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CHAPTER 1

INTRODUCTION

1.0 GENERAL

Concrete is the abundantly utilized building product in the whole world because of its
greater compressive strength, durability and abundantly attainability. Among the
ingredients of the concrete, Ordinary Portland Cement is the prime construction
product used in huge quantities. The contribution towards CO2 emission in the
atmosphere by the cement industry is of 4-8% of total CO2 production in the world
[1]. As noticeable amount of Ordinary Portland cement are generated worldwide,
even a little decrement in its manufacturing could lead to valid environmental profits
in terms of CO2 emission [3].

India is the 2nd biggest cement manufacturing country within the world once China
[2]. The country’s cement producing was 3M tons throughout the year 2011 and also
it is anticipated to double, i.e., 550 million tons by 2022, as per the predictions by the
Cement Manufacturers Association (CMA) [11]. On the other hand, warming had
become a primary concern for changes in climate [4]. The global warming is causing
raise of Earth’s mean peripheral temperature and it results to greenhouse gas effect
[5].

Because a huge amount of Portland cement was produced around the world, even a
small reduction in production could result in significant CO2 discharge reductions. To
date, Portland cement remains the most common cementitious binder in the
construction sector, so research into environmentally acceptable alternatives is even
more important [6]. Inorganic waste products from specific manufacturing industries
have been used to partially replace conventional Portland cement [7]. Fly ash, crushed
granulated blast-furnace slag, and micro-silica are among them. Significant research
on the aforesaid materials combined with Portland cement in binary and ternary
combinations has recently been published, highlighting the increased mechanical and
durability capabilities over plain Portland cement [8]. Emerging technology makes it
possible to develop sustainable ways for the development of cement and concrete
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materials, with the goal of creating high strength and durability at a reasonable cost of
energy.

Davidovits (1999) proposed in 1978 that binders may be produced by a polymeric

reaction of alkaline liquids with silicon and aluminum in geologically derived base
materials or by-product materials such as fly ash. Geopolymers [9] is the name he
gave to these binders. Geopolymers are made up of two primary components: source
materials and alkaline liquids. Aluminum (Al) and silicon (Si) should be abundant in
alumino-silicate source materials (Si)

1.1 SCHEMATIC REPRESENTATION OF GEOPOLYMERISATION

MECHANISM

The schematic representation of Geopolymer material can be illustrated by the

following Equations shown in equation (1.1.1) [10].

n(Si2 O5 ,Al2 O2) + 2nSi O5 + 4nH2 O + NaOH Na+ + 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 (Na+) – (Si – O – Al – O – Si –

O) + 4nH2O

(OH)2 O O O

(Geopolymer – backbone)

-Si – O – Al - =O +OH- Na+ , H2O – Si – ONa+ - Al- OH

O O OH

Si Si

Fig. 1.1 (1.1.1) [10]

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Step 1: Alkalization and production of tetravalent Al in the side group sialate -Si-O-
Al-(OH)3-Na+ [12].

Step 2: Alkaline dissolution starts with the attachment of the base OH- to the silicon
atom [12].

Step 3: Cleavage of the oxygen in Si-O-Si through transfer of the electron from Si to
O [12].

Step 4: Further formation of silanol Si-OH groups and isolation of the ortho-sialate
molecule, the primary unit in Geopolymerization.

Step 5: Reaction of the basic siloxo Si-O- with the sodium cation Na+ and formation
of Si-O-Na terminal bond [11].

Step 6: Condensation between reactive groups Si-O-Na and aluminum hydroxyl OH-
Al, with production of NaOH, creation of cyclo-tri.

1.2 Fly Ash

In the construction sector, fly ash is one of the most extensively utilized alternative
cementitious materials. Fly ashes are noncombustible, inorganic finely divided
residue produced by any industrial furnace's exhaust gases [13]. Solids, cenospheres,
and plerospheres are among the particles found in fly ash [14]. Particle sizes in fly ash
range from 1 m to 100 m, with the average particle size being less than 20 m. The
particles in fly ash have a surface area of about 350 to 550 m2/kg on an average.
Silica, alumina, iron, and calcium are the main components of silicate glass [15]. Fly
ash has a specific gravity of 1.9 to 2.8 and is often greenish grey in colour [16].

1.3 FLY ASH BASED GEOPOLYMER CONCRETE

The aim for a "greener" concrete to reduce CO2 emissions from the cement industry
prompted the creation of fly ash-based geopolymer concrete. Fly ash-based
geopolymer concrete is mostly made up of silica and alumina [18]. It offers a once-in-
a-lifetime opportunity to make "green" concrete by allowing an industrial by-product,
such as fly ash, to totally replace ordinary Portland cement in concrete, reducing
carbon dioxide emissions to the atmosphere [19]. The strength properties of
geopolymer concrete have been documented in a number of publications. More
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research is needed [20] because these are essential material features of geopolymer
concrete, particularly in the design of structural concrete parts.

Many researchers have demonstrated that fly ash-based geopolymer concrete can
withstand extreme environmental conditions. As a result, this competitive advantage
can be used to build a building in a marine environment [21]. In any case, due to
differing chemical compositions, various samples of fly ash may yield different levels
of reactivity [22]. The current state of knowledge indicates that the molarity of the
NaOH solution, the fly ash/alkaline liquid activator ratio, the Na2 SiO3 /NaOH ratio,
and curing conditions are all important factors in achieving the best mechanical
strength of fly ash-based geopolymer concrete [23]. Furthermore, when exposed to a
harsh environment, the fly ash-based geopolymer concrete is more durable than OPC
[24].

1.4 BIOMASS ASH

Biomass ash is the solid residue left behind from the incineration of plant and animal
waste biomass for heat and electricity generation, accounting for 2–20 percent of the
input material. Even within the same facility, the physical and chemical
characteristics of biomass ash vary widely because they are heavily impacted by plant
type, origin and sections used for combustion, process parameters, and storage
conditions. Ash must be recycled properly since it contains critical macro- and
micronutrients from combusted biomass. Because of its high value, biomass ash is
now regularly disposed of in landfills, resulting in substantial expenditures for
biomass plant owners.
This last field's applications include road construction, surface layer in landfills, and
ash additive for concrete, brick, and cement manufacturing. Several authors have
investigated the feasibility of employing fly and bottom ash as geopolymer source
materials. According to studies, the optimal SiO2/Al2O3 ratio in ash for producing
high-quality geopolymers is between 3.3 and 4.5.
Sugar production around the world generates massive amounts of bagasse trash,
which is subsequently burned in an unregulated manner for boiler heating before
being buried in landfills, causing environmental damage. Bagasse ash is extensively
used as a Supplementary Cementing Material (SCM) in the building industry.
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Geopolymer concrete production is impossible without a thorough understanding of

pozzolanic material characterization. The use of bagasse ash for silica sources is one
of the most common applications for agricultural wastes and valuable biomass by
products in sugar milling [2]. The silica source for sodium silicate solution was
bagasse ash, which has a high concentration of silica. Different heating temperatures,
durations, and acid treatments were tested for silica extraction. Heating bagasse ash at
660°C for 3.5 hours under oxygen feeding and HCl treatment resulted in a silica
content of 91.57 percent [3].
The properties of ground nut shell ash (GNSA) produced at 5500C demonstrated that
the ash is a pozzolanic material, according to the researchers [12]. It has the ability to
boost concrete's compressive strength; a 4% replacement of OPC with GSA resulted
in a higher compressive strength. The compressive strength of OPC concrete and 12%
GNSA concrete is also found to be very similar [12]. Chemical examinations of the
ashes were performed to determine its cementing characteristics, and OPC was
partially replaced with GNSA in the concrete was varied from 0% to 20%. The
compressive and split tensile strengths of 80 specimens GNSA/OPC concrete cubes of
150mm dimension were determined after they were cured in water for 21, 28, and 56
days. According to the findings [13], the compressive strengths of the control (0%)
and various percentage mixtures increased with curing time, but decreased with larger
GSA percentages. The compressive strengths of the control and other combinations
grew with curing time, but fell as the ash %age increased. Although the control had a
higher strength, replacing up to 30% of the cement with ash would be superior to the
alternatives [14].
Cattle Dung Cake Ash (CDCA) is an agricultural waste released by biomass power
plants, domestic furnaces etc [15]. A muffle furnace was utilised to simulate the
biomass power combustion temperature in order to generate varied particle sizes of
(CDCA) (500 C, 650 C, and 800 C). Cattle Dung Cake Ash (CDCA) possesses
pozzolanic characteristics, making it pozzolanic [16]. CDCA can be used as a set
retarder for concrete in hot weather since it slows down the setting time of the
concrete [16]. In the manufacturing of concrete, cattle dung cake ash and coconut
fibre are used as a substitute for cement. About 2.5, 3 and 3.5 percent of the cement is
replaced with cattle dung cake ash, while 1 percent of the cement is replaced with
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coconut fibre. Concrete's compressive and tensile strengths were measured at various
curing times (7, 14 & 28 days). According to the results of this investigation, these
replacements will improve the strength qualities of concrete by roughly 55-70 percent.
The use of CF instead of CDCA is cost-effective, and it avoids the problem of
landfills, decreasing environmental danger and maintaining the ecological balance
that our country so desperately needs [18].
One of the most pressing concerns in the civil engineering world is the long-term
durability of concrete. This is especially true for geopolymer-based concrete, since it
is still considered one of the unsolvable issues in large-scale production and
commercialization [22]. Geopolymer has been discovered to have strong engineering
qualities and a low carbon footprint due to its lack of cement. The practicality and
durability of geopolymer concrete for pre-cast products (box culverts with dimensions
of 1200x600x1200mm) were investigated lately. Main Roads Western Australia
conducted the study in collaboration with a local pre-cast industry and Curtin
University of Technology. It was discovered that the permeability of the concrete
matrix affects the durability metrics. Geopolymer concrete has the potential to be a
durable concrete, according to tests that measured absorption, void, and permeability
coefficient. In terms of mass loss, geopolymer concrete is very resistant to sulphuric
acid, with less than 3% loss. The Geopolymer cubes were also structurally robust and
had a significant load capacity even after the entire section had been neutralised by
sulphuric acid. OPC concrete has a lower water absorption and sorptivity than
geopolymer concrete. Furthermore, sodium sulphate has the largest effect on
geopolymer concretes, whereas OPC concrete is more vulnerable to sulfuric acid
attack. In general, geopolymer concrete beats OPC concrete in terms of durability
over the exposure range evaluated, according to the data. Because of its
environmentally friendly nature, geopolymer cement is an excellent alternative to
OPC. This is because geopolymer cement can be used instead of Portland cement in
the manufacturing of concrete. The durability investigations of geopolymer concrete,
such as acid resistance, high temperature resistance, sulphate and chloride resistance,
are briefly reviewed in this work.
Oven-cured specimens had a higher compressive strength than ambient-cured
specimens. When comparing ambient curing to hot air oven curing at 60°C, the
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strength increase after 28 days was 46 percent for 10% BRHA replacement and nearly
three times for 20% BRHA replacement. The 10% BRHA replacement specimens
nevertheless exceeded the goal strength of 40 MPa after normal (room temperature)
curing [42]. As geopolymerization and gel generation continue, fractures and spaces in the
gel matrix of all geopolymer concretes become filled, resulting in a more uniform and denser
pore structure, which leads to an improvement in their durability characteristics over time
[42]. Because geopolymer concrete varies from ordinary Portland cement concrete and
mixed concretes in chemical composition, it is not suggested to apply current
standards and durability test techniques to it. Instead, prior using geopolymer
concrete, the development of a specific standard accounting for mix design and long-
term performance testing is recommended.

1.5 LAYOUT OF THESIS INTRODUCTION

LITERATURE REVIEW

OBJECTIVES AND
METHODOLOGY

MATERIALS AND PRELIMINARY

LABOURATORY INVESTIGATIONS

EXPERIMENTAL
PROGRAM

RESULTS AND
DISCUSSIONS

CONCLUSIONS AND
SCOPE OF FURTHER
WORK
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1.6 SUMMARY:
This chapter gave a brief overview of the geopolymer mechanism. The purpose of
this study was outlined in detail, as well as the introduction of the fly ash based
geopolymer concrete was also explained. The work's approach has been presented
in the form of a flow chart. Further in this chapter the introduction on biomass
ashes was discussed. The following chapter focuses on a literature study of
geopolymer concrete, three different biomass ashes (Sugarcane bagasse ash,
Groundnut shell ash and Cattle Dung Cake ash) and the durability studies of the
geopolymer concrete.