CHAPTER 1

INTRODUCTION

GENERAL

Cement is considered to be one of the most vital building materials

being used for the production of concrete and now, it plays a pivotal role in
developing the infrastructure across the world. Global cement production is
expected to increase from 3.27 billion metric tons in 2010 to 4.83 billion
metric tons in 2030.The present statistics report reveal that China currently
produces over half of the world’s cement by which China becomes the top
leader in the global production of the cement. It is estimated that China has
produced an amount of 2.41 billion metric tons in 2016 [7]. It is estimated that
India's cement production will reach more than 280 million metric tons by
2017[8]. India is the second largest producer of cement in the world.

From the above statistics reports, it clearly shows that cement is

one of the integral parts used for the construction and it play significant role
to develop infrastructure across the world. The use of concrete around the
world is considered as a second commodity after water. The environmental
issues associated with the production of Ordinary Portland Cement (OPC) are
well studied. The amount of the carbon dioxide 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. It is
estimated that the production of CO2 is approximately half from the
calcination and other half from the combustion processes.
 The cement industry thus contributes conservatively 5-8% of global
carbon dioxide (CO2) emissions [2&3], mainly through decomposition of
limestone and combustion of fossil fuels during cement production. Grinding
the ingredients of cement and their transport to the production site are
also significant contributors to the environmental footprint of the cement
industry. This emission of greenhouse gas into the atmosphere is the prime
reason for global warming. Replacing Portland (cement), either partially or
entirely, with alternative cements is also being investigated as an approach for
tackling concrete’s CO2 emissions.

Dumping and disposal of industrial wastes and by products, which

are more toxic and hazardous, are very serious issues. The industrial wastes
are dumped in open space and nearby water sources by which, they can
deteriorate air quality and water quality over a location and they affect natural
resources. Amongst industrial by products of solid wastes, the most prominent
materials are Fly Ash (FA), Ground Granulated Blast furnace Slag (GGBS),
Copper Slag (CS), Rice Husk and Silica Fume which can be used as excellent
binding materials for making concrete. Being copper slag as an economic
alternative to sand, it can reduce the environmental pollution and in addition,
it can make way for avoiding the ill effects of uncontrolled exploitation of
natural resources.

Thus, a new science of concrete has been developed after realizing

the use of industrial waste to make the eco-friendly green and smart concrete
which can reduce global warming. This demands an innovative science and
technology for the development of admixtures and the use of sophisticated
scientific apparatus to observe concrete microstructure and even
nanostructure. It is expected to produce innovative new binding materials to
make eco friendly superior concrete in the forth coming days. Geopolymer
 Concrete is one of the clear cut substitutes used for the reduction of
greenhouse gases and it is environmental friendly.

GEOPOLYMERS

Davidovits [9] developed Geopolymer which was derived from the

polymeric reaction of alkaline liquids with the source materials that were of
geological origin or by product materials rich in silicon (Si) and Aluminum
(Al). Source materials, which are used for binding with Geopolymer
chemicals, are fly ash, metakaolin, blast furnace slag and rice husk ash. The
choice of the source materials for making Geopolymer primarily depends on
factors such as availability, cost type of application, and specific demand of
the users. The alkaline liquids are made from soluble alkali metals that are
usually sodium or potassium based. The most common alkaline liquid
generally used in Geopolymerisation is a combination of sodium hydroxide
(NaOH) or potassium hydroxide (KOH) and sodium silicate or potassium
silicate. The chemical reactions of making Geopolymer are extensively
reported in the literature which comprises the following steps Davidovits
1999[3]; Xu & van Devemter 2000 [10].

 Dissolution of Si and Al atoms from the source material through the

action of hydroxide ions from alkaline solutions

 The dissolved ions then undergo a condensation reaction forming

monomer in the form of –Si-O-Al-O,-Si-O-Al-O-Si-O.

 Applying heat between the temperature of 60 degree centigrade and 80

degree centigrade for the period of approximately 6 to 12 hours to
these monomers causes them to polymerize, or links together and
forms rigid cgaubs. The polymer is then allowed to harden. It is this
process that allows the creation of Geopolymer concrete.
GEOCEMENT

Geocement is a promising building material which reduces global

warming by declining carbon dioxide emission using a proprietary liquid
Geobinder with various industrial bye products viz. Fly Ash (FA), Ground
Granular Blast furnace Slag (GGBS), Geo powder etc., and ensures eco-
friendly. By using geocement, the environment must be protected by
preventing dumping of waste by-product materials in uncontrolled manner
and by stopping Carbon dioxide (CO2) emission. GEOCEMENT comes in a 2
part packing 35 Kg + 15 Kg (Geocement powder & Geobinder liquid) which
can be mixed at site like normal cement with aggregates.

PROPERTIES OF GEOCEMENT

 Compressive Strength

The stronger interface between aggregate and binder of Geocrete

cement leads to the superior mechanical properties and long-term durability of
Geocrete.

 Tensile Strength

The tensile strength of Geocrete is same as in the case of Portland

cement concrete.

 Unit-Weight

The unit-weight varies between 2330 and 2430kg/m3.

 Sulphate Resistance

Geocement is not susceptible to sulphate attack, as there is no

gypsum or ettringite formation in geocement use.
 Acid Resistance

Geocement has got a significantly better acid resistance.

 Reinforced Geocrete Columns And Beams

The nominal compressive strength of Geocrete is between 40 MPa

and 90 MPa. Geocement-based Geocrete structures can be designed using the
standard design provisions

 Fire Resistance

Geocement is fire resistant and can take up temperature upto

700°C. Chimneys and GASIFIERS can be made with Geocrete. The
Geocement and Geocrete gain additional strength after the exposure to high
temperature.

 Geocement Precast Concrete Products

The early-age strength gain is a unique characteristic that can be

exploited in the precast industry and it can be used to maximize the
productivity.

 Excellent Resistance To Chemical Attack

Geocrete has shown to have superior acid resistance and is very

suitable for manufacturing industries for sewage systems and waste water
effluent treatment.
ECONOMIC BENEFITS OF GEOCRETE AND GEOCEMENT

Geocrete offers several economic benefits together with better

performance level and they are given below:

 Geocrete is a carbon emission free product – green cement

 Saves labour in construction

 Excellent for precast – pre finished buildings

 Saves cost, due to early setting and better mould/ form work
recycling

 Roads are usable within hours of casting

 No water curing required

 No special admixture additives required

 Low drying shrinkage

 Better shelf life

 Improved resistance towards microbiologically induced

corrosion

 Anti bacterial and termite resistant

 High initial strength gain

 Low creep

 Excellent sulphate attack resistance

 Good acid/chemical resistance

 Excellent fire resistance

 Ideal for radioactive / waste encapsulation

GEOCEMENT FOR ADVANCE APPLICATIONS

 Eco friendly green buildings

 Earth quake proof construction of buildings

 Pre-cast concrete products

 Structural and non-structural members for building systems

and bridge structures,

 Railway sleepers,

 Electric power poles,

 Precast Ready to use toilets

 Modular houses

 Sewage system,

 Other products of infrastructure.

 Fire protection systems

 Waste containment/encapsulation.

 Road bases,

 Marine structures.

 Architectural finishes with pigmenting

GEOPOLYMER CONCRETE

Vijayarangan [11] of Curtin University of Technology, Australia

conducted advanced research in Geopolymer and produced concrete by using
Australian fly ash. Concrete is produced by ingredients of Ordinary Portland
Cement with binding aggregates such as, coarse and fine, together to make a
homogeneous mass. Portland cement when mixed with water reacts to form
 In Geopolymer concrete, the formation of C-S-H gel is very
minimal, due to the presence of low calcium content in fly ash. The usage of
cement is totally nullified in the manufacturing of Geopolymer concrete and it
makes more environmental friendly. Hence, it is termed as No Cement
Concrete.

Geopolymer concrete may also be named as Adaptable Concrete by

virtue of its adaptability in curing regime. In general, the geopolymer concrete
is cured by steam curing or heat curing adopt for 24 hours by maintaining the
temperature of 65-750C. This concrete can be cured immediately after casting
or can be cured after allowing it to set in room temperature.

Inorganic polymer concrete or Geopolymer has emerged as novel

engineering material with the potential to form a sustainable element of
environmentally sustainable construction and building products in industry.
These concretes have a very small green house footprint compared to concrete
made out of conventional cement. By the proper mix design and formulation
of geopolymer materials derived from coal ash of any type that is either
ASTM class C, can exhibit superior engineering properties than the ordinary
Portland cement or they are highly cost-effective.

One of the unique characteristics of Geopolymer concrete is its

robustness and versatility in the manufacturing process. It enables products to
be tailor made from a range of coal ash sources to other alumina – silicate raw
materials [11]. Hence, they have specific properties for a given application at
a competitive cost. The successful adoption of Geopolymer technology in
future will be governed by cost factors. While the development of products is
easy to achieve on a laboratory scale by simply empirical mix formulation,
the capability to understand and control the setting process and repeatability
using variable material sources will always be considered in large scale
productions.
 A significant research has been pursued to investigate the durability
of Geopolymer exposed to various aggressive scenarios, generally in the
format of accelerated leaching tests. The outcomes are very well being
implemented in the metropolitan cities and offshore structures where high
pollutants are in excess to disintegrate the traditional OPC concrete buildings.

In defining the role of inorganic polymer technology in the

development of “Green Concrete”, the composition range must be from
1< Si/Al <5, and with Na/Al ratios not too dissimilar from 1.

CONSTITUENTS OF GEOPOLYMER CONCRETE

The main constituents of Geopolymer concrete are low calcium

ASTM class F fly ash (FA), Ground Granular Blast furnace Slag (GGBS),
alkaline liquid, coarse and fine aggregates and Copper Slag (CS). Unlike
ordinary cement concrete, in which cement is mixed in the range of 350 kg/m 3
to 450 kg/m3 depending upon the grade of concrete, an equivalent quantity of
fly ash is taken and mixed in the case of Geopolymer concrete. Class F fly ash
has been obtained from Tuticorin Thermal Power Station, Ground Granular
Blast furnace Slag (GGBS) has been got from M/s JSW Cement, Madurai
dealer and Copper Slag has been procured from M/s Sterlite Industries (India)
Ltd. They are used to manufacture Geopolymer concrete throughout the
research.

CURING OF GEOPOLYMER CONCRETE

Geopolymer concrete is cured by steam curing, heat curing and

curing at ambient temperature. Steam required in steam curing process needs
boiler and fire wood to generate steam but in hot curing, the concrete is cured
while it is exposed to electrical filament maintained at desired temperature. In
natural curing, the Geopolymer concrete specimen is allowed to expose direct
 sun light or in ambient heating. But, it takes days to cure the concrete in
ambient temperature.

Throughout this research, heat curing is adopted to cure the

Geopolymer concrete elements in the range of 65 oC to 70oC in a heat curing
chamber which is attached with a thermal sensor for automatic cut off for
desired temperature range. Harjito and Rangan (2005) [13] have reported that
the heat curing enhances the compressive strength of Geopolymer concrete by
15%, than steam curing and also attains its full strength in 24 hours. This is in
contrast to 28 days curing of cement concrete elements and hence,
Geopolymer concrete can also be termed as “one day concrete.” This method
of curing can eliminate water curing by which it is quite ideal for conserving
natural resource of water.

AN OVERVIEW OF GEOPOLYMERS DERIVED FROM

INDUSTRIAL BY- PRODUCTS.

Fly Ash

Pulverized Fuel Ash (PFA) is the residue from the combustion of

pulverized coal collected by the mechanical dust collectors or electrostatic
precipitators or separators from the fuel gases of thermal power plants. Its
composition varies with the type of fuel burnt, load on the boiler and the type
of separators. Fly ash contains oxides of calcium, aluminum and silicon, but
the amount of calcium oxide is considerably less. The carbon content in the
fly ash should be as low as possible, whereas the silica content should be as
high as possible

Classification of Fly Ash

There are two classes of fly ashes which are defined by ASTM
C618: Class C fly ash and Class F fly ash. The main difference between these
 two classes is the percentage of calcium, silica, alumina, and iron present in
the ash. The chemical properties of the fly ash are mainly influenced by the
presence of chemicals contents in the coal burned (i.e., anthracite, bituminous,
and lignite).

Class C Fly Ash

Besides the pozzolanic properties the fly ash produced from the
burning of younger lignite or sub bituminous coal has some self-cementing
properties. In the presence of water, Class C fly ash gets harden and gains
strength over time. Class C fly ash comprises more than 20% lime (CaO) and
it does not require an activator.

Class F Fly Ash

The class F fly ash is typically produced by the burning of harder,

older anthracite and bituminous coal. This type of fly ash is pozzolanic in
nature, and consists of less than 10% lime (CaO). Because of pozzolanic
properties, the silica and alumina of Class F fly ash require a cementing agent,
such as Portland cement, quicklime, or hydrated lime, in order to react with
the water. It also producescementitious compounds. The Table 1.1 shows the
Chemical requirements as per the ASTM Standards.
 Table 1.1 Chemical requirements of class F and class C fly ash

Requirements
Characteristics Class F Class C
(Siliceous fly ash) (Calcareous fly ash)
Silicon dioxide
(SiO2)+Aluminum(Al2O3)+Iron 70 50
Oxide(Fe2O3), in percent by mass.
Sulfur trioxide (SO3), max. percent 5 5
Moisture content, max., percent 3 3
Loss on ignition, max., percent 6 6

Physical Properties

Fly ash is a fine, grey, amorphous powder and it is rich in silica and
alumina. It is spherical in shape. The properties of fly ash may vary both
physically and chemically. Depending upon the nature of the coal and the
efficiency of the coal combustion process, Specific gravity and Blaine
fineness modulus (m2/kg) are 2.42.

Chemical Composition

Silica (SiO2), Alumina (Al2O3), Ferric oxide (Fe2O3) and Calcium

oxide (CaO), are the major constituents of fly ash and MgO, NaO, and KO,
SO, MnO, TiO and unburnt carbon are the other minor constituents of the fly
ash. When the sum of the constituents of Silica (SiO 2), Alumina (Al2O3),
Ferric oxide (Fe2O3) is 70% or more and the reactive calcium oxide is less
than 10%, the fly ash is technically considered as siliceous fly ash or class F
fly ash. Chemical composition of FA as mentioned by Yilmaz & Degirmenci
(2009) [14], Nath & Sarker (2011)[15], Uysal & Akyuncu (2012)[16] and
Gencel et al. (2012) [17] is presented in Table 1.2.
 Table 1.2 Chemical composition of fly ash

Chemical Yilmaz & Nath & Uysal & Gencelet

Mohammed &
Composition in Degirmenci Sarker Akyuncu
Fang (2011) et al. (2012)
% (2009) (2011) (2012)
SiO2 56.26 50.5 62.5 58.58 57.2
Al2O3 28.54 26.57 23.4 23.4 25.5
Fe2O3 5.42 13.77 3.5 6.97 6.01
CaO 4.54 2.13 1.8 1.55 1.14
MgO 1.37 1.54 0.34 2.76 2.42
SO3 0.28 0.41 1.2 0.45 0.16
K2O 1.74 0.77 0.95 4.11 4.6
Na2O 0.15 0.45 0.24 0.46 0.42
P2O5 - 1 - - -
Loss of ignition 1.35 0.6 5.61 0.2 1.12

Fly Ash Generation and Utilization in India

In India, the production of electricity depends on the coal based

thermal power plant. Moreover, the Indian coal possesses low calorific value
(3000-3500 kcal) and very high ash content (30-45%). Hence, huge amount of
ash is being generated in the coal based thermal power plants. During the year
2005-2006, more or less 112 million tonnes of ash were generated in 125
power stations. The CEA has reported that in the year 2014-2015, about
184.14 million tonnes of ash were generated in 145 power stations. Further
the NTPC has reported that it is being the ash generation has reached 225
million tonnes by 2017. If the large amount of FA is produced and is not
utilized in right quantity, it will be hazardous to environment.

From 1996 onwards, the Central Electricity Authority has been

monitoring the fly ash generation and its utilization in coal/lignite based
thermal power stations in India. CEA reports that India has reached the
highest utilization of FA that is 63 percentage in 2009-10 and 55.69
percentage in 2014-15.

However, it requires lot of effort to reach 95-100 percentage

utilization. Fly ash generation and its utilization in India are shown in Figure
1.1. The utilization of fly ash in various fields is depicted in the Figure 1.2.
During the last 30 years, extensive research has been carried out to utilize the
fly ash in various sectors. Broadly, fly ash utilization can be seen in two
angles, i.e. mitigating environmental effects and addressing disposal
problems.

(Source: CEA Report 2014-2015)

Figure 1.1 FA Generation and Utilization in India
 (Source: General electricity authority, new delhi, 2014- 2015)(10)

Figure 1.2 Fly ash Application in Various Fields

Advantages of Fly Ash

 Concrete workability is enhanced by Fly Ash and water

requirement is reduced.

 Generally less bleeding and segregation are exhibited by Fly

Ash than plain concretes.

 Fly Ash possesses sulfate and alkali aggregate resistance.

 Fly Ash shows lower heat of hydration.

 Fly Ash generally reduces the permeability and absorption of

concrete.

GGBS

Granulated Blast Furnace Slag is obtained by rapidly chilling

(quenching) the molten ash from the furnace with the help of water. During
this process, the slag gets fragmented and transformed into amorphous
granules (glass) by meeting the requirement of IS 12089:1987.
 (manufacturing specification for granulated slag used in Portland Slag
Cement). The granulated slag is ground to desired fineness for producing
GGBS. Over the period of time, its load-bearing properties continue to
increase as it absorbs surplus lime released during hydration to form more
calcium silicate hydrates. These hydrates add strength to the cement.

Granulated blast furnace slag is highly cementitious and after

drying and grinding to a fine powder, it can be used as a replacement for
conventional cement. The first commercially available Blast furnace cement
(a blend of Portland cement and GGBS) was produced in Germany in 1865
and currently over 200 million tonnes/annum of Blastfurnace slag cement are
used worldwide.

CHEMICAL COMPOSITION OF BLAST FURNACE SLAG

Blast furnace slag is composed of the following oxides,

Table 1.3 Oxides Composition of the Blast furnace Slag

Oxides Content
SiO2 19.71
Al2O3 5.20
Fe2O3 3.73
CaO 62.91
MgO 2.54
LOI 0.96
SO3 2.72
K2 O 0.90
Na2O3 0.25
 This composition is quite closer to the composition of Portland
cement.

HISTORY OF USING GGBS IN CONCRETE

There are many examples of using the GGBS concrete in the

construction and the following are some examples where the GGBS concretes
are used.

1. World Trade Centre, New York (about 40% replacement).

2. Airfield Pavement of Minneapolis Airport (35 % replacement)

3. Atlantas Georgia Aquarium (worlds one of the largest

aquarium), (20% to 70% replacements).

4. Detroit Metro Terminal Expansion (30% Replacement).

5. The Air Train linking New York John Kennedy International

Airport with Long Island Rail Road Trains (20%-30%
replacements).

6. Testing Ma Bridge, Hong Kong (59%-65% replacement).

ADVANTAGES OF GGBS

 The advantage of incorporating GGBS in concrete is the

reduction of heat of hydration

 Improved chloride and sulphate resistance, improved

corrosion resistance

 Decreased pore volume and reduced shrinkage

 Better resistance to alkali-silica reaction

  Improve the durability, reduce the maintenance cost and
increase the service life

 Reduce the carbon footprints

Road Construction

Steel slag can be used in both bound and unbound road

construction products, which generally comprise asphalt and surface dressing
in accordance with EN 13043 and sub-base, capping and fill materials in
accordance with EN 13242.

Steel slag is an ideal aggregate to be used in asphalt surfacing

materials due to the following properties: -

 Cubical shape – forms interlocking structures in the asphalt

material and providing excellent resistance to deformation

 Basic in nature - having a strong affinity to the bitumen

binders therefore resisting stripping

 High resistance to abrasion – durability of aggregate

 Good skid resistance – frictional properties are maintained

throughout the whole life of the surfacing

Hydraulic Engineering

As steel slag is hard and dense, it provides an excellent material in

hydraulic engineering as armour stone for the protection against both river
and sea coastal erosion.
Railway Ballast

Steel slag is hard dense and resistant to both attrition and abrasion
making it a suitable for use as railway ballast aggregate.

Stone Column Ground Stabilisation

In areas where the ground conditions are not suitably strong for
standard foundations of buildings, stone column piling can be implemented to
stabilise the ground. Steel slag is an ideal material for this application as it is
strong, has a cubical shape, which help the interlock and it is also has an
excellent resistance to abrasion.

Over one million tonnes of steel slag have been used extensively in
Saudi Arabia in this application and is the preferred material due to both its
physical and chemical stabilities.

Agriculture

As a result of acid rain, many fields require pH adjustment to

enable healthy and productive growth from the crops. BOS slag is used as a
basic soil conditioner with the added benefit of the release of several trace
elements essential to life.

1.14.5.1 Environmental Land Remediation

In addition to the utilisation on agriculture, a relatively new

application has been developed to help remediate brown field sites incapable
of plant growth. The BOS slag fines release calcium oxide and other trace
elements, slowly into the soil enabling the growth of grasses and trees in soft
landscaping.
COPPER SLAG

Copper industries in India have taken up nearly 3% of the entire

world market of copper. Indian copper companies - Sterlite Industries,
Hindalco, and Hindustan have contributed to the production of major
quantities of copper. Copper slag, which is produced during pyrometallurgical
production of copper from copper ores and it contains materials like iron,
alumina, calcium oxide, silica etc. For the production of one tonne of metal,
about 2.2 tonnes of slag are generated. BipraGorai (2003) [19] have stated
that Copper slag contains very small quantity of copper and the separation of
copper from slag is a very complex and tedious process. The physical-
mechanical characteristics of copper slag can be used to make the products
like cement, fill, ballast, abrasive, aggregate, roofing granules, glass, tiles etc.
Air-cooled and granulated copper slag possesses many mechanical properties
to be used as aggregate, as well as excellent soundness characteristics, good
abrasion resistance and good stability. Caijun shi et al. (2008) [20] have
expressed that copper slag is used in the production of cement, mortar and
concrete as raw materials for clinker, cement replacement, coarse and fine
aggregate, respectively.

Physical Properties

Jabri et al. (2009) [21] have insisted that the specific gravity of
copper slag is 3.4and it is higher than that of natural sand. Hence, copper slag
can be used as sand substitution for the production of high density concrete.
Water absorption of CS is 0.17%, which is very less compared to fine
aggregate and also the copper slag is glassy in nature. Wu et al. (2010) [22]
have presented that the copper slag possesses black and glassy appearance
along with a specific gravity of 3.66 and its fineness modulus is 1.78. Copper
Slag is irregular in shape, black and glassy appearance as expressed by
Brindha & Nagan (2011)[23].
 The density of copper slag varies between 3.16 and 3.87g/cm3
based on the amount of iron content. Shi et al. (2008) [24] have reported that
copper slag has the average specific gravity of about 3.5 which means, copper
slag is denser than the ordinary natural aggregates.

Chemical Composition

Copper slag has high concentration of SiO 2 and Fe2O3 but has very
low lime content which is approximately 6%. It indicates that the CS is not
chemically a very reactive material to be used as a cementitious material,
reported by Jabri et al. (2009) [25]. The total content of the silica, alumina
and iron oxide in copper slag is nearly 89%, and it exceeds 70% percentile
requirement of class N raw and calcined natural pozzolans. As reported by
Washington et al. (2007) [26]; Jabri et al. (2009) [21]; Mostafakhanzadi & Ali
Behnood (2009); [27] Wu et al. (2010) [22]; Brindha & Nagan (2011) [23]
and Najimi et al. (2011) [28] is the chemical composition of copper slag is
shown in Table 1.4.

Table 1.4 Chemical Composition of Copper Slag

Jabri Brindha
Chemical Adi and Najimi
Washington Wu et al. and
composition et al. Ali et al.
et al. (2007) (2010) Nagan
(%) (2009) (2009) (2011)
(2011)
SiO2 26.0 33.05 27.80 31.92 25.84 22.25
Al2O3 3.3 2.79 7.80 2.52 0.22 4.43
Fe2O3 55.0 53.45 52.50 59.11 68.29 57.42
CaO 2 6.06 4.60 1.25 0.15 9.57
MgO 2.7 1.56 1.2 1.65 1.56
SO3 - 1.89 0.98 1.34 0.11
K2O 0.6 0.61 1.6 0.81 0.23 -
Continued
 Na2O 1.1 0.28 - 1.40 0.5 1.47
Chloride - 0.01 - - 0.018 -
Loss of ignition - 0 - - 6.59 -
CuO 1.4 0.46 1.2 - 1.2 1.24
Insoluble
- - - - 14.88 -
residue
Sulphidesulphur - - - - 0.25 -
Mn2O3 - 0.06 - - 0.22
TiO2 - 0 0.49 - 0.41 -
ZnO 0.9 0.84 0.94

Copper Slag Production and Utilization in India

Presently, nearly 33 million tonnes of copper slag have been

generated annually worldwide and in which, India has contributed 6 to 6.5
million tonnes. To obtain mortar and concrete with required performance,
strength and durability 50 % copper slag can be used as replacement of
natural sand. Chandrasekhar et al. (2015)[29] have quoted that copper slag
may be used as fine aggregate in concrete up to 50% in pavement concrete
without any loss of compressive and flexural strength as a partial replacement
for river sand. Moreover, such concretes prove that they have about 20%
higher strength than that of conventional cement concrete of the same grade
and this is analysed by Central Road Research Institute (CRRI).
Various Applications of Copper Slag

Cement

Khalifa et al. (2009)[30] have proved that copper slag utilized in

Portland cement as substitution or as aggregate has threefold advantages like
eliminating the costs of dumping, reducing the cost of concrete and
minimizing air pollution problems. Caijunshi et al. (2008)[31] have remarked
that copper slag is used in the production of cement, mortar and concrete as
raw materials for clinker, cement replacement, coarse and fine aggregate,
respectively.

Concrete

Shi et al. (2008)[24] have tested that the strength of the mixtures
with 20-80% substitution of copper slag is higher than that of the
control specimens. The effects of copper slag aggregate on the sulphate
attack resistance and the depth of carbonation have not found any significant
attack and they have not lowered the rate of carbonation. Madheswaran et al.
(2014)[32] have opined that copper slag can be used for plastering of
floorings and horizontal surfaces upto 50% by mass of fine aggregate. For
vertical surfaces, such as brick/block walls can be used about 25% by mass of
fine aggregate. In concrete, 100% replacement of sand by copper slag yields
higher compressive strength compared to that of control mix.

Geotechnical

Chandrasekhar et al. (2015)[29] and Lavanya et al. (2011)[33] have

experimented that engineering behaviour of expansive soil can be improved
by utilizing 60% of copper slag along with 40% of soil for embankment
construction, land reclamation and for improving sub-grade soil conditions.
Pavement

Pundir et al. (2005)[34] have pointed out that the copper slag with
30% aggregates could be used in the design of Bituminous Macadam,
Dense Bituminous Macadam, Bituminous concrete and Semi-dense
bituminous concrete. Mechanical properties such as Marshall Stability,
Indirect tensile strength of mix are determined and it is found that 30%FA and
70% CS mix is optimum to be used in sub base layers of the flexible
pavements as this has been tested by Patel et al. (2012)[35]. Addition of CS
as fine aggregate in various bituminous mixes provides good interlocking
and eventually improves volumetric and mechanical bituminous strength
properties. This helps in conserving the natural aggregates and this can be
used for sub base. It will eliminate the problems related to disposal of
industrial waste like CS and FA.

Uses of Copper Slag

• Copper slag has also gained the popularity of using as a fill material in
the building industry.

• During construction the contractor may also utilize copper slag instead
of sand, Copper slag can also be used as a building material in the form
of concrete blocks.

• Copper slag has been widely used in the sand blasting industry and it
has been used in the manufacturing of abrasive tools.

• Copper slag have been utilized an abrasive media to remove rust, old
coating and others.

Generally, the waste disposal has become a severe social and

environmental problem. As a result, the waste materials should be converted
in to raw materials especially for cement production. While the cement is
being manufactured, equivalent amount of CO2 is released and it is very
harmful to the nature. When the fly ash is present in the concrete mass, it
plays dual role for the strength development. FA reacts with surplus lime
resulting from the hydration of cement and produces additional C-S-H gel
which gives additional strength to the concrete. The un-reactive portion of fly
ash acts as micro aggregates and fills up the matrix to condense the packing
effect. It results in the increased strength as reported by Sabat et al. (2011).
The unit weight of concrete decreases with the increasing quantity of fly ash
content compared to cement due to less specific gravity. Reducing the particle
size of fly ash in blended Portland cement results in reducing in the
compressive strength. It shows that fineness is an effective parameter than the
chemical composition and it has enhanced the strength development as
expressed by Ozlem et al. (2008)[36].

Copper slag micrography focuses that the material grains are

originally spherical, with a smooth and nonporous surface. The X-ray
diffraction results show the presence of fayalite and magnetite. Gonc et al.
(2007) have expressed that some peak frequencies are observed and they
suggest a basically crystalline structure. The compressive strength of High
Strength Performance Concrete (HSPC) has been improved by 20% with
100% copper slag substitution compared to the control mixture at the same
workability. The early strength of concrete has not been adversely affected by
the addition of copper slag in all High Strength Concrete (HSC) mixtures.
Cement mortars prove that all the mixtures with different copper slag
proportions yield higher compressive strength than that of the control mixture.
Khalifa et al. (2011)[30] have noted that compared to the control mixture 50%
copper slag substitution enhances the compressive strength by 70%. Mostafa
& Ali (2009)[37] have reported that in general, the addition of copper slag as
coarse aggregate increases the mechanical properties of high-strength
concrete. It may be due to the strength characteristics of copper slag and
 because of the stronger bonding between copper slag aggregate and the
cement paste matrix.

Thus, many researchers have analysed about the effects of CS

replaced for fine aggregate and fly ash partially replaced by cement in
concrete. Similarly, many researchers have reported that, durability properties
increase with the increasing quantity of FA, due to the reaction of surplus
lime with FA and it gives additional C-S-H gel to the concrete. Consequently,
it fills the pores in the concrete.

Patel et al. (2012)[35] have analysed the feasibility of copper slag

and fly ash mix by using in sub base course of the flexible pavements. From
this study, it has been suggested that the mix of 30% fly ash and 70% copper
slag is found to be optimum to be used in sub-base layers of the flexible
pavements.

It is found that the combined use of fly ash, GGBS as a binder

materials and incorporating copper slag as a filler materials in Geopolymer
concrete has not been performed. Therefore, in the present research,
experiments are carried out on strength and durability properties of
Geopolymer concrete incorporating GGBS, partially replaced by fly ash as a
binder materials and copper slag is partially replaced with sand as filler
materials in Geopolymer concrete.

OBJECTIVE

The main objective of this research work is to investigate the

strength and durability properties of Fly Ash (FA) and Ground Granulate
Blast Furnace Slag (GGBS) based Geopolymer concrete incorporating Copper
Slag (CS). The individual objective is framed as follows
  To determine the optimum proportion of GGBS slag in Geoploymer
concrete for the replacement of fly ash asabinder material.

 To determine the effective use of copper slag, replaced by sand as a

filler material in Geopolymer concrete.

 To investigate the hardened properties of Geopolymer concrete like

compressive strength, split tensile strength and flexural strength.

 To investigate the micro structure analysis of Geopolymer concrete

made of Fly Ash, GGBS and Copper Slag (CS)

 To study the durability property of Geopolymer concrete made of fly

ash, GGBS and copper slag.

 To determine the flexural and shear behaviors of Pre Stress Railway

concrete sleeper made by conventional and Geopolymer concrete.

SCOPE OF THE INVESTIGATION

For the present research low- calcium (ASTM class F) Indian fly
ash, Ground Granular Blast furnace Slag (GGBS) and Copper Slag as the
source materials for manufacturing Geopolymer concrete specimens. This fly
ash has been obtained from Tuticorin Thermal Power Stations, Tamilnadu,
India. Ground Granular Blast furnace Slag (GGBS) has been procuring from
M/s JSW Cement, Madurai. The Copper Slag has been collected from
M/s Sterlite Industries (India) Ltd and it is used to manufacture Geopolymer
concrete throughout the research. The concrete technology currently used to
manufacture OPC concrete is followed throughout the work.

The scope of the work involves the following:

 Based on the research described, twelve discrete samples have

been chosen of which nine samples belong to geopolymer
 concrete with class F Indian fly ash and GGBS as a binder
material and copper slag as a filler material. The remaining
three specimens belong to conventional concrete with suitable
proportions of concrete mixtures have been chosen.

 The durability of Geopolymer concrete cubes subjected to

water absorption, Sulphuric Acid (H2SO4) and sulfate
resistance is studied and the test results are compared with that
of the specimens made out of ordinary portland cement
concrete.

 Three numbers of Pre-Stressed Railway sleepers manufactured

of Ordinary Portland Cement (OPC) concrete and nine
specimens of Geopolymer concrete have undergone flexural
test.

 The computations are performed to predict the strength and

the deflection of Geopolymer concrete test of railway sleepers
by using the methods currently available for Portland cement
concrete members.

 The cost analysis has been compared to ascertain the

affordability of this Geopolymer concrete.