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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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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.

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Chapter 1: General Introduction

Figure 1.2 Geopolymer framework [10]

6
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

[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
Chapter 1: General Introduction

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].

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Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

Figure 1.4 Applications of geopolymer materials based on the Si:Al ratio

15
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

 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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

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
Chapter 1: General Introduction

Figure 1.6 Aluminium hydroxide waste powder

Figure 1.7 The etching solution cycle

23
Chapter 1: General Introduction

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 1: General Introduction

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
Chapter 1: General Introduction

1.4 References

[1] P. Chindaprasirt, T. Chareerat, V. Sirivivatnanon, Workability and strength of

coarse high calcium fly ash geopolymer, Cem. Concr. Compos., 29 (2007) 224-229.

[2] A. Hasanbeigi, L. Price, E. Lin, Emerging energy-efficiency and CO2 emission-

reduction technologies for cement and concrete production: A technical review,

Renewable and Sustainable Energy Reviews, 16 (2012) 6220-6238.

[3] D.J.M. Flower, J.G. Sanjayan, Green house gas emissions due to concrete

manufacture, The International Journal of Life Cycle Assessment, 12 (2007) 282-

288.

[4] S.R.Z. Alaa M. Rashad, The effect of activator concentration on the residual

strength of alkali-activated fly ash pastes subjected to thermal load, Construction

and Building Materials, 25 (2011) 3098-3107.

[5] S. Pangdaeng, T. Phoo-ngernkham, V. Sata, P. Chindaprasirt, Influence of curing

conditions on properties of high calcium fly ash geopolymer containing Portland

cement as additive, Materials & Design, 53 (2014) 269-274.

[6] A. Heath, K. Paine, M. McManus, Minimising the global warming potential of

clay based geopolymers, Journal of Cleaner Production, 78 (2014) 75-83.

[7] P. Rovnaník, Effect of curing temperature on the development of hard structure

of metakaolin-based geopolymer, Constr. Build. Mater., 24 (2010) 1176-1183.

[8] J. Davidovits, Properties of geopolymer cements, First international conference

on alkaline cements and concretes, 1 (1994) 131-149.

[9] K. Komnitsas, D. Zaharaki, Geopolymerisation: A review and prospects for the

minerals industry, Miner. Eng., 20 (2007) 1261-1277.

26
Chapter 1: General Introduction

[10] J. Davidovits, GEOPOLYMER Chemistry&Applications, Institut

Géopolymère 16 rue Galilée F-02100 Saint-Quentin France, France, 2008.

[11] J. Davidovits, Mineral polymers and methods of making them, Google Patents,

1982.

[12] J. Davidovits, Synthetic mineral polymer compound of the silicoaluminates

family and preparation process, Google Patents, 1984.

[13] J. Davidovits, Geopolymers - Inorganic polymeric new materials, Journal of

Thermal Analysis, 37 (1991) 1633-1656.

[14] R. Cioffi, L. Maffucci, L. Santoro, Optimization of geopolymer synthesis by

calcination and polycondensation of a kaolinitic residue, Resources, Conservation

and Recycling, 40 (2003) 27-38.

[15] P. Rovnaník, Effect of curing temperature on the development of hard structure

of metakaolin-based geopolymer, Construction and Building Materials, 24 (2010)

1176-1183.

[16] O.A. Abdulkareem, A.M. Mustafa Al Bakri, H. Kamarudin, I. Khairul Nizar,

A.e.A. Saif, Effects of elevated temperatures on the thermal behavior and

mechanical performance of fly ash geopolymer paste, mortar and lightweight

concrete, Constr. Build. Mater., 50 (2014) 377-387.

[17] P. Duxson, A. Fernández-Jiménez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J.

van Deventer, Geopolymer technology: the current state of the art, Journal of

Materials Science, 42 (2007) 2917-2933.

[18] V. Barbosa, Synthesis and characterisation of materials based on inorganic

polymers of alumina and silica: sodium polysialate polymers, International Journal

of Inorganic Materials, 2 (2000) 309-317.

27
Chapter 1: General Introduction

[19] M. Alshaaer, Two-phase geopolymerization of kaolinite-based geopolymers,

Appl. Clay Sci., 86 (2013) 162-168.

[20] A. Elimbi, H.K. Tchakoute, D. Njopwouo, Effects of calcination temperature

of kaolinite clays on the properties of geopolymer cements, Constr. Build. Mater.,

25 (2011) 2805-2812.

[21] K. Hemra, P. Aungkavattana, Effect of cordierite addition on compressive

strength and thermal stability of metakaolin based geopolymer, Advanced Powder

Technology, 27 (2016) 1021-1026.

[22] V. Medri, S. Fabbri, J. Dedecek, Z. Sobalik, Z. Tvaruzkova, A. Vaccari, Role

of the morphology and the dehydroxylation of metakaolins on geopolymerization,

Appl. Clay Sci., 50 (2010) 538-545.

[23] X.-m. Cui, L.-p. Liu, G.-j. Zheng, R.-p. Wang, J.-p. Lu, Characterization of

chemosynthetic Al2O3–2SiO2 geopolymers, Journal of Non-Crystalline Solids, 356

(2010) 72-76.

[24] S.-D. Wang, The role of sodium during the hydration of alkali-activated slag,

Advances in Cement Research, 12 (2000) 65-69.

[25] L.N. Tchadjié, J.N.Y. Djobo, N. Ranjbar, H.K. Tchakouté, B.B.D. Kenne, A.

Elimbi, D. Njopwouo, Potential of using granite waste as raw material for

geopolymer synthesis, Ceram. Int., 42 (2016) 3046-3055.

[26] C. Li, T. Zhang, L. Wang, Mechanical properties and microstructure of alkali

activated Pisha sandstone geopolymer composites, Constr. Build. Mater., 68 (2014)

233-239.

28
Chapter 1: General Introduction

[27] P.S. Deb, P.K. Sarker, S. Barbhuiya, Effects of nano-silica on the strength

development of geopolymer cured at room temperature, Constr. Build. Mater., 101,

Part 1 (2015) 675-683.

[28] U. Rattanasak, P. Chindaprasirt, P. Suwanvitaya, Development of high volume

rice husk ash alumino silicate composites, International Journal of Minerals,

Metallurgy, and Materials, 17 (2010) 654-659.

[29] X.Y. Zhuang, L. Chen, S. Komarneni, C.H. Zhou, D.S. Tong, H.M. Yang, W.H.

Yu, H. Wang, Fly ash-based geopolymer: clean production, properties and

applications, Journal of Cleaner Production, 125 (2016) 253-267.

[30] 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.

[31] L. Le-ping, C. Xue-min, Q. Shu-heng, Y. Jun-li, Z. Lin, Preparation of

phosphoric acid-based porous geopolymers, Appl. Clay Sci., 50 (2010) 600-603.

[32] H. Douiri, S. Louati, S. Baklouti, M. Arous, Z. Fakhfakh, Structural, thermal

and dielectric properties of phosphoric acid-based geopolymers with different

amounts of H3PO4, Materials Letters, 116 (2014) 9-12.

[33] S. Hanjitsuwan, S. Hunpratub, P. Thongbai, S. Maensiri, V. Sata, P.

Chindaprasirt, Effects of NaOH concentrations on physical and electrical properties

of high calcium fly ash geopolymer paste, Cem. Concr. Compos., 45 (2014) 9-14.

[34] M.S. Muñiz-Villarreal, A. Manzano-Ramírez, S. Sampieri-Bulbarela, J.R.

Gasca-Tirado, J.L. Reyes-Araiza, J.C. Rubio-Ávalos, J.J. Pérez-Bueno, L.M.

Apatiga, A. Zaldivar-Cadena, V. Amigó-Borrás, The effect of temperature on the

29
Chapter 1: General Introduction

geopolymerization process of a metakaolin-based geopolymer, Materials Letters, 65

(2011) 995-998.

[35] X. Yao, Z. Zhang, H. Zhu, Y. Chen, Geopolymerization process of alkali–

metakaolinite characterized by isothermal calorimetry, Thermochimica Acta, 493

(2009) 49-54.

[36] J.M. Blackstock, J. Neill, J.A. Mcintosh, Geopolymeric structural building

units and methods of manufacture thereof, Google Patents, 2012.

[37] D.C. Comrie, W.M. Kriven, Composite Cold Ceramic Geopolymer in a

Refractory Application, Advances in Ceramic Matrix Composites IX, John Wiley

& Sons, Inc.2006, pp. 211-225.

[38] K. Somna, C. Jaturapitakkul, P. Kajitvichyanukul, P. Chindaprasirt, NaOH-

activated ground fly ash geopolymer cured at ambient temperature, Fuel, 90 (2011)

2118-2124.

[39] I. Lecomte, C. Henrist, M. Liégeois, F. Maseri, A. Rulmont, R. Cloots, (Micro)-

structural comparison between geopolymers, alkali-activated slag cement and

Portland cement, Journal of the European Ceramic Society, 26 (2006) 3789-3797.

[40] J. He, Y. Jie, J. Zhang, Y. Yu, G. Zhang, Synthesis and characterization of red

mud and rice husk ash-based geopolymer composites, Cem. Concr. Compos., 37

(2013) 108-118.

[41] G.S. Ryu, Y.B. Lee, K.T. Koh, Y.S. Chung, The mechanical properties of fly

ash-based geopolymer concrete with alkaline activators, Constr. Build. Mater., 47

(2013) 409-418.

30
Chapter 1: General Introduction

[42] M.B. Karakoç, İ. Türkmen, M.M. Maraş, F. Kantarci, R. Demirboğa, M. Uğur

Toprak, Mechanical properties and setting time of ferrochrome slag based

geopolymer paste and mortar, Constr. Build. Mater., 72 (2014) 283-292.

[43] H.K. Tchakouté, C.H. Rüscher, S. Kong, E. Kamseu, C. Leonelli, Geopolymer

binders from metakaolin using sodium waterglass from waste glass and rice husk

ash as alternative activators: A comparative study, Constr. Build. Mater., 114 (2016)

276-289.

[44] A. Seco, B. García, E. Prieto, F. Ramirez, L. Miqueleiz, P. Urmeneta, V. Oroz,

Types of Waste for the Production of Pozzolanic Materials-A Review, INTECH

Open Access Publisher2012.

[45] J.C. Swanepoel, C.A. Strydom, Utilisation of fly ash in a geopolymeric

material, Applied Geochemistry, 17 (2002) 1143-1148.

[46] S. Kumar, R. Kumar, Mechanical activation of fly ash: Effect on reaction,

structure and properties of resulting geopolymer, Ceram. Int., 37 (2011) 533-541.

[47] A. Palomo, M.W. Grutzeck, M.T. Blanco, Alkali-activated fly ashes: A cement

for the future, Cem. Concr. Res., 29 (1999) 1323-1329.

[48] A. Fernández-Jiménez, J.G. Palomo, F. Puertas, Alkali-activated slag mortars:

Mechanical strength behaviour, Cem. Concr. Res., 29 (1999) 1313-1321.

[49] H. Xu, J.S.J. Van Deventer, Geopolymerisation of multiple minerals, Miner.

Eng., 15 (2002) 1131-1139.

[50] J.G.S. van Jaarsveld, J.S.J. van Deventer, Effect of the Alkali Metal Activator

on the Properties of Fly Ash-Based Geopolymers, Industrial & Engineering

Chemistry Research, 38 (1999) 3932-3941.

31
Chapter 1: General Introduction

[51] S.E.W.D.M.J.S. Djwantoro Hardjito, B.V. Rangan, On the Development of Fly

Ash-Based Geopolymer Concrete, Materials Journal, 101.

[52] M.M.A.B. Abdullah, L. Jamaludin, K. Hussin, M. Bnhussain, C.M.R. Ghazali,

M.I. Ahmad, Fly Ash Porous Material using Geopolymerization Process for High

Temperature Exposure, International Journal of Molecular Sciences, 13 (2012)

4388.

[53] A. Nazari, A. Bagheri, S. Riahi, Properties of geopolymer with seeded fly ash

and rice husk bark ash, Materials Science and Engineering: A, 528 (2011) 7395-

7401.

[54] P. Chindaprasirt, C. Jaturapitakkul, W. Chalee, U. Rattanasak, Comparative

study on the characteristics of fly ash and bottom ash geopolymers, Waste Manage.,

29 (2009) 539-543.

[55] G. Görhan, G. Kürklü, The influence of the NaOH solution on the properties of

the fly ash-based geopolymer mortar cured at different temperatures, Composites

Part B: Engineering, 58 (2014) 371-377.

[56] U. Rattanasak, P. Chindaprasirt, Influence of NaOH solution on the synthesis

of fly ash geopolymer, Miner. Eng., 22 (2009) 1073-1078.

[57] Z. Zuhua, Y. Xiao, Z. Huajun, C. Yue, Role of water in the synthesis of calcined

kaolin-based geopolymer, Appl. Clay Sci., 43 (2009) 218-223.

[58] W.K.W. Lee, J.S.J. van Deventer, The effects of inorganic salt contamination

on the strength and durability of geopolymers, Colloids Surf., A, 211 (2002) 115-

126.

[59] T. Bakharev, Geopolymeric materials prepared using Class F fly ash and

elevated temperature curing, Cem. Concr. Res., 35 (2005) 1224-1232.

32
Chapter 1: General Introduction

[60] P.D. Silva, K. Sagoe-Crenstil, V. Sirivivatnanon, Kinetics of

geopolymerization: Role of Al2O3 and SiO2, Cem. Concr. Res., 37 (2007) 512-518.

[61] A. Nazari, J.G. Sanjayan, Synthesis of geopolymer from industrial wastes,

Journal of Cleaner Production, 99 (2015) 297-304.

[62] P. Pavithra, M. Srinivasula Reddy, P. Dinakar, B. Hanumantha Rao, B.K.

Satpathy, A.N. Mohanty, A mix design procedure for geopolymer concrete with fly

ash, Journal of Cleaner Production, 133 (2016) 117-125.

[63] Y. Park, A. Abolmaali, Y.H. Kim, M. Ghahremannejad, Compressive strength

of fly ash-based geopolymer concrete with crumb rubber partially replacing sand,

Constr. Build. Mater., 118 (2016) 43-51.

[64] K. Al-Zboon, M.S. Al-Harahsheh, F.B. Hani, Fly ash-based geopolymer for Pb

removal from aqueous solution, J. Hazard. Mater., 188 (2011) 414-421.

[65] S. Wang, L. Li, Z.H. Zhu, Solid-state conversion of fly ash to effective

adsorbents for Cu removal from wastewater, J. Hazard. Mater., 139 (2007) 254-259.

[66] L. Li, S. Wang, Z. Zhu, Geopolymeric adsorbents from fly ash for dye removal

from aqueous solution, Journal of Colloid and Interface Science, 300 (2006) 52-59.

[67] J.G.S. Van Jaarsveld, J.S.J. Van Deventer, L. Lorenzen, The potential use of

geopolymeric materials to immobilise toxic metals: Part I. Theory and applications,

Miner. Eng., 10 (1997) 659-669.

[68] S. Lee, A. van Riessen, C.-M. Chon, N.-H. Kang, H.-T. Jou, Y.-J. Kim, Impact

of activator type on the immobilisation of lead in fly ash-based geopolymer, J.

Hazard. Mater., 305 (2016) 59-66.

33
Chapter 1: General Introduction

[69] G. Roviello, L. Ricciotti, C. Ferone, F. Colangelo, O. Tarallo, Fire resistant

melamine based organic-geopolymer hybrid composites, Cem. Concr. Compos., 59

(2015) 89-99.

[70] K. Sakkas, D. Panias, P.P. Nomikos, A.I. Sofianos, Potassium based

geopolymer for passive fire protection of concrete tunnels linings, Tunnelling and

Underground Space Technology, 43 (2014) 148-156.

[71] S.K. Nath, S. Maitra, S. Mukherjee, S. Kumar, Microstructural and

morphological evolution of fly ash based geopolymers, Constr. Build. Mater., 111

(2016) 758-765.

[72] R. Pouhet, M. Cyr, Formulation and performance of flash metakaolin

geopolymer concretes, Constr. Build. Mater., 120 (2016) 150-160.

[73] X. Huang, T. Huang, S. Li, F. Muhammad, G. Xu, Z. Zhao, L. Yu, Y. Yan, D.

Li, B. Jiao, Immobilization of chromite ore processing residue with alkali-activated

blast furnace slag-based geopolymer, Ceram. Int., 42 (2016) 9538-9549.

[74] S. Ahmari, L. Zhang, Durability and leaching behavior of mine tailings-based

geopolymer bricks, Constr. Build. Mater., 44 (2013) 743-750.

[75] P. Duan, C. Yan, W. Zhou, D. Ren, Development of fly ash and iron ore tailing

based porous geopolymer for removal of Cu(II) from wastewater, Ceram. Int.

[76] R.M. Novais, G. Ascensão, M.P. Seabra, J.A. Labrincha, Waste glass from end-

of-life fluorescent lamps as raw material in geopolymers, Waste Manage., 52 (2016)

245-255.

[77] Z. Sun, H. Cui, H. An, D. Tao, Y. Xu, J. Zhai, Q. Li, Synthesis and thermal

behavior of geopolymer-type material from waste ceramic, Constr. Build. Mater.,

49 (2013) 281-287.

34
Chapter 1: General Introduction

[78] P.K. Mehta, Role of Pozzolanic and Cementious Material in Sustainable

Development of the Concrete Industry, Special Publication, 178.

[79] S.V. Mattigod, D. Rai, L.E. Eary, C.C. Ainsworth, Geochemical Factors

Controlling the Mobilization of Inorganic Constituents from Fossil Fuel

Combustion Residues: I. Review of the Major Elements, Journal of Environmental

Quality, 19 (1990) 188-201.

[80] W.R. Roy, R.G. Thiery, R.M. Schuller, J. Suloway, Coal fly ash: a review of

the literature and proposed classification system with emphasis on environental

impacts, Illinois State Geological Survey, Urbana (USA), 1981.

[81] S. Onutai, S. Jiemsirilers, P. Thavorniti, T. Kobayashi, Aluminium hydroxide

waste based geopolymer composed of fly ash for sustainable cement materials,

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

Chemistry Research, 40 (2001) 1140-1145.

35
Chapter 2: Aluminium hydroxide waste based geopolymer
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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

a)

b)

Figure 2.4 Comparision of a) flexural strength and b)compressive strength of


geopolymer paste at age of 7 days.

51
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

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
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

2.5 References

[1] 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.

[2] 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.

[3] E. Álvarez-Ayuso, Approaches for the treatment of waste streams of the

aluminium anodising industry, J. Hazard. Mater., 164 (2009) 409-414.

[4] C. Hu, Microstructure and mechanical properties of fly ash blended cement

pastes, Constr. Build. Mater., 73 (2014) 618-625.

[5] S. Detphan, P. Chindaprasirt, Preparation of fly ash and rice husk ash

geopolymer, International Journal of Minerals, Metallurgy and Materials, 16 (2009)

720-726.

[6] X. Guo, H. Shi, W.A. Dick, Compressive strength and microstructural

characteristics of class C fly ash geopolymer, Cem. Concr. Compos., 32 (2010) 142-

147.

[7] M.M.A.B. Abdullah, L. Jamaludin, K. Hussin, M. Bnhussain, C.M.R. Ghazali,

M.I. Ahmad, Fly Ash Porous Material using Geopolymerization Process for High

Temperature Exposure, International Journal of Molecular Sciences, 13 (2012)

4388-4395.

[8] P. Chindaprasirt, C. Jaturapitakkul, W. Chalee, U. Rattanasak, Comparative

study on the characteristics of fly ash and bottom ash geopolymers, Waste Manage.,

29 (2009) 539-543.

65
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

[9] P. Duxson, J.L. Provis, G.C. Lukey, J.S.J. van Deventer, The role of inorganic

polymer technology in the development of 'green concrete', Cem. Concr. Res., 37

(2007) 1590-1597.

[10] L. Zhang, S. Ahmari, J. Zhang, Synthesis and characterization of fly ash

modified mine tailings-based geopolymers, Constr. Build. Mater., 25 (2011) 3773-

3781.

[11] A. Nazari, A. Bagheri, S. Riahi, Properties of geopolymer with seeded fly ash

and rice husk bark ash, Materials Science and Engineering: A, 528 (2011) 7395-

7401.

[12] M.B. Karakoç, İ. Türkmen, M.M. Maraş, F. Kantarci, R. Demirboğa, M. Uğur

Toprak, Mechanical properties and setting time of ferrochrome slag based

geopolymer paste and mortar, Constr. Build. Mater., 72 (2014) 283-292.

[13] P. Rovnaník, Effect of curing temperature on the development of hard structure

of metakaolin-based geopolymer, Constr. Build. Mater., 24 (2010) 1176-1183.

[14] G.S. Ryu, Y.B. Lee, K.T. Koh, Y.S. Chung, The mechanical properties of fly

ash-based geopolymer concrete with alkaline activators, Constr. Build. Mater., 47

(2013) 409-418.

[15] U. Rattanasak, P. Chindaprasirt, Influence of NaOH solution on the synthesis

of fly ash geopolymer, Miner. Eng., 22 (2009) 1073-1078.

[16] H. Xu, J.S.J. Van Deventer, The geopolymerisation of alumino-silicate

minerals, International Journal of Mineral Processing, 59 (2000) 247-266.

[17] H. Xu, J.S.J. Van Deventer, Microstructural characterisation of geopolymers

synthesised from kaolinite/stilbite mixtures using XRD, MAS-NMR, SEM/EDX,

TEM/EDX, and HREM, Cem. Concr. Res., 32 (2002) 1705-1716.

66
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

[18] J.W. Phair, Compositional effects and microstructure of fly ash-based

geopolymers., Department of Chemical Engineering,, University of Melbourne,

Victoria, Australia., 2001.

[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

(2001) 289-304.

[20] K. Ikeda, Recent development of geopolymer technique in relevance to carbon

dioxide and waste management issues, 2008, pp. 293-307.

[21] K. Somna, C. Jaturapitakkul, P. Kajitvichyanukul, P. Chindaprasirt, NaOH-

activated ground fly ash geopolymer cured at ambient temperature, Fuel, 90 (2011)

2118-2124.

[22] S. Songpiriyakij, T. Kubprasit, C. Jaturapitakkul, P. Chindaprasirt,

Compressive strength and degree of reaction of biomass- and fly ash-based

geopolymer, Constr. Build. Mater., 24 (2010) 236-240.

[23] F. Puertas, S. Martıń ez-Ramıŕ ez, S. Alonso, T. Vázquez, Alkali-activated fly

ash/slag cements: Strength behaviour and hydration products, Cem. Concr. Res., 30

(2000) 1625-1632.

[24] P. Chindaprasirt, T. Chareerat, V. Sirivivatnanon, Workability and strength of

coarse high calcium fly ash geopolymer, Cem. Concr. Compos., 29 (2007) 224-229.

[25] J.C. Swanepoel, C.A. Strydom, Utilisation of fly ash in a geopolymeric

material, Applied Geochemistry, 17 (2002) 1143-1148.

[26] D. Panias, I.P. Giannopoulou, T. Perraki, Effect of synthesis parameters on the

mechanical properties of fly ash-based geopolymers, Colloids Surf., A, 301 (2007)

246-254.

67
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

[27] T. Bakharev, Geopolymeric materials prepared using Class F fly ash and

elevated temperature curing, Cem. Concr. Res., 35 (2005) 1224-1232.

[28] K. Komnitsas, D. Zaharaki, Geopolymerisation: A review and prospects for the

minerals industry, Miner. Eng., 20 (2007) 1261-1277.

[29] P. Duxson, A. Fernández-Jiménez, G.C. Lukey, A. Palomo, J.L. Provis, J.S.J.

Van Deventer, Geopolymer technology: the current state of the art, Journal of

Materials Science, 42 (2007) 2917-2933.

[30] W.K.W. Lee, J.S.J. van Deventer, Structural reorganisation of class F fly ash

in alkaline silicate solutions, Colloids Surf., A, 211 (2002) 49-66.

[31] J. Temuujin, A. van Riessen, Effect of fly ash preliminary calcination on the

properties of geopolymer, J. Hazard. Mater., 164 (2009) 634-639.

[32] A. Nazari, J.G. Sanjayan, Synthesis of geopolymer from industrial wastes,

Journal of Cleaner Production, 99 (2015) 297-304.

[33] H. Xu, W. Gong, L. Syltebo, K. Izzo, W. Lutze, I.L. Pegg, Effect of blast

furnace slag grades on fly ash based geopolymer waste forms, Fuel, 133 (2014) 332-

340.

[34] A. Poulesquen, F. Frizon, D. Lambertin, Rheological behavior of alkali-

activated metakaolin during geopolymerization, Journal of Non-Crystalline Solids,

357 (2011) 3565-3571.

[35] S. Hanjitsuwan, S. Hunpratub, P. Thongbai, S. Maensiri, V. Sata, P.

Chindaprasirt, Effects of NaOH concentrations on physical and electrical properties

of high calcium fly ash geopolymer paste, Cem. Concr. Compos., 45 (2014) 9-14.

[36] G. Görhan, G. Kürklü, The influence of the NaOH solution on the properties of

the fly ash-based geopolymer mortar cured at different temperatures, Composites

Part B: Engineering, 58 (2014) 371-377.

68
Chapter 2: Aluminium hydroxide waste based geopolymer
composed of fly ash for sustainable cement materials

[37] F.J. López, S. Sugita, T. Kobayashi, Cesium-adsorbent Geopolymer Foams

Based on Silica from Rice Husk and Metakaolin, Chemistry Letters, 43 (2014) 128-

130.

[38] O.A. Abdulkareem, A.M. Mustafa Al Bakri, H. Kamarudin, I. Khairul Nizar,

A.e.A. Saif, Effects of elevated temperatures on the thermal behavior and

mechanical performance of fly ash geopolymer paste, mortar and lightweight

concrete, Constr. Build. Mater., 50 (2014) 377-387.

[39] R.A. Fletcher, K.J.D. MacKenzie, C.L. Nicholson, S. Shimada, The

composition range of aluminosilicate geopolymers, Journal of the European

Ceramic Society, 25 (2005) 1471-1477.

[40] S. Pangdaeng, T. Phoo-ngernkham, V. Sata, P. Chindaprasirt, Influence of

curing conditions on properties of high calcium fly ash geopolymer containing

Portland cement as additive, Materials & Design, 53 (2014) 269-274.

[41] S. Kumar, R. Kumar, Mechanical activation of fly ash: Effect on reaction,

structure and properties of resulting geopolymer, Ceram. Int., 37 (2011) 533-541.

69
Chapter 3: Fast microwave syntheses of fly ash based porous
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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

(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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

Figure 3.1 Temperature profile of geopolymers in different power


of microwave 1 min

75
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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 Results and discussion

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

Figure 3.2 (continued).

79
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

(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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

Figure 3.4 (continued).

84
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

1.6

1.5
Apparent bulk density (g/cm3)

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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


radiation at power 200-850 W for 1 min and by curing at 80 oC 24 h

90
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

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
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

3.5 References

[1] S. Kumar, R. Kumar, Mechanical activation of fly ash: Effect on reaction,

structure and properties of resulting geopolymer, Ceram. Int., 37 (2011) 533-541.

[2] A. Nazari, J.G. Sanjayan, Synthesis of geopolymer from industrial wastes,

Journal of Cleaner Production, 99 (2015) 297-304.

[3] J. Davidovits, GEOPOLYMER Chemistry&Applications, Institut Géopolymère

16 rue Galilée F-02100 Saint-Quentin France, France, 2008.

[4] J. Davidovits, Geopolymers - Inorganic polymeric new materials, Journal of

Thermal Analysis, 37 (1991) 1633-1656.

[5] D. Tavor, A. Wolfson, A. Shamaev, A. Shvarzman, Recycling of Industrial

Wastewater by Its Immobilization in Geopolymer Cement, Industrial & Engineering

Chemistry Research, 46 (2007) 6801-6805.

[6] 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.

[7] B. Nematollahi, J. Sanjayan, F.U.A. Shaikh, Synthesis of heat and ambient cured

one-part geopolymer mixes with different grades of sodium silicate, Ceram. Int., 41

(2015) 5696-5704.

[8] S. Onutai, S. Jiemsirilers, P. Thavorniti, T. Kobayashi, Aluminium hydroxide

waste based geopolymer composed of fly ash for sustainable cement materials,

Constr. Build. Mater., 101, Part 1 (2015) 298-308.

[9] P. Duxson, A. Fernández-Jiménez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J.

van Deventer, Geopolymer technology: the current state of the art, Journal of

Materials Science, 42 (2007) 2917-2933.

97
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

[10] S. Andini, R. Cioffi, F. Colangelo, T. Grieco, F. Montagnaro, L. Santoro, Coal

fly ash as raw material for the manufacture of geopolymer-based products, Waste

Manage., 28 (2008) 416-423.

[11] H. Wang, H. Li, Y. Wang, F. Yan, Preparation of macroporous ceramic from

metakaolinite-based geopolymer by calcination, Ceram. Int., 41 (2015) 11177-

11183.

[12] M. Strozi Cilla, M. Raymundo Morelli, P. Colombo, Effect of process

parameters on the physical properties of porous geopolymers obtained by gelcasting,

Ceram. Int., 40 (2014) 13585-13590.

[13] A.R. Studart, U.T. Gonzenbach, E. Tervoort, L.J. Gauckler, Processing routes

to macroporous ceramics: A review, Journal of the American Ceramic Society, 89

(2006) 1771-1789.

[14] F.J. López, S. Sugita, T. Kobayashi, Cesium-adsorbent Geopolymer Foams

Based on Silica from Rice Husk and Metakaolin, Chemistry Letters, 43 (2014) 128-

130.

[15] M.M.A.B. Abdullah, L. Jamaludin, K. Hussin, M. Bnhussain, C.M.R. Ghazali,

M.I. Ahmad, Fly Ash Porous Material using Geopolymerization Process for High

Temperature Exposure, International Journal of Molecular Sciences, 13 (2012)

4388.

[16] V. Vaou, D. Panias, Thermal insulating foamy geopolymers from perlite,

Miner. Eng., 23 (2010) 1146-1151.

[17] W.D.A. Rickard, L. Vickers, A. van Riessen, Performance of fibre reinforced,

low density metakaolin geopolymers under simulated fire conditions, Appl. Clay

Sci., 73 (2013) 71-77.

98
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

[18] G. Masi, W.D.A. Rickard, L. Vickers, M.C. Bignozzi, A. van Riessen, A

comparison between different foaming methods for the synthesis of light weight

geopolymers, Ceram. Int., 40 (2014) 13891-13902.

[19] J. Somaratna, D. Ravikumar, N. Neithalath, Response of alkali activated fly ash

mortars to microwave curing, Cem. Concr. Res., 40 (2010) 1688-1696.

[20] T.A. Gubb, I. Baranova, S.M. Allan, M.L. Fall, H.S. Shulman, W.M. Kriven,

Microwave Enhanced Drying and Firing of Geopolymers, Developments in

Strategic Materials and Computational Design II, John Wiley & Sons, Inc.2011, pp.

35-43.

[21] P. Chindaprasirt, U. Rattanasak, S. Taebuanhuad, Resistance to acid and sulfate

solutions of microwave-assisted high calcium fly ash geopolymer, Mater Struct, 46

(2013) 375-381.

[22] P. Chindaprasirt, U. Rattanasak, S. Taebuanhuad, Role of microwave radiation

in curing the fly ash geopolymer, Advanced Powder Technology, 24 (2013) 703-

707.

[23] 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.

[24] C.K.Y. Leung, T. Pheeraphan, Determination of optimal process for microwave

curing of concrete, Cem. Concr. Res., 27 (1997) 463-472.

[25] X. Xu, Y. Bao, C. Song, W. Yang, J. Liu, L. Lin, Microwave-assisted

hydrothermal synthesis of hydroxy-sodalite zeolite membrane, Microporous and

Mesoporous Materials, 75 (2004) 173-181.

99
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

[26] X. Xu, W. Yang, J. Liu, L. Lin, Synthesis of NaA zeolite membrane by

microwave heating, Separation and Purification Technology, 25 (2001) 241-249.

[27] H. Tanaka, A. Fujii, S. Fujimoto, Y. Tanaka, Microwave-Assisted Two-Step

Process for the Synthesis of a Single-Phase Na-A Zeolite from Coal Fly Ash,

Advanced Powder Technology, 19 (2008) 83-94.

[28] E. Ul Haq, S. Kunjalukkal Padmanabhan, A. Licciulli, Microwave synthesis of

thermal insulating foams from coal derived bottom ash, Fuel Processing

Technology, 130 (2015) 263-267.

[29] M. Vollmer, Physics of the microwave oven, Physics Education, 39 (2004) 74.

[30] J. Anwar, U. Shafique, Z. Waheed uz, R. Rehman, M. Salman, A. Dar, J.M.

Anzano, U. Ashraf, S. Ashraf, Microwave chemistry: Effect of ions on dielectric

heating in microwave ovens, Arabian Journal of Chemistry, 8 (2015) 100-104.

[31] S. Jumrat, B. Chatveera, P. Rattanadecho, Dielectric properties and temperature

profile of fly ash-based geopolymer mortar, International Communications in Heat

and Mass Transfer, 38 (2011) 242-248.

[32] S. Hanjitsuwan, S. Hunpratub, P. Thongbai, S. Maensiri, V. Sata, P.

Chindaprasirt, Effects of NaOH concentrations on physical and electrical properties

of high calcium fly ash geopolymer paste, Cem. Concr. Compos., 45 (2014) 9-14.

[33] G. Leofanti, M. Padovan, G. Tozzola, B. Venturelli, Surface area and pore

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.

Int., 40 (2014) 8479-8488.

100
Chapter 3: Fast microwave syntheses of fly ash based porous
geopolymers in the presence of high alkali concentration

[35] S. Pangdaeng, T. Phoo-ngernkham, V. Sata, P. Chindaprasirt, Influence of

curing conditions on properties of high calcium fly ash geopolymer containing

Portland cement as additive, Materials & Design, 53 (2014) 269-274.

[36] K. Somna, C. Jaturapitakkul, P. Kajitvichyanukul, P. Chindaprasirt, NaOH-

activated ground fly ash geopolymer cured at ambient temperature, Fuel, 90 (2011)

2118-2124.

[37] A. Fernández-Jiménez, A. Palomo, Mid-infrared spectroscopic studies of

alkali-activated fly ash structure, Microporous and Mesoporous Materials, 86 (2005)

207-214.

[38] U. Rattanasak, P. Chindaprasirt, Influence of NaOH solution on the synthesis

of fly ash geopolymer, Miner. Eng., 22 (2009) 1073-1078.

[39] 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.

[40] P. Chindaprasirt, C. Jaturapitakkul, W. Chalee, U. Rattanasak, Comparative

study on the characteristics of fly ash and bottom ash geopolymers, Waste Manage.,

29 (2009) 539-543

101
Chapter 4: Dense geopolymer cements prepared with
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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

Figure 4.1 Protocal of synthesis geopolymer

107
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

4.3 Results and discussion

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

1.70
25oC
1.65 80oC 24 h
200W 1 min
1.60 200W 3 min
Apparent bulk density (g/cm3)

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

1.70
25oC
1.65 80oC 24 h
200W 1 min + 80oC 24 h
1.60 200W 3 min + 80oC 24 h
Apparent bulk density (g/cm3)

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
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)

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

c) 100
25oC NaOH 5 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
d) 25oC NaOH 10 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)

Figure 4.9 (continued).

122
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

Figure 4.10 The XRD pattern of geopolymer sample synthesized using


NaOH concentration at 1 M and 10 M

124
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

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

Chemistry Research, 44 (2005) 832-839.

[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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

[9] P. Duxson, A. Fernández-Jiménez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J.

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.

[11] S. Onutai, S. Jiemsirilers, P. Thavorniti, T. Kobayashi, Aluminium hydroxide

waste based geopolymer composed of fly ash for sustainable cement materials,

Constr. Build. Mater., 101, Part 1 (2015) 298-308.

[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.

[13] P. Rovnaník, Effect of curing temperature on the development of hard structure

of metakaolin-based geopolymer, Constr. Build. Mater., 24 (2010) 1176-1183.

[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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

[18] P. Chindaprasirt, C. Jaturapitakkul, W. Chalee, U. Rattanasak, Comparative

study on the characteristics of fly ash and bottom ash geopolymers, Waste Manage.,

29 (2009) 539-543.

[19] K. Somna, C. Jaturapitakkul, P. Kajitvichyanukul, P. Chindaprasirt, NaOH-

activated ground fly ash geopolymer cured at ambient temperature, Fuel, 90 (2011)

2118-2124.

[20] A. Nazari, A. Bagheri, S. Riahi, Properties of geopolymer with seeded fly ash

and rice husk bark ash, Materials Science and Engineering: A, 528 (2011) 7395-

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
Chapter 4: Dense geopolymer cements prepared with
microwave pre-curing

[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.

[29] S. Pangdaeng, T. Phoo-ngernkham, V. Sata, P. Chindaprasirt, Influence of

curing conditions on properties of high calcium fly ash geopolymer containing

Portland cement as additive, Materials & Design, 53 (2014) 269-274.

[30] S. Kumar, R. Kumar, Mechanical activation of fly ash: Effect on reaction,

structure and properties of resulting geopolymer, Ceram. Int., 37 (2011) 533-541.

[31] U. Rattanasak, P. Chindaprasirt, Influence of NaOH solution on the synthesis

of fly ash geopolymer, Miner. Eng., 22 (2009) 1073-1078.

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