulated blast
furnace slag, Rice-husk ash and Metakaolin, require large landfills.

So the best effort to address these issues is the utilization of these waste materials as the
development of alternative binders to Portland cement. There are two ways to utilize these
one is to development and application of high volume fly ash concrete, which enabled the
replacement of OPC up to 60-65% by mass (Malhotra 2002; Malhotra and Mehta 2002), can
be regarded as a landmark in this attempt. Other way is to activate these using alkaline
liquids to form a binder and hence totally replace the use of OPC in concrete. In this scheme,
the alkalinity of the activator can be low to mild or high. In the first case, with low to
medium alkalinity of the activator, the main contents to be activated are silicon and calcium
in the by-product material such as blast furnace slag. The main binder produced is a C-S-H
gel, as the result of a hydration process. In the later case, the main constituents to be
activated with high alkaline solution are mostly the silicon and the aluminum present in the
by-product material such as low calcium (ASTM Class F) fly ash (Palomo, Grutzeck et al.
1999). The binder produced in this case is due to polymerization. Davidovits (1999) in 1978
named the later as Geopolymers, and stated that these binders can be produced by a
polymeric synthesis of the alkali activated material from geological origin or by-product
materials such as fly ash and rice husk ash.
In 2001, when the research reported in this thesis began, several research publications were
available regarding geopolymer pastes and geopolymer coating materials (Davidovits 1991;
Davidovits 1994; Davidovits, Davidovits et al. 1994; Balaguru, Kurtz et al. 1997; van
Jaarsveld, van Deventer et al. 1997; Balaguru 1998; van Jaarsveld, van Deventer et al. 1998;
Davidovits 1999; Kurtz, Balaguru et al. 1999; Palomo, Grutzeck et al. 1999; Barbosa,
MacKenzie et al. 2000). However, not a great deal was known regarding using the
geopolymer technology to make fly ashbased geopolymer concrete.
The research reported in this thesis was dedicated to investigate the process of making fly
ash-based geopolymer concrete and the short-term engineering properties of the fresh and
hardened concrete.

In this respect, geopolymer concrete with a much lower environmental footprint shows
considerable promise for application in the concrete industry. In terms of global warming,
the geopolymer technology could significantly reduce the CO2 emission to the atmosphere
caused by the cement industries as shown by the detailed analyses by Gartner.

Figure 1: Cement Production Figure 2: A huge volume of fly ash

1.2 CHEMISTRY BEHIND GEOPOLYMER CONCRETE
As the basic fundamental in the hardening of ordinary Portland concrete is the production of
C-S-H (calcium silicate hydrate) gel, the basic phenomena in the geopolymer concrete is the
Polycondensation of Geopolymers.
1.2.1 Geopolymers
Polymer is a class of materials made from large molecules that are composed of a large
number of repeating units (monomers). The molecular structure of the unit that makes up
the large molecules controls the properties of the material. The noncrystalline or
amorphous state is the state when the regularity of atomic packing is completely absent.
The most familiar kind of an amorphous solid is glass (Young, Mindness et al. 1998).
Geopolymers are a member of the family of inorganic polymers, and are a chain
structures formed on a backbone of Al and Si ions. The chemical composition of this
geopolymer material is similar to natural zeolitic materials, but they have amorphous
microstructure instead of crystalline (Palomo, Grutzeck et al. 1999; Xu and van Deventer
2000). The polymerization process involves a substantially fast chemical reaction under
highly alkaline condition on Si-Al minerals, that results in a three-dimensional polymeric
chain and ring structure consisting of Si-O-Al-O bonds, as follows (Davidovits 1999):
Mn [-(SiO2) z–AlO2] n. wH2O
Where: M = the alkaline element or cation such as potassium, sodium or calcium; the
symbol – indicates the presence of a bond, n is the degree of polycondensation or
polymerization; z is1, 2, 3, or higher, up to 32.
The schematic formation of geopolymer material can be shown as described by Equations
below (van Jaarsveld, van Deventer et al. 1997; Davidovits 1999). These formations
indicate that all materials containing mostly Silicon (Si) and Aluminum (Al) can be
processed to make the geopolymer material.
 n(Si2O5,Al2O2)+2nSiO2+4nH2O+NaOH or KOH Na+,K+ + n(OH)3-Si-O-Al--O-Si-(OH)3

(OH) 2
(Geopolymer precursor)

n(OH)3-Si-O-Al--O-Si-(OH)3 + NaOH or KOH (Na+,K+)-(-Si-O-Al--O-Si-O-) + 4nH2O

(OH)2 O O O
(Geopolymer backbone)
To date, the exact mechanism of setting and hardening of the geopolymer material is not
clear, as well as its reaction kinetics. However, most proposed mechanism consist of the
following (Davidovits 1999; Xu and van Deventer 2000):
 Dissolution of Si and Al atoms from the source material through the action of
hydroxide ions.
 Transportation or orientation or condensation of precursor ions into monomers.
 Setting or polycondensation/polymerization of monomers into polymeric
structures.
However, these three steps can overlap with each other and occur almost simultaneously,
thus making it difficult to isolate and examine each of them separately (Palomo, Grutzeck
et al. 1999).
A geopolymer can take one of the three basic forms (Davidovits 1999), i.e:
 Poly(sialate), which has [-Si-O-Al-O-] as the repeating unit.
 Poly(sialate-siloxo), which has [-Si-O-Al-O-Si-O-] as the repeating unit.
 Poly(sialate-disiloxo), which has [-Si-O-Al-O-Si-O-Si-O-] as the repeating unit.
Sialate is an abbreviation of silicon-oxo-aluminate.
Davidovits (1999) proposed the possible applications of the geopolymer material
depending on the molar ratio of Si to Al, as given in Table below

Table 1 Applications of Geopolymer Material

Si/Al Application
1 Bricks, ceramics, fire protection
2 Low CO2 cements, concrete, radioactive &
toxic waste
Encapsulation
3 Heat resistance composites, foundry
equipment’s, fiber glass
Composites
>3 Sealants for industry
20< Si/Al >35 Fire resistance and heat resistance fiber
composites

Figure 3 Different Linkages of Geopolymer

 Figure 4: Typical framework of Geopolymer Gel

1.2.2 Constituents of Geopolymer Concrete

The basic constituents of Geopolymer concrete is
 Source material
 Catalytic liquid system
 Fine aggregates
 Coarse aggregate
 Water

1.2.2.1 Source Material

Any material that contains mostly Silicon (Si) and Aluminium (Al) in amorphous
form is a possible source material for the manufacture of geopolymer. Several
minerals and industrial by-product materials have been investigated in the past.
Following are the materials which are generally used as source material in GPC:-
 Rice husk ash
 Fly ash
 Silica fumes
 Ground granulated based slag
 Silica fumes
 Metakaolin

1.2.2.2 Alkali Activated Solution

The most common alkaline activator used in geopolymerisation is a combination of
sodium hydroxide (NaOH) or potassium hydroxide (KOH) and sodium silicate or
potassium silicate (Davidovits 1999; Palomo, Grutzeck et al. 1999; Barbosa,
MacKenzie et al. 2000; Xu and van Deventer 2000; Swanepoel and Strydom 2002;
 Xu and van Deventer 2002). The use of a single alkaline activator has been reported
(Palomo, Grutzeck et al. 1999; Teixeira-Pinto, Fernandes et al. 2002).
Palomo et al (1999) concluded that the type of activator plays an important role in the
polymerisation process. Reactions occur at a high rate when the alkaline activator
contains soluble silicate, either sodium or potassium silicate, compared to the use of
only alkaline hydroxides. Xu and van Deventer (2000) confirmed that the addition of
sodium silicate solution to the sodium hydroxide solution as the alkaline activator
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.

1.2.3 Fly ash Based Geopolymer Concrete

In this work, fly ash-based geopolymer is used as the binder, instead of Portland or any
other hydraulic cement paste, to produce concrete. The fly ash-based geopolymer paste
binds the loose coarse aggregates, fine aggregates and other un-reacted materials together
to form the geopolymer concrete, with or without the presence of admixtures. The
manufacture of geopolymer concrete is carried out using the usual concrete technology
methods.
As in the OPC concrete, the aggregates occupy the largest volume, i.e. about 75-80 % by
mass, in geopolymer concrete. The silicon and the aluminium in the low calcium (ASTM
Class F) fly ash are activated by a combination of sodium hydroxide and sodium silicate
solutions to form the geopolymer paste that binds the aggregates and other un-reacted
materials.
1.2.3.1 Advantages of Fly ash Based Geopolymer concrete
 High early strength: The past study shows high compressive strength than
that of ordinary concrete. It also has rapid strength gain and cures very
quickly, making it excellent options for precast structure. Geopolymer
concrete has high tensile strength. It is less brittle than Portland cement and
can withstand more movement in comparison to ordinary one.
  Very low creep and shrinkage: Shrinkage can cause severe and even danger
cracks I the concrete from the drying and heating of concrete or even the
evaporation of water from the concrete. Geopolymer concrete does not
hydrate. It is not as permeable and will not experience significance shrinkage.
The creep of Geopolymer concrete is very low. When of creep in concrete
terms it means the tendency of the concrete forces being applied against it.
 Resistant to Thaw and freeze: It has high ability to stay stable even at
temperature of more than 2200 °F. Excessive heat can reduce the stability of
concrete causing it to spall or have layers break off. Geopolymer concrete
does not experience spalling unless it reaches over 2200 °F. As for cold
temperature, it is resisting to freezing. The pores are very small but water can
still enter cured concrete. When temperature dip to below freezing that water
freezes and expand this will cause cracks to form. Geopolymer concrete will
not freeze.
 Chemical resistance: It has very strong chemical resistance, acid toxics and
salt water will not have an effect on geopolymer concrete. Corrosion is not
likely to occur with this concrete as it is with traditional Portland concrete.
 Economical: The cost of production of mass Geopolymer concrete precast
members are far cheaper as compared to ordinary Portland cement concrete.

1.2.3.2 Disadvantages of Fly ash Based Geopolymer concrete

While Geopolymer concrete appears to be the super concrete for the modern times it
has certain drawbacks which are tried to be addressed in the current study. Some of
the disadvantages are given below:
 Pre-mix only: Geopolymer concrete is widely used for ex-situ construction
only project. No practical advantage in the in-situ cast concrete work because
of highly alkaline chemicals are involved in its production having high danger
indications.
 Geopolymerization process is sensitive: Ordinary concrete influenced by
less number of parameters in comparison to Geopolymer concrete, thus very
 high precision should be taken care while preparing geopolymer concrete and
any little variations cause major setbacks.
 Lack of curing at normal temperature: The geopolymer concrete require
high for its activation and to form links of silicate and aluminate. Most of the
time temperature require is 60°C

1.2.3.3 Recent Application of Fly ash based Geopolymer Concrete

Although use of Geopolymer concrete at ground level is still at nascent stages but
recently structures have been constructed using geopolymer concrete. Some of the
interesting structures where GPC has been successfully developed and used are
discussed below.
 Road: In India, NTPC NETRA and CSIR-Central Building Research Institute
(CBRI), Roorkee have jointly developed high strength fly ash based geo-
polymer concrete for road construction.
 Airport: Geopolymer concrete has been used in regional airport in southeast
Queensland (Australia). In airport concrete pavements having thickness of
400-500 mm have been constructed.
 Precast industry: when Geopolymer concrete is subjected to dry heat or
steam cured it gives a high value of early age strength. This characteristics of
high early age strength makes it useful for the precast industry and moreover
facilities such as steam curing or heated bed curing can be carried out for
components in precast industry.
Precast Railway Sleepers
Reinforced box culverts
Precast footway panels
 Structural application: the global change institute (GCI) situated inside
University of Queensland’s (Australia) has been constructed with the use of
Geopolymer concrete. It is a four storey high building for public use.

Thus Geolpolymer concrete has very wide and bright future in construction
industry.
1.3 Aims of the Research
 The aim of the project is to move a step ahead and overcoming the flaw of
heat curing required in the development of Low calcium Fly ash based
Geopolymer concrete, a revolutionizing technology in itself in the field of
construction developed by J.Davidovits in 80s. It will reduce the dependency
on the rapidly depletion of non-renewable energy source.
 It aims to utilize the ultrafine component of effluent gas from Power Plant
which are generally blown away by authorities and require again energy
consumption to blend it in the ball mill to produce ultrafine fly ash.
 Compressive strength generally depends on the density of the material, thus it
aims to increase the density of concrete using Packing Density method, which
may give fight to Gradation theory of Aggregate used in the production of
conventional concrete.
 It also aims to design a mix having both sufficient strength and pump able
which can be utilized for in-situ construction.
 Lastly to determine the viability in terms of economy of the fly ash based
Geopolymer concrete.
The developed Geopolymer concrete in the project is tested for different Rheological,
Mechanical and Durability aspects of concrete as given below:
 Compressive strength test
 Split tensile strength test
 Flexural strength test
 Modulus of Elasticity
 Rapid chloride permeability test.
 Chloride diffusion test.
 Acid attack test
1.4 Scope of Work
The research utilized low calcium (ASTM Class F) fly ash as the base material for making
geopolymer concrete. The fly ash was obtained from only one source, because the main
 focus of this study was the short-term behavior and the engineering properties of fly ash-
based geopolymer concrete. As far as possible, the technology and the equipment currently
used to manufacture OPC concrete were also used to make the geopolymer concrete.

The concrete properties studied included the compressive and indirect tensile strengths, the
elastic constants, the stress-strain relationship in compression, and the workability of fresh
concrete.
1.5 Propositum Ordinatio
The remainder of the thesis is arranged as the follows:
Chapter 2: It describes all the past studies and literature available on the properties of
Geopolymer concrete and any advancement in the field of the ambient curing of
Geopolymer concrete.
Chapter 3: Describes the experimental program carried out to develop the mixture
proportions, the mixing process, and the curing regime of geopolymer concrete. The tests
performed to study the behavior and the short term engineering properties of the fresh
concrete and the hardened concrete are also described.
 CHAPTER 2

LITERAUTURE REVIEW

2.1 Density of Concrete

B. Bhattacharjee et.al gives the method of packing density of mix design i.e. to optimize
the particle packing density of concrete in such a way that the particles selected filled up all
the voids between large particles with smaller particles and so on, in order to obtain a dense
and stiff particle structure of concrete.
V.L. Kantha rao & S. Krishnamoorthy have studied the proportions required for least
void content followed a linear trend fairly similar to what one would obtained from the
theoretical gradings of fuller. An empirical equation has been fitted for this linear trend so
that it can be used to determine the proportions of coarse and fine aggregate of least void
contents
.
2.2 Geopolymer concrete
Davidovits,(1988a; 1988b) gave the alternative binding material to the concrete industry
which helps in reducing the global warming by reducing the emission of CO2 by 80 %.Geo-
polymeric materials have a wide range of applications which is determined by the chemical
structure in terms of atomic ratio of Si:Al in the polysialate. He also reported that
geopolymer concrete rapidly gets hardened at room temperature and gain the compressive
strength up to 20MPa after curing period of 4 hours at 200C and about 70-100MPa after 28
days. He finally conducted that the geo-polymeric mortar attains most of its strength in first 2
days of curing period.
Davidovits,(1988c; 1988d) worked with kaolinite source material with alkalis (NaOH,
KOH) to produce geopolymers.The technology for making the geopolymers has been
disclosed in various patents issued on the applications of the so-called “Siliface-Process”.
Davidovits,(1988b;1994b)stated that geo-polymeric cement was superior to Portland cement
in terms of heat and fire resistance ,as the Portland cement experienced a rapid deterioration
in compressive strength at 3000C,whereas the geo-polymeric cements were stable up to
6000C. It has also been shown that compared to Portland cement, geo-polymeric cement has
extremely low shrinkage.
 Davidovits,(1994a;1994b)demonstrated based on ASTM C227 bar expansion test,
geopolymer cements with much higher alkali content compared to Portland cement did not
generate any dangerous alkali-aggregate reaction where the Portland cement did. The
presence of alkalis in the normal Portland cement or concrete could generate dangerous
Alkali-Aggregate-Reaction. However the geo-polymeric system is safe from that
phenomenon even with higher alkali content.
Davidovits,(1999)also a pure calcined kaolinite called KANDOXI (Kaolinite, Nacrite
,Dickite Oxide) which is calcined for 6 hours at 7500C. The calcined kaolinite like other
calcined materials performed better in making geopolymers compared to the natural ones.

2.3 Rheological properties of Geopolymer concrete

Nuruddin et al(2011), Study the workability and development of compressive strength of
self-compacting geopolymer concrete prepared by thermal reaction of low calcium chloride
with Sodium hydroxide, Sodium silicate and superplasticizer. The effects of water to
geopolymer solids and fresh properties such as filling ability passing ability and resistance to
segregation was studied.
Mallikarjuna Rao (2015), Investigated the normal consistency final setting time and
compressive strength of geopolymer concrete based on fly ash which are routine test
generally conducted for cement. The procedure adopted for determining the normal
consistency final setting time and compressive strength of geopolymer is same as the process
adopted for cement.

2.4 Mechanical Properties of Geopolymer concrete

D.Hardjito and B.V.Rangan (2005) they reported on the development of a mixture
proportioning process as to manufacture low-calcium (ATM Class F) fly ash based
geopolymer concrete with the help of existing technology used for the manufacturing of OPC
concrete, they studied on the parameters such as compressive, indirect tensile strengths, the
elastic constants and other short term engineering properties that affects the geo-polymeric
concrete.
S.E.Wallah and B.V.Rangan, (2006) reported on the properties of low–calcium fly ash-
based geopolymer concrete such a creep behavior under sustained load, drying shrinkage,
sulfate resistance etc.
B Rajini et al, (2014) studies the compressive strength and split tensile strength of fly ash
and GGBS based GPC mixes with different proportions at various curing period at ambient
room temperature curing.
More Pratap Kishanrao, (2013) study the residual compressive strength of GPC prepared
with flyash and Ground granulated blast furnace slag in 50:50 proportion after heating to
temperature upto 500 ºC .
P.V.Premlatha et al, (2017) develop a High strength Geopolymer concrete by adding steel
slag to it and varying proportion of slag upto 3.5% and compare the strength of samples
cured at ambient temperature and sunlight curing.
Ganapati Naidu P, (2012) studies the strength properties of Geopolymer concrete mixture
with GGBS replaced in percentage to flyash.
Sarker et al (2017), studies the rheological and mechanical properties of GPC containing
ultrafine flyash as partial replacement to flyash.
Gnanasundram et al (2013) studies the development of GPC using flyash and GGBS with
different combinations and studies the influence of GGBS in GPC and also studies the effect
of molarity of NaOH on GPC.
Somna et al (2011), study the mechanical and microstructure of the Geopolymer concrete
based on ground flyash having particle median size of 10.5µ with NaOH based alkaline
activating system with varying molarity between 4.5 M to 16 M and compare the strength
with normal flyash concrete.
 CHAPTER 3

MATERIALS AND METHODOLOGY

3.1 General
In all the previous chapters a brief overview on the Geopolymer concrete and its usage has
given. This chapter deals with the all the materials that are used, mix design, procedure
adopted for the casting and curing of the concrete for test specimens. This is then followed
by description of types of specimens used and the tests conducted on the specimens.

3.2 Properties of Materials used in the Project

3.2.1 Fly Ash
Two types of low calcium fly ash used in this study comply with IS 3812-2003 (1).

3.2.2 Source Material

3.2.3
 Density

1300
1350
1400
1450
1500
1550
1600
1650
1700
1750

0
1561.3

10
1588.67

20
1594.67

30
1661.067

40
50 1688.67

1655.5
10mm :20mm
60

1616.67
70

1594.4
80

1583.3
90

1555.5
100

1455.33
% 20mm %10mm Density Voids
100 0 1561.3 42.18%
20 10 1588.67 41.18%
80 20 1594.67 40.960%
70 30 1661.067 38.48%
60 40 1688.67 37.48%
50 50 1655.5 38.70%
40 60 1616.067 40.140%
30 70 1594.4 40.96%
20 80 1583.3 41.30%
10 90 1555.5 42.47%
0 100 1455.33 46.1%
 Serial Sieve size Quantity % retained % %Passing Remarks as
number (µ) retained Cumulative per IS 383
(g) of retained Zone III
1 4.75 5 0.5 0.5 99.5 100
2 2.36 83 8.3 8.8 91.2 90-100
3 1.18 150 15 23.8 76.2 85-100
4 600 85 8.5 32.3 67.7 75-100
5 300 280 28 60.3 39.7 60-79
6 150 204 20.4 80.7 24.9 12-40
7 Pan 193 19.3 100 0 0-10

Fine aggregate
Fine aggregate (Sand) which is naturally occurring granular material composed of divided rocks
and mineral particles obtained from Raipur were used the experimental work. Sieve analysis was
carried out in the laboratory conforming as per IS 383-1970 and the results are tabulated.
3.2.4

3.3 jkjk