COMPARATIVE STUDY ON SYNTHESIS AND PROPERTIES

OF GEOPOLYMER FINE AGGREGATE FROM FLY ASHES

A PROJECT REPORT

Submitted by

CB.EN.P2SCE16020 SETHU PARVATHY. S

In the partial fulfilment for the award of the degree

Of

MASTER OF TECHNOLOGY

IN

STRUCTURAL AND CONSTRUCTION ENGINEERING

AMRITA SCHOOL OF ENGINEERING,COIMBATORE

AMRITA VISHWA VIDYAPEETHAM

COIMBATORE 641112

JUNE 2018
 AMRITA VISHWA VIDYAPEETHAM

AMRITA SCHOOL OF ENGINEERING, COIMBATORE 641112

BONAFIDE CERTIFICATE

This is to certify that the project report entitled “COMPARATIVE

STUDY ON SYNTHESIS AND PROPERTIES OF GEOPOLYMER FINE
AGGREGATE FROM FLY ASHES” submitted by “SETHU PARVATHY. S
(CB.EN.P2SCE16020)” in partial fulfilment of the requirements for the award of
the Degree Master of Technology in “STRUCTURAL AND CONSTRUCTION
ENGINEERING” is a bonafide record of the work carried out under my
guidance and supervision at Amrita School of Engineering, Coimbatore.

Dr. ANIL KUMAR SHARMA Dr. K.B. ANAND

Assistant Professor Professor
Department Of Civil Engineering Department of Civil Engineering

Dr.K.M.MINI
Chairperson
Department of Civil Engineering

This dissertation was evaluated by us on …………….

INTERNAL EXAMINER EXTERNAL EXAMINER

 AMRITA VISHWA VIDYAPEETHAM

AMRITA SCHOOL OF ENGINEERING, COIMBATORE

DEPARTMENT OF CIVIL ENGINEERING

DECLARATION

I, SETHU PARVATHY. S (Reg No. CB.EN.P2SCE16020) hereby declare that

this project report, entitled “COMPARATIVE STUDY ON SYNTHESIS AND

PROPERTIES OF GEOPOLYMER FINE AGGREGATE FROM FLY ASHES”, is

a record of the original work done by me under the guidance of Dr. Anil Kumar Sharma,

Assistant Professor, Department of Civil Engineering, Amrita School of Engineering,

Coimbatore and Dr.K.B. Anand, Professor, Department of Civil Engineering, Amrita

School of Engineering, Coimbatore and that this work has not formed the basis for the

award of any degree / diploma / associate ship/ fellowship or a similar award, to any

candidate in any University, to the best of my knowledge.

Signature of the student

Place:

Date:

COUNTERSIGNED

Dr. ANIL KUMAR SHARMA Dr.K.B. ANAND

Assistant Professor Professor
Department of Civil Engineering Department of Civil Engineering
 ACKNOWLEDGEMENT

The satisfaction that accompanies the successful completion of my project

would be incomplete without mentioning the people who made it possible, whose

constant guidance and encouragement crowned my efforts with success.

I express my sincere gratitude to the Almighty, for giving me the strength

and power to complete this dissertation work on time.

I owe my sincere thanks to Dr.K.M.Mini, Head of Civil Engineering

Department, Amrita Vishwa Vidyapeetham, Coimbatore for her consent, moral

support and encouragement throughout the project work.

I wish to express my heartfelt gratitude and sincere thanks to my guide Dr.

Anil Kumar Sharma, Assistant Professor, Department of Civil Engineering,

Amrita School of Engineering, Coimbatore and Dr.K.B. Anand, Professor,

Department of Civil Engineering, Amrita School of Engineering, Coimbatore, for

their inspiring guidance, invaluably constructive criticism and friendly advice

during the project work.

I would like to thank all the staff members of my department,

friends and parents who have been a source of constant support and help to me in

completing my project work successfully.

 TABLE OF CONTENTS

TITLE PAGE
CHAPTER
NO

LIST OF FIGURES i

LIST OF TABLES iii

LIST OF NOTATIONS AND

iv
ABBRIVATIONS

ABSTRACT 1

1 1.1 General Introduction 2

1.2 Objectives 4

1.3 Organisation of the report 4

2. LITERATURE REVIEW

2.1 Introduction 5

2.1.1 Geopolymers 5

2.1.2 A conceptual model for geopolymerization 6

2.1.3 Fly ash based geopolymer mortar and concrete 7

2.1.4 Effect of temperature and curing duration 8

2.1.5 Effect of NaOH molarity and Na2SiO3/NaOH

9
ratio

2.1.6 Effect of water content 9

2.1.7 Geopolymer fly ash sand 10

3. EXPERIMENTAL WORK 11

3.1 Introduction 11

3.2 Materials Used 11

3.2.1 Fly ash 11

3.2.2 Geopolymer Solution 13

3.3 Optimisation of geopolymer solution 13

3.4 Synthesis of geopolymer fine aggregate 16

4 RESULTS AND DISCUSSION 18

4.1 Introduction 18

4.2 Physical Properties of geopolymer fine aggregate 18

4.2.1 Specific Gravity 19

4.2.2 Water Absorption 19

4.2.3 pH 19

4.2.4 Particle size distribution 20

4.2.5 Angle of internal friction 21

4.3 Durability tests 24

4.3.1 Soundness test 24

4.3.2 Alkali aggregate reaction 25

4.4 Minerological and microstructural studies 26

4.4.1 X-Ray Diffraction 26

 PAGE
CHAPTER TITLE
NO

4.4.2 Scanning Electron Microscope analysis 29

4.5 Compressive strength of mortar and concrete 31

4.5.1 Compressive strength of mortar 31

4.5.2 Compressive strength of concrete 32

5 CONCLUSIONS 35

REFERENCES 37

List of Publications 42
 LIST OF FIGURES

FIG TITLE PAGE

NO
NUMBER

1 Simplified reaction mechanism 7

2 Particle size analysis for class C and class F fly 11

ash

3 Optimisation of geopolymer solution for CFA 15

4 Optimisation of geopolymer solution for FFA 15

5 Synthesised C-GFA and F-GFA 16

6 Particle size distribution for C-GFA, F-GFA, 20

Natural sand and M-sand

7 Shear stress to shear strain for C-GFA, F-GFA, 23

Natural sand and M-sand

8 Failure envelops of C-GFA, F-GFA, Natural sand 24

and M-sand

9 Class C-GFA and F-GFA mortar bars before ASR 25

and after ASR

10 XRD diffraction peaks of CFA and C-GFA 27

i
11 XRD diffraction peaks of CFA and C-GFA 28

12 SEM analysis of C-GFA 29

13 SEM analysis of C-GFA 30

14 Compressive strength of mortar 32

15 Compressive strength of concrete 33

ii
 LIST OF TABLES

TABLE NO TITLE PAGE NO

1 Physical properties of CFA and FFA 12

2 Oxide proportion CFA and FFA 12

3 Chemical properties of Sodium Hydroxide 13

4 Mix design for optimisation of CFA to 14

geopolymer solution in 1.75:1 ratio

5 Mix design for optimisation of FFA to 14

geopolymer solution in 3:1 ratio

6 Aggregate properties 18

7 Concrete Mixture Proportions 33

iii
 LIST OF NOTATIONS AND ABBRIVATIONS

1. GFA- Geopolymer Fine aggregate

2. CFA- Class C fly ash

3. FFA- Class F fly ash

4. C-GFA- Class C fly ash geopolymer fine aggregate

5. F-GFA-Class F fly ash geopolymer fine aggregate

6. M-sand- Manufacturing sand

7. Cu – Coefficient of uniformity

8. Cc – Coefficient of curvature

iv
Abstract
The growing demand for river sand has caused rapid depletion and
exploitation of this natural resource. With the increase in construction activities, it
is necessary to find an alternative to replace natural river sand. In this aspect, few
recent studies has shown the potential of using geopolymerization reactions to
produce fine aggregates using class F fly ash (FFA) to replace natural sand. In this
study an attempt has been made to utilise waste coal ash (class C and class F fly
ash) to produce artificial fine aggregate by using geopolymerization reactions. The
physical properties of both class C fly ash geopolymer fine aggregate (C-GFA) and
class F fly ash geopolymer fine aggregate (F-GFA) were compared with the
properties of natural sand and M-sand. Both C-GFA and F-GFA has comparable
physical properties like specific gravity of 2.4 and 2.45, frictional angle of 36˚and
39˚ and particle size distribution conforming to zone I. Even though, the water
absorption (6.05% for C-GFA and 5.51% for F-GFA) and pH values (12.6 for C-
GFA and 12.7 for F-GFA) were higher than that of natural sand and M-sand, it
gained satisfactory strength when used in mortar and concrete. Soundness test and
Alkali Silica Reaction (ASR) test gave positive results which proves that both C-
GFA and F-GFA have sufficient durability. The mortar specimen using C-GFA and
F-GFA gained a strength of 83% and 75% of 28 day compressive strength of natural
sand mortar cubes and 89.01% and 81% of M-sand mortar cubes respectively. The
concrete specimen using C-GFA and F-GFA gained 80.24% and 75% of 28 day
compressive strength of natural sand concrete cubes and 83.9% and 77% of M-sand
concrete cubes respectively. This study shows that both C-GFA and F-GFA can be
used an alternatives for natural sand and M-sand in construction activities.

1
 CHAPTER 1

1.1 General Introduction

Building industry is considered to be one of the most rapidly growing
industrial sector of the world and the increase in construction activities result in
exploitation and depletion of natural river sand. According to UNEP report [1]
global use of aggregates can be estimated as 25.9 billion to 29.6 billion tonnes a
year. Owing to increased environmental concerns as well as diminishing natural
resources, geopolymer fine aggregates has been identified as a valuable alternative
for natural aggregates.[2,3]
At present, about 170 million tonnes of fly ash is generated from 155
existing coal based thermal power plants in India but only about 40% of the fly ash
is utilised for various applications such as brick making, road construction, for
manufacture of cement and asbestos and the rest is dumped into landfills (Central
Electricity Authority 2016-17 report [4]). In order to reduce the health hazards
caused by the disposal of coal ash (both fly ash and bottom ash), one of the most
effective methods is to convert them into value added construction materials like
aggregates [5]. Extensive research has been done on geopolymers as an alternative
to OPC as they offer good binding properties when used in mortar and concrete,
they are proved to have good resistance against acid, fire and sulphate attack [6,7].
Geopolymer technology is capable of reducing the CO2 emission to the atmosphere
caused by cement and aggregates industries by about 80% and thereby reducing
global warming [8]. Various researchers attempted the complete replacement of
natural river sand with fly ash, but studies show that complete replacement of
aggregate with fly ash is considered to be unfeasible. By the study conducted by
Turhan Bilir et al. [9], a reduction in compressive strength and workability has been
observed when natural sand was completely replaced with fly ash. The study
suggests that the reduction could be due to the increase in fly ash content and large
surface area of fly ash per unit volume, resulting in weak bonding between fly ash
and cement paste. Another study conducted by N.P Rajamane et al. [10] observed
that fly ash has the potential to replace natural sand up to 60% without affecting the

2
workability and strength properties. Fly ash is also used as a filler in concrete, in
the study conducted by Jakub et al. [11] a reduction in compressive strength was
observed when the fly ash filler content was above 70% of the weight of total
mixture. According to this study 60% is the optimum fly ash filler content required
to achieve sufficient compressive strength. These studies showed the potential of
using fly ash as a partial replacement material for fine aggregate in concrete. The
optimum content of fly ash required for replacement of fine aggregate in concrete
is still undetermined, Parvati et al. [12] reported 40% is optimum, Siddique et al.
[13] reported 50% is optimum, whilst N.P Rajamane et al.[9]; Joseph and
Ramaamurthy [14] reported 60% is the optimum fly ash required.
Geopolymer technology has beguiled the researchers with its wide range of
application since its first discovery by Joseph Davidovits in late 1970s.
Geopolymers are inorganic alumino-silicate network having Si–O–Al–O bonds in
polymeric form, which are formed by dispersion of a precursor material such as fly
ash or metakaolin (which has silica and alumina) in an alkaline solution which
contains reagents such as sodium hydroxide (NaOH) and sodium silicate (Na2SiO3)
or potassium hydroxide (KOH) and potassium silicate (K2SiO3) [7]. The reaction
product is mainly an amorphous alumino-silicate glass phase built up of interlinked
SiO44- and AlO45- tetrahedron forming a 3D-structure [15]. The study conducted by
Rao et al. [2] suggested complete replacement of natural river sand in concrete with
class F fly ash by utilizing geopolymerization reactions. Aggregate properties such
as specific gravity, particle size distribution, pH, and frictional angle was
determined and it was compared with natural river sand. The surface topography as
well as composition of the geopolymer fly ash sand was determined by using SEM
imaging and XRD. The compressive strength of mortar using synthesised fly ash
geopolymer sand was also determined and was compared with natural river sand.
In a recent study conducted by U.S Agrawal et al. [3] in which the curing duration
of the synthesised geopolymer fly ash sand was reduced to only one hour when
compared to the previous study [2]. The properties of the synthesized geopolymer
fly ash sand was similar to the properties of natural sand.

3
1.2 Objectives
 To determine the feasibility of using class C fly ash (CFA) for the synthesis
of fine aggregate by using geopolymerization reactions.
 To compare the properties of synthesised class C fly ash geopolymer fine
aggregate (C-GFA) and class F fly ash geopolymer fine aggregate (F-GFA)
with natural sand and M-sand.
 To determine the effect of using both C-GFA and F-GFA on mortar and
concrete.

1.3 Organisation of the report

Chapter 2 gives a brief review of geopolymer technology and past research on
geopolymers.
Chapter 3 describes the experimental work including the materials used, mixture
proportions, manufacture and curing of the artificial fine aggregates, test
parameters, test procedures and equipment used for the conduct of the tests.
Chapter 4 presents and discusses the experimental results and the analysis of the
results.
Chapter 5 summarises and concludes the results of this study.
A list of References are given at the end of the Report.

4
 CHAPTER 2
LITERATURE REVIEW

2.1 Introduction
Concrete is one the most used construction material around the world and
fine aggregate is one of the most important component in it. Increased construction
activities has caused a rapid depletion of the natural river sand. Hence researchers
investigate for alternative synthetic fine aggregates in order to satisfy the rising
demand and to produce concrete with minimum impact on environment and
satisfying durability.

2.1.1 Geopolymers
The term geopolymers was first used by Davidovits in the 1970’s for alkali-
activated alumino-silicate binders. According to Davidovits (1970) [6] the reaction
of a solid alumino-silicate with a highly concentrated aqueous alkali hydroxide or
silicate solution produces a synthetic alkali alumino-silicate material generically
called a ‘geopolymer’. A. Palomo et al. (1999) [16] have done researches about the
alkali activation of fly ash and the results were compared with the alkali activation
of metakaolin. According to their research the main difference between alkali
activation of fly ash and metakaolin is,
i. The composition of the material to be activated : For fly ash, Si and Ca
dominates while for metakaolin the main components that dominate are Si
and Al
ii. Concentration of activator : low to mild for fly ash and high concentration
for metakaolin
The products synthesized by using geopolymerization method constitute a
unique family of materials with properties varying from that of cements, ceramics
or zeolites. Also, for the case of geopolymer concrete derived from fly ash the
technological characteristics show promising improvements P. Duxson et al.
(2007) [7]. Their research also suggests that the geopolymers derived from
metakaolin require too much water (which increases porosity) and are too soft to be

5
of much practical importance in construction applications. Metakaolin can be used
in making geopolymers for applications as adhesives, coatings and hydro-ceramics.
The various parameters that has to be considered while preparing geopolymers are
curing, volume stability, rheology, efflorescence and high pH Klaartje De Weerdt
(2011) [17].

2.1.2 A conceptual model for geopolymerization

In the 1950s Glukhovsky [18] proposed a general mechanism for the alkali
activation of materials primarily comprising silica and reactive alumina. The
Gluhhovsky model divides the process into three stages: (a) destruction–
coagulation; (b) coagulation– condensation; (c) condensation–crystallization. Later
P. Duxson and A. Ferna´ndez-Jime´nez (2007) [7] proposed a highly simplified
reaction mechanism for geopolymerization. It shows the key processes occurring in
the transformation of a solid alumino-silicate source into a synthetic alkali alumino-
silicate. According to this model the dissolution of solid alumino-silicate source by
alkaline hydrolysis produce aluminate and silicate species and this mechanism is
considered to be the mechanism responsible for conversion of solid particles during
geopolymerization. Once the dissolution is completed, a complex mixture of
silicate, aluminate and alumino- silicate species is thereby formed. In concentrated
solutions this results in formation of a gel.

6
 Fig 1: Simplified reaction mechanism [Source: P. Duxson et al. [7], 2007]

This type of gel structure is referred as bi-phasic with alumino-silicate and

water forming two phases. After gelation the system continues to rearrange and
reorganize, as the connectivity of gel network increases a three dimensional
alumino-silicate network is formed which is commonly attributed to geopolymers.

2.1.3 Fly ash based geopolymer mortar and concrete

Fly ash and metakaolin showed potential for development of binders by
geopolymerization method A. Palomo et al. (1999) [7]. Sodium hydroxide-
activated ground fly ash cured at room temperature can be produced with reasonable
strength. The compressive strength and microstructure of the geopolymer pastes are
dependent on NaOH concentrations Kiatsuda Somna et al. (2011) [19]. According

7
to their observations a reasonable 28 day compressive strength of 20.0–23.0 MPa
was obtained with NaOH concentration in the range 9.5–14M. The experimental
work by Rangan (2006) [20] describes the long-term properties of low-calcium fly
ash-based geopolymer concrete and the short-term properties of low-calcium fly
ash-based geopolymer concrete and it also describes the behaviour and strength of
reinforced geopolymer concrete structural beams and columns. His studies
confirmed that the heat-cured low-calcium fly ash-based geopolymer concrete has
excellent compressive strength, suffers very little drying shrinkage and low creep,
excellent resistance to sulfate attack, and good acid resistance but there is no
substantial gain in the compressive strength of heat-cured fly ash based geopolymer
concrete with age. It can be used in many infrastructure applications. Low water to
fly ash ratio could meet the demand for an approving fluidity and the increase in
concentration of NaOH decreased the fluidity of the mixes Xueying Li et al. (2013)
[21]. When Class C fly ash was activated by mixed alkali activator (sodium
hydroxide and sodium silicate solution) with optimum modulus, an increase in
compressive strength is observed Xiaolu Guo, Huisheng Shi et al. (2010) [22]. The
XRD pattern from their studies revealed that the original CFA consists of a series
of spherical vitreous particles of different sizes. When CFA is alkali activated the
sphere seems to be attacked and broken due to the dissolution of alumino-silicate
in the high pH alkali solution. Hereafter, geopolymeric gel (Na)-poly
(sialatedisiloxo-), i.e. Nan–(–Si–O–Al–O–Si–O–Si–O–)n– is formed and observed
co-existing with calcium silicate hydrate (C–S–H) gel and some remaining
unreacted spheres.

2.1.4 Effect of temperature and curing duration

When geopolymers are cured at high temperature, the samples will not have
enough moisture to develop better strength. Moreover, curing at high temperature
also cause the samples to crack. A.M. Mustafa Al Bakriaa et al. (2011) [23]. When
the geopolymer mortar mixture subjected to heat curing process, the compressive
and flexural tensile strength increase as the heat curing temperature increases up to
an optimal point. C.D.Atis et al. (2015) [24]. At elevated temperatures,
mineralogical changes are characterized by formation of albite and nepheline. The

8
performance of specimens with higher Si/Al ratios was significantly better in
elevated temperature exposure. Suresh Thokchom et al. (2012) [25]. Ambient-
cured geopolymer coupled with lower water content can achieve comparable
strength and adequate structural performance as the short-term heat-cured
geopolymer Jiting Xie et al. (2014) [26]. Heat curing for geopolymer is needed in
order to obtain sufficient strength and with heat curing, the geopolymerization
becomes more rapid. The morphology of the geopolymer samples showed changes
in the matrix when the curing temperature was increased. Zarina Yahya et al. (2015)
[27].

2.1.5 Effect of NaOH molarity and Na2SiO3/NaOH ratio

As the alkali activator concentration increases in the geopolymer mortar
mixture, the compressive and flexural tensile strengths increase up to an optimal
point that also depends on heat curing temperature. Similarly when the geopolymer
mortar mixture subjected to heat curing process, the compressive and flexural
tensile strength increase as the heat curing temperature increases up to an optimal
point that also depends on Na concentration C.D.Atis et al. (2015)[24]. For palm
oil based geopolymers when the ratio of Na2SiO3/NaOH is more than 2.5, the
compressive strength for S/L (1.0, 1.25, and 1.5) tends to decrease due to excessive
alkali content that retards the geopolymerization process. Zarina Yahya et al. (2015)
[27]. Single activator either sodium hydroxide or sodium silicate alone is not much
effective in fly ash based geopolymers. Patankar SV et al. (2013) [28]

2.1.6 Effect of water content

The water content can be varied in two stages of geopolymer synthesis.
These are: the initial mix design and during the curing processes. Less water content
in the initial design resulted in higher strength development. A combination of long-
term curing with low water content could improve ambient-cured geopolymers and
produce strength results comparable with those of geopolymers that were heat
treated. Jiting Xie (2014) [26]. For class C based geopolymer paste low water to fly
ash ratio could meet an approving fluidity. Increase in concentration of sodium
hydroxide decreased the fluidity of the mixes Xueying Li et al. (2013) [21]. From

9
the chemical reaction the water comes out from the mix during the polymerization
process. Similarly the demand of water increases with increase in fineness of source
material for same degree of workability. So, the minimum quantity of water
required to achieve desired workability is selected on the basis of degree of
workability, fineness of fly ash and grading of fine aggregate. Jamkar SS (2013)
[29].

2.1.7 Geopolymer fly ash sand

The rapid growth of the construction and infrastructure industry in India is
quickly depleting the natural river sand. To meet the burgeoning need, sand is being
produced in an unsustainable manner involving washing surface soils (termed filter
sands) and crushing of rocks to appropriate sizes (termed manufactured sand)
(Reddy 2012) [30]. Fly ash is extensively used as a replacement of natural sand but
many researches proved that it can only be used as a partial replacement material
R. Siddique et al. (2016) [13]. As per the work conducted by E J Guades (2016)
[31], they have replaced fly ash with natural sand in the preparation of geopolymer
fly ash mortar and observed that with the increase in the amount of sand the
compressive and tensile strength of the mortar reduces. Class F fly ash Geopolymer
sand with NaOH concentration of 10M and sodium silicate to sodium hydroxide
ratio of 2 showed properties similar to that of natural aggregate. Sudhakar M Rao
et al. [2]. This geopolymer fly ash sand was synthesised at a curing temperature of
100˚C and curing duration of about 7 days. The curing duration can be reduced to
1 h U.S Argrawal et al. (2017) [3]. They observed that, due to the reduction in
curing period caused incomplete dissolution of fly ash particles which caused a later
strength development of concrete.

10
 CHAPTER 3
EXPERIMENTAL METHODOLOGY
3.1 Introduction
This Chapter describes the materials, test parameters, manufacturing and
curing of artificial fine aggregates. Preliminary investigations were done to find the
optimum quantity of geopolymer solution required for class C fly ash (CFA) and
class F fly ash (FFA) for the synthesis of artificial fine aggregates using
geopolymerization reactions. With the optimised values larger quantities of both
types of geopolymer fine aggregate was produced and the various tests were
conducted.

3.2 Materials Used

3.2.1 Fly ash
Geopolymer fine aggregates were prepared using CFA obtained from
Neyveli Thermal power plant and FFA obtained from Mettur Thermal power plant
both located in Tamil Nadu, India. The physical properties of the material such as
specific gravity as per IS 1727(1967) [32], particle size distribution as per IS 2720
part IV [33] is given in Fig 2 and is tabulated in Table 1.

Fig. 2. Particle size analysis of CFA and FFA

11
Table. 1. Physical properties of CFA and FFA
Physical Properties CFA FFA

Specific gravity 2.61 2.18

Colour Grey Light Grey
Particle size distribution 9-400 µm 10-300 µm
Median particle size 34 µm 38µm

The various oxide proportion of CFA and FFA is given in Table 2. On the
basis of CaO content the fly ashes were identified as Class C fly ash (CFA) and
Class F fly ash (FFA) according to ASTM C618 [34], CaO content in CFA= 32.86%
and in FFA=10.19%.
Table 2: Oxide proportion CFA and FFA

Proportion %
Oxide

CFA FFA

CaO 32.86 10.19

SiO2 21.23 56.52
Al2O3 25.16 22.52
MgO 4.95 3.16
Fe2O3 4.86 5.78
Na2O 0.43 0.48
SO3 9.28 -
TiO2 0.95 0.86

Loss on ignition 0.03 0.08

Total 99.75 99.59

12
3.2.2 Geopolymer Solution
The geopolymer solution used was a combination of sodium silicate
solution and sodium hydroxide solution. Generally sodium hydroxide is available
in pellet form or in powdered form and sodium hydroxide used in this investigation
is of pellet form. The chemical properties given by the manufacturer is shown in
Table 3. Sodium silicate solution is also known as water glass. As per the
manufacturer the sodium silicate used in this study is usually adopted as a bonding
agent in detergent and textile industries.

Table 3: Chemical properties of Sodium Hydroxide

Min Assay 98%
Carbonate (Na2CO3 ) 1.0%
Chloride (Cl) 0.01%
Sulphate (SO2) 0.003%
Lead (Pb) 0.001%
Iron (Fe) 0.001%
Potassium (K) 0.1%
Zinc (Zn) 0.02%

The other materials that required for this study viz., 53 grade cement
confirming to IS 12269: 2013[35], water, natural river sand and M-sand were
obtained locally.

3.3 Optimisation of Geopolymer Solution

The first step in synthesis of geopolymer fine aggregate (GFA) was to
determine the quantity of NaOH and Na2SiO3 required for the preparation of
geopolymer solution (mixture of NaOH and Na2SiO3 solution). For this purpose it
is necessary to optimise the amount of NaOH and Na2SiO3 solution. In order to
optimise the solution, cubes of 70.6x70.6x70.6 mm were cast by mixing fly ash and
geopolymer solution, by varying the molarity of NaOH from 6 M-12 M and the

13
ratio of Na2SiO3/NaOH from 0.5 to 2.5 respectively by following the study
conducted by U.S Agrawal et al. [3]. The mix proportion is given in Table 4 and
5. Fly ash to geopolymer solution ratio for CFA was kept 1.75:1 and for FFA was
kept 3:1 throughout the experiment. Heat curing duration was chosen as 1h at
100˚C.

Table 4. Mix design for optimisation of CFA to geopolymer solution in 1.75:1

ratio

Mass of Na2SiO3 NaOH

Na2SiO3/NaOH solid solution solution

(g) (g) (g)

0.5 114 230

1 172 172

1.5 600 206 138

2 230 114

2.5 246 98

Table 5. Mix design for optimisation of FFA to geopolymer solution in 3:1

ratio

Mass of Na2SiO3 NaOH

Na2SiO3/NaOH solid solution solution

(g) (g) (g)

0.5 67 133

1 100 100

1.5 600 120 80

2 133 67

2.5 142 57

14
 The compressive strength of the cubes tested after curing the cube in
ambient temperature for 1 day are shown in Fig 2 and 3. It is observed that, for
CFA maximum compressive strength was attained by the cube at 10 M NaOH and
Na2SiO3/NaOH ratio of 1.5 and for FFA 10 M NaOH and Na2SiO3/NaOH ratio of
2. These values were selected as the optimum values for preparing geopolymer
solution.

Fig.3. Optimisation of geopolymer solution for CFA

Fig. 4. Optimisation of geopolymer solution for FFA

15
3.4 Synthesis of geopolymer fly ash fine aggregate
C-GFA was prepared by mixing CFA with optimum amount of geopolymer
solution (10 M NaOH and Na2SiO3/NaOH =1.5) for 10 minutes in the proportion
1.75: 1 to produce a dry mix. This mix was sieved through sieves ranging from
4.75mm to 0.075mm to produce fine aggregates having size and shape similar to
that of natural sand. Similarly, F-GFA was produced by mixing FFA with optimum
quantity of geopolymer solution (10M NaOH and Na2SiO3/NaOH= 2) for 10 min
in the proportion 3:1 are shown in Fig. 4.

(a) (b)

Fig. 5. Synthesised (a) C-GFA and (b) F-GFA

Both C-GFA and F-GFA particles were heated at 100˚C for 1 h and was
kept at ambient temperature for one day. Physical properties such as specific
gravity, particle size distribution, pH and frictional angle was determined. Tests
such as soundness test, alkali silica reaction test (ASR test) were conducted on both
types of fly ash geopolymer fine aggregate.
X-ray Diffraction method (XRD) was used for the mineralogical studies of
C-GFA and F-GFA and microstructural imaging of the material was done by using
Scanning Electron Microscope (SEM) analysis. In this study, Bruker D8 Advance
X-ray Diffractometer was used to identify the various minerals present in the

16
material. The sample was finely ground to powder form prior to XRD test. The tube
conditions were set at 40kV and 40mA. The XRD patterns were obtained from
intensity (counts) and angle (2θ), with angle ranging from 10˚ to 90˚ (step size 0.02˚
2θ and speed 2˚/min). SEM analysis gives the surface topography of the material.
The SEM images were obtained using Field Emission Scanning Electron
Microscope (FE-SEM) by Carl Zeiss Micrography ltd.
The effects of using these geopolymer fine aggregates (C-GFA and F-GFA)
in mortar and concrete was determined by compressive strength tests. A
comparative study was performed between fly ash geopolymer fine aggregates with
river sand and M-sand, and the same has been discussed in the next section.

17
 CHAPTER 4
RESULTS AND DISCUSSION

4.1 Introduction
In this Chapter, the test results are presented. It discusses the physical properties of
C-GFA and F-GFA and the same is compared with natural sand and M-sand.
Durability studies such as soundness test and ASR test has been conducted on C-
GFA and F-GFA. The test results also cover the effect of using C-GFA and F-GFA
as a complete replacement for natural river sand and M-sand in mortar and concrete.

4.2 Physical properties of geopolymer fine aggregate

The physical properties of synthesised aggregates (C-GFA and F-GFA) has
been tabulated in Table 6 below. The physical properties of C-GFA and F-GFA has
been compared with that of natural sand and M-sand.

Table 6. Aggregate properties

Parameter C-GFA F-GFA Natural M-sand
sand

Specific 2.40 2.45 2.65 2.64

Gravity
pH 12.6 12.7 8.12 10.09

Water 6.05% 5.51% 1.03% 0.982%

absorption
Cc 1.14 1.30 0.8962 0.833

Cu 4.13 4.44 1.66 2.88

Frictional angle 36˚ 39˚ 38˚ 39˚

18
4.2.1 Specific Gravity
Specific gravity test was conducted as per IS 2386 (part 3): 1963 [36]. The
specific gravity of C-GFA and F-GFA was found out to be 2.40 and 2.45
respectively. These values are less compared to those of natural river sand and M-
sand (Table 6), which makes it lighter in weight. An earlier study [3] also
characterised F-GFA as lighter in weight compared to natural sand. There was an
increase in specific gravity for FFA after the geopolymerization process. The low
specific gravity of the FFA could be due to the presence of hollow particles, such
as cenospheres or plerospheres. During geopolymerization process Si-O-Al-O
bonds are formed which increases the specific gravity of F-GFA compared to that
of FFA [21]. There was a reduction in specific gravity of CFA after
geopolymerization process, which could be due to the utilisation of calcium during
geopolymerization process [16,27].

4.2.2 Water absorption

For mortar and concrete, with respect to compressive strength the water cement
ratio is a key parameter. When calculating the w/c ratio only the effective water
content is used which is the difference between total water present in the concrete
and the water absorbed by the aggregates. To calculate the free water it is necessary
to know the water absorption of aggregates. The water absorption of C-GFA and F-
GFA was determined as per IS 383: 2016 [37], and was found out to be 6.05% and
5.51% respectively which is higher than the water absorption of natural river sand
and M-sand (water absorption of 1.03% and 0.982% respectively). This explains
the porous nature of synthesised C-GFA and F-GFA.

4.2.3 pH Value
The pH values were determined as per IS 2720 (part 26) [38]. The pH of
class C fly ash GFA and class F fly ash GFA was found out to be 12.6 and 12.7
respectively, which is higher than that of natural sand and M-sand which has pH of
8.12 and 10.09 respectively. Higher pH value indicates alkaline nature of C-GFA
and F-GFA. This results in the development of alkaline environment on mixing
with cement. But this does not affect the properties of mortar and concrete, as

19
hydration of cement also results in the development of alkaline environment (pH of
12.8-13.3) [39].

4.2.4 Particle Size Distribution

The particle size distribution is necessary to understand the physical
property of a material. It was determined by sieve analysis. C-GFA and F-GFA was
identified to be coarser in nature as they have fineness modulus of 3.033 and 3.027
respectively (fineness modulus between 2.9-3.2) IS 2386 (Part 1):1963 [40]. Fig. 6.
Represents the grain size distribution of C-GFA, class F-GFA, natural sand and M-
sand.

Fig.6. Particle size distribution curves of C-GFA, F-GFA, natural sand and M-
sand

The figure shows that the C-GFA and F-GFA belongs to zone I as per IS
383: 2016 [37]. The coefficient of uniformity Cu and the coefficient of curvature Cc
was determined as per IS 2386 (part 1): 1963 [40] and is tabulated in Table. 6. It
was observed from the Table. 6 that natural sand, M- sand, class C-GFA and F-
GFA were poorly graded (SP) (according IS 1498: 1970 [41] for well graded sand
Cu >6 and Cc =1-3). Both C-GFA and F-GFA has similar curves, and the curves
overlapped one another in the figure, which indicates that both C-GFA and F-GFA

20
has particles of similar gradation, Rao et al. [2] and Agrawal et al. [3] also graded
F-GFA as poorly graded.

4.2.5 Angle of Internal Friction

Direct shear test was used to determine the internal frictional angle of the
sand, frictional angle is necessary to understand the type of particles as well as the
packing of the aggregate. The frictional properties were determined as per IS 2720
part (Part 13) [42]. Fig 7 gives shear stress to shear strain graphs for C-GFA, F-
GFA, sand and M-sand. The shear stress increases gradually to an ultimate value
without a prior peak for C-GFA, F-GFA, natural sand and M-sand.

(a)

21
(b)

(c)

22
 (d)

Fig. 7. shear stress to shear strain for (a) C-GFA, (b) F-GFA, (c) Natural sand and
(d) M-sand

From the normal stress values and shear stress values a graph was plotted,
Fig 8. gives the failure envelops of C-GFA, F-GFA, natural sand and M-sand. The
slope of the line will give the internal friction angle.

23
 Fig. 8. Failure envelops of C-GFA, F-GFA, Natural sand and M-Sand

C-GFA and F-GFA has a frictional angle of 36˚ and 39˚ respectively, which
is very close to natural sand and M-sand which has a frictional angle of 38˚ and 39˚
respectively , according to Das et al. [43] 27˚ indicates loosely packed rounded
grains and 45˚ indicates densely packed angular grains. It shows that C-GFA
contains more of rounded grains while F-GFA, natural sand and M-sand contains
more of angular shaped particles, (Angularity increases with increase in internal
friction angle [44]). U.S Agrawal et al. [3] achieved a frictional angle of 42˚ for F-
GFA, which indicates that F-GFA contains more of angular particles compared to
the rounded grain F-GFA particles characterised by Rao et al. [2] which has a
frictional angle of 35.5˚.

4.3 Durability tests

4.3.1 Soundness test
Soundness of geopolymer fine aggregates was determined according to IS 2386
(part 5): 1986 [45]. Soundness test of an aggregate determines the resistance of the
aggregate under severe weathering conditions. In this test, the aggregates were
subjected to repeated wetting and drying for a number of cycles (usually 5 cycles).
C-GFA and F-GFA was subjected to 5 cycles by immersing it into saturated sodium

24
sulphate solution for 16h and then drying in oven at 110˚C for 4 h. An average
weight reduction of 7% and 6% was obtained for C-GFA and F-GFA based on 5
cycles. It was observed to be within the limits recommended by IS 383:2016 [37]
(less than 10% loss after 5 cycles). Thus both C-GFA and F-GFA has comparable
soundness value and can resist volume changes when subjected to weathering
action.

4.3.2 Alkali Silica Reaction (ASR) test

The alkali from the cement can react with siliceous content from the fine or
coarse aggregates which results in alkali silica reaction. Hence, it is necessary to
perform this test to determine the reactivity of aggregates. In order to determine the
alkali silica reaction, mortar bars are prepared by mixing both C-GFA and F-GFA
with cement as per ASTM C1260 [46]. These bars were immersed in 1M NaOH
solution and kept at 80˚ C for a period of 14 days. The percentage of expansion of
the bars after 14 days was determined. The bars exposed to ASR test are shown in
Fig 9.

(a) (b)

Fig. 9. Class C-GFA and F-GFA mortar bars before ASR (a) and after ASR (b)

The average expansion of the C-GFA and F-GFA was observed to be 0.04%
and 0.05% which was less than the limit given by IS 383: 2016 [37] (expansions

25
less than 0.1% after 16 days indicates innocuous behaviour). In case of geopolymers
a cementitious binder is formed by utilising the alkali from the chemical reaction
and thus decreasing the expansion, in this case the main reaction product was
calcium silicate hydrate (CSH) with low Na and Al content [15,47]. C-GFA and F-
GFA with pH level as high as 12.6 and 12.7 did not undergo any ASR reaction. But
from visual examination, change in colour of the surface layer due to white
chemical precipitate along with surface cracks were observed in both C-GFA and
F-GFA bars.

4.4 Mineralogical and Microstructural studies

It is required to determine the minerals present in the synthesised
geopolymer aggregates (C-GFA and F-GFA) to analyse the impact of
geopolymerization process. SEM analysis was carried out to study the
microstructural properties of C-GFA and F-GFA.

4.4.1 X-Ray Diffraction (XRD)

Fig. 10. shows the XRD diffraction peaks of CFA and C-GFA, quartz and
mullite are the major crystalline minerals which are observed in fly ashes. However,
peak of hematite is also observed along with quartz and mullite [19].

26
 Fig. 10. XRD diffraction peaks of CFA and C-GFA

In case of diffraction patterns of CFA, the intensity of quartz at 2θ = 50°

reduced significantly and thereby a new CSH phase is observed in diffraction
patterns of C-GFA, which indicates the reaction of quartz in the alkaline solution.
A broad hump is also seen between 2θ = 20° to 40° which usually represents
amorphous silicates in geopolymers [48]. These amorphous phases are difficult to
characterize [49]. This indicates that some of the silica has been utilized for
geopolymerization reactions. The observed peak at 2θ= 50° were relatively lower
than that of CFA which may be due to geopolymerization reactions. This shows the
progress of the reactions to form geopolymer.
Fig. 11 shows the XRD diffraction patterns of F-GFA. Presence of silica,
quartz and alumina can be seen in both class C and F fly ashes. It can be observed
from the figure that the formation of C-S-H in F-GFA is lower compared to C-GFA.

27
It is also observed that the prevailing reaction product is amorphous in nature.
However, minor amount of crystalline phases are also seen in the sample [50].

Fig. 11. XRD diffraction patterns of FFA and F-GFA

When fly ash is mixed with alkaline solution containing NaOH and
Na2SiO3, it releases the silicon and aluminium ions into the solution, this results in
the formation of Si-O-Al-O bonds. It is considered to be a strong binder and imparts
strength to the geopolymer material [7, 47]. The XRD patterns of C-GFA and F-
GFA show that the intensity of the parent minerals decreased after the
geopolymerization process, but it indicates that these minerals were not completely
dissolved in alkaline solution [51]. Sharp peaks of quartz can be seen in the XRD
patterns of C-GFA and F-GFA which was inherited from the parent fly ash proves
that the involvement of crystalline phase was less compared to amorphous phase
[52].

28
4.4.2 Scanning Electron Microscope Analysis (SEM)
Fig. 12 shows the SEM micrographs of C-GFA, the micrographs are
arranged in the increasing order of their magnification ranging from 500 X to 5 KX.

Fig. 12. SEM analysis of C-GFA

From the micrographs, it can be observed that C-GFA and F-GFA are
porous in nature and the particles are irregular in shape. The irregular particles seen
on the SEM images were quartz, unburned coal and agglomerates while the
regularly shaped particles were mostly spheres such as cenospheres and
plerospheres [53]. The porous nature and cracks might have contributed to
increased water absorption. The SEM analysis did not show a homogenous
microstructure, however, a continuous matrix with fly ash particles and pores were
found to be embedded within the microstructure. The fly ash particles were
combined due to the cementations reactions which provided a dense microstructure.
In a similar study on NaOH activated geopolymers, Somna et al. [19] had also

29
observed similar kind of microstructure in their geopolymeric samples. It is also
interesting to observe the fly ash particles coated with the cementitious products
serving as nucleation sites for further reactions.
In case of micrographs of F-GFA as shown in Fig. 13, the homogeneity of
the microstructure was quite less than that of C-GFA. From the micrographs,
presence of unreacted fly ash particles are also identified i.e., fly ash particles that
are unutilized during geopolymerization reactions. An interlocking network of fly
ash particles are observed which is supposed to provide strength to the GFA. Some
of the fly ash particles are also seen to act as a nucleation site for further chemical
reactions. Studies done by U.S Agrawal [3] et al. also observed similar results and
it is reported that these unreacted fly ash particles could act as fillers and also
contribute in increasing strength of mortar and concrete.

Fig. 13. SEM analysis of F-GFA

From Fig. 13 at 5KX magnification, it can be observed that fly ash particles
that has undergone geopolymerization are co-existing with some unreacted fly ash

30
spheres and also with particles that are partially covered with reaction products [54].
The heterogeneity of both C-GFA and F-GFA was mainly due to the heterogeneity
of parent fly ash.

4.5 Compressive strength of mortar and concrete

4.5.1 Compressive strength of mortar
The effect of using C-GFA and F-GFA was determined by conducting
compression tests on mortar and concrete cubes according to IS 2386 (Part 6), IS
2250-1981 [55,56]. The results were compared with compressive strength of mortar
and concrete prepared with river sand and M-sand. The 28 day compressive strength
was determined by casting six mortar cubes (3 using C-GFA and 3 F-GFA) of size
70.7x70.7x70.7 mm. To prepare mortar cubes C-GFA and F-GFA was mixed with
cement and water in 1:3 proportion by volume, with w/c ratio of 0.7 for C-GFA and
0.6 for F-GFA to achieve a flow of 100± 5mm. The slight increase in w/c ratio of
C-GFA could be due to the higher water absorption (6.05%) caused by the presence
of cracks along with the pores. Similarly, mortar cubes were prepared using natural
river sand and M-sand in 1:3 proportion and w/c ratio of 0.45 to achieve a flow of
110±5 (IS 4031 (Part 7) [57]). C-GFA, F-GFA, natural sand and M-sand mortar
cubes were cured for 28 days. The average 28 day compressive strength of C-GFA
mortar and F-GFA mortar is given in Fig 14. Similar results were reported by U.S
Agrawal et al. [3] for class F fly ash, they reported a compressive strength of 22.406
MPa for class F fly ash GFA and 23.94 MPa for natural sand.

31
 Fig. 14. Compressive strength results of mortar cube

The compressive strength of C-GFA and F-GFA mortar were 83% and 75%
of natural sand and 89.01% and 81% of M-sand respectively. According to T.Bilir
et al. [9] the compressive strength of mortar reduced by 73.1% when natural river
sand was replaced completely with class F fly ash which is lower than the values
obtained in this study. J. Temuujin et al [58] varied weight ratio of the binder to
sand aggregate from 9-1, and sand was replaced up to 50%. Geopolymer mortars
with 50% aggregate replacement were stiff and difficult to work with but the
compressive strength did not undergo much deviation (strength deviation of 33%)
from 10% replacement level.

4.5.2 Compressive strength of concrete

The compressive strength of C-GFA and F-GFA concrete (cubes of 10cm
size) was determined after 28 days. Concrete was proportioned for M20, the mix
design based on IS 10262: 2009 [59] and SP: 23-1982 [60]. The mix proportion is
given in Table 7.

32
 Table 7. Concrete Mixture Proportions
Materials C-GFA F-GFA Natural sand M-sand
Cement
372 kg/m3 372 kg/m3 372 kg/m3 372 kg/m3

Fine
647 kg/m3 634 kg/m3 700 kg/m3 697 kg/m3
Aggregate
Coarse 1155
3
1155 kg/m3 1155 kg/m3 1155 kg/m3
Aggregate kg/m
Water
186 litres 186 litres 186 litres 186 litres

As the water absorption of geopolymer fine aggregate is more, both C-GFA

and F-GFA was pre-wetted for 15 minutes before using in concrete in saturated
surface dry condition. Later, it was mixed with cement, coarse aggregate and water
with w/c of 0.5 to achieve a slump of 55 mm, six cubes were casted (3 using class
C fly ash GFA and 3 using class F fly ash GFA) and was cured for 28 days. The
average compressive strength of C-GFA and F-GFA mortar is given in Fig. 15.

Fig. 15. Compressive strength results of concrete cube

33
 The average 28 day compressive strength of C-GFA and F-GFA were
80.24% and 75% of natural sand and 83.9% and 77% of M-sand respectively.
Previous studies [10-14] showed that replacement of fine aggregate with fly ash is
possible only up to 60%. In the study conducted by R. Siddique et al. [13] the
strength of concrete increased with increase in fly ash percentage, but the rate of
increase in strength decreased at higher percent replacement, particularly between
40-50% replacement level. In another study [61], fly ash was used as a binder in
concrete. With the increase in the binder, the aggregate quantity was reduced. The
replacement of cement ranged from 0- 55%. At replacement level of 55% the
strength of concrete reduced by 44% when compared to normal concrete.
In both C-GFA and F-GFA the unreacted fly ash particles will react with
lime released during hydration process and this imparts higher strength to both
mortar and concrete [2].

34
 CHAPTER 5
CONCLUSIONS

Based on the results obtained from this study of geopolymerizing fly ash
(class C and class F) into fine aggregates and using as an alternative to natural river
sand and M-sand, the following conclusions can be made.
 The physical properties such as specific gravity, particle size analysis, direct
shear test, soundness test and ASR tests provided comparable results with
natural sand and M-sand.
 Water absorption of both C-GFA and F-GFA (6.05% and 5.51%
respectively) was higher compared to natural sand and M- sand (1.033%
and 0.982% respectively). The aggregates are considered to be porous in
nature. The SEM images exhibited presence of pores on both C-GFA and
F-GFA.
 In the XRD patterns of C-GFA and F-GFA, presence of amorphous phase
was predominant than crystalline phase and it was also identified that the
parent mineral did not undergo complete dissolution after the
geopolymerization.
 SEM images revealed the porous nature of C-GFA and F-GFA. Presence of
unreacted fly ash particles was also identified.
 Introduction of both C-GFA and F-GFA in mortar and concrete reduces the
compressive strength when compared to natural sand and M-sand but meets
the required strength to be used as a structural material.

Both C-GFA and F-GFA can be used as a complete replacement material

for natural sand and M-sand in mortar and concrete. C-GFA and F-GFA are lighter
in weight compared to river sand and M-sand. These light weight aggregates can be
used for the manufacture of concrete blocks, construction of partition walls and
panel walls as well as for the heat insulation on roofs. These aggregates are cheaper
compared to conventional light weight aggregates and it is environment friendly.
But the water absorption of C-GFA and F-GFA was very high and further studies

35
are needed to reduce the water absorption through different processes for synthesis.
Future works can be done to determine the fire resistance property of C-GFA and
F-GFA.

36
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List of Publications
Sethu Parvathy.S, Anil Kumar Sharma, Kalpathy.B. Anand, Comparative Study on
Synthesis and Properties of Geopolymer Fine aggregate from Fly ashes,
Construction and Building Materials (Under review)

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