Development of Geopolymer Cement from Industrial WasteTITLEFly Ash and Waste-Based Geopolymer for Sustainable Construction

Development of Geopolymer Materials Sourced with
Fly Ash and Industrial Waste

（飛灰や産業廃棄物を用いたジオポリマー材料の開発）
SUJITRA ONUTAI
Energy and Environment Science

Nagaoka University of Technology, Nagaoka, Japan
August 2016
Acknowledgment
This thesis could not have been realized without a great deal of guidance, and
both mental and practicalsupport. I would like to thank deeply those people who,
during two years of my double doctoral program, provided me everything I needed.
First and foremost, I would like to express my deepest gratitude to my
supervisor Prof. Dr. Takaomi Kobayashi for the continuous support of my double
doctoral program and research, for his patience, motivation, enthusiasm, and
immense knowledge. His excellent guidance helped me in all the time of
investigation and writing of this thesis. I could not have imagined having a better
advisor and mentor for my doctoral degree in Energy and environment science at
the Nagaoka University of Technology (NUT), Japan.
Grateful acknowledgment is made to my co-advisor Assist. Prof. Dr. Sirithan
Jiemsililers of Department of Materials Science at Chulalongkorn University (CU),
Thailand, for discussing, good advising supporting, and helping in my research.
I especially would like to thank the rest of my thesis committees: Assoc. Prof.
Dr. Nobuo Saitou, Assoc. Prof. Dr. Tatsurou Imabuko, Assoc. Prof. Dr. Motohiro
Tagaya and Assist. Prof. Dr. Siriporn Taokeaw from Nagaoka University of
Technology and Assoc. Prof. Dr. Minoru Satoh from Ibaraki National college of
Technology whose support, and guidance made my thesis work possible. They have
been actively interested in my work and have always been available to advise me.
Also, I am very grateful for their patience, motivation, encouragement, insightful
comments, hard questions, and immense knowledge of geopolymer that, taken
together, make them a great mentor.
I would like to thank present and past members also the secretary of the
Biosustainable Environmental Materials engineering Laboratory for sharing their
discussions, experiences, and knowledge during the time of the study. Special thanks
to Mr. Kotaroh Nakamoto, Ms. Lisa Nakajima, Mr. Tatsuya Murayama, Mr. Kazuki
Nakasone and Mr. Yuta Watanabe for helping to finish up my various projects. Also
thanks to NUT’s Thai member for helping, supporting and having fun live at
Nagaoka city. Moreover, Also, I greatly appreciate the support from
Ms. Pronchanok Lawita from Department of Materials Science at Chulalongkorn
University, Thailand and Mr. Sarayut Tunmee from Department of Materials
Science at Nagaoka University of Technology, Japan who partly motivated me to
continue my study in double doctoral program at NUT and CU.
The author is grateful to the Cultivation of Global Engineering by Pacific
Rim Green Innovation project of Nagaoka University of Technology and also the
100th Anniversary Chulalongkorn University Fund for financial support in the form
of grants and Doctoral scholarships.
Finally, I would also like to thank my parents, family, as well as my friends,

for their continuing support and encouragement.
SUJITRA ONUTAI
August 2016
Contents
Chapter 1: General Introduction .......................................................................... 1
1.1 Geopolymers ................................................................................................... 1
1.1.1 Background and definition ....................................................................... 1
1.1.2 Geopolymer structure and preparation techniques ................................... 4
1.1.3 Geopolymerization reaction ..................................................................... 7
1.1.4 Synthesis of geopolymers ......................................................................... 9
1.1.5 Geopolymer applications ........................................................................ 12
1.2 Raw materials of fly ash and industrial wastes used to
synthesis geopolymer .......................................................................................... 16
1.2.1 Fly ash .................................................................................................... 17
1.2.2 Industrial wastes for geopolymer source ................................................ 21
1.3 Objective of thesis and Outlines of thesis ..................................................... 24
1.4 References ..................................................................................................... 26
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials ...................................... 36
2.1 Introduction ................................................................................................... 37
2.2 Experimental procedure ................................................................................ 39
2.2.1 Raw materials of geopolymers ............................................................... 39
2.2.2 Geopolymerization ................................................................................. 42
2.3 Results and discussion .................................................................................. 45

2.3.1 Properties of the waste slurry for geopolymerization .............................45
2.3.2 Mechanical properites of geopolymer bulk ............................................49
2.3.3 Morphological properties of geopolymers .............................................54
2.3.4 Reactive phases and chemical bonds of geopolymer .............................60
2.4 Conclusions ...................................................................................................64
2.5 References .....................................................................................................65
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration ................................70
3.1 Introduction ...................................................................................................71
3.2 Experimental procedures ...............................................................................73
3.2.1 Materials .................................................................................................73
3.2.2 Synthesis of geopolymer sample in a microwave oven ..........................74
3.2.3 Characterization of pastes and geopolymers ..........................................76
3.3 Results and discussion...................................................................................76
3.3.1 Geopolymerization in microwave heating for porous matrix .................76
3.3.2 Properties of the geopolymer matrix cured with microwaves ................85
3.3.3 Geopolymers containing aluminosilicate formed with
microwave cure................................................................................................92
3.4 Conclusion.....................................................................................................96
3.5 References .....................................................................................................97

Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing ........................................................................................ 102
4.1 Introduction ................................................................................................. 103
4.2 Experimental procedure .............................................................................. 105
4.2.1 Raw materials and preparation of geopolymers ................................... 105
4.2.2 Characterizations of bulk geopolymer ................................................. 106
4.3 Results and discussion ................................................................................ 109
4.3.1 Microwave pre-curing fly ash-alkali pastes for geopolymers .............. 109
4.3.2 Properties of geopolymers cured in different NaOH concentration ..... 112
4.3.3 Effect of post heating to the microwave cured geopolymers ............... 117
4.4 Conclusions ................................................................................................. 126
4.5 References ................................................................................................... 127
Chapter 5: Summary .......................................................................................... 131
List of Achievements........................................................................................... 133
Presentations in International Conferences ..................................................... 134

List of Tables
Table 1.1 Geopolymers presently developed and applied in
main classes of materials ........................................................................................3
Table 1.2 Summarize geopolymer applications ..................................................14
Table 1.3 Raw materials for synthesis geopolymer ................................................16
Table 2.1 Chemical composition of fly ash and aluminium hydroxide waste. .......40
Table 2.2 Mixture proportions for geopolymerization. ..........................................44
Table 2.3 Composition of ions in geopolymer bulk. ..............................................52
Table 4.1 Surface area of bulk geopolymer curing in microwave
at different times ...................................................................................................114
Table 4.2 Surface area of bulk geopolymer curing in microwave
at different times and post heating at 80 oC for 24 h ............................................114

List of Figures
Figure 1.1 Chemical structure of polysialates .......................................................... 2
Figure 1.2 Geopolymer framework .......................................................................... 6
Figure 1.3 A sketched model of the geopolymerization process. M+ refers
to alkali cations (usually Na+ and/or K+). SiO44 + refers to dissolved silicate .......... 8
Figure 1.4 Applications of geopolymer materials based on the Si:Al ratio............ 15
Figure 1.5 The process of producing fly ash at a power station. ............................ 18
Figure 1.6 Aluminium hydroxide waste powder .................................................... 23
Figure 1.7 The etching solution cycle..................................................................... 23
Figure 2.1 SEM micrograph of a) Aluminium hydroxide waste and
b) Fly ash and paticle size distribution of c) Aluminium hydroxide waste
and d) Fly ash.......................................................................................................... 41
Figure 2.2 G' ,G'' and tan δ as a function of time and constant temperature
at 25oC with diferrent proportions of raw materials at 5 M NaOH. ....................... 47
Figure 2.3 G', G'' and tan δ as a function of temperature with differrent
proportion of raw materials at 5 M NaOH.............................................................. 48
Figure 2.4 Comparision of a) flexural strength and b)compressive strength of
geopolymer paste at age of 7 days. ......................................................................... 51
Figure 2.5 Bulk density of geopolymer bulk at age of 7 days. ............................... 53
Figure 2.6 Effect of Al-waste amount on microstructure of geopolymer
specimens: a-b) 0 wt % , c-d) 20 wt %, e-f) 40 wt % and g-h) 60 wt %
Al-waste with 10 M NaOH and cured at 80 oC for 24 h........................................ 55

Figure 2.7 Effect of NaOH concentrations on microstructure of
geopolymer specimens, a-b) 5 M NaOH and c-d) 15 M NaOH with
40 wt% of Al-waste and cured at 80 oC for 24 h....................................................56
Figure 2.8 Effect of curing temperature on microstructure of geopolymer
specimens, a-b) at room temperature and c-d) at 80 oC for 24 h with 40 %
by weight of Al- waste and 10 M NaOH. ...............................................................57
Figure 2.9 X-ray CT images of geopolymer sepecimens with different
amounts of Al-waste on structure of geopolymer specimens: a) 0 wt % ,
b) 20 wt %, c) 40 wt % and d) 60 wt % Al-waste with 10 M NaOH and
cured at 80 oC for 24h. ............................................................................................58
Figure 2.10 XRD patterns of Al-waste, FA and geopolymer paste with
different proportions of raw materials with 10 M NaOH and cured at 80 oC
for 24 h: G=Gibbsite, Q=Qartz, Ma=Magnetite, M=Mullite and H=Hematite. .....62
Figure 2.11 Infrared analysis of Al-waste, FA and geopolymer paste
with different compositions of raw materials with 10 M NaOH, cured
at 80 oC for 24 h. .....................................................................................................63
Figure 3.1 Temperature profile of geopolymers in different power
of microwave 1 min ................................................................................................75
Figure 3.2 Pictures of geopolymers cured from components containing
different NaOH concentration and X-ray micro CT for the cross-section of
geopolymers. The microwave radiation was carried out at power 850W
for 1 min. a-b) 2M c-d) 5M e-f ) 10M and g-h ) 15 M NaOH .............................78
Figure 3.3 Microstructure of geopolymer sample synthesized by curing
at 80 oC 24 h and using microwave radiation at power 200 and 850 W
for 1 min ................................................................................................................. 82
Figure 3.4 The effect of Na2SiO3/NaOH ratios on a) the volume and
b) apparent bulk density of porous geopolymer by using microwave
radiation at 850 W for 1 min................................................................................... 83
Figure 3.5 Apparent bulk density of geopolymers synthesized by using
microwave radiation at power 200-850 W for 1 min and by curing
at 80 oC 24 h ........................................................................................................... 88
Figure 3.6 Nitrogen adsorption desorption isotherms of geopolymers
synthesized by curing at 80 oC 24 h and using microwave radiation
at power 200 and 850 W for 1 min ......................................................................... 89
Figure 3.7 Volume of open pores of geopolymers synthesized by
using microwave radiation at power 200-850 W for 1 min and by
curing at 80 oC 24 h ................................................................................................ 90
Figure 3.8 Water absorption of geopolymers synthesized by using
microwave radiation at power 200-850 W for 1 min and by curing
at 80 oC 24 h ........................................................................................................... 91
Figure 3.9 XRD pattern of geopolymer sample synthesized by
curing at 80 oC 24 hand using microwave radiation at power 200
and 850 W for 1 min ............................................................................................... 94
Figure 3.10 IR spectra of geopolymers synthesized by curing at 80 oC 24 h

and using microwave radiation at power 200 and 850 W for 1 min
................................................................................................................................ 95
Figure 4.1 Protocal of synthesis geopolymer ........................................................107
Figure 4.2 The temperature profile of geopolymer in different curing time
and NaOH concentration at incident power 200W ..............................................108
Figure 4.3 The pictures of geopolymer with 1 M NaOH cured in microwave
radiation at different times; a) 25oC b) 80 oC 24 h c) 1 min d) 3 min
e) 5 min and f) 10 min...........................................................................................110
Figure 4.4 Microstructure of geopolymer with 1 M NaOH sample synthesized
by curing in microwave radiation at different times; a) 25oC b) 80 oC 24 h
c) 1 min d) 3 min e) 5 min and f) 10 min .............................................................111
Figure 4.5. Apparent bulk density of geopolymer synthesized by using
conventional oven at 80 oC and using microwave radiation at power 200 W in
different time .........................................................................................................115
Figure 4.6 Compressive strength at age of 7 days of geopolymer synthesized
by using conventional oven at 80 oC and using microwave radiation at
power 200 W in different time ..............................................................................116
Figure 4.7 Apparent bulk density of geopolymer synthesized by using
conventional oven at 80 oC and using microwave radiation at power
200 W with post heating in different time ............................................................119
Figure 4.8 Compressive strength at age of 7 days of geopolymer synthesized
by using conventional oven at 80 oC and using microwave radiation
at power 200 W with post heating in different time .............................................120
Figure 4.9 Nitrogen adsorption desorption isotherm of geopolymers
synthesized by using different curing method and different NaOH
concentration: a) 1 M b) 2 M c)5 M and d) 10 M ................................................121

Figure 4.10 The XRD pattern of geopolymer sample synthesized
using NaOH concentration at 1 M and 10 M ....................................................... 124
Figure 4.11 FT-IR spectra of geopolymer sample synthesized
using NaOH concentration at 1 M and 10 M ....................................................... 125

Chapter 1: General Introduction
1. Chapter 1: General Introduction
1.1 Geopolymers
1.1.1 Background and definition
As a construction materials, the Portland cement and concrete are the most
of essential and widely used in the world. The demand of using cement and concrete
has continuously increased and tend to grow up in the future [1]. In the estimation,
the usage of cement was approximately 2540 million tons (Mt) in 2006 and the
cement production in 2050 will be estimated around 3680 Mt to 4830 Mt [2]. In this
circumstance, there are problems in the cement industry of environmental fields. In
the industry, the greenhouse gases have been liberated into the atmosphere for
production process such emitting is the main problem of the global warming, by
carbon dioxide emission during the production processes [3]. The amount of carbon
dioxide is released into the atmosphere approximately 0.8 tons/ 1tons in the cement
industry [4-6]. In order to reduce the emission in the cement processes, many effort
has been paid to find the other cementitious materials to replace cement [7, 8].
Therefore, development of sustainable material is needed for cement and concrete.
In 1950s, Victor Glukhovsky et al. developed alkali activated systems
containing calcium silicate hydrated and alumino-silicate phases, which were used
to build a tall building. These alkaline alumino-silicate cementatious systems were
called “soil silicate” [9]. After 1972, Joseph Davidovits [10-12] reported another
form of cementitious materials using silicon and aluminum activated in a high alkali
solution. The new materials are called “Geopolymer” which are inorganic polymers
1
Figure 1.1 Chemical structure of polysialates
that have three dimensional alumino-silicates in the cementitious materials [1, 13,
14]. As shown in Figure 1.1, these materials have frame work of sialate. On the time,
these were new materials having silica-alumina networking in the molecular
framework and easily applied for coating and adhesives, new binder for fiber
composites, waste encapsulation [10]. In addition new cement materials for concrete
was proposal for geopolymer produced by condensation reaction. The polymeric
process of alumino-silicate and alkali activators, is the one of other options as
alternative green cement. This is due to that it can reduce approximately 80% of
CO2 emission to the atmosphere compared with the cement. Moreover, geopolymer
has an advantage in the production which is able to synthesis at low temperature and
2
low pressure by using alumino-silicate sources. So, it can be prepared from natural
source in nature and industry such as metakaolin, fly ash, blast furnace slag etc. with
a strong alkaline solution [15, 16]. Table 1.1 show summarizes experimental reports
of geopolymers which have been reported. Geopolymers have excellent properties
such as high mechanical properties, low shrinkage, fire resistance and durability [17].
Table 1.1 Geopolymers presently developed and applied in main classes of
materials
Class of geopolymer materials References
Waterglass-based geopolymer, poly(siloxonate), soluble silicate,

[18]
Si:Al=1:0
Kaolinite / Hydrosodalite-based geopolymer, poly(sialate) Si:Al=1:1 [19-21]
Metakaolin MK-750-based geopolymer, poly(sialate-siloxo) Si:Al=2:1 [22, 23]
Calcium-based geopolymer, (Ca, K, Na)-sialate, Si:Al=1, 2, 3 [24]
Rock-based geopolymer, poly(sialate-multisiloxo) 1< Si:Al<5 [25, 26]
Silica-based geopolymer, sialate link and siloxo link in poly(siloxonate)

[27, 28]
Si:Al>5
Fly ash-based geopolymer [29, 30]
Phosphate-based geopolymer, AlPO4-based geopolymer [31, 32]
3
1.1.2 Geopolymer structure and preparation techniques
The structures of geopolymer are composed of sialate (silicon-oxo-
aluminate) segments in the chemical framework (Figure 1.1). This consists of SiO4
and AlO4 tetrahedra linked alternately by sharing all oxygen atoms. Alkali cations
or positive ions such as Na+, K+ and Ca ++

are charged-balanced of the negative
charge of Al3+ in IV-fold coordination [8]. A polymeric structure of (poly)sialate
formed constitutes the main building blocks of geopolymeric structure and the
empirical formula of polysialates is displayed as follow [33]:
Mn [(-Si-O2)z-Al-O2-]n, wH2O (1)
where M is monovalent cation such as sodium or potassium
n is degree of polycondensation
z is amount of Si-O2 (1, 2, 3 or higher)
w is amount of water
It is common that geopolymerization can start from room temperature
containing silica and alumina unit to be oligomer (dimer, trimer) which provide the
actual unit structures of the three dimensional macromolecular edifice. The
geopolymerization stages can be supposed into three stages: (I) deconstruction, (II)
polymerization and (III) stabilization [34-36]. In geopolymer, the polymerize
sialates are linkages together type of sialate (Si-O-Al) and siloxo (Si-O-Si). The
chemical structure of polysialate geopolymers includes the classified of polysialate,
which are separated into four elementary units according to terms of the Si/Al
atomic ratio as followed [8, 11, 12]. As Figure 1.1 illustrates, for the units, first is
4
sialate and poly(sialate) at Si:Al = 1. There have -Si-O-Al-O- included in the chain
and ring polymers from the polycondensation reaction of monomer, ortho-sialate
(OH)3-Si-O-Al-(OH)3. In second unit, sialate- siloxo and poly(sialate- siloxo) at
Si:Al = 2, (-Si-O-Al-O-Si-O-) are the chain and ring polymer from the result of
condensation between ortho-silicic acid Si(OH)4. These chains have three
isomorphs as a linear, mono-siloxo-sialate and 3 cycles. In the third unit, sialate-
disiloxo and poly(sialate- disiloxo) at Si:Al = 3, (-Si-O-Al-O-Si-O-Si-O-) are
described from the result of condensation reaction between two ortho-silicic acid
Si(OH)4. The sialate units are corresponded to six isomorphs: 2 linear, 2 branched
and 2 cycles. Finally for fourth unit, sialate link and poly(sialate- multisiloxo) unit
at Si:Al > 3 which are chains from bridge Si-O-Al between two poly(siloxonate),
poly(silanol) or poly(sialate) chains.
As seen in the geopolymer framework, Figure 1.2 describes the poly(sialate)
chain and ring connected together by coordination with oxygen atom to the 3D
structure. The macromolecular structure of geopolymer could be produced from
natural silicate and aluminosilicate. In geopolymer chemistry, five main types of
silicates and aluminosilicates are divided by island structures (orthosilicate,di-
silicate), group structures (ring silicates,tri-silicate, tetra-silicate, hexa-silicate),
chain structures (linear, branch, ribbon), sheet structures and framework structures.
5
Figure 1.2 Geopolymer framework [10]
6
1.1.3 Geopolymerization reaction
As illustrated in Figure 1.3, the geopolymerization process involves (I)
deconstruction, (II) polymerization and (III) stabilization. In the (I) deconstruction
process, leaching of the solid aluminosilicate materials by alkaline hydrolysis
produces aluminate and silicate species [37]. The dissolution of the solid particles
of the source for geopolymerization occurs at the surface. In high pH alkali
solutions, the Si-O-Si, Al-O-Al and Al-O-Si of aluminosilicate source are dissolved
[38]. The alkali metal cations from the activated solution play important role in the
geopolymerization. They balance out the charge of the aluminium in form of four-
fold coordination with oxygen [39]. Then, (II) polymerization process occurs in the
solution. The neighbouring reactive groups formed as Si-O-Na and O-H-Al and
small silicate molecules from the alkali silicate thereafter undergo condensation
reaction with the liberation of alkali hydroxide to form the preliminary unit for the
geopolymerization. In the (III) Stabilization, the application of mild heat typically
between room temperature up to 90 oC causes formation of the preliminary units in
the terms of polycondensation. This can form rigid chains or nets of oxygen bonded
aluminate and silicate tetrahedral which are similarly to cement chemical structure.
The higher "curing" temperature produces stronger geopolymer cements as each of
the hydroxyl groups in these macromolecules are capable of condensing with one
from a neighbouring molecule. It is theoretically possible for any one silicon to be
bonded via an oxygen bond, to four neighbouring silicon or aluminium sites. As a
result, very rigid polymer network is formed.
7
Figure 1.3 A sketched model of the geopolymerization process. M+ refers to alkali

cations (usually Na+ and/or K+). SiO44 + refers to dissolved silicate [35]
8
1.1.4 Synthesis of geopolymers
In geopolymer preparation, the starting materials is an important role in the
formation of geopolymer. For the synthesis, the sources for geopolymers are needed
as followed in (I) raw materials and inactive filler and (II) geopolymer liquor. It was
reported that raw materials for synthesis of geopolymer could be natural in alumino-
silicate minerals or industrial wastes such as rice husk ash [40], fly ash [41], slag
[42], and waste glass [43]. Moreover, inactive filler was used for the supply of Al3+
ions such as kaolinite or metakaolinite [19]. All of suitable fillers should be the
pozzolanic materials [44]. As seen, pozzolanic materials contain appreciable
amounts of reactive Ca, Si or Al oxides. The composition and the quality of wastes
with potential pozzolanic properties can vary from high to less reactivity depending
on, (1) the original materials and (2) the production processes. The pozzolanic
materials are high in contents of SiO2 and Al2O3 and are sufficiently reactive that
mixtures with water and CaO producing calcium silicate hydrate (CSH) at ordinary
temperatures and thereby act as hydraulic cements. The CSH has the properties of a
rigid gel formed by these reactions which can be obtained by calcining clay or using
fly ashes low in CaO. This fact has encouraged the use of fly ash in pozzolanic
reactions which are accelerated by temperature increment in particular the presence
of an alkali metal hydroxide [45]. The particle size of raw materials also affects the
geopolymerization process. The particle size less than 5-7 µm increases vary rapidly
the reactivity [46]. For the (II) Geopolymer liquor, the essential constituent of the
initial geopolymerization is concerned with a chemical activator such as alkali
hydroxides or silicates at high pH. The common alkali hydroxides used as activators
in the geopolymer synthesis are sodium or potassium (NaOH or KOH) with high pH
9
[45, 47-49]. The NaOH alkali source is mostly and popularly used as hydroxide
activator in the gepolymer synthesis because of the cheapest reason. Also leaching
of Al3+and Si4+ ions is generally high in the NaOH solution compared to KOH case
[50]. This nature is most widely available of alkali hydroxides in NaOH to be a
hydroxide activator. As mixed with an alkali silicate aqueous solution, generally
Na2SiO3 solution is formed. The alkali solution activates a role in dissolving initial
aluminate and silicate of raw material to rupture them into monomer, while the alkali
silicate solution arranges the new alumino-silicate structures [38]. The variation in
the ratio of sodium silicate to NaOH ratio affects the pH conditions and thus would
have some effects on the strength development of the geopolymer [1]. For example,
it was reported that the case of low calcium fly ash indicated that the high ratio of
sodium silicate to NaOH provided a higher compressive strength [51]. Moreover,
an alkali hydroxide solution required for the dissolution of the raw materials while,
sodium (or potassium) silicate solution acts as binder, alkali activator and dispersant
or plasticizer [52, 53]. After the raw materials are mixed with alkali solutions, the
geopolymer paste becomes to be solid phase. The geopolymer sample which
transforms to solid have high strength like ceramics. For the strength of geopolymer
factor affecting is known that the strength of sample increased with a NaOH
increasing. This was because that high concentrations of NaOH increased dissolved
silica and alumina in raw materials [54]. With an increase in NaOH concentration,
the setting time and compressive strength increased resulting dense matrix with less
unreacted fly ash in microstructure [33, 55]. The mixing geopolymer in 10 M NaOH
solution was appropriate for the synthesis of geopolymers [56]. However, the
strength started decreased when the concentration of sodium hydroxide was over
10
14.0-15.0 M in the NaOH concentration. This was because of over hydroxide ion
concentration for the dissolution of raw materials. Therefore, the polycondensation
was hindered in these case [56, 57] . This result indicated that an increase in alkali
concentration enhanced development of the geopolymers strength, but excess
hydroxide ion concentration caused aluminosilicate gel precipitation at the very
early stages, resulting in lower strength geopolymers [39, 58]. Moreover, there is
another important factor for geopolymerization. The curing temperature strongly
affects the strength of geopolymer since the temperature affects the setting and
hardening of sample. It was seen that the strength increase with an increase in the
curing time [51] and temperature [1]. However, the strength reduced after cured at
temperature over 80 oC, So the higher temperature could break down the structure
of geopolymer resulting over hydration and over shrinkage [16, 55, 59].The
geopolymerization process at different curing temperature obtained the best process
at 60-80 oC [35]. In initial Si/Al ratio, the mechanical properties and microstructure
of geopolymer strongly depends on the initial Si/Al ratio. High strength properties
have been reported for mixtures with SiO2/Al2O3 ratios in the range of 3.0–3.8. The
changes in the SiO2/Al2O3 ratio was beyond this range usually resulted in low
strength systems [60, 61].
11
1.1.5 Geopolymer applications
There are many attractive properties of geopolymers such as resistance to
high temperature and chemical agents, durability, quick solidification with high
strength and low shrinkage etc. Table 1.2 shows the geopolymers applied for many
useful uses. Moreover, the application of geopolymer can divided as fllowed by the
atomic ratio of Si:Al in the poly(sialate) structure as shown in Figure 1.4. A low
ratio Si:Al (1,2,3) initiates a 3D-network that is very rigid. A high ratio of Si:Al
which is higher than 15, provides polymeric character to the geopolymeric
material. The geopolymer materials can be apply for many fields depending on
the properties of geopolymer and also can be used in many kinds of raw
materials to synthesis geopolymer materials. Several reports describe the use of
metakaolin and fly ash as starting materials in geopolymerization. Moreover,
industrial wastes of various types are used to synthesize geopolymer materials. For
example, im cement and concrete, Pavithra et al.[62] developed the geopolymer
concrete with fly ash. Moreover, Yeonho et al. [63] studied the feasibility of
geopolymer concrete to which crumb rubber from recycled tires. Geopolymer
cement and concrete show low shrinkage after drying, less cracks and high strength.
Therefore, the production cost of the geopolymer cement and concrete could be in
10-30 % cheaper than Portland cement production. In the adsorption of heavy metal
application, geopolymer can be used as the materials for absorbing heavy metal from
waste water. In recent years, fly ash based geopolymer was used for Cu and Pb
removal from an aqueous solution. The absorption capacity was reached to 92 mg/g
and 80 mg/g of Cu and Pb, respectively [64, 65]. Moreover, the geopolymer not only
absorbed heavy metal but also could absorbed dye from waste water. The absorption
12
capacity of fly ash based geopolymer demonstrated approximately 0.12 mmol/g [66].
In the application for immobilization heavy metal and radioactive waste,
geopolymer have been used to immobilize, stabilize and absorption low amount of
radioactive waste in pure and mixed form [67]. The results indicated that the fly ash
based geopolymer had high property to immobilize lead ion [68]. Geopolymers
acted as the binder to convert semi solid waste to adhesive solid and also
immobilized hazardous waste by locking in the three dimensional framework.
Moreover, the geopolymer materials could be apply for composites materials,
hybrid composite materials for geopolymer and epoxy melamine resins were
designed to produce a novel material showing high compatibility between the
organic and inorganic phases. To use for the applications, requiring high
temperature resistance is for kitchen tools and plates, coatings and flooring [69]. In
addition, the geopolymer materials can apply for fire protection, geopolymers
possess excellent physicochemical, thermal and mechanical properties. So, fire
resistant geopolymers have been developed for many researcher. The potassium
based geopolymers (K-geopolymer) was prepared by mixing ferronickel (FeNi) slag,
doped with pure alumina. The results show that K-geopolymer has excellent fire
resistant properties [70].
13
Table 1.2 Summarize geopolymer applications
Geopolymer applications References
Concrete and cement [62] [63]

Composites [69]
Immobilisation of toxic and radioactive waste [49]
Adsorbent for heavy metal ion [66]
Fire resistant and protection matrix [70]
14
Figure 1.4 Applications of geopolymer materials based on the Si:Al ratio
15
1.2 Raw materials of fly ash and industrial wastes used to synthesis
geopolymer
As mention above, the sources for the geopolymers are interesting to use fly
ash and industrials wastes, owing to their sustainable aspect. In addition to fly ash,
metakaolin, blast furnace slag, rice husk ash and others are used as sources for the
geopolymerization. Therefore, the investigation of geopolymer sources from fly ash
and industrial wastes and details is summarized in Table 1.3.
Table 1.3 Raw materials for synthesis geopolymer
Raw materials References
Fly ash [71]
Metakaolin [72]
Blast furnace slag [73]
Rice husk bark ash [53]
Mine tailing, iron ore tailing [74, 75]
Waste glass, waste ceramics [76, 77]
Aluminium and grey cast iron slags [61]
16
1.2.1 Fly ash
1.2.1.1 Fly ash souced for geopolymer

Fly ash is commonly composed of a fine powder consisting mostly of
spherical glassy particles and is produced as a by-product in coal fired power
stations. Fly ash has pozzalonic properties and for example reacts with lime to form
cementitious compounds. It is commonly known as a supplementary cementitious
materials [5]. In Thailand, the annual output of fly ash and bottom ash from large
and small electric power plants totals about 4.0 million tons. Mae Moh power plant
produced 95% of all fly ash in Thailand. The particle size of the fly ash from Mae
Moh power plant is 1 - 150 µm. There are about the same size with cement. In
addition, approximately 1.8 million tons of fly ash are used as a pozzolanic material
in the Thai concrete industry [54]. The partial replacement of Portland cement with
fly ash reduces the heat energy of hydration and improves the workability and
durability of the concrete. However, the level of fly ash replacement is normally
restricted to be less than 40% of Portland cement [78]. So, Thailand still improves
and uses the fly ash for cement, concrete and other applications.
As mentioned for instance, fly ash is a byproduct of power generation in coal
fired power stations (Figure 1.5). Within electric power station, coal has been fed to
a series of mills that pulverize the coal to a very fine powder. The powder is then
fed into a boiler which combusts the coal to produce heat energy. During the coal
combustion process, minerals in the coal fuse to form glassy alumino-silicate
spheres. These spheres remain in suspension within the flue gas from the boiler.
Finally the fly ash is ultimately collected downstream by either electrostatic or
mechanical precipitation.
17
In type of fly ash, the composition is important for geopolymerization.
Generally, fly ash consists primarily of oxides of silicon, aluminum iron and calcium.
Magnesium, potassium, sodium, titanium, and sulfur are also present to a lesser
degree. As used as a mineral admixture in concrete, fly ash is classified as either
Class C or Class F ash based on its chemical composition. American Association of
State Highway Transportation Officials (AASHTO) M 295 [American Society for
Testing and Materials (ASTM) Specification C 618] defines the chemical
composition of Class C and Class F fly ash.
Figure 1.5 The process of producing fly ash at a power station.
18
 Class C: This is generally derived from sub-bituminous coals and consist
primarily of calcium alumino-sulfate glass, as well as quartz, tricalcium
aluminate, and free lime (CaO). It is noted that the class C ash is also referred
to as high calcium fly ash because it typically contains more than 20 % CaO.
 Class F: The ashes are typically derived from bituminous and anthracite
coals and consist primarily of an alumino-silicate glass, with quartz, mullite,
and magnetite also present. Sometime, the low calcium fly ash is less than
10 % in CaO content.
On the other hand, fly ash is typically finer than powders of Portland cement
and lime. Fly ash consists of silt-sized particles which are generally spherical,
typically ranging in size between 10 and 100 micron [53]. The specific gravity of
fly ash usually ranges from 2.1 to 3.0, while its specific surface area may vary from
170 to 1000 m2/kg [79, 80]. These small glass spheres improve the fluidity and
workability of fresh concrete. Fineness is one of the important property contributing
to the pozzolanic reactivity of fly ash. In the color of the powders, fly ash usually
dark gray color, depending on its chemical and mineral constituents. Tan and light
colors are typically associated with high lime content. A brownish color is typically
associated with the iron content. A dark gray to black color is typically attributed to
an elevated unburned carbon content. Fly ash color is usually very consistent for
each power plant and coal source.
19
As seen in Table 1.2, it can be seen that the use of fly ash in concrete leads
to many improvements in overall concrete performance. Some key benefits are
included: reduced water content, improved workability, reduced segregation, low
heat of hydration, improved finishing, lower drying shrinkage, increased durability,
improved long term strength, good carbonation protection, improved resistance to
sulfate attack and improved resistance to alkali silica reactivity.
1.2.1.2 Typical cement application of fly ash
Currently, over 20 million metric tons (22 million tons) of fly ash are used
annually in a variety of engineering applications. Typical highway engineering
applications include as following products: Portland cement concrete (PCC),
geopolymer concrete, soil and road base stabilization, mine and Land Fill, bricks
and blocks, flowable fills, grouts, structural fill and asphalt filler. In the
construction/cement applications, the utilization of fly ash appears to be technically
feasible in the cement industry. There are essentially three applications for fly ash
in cement, including (1) replacement of cement in Portland cement concrete (2)
pozzolanic material in the production of pozzolanic cements, and (3) set retardant
ingredient with cement as a replacement of gypsum.
20
1.2.2 Industrial wastes for geopolymer source
Recently, the waste coming from many industrials was produced as by
product, so the company want and try to reuse the industrial waste for many
application. In order to alleviate environmental pressures and attain sustainability,
one feasible solution is to reuse waste materials as secondary resources such as
precursors in producing geopolymer. The value of using industrial by products to
produce geopolymer has already been widely recognized. The industrials wastes are
already reported for synthesis geopolymer. For example aluminium and grey cast
iron slags [61]. This waste is produced from extracting metal processes. The
aluminium and grey cast iron slags geopolymer had high strength and good
Workability in acceptable range for use in constructions. Moreover, mine tailing and
iron ore tailing can be use as raw materials for synthesis geopolymer. Iron ore tailing
is a mining and mineral waste obtained from the iron ore mining industry and mine
tailings are major wastes material in the reused generated by mining operations [74,
75]. The iron ore mining porous geopolymer was used for the absorbent of heavy
metal in removal aspect. Therefore, mine tailings geopolymer is apply for eco-
friendly bricks. Also geopolymer could be synthesized by waste ceramic [77].
Waste ceramic is the waste from part of the feedstock for the production of ceramics
and the amount of wastes reused in that way was negligible. The waste ceramics
geopolymer was a successful with high compressive strength and good high-
temperature properties.
As mentioned, geopolymer can prepared from several naural and wastes
source. Among them, in this work, raw material from industrial waste used to
prepare geopolymer is aluminium hydroxide waste as shown in Figure 1.6. From
21
anodizing is a process for producing decorative and protective films on aluminium
and its alloys [81]. Before anodizing the surface, the aluminium and alloy must be
thoroughly cleaned, normally using a detergent based process, and etched with a
solution of sodium hydroxide. In this step, the aluminium hydroxide waste is
generated as industrial waste. Al-waste in gibbsite phase (Al(OH)3) is wasted
typically about 360 tons/year from various industries are discarded in landfills [82-
84]. Each ton of anodized aluminum one ton of Al-waste is generated in the world
as shown in Figure 1.7 [85]. The waste appears in the etching solution cycle. Etching
is most often achieved according to following reactions (a)- (b);
(a) Etching reaction: 2Al + 2NaOH + 2H2O → 2NaAlO2 + 4H2
(b) Dissolution of the aluminate: NaAlO2 + H2O → NaOH + Al (OH)3
(c) Dehydration of the solid hydroxide: 2Al(OH)3 → Al2O3 + 3H2O by the use of a
warm, 10 % (2.5 mol/L) sodium hydroxide solution.
In the process, the Al3+ and other metal ions released. In the eatching surface
of alunimium by alkali solution, the waste in this process is call “aluminium
hydroxide waste”. Foaming agents are also a constituent of the etching solution.
Their action is to reduce the pungent mists/fumes that results from the vigorous
reactions occuring. It is important to note that the appearance of the end result is
determined at this stage. Work which is poorly etched may reveal scratches or
blemishes no matter. So, the reason is well are anodized or colored it.
22
Figure 1.6 Aluminium hydroxide waste powder
Figure 1.7 The etching solution cycle
23
1.3 Objective of thesis and Outlines of thesis
The objective of this study is to synthesis the new geopolymer materials by
using fly ash and Al-waste as raw material. In addition, the microwave cure
treatment is related as new polymerization method. This research is divided into
three issues as following by navigation with this chapter1;
(i.) To study the geopolymer from fly ash and aluminium hydroxide waste as
raw materials and investigate the properties of produced geopolymer.
(ii.) To establish the porous fly ash based gepolymer using the microwave
radiation in different incident power and concentration of alikali solution.
(iii.) To improve the degree of reaction and properties of bulk fly ash based
geopolymer curing in microwave radiation.
Chapter 1 “General Introduction” comprises the background, the geoplymer
process, structural and application of geopolymer, Morover, the raw materials and
objectives of this research also are presented.
Chapter 2 describes “Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials”. In geopolymers prepared
from FA and Al-waste, the synthesis process was evaluated from the perspective of
the slurry and bulk geopolymer, with different NaOH concentrations and different
curing temperatures used to produce various geopolymers.
Chapter 3 mentions about “Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration”. This chapter is concerned
with the performance of the porous fly ash based geopolymer using microwave
energy. These results in this chapter can be believed to be edges of new development
of geopolymer production in alternative technology.
24
Chapter 4, “Dense geopolymer cements prepared with microwave pre-
curing” is described. In order to investigate fly ash based geopolymer in dense
materials, curing with microwave radiation successfully prepares dense ceramics
materials, especially in low concentration of alkali solution. On this chemical
components, general geopolymer in heating furnace is impossible to form strong
bulk materials. However, this chapter describes the geopolymerization reaction by
aid of microwave heating.
Finally, Chapter 5 is “General Conclusions” as summarized for all works in
this thesis.
25
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Constr. Build. Mater., 101, Part 1 (2015) 298-308.
[82] E. Álvarez-Ayuso, Approaches for the treatment of waste streams of the
aluminium anodising industry, J. Hazard. Mater., 164 (2009) 409-414.
[83] M.J. Ribeiro, J.A. Labrincha, Properties of sintered mullite and cordierite
pressed bodies manufactured using Al-rich anodising sludge, Ceram. Int., 34 (2008)
593-597.
[84] E. Colonetti, E. Hobold Kammer, A. De Noni Junior, Chemically-bonded
phosphate ceramics obtained from aluminum anodizing waste for use as coatings,
Ceram. Int., 40 (2014) 14431-14438.
[85] J. Dufour, V. González, A. La Iglesia, Synthesis of 13X Zeolite from Alkaline
Waste Streams in the Aluminum Anodizing Industry, Industrial & Engineering
35
composed of fly ash for sustainable cement materials
2. Chapter 2: Aluminium hydroxide waste based

geopolymer composed of fly ash for sustainable
cement materials
ABSTRACT: This chapter related to the first description of reuse of aluminium
hydroxide waste (Al-waste) for geopolymers. For cement materials, both Al-waste
and fly ash (FA) were mixed at different Al-waste contents of 10–60 wt%. The mass
ratio of sodium silicate (Na2SiO3) to sodium hydroxide (NaOH) solution was fixed
at 2.5. Here, the NaOH concentrations of 5, 10, and 15 M were used as alkaline
activators for geopolymerization. Slurry properties for the geopolymers were
evaluated using viscoelasticity measurements, which demonstrated that slurry
containing higher alumina had a higher elastic modulus and that the setting time was
greater than that for pure FA. Then, cured at room temperature for a week and also
in an oven at 60 °C and 80 °C for 24 h, the geopolymerization was enhanced in the
curing behavior with increasing NaOH concentration. After curing, the mechanical
properties, microstructure, bonding, and phases of the resultant geopolymers were
ascertained. The contents of the Al-waste in the geopolymer influenced the
geopolymer strength, when NaOH concentration was changed at different curing
temperatures. The Al-waste content in the resultant geopolymer at 40 wt% cured at
80 °C showed the highest compressive strength of about 40 MPa and also the highest
bulk density of about 2.8 g/cm3. Furthermore, x-ray CT scanning results indicated
that the geopolymer with Al-waste content at 40 wt% cured at 80 °C exhibited a
dense structure, supporting the results obtained for mechanical strength.
36
2.1 Introduction
Every year, aluminium consumption is increasing for many applications
such as anodizing processes for producing decorative and protective films on
aluminium and alloys. The first step of anodizing processes is pre-treatment of the
metal. The second step is etching the surface of the aluminium metal in pre-
treatment before sealing and coloring. This step, which most often uses NaOH in
warm solution, gives the metal surface a light grey satin finish. After etching, Al-
waste in gibbsite phase (Al(OH)3) is wasted: typically about 360 tons/year from
various industries are discarded in landfills [1-3]. Consumption of fossil fuels in
power plants for energy production is increasing, leaving fly ash waste. About 3
million tons/year of such industrial waste are produced by large and small power
plants. For fly ash, pozzolanic materials are normally reused in cement and concrete
industries [4]. Therefore, these wastes should be regenerated to produce novel
materials. If people can do this, then such materials can become sustainable products
that provide environmental, social, and economic benefits. Especially, as renewable
resources of both aluminium hydroxide waste and fly ash, these seem to be
applicable for reuse in concrete materials. Approximately 13,500 million tons of
Portland cement are manufactured annually using processes that incorporate high
heating energy of 1400–1600 °C for calcining raw materials [5].
Therefore, in 1978 Davitdovits introduced the word “geopolymer” to
describe the replacement of Portland cement which has cementitious materials and
properties similar to those of ceramics [6-8]. Such geopolymers have several
attractive properties of high strength, low permeability, excellent adherence to
aggregates, high acid resistance, hazardous materials, and immobilization of toxic
37
materials [9-11]. Generally, geopolymers are made from alumino-silicate materials
such as slag [12], metakaolin [13], and fly ash [14] mixed with alkaline solution.
Then, the paste slurry can form and transform quickly into a rigid geopolymer.
Sufficient strength at low temperatures can be gained [15-17]. For geopolymer
synthesis, raw materials containing silica and alumina and alkaline liquor are
necessary [18-20]. Generally, geopolymers are prepared from an alkaline solution.
For example, sodium or potassium hydroxide is necessary for dissolving silicon and
aluminium atoms from raw materials of natural minerals or industrial waste. The
silicate alkaline solution includes a binder, alkaline activator, and a dispersant or
plasticizer [7, 11, 21]. The basic forms of structure have silicon-aluminate 3D
structures with cross-linked chain bonds together in the geopolymer matrix [22].
The reaction of geopolymers was greatly slowed at room temperature [23]. At
elevated temperatures of 40–95 °C, geopolymerization is known to improve the
strength of specimens [24-27].
Several reports describe the use of metakaolin and fly ash as starting
materials in geopolymerization [28, 29]. That fly ash contains a mixture of
amorphous and crystalline phases of silicate, whereas the typical major chemical
constituents of fly ash are SiO2 and Al2O3 [11, 30, 31]. Moreover, industrial wastes
of various types are used to synthesize geopolymer materials. Nazari et al.[32]
produced geopolymers from aluminium slag and grey cast iron slag with different
SiO2/Al2O3 ratios and different concentrations of NaOH solutions. Xu et al. [33]
prepared a fly ash and blast furnace slag geopolymer using an activating solution
prepared from concentrated Hanford secondary waste (HSW) simulant.
Nevertheless, no report has described the use of etching surface waste such as
38
aluminium hydroxide for geopolymers. In the aluminium frame industry, if reuse
is possible, a new approach is appropriate to produce raw materials of geopolymer
cements. The Al-waste has high aluminium contents, making it suitable for the
synthesis of geopolymers. Therefore, it is extremely interesting and attractive to
investigate the geopolymerization of fly ash and Al-waste.
For alkaline media at different temperatures, this study investigated
geopolymers prepared from FA and Al-waste. The synthesis process was evaluated
from the perspective of the slurry and bulk geopolymer, with different NaOH
concentrations and different curing temperatures used to produce various
geopolymers.
2.2 Experimental procedure
2.2.1 Raw materials of geopolymers
Raw materials of geopolymer were aluminium hydroxide waste ( Al-waste)
from the aluminium frame industry in Pathumthanee ( Thailand) and fly ash ( FA)
supplied from Mae Moh power plant in Lumpang ( Thailand) . Their chemical
compositions are presented in Table 2.1. Figure 2.1 shows SEM micrograph of the
raw materials at 200× magnification for a) Al-waste and b) FA. The SEM
micrographs were taken (JSM – 6480LV, JEOL) after gold sputtering of their
powders. The Al-waste particles were irregularly shaped, with diameter of about
100 µm. The particle distribution of the Al-waste (Figure 2.1c) was 40–110 µm. In
contrast, the FA contained spherical particles with about 40 µm diameter in the fine
powder. The laser-scattered particle distribution of fly ash (Figure 2.1d) showed that
the powder size was 0.2–130 µm.
39
Table 2.1 Chemical composition of fly ash and aluminium hydroxide waste.
Chemical compound Fly ash (%) Aluminium waste (%)

SiO2 31.94 0.18
Al2O3 18.37 63.28
Fe2O3 17.39 -
CaO 19.84 0.01
MgO 1.86 0.31
SO3 5.13 < 0.01
Na2O 1.20 -
K2O 3.05 0.05
MnO 0.07 2.05
P2O5 0.16 0.01
TiO2 0.40 0.01
L.O.I 1.47 34.02
40
a) b)
c) d)
Particle size (µm) Particle size (µm)
Figure 2.1 SEM micrograph of a) Aluminium hydroxide waste and b) Fly ash and
paticle size distribution of c) Aluminium hydroxide waste and d) Fly ash.
41
2.2.2 Geopolymerization
Geopolymerization was conducted for Al-waste and FA, when the wastes
were mixed with aqueous NaOH solutions of 5, 10, and 15 M concentrations.
Sodium silicate solutions containing 10.15% Na2O, 31.38% SiO2, and 58.47% H2O
were used as alkaline activators. For all mixtures, the weight of the sodium silicate
to sodium hydroxide solution was fixed at 2.5 for fly ash based geopolymer [11]. In
this case, the Al-waste was heated at 110 °C for 24 h and then sieved through a 100
mesh screen before use. As presented in Table 2.2, different contents of the mixtures
of FA and the Al-waste were used for 0, 10, 20, 40, and 60 wt% for the Al-waste at
different NaOH concentrations. First, the sodium silicate (Na2SiO3) and NaOH
solutions were premixed in each plastic container and were then left until the
solutions reached room temperature. In the four mixed proportions of the Al-waste
described above, geopolymerization was conducted using 5, 10 or 15 M NaOH
solutions.
To ascertain slurry properties, viscoelasticity was measured using a
rheometer (MRC 301; Anton Paar Physica). Rheological measurements of the waste
slurry were conducted using a control stress mode to operate in control strain mode.
The geopolymer slurry was mixed together from raw materials and alkaline
solutions. Then the slurry was put in a rheometer bowl. The liquid paste was
transferred to the measurement cell. Strain at a frequency 1 Hz was applied in each
test to investigate the time sweep and temperature sweep of the waste slurry. The
elastic modulus (G'), viscous modulus (G'') and the loss tangent determined by tan
δ = G''/G' were analyzed during geopolymerization.
42
The geopolymer samples were prepared from the mixed raw materials as
shown in Table 2.2. The FA and Al-waste were mixed together and then mixed as a
powder with alkaline solutions by shaking for 1 min to achieve good homogeneity.
After mixing, the liquid pastes were poured into a plastic cubic container with
50×50×50 mm3. Then these geopolymers were cured at room temperature, 60 °C
and 80 °C for 24 h. The compressive strength of geopolymer specimens was tested
using a testing machine (5882; Instron Corp.). The rate of compression the
specimens was 5 mm/min. For characterization of these specimens, Fourier
transform infrared spectroscopy was used ( FT-IR, Spectrum one Spectrometer;
PerkinElmer Inc.) , High resolution micro-CT ( Skyscan 1172; Bruker Analytik
GmbH) , XRD ( D8 Advanced machine; Bruker Analytik GmbH) , XRF ( XRF-zsx-
Primus), and SEM (JSM – 6480LV; JEOL) were used. The geopolymer sample was
ground and pass through a 120 mesh. FT–IR samples were prepared by mixing the
geopolymer powder with KBr at concentrations of 0.2–1.0 wt% to produce KBr
disks. High-resolution micro-CT (HRM-CT) was used for observing pore and crack
structure inside geopolymers. For the HRM-CT, the geopolymer samples (1×1×1
cm3) were measured with a scanning rotation step of 0.1 deg. To analyze the
geopolymer components and phases, X-ray diffractrometry was used with a
scanning angle of 5–70 deg. In the SEM micrograph of the geopolymers, the
fractured surfaces of geopolymer samples were fixed on aluminium stubs with
carbon tabs. Then the samples were coated with a thin layer of gold. Secondary
electron detectors were used to investigate the geopolymer samples.
43
Table 2.2 Mixture proportions for geopolymerization.
Mix proportion by weight (g per 100 g)

Series Symbol* FA Al-waste Na2SiO3 NaOH
5M 10 M 15 M
1 0 Al 5 M 2.5 65 - 25 10
10 Al 5 M 2.5 58.5 6.5 25 10
20 Al 5 M 2.5 52 13 25 10
40 Al 5 M 2.5 39 26 25 10
60 Al 5 M 2.5 26 39 25 10
2 0 Al 10 M 2.5 65 - 25 10
10 Al 10 M 2.5 58.5 6.5 25 10
20 Al 10 M 2.5 52 13 25 10
40 Al 10 M 2.5 39 26 25 10
60 Al 10 M 2.5 26 39 25 10
3 0 Al 15 M 2.5 65 - 25 10
10 Al 15 M 2.5 58.5 6.5 25 10
20 Al 15 M 2.5 52 13 25 10
40 Al 15 M 2.5 39 26 25 10
60 Al 15 M 2.5 26 39 25 10
44
2.3 Results and discussion
2.3.1 Properties of the waste slurry for geopolymerization
Viscoelastic behavior of the liquid pastes was observed for
geopolymerization reactions. The storage modulus is the elastic solid like behavior
(G'). The loss modulus is the viscous response (G''). The evolution of the elastic
modulus and viscous modulus were studied in the linear viscoelastic range. When
the G' value is lower than the G'' value, the materials still flow. When the G' value
is higher than the G' value, the materials are mostly solid [34]. Figure 2.2 presents a
time sweep of G' and G'' for the Al-waste at 25 °C. The liquid paste in 5 M NaOH
concentration was used for a) G’ and b) G’’. A tendency is apparent by which both
G' and G'' of all mixture slurries increase with increasing time for
geopolymerization. In addition, the viscoelastic behavior was measured using the
time course for NaOH concentrations of 10 and 15 M. However, the liquid pastes
exhibited a strong tendency to cure quickly when the increased NaOH concentration
was used. Therefore, the measurement was limited to only 5 M NaOH concentration
for the viscoelasticity measurement, which confirmed that the high NaOH
concentrations accelerated geopolymerization. As presented in Figure 2.2a, when
the Al-waste contents increased in the mixture of geopolymer paste, the G' and G''
increments were retorted. That result shows that non-addition of the Al-waste
increased the slurry elastic from 101 to 106 Pa more rapidly: within about 300
seconds. In 40 and 60 wt% Al-waste amounts, increases of the modulus values ( G'
and G'') were slower than 0, 10 and 20 wt% and then came to be constant about 1000
seconds. Figure 2.3 depicts the viscous behavior of the waste paste, when the
temperature was increased from 25 °C to 60 °C within an interval of 6 °C/min.
45
Geopolymerization was completed. The slurry solidified at temperatures of 40–
50 °C. As shown there, the value was constant at about 40 °C for 0 wt% of Al-waste
and about 45–50 °C for other slurries. For the loss tangent (tan δ) properties in both
Figures. 2.2c and 2.3c, tan δ of the geopolymer slurry suggests precursor standards
of the glassy state transition of the geopolymerization. When tan δ tends to zero, the
slurry solidifies. For G' values higher than G'' values, the values of the tan δ decrease
and remain always less than 1. For example, in the 0 wt% Al-waste, the values of
tan δ decreased more rapidly than in other cases, which indicates that the 0 wt% Al-
waste solidified too quickly. Figure 2.3c shows that at increasing temperatures, tan
δ decreased more rapidly than at lower temperatures. The three-dimensional gel
framework formed and accelerated at high temperatures.
46
107
a)
106
105
G' 104
[Pa]
103
102
0% Al-waste
10% Al-waste
101 20% Al-waste
40% Al-waste
60% Al-waste
100
0 200 400 600 800 1000 1200
Time [s]
107
b)
106
105
G'' 104
[Pa]
103
102
0% Al-waste
10% Al-waste
10 1 20% Al-waste
40% Al-waste
60% Al-waste
100
0 200 400 600 800 1000 1200
Time [s]
4.0
0% Al-waste
c) 3.5
10%
20%
Al-waste
Al-waste
40% Al-waste
3.0 60% Al-waste
2.5
tan 
2.0
1.5
1.0
0.5
0.0
0 200 400 600 800 1000 1200

Time [s]
Figure 2.2 G' ,G'' and tan δ as a function of time and constant temperature at 25oC
with diferrent proportions of raw materials at 5 M NaOH.
47
107
a)
106
105
G' 104
[Pa]
103
102 0% Al-waste
10% Al-waste
20% Al-waste
101 40% Al-waste
60% Al-waste
100
25 30 35 40 45 50 55 60
o
Temp [ C]
107
b)
106
105
G'' 104
[Pa]
103
102 0% Al-waste
10% Al-waste
20% Al-waste
101 40% Al-waste
60% Al-waste
100
25 30 35 40 45 50 55 60
o
Temp [ C]
c) 4.0
0% Al-waste
10% Al-waste
3.5
20% Al-waste
40% Al-waste
3.0 60% Al-waste
2.5
tan 
2.0
1.5
1.0
0.5
0.0
25 30 35 40 45 50 55 60
o
Temp [ C]
Figure 2.3 G', G'' and tan δ as a function of temperature with differrent proportion
of raw materials at 5 M NaOH.
48
2.3.2 Mechanical properites of geopolymer bulk
Geopolymerization in alkaline solution is known to increase the mechanical
property of the resultant geopolymers. The properties depend strongly upon silicate
and aluminium ratios and on the curing temperature [11, 21, 35, 36]. It is important
for the present study to examine the dependence of the curing temperature and the
NaOH concentration. Figure 2.4 depicts the flexural strength and compressive
strength for each specimen prepared using different aluminium hydroxide contents
and NaOH concentrations. Actually, a tendency was observed by which the
geopolymer strength increased as the NaOH concentration increased. In addition,
amounts of the Al-waste also depended upon the geopolymer strength. As portrayed
in Figure 2.4a) for the flexural strength, the results showed high strength in 40 wt%
of the Al-waste contents in each NaOH concentration system. This might be because
of the fact that the higher concentrations of NaOH are able to dissolve both silica
and alumina in a homogeneous slurry paste. Especially, high strength appeared for
80 °C. However, when the increased Al-waste amount was 60 wt% in the
geopolymer, the bulk strength was somewhat lower than that of 40 wt%. Addition
of the Al-waste at 60 wt% affected the excess alumina component in the matrix. The
curing temperature affected the geopolymer strength. Especially, after curing at
higher temperature, increased bulk strength for the 40 wt% of Al-waste was
observed. At higher temperatures, the flexural strength of 60 wt% was less than that
of 40 wt%. The maximum flexural strength of 6.05 MPa was obtained with 40 wt%
of Al-waste at 15 M NaOH cured at 80 °C. A similar temperature tendency was also
apparent for compressive strength (Figure 2.4b). As a result, slurry containing high
alkaline solution was preferred for the condensation reaction to form Si–O and Al–
49
O in the geopolymers. As reported by Görhan G et al. [36] , this preference was
mainly attributable to the excellent dissolution of silica and alumina components in
the slurry. Therefore, high temperatures enhanced the geopolymerization in the Si–
O–Al formation by the condensation.
Regarding development of compressive strength in Portland cement pastes
and concrete specimens, the strength increased with increased curing temperature
[21, 24]. However, when the NaOH concentration was 15 M, the compressive
strength started to drop. Excess NaOH was the cause of the compressive strength
decrease attributable to the alumino-silicate gel precipitation at the early stage [21].
In this work, high compressive strength of 40 MPa was obtained for 40 wt% of Al-
waste used in 10 M of NaOH concentration at 80 °C. When the temperature was
higher than 80 °C, water in the geopolymer slurry was evaporated to produce a
porous structure [37]. In addition, the mass loss was capable of forming cracks in
the geopolymer matrix because of the thermal shrinkage [38]. To evaluate Si and Al
contents and others in geopolymers, the geopolymer specimens were ground and
sieved at 120 mesh to the powder. Then the powder geopolymer was characterized
to ascertain the atomic composition using XRF. Results are shown in Table 2.3 as
the amounts of the Al-waste increased in the geopolymer, the Si component
decreased and the Al component increased. The additional Al component can be
incorporated into the geopolymer framework, depending on the addition of the Al-
waste. In addition, higher concentrations of NaOH retained the Na ions in
geopolymers. Moreover, the Ca component decreased concomitantly with
increasing NaOH concentration. This fact indicated the Na component tendency to
replace the Ca component in the geopolymer matrix.
50
a)
b)
Figure 2.4 Comparision of a) flexural strength and b)compressive strength of

geopolymer paste at age of 7 days.
51
Table 2.3 Composition of ions in geopolymer bulk.
Composition of ions in geopolymer bulk (%)

Series Symbol*
Si Al Na Ca Fe
1 0 Al 5 M 2.5 16.60 7.70 4.36 10.3 8.81
20 Al 5 M 2.5 17.40 9.79 4.56 10.9 9.68
40 Al 5 M 2.5 15.70 12.10 4.70 10.1 7.79
60 Al 5 M 2.5 13.90 15.40 4.64 8.51 6.23
2 0 Al 10 M 2.5 16.20 7.98 4.80 8.36 6.18
20 Al 10 M 2.5 16.20 9.71 5.49 8.06 5.76
40 Al 10 M 2.5 14.70 12.90 5.32 7.01 4.84
60 Al 10 M 2.5 13.50 15.30 5.89 6.34 4.84
3 0 Al 15 M 2.5 16.50 7.93 5.88 6.24 4.41
20 Al 15 M 2.5 15.90 10.20 5.52 4.73 3.27
40 Al 15 M 2.5 14.40 13.10 5.79 4.63 3.24
60 Al 15 M 2.5 12.60 15.50 6.14 4.59 3.09
* yy Al zz M n : yy = % of Aluminium hydroxide waste in solid fraction, zz = molarities of
NaOH and n = Na2SiO3/NaOH ratio
52
room temperature 60 oC 80 oC
3.3
5M
10M
3.0
15M
Apparent bulk density (g/cm3)
2.7
2.4
2.1
1.8
1.5
0 20 40 60 0 20 40 60 0 20 40 60
Aluminium waste (%)
Figure 2.5 Bulk density of geopolymer bulk at age of 7 days.
53
Figure 2.5 shows the apparent bulk density of the geopolymer specimens
measured using Archimedes method. The values of the apparent bulk density of the
geopolymer bulk increased when increasing the amount of the Al-waste to 40 wt%.
However, as the Al-waste was added with 60 wt%, the apparent bulk density
decreased. In addition, the value of the bulk density was increased when the NaOH
concentration was 10 M, meaning that the NaOH concentrations densified the
geopolymers. Regarding curing temperature effects, the apparent bulk density of
geopolymer tended to be extremely dense at 80 °C. The bulk density was probably
influenced by the formation of pores and cracks in the matrix, thereby weakening
the matrix.
2.3.3 Morphological properties of geopolymers
These properties of the geopolymers depend strongly upon the matrix
structure. Therefore, SEM micrographs for the geopolymer were measured in
different amounts of the Al-waste ( Figure 2.6) . Here, the NaOH concentration was
10 M. The curing temperature was 80 °C for the geopolymers. Those prepared at 40
wt% of the Al-waste showed that the matrix exhibited a denser structure than those
of others, perhaps because of the fact that the increase in the aluminium content
enhanced geopolymerization. Moreover, increasing amounts of the Al-waste more
than 40 wt% showed that the Al-waste in the matrix might be excess to the alumina
source. Therefore, the unreacted Al-waste in the geopolymer structure remained in
the geopolymer. As reported by Somna et al. [21] and Fletcher et al. [39], the lower
ratio of Si/Al showed lower strength in geopolymers because the slurry became less
54
a) 0 wt% Al-waste b) 0 wt% Al-waste
c) 20 wt% Al-waste d) 20 wt% Al-waste
40 wt% Al-waste 40 wt% Al-waste

e) f)
g) 60 wt% Al-waste h) 60 wt% Al-waste
Figure 2.6 Effect of Al-waste amount on microstructure of geopolymer specimens:

a-b) 0 wt % , c-d) 20 wt %, e-f) 40 wt % and g-h) 60 wt % Al-waste
with 10 M NaOH and cured at 80 oC for 24 h.
55
NaOH 5 M
a)
)
NaOH 5 M
b)
NaOH 15 M
c)
NaOH 15 M
d)
Figure 2.7 Effect of NaOH concentrations on microstructure of geopolymer

specimens, a-b) 5 M NaOH and c-d) 15 M NaOH with 40 wt%
of Al-waste and cured at 80 oC for 24 h.
56
a) Curing temp 25 oC
b) Curing temp 25 oC
c) Curing temp 80 oC
d) Curing temp 80 oC
Figure 2.8 Effect of curing temperature on microstructure of geopolymer

specimens, a-b) at room temperature and c-d) at 80 oC for 24 h with 40 %
by weight of Al- waste and 10 M NaOH.
57
Figure 2.9 X-ray CT images of geopolymer sepecimens with different amounts of

Al-waste on structure of geopolymer specimens: a) 0 wt % , b) 20 wt %, c) 40 wt
% and d) 60 wt % Al-waste with 10 M NaOH and cured at 80 oC for 24h.
58
elastic with increasing Al2O3 contents. Figure 2.7 shows SEM micrographs for 5 M
NaOH (a, b) and 15 M NaOH (c, d), with curing temperatures at 80 °C in 40 wt%
of the Al-waste. Figure 2.8 depicts similar micrographs for the Al-waste content
prepared at 25 °C ( a, b) and 60 °C (c, d) . Relative to the surface morphology of
Figures. 2.6(e, f) for the 40 wt% of the Al-waste at 80 °C, these surfaces included
some microcracks and pores in the matrix.
For observations inside the matrix, micro CT-x ray technique was applied.
Figure 2.9 shows the interior structure of geopolymer matrix in different amounts of
the Al-waste. These geopolymers were prepared in the 40 wt% of the Al-waste at
80 °C with 10 M NaOH concentration. The inside geopolymer exhibited numerous
cracks and pores for Figure 2.9a in the no addition of the Al-waste. In cases b and d
for 20 and 60 wt% of the Al-waste contents, the inside structures had fewer cracks,
but round pores existed in these geopolymers’ morphological structure. In contrast,
a denser structure was observed in the 40 wt% of the Al-waste ( Figure 2.9c) .
Especially, in Figure 2.9d for 60 wt% the Al-waste, many pores were visible in the
geopolymer. This result suggests that excess Al-waste caused the decrease of the
geopolymer strength.
59
2.3.4 Reactive phases and chemical bonds of geopolymer
The X-ray powder diffraction patterns of the Al-waste and FA were
compared with those of geopolymers. From Figure 2.10, it was apparent that the FA
consisted of the higher contents of amorphous phase of silica and some crystalline
phases of quartz (Q), mullite (M), magnetite (Ma), and hematite (H). In the Al-
waste, the data showed that the main component was gibbsite phase (Al(OH)3). For
geopolymers without Al-waste, the XRD pattern presented that the major phase of
geopolymer was amorphous, as indicated by appearance of the broad hump at 25–
35° (2theta). After geopolymerization, the crystalline phase for the peak quartz was
decreased. When the Al-waste was added, the XRD pattern of the geopolymer
showed that the gibbsite phase remained predominant in geopolymers. The peak
intensity of gibbsite phase increased with increasing contents of the Al-waste
amount. Moreover, the amorphous peaks remained in the geopolymer sample.
However, the peak position of the board hump was shifted toward about 30° in the
Al-waste geopolymer. This result indicated that the Al-waste was activated with the
alkaline solutions. Then the glassy component formed a phase of alkaline
aluminosilicate gel with apparent shift a broad hump centered at about 30° ( 2theta)
[ 4 0 ] . For curing at other temperatures, XRD patterns of geopolymer were not
changed in each datum. In addition, the crystalline peaks of XRD patterns in Figure
2.10 are almost identical.
60
To confirm the formation of alumino-silicate, -Al-O-Si-, infrared
spectroscopic results were obtained for Al-waste, FA and geopolymers ( Figure
2.11). Sodium carbonate was detected at a wavenumber of about 1460 cm-1 [8]. The
distinct peak bands at 450-460 cm-1 represented Si-O-Si bending vibration [8, 15,
21, 41] and Si-O-Si asymmetric stretching vibration for 1012 and 1109 cm-1 in FA
[21, 41]. These peaks, which were the main band and other major band observed in
the spectra were assigned to O-H bending and O-H stretching vibration at 3400-
3500 cm-1 and 1654 cm-1, respectively [8, 13, 15]. In addition, the -Al-O-Si- bond
appears in the geopolymers near 1002-1018 cm-1. The band peak was shifted to the
longer wavenumber side when the Al-waste was added. This shift indicated that the
tetrahedral positioned alumunium segment was contained in the geopolymer [21].
Therefore, the geopolymerization of the present geopolymer is followed by same
reaction with general mechanism in the reaction [3,4, 21]. So the aluminium waste
could be used as condensation of silica-oxigen-alimina-oxigen segments in the
geopolymers. However, resultant data suggested that the mechanical properties of
the bulk geopolymers depended on the ratio of Si/Al components, meaning that
higher Al components decreased the bulk strength. This might be due to that excess
aluminium waste to the silica components could not condensate with the silica
components. Therefore, the remaining aluminium waste without then condensation
was dissolubled by washing with water after geopolymerization and casued crackes
in the geopolymers.
61
60 wt% Al-waste
40 wt% Al-waste
20 wt% Al-waste
10 wt% Al-waste
0 wt% Al-waste
Q
Ma Q FA
Ma M H M H Ma Ma
G G G Al-waste
G G
G G G
G G G G G G G
G
10 20 30 40 50 60 70
2theta
Figure 2.10 XRD patterns of Al-waste, FA and geopolymer paste with different
proportions of raw materials with 10 M NaOH and cured at 80 oC for 24 h:
G=Gibbsite, Q=Qartz, Ma=Magnetite, M=Mullite and H=Hematite.
62
4000 3500 3000 2000 1500 1000 500

Wavenumber (cm-1)
Figure 2.11 Infrared analysis of Al-waste, FA and geopolymer paste with different
compositions of raw materials with 10 M NaOH, cured at 80 oC for 24 h.
63
2.4 Conclusions
This paper described that FA and Al-waste were suitable sources for
geopolymer materials. Five different ratios of FA to Al-waste were studied with
100/0, 90/10, 80/20, 60/40, and 40/60. Concentrations of NaOH solutions were 5,
10 and 15 M. Curing temperatures of specimens were used at room temperature, 60
°C and 80 °C. Details related to geopolymers were examined in contents of Al-
waste, NaOH concentrations, and curing temperature in paste and geopolymers.
Evidence showed that 10 M concentration at a curing temperature of about 80 °C
was suitable for geopolymerization when the Al-waste content was 40 wt%. In this
condition, fewer pores and cracks were observed inside the structure. Results show
that 40 MPa of the bulk matrix strength was achieved for the geopolymer.
64
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[18] J.W. Phair, Compositional effects and microstructure of fly ash-based
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[19] J.W. Phair, J.S.J. Van Deventer, Effect of silicate activator pH on the leaching
and material characteristics of waste-based inorganic polymers, Miner. Eng., 14
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material, Applied Geochemistry, 17 (2002) 1143-1148.
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[27] T. Bakharev, Geopolymeric materials prepared using Class F fly ash and
elevated temperature curing, Cem. Concr. Res., 35 (2005) 1224-1232.
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minerals industry, Miner. Eng., 20 (2007) 1261-1277.
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Van Deventer, Geopolymer technology: the current state of the art, Journal of
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in alkaline silicate solutions, Colloids Surf., A, 211 (2002) 49-66.
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properties of geopolymer, J. Hazard. Mater., 164 (2009) 634-639.
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furnace slag grades on fly ash based geopolymer waste forms, Fuel, 133 (2014) 332-
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activated metakaolin during geopolymerization, Journal of Non-Crystalline Solids,
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the fly ash-based geopolymer mortar cured at different temperatures, Composites
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composition range of aluminosilicate geopolymers, Journal of the European
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69
geopolymers in the presence of high alkali concentration
3. Chapter 3: Fast microwave syntheses of fly ash

based porous geopolymers in the presence of high
alkali concentration
ABSTRACT: Microwave synthesis of porous fly ash geopolymers was achieved
using a household microwave oven. Fly ash paste containing SiO2 and Al2O3
component was mixed with sodium silicate (Na2SiO3) solutions at different
concentrations of sodium hydroxide (NaOH) of 2, 5, 10, and 15 M, which were used
as NaOH activators of geopolymerization. The mass ratio of Na2SiO3/NaOH was
fixed at 2.5 with SiO2/Al2O3 at 2.69. After the fly ash and alkali activators were
mixed for 1 min until homogeneous, the geopolymer paste was cured for 1 min using
household microwave oven at different output powers of 200, 500, 700, and 850 W.
Porous geopolymers were formed immediately. Micro X-ray CT and SEM results
showed that the porous structure of the geopolymers was developed at higher NaOH
concentrations when using 850 W power of the microwave oven. These results
derive from the immediate increase of the temperature in the geopolymer paste at
higher NaOH concentrations, meaning that aluminosilicate bonds formed easily in
the geopolymers within 1 min.
70
3.1 Introduction
Geopolymers are known as sustainable materials with eco-friendly process,
simply, uses waste for raw materials and excellent mechanical properties [1, 2].
Usually, the geopolymer materials are activated in a high alkali solution [3] because
alumino silicate geopolymers consist of tetrahedral AlO4 and SiO4 units that occur
easily in a polycondensed polymer framework in high-alkali conditions [4].
Geopolymer materials can be prepared at low temperatures with high alkali
solutions. Furthermore, it is possible to use fly ash containing a high percentage of
non-crystalline phase and crystalline elements as a sustainable source of
geopolymers [3, 5]. Therefore, fly ash based geopolymer is an important material
because fly ash waste is the one of huge waste resulting from the coal burning or
lignite at power generation facilities. Consequently, coal fly ash obtained needs to
be disposed of using an environmentally friendly way [6]. Fly ash based geopolymer
displays high mechanical properties, low creep and good resistance to sulfate and
acid, with better bulk strength for cement substitution [7, 8].
In general, the geopolymer can be prepared with paste fly ash dissolved in
highly alkaline materials via hydrolysis. The geopolymerization follows
oligomerization, polymerization and condensation [9]. Geopolymers are dense
materials having apparent density higher than 1 g/cm3 and can apply for constrution
materials [10]. In contrast, foam geopolymers can be synthesized in high- or low-
temperature processing conditions, presenting benefits for widely diverse
applications such as in carriers of catalyzer, adsorbents, sensors, hot gas filters,
solid–liquid separation processes, and thermal insulators [11-14]. In high-
temperature processing, the raw materials are mixed with foaming agents
71
(aluminium powder or hydrogen peroxide) and silica fume in situ foaming
techniques. After geopolymerization, the geopolymer sample was sintered at 1000-
1200 oC to produce in the high strength of porous geopolymer [15]. Moreover, a low
temperature process can achieve geopolymerization in an alkaline environment with
a foaming agent. This can be decomposed into the water and oxygen. Aluminium
and silicon in fumed silica also initiated the release of hydrogen gas, leading to a
porous structure. Porous geopolymer was cured in a conventional oven at 40-70 oC
for 24–48 h in a long curing period [6, 16-19]. Therefore, several researcher have
developed noble methods for synthesis of porous geopolymer with reduced curing
time.
Heat curing has been applied to improve the reaction and the strength of
geopolymer materials. Recently, microwave energy has been reported as an
innovative tool for heating to influence chemical reactions. Samples that absorb
microwave energy can heat volumetrically but cool from the surface, thereby
creating an inverse temperature profile [20]. Benefits of microwave heating also
include instantaneous, very rapid heat-up time, and easy to control [21]. An
additional benefit of microwave energy is transferred directly to the materials
through interactions with electromagnetic fields at the water molecule level [19, 22].
The microwave energy has been useful as a source of heating materials. For those
reasons, microwave-assisted synthesis of concrete [19, 23, 24] and zeolite [25-27]
have been reported because the activation time in hydrothermal synthesis is reduced
automatically. Microwave had the ability to penetrate deep into the materials being
electromagnetic in nature within a short time. Therefore, microwave devices are
extremely convenient for influencing material reactions related to water the entire
72
body quickly reaches a higher temperature by volumetric heating [20]. Moreover, it
has been reported that fly ash based geopolymer has been synthesized using
microwave method. Ul Haq et al. [28] studied thermal isulating foams from bottom
ash using microwave synthesis with various amounts of sodium silicate.
Nevertheless, reports are few in the literature about microwave cured geopolymers.
This work investigated the feasibility of synthesis the porous fly ash based
geopolymer using microwave energy. The geopolymer pastes were cured for
approximately 1 min when a household microwave oven was operated at 200-850
W with high alkali concentration. Moreover, the conventional heat was applied at
80 °C for 24 h for comparison with porous materials. After synthesis geopolymer,
the porous and bulk products were evaluated.
3.2 Experimental procedures
3.2.1 Materials
Fly ash was obtained from Mae Moh Power Plant in Lamphang, Thailand
[8] for used as a raw materials. The chemical compositions of fly ash was tested
by XRF as followed: SiO2 29.80 %, Al2O3 18.50 %, CaO 19.80 %, Fe2O3 16.80 % ,
MgO 1.89 %, SO3 4.85 %, Na2O 1.14 %, K2O 2.90 % and LOI 4.32 %. The particle
size distribution of the ash powder was 0.2-130 µm. For geopolymerization, sodium
hydroxide solutions and sodium silicate solutions were used as activators. The solid
fraction in geopolymer mixture was 65 wt%. The ratio of Na2SiO3/NaOH solution
and SiO2/Al2O3 were fixed at 2.5 and 2.69 at 2-15 M respectively, The
concentration of NaOH is varied from 2 to15 M.
73
3.2.2 Synthesis of geopolymer sample in a microwave oven
Fly ash, sodium hydroxide and sodium silicate solutions were mixed for 1
min and were put in a 25×25×25 cm3 plastic container. The geopolymer paste was
cured by heating in a microwave oven (JM-17E; Haier Group) at the different power
setting ( 200-850 W) for 1 min. During microwave heating, the geopolymers
temperature were detected by using an infrared thermal scanner as presented in
Figure 3.1. The temperature development was the function of microwave power and
sodium hydroxide concentrations. The specimen temperature increased with an
increasing incident power and sodium hydroxide concentration. The temperature
reached to 65-130 oC within 1 min. For traditional oven curing (EO-300B; ETTAS),
geopolymers were prepared at 80 oC for 24 h and then a comparison between oven
heating and microwave curing was studied.
74
Figure 3.1 Temperature profile of geopolymers in different power

of microwave 1 min
75
3.2.3 Characterization of pastes and geopolymers
The apparent density, volume of open pores and water adsorption of porous
geopolymers were measured. Moreover, X-ray diffraction pattern were recorded
(D8 Advance; Bruker Analytik) with 40 kv and 40 mA, CuKα radiation and
scanning at 5 o to 80 o in 2θ at a rate of 2 o per minute. FT-IR samples were prepared
by mixing the powder with KBr at concentrations of 0.2-1.0 wt% by KBr disks and
then were tested by using Spectrometer (Spectrum one; PerkinElmer Inc.). For SEM
micrograph of the geopolymers, the geopolymer sample were ground. Then the
ground samples were fixed on aluminium stubs with carbon tabs. Subsequently, the
samples were coated with a thin layer of gold. Secondary electron detectors were
used to investigate the fractured surface of geopolymer samples using JSM–
6480LV. For the high resolution micro-CT (HRM-CT), the geopolymer samples
were cut to 1×1×1 cm3 and were measured using scanning rotation steps of 0.1 deg.
HRM-CT was used to observe cracks and pores in gepolymer samples.
3.3.1 Geopolymerization in microwave heating for porous matrix
Figure 3.1 shows the geopolymer paste temperature at different levels of
microwave output power. The aqueous paste of fly ash and sodium silicate contained
different NaOH concentrations of 2 M-15 M were cured in the household microwave
oven and then the geopolymer paste adsorbed microwave energy. The microwave
heating occurred due to the dipolar polarization and ionic conduction mechanisms.
Polar molecules such as water produce heat because the water absorbs microwaves
76
as a result of the polarization induced by the external oscillating electric field [29].
Therefore, the conduction mechanism from charged particles such as Na+ and OH-
can oscillate back and forth under electric force producing an electric current to
heats up neighboring materials through molecular collisions of charged species [29,
30]. Figure 3.1 shows the high NaOH concentration can generate high temperatures
of geopolymer paste during 1 min curing in the microwave oven. Moreover, the heat
of geopolymers are increased during geopolymerization as a fact that the
geopolymerization process is exothermic chemical reaction [4, 31]. When the
geopolymer paste was processed to the solid geopolymer, microwave heating was
able to achieve higher temperatures in a very short time depending on the NaOH
concentration. From Figure 3.1, when the microwave power was increased, a
tendency to increase the paste temperature was observed. A higher NaOH
concentration at 850 W enhanced the temperature increase. Especially with 15 M
NaOH concentration, the temperature reached over 100 oC at 700 and 850 W within
1 min of exposure. One can readily infer that the water and ions inside the mixture
adsorbed microwave energy to produce the geopolymerization. During the process,
the volume of geopolymer specimen are immediately increased. Consequently, the
water was vaporized easily at temperatures higher than 100 oC. Vaporization of the
water might influence the morphology of the geopolymers. Bubbles from
evaporation of water were fixed inside the geopolymer sample along with the
general heat curing process, producing a porous geopolymer structure [32].
77
Figure 3.2 Pictures of geopolymers cured from components containing different

NaOH concentration and X-ray micro CT for the cross-section of geopolymers.
The microwave radiation was carried out at power 850W for 1 min.
a-b) 2M c-d) 5M e-f ) 10M and g-h ) 15 M NaOH
78
Figure 3.2 (continued).
79
Figure 3.2 shows the geopolymer sample and X-ray CT images of the
synthesized geopolymers using microwave radiation power 850 W for 1 min. The
up-side images show the appearance of the geopolymer prepared using different
NaOH concentrations. The macro-structure of geopolymer sample is readily
apparent in Figures. 3.2a) and 3.2c) : the geopolymers prepared at 2 M and 5 M of
NaOH concentration exhibited dense morphology. Therefore, the geopolymer
interior showed large cracks, which might result from shrinkage during drying of
the geopolymer. When the concentration was increased to 10 M, small pores
appeared inside the geopolymer (Figure 3.2e). Moreover, it is worthwhile to mention
that when the NaOH concentration was at 15 M, not only the number of pores is
increased but also the pore size is larger than those at 10 M NaOH (Figure 3.2g).
The X-ray CT images of the geopolymers clearly present porous structure of the
geopolymer in the cross-section, which was enhanced considerably in the high
NaOH concentration, as presented for comparison in Figures. 3.2b), 2d), 2f) and 2h).
The porous geopolymer morphology in the microstructure was compared in
each sample synthesized in a conventional oven at 80 oC, with household microwave
at 200 W and 850 W power for 1 min. Figure 3.3 shows SEM micrographs of the
geopolymer containing each NaOH concentration. Morphological analysis
elucidated that the microstructural changes occurred with heating and curing at 80
o
C and microwave curing. All samples showed that the ash particles remained in the
geopolymer matrix. In addition, Figures. 3.3a), 3d), 3g) and 3j) were seen similarly
in the dense morphology of the matrix, whereas the microstructure changed to a
dense surface occurred at 15 M NaOH concentration. In contrast, the dense
geopolymer was created with 2 M NaOH at 200 W and 850 W of microwave curing
80
(Figure 3.3 b-c). The rough surface of the geopolymers was observed in these
geopolymers, when household microwave curing was done for paste having 10 M
and 15 M NaOH concentrations. At 850 W of microwave curing, the tendency was
extremely effective at higher NaOH concentrations, as depicted in Figures. 3.3i) and
3.3l) . The results demonstrated that the synthesis geopolymers using microwave
radiation can be able to produce porous geopolymers.
To confirm porous geopolymerization, different water contents in the
geopolymer paste were examined in the volume increase as shown in Figure 3.4a) .
For the experiments, the fly ash and sodium silicate were mixed with different
proportions of Na2SiO3/NaOH at 2 M and 15 M NaOH concentration in the range
of 1.25-5 by fixed the amount of Na2SiO3. The water content was changed from 4.87
to 16.84 wt% in 2 M and from 3.02 to 10.44 wt% in 15 M NaOH concentration
when added more amount of NaOH solution. Results of 15 M NaOH showed that
the water content affected the volume and the porosity of the geopolymer sample.
In Figure 3.4b) , the apparent density decreased with increasing water contents in
solutions. Results show that the geopolymer volume increased when higher water
contents were used because the water evaporated to leave bubbles in the material.
Then these bubble volumes in the paste were fixed to become porous in the
geopolymer. For the 2 M NaOH concentration as shown in Figure 3.4b), the density
was decreased when the water contents in the paste were increased. The images of
geopolymer sample show that the large cracking occurred when the water contents
were increased.
81
80 oC 24 h 200 W 850 W
a) 2M NaOH b) c)
d) 5M NaOH e) f)
g) 10M NaOH h) i)
j) 15M NaOH k) l)
Figure 3.3 Microstructure of geopolymer sample synthesized by curing at

80 oC 24 h and using microwave radiation at power 200 and 850 W for 1 min
82
Figure 3.4 The effect of Na2SiO3/NaOH ratios on a) the volume and

b) apparent bulk density of porous geopolymer by using microwave
radiation at 850 W for 1 min
83
84
3.3.2 Properties of the geopolymer matrix cured with microwaves
Figure 3.5 shows the apparent density of the resultant geopolymers
synthesized by curing in a traditional oven at 80 oC for 24 h and in a household
microwave oven at 200, 500, 700 and 850 W for different pastes containing NaOH.
These results indicated that in the geopolymers cured geopolymer with 15 M of
NaOH concentration, the apparent density was increased markedly when the
microwave was operated at 500-850 W. The values of apparent bulk density showed
about 0.9 g/cm3 for the 15 M NaOH concentration at 500-850 W, while these were
1.4-1.5 g/cm3 for the 2 M and 5 M NaOH concentrations. Regarding the apparent
density of geopolymers prepared with the different microwave power, the values of
apparent density decreased with increasing incident power of the household
microwave oven. Moreover, the apparent density of geopolymers decreased as the
concentration of NaOH increased. This tendency corresponded closely to the results
presented in Figure 3.1. When the NaOH concentration was increased, the strong
alkali rapidly increased the interior temperature, especially in 10 M and 15 M
materials at 700 and 850 W. Therefore, the bubbles of the water evaporation seemed
to be increased in the bulk porous structure, thereby decreasing the apparent density.
The lowest value was obtained in NaOH concentration at 15 M, as operated with
household microwaves at 850 W.
To evaluate the geopolymer matrix further, nitrogen adsorption-desorption
analysis was performed. Figure 3.6 shows the nitrogen adsorption desorption
isotherm of the geopolymer matrix cured by heating at a) 80 oC for 24 h, microwave
cured at b) 200 and c) 850 W. The porous structure was observed from the isotherm
shape according to International Union of Pure and Applied Chemistry (IUPAC)
85
classification of the isotherms [6, 33], the isotherm corresponded to type IV
isotherms with hysteresis loops (Figure 3.6). These were indicative of capillary
condensation of the mesopores [34]. However, these changed according to the
quantity of the adsorbed nitrogen, when the NaOH concentration was different and
also higher microwave power at 850 W was used. In the case of non-microwave
curing at 80 oC, the nitrogen adsorption decreased with the increment of NaOH
concentration. This indicates that the surface area of geopolymers was reduced if
the concentration of NaOH became higher. The higher NaOH concentration
produced a dense structure of the geopolymer matrix, as shown in SEM micrographs
at Figures. 3.3a), 3d), 3g) and 3j). However, the microwave curing results had a
reciprocal tendency on the NaOH concentration to the N2 adsorbed to the
geopolymer matrix. The results showed that the quantity of N2 adsorption depended
on the NaOH concentration. The geopolymer specimens with higher NaOH
concentration adsorbed N2 better than those specimens with lower NaOH
concentration. The tendency of the N2 adsorption was greatly enhanced at the 15 M
NaOH concentration. In the relative pressure (P/Po) started at ≈ 0.5-0.8, significant
increase in the adsorption pressure was observed in the cases of the 5, 10 and 15 M
at 850 W. Hysteresis loops in type H3 are known to occur usually because of
aggregation of N2 molecules covering slit-shaped pores.
The open pore volumes of the geopolymer were calculated as shown in
Figure 3.7.The values of the volume of open pores with the microwave curing
showed a slight change was observed when the NaOH concentrations were used in
2 M and 5 M NaOH concentrations. However, the open pore volume exhibited high
values for 15 M NaOH concentration. The comparison between conventional cured
86
and microwave cured indicated that the geopolymers which were cured in the
conventional oven at 80 oC had higher density than those with microwave cured.
The volume of open pores of conventional cured was around 1.5-2.0 cm3 for
conventional cured, whereas, the volume of open pores of microwave cured
increased with an increasing of microwave power used during the curing process. In
this study the volume of open pores was around 3.1-3.4 cm3 for the 2 M and 5 M
NaOH concentrations. The volume of open pores laid in between 5.5-6.0 cm3 for the
cases of 15 M NaOH at 700-850 W. As a result, the higher incident power of the
microwave at 850 W produced almost two times larger volume pores in the
geopolymer matrix.
It was expected that the porous morphology of the resultant geopolymer
reflected water adsorption. Figure 3.8 shows water absorption of the geopolymers
prepared with different microwave powers. The water absorption values depended
on the open pores volume in the matrix, meaning that higher volume of the open
pores increased the water absorption effects. Therefore, almost 45-47% of water
adsorption was obtained in the cases of 15 M NaOH concentration at 700-850 W.
87
1.6
1.5
1.4
1.3
1.2
1.1
2M
1.0
5M
10M
0.9
15M
0.8
80 oC 200 W 500 W 700 W 850 W
Figure 3.5 Apparent bulk density of geopolymers synthesized by using microwave

radiation at power 200-850 W for 1 min and by curing at 80 oC 24 h
88
Figure 3.6 Nitrogen adsorption desorption isotherms of geopolymers synthesized

by curing at 80 oC 24 h and using microwave radiation at power 200 and 850 W
for 1 min
89
6 2M
5M
Volume of Open Pores (cm3)
10M
5 15M
1
80 oC 200 W 500 W 700 W 850 W
Figure 3.7 Volume of open pores of geopolymers synthesized by using microwave

90
Figure 3.8 Water absorption of geopolymers synthesized by using microwave

91
3.3.3 Geopolymers containing aluminosilicate formed with
microwave cure
Figure 3.9 shows X-ray diffraction patterns of geopolymers cured in the
household microwave at 200 W and 850 W for 1 min and cured in a traditional oven
at 80 oC for 24 h. The results for original fly ash are also presented. The crystalline
peaks of quartz (Q) and magnetite (Ma) predominantly in the XRD patterns of
original fly ash are apparent. In addition, the non-crystalline phase of the original
fly ash was regarded as the broad hump at 2θ = 25 o. After geopolymerization in the
traditional oven, the crystalline peak and amorphous phase remained in the
geopolymer sample. The quartz and magnetite peaks were smaller in the XRD
patterns of the geopolymer cured in the microwave at 200 W and 850 W, when 15
M NaOH was used. It is noteworthy that the broad hump positions were shifted
toward 30 o in the geopolymer. The results indicated that the geoplymer was reacted
with alkaline solutions. Then the amorphous gel was formed in the geopolymr
matrix [8, 35]. Comparison of the hump peak at about 30 o was made in each XRD
pattern. Heating at 80 oC for 24 h produced fewer geopolymers when the 30 o hump
was contained. However, the curing time was only 1 min for each microwave curing.
The resultant geopolymer had the appearance of the 30 o hump in the XRD patterns.
Especially in the 15 M NaOH, the crystalline peak was strongly pronounced for the
geopolymers produced at 200 W and 850 W, which strongly suggests that the
geopolymer sample was ascribable to strong alkali solutions and accelerated to form
an aluminosilicate structure [36]. Transform geopolymer paste to solid geopolymer
which affect crystalline phase raw materials.
92
Figure 3.10 shows FT-IR spectra of the original fly ash and geopolymers.
The constituents forming the original fly ash are glassy with a surface layer (SiO2)
component. The Si-O-Si was contributed by crystalline matrix components such as
quartz and magnetite [6, 37]. Consequently, the overlapping peaks gave rise to broad
fly ash band at 1080 cm-1. Furthermore, the band was assigned to asymmetric
stretching vibration of Si-O-M (M= Si or Al) near 1000 cm-1, which indicated the
presence of tetrahedral SiO2 and AlO4 in the fly ash. For microwave curing (Figures.
3.10b-10c), the center of the broad band at 1080 cm-1 apparently shifted to a lower
wavenumber at 1000 cm-1 in each geopolymer spectrum. That shift indicated that
the microwave curing formed an Si–O–Si structure that incorporated Al [6]. The
peaks at 480 cm-1 represented O-Si-O bending vibration [1, 36, 38]. A strong
tendency was observed in the case of 850 W at lower NaOH concentration. It is
noteworthy that the broad band around 3400 and 1650 cm-1 respectively
corresponded to O–H stretching and bending [39]. Moreover, the peaks at 1450
cm-1 were attributed from sodium carbonates, which formed during absorption of
CO2 gas from the atmosphere to the sodium silicate [39, 40]. The presence of an
organic hydrocarbon component (C-H) at band 2900-3000 cm-1 was unpurified in
the fly ash.
93
Figure 3.9 XRD pattern of geopolymer sample synthesized by curing at 80 oC 24

hand using microwave radiation at power 200 and 850 W for 1 min
94
Figure 3.10 IR spectra of geopolymers synthesized by curing at 80 oC 24 h

and using microwave radiation at power 200 and 850 W for 1 min
95
3.4 Conclusion
Microwave curing of fly ash based geopolymer was effective to prepare
porous geopolymers with higher NaOH concentrations. The higher NaOH
concentration at 850 W was supported strongly by the higher temperature of the fly
ash paste and geopolymer curing within 1 min at 130 oC. X-ray CT and SEM
micrographs confirmed porous structures formed in the case of the microwave
curing at 850 W. The lowest density of the resultant geopolymer was 0.85 g/cm3 and
the voloume of open pores was 5.77 cm3 in the mesopores. The high microwave
output power was effective for the formation of aluminosilicate bonds in the porous
geopolymers within 1 min of curing.
96
3.5 References
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Wastewater by Its Immobilization in Geopolymer Cement, Industrial & Engineering
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curing of concrete, Cem. Concr. Res., 27 (1997) 463-472.
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microwave heating, Separation and Purification Technology, 25 (2001) 241-249.
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Process for the Synthesis of a Single-Phase Na-A Zeolite from Coal Fly Ash,
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heating in microwave ovens, Arabian Journal of Chemistry, 8 (2015) 100-104.
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profile of fly ash-based geopolymer mortar, International Communications in Heat
and Mass Transfer, 38 (2011) 242-248.
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texture of catalysts, Catalysis Today, 41 (1998) 207-219.
[34] V. Nikolić, M. Komljenović, N. Marjanović, Z. Baščarević, R. Petrović, Lead
immobilization by geopolymers based on mechanically activated fly ash, Ceram.
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29 (2009) 539-543
101
microwave pre-curing
4. Chapter 4: Dense geopolymer cements prepared

with microwave pre-curing
ABSTRACT: This work described that microwave cure of fly ash alkali paste
enhanced formation of dense geopolymer. The geopolymerization was carried out
at 1, 2, 5 and 10 M of NaOH and curing in microwave at output power 200 W for
1, 3, 5 and 10 min. The compressive strength and bulk density increased with curing
in microwave output power at 200 W for 1 min. The microwave cured enabled to
obtain dense geopolymer bulk having 1.41-1.59 g/cm3 and maximum compressive
strength about 24 MPa for 1 min and followed by conventional curing at 80 oC for
24 h. It was observed from the results that geopolymer prepared with longer
microwave cured had over hydration and drying shrinkage made the cracking in the
geopolymer matrix. In addition with the shorter microwave precure, the microwave
cured geopolymers were subsequently heated at 80 oC for 24 h. The post heating
was effectively to prepared for dense geopolymers. The results indicated that the
denser structure of the fly ash geopolymer was obtained by microwave curing, when
high NaOH and shorter curing time.
102
4.1 Introduction
Recently, construction engineering along with cementitious, cementitious
composites and concrete trends to use environmentally-friendly materials in cement
industry [1]. Fly ash [2], metakaolin [3] and silica fume [4] are pozzolanic materials
which are used for replacement of Ordinary Portland Cement (OPC). Cement based
pozzolanic systems have positive effects such as high mechanical properties at early
stage, improvement of strength, increases in the freezing, fire resistance and
permeability reduction were reported [3]. However, These systems have limits for
cement replacement (40-60 wt %) [2]. To this end, the material is moving towards
cementitious materials. Therefore, attractive focus has been paid in environmentally
friendly materials called “geopolymer” for substitute cements [5, 6]. It is known that
geopolymer is an alumino silicate material and a new inorganic polymeric materials
[7]. Basically, the geopolymer structure is composed of Si-O-Al bonding and these
are connected together with covalent bonds to be 3D structures by polycondensation
reaction. In the geopolymerization, three polymerization steps are occurred in first
step, pozzolanic materials are dissolved by alkaline solutions to be silicate,
aluminate and aluminosilicate species and then the species formed a gel as oligomers
form long chains and networks. The gel continues to re-arrange and form to large
three-dimensional aluminosilicate network at last step [8, 9]. Generally, these
materials are prepared by mixing pozzolanic materials containing rich silica and
alumina with alkali activators like a sodium hydroxide, potassium hydroxide,
sodium silicate and potassium silicate solutions [10]. The mechanical properties of
geopolymer depends on the temperature in the condensation cure and the
concentration of alkali solutions which acts as activators [11]. There was tendency
that the compressive strength of geopolymer increased with increasing the activator
103
concentration and in the high curing temperature caused geopolymerization
increased. It was common that the suitable curing temperature was about 60-80 oC
[11-14].
On the other hand, fly ash is raw material of the one candidate to the substitute
of geopolymer cements. The performance and properties of the fly ash based
geopolymer depends on chemical compositions, mineralogy, morphology, particle
size distributions or unburned carbon content [15-17]. Prinya et al. [18] studied
geopolymers made from original fly ash. In the ratio of sodium silicate and soudium
hydroxide solutions at 1.5, the geopolymer was cured at 65 oC for 48 h with longer
curing time. Also, Kiatsuda et al. [19] synthesized ground fly ash geopolymer in the
range of NaOH at 9.5-14.0 M. The higher NaOH concentration solution in the fly
ash showed the maximum strength of 25.5 MPa for 60 days curing. In our report,
higher NaOH concentration easily occurred geopolymer, however non curable
NaOH components, meaning that the excess NaOH was remained and lower
performance of geopolymers [11]. In contrast, at lower concentration, the
geopolymer condensation reaction depressed. Moreover, many researcher
synthesized geopolymers by using other raw materials of rice husk bark ash [20],
copper mine tailings [21], silica fume [22] or aluminium hydroxide waste [11] for
increase the mechanical properties of the materials. On the other way, the
researchers improved properties of geopolymer by using the microwave radiation.
In this case, the geopolymerization reaction was accelerated by microwave heating
which provided immediate increase of temperature of the geopolymer pastes [23,
24] . Therefore, the benefit can be proposed to apply for geopolymerization in lower
alkali concentration. In the present research, the fly ash based geopolymer at low
NaOH concentration was prepared in microwave radiation. The condition of
104
geopolymerization was studied for high mechanical strength of geopolymers, which
suitable for cement materials.
4.2 Experimental procedure
4.2.1 Raw materials and preparation of geopolymers
Fly ash (FA) from Mae Moh power plant, Lampang province, Thailand was
the raw materials used. The particle size distribution of FA was 0.3-130 µm. The
FA consisted of 29.80% SiO2, 18.50% Al2O3, 16.80% Fe2O3 and high Cao content
at 19.80% [11]. The alkaline solution was used in 1, 2, 5 and 10 M concentration of
sodium hydroxide solution ( NaOH) and sodium silicate solution ( Na2SiO3) with
31.38% SiO2, 10.15% Na2O and 58.47% H2O. The solid/liquid ratio of all mixtures
and Na2SiO3/NaOH ratio were 1.5 and 2.5, respectively.
Figure 4.1 showed protocol of geopolymer preparation of FA. For mixing of
geopolymer paste, FA and alkaline solution were mixed well until a uniform mixture
which took approximately 2 min in an air conditioned room at around 25 oC. Then,
the geopolymer paste was poured in plastic mould for microwave cured.
Geopolymer bulk were separated to cure in household microwave radiation ( JM-
17E; Haier Group) at power output 200 W for 1, 3, 5 and 10 min. Then, post heating
geopolymer after the microwave cure carried out at 80 oC for 24 h. Moreover, the
geopolymers obtained from the microwave radiation were compared with those
cured at 25 oC and 80 oC for 24 h by conventional oven ( EO-300B; ETTAS) . All
mixtures were continuously cured at 25 oC until 7 days. The temperature was
measured during the cure for the microwave radiation at different NaOH
concentration, as detected using an infrared thermal scanner. Figure 4.2 showed the
105
temperature profiles for the geopolymer paste containing different NaOH
concentration and curing time.
4.2.2 Characterizations of bulk geopolymer
Geopolymer samples were tested for apparent density by Archimedes's
method and compresiiver strength for observed the mechanical property ( AG-G;
SHIMADZU). After the geopolymers obtained were ground, the fracture surface of
geopolymer was observed using scanning microscope ( JSM-5300LV; JEOL) .
Moreover, BET surface area and the nitrogen adsorption desorption isotherm of
geopolymers were characterized (TristarII; SHIMADZU). For XRD pattern and FT-
IT spectra, the geopolymer powder were used for XRD equipment (D8 Advance;
Bruker Analytik) and spectrometer (Spectrum one; PerkinElmer Inc.) . The XRD
scans were performed 2θ=10-50o, with a sampling width of 0.02 deg/step and a scan
speed of 2.0 deg/min and FT-IR sample was prepared with KBr method.
106
Figure 4.1 Protocal of synthesis geopolymer
107
240 200W 1 min

200W 3 min
220 200W 5 min
200W 10 min
200
195
180
Temperature (oC)
186
160
154
140 146 143
134
120 128
107
100
73 88 92
80 68
60 63
65 67
55
40
0 1 2 3 4 5 6 7 8 9 10 11
NaOH concentration
Figure 4.2 The temperature profile of geopolymer in different curing time and
NaOH concentration at incident power 200W
108
4.3.1 Microwave pre-curing fly ash-alkali pastes for geopolymers
As seen in Figure 4.2, the temperature profile of geopolymer pastes during
increased longer heating in microwave oven. Also, the temperature increased with
an increasing NaOH concentration. In the microwave heating of the paste, it was
known that the dipolar polarization and ionic conduction was occurred for the higher
temperature [25], because polar molecules and charge species easily oscillated in the
microwave atmosphere. In high concentration of NaOH, the paste contained high
charge species. For heating up the geopolymer paste, the heating time seemed to be
influenced. As known, the geopolymerization could be improved by heat curing at
high temperature and also increase the mechanical property of geopolymer [11]. The
fact was due to that high temperature curing enhanced the Si-O-Si and Si-O-Al
segment formation by the condensation reaction. Figure 4.3 showed pictures of outer
view of the resultant geopolymers. The geopolymers were obtained as dense samples,
when each geopolymers were cured at 25 oC and 80 oC by conventional oven or
microwave heating for 1min. Furthermore, the cracks on geopolymer sample were
occurred with curing in the microwave over 1 min. It was noted that the cracks was
found to be large cracks after cured geopolymer for 10 min.
SEM micrographs for the geopolymer were measured in different curing
times with 1 M NaOH concentartion as presented in Figure 4.4. The matrix appeared
dense structure in comparison with the geopolymer when cured at 80 oC for 24 h. In
Figures. 4.4c and 4.4d, the dense geopolymer structure were observed a little crack
inside because of heating in microwave radiation. Moreover, Figures. 4.4e and 4.4f
109
a) b)
c) d)
e) f)
Figure 4.3 The pictures of geopolymer with 1 M NaOH cured in microwave

radiation at different times; a) 25oC b) 80 oC 24 h c) 1 min
d) 3 min e) 5 min and f) 10 min
110
a) b)
c) d)
e) f)
Figure 4.4 Microstructure of geopolymer with 1 M NaOH sample synthesized by

curing in microwave radiation at different times; a) 25oC b) 80 oC 24 h c) 1 min
d) 3 min e) 5 min and f) 10 min
111
showed many large cracks inside the geopolymer structure. In these case, the over
hydration and drying shrinkage was occurred in geopolymer matrix.
4.3.2 Properties of geopolymers cured in different NaOH
concentration
Figure 4.5 showed the comparison of apparent bulk density for the cured
geopolymers in each microwave radiation times. The geopolymers were cured at 80

o
C for 24 h as shown in the high value of bulk density. It was suggested that the
geopolymer cured in conventional oven had dense structure. Also the geopolymer
which were cured in microwave for 1 min showed a little lower the bulk density
relative to samples were cured at 25 oC. However, the geopolymers were cured in
microwave at 3, 5 and 10 min, the density values were more decreased. From the
results, it was indicated that the denser geopolymers were obtained when the pastes
were cured for 1 min heating. Moreover, the geopolymer were synthesized with
different NaOH concentrations showed different in the value of the bulk density.
The bulk density increased with increasing the NaOH concentration in all mixtures.
This was because that the high NaOH concentration dissolved easily the Si and Al
ions in the paste for geopolymerization. So, the geopolymer with high NaOH
concentration was occurred the dense sample and the high value of bulk density.
Table 4.1 showed the surface area of each geopolymer which was cured at different
times and NaOH concentration. The low surface area meant the dense geopolymer
sample. Therefore, the value of the high surface area indicated that the sample had
pore and cracks inside. The increasing of NaOH concentration, the surface area
decreased. This meant that the resultant geopolymer was denser in the higher NaOH
112
condition. Moreover, the geopolymers were obtained the low surface area after
cured at 80 oC for 24 h or microwave cured for 1 min. In geopolymers were cured
over 1 min longer, the surface area increased. Moreover, the mechanical properties
of the geopolymer were tested by compressive strength as presented in Figure 4.6.
The compressive strength increased with increasing NaOH concentration in the
paste. It was noted that the compressive strength showed the highest value of 19
MPa when the sample was cured at 80 oC for 24 h. In the cases of microwave curing
for 1 min, the compressive strength value was obtained about 10 MPa which was
lower than non-microwave cure. The concentration of NaOH and curing
temperature affected the dense geopolymer. The high bulk density and high strength
of geopolymer was synthesized by curing in conventional curing and microwave
curing for 1 min.
113
Table 4.1 Surface area of bulk geopolymer curing in microwave at different times
Surface area (m2/g )

[NaOH]
80 oC Microwave cuing at power 200 W
(Molar) 25 oC
24 h 1 min 3 min 5 min 10 min
1 35.4 8.4 10.5 20.5 25.8 34.3
2 28.8 7.3 9.2 15.1 22.7 29.5
5 25.8 5.4 6.3 13.8 17.2 24.3
10 20.7 1.7 2.9 10.9 14.5 21.5
Table 4.2 Surface area of bulk geopolymer curing in microwave at different times
and post heating at 80 oC for 24 h
Surface area (m2/g )

[NaOH]
80 oC Microwave cuing + post heating
(Molar) 25 oC
24 h 1 min 3 min 5 min 10 min
1 35.4 8.4 6.1 17.4 20.7 30.5
2 28.8 7.3 5.6 12.9 20.3 25.6
5 25.8 5.4 3.3 9.8 12.9 21.2
10 20.7 1.7 1.7 5.7 11.1 18.4
114
1.70
25oC
1.65 80oC 24 h
200W 1 min
1.60 200W 3 min
200W 5 min
1.55 200W 10 min
1.50
1.45
1.40
1.35
1.30
1.25
0 1 2 3 4 5 6 7 8 9 10 11
NaOH concentration
Figure 4.5. Apparent bulk density of geopolymer synthesized by using

conventional oven at 80 oC and using microwave radiation at power 200 W in
different time
115
30
25oC
80oC 24 h
200W 1 min
25 200W 3 min
Compressive strength (MPa)
200W 5 min
200W 10 min
20
15
10
0
0 1 2 3 4 5 6 7 8 9 10 11
NaOH concentration
Figure 4.6 Compressive strength at age of 7 days of geopolymer synthesized by

using conventional oven at 80 oC and using microwave radiation at power 200 W
in different time
116
4.3.3 Effect of post heating to the microwave cured geopolymers
Although the microwave cure was benefited in the reduced cure time, the
bulk strength of the fly ash geopolymer was still inferior in the strength. The short
time cure was insufficient in the conclusion reaction. Therefore, following
experiment in post-cure was carried out. The apparent bulk density of geopolymer
after post-cure is presented in Figure 4.7. The values of the apparent bulk density
increased, when increasing NaOH concentration was used until 10 M. In addition,
the value of the bulk density was increased in microwave radiation at 200 W for 1
min and the post heating. This meant that the curing in microwave radiation could be
increased the density values of geopolymer during the post-heating. As increasing
the time for curing to 3, 5 and 10 min, the apparent bulk density of geopolymer tended
to be more decreased. For the longer microwave, the samples had over drying
shrinkage which were made the cracking in geopolymer samples. However, in the
low and high NaOH concentration for synthesis geopolymer, the apparent density of
geopolymer became the highest values in the sample when cured in microwave
radiation for 1 min and then post-heatind at 80 oC for 24 h. Moreover, the geopolymer
sample that cured in 25 oC in all conditions of curing showed the lowest apparent
bulk density values. Table 2 showed the values of surface area of geopolymers with
post curing. The results showed the same tendency without post-curing but when the
post-curing was over, the geopolymer had lower surface area. It was indicated that
the denser geopolymer samples were obtained by post-heating. From Figure 4.8, the
compressive strength highly increased in the 1 min microwave cure with increasing
the NaOH concentration. The geopolymer sample were obtained by post-curing
showed the high strength about 5-24 MPa with 1-10 M of NaOH concentration.
Moreover, the strength of geopolymer about 3-18 MPa was observed with cured at
117
80 oC for 24 h. From the results, it was concluded that the microwave curing was pre-
cured for reduce curing time and then the post-heating at 80 oC for 24 h improved
the mechanical properties and strength of geopolymer sample.
Nitrogen adsorption-desorption analysis was performed to evaluate the
geopolymer matrix. Figure 4.9 showed the isotherm of the geopolymer matrix cured
by different heating process in different NaOH concentrations a) 1 M, b) 2 M, c) 5
M and c) 10 M. The porous structure and the ability for adsorption-desorption were
observed from the shape and amount of an isotherm. As seen, the nitrogen
adsorption-desorption isotherm corresponded to type IV with hysteresis loops
according to IUPAC (International Union of Pure and Applied Chemistry)
classifications [26, 27]. These results indicated that the pores of geopolymer sample
was mesopores in the geopoltmer matrix [28]. The quantity of the adsorbed nitrogen
was changed when curing process was changed and NaOH concentration was
varied. The higher NaOH concentration showed the values of nitrogen adsorption-
desorption decreased. This result supported the less surface area was formed in the
higher NaOH concentration. This confirmed that the higher NaOH concentration
made dense structure of the geopolymer matrix. As known, the hysteresis loops in
type H3 were usually occurred due to aggregation of N2 molecules covering like
slit-shape pores. Moreover, in different curing process, the quantity of absorbed N2
was significantly decreased when the sample was cured in the post-heating for 1 min
microwave pre-curing. This results demonstrated that the geopolymer samples were
dense.
118
1.70
25oC
1.65 80oC 24 h
200W 1 min + 80oC 24 h
1.60 200W 3 min + 80oC 24 h
200W 5 min + 80oC 24 h

1.55 200W 10 min + 80oC 24 h
1.50
1.45
1.40
1.35
1.30
1.25
0 1 2 3 4 5 6 7 8 9 10 11
NaOH concentration
Figure 4.7 Apparent bulk density of geopolymer synthesized by using

conventional oven at 80 oC and using microwave radiation at power 200 W with
post heating in different time
119
30
25oC
80oC 24 h
200W 1 min + 80oC 24 h
25
Compressive strength (MPa)
200W 3 min + 80oC 24 h

200W 5 min + 80oC 24 h
20 200W 10 min + 80oC 24 h
15
10
0
0 1 2 3 4 5 6 7 8 9 10 11
NaOH concentration
Figure 4.8 Compressive strength at age of 7 days of geopolymer synthesized by using

conventional oven at 80 oC and using microwave radiation at power 200 W with post
heating in different time
120
100
a) 25oC NaOH 1 M
90
80oC
80 200W 1m + 80oC 24h
200W 3m + 80oC 24h
Quantity absorbed (cm3/g)
70
60
50
40
30
20
10
0.0 0.2 0.4 0.6 0.8 1.0

Relative pressure (p/po)
100
b) 25oC NaOH 2 M
90
80oC
80 200W 1m + 80oC 24h
200W 3m + 80oC 24h
70
60
50
40
30
20
10
0.0 0.2 0.4 0.6 0.8 1.0

Figure 4.9 Nitrogen adsorption desorption isotherm of geopolymers synthesized by

using different curing method and different NaOH concentration:
a) 1 M b) 2 M c)5 M and d) 10 M
121
c) 100
25oC NaOH 5 M
90
80oC
80 200W 1m + 80oC 24h
200W 3m + 80oC 24h
70
60
50
40
30
20
10
0.0 0.2 0.4 0.6 0.8 1.0

100
d) 25oC NaOH 10 M
90
80oC
80 200W 1m + 80oC 24h
200W 3m + 80oC 24h
70
60
50
40
30
20
10
0.0 0.2 0.4 0.6 0.8 1.0

122
X-ray powder diffraction pattern of fly ash and the geopolymer obtained
with different curing process in 1 and 10 M of NaOH concentration is shown in
Figure 4.10. For geopolymers, the pattern showed that the major phase of
geopolymer was amorphous, as indicated by the broad hump at 20-35o ( 2theta) .
After the geopolymerization, the crystalline phase peak of quartz at 25o decreased
and intensity was lower than the original fly ash. The peak intensity of quartz phase
decreased with an increasing the time for curing in microwave. Moreover, the
amorphous still remained in the geopolymer sample. This indicated that the raw
materials was activated with the alkaline solutions and then the amorphous
component was formed in the alkaline aluminosilicate gel with apparent shift of a
broad hump at 20-35o (2theta)[29].
To confirm the formation of alumino-silicate bonding of -Al-O-Si- and –Si-
O-Si-, Fourier transform infrared spectroscopy results was measured for FA and
geopolymers (Figure 4.11). The sodium carbonate was detected at 1460 cm-1 [18].
The peak distinct bands at 450-460 cm-1 represented to Si-O-Si bending vibration
[18, 19, 30, 31] and Si-O-Si asymmetric stretching vibration for 1012 and 1109
cm-1 in FA [19, 30]. This peak was for main band and other major bands observed
in the spectra were assigned to O-H bending and O-H stretching vibration at 3400-
3500 cm-1 and 1654 cm-1, respectively [13, 18, 31]. In addition the –Al-O-Si- bond
appear in the geopolymers near 1002-1018 cm-1. The band peak was shifted toward
lower wave number side, when the FA was synthesized to be geopolymer by
condensation in microwave pre-cure. This indicated that the tetrahedral positioned
alumunium segment was contained in the geopolymer [19], when the microwave
pre-cure was done and the post-heating was finished for the dense geopolymer
matrix.
123
Figure 4.10 The XRD pattern of geopolymer sample synthesized using

NaOH concentration at 1 M and 10 M
124
NaOH concentration = 1 M
O-H O-H Si-O-M O-M

M= Si,Al O-C-O
200 W 3m + 80 oC 24h
200 W 1m + 80 oC 24h
80 oC 24h
25 oC
Fly ash
4000 3500 3000 2000 1500 1000 500

-1
wavenumber (cm )
NaOH concentration = 10 M
O-H O-H Si-O-M O-M

M= Si,Al O-C-O
200 W 3m + 80 oC 24h
200 W 1m + 80 oC 24h
80 oC 24h
25 oC
Fly ash
4000 3500 3000 2000 1500 1000 500

-1
wavenumber (cm )
Figure 4.11 FT-IR spectra of geopolymer sample synthesized using

NaOH concentration at 1 M and 10 M
125
4.4 Conclusions
Improvement of the geopolymerization was achieved by short microwave
pre-curing and then post-heating. The mechanical properties of geopolymers were
improved by the short time in radiation of 200 W and following conventional
heating at 80 oC for 24 h. In these processes, the geopolymers were produced with
high strength and high density compared with room temperture curing and
conventional curing. The densification of geopolymer was occured with microwave
pre-cured.
126
4.5 References
[1] P. Timakul, W. Rattanaprasit, P. Aungkavattana, Improving compressive
strength of fly ash-based geopolymer composites by basalt fibers addition, Ceram.
Int., 42 (2016) 6288-6295.
[2] K. Hoang, H. Justnes, M. Geiker, Early age strength increase of fly ash blended
cement by a ternary hardening accelerating admixture, Cem. Concr. Res., 81 (2016)
59-69.
[3] A. Subaşı, M. Emiroğlu, Effect of metakaolin substitution on physical,
mechanical and hydration process of White Portland cement, Constr. Build. Mater.,
95 (2015) 257-268.
[4] J. Liu, Y. Li, P. Ouyang, Y. Yang, Hydration of the silica fume-Portland cement
binary system at lower temperature, Constr. Build. Mater., 93 (2015) 919-925.
[5] K.T. Nguyen, N. Ahn, T.A. Le, K. Lee, Theoretical and experimental study on
mechanical properties and flexural strength of fly ash-geopolymer concrete, Constr.
Build. Mater., 106 (2016) 65-77.
[6] P. Duxson, G.C. Lukey, F. Separovic, J.S.J. Van Deventer, Effect of alkali
cations on aluminum incorporation in geopolymeric gels, Industrial and Engineering
[7] H. Su, J. Xu, W. Ren, Mechanical properties of geopolymer concrete exposed to
dynamic compression under elevated temperatures, Ceram. Int., 42 (2016) 3888-
3898.
[8] M. Soutsos, A.P. Boyle, R. Vinai, A. Hadjierakleous, S.J. Barnett, Factors
influencing the compressive strength of fly ash based geopolymers, Constr. Build.
Mater., 110 (2016) 355-368.
127
Deventer, Geopolymer technology: the current state of the art, Journal of Materials
Science, 42 (2006) 2917-2933.
[10] A. Gharzouni, L. Vidal, N. Essaidi, E. Joussein, S. Rossignol, Recycling of
geopolymer waste: Influence on geopolymer formation and mechanical properties,
Materials & Design, 94 (2016) 221-229.
[12] M.A. Salih, N. Farzadnia, A.A. Abang Ali, R. Demirboga, Effect of different
curing temperatures on alkali activated palm oil fuel ash paste, Constr. Build.
Mater., 94 (2015) 116-125.
[14] E. ul Haq, S. Kunjalukkal Padmanabhan, A. Licciulli, Synthesis and
characteristics of fly ash and bottom ash based geopolymers–A comparative study,
Ceram. Int., 40 (2014) 2965-2971.
[15] H.Y. Leong, D.E. Leong Ong, J.G. Sanjayan, A. Nazari, Suitability of Sarawak
and Gladstone fly ash to produce geopolymers: A physical, chemical, mechanical,
mineralogical and microstructural analysis, Ceram. Int.
[16] A. Fernández-Jiménez, A. Palomo, Characterisation of fly ashes. Potential
reactivity as alkaline cements☆, Fuel, 82 (2003) 2259-2265.
[17] S.V. Vassilev, C.G. Vassileva, A new approach for the classification of coal fly
ashes based on their origin, composition, properties, and behaviour, Fuel, 86 (2007)
1490-1512.
128
29 (2009) 539-543.
2118-2124.
7401.
[21] L. Zhang, S. Ahmari, J. Zhang, Synthesis and characterization of fly ash
modified mine tailings-based geopolymers, Constr. Build. Mater., 25 (2011) 3773-
3781.
[22] F.N. Okoye, J. Durgaprasad, N.B. Singh, Effect of silica fume on the
mechanical properties of fly ash based-geopolymer concrete, Ceram. Int., 42 (2016)
3000-3006.
[23] P. Chindaprasirt, U. Rattanasak, S. Taebuanhuad, Role of microwave radiation
in curing the fly ash geopolymer, Advanced Powder Technology, 24 (2013) 703-
707.
[24] P. Rattanadecho, N. Suwannapum, B. Chatveera, D. Atong, N. Makul,
Development of compressive strength of cement paste under accelerated curing by
using a continuous microwave thermal processor, Materials Science and
Engineering: A, 472 (2008) 299-307.
[25] S. Onutai, S. Jiemsirilers, P. Thavorniti, T. Kobayashi, Fast microwave
syntheses of fly ash based porous geopolymers in the presence of high alkali
concentration, Ceram. Int., 42 (2016) 9866-9874.
129
[26] N. Böke, G.D. Birch, S.M. Nyale, L.F. Petrik, New synthesis method for the
production of coal fly ash-based foamed geopolymers, Constr. Build. Mater., 75
(2015) 189-199.
[27] G. Leofanti, M. Padovan, G. Tozzola, B. Venturelli, Surface area and pore
texture of catalysts, Catalysis Today, 41 (1998) 207-219.
[28] V. Nikolić, M. Komljenović, N. Marjanović, Z. Baščarević, R. Petrović, Lead
immobilization by geopolymers based on mechanically activated fly ash, Ceram.
Int., 40 (2014) 8479-8488.
130
Chapter 5: Summary
5. Chapter 5: Summary
This thesis describes to reused fly ash and industrial wastes for producing to
be sustainable and green materials. This because that fly ash and aluminium
hydroxide waste are useful for convert to functional materials in the point of
sustainable geopolymer. In the waste materials geopolymers, bulk and porous
structure were developed. The most important conclusion obtained in this thesis and
the details are summarized below.
In chapter 1, introduction of geopolymer materials is mentioned for
understanding basic and condensation reaction of geopolymers in addition with their
syntheses methods and applications. The raw materials used to synthesis
geopolymer such as fly ash and aluminium hydroxide waste are also described in
this chapter.
Chapter 2 describes geopolymers which are synthesized from fly ash and
aluminium waste with different proportions of raw materials for alternative cement.
Moreover, when different NaOH concentration and different curing temperature
was changed, geopolymer was synthesized. The geopolymer bulk was cured in
conventional oven at 25 oC, 60 oC and 80 oC for 24h. The results indicated that
increasing amount of the Al-waste in FA increased compressive strength of the
geopolymer bulk. The highest compressive strength was about 40 MPa, when the
sample was synthesized from 60 % FA and 40 % Al-waste with 10 M NaOH at 80

o
C for 24 h. As a results, the materials for cement and concrete by alternative FA
and Al-waste geopolymers were successfully produced.
131
Chapter 5: Summary
Chapter 3 mentioned about synthesis porous geopolymer using microwave
radiation from household microwave. Here, fly ash is raw material for synthesis of
porous geopolymers by using microwave cured. At 2, 5, 10, and 15 M of NaOH,
geopolymerization was occurred when cured in microwave radiation output at 200-
850 W for 1 min. The results showed that porous geopolymer was produced at 10
or 15 M NaOH with 850 W of microwave radiation power. It was observed that the
high power of microwave radiation increased the slurry temperature and affect water
evaporation in the geopolymr paste.
In chapter 4, geopolymerization reaction in microwave cure was suitable for
preparing dense materials, when fly ash based geopolymer were mixed and cured in
microwave radiation at power 200 W for 1 - 10 min. The results showed the
microwave radiation with lower power at 200 W increased the dense structure. The
density and mechanical property are enhanced by the low power microwave
operation. When the curing time was 1 min, the geopolymer sample had over
shrinkage and presence of produced cracks in geopolymers.
In conclusion, the bulk and porous geopolymer were successfully produced
by using FA and Al-waste. It was seen that FA and aluminium hydroxide waste were
suitable sources for geopolymer. Moreover, the microwave radiation was enable for
synthesis porous geopolymer and improve the geopolymer bulk strength.
132
List of Achievements
List of Achievements
Publications papers
1. Aluminium hydroxide waste based geopolymer composed of fly ash for
sustainable cement materials
Sujitra Onutai, Sirithan Jiemsirilers, Parjaree Thavorniti, Takaomi Kobayashi
Construction and Building Materials 101 (2015) 298–308
2. Fast microwave syntheses of fly ash based porous geopolymers in the presence
of high alkali concentration
Sujitra Onutai, Sirithan Jiemsirilers, Parjaree Thavorniti, Takaomi Kobayashi
Ceramics International 42 (2016) 9866–9874
133
Presentations in International Conferences
Presentations in International Conferences
1. The HUST-NUT Joint Symposium 2014 at Hanoi University of Science and
Technology, Vietnam, Influence of alkali solution on the synthesis of fly ash
geopolymer, Sujitra Onutai, Sirithan Jiemsirilers, Takaomi Kobayashi
(November 2014)
2. The NUT-CU MST Colloquium 2014 at Nagaoka University of Technology,
Japan, Microwave syntheses and characterization of fly ash based geopolymer
foams, Sujitra Onutai, Sirithan Jiemsirilers, Takaomi Kobayashi (November 2014)
3. The 3rd CU-NUT symposium in science and technology at Chulalongkorn
University, Thailand, Influence of microwave radiation for curing the fly ash
based geopolymer, Sujitra Onutai, Sirithan Jiemsirilers, Takaomi Kobayashi
(January 2015)
4. The 4th International GIGAKU Conference (IGCN 2015) at Nagaoka University
of Technology, Japan, Influence of microwave radiation to synthesis of fly ash
geopolymer foam, Sujitra Onutai, Sirithan Jiemsirilers, Takaomi Kobayashi
(June 2015)
134

Development of Geopolymer Cement from Industrial WasteTITLEFly Ash and Waste-Based Geopolymer for Sustainable Construction

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Development of Geopolymer Cement from Industrial WasteTITLEFly Ash and Waste-Based Geopolymer for Sustainable Construction

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Development of Geopolymer Materials Sourced with

Fly Ash and Industrial Waste

Energy and Environment Science

The author is grateful to the Cultivation of Global Engineering by Pacific

of grants and Doctoral scholarships.

Finally, I would also like to thank my parents, family, as well as my friends,

1.1 Geopolymers ................................................................................................... 1

1.1.1 Background and definition ....................................................................... 1

1.1.2 Geopolymer structure and preparation techniques ................................... 4

1.1.3 Geopolymerization reaction ..................................................................... 7

1.1.4 Synthesis of geopolymers ......................................................................... 9

1.1.5 Geopolymer applications ........................................................................ 12

1.2 Raw materials of fly ash and industrial wastes used to

synthesis geopolymer .......................................................................................... 16

1.2.1 Fly ash .................................................................................................... 17

1.2.2 Industrial wastes for geopolymer source ................................................ 21

1.3 Objective of thesis and Outlines of thesis ..................................................... 24

1.4 References ..................................................................................................... 26

Chapter 2: Aluminium hydroxide waste based geopolymer

composed of fly ash for sustainable cement materials ...................................... 36

2.1 Introduction ................................................................................................... 37

2.2 Experimental procedure ................................................................................ 39

2.2.1 Raw materials of geopolymers ............................................................... 39

2.2.2 Geopolymerization ................................................................................. 42

2.3 Results and discussion .................................................................................. 45

2.3.2 Mechanical properites of geopolymer bulk ............................................49

2.3.3 Morphological properties of geopolymers .............................................54

2.3.4 Reactive phases and chemical bonds of geopolymer .............................60

2.4 Conclusions ...................................................................................................64

2.5 References .....................................................................................................65

Chapter 3: Fast microwave syntheses of fly ash based porous

geopolymers in the presence of high alkali concentration ................................70

3.1 Introduction ...................................................................................................71

3.2 Experimental procedures ...............................................................................73

3.2.1 Materials .................................................................................................73

3.2.2 Synthesis of geopolymer sample in a microwave oven ..........................74

3.2.3 Characterization of pastes and geopolymers ..........................................76

3.3 Results and discussion...................................................................................76

3.3.1 Geopolymerization in microwave heating for porous matrix .................76

3.3.2 Properties of the geopolymer matrix cured with microwaves ................85

3.3.3 Geopolymers containing aluminosilicate formed with

3.5 References .....................................................................................................97

microwave pre-curing ........................................................................................ 102

4.1 Introduction ................................................................................................. 103

4.2 Experimental procedure .............................................................................. 105

4.2.1 Raw materials and preparation of geopolymers ................................... 105

4.2.2 Characterizations of bulk geopolymer ................................................. 106

4.3 Results and discussion ................................................................................ 109

4.3.2 Properties of geopolymers cured in different NaOH concentration ..... 112

4.4 Conclusions ................................................................................................. 126

4.5 References ................................................................................................... 127

Chapter 5: Summary .......................................................................................... 131

List of Achievements........................................................................................... 133

Presentations in International Conferences ..................................................... 134

Table 1.1 Geopolymers presently developed and applied in

main classes of materials ........................................................................................3

Table 1.2 Summarize geopolymer applications ..................................................14

Table 1.3 Raw materials for synthesis geopolymer ................................................16

Table 2.2 Mixture proportions for geopolymerization. ..........................................44

Table 2.3 Composition of ions in geopolymer bulk. ..............................................52

Table 4.1 Surface area of bulk geopolymer curing in microwave

at different times ...................................................................................................114