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UNIVERSITI PUTRA MALAYSIA

MOSLIH AMER SALIH

FK 2015 164

NEW GEO-POLYMERIZATION PROCESS FOR HIGH STRENGTH ALKALI-ACTIVATED BINDER WITH PALM OIL FUEL ASH AND

GROUND GRANULATED BLAST FURNACE SLAG

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NEW GEO-POLYMERIZATION PROCESS FOR HIGH STRENGTH

ALKALI-ACTIVATED BINDER WITH PALM OIL FUEL ASH AND


By

MOSLIH AMER SALIH

Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia,

in Fulfilment of the Requirements for the Degree of Doctor of Philosophy

March 2015

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COPYRIGHT

All materials contained within this thesis, including without limitation text, logos,

icons, photographs and all other art work, is copyright material of Universiti Putra

Malaysia unless otherwise stated. Use may be made of any material contained within

the thesis for non-commercial purposes from copyright holder. Commercial use of

material may only be made with the express, prior, written permission of Universiti

Putra Malaysia.

Copyright ©Universiti Putra Malaysia

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DEDICATIONS

I dedicate this thesis to, my father, my mother, my brothers and my small family, my

wife and children Mina, Ameen and Dima.

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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment

of the requirement for the degree of Doctor of Philosophy

NEW GEO-POLYMERIZATION PROCESS FOR HIGH STRENGTH

ALKALI-ACTIVATED BINDER WITH PALM OIL FUEL ASH AND


By

MOSLIH AMER SALIH

March 2015

Chairman: Professor Dato’ Ir Abang Abdullah Abang Ali,PhD

Faculty: Engineering

This study investigated a new geopolymerization process for the production of high

strength alkali activated binder, using high volume palm oil fuel ash (POFA) mixed

with ground granulated blast furnace slag (GGBS). The experimental work was

designed for the geopolymer paste and mortar. In the paste, the optimum alkali

activation parameters of POFA were identified. These parameters included Sodium

Hydroxide concentration, Solid/Liquid ratio (S/L), and Sodium Silicate to Sodium

Hydroxide ratio (SS/SH). The role of curing regime and its effect on the alkali

activation of POFA was investigated at ambient and different temperatures. GGBS

was introduced as a partial replacement of POFA in five percentages (10-50%) to study

the role of Calcium ions and mechanisms to improve the load bearing capacity of the

resulting gel to a high strength geopolymer binder.

The production of high strength geopolymerized mortar cured at ambient temperature

was initially targeted by applying the activation parameters with the same replacement

levels of GGBS as in the paste. The durability of the proposed alkali activated binder

was investigated by exposing the mortar to extreme environments, namely elevated

temperatures and sulfate attack. The compressive strength test, microstructural and

chemical tests such as Scanning Electron Microscopy/Energy-Dispersive X-Ray

Spectroscopy (SEM/EDX), X-Ray Diffraction (XRD), Thermogravimetric

Analysis/Derivative Thermogravimetry (TGA/DTG), Differential Scanning

Calorimetry (DSC) and Fourier Transform Infra-Red (FTIR), were conducted to study

the underlying mechanisms of strength development.

The results showed that liquid Sodium Hydroxide at 12 Molarity, S/L ratio at 1.32,

and SS/SH ratio at 2.5 were applicable to alkali activate 100% POFA and produce

geopolymer paste with 32.84 MPa at the age of 28 days. One major finding was

identifying the Calcium Silicate Hydrate gel (C-S-H) as the main binding phase; with

no Calcium Hydroxide Ca(OH)2 detected in the system. The test results showed that

100% POFA geopolymer paste can set and harden at ambient temperature with a

comparable compressive strength to samples cured in the oven. Calcium ions dissolved

from GGBS participated in increasing the binder strength by the formation of more C-

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S-H gel. Aluminum ions provided by GGBS led to a higher degree of polymerization

and significant degree of crosslinking between C-S-H chains and shifting it to

C-(A)-S-H gel. The compressive strength for binary geopolymer paste was 78.12 MPa

at the age of 28 days.

The alkali activated binder from the alkali activation of POFA as the only

aluminosilicate material was able to produce geopolymer mortar with normal strength

of 33.91 MPa at the age of 28 days. Inclusion of GGBS with POFA was effective to

produce high strength geopolymer mortar with compressive strength of 70.25 MPa at

the age of 28 days. Results from residual compressive test at elevated temperatures

showed that samples maintained their dimensional stability at elevated temperatures

due to the presence of evacuation routes (pore system) in the mortar which allowed

water to be evaporated. Moreover, glass transition was detected between 600 ºC and

800 ºC which provided a relative increase in the strength of the geopolymer mortar.

Test results showed that the proposed geopolymer mortar performed better than

Portland cement mortar when exposed to sulfate attack. The results indicated that

although Sodium sulfate and Magnesium sulfate had deterioration effect due to

decomposing of Si and Ca ions from both C-S-H and C-A-S-H gels, the proposed

geopolymer mortar experienced less strength depletion which can be related to the

absence of calcium hydroxide in the matrix.

Keywords: POFA, Geopolymer binder, Geopolymer cement, GGBS, Alkali

activation, Geopolymer mortar.

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai

memenuhi keperluan untuk ijazah Doctor Falsafah

PROSES GEO-POLIMERISASI BARU UNTUK PENGIKAT ALKALI

TERAKTIF BERKEKUATAN TINGGI DENGAN ABU SISA BAHAN API

KELAPA SAWIT DAN SANGA RELAU BAGAS BERBUTIR

Oleh

MOSLIH AMER SALIH

Mac 2015

Pengerusi: Professor Dato’ Abang Abdullah Abang Ali, PhD

Fakulti: Kejuruteraan

Kajian ini telah menyiasat proses geo-polimerisasi untuk penghasilan pengikat alkali

teraktif berkekuatan tinggi menggunakan abu sisa bahan api kelapa sawit (POFA)

berisipadu tinggi diadunkan dengan sanga relau bagas berbutir (GGBS). Ujian-ujian

telah dirancang untuk adunan dan mortar geopolimer. Dalam adunan, parameter-

parameter alkali teraktif optimum telah dikenalpasti. Parameter-parameter ini

termasuk kepekatan Sodium Hidroksida (kemolaran), nisbah pepejal kepada cecair

(S/L) dan nisbah Sodium Silika kepada Sodium Hidroksida (SS/SH). Peranan rejim

pengawetan dan kesannya terhadap alkali teraktif POFA telah dikaji dengan

menggunakan suhu ambien and suhu yang berlainan. GGBS telah diperkenalkan

sebagai gantian separa POFA sebanyak lima peratus (10-50%) untuk mengkaji

peranan ion-ion kalsium dan mekanisma-mekanisma untuk memperbaiki kapasiti

beban tahan galas gel yang terbentuk kepada pengikat geopolimer berkekuatan tinggi.

Penghasilan mortar geopolimer berkekuatan tinggi pada yang terawet pada suhu

ambien mulanya disasarkan dengan menggunakan parameter-parameter pengaktifan

dengan aras-aras gantian GGBS yang sama seperti dalam adunan. Ketahanlasakan

pengikat alkali teraktif yang dicadangkan telah dikaji selepas pendedahan mortar

tersebut kepada sekitaran melampau seperti suhu ternaik dan serangan sulfat. Ujian

kekuatan mampatan, ujian-ujian kimia dan mikrostruktur seperti XRD, SEM/EDX,

TGA/DTG, DSC dan FTIR telah dijalankan untuk mengkaji mekanisma-mekanisma

di sebalik perkembangan kekuatan. Hasil keputusan telah menunjukkan bahwa cecair

Sodium Hidroksida pada kemolaran 12, nibah S/L pada 1.32 dan nisbah SS/SH pada

2.5 telah digunakan untuk aktif alkali 100% POFA dan menghasilkan 32.84 MPa

kekuatan mampatan pada hari ke-28. Satu penemuan utama telah mengenalpasti

struktur gel yang dominan – gel Kalsium Silika Terhidrat gel (C-S-H) – sebagai fasa

pengikatan yang terhasil daripada 100% POFA alkali teraktif; lebih-lebih lagi tiada

Kalsium Hidroksida Ca(OH)2 telah dikesan di dalam sistem.

Keputusan ujian menunjukkan 100% POFA adunan geopolimer boleh set dan

menhgeras pada suhu ambien dengan perbandingan kekuatan mampatan dengan

sampel-sampel yang diawet di dalam ketuhar. Ion-ion kalsium terlarut daripada GGBS

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yang terlibat dalam peningkatan kekuatan pengikat dengan pembentukan lebih banyak

gel C-S-H. Ion-ion Aluminium yang juga terhasil daripada GGBS membawa kepada

tahap yang lebih tinggi polimerisasi dan tahap sambung-silang yang ketara di antara

rantaian C-S-H beralih kepada gel C-(A)-S-H. Kekuatan mampatan pada adunan

geopolimer binari adalah 78.12 MPa pada umur ke-28 hari.

Pengikat geopolimer yang terhasil daripada 100% POFA alkali teraktif sebagai bahan

aluminosilikat sahaja dapat menghasilkan mortar geopolimer dengan kekuatan normal

33.91 MPa pada umur ke-28 hari. Kemasukan GGBS ke dalam POFA telah

menunjukkan keberkesanan dalam penghasilan mortar geopolimer berkekuatan tinggi

dengan kekuatan mampatan sebanyak 70.25 MPa telah tercapai pada umur ke-28 hari.

Keputusan-keputusan daripada baki ujian mampatan pada suhu ternaik menunujukkan

sampel-sampel mengekalkan kestabilan dimensi pada suhu-suhu ternaik disebabkan

kehadiran laluan pemindahan yang sedia ada (sistem liang) dalam mortar di mana ia

membenarkan air disejat. Tambahan pula, transisi kaca telah dikesan di antara 600 ºC

dan 800 ºC yang menyediakan peningkatan relatif dalam kekuatan. Ujian-ujian

menunjukkan bahawa mortar geopolimer yang dicadangkan lebih baik daripada mortar

simen Portland apabila didedahkan kepada serangan sulfat. Keputusan menunjukkan

walaupun Sodium Sulfat dan Magnesium Sulfat telah merosot kesan akibat penguraian

ion-ion Si dan Ca daripada kedua-dua gel C-S-H dan C-A-S-H, geopolimer mortar

dicadangkan mengalami susutan kekuatan di mana boleh dikaitkan dengan kehadiran

Kalsium Hidroksida di dalam matriks.

Kata Kunci: POFA, pengikat Geopolimer, Simen Geopolimer, GGBS, Alkali teraktif,

mortar geopolymer

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ACKNOWLEDGEMENTS

First and foremost, I would like to thank ALLAH my God, without him I would never

have the faith, power, determination to live, work, and finish all the work involved in

my thesis.

All thanks to my supervisor, Prof. Dato Ir. Abang Abdullah Abang Ali, for his

guidance, help and support during my study. Special thanks to Prof. Ramazan

Demirboga for his support and directions. I warmly thank Dr. Nima Farzadina for his

generous guidance, invaluable advices for my research. I would like also to thank Dr.

Mohd Mustafa Al Bakri Abdullah for his kindness to have the training at University

Malaysia Perlis (UniMAP) and also special thanks to his staff for their support.

Thanks to Dr. Noor Azline for her support. Special thanks and appreciation to the

Housing Research Center (HRC) staff at Universiti Putra Malaysia (UPM), especially

Mrs. Erna and Miss Liayna, who were very kind and supportive during my study.

I would like to express my deepest appreciation to my beloved wife, and my children

for their sacrifices and the patience all the time I was away from them for the sake of

my study. Great thanks to my father, Mr. Amer Salih Hadi Al Khafagy for his great

encouragement and support all the way in my PhD journey.

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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been

accepted as fulfilment of the requirement for the degree of Doctor of Philosophy.

The members of the Supervisory Committee were as follows:

Abang Abdullah Abang Ali, PhD

Professor, Ir

Faculty of Engineering

Universiti Putra Malaysia

(Chairperson)

Ramazan Demirboga, PhD

Associate Professor



(Member)

Noor Azline Mohd. Nasir, PhD

Lecturer



(Member)

BUJANG BIN KIM HUAT, PhD

Professor and Dean

School of Graduate Studies


Date:

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Declaration by graduate student

I hereby confirm that:

this thesis is my original work

quotations, illustrations and citations have been duly referenced

the thesis has not been submitted previously or comcurrently for any other degree

at any institutions

intellectual property from the thesis and copyright of thesis are fully-owned by

Universiti Putra Malaysia, as according to the Universiti Putra Malaysia

(Research) Rules 2012;

written permission must be owned from supervisor and deputy vice –chancellor

(Research and innovation) before thesis is published (in the form of written,

printed or in electronic form) including books, journals, modules, proceedings,

popular writings, seminar papers, manuscripts, posters, reports, lecture notes,

learning modules or any other materials as stated in the Universiti Putra Malaysia

(Research) Rules 2012;

there is no plagiarism or data falsification/fabrication in the thesis, and scholarly

integrity is upheld as according to the Universiti Putra Malaysia (Graduate

Studies) Rules 2003 (Revision 2012-2013) and the Universiti Putra Malaysia

(Research) Rules 2012. The thesis has undergone plagiarism detection software

Signature: Date:

Name and Matric NO.: Moslih Amer Salih (GS28688)

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Declaration by Members of Supervisory Committee

This is to confirm that:

the research conducted and the writing of this thesis was under our supervision;

supervision responsibilities as stated in the Universiti Putra Malaysia (Graduate

Studies) Rules 2003 (Revision 2012-2013) were adhered to.

Signature: Signature:

Name of Name of

Chairman of Member of

Supervisory Supervisory

Committee: Committee:

Signature:

Name of

Member of

Supervisory

Committee:

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TABLE OF CONTENTS

Page

ABSTRACT i

ABSTRAK iii

ACKNOWLEDGEMENTS v

APPROVAL vi

DECLARATION viii

LIST OF TABLES xv

LIST OF FIGURES xvii

LIST OF ABBREVIATIONS AND ACRONYMS xxvii

CHAPTER

1 INTRODUCTION

1.1 Background 1

1.2 Research Problem 2

1.3 Hypothesis of the Research 4

1.4 Research Objectives 4

1.5 Research Questions 4

1.6 Research Contribution 5

1.7 Significance of the Study 5

1.8 Scope and Limitations of the study 6

1.9 Thesis Layout 6

2 LITERATURE REVIEW

2.1 Introduction 8

2.2 Definition of the Alkali-Activated Materials and

Geopolymers

8

2.3 History of Alkali-Activated Materials 10

2.4 Binding Phase Structure in Alkali-Activated Materials 10

2.4.1 Binding Phase Structure in Alkali Activated

Aluminosilicate Materials Categorized with Low

Calcium Content

10

2.4.2 Binding Phase Structure in Alkali Activated

Aluminosilicate Materials Categorized with Higher

Calcium Content

13

2.5 The Most used Alkaline Activators in the Alkali Activation

Process

14

2.5.1 The Sodium Hydroxide (NaOH): Definition,

Manufacturing and the use in the Industry

15

2.5.2 The Sodium Silicate (Na2Si2O5): Definition,

Manufacturing and the use in the Industry

15

2.6 The Impact of a Combination of Two Activators on the

alkali activation process

16

2.7 The Most Used Activation Method-The Activation

Parameters

17

2.7.1 Sodium Ion Concentration and Sodium Oxide Content

In the Alkaline Activator as a Percentage of the

Aluminosilicate Material

17

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2.7.2 The Aluminosilicate Material to the Alkaline

Activator Ratio (Solid to Liquid) Coupled with

Sodium Silicate to Sodium Hydroxide Ratio (SS/SH)

17

2.8 Curing Conditions Associated with the Alkali Activation of

the Aluminosilicate Materials

19

2.9 The Most used Aluminosilicate Materials (Waste

Materials) to produce Geopolymer Binders

19

2.10 Palm Oil Fuel Ash (POFA) 22

2.10.1 POFA Classification as a Supplementary

Cementing Material

20

2.10.2 POFA as an Aluminosilicate Source in The Alkali

Activation Process

24

2.11 Alkali Activated Binders and the Strength Rate 25

2.12 Mechanisms of Participation of the Calcium Ions in The

Alkali Activation Process

27

2.13 Behavior of Alkali-Activated Materials Exposed to

Elevated Temperatures

27

2.14 Durability and Deterioration Mechanisms of Alkali-

Activated Materials Exposed to Sulfate Attack

28

2.15 Testing Techniques for Characterization of Alkali

Activated Materials

28

2.15.1 Compressive Strength 29

2.15.2 X-Ray Diffraction (XRD) 30

2.15.3 Scanning Electron Microscopy/Energy-Dispersive

X-Ray Spectroscopy Analysis (SEM/EDX)

33

2.15.4 Thermogravimetric Analysis/Derivative

Thermogravimetric Analysis (TGA/DTG)

35

2.15.5 Fourier Transform Infra-Red Spectroscopy

Analysis (FTIR)

37

2.16 Summary and the Research Gap 41

3 METHODOLOGY

3.1 Introduction 43

3.2 Preliminary Laboratory Work to Practice the Alkali

Activation Technology

45

3.3 Materials 45

3.3.1 Palm Oil Fuel Ash (POFA): Preparation and

Characterization

45

3.3.2 Portland Cement Used in Preparation of the

Reference Mortar

51

3.3.3 Sand 51

3.3.4 Tap Water 52

3.3.5 Ground Granulated Blast Furnace Slag (GGBS) 52

3.3.6 Alkaline Activators 54

3.3.6.1 Sodium hydroxide (NaOH) 54

3.3.6.2 Sodium Silicate Solution (Na2Si2O5) 54

3.3.7 Distilled Water 55

3.3.8 Sodium Sulfate (Na2SO4) 55

3.3.9 Magnesium Sulfate (MgSO4.7H2O) 55

3.4 Experimental Procedure 55

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3.4.1 Activation Parameters: S/L ratio and SS/SH ratio 55

3.4.2 S/L ratio and SS/SH ratio Calculations 56

3.4.3 Step by Step Activation Approach 56

3.4.4 Geopolymer Paste Production: Mixing Procedure 57

3.4.5 Activities Applied to Achieve the Study Objectives 57

3.4.5.1 Objective One 57

3.4.5.1.1 Investigating the Sodium

Hydroxide (NaOH) Concentration

57

3.4.5.1.2 Investigating the Solid to Liquid

ratio (S/L) and Sodium Silicate to

Sodium Hydroxide ratio (SS/SH)

58

3.4.5.2 Objective Two 59

3.4.5.2.1 Investigating the Curing Regime 59

3.4.5.3 Objective Three 59

3.4.5.3.1 High Strength Binder by Partial

Replacement of POFA with GGBS

59

3.4.6 The Mortar 60

3.4.6.1 Portland Cement Mortar Production

(Reference Mortar)

60

3.4.6.2 Objective Four 61

3.4.6.2.1 Production of the Geopolymer

Mortar

61

3.4.6.2.2 Exposure to Elevated Temperatures 61

3.4.6.2.3 Exposure to Sulfate Attack 63

3.4.6.2.3.1 Sodium Sulfate Attack 63

3.4.6.2.3.2 Magnesium Sulfate

Attack

64

3.5 Tests Applied in the Study 64

3.5.1 X-Ray Fluorescence (XRF) Spectroscopy 64

3.5.2 Setting Time 65

3.5.3 Flow Table Test 65

3.5.4 Bulk Density 66

3.5.5 Compressive Strength Test 66

3.5.6 Scanning Electron Microscopy/Energy-Dispersive

X-Ray Spectroscopy Analysis (SEM/EDX)

67

3.5.7 X-Ray Diffraction (XRD) 69

3.5.8 Thermo Gravimetric Analysis/Derivative

Thermogravimetriy (TGA/DTG)

70

3.5.9 Differential Scanning Calorimetry (DSC) 71

3.5.10 Fourier Transform Infra-Red Spectroscopy

(FTIR)

72

4 RESULTS AND DISCUSSIONS

4.1 Introduction 73

4.2 Preliminary Laboratory Work 73

4.3 Activation Parameters 73

4.3.1 Investigating NaOH Concentration (Molarity) 73

4.3.2 Qualitative Observations 74

4.3.2.1 Soundness in water 74

4.3.2.2 Color 75

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4.3.3 Effect of Different S/L Ratios and Different SS/SH

ratios

75

4.3.3.1 Efflorescence 75

4.3.3.2 Flowability 79

4.3.3.3 Bulk Density 80


4.3.5 Microstructural and Chemical Analysis 83

4.3.5.1 X-Ray Diffraction (XRD) 83

4.3.5.2 Scanning Electron Microscope (SEM) 86

4.3.5.3 Energy-dispersive X-Ray spectroscopy

analysis (EDX)

87

4.3.5.4 Fourier Transform Infra-Red (FTIR) 89

4.3.5.5 Differential Scanning Calorimetry (DSC) 91

4.4 Investigating Different Curing Temperatures 92


4.4.2 Hardening Time 94



4.4.3.2 Energy-dispersive X-Ray Spectroscopy

Analysis (EDX)

100



4.4.3.5 Thermo Gravimetric Analysis/Derivative


104

4.5 High Strength Alkali Activated Binder - Effect of GGBS 104

4.5.1 Setting Time 104





4.5.3.3 Energy-Dispersive X-Ray spectroscopy

analysis (EDX)/Scanning Electron

Microscope (SEM)

111

4.5.3.4 Thermogravimetric Analysis/Derivative


116


4.6 Geopolymer Mortar from POFA Blended with GGBS 119

4.6.1 Flowability 119

4.6.2 Bulk Density for Geopolymer Mortar 119





4.6.4.3 Energy-dispersive X-Ray spectroscopy

analysis (EDX)

131


4.6.4.5 Thermogravimetric Analysis/Derivative


134


4.7 POFA Geopolymer Mortar Exposed to Elevated 139

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Temperatures






4.7.2.4 Thermogravimetric Analysis/ Derivative

Thermogravimetric Analysis(TGA/DTG)

148


4.8 Durability of Geopolymer Mortar Exposed to Sodium

Sulfate and Magnesium Sulfate Attack

154



4.8.2.1 Scanning Electron Microscope/Energy-

Dispersive X-Ray Spectroscopy Analysis

(SEM/EDX)

159


4.8.2.3 Thermogravimetric Analysis/ Derivative

Thermogravimetric Analysis(TGA/DTG)

173


4.9 The relation of the results with the hypothesis used in

this study

180

5 CONCLUSIONS AND RECOMMENDATIONS

5.1 The Effect of the Activation Parameters on the

Compressive Strength, Microstructure and Chemical

Properties

182

5.2 The Effect of Curing Temperatures on the Compressive

Strength, Microstructure and Chemical Properties of

POFA Geopolymer Binder

183

5.3 The Effect of the Binary Mix of POFA-GGBS and its

Underlying Mechanisms in Order to Produce High

Strength Geopolymer Binder at Ambient Temperature

184

5.4 High Strength POFA-GGBS Mortar and its Compressive

Strength and Durability

185

5.5 Recommendations for Future Research 186

BIBLIOGRAPHY 187

BIODATA OF STUDENT 206

LIST OF PUBLICATIONS 207

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LIST OF TABLES

Table Page

2.1 Sialate and Poly (sialate) terminology (Davidovits, 2011)

9

2.2 The chemical composition for different aluminosilicate

materials used in alkali activation

21

2.3 FTIR characteristic bands (Panias et al. 2007; Ahmari et al.

2012; Davidovits, 2011; Nath and Kumar, 2013)

40

3.1 Chemical composition of POFA by XRF test

46

3.2 Chemical composition and physical properties of cement

used. Data provided by the company

51

3.3 River sand sieve analysis and grading according to ASTM

C 33-2004

51

3.4 Chemical composition of ground granulated blast furnace

slag

53

3.5 NaOH weight related to each concentration

54

3.6 Sodium silicate chemical composition

54

3.7 Sodium silicate physical properties

55

3.8 Mixes proportions for selecting the sodium hydroxide

concentration.

58

3.9 Mixes proportions for selecting the right solid to liquid

ratio and right sodium silicate to sodium hydroxide ratio

58

3.10 Mixes for selecting the curing temperature

59

3.11 Mix design for POFA geopolymer paste and POFA

blended with GGBS as partial replacement by weight

59

3.12 Mix proportion for Portland cement mortar according to

ASTM C 109/C 109M-2012

61

3.13 Mix design for POFA geopolymer mortar and POFA

blended with GGBS as partial replacement by weight

61

4.1 Bulk density for POFA geopolymer paste (group one and

two) at different sodium silicate to sodium hydroxide ratios

80

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4.2 Compressive strength for POFA geopolymer paste

106

4.3 Bulk density (kg/m3) for POFA geopolymer mortar and

POFA blended with GGBS

120

4.4 Compressive strength results for POFA geopolymer mortar

and Portland cement mortar

121

4.5 Relative residual compressive strength for mortar after one

hour of exposure to elevated temperatures

140

4.6 Residual compressive strength and reduction percentage

after six months exposure to sulfate attack

158

4.7 EDX Spectrum spots analysis for 100% POFA geopolymer

mortar after six months of exposure to 8.0% sodium sulfate

161

4.8 EDX Spectrum spots analysis for 100% POFA geopolymer

mortar after six months of exposure to 8.0% magnesium

sulfate

162

4.9 EDX Spectrum spots analysis for (70% POFA+30%

GGBS) geopolymer mortar after six months of exposure

to 8.0% sodium sulfate

165

4.10 EDX Spectrum spots analysis for (70% POFA + 30%

GGBS) geopolymer mortar after six months of exposure to

8.0% magnesium sulfate

165



8.0% sodium sulfate

168



8.0% magnesium sulfate

169

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LIST OF FIGURES

Figure Page

2.1 Tetrahedral configuration of ionic concept (Davidovits,

2011)

9

2.2 Conceptual model for geopolymerization process (Duxson

et al., 2007a)

12

2.3 Conceptual model for alkali activation of low Ca

aluminosilicate sources (Provis, 2014a)

13

2.4 Dissolution mechanism of an aluminosilicate glass during

early stages of reaction (Duxson and Provis, 2008)

14

2.5 XRD pattern of Fly ash and ground waste concrete powders

and geopolymer specimens prepared with 0% and 50%

GWC at 10 M NaOH and SS/N=2.0 and cured at ambient

temperature for 7 days (A: anorhite, M: mullite, P:

portlandite, Q: quarts, T: 1.1-nm tobermorite) (Ahmari et

al., 2012)

32

2.6 XRD pattern of fly ash blended with slag, GFACS10=fly

ash blended with 10% slag, GFABF25=fly ash blended

with 25% slag, GFABF40=fly ash with 40% slag,

GFABF50=fly ash blended with 50% slag, M=Mulite,

X=Quartz, *=C-S-H (Nath and Kumar, 2013)

32

2.7 SEM image of paste having (a) 10% GGBS and (b) 50%

GGBS, where A=un-reacted or partially reacted slag

particles, B=un-reacted or partially reacted fly ash

particles, C=aluminosilicate geopolymer gel containing

calcium as indicated in EDX spectrum and D=pure

aluminosilicate geopolymer gel (Nath and Sarker, (2014)

34

2.8 SEM Micrograph showing the microstructure of

geopolymer cured at (a) 23 ºC, (b) 30 ºC, (c) 60 C, and (d)

70 ºC (Nasvi et al., 2014)

35

2.9 DTG curve generated from TGA/DTG test for metakaolin

and fly ash-based geopolymer paste. MK=Metakaolin,

FA=Fly Ash (Kong et al., 2007)

36

2.10 TGA curve showing the thermal behavior of

geopolymerised paste prepared from metakaolin (Elimbi et

al., 2014)

36

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2.11 FTIR Spectra for fly ash, ground waste concrete and

geopolymer specimens prepared with 100% fly ash and

50% ground waste concrete at 10 M NaOH and SS/SH=2.0

and cured at ambient temperature at the age of 7 days

(Ahmari et al., 2012)

38

2.12 FTIR Spectra analysis of ground fly ash (GFA) and

geopolymer paste (Somna et al., 2011)

39

3.1 Research Methodology Flowchart

44

3.2 Palm Oil Shells, husk and fibers before burning

46

3.3 Raw POFA as a wet ash coming out of the incinerator at

Palm Oil Mill

47

3.4 XRD pattern for POFA

47

3.5 SEM micrograph showing irregular particles of raw POFA

48

3.6 SEM micrograph showing porous cellular particles of raw

POFA

48

3.7 SEM micrograph for ground POFA

49

3.8 SEM micrograph for ground POFA with particle size

49

3.9 POFA stored after sieving and grinding-ready to be used

for experimental work

50

3.10 Particle size distribution for POFA after grinding

50

3.11 Clean graded river sand used in mortar production

52

3.12 XRD pattern for ground granulated blast furnace slag

(GGBS)

53

3.13 SEM micrograph for GGBS showing crushed shape

particles

53

3.14 GGBS particle size distribution

54

3.15 Hobart mixer

60

3.16 Example of heating rate and the thermal steady state

demonstrated by the furnace

62

3.17 Placing specimens before exposure to elevated

temperatures

62

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3.18 Nabertherm high temperature laboratory furnace

63

3.19 Geopolymer mortar and Portland cement mortar immersed

in sulfates

64

3.20 Vicat Needle Apparatus for setting time

65

3.21 Flow Table

66

3.22 Compression machine, Unit Test Scientific

67

3.23 Hitachi S-3400N for SEM images and EDX spots elements

analysis

68

3.24 Gold coating of samples using Emitech K550X Sputter

Coater

68

3.25 SEM/EDX sample holder

68

3.26 Shimadzu XRD 6000

69

3.27 Thermogravimetric analyzer (TGA/DTG) (Mettler Toledo,

TGA/SDTA 851, Switzerland)

70

3.28 Differential Scanning Calorimetry instrument (Mettler

Toledo, DSC 832e/500)

71

3.29 Perkin Elmer Spectrum 100, FT-IR Spectometer

72

4.1 Compressive strength results for POFA geopolymer paste

with different concentration of NaOH

74

4.2 POFA geopolymer paste specimens-Black Color

75

4.3 Visual percentage of efflorescence in group one (S/L=1.0)

with SS/SH ratio of a) 1.0, b) 1.5, c) 2.0, d) 2.5, e) 3.0 at

28 days

77

4.4 Visual percentage of efflorescence in group two (S/L=1.32)

with SS/SH ratio of a) 1.0, b) 1.5, c) 2.0, d) 2.5, e) 3.0 at 28

days

78

4.5 Flow of POFA geopolymer paste (S/L=1.0) with different

SS/SH ratios

79

4.6 Flow of POFA geopolymer paste (S/L=1.32) with different

SS/SH ratios

79


group one, S/L ratio 1.0

81

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group two, S/L ratio 1.32

81

4.9 XRD patterns for POFA geopolymer paste group one,

(S/L=1.0) with different SS/SH ratios a) 1.0, b) 1.5, c) 2.0,

d) 2.5, e) 3.0

84

4.10 XRD patterns for POFA geopolymer paste group two,

(S/L=1.32) with different SS/SH ratios a) 1.0, b) 1.5, c) 2.0,

d) 2.5, e) 3.0

85

4.11 SEM image of geopolymerised POFA

86

4.12 EDX spot analysis of POFA geopolymer paste with S/L

ratio 1.32, SS/SH ratio 2.5 at different points

87

4.13 EDX spectrum of points 1 to 7 (pt1 to pt7)

88

4.14 Ca/Si ratio in different points (pt1 to pt 7) from EDX test

89

4.15 FTIR spectra of raw POFA and geopolymerised POFA of

group 2.0 S/L ratio 1.32

90

4.16 DSC diagrams of raw POFA and alkali activated POFA

(S/L=1.32)

91

4.17 Compressive strength results of POFA geopolymer paste

cured at different curing temperatures measured at 7, 28,

90, and 180 days

92

4.18 Strength development rates for POFA geopolymer pastes

from 7-28, 28-90, and 90-180 days

93

4.19 Hardening time for POFA geopolymer pastes cured at 60

ºC, 70 ºC, and 80 ºC and ambient temperature

94

4.20 Cracks generated in POFA geopolymer paste specimens at

60 ºC after 24 hours curing time, a) Top View, b) Side View

95

4.21 XRD patterns for POFA geopolymer pastes cured at a)

ambient temperature, b) 60 ºC, c) 70 ºC, d) 80 ºC at 7 and

28 days

96

4.22 Energy-dispersive X-Ray Spectrums (EDX) for POFA

geopolymer pastes cured at ambient temperature, 60 ºC, 70

ºC, and 80 ºC

98

4.23 Ca/Si ratio resulted from EDX test

99

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4.24 SEM images for POFA geopolymer pastes cured at

different curing temperatures, A) ambient temperature, B)

70 ºC, C) 80 ºC

101

4.25 FTIR Spectra for raw POFA and alkali activated POFA

cured at different curing temperatures

102

4.26 TGA Spectra for raw POFA and POFA geopolymer pastes

cured at different curing temperatures

104

4.27 Initial and final setting time

105


and POFA blended with GGBS as partial replacement by

weight

107

4.29 XRD patterns for alkali activated POFA blended with

GGBS

109

4.30 FTIR Spectra for raw POFA, raw GGBS, and POFA

blended with GGBS in different percentages after alkali

activation

110

4.31 Energy-dispersive X-ray spectroscopy (EDX), A) 100%

POFA, B) 10% GGBS, C) 20% GGBS, D) 30% GGBS, E)

40% GGBS, F) 50% GGBS

112

4.32 Si/Al ratio at the age of 28 days resulted from EDX test

analysis

113

4.33 Ca/Si ratio at the age of 28 days resulted from EDX test

113

4.34 SEM images and EDX spot points elements analysis

115

4.35 TGA results for POFA geopolymer paste blended with 10,

20, 30, 40 and 50% GGBS

116

4.36 DTG results for POFA geopolymer paste blended with 10,

20, 30, 40 and 50% GGBS

117

4.37 Peak temperatures resulted from the analysis of TGA/DTG

test

117

4.38 DSC thermograms of POFA geopolymer paste and POFA

blended with GGBS

118

4.39 Flow results for POFA geopolymer mortar by flow table

test

119

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4.40 Compressive strength of POFA geopolymer mortar and

POFA blended with GGBS geopolymer mortar

121

4.41 XRD pattern for POFA geopolymer mortar blended with

GGBS at the age of 7 days

124

4.42 XRD pattern for POFA geopolymer mortar blended with

GGBS at the age of 28 days

126

4.43 SEM images for geopolymer mortar at the age of 7 days: a)

100% POFA, b) 10% GGBS, c) 20% GGBS, d) 30%

GGBS, e) 40% GGBS, f) 50% GGBS

128

4.44 SEM images for geopolymer mortar at the age of 28 days:

a) 100% POFA, b) 10% GGBS, c) 20% GGBS, d) 30%

GGBS, e) 40% GGBS, f) 50% GGBS

129

4.45 SEM images for geopolymer mortar at the age of 90 days:

a) 100% POFA, b) 10% GGBS, c) 20% GGBS, d) 30%

GGBS, e) 40% GGBS, f) 50%

130

4.46 SEM/EDX images for geopolymer mortar at the age of 90

days: a) 100% POFA, b) 10% GGBS, c) 20% GGBS, d)

30% GGBS, e) 40% GGBS, f) 50% GGBS

131

4.47 FTIR Spectra for geopolymer mortar at the age of 7 days

132

4.48 FTIR Spectra for geopolymer mortar at the age of 28 days

133

4.49 TGA results analysis for geopolymer mortar at the age of 7

days

135

4.50 TGA results analysis for geopolymer mortar at the age of

28 days

135

4.51 DSC Spectra for geopolymer mortar at the age of 7 days

137

4.52 DSC Spectra for geopolymer mortar at the age of 28 days

138

4.53 Compressive strength results for geopolymer mortar and

Portland cement mortar at the age of 28 days cured at

ambient temperature before exposure to elevated

temperatures

139

4.54 Residual compressive strength for geopolymer mortar and

Portland cement mortar after exposure to elevated

temperatures

140

4.55 Geopolymer mortar and Portland cement mortar cubes after

exposure to 700 ºC (left group) and 800 ºC (right group)

142

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4.56 Geopolymer mortar maintained its shape and dimensions

after exposure to 700 ºC for one hour

142

4.57 XRD patterns for 100% POFA geopolymer mortar before

and after exposure to elevated temperatures.

143

4.58 XRD pattern for POFA replaced with 30% GGBS

geopolymer mortar before and after exposure to elevated

temperatures.

144

4.59 XRD pattern for POFA replaced with 50% GGBS

geopolymer mortar before and after exposure to elevated

temperatures.

144

4.60 SEM images for geopolymer mortars before and after

exposure to elevated temperatures: a) 100% POFA before

exposure, b) 100% POFA after exposure to 800 ºC, c) 50%

GGBS replacement before exposure, d) 50% GGBS

replacement after exposure to 800 ºC

145

4.61 FTIR Spectra for geopolymer mortar before exposure to

elevated temperatures

146

4.62 FTIR Spectra for geopolymer mortar after exposure to 400

ºC elevated temperature

147



147



148

4.65 TGA results for geopolymer mortar and Portland cement

mortar before exposure to elevated temperatures

149


mortar after exposure to 400 ºC elevated temperatures

150



150



151

4.69 DSC results for geopolymer mortar at ambient temperature

152

4.70 DSC results for geopolymer mortar after exposure to 400

ºC

153

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ºC

153


ºC

153

4.73 Residual compressive strength after 6 months of exposure

to 3.0% sulfates

155


to 5.0% sulfates

156


to 8.0% sulfates

157

4.76 SEM images for 100% POFA geopolymer mortar after 6

months exposure to 8% sodium sulfate solution

159

4.77 SEM images for 100% POFA geopolymer mortar after 6

months exposure to 8% magnesium sulfate solution

160

4.78 SEM/EDX spectrum spot analysis for 100% POFA

geopolymer mortar after 6 months exposure to 8%

magnesium sulfate solution

161

4.79 SEM/EDX spectrum spot analysis for 100% POFA

geopolymer mortar after 6 months exposure to 8%

magnesium sulfate solution

162

4.80 SEM images for geopolymer mortar (70% POFA+30%

GGBS) after 6 months of exposure to 8% sodium sulfate

163


GGBS) after 6 months of exposure to 8% magnesium

sulfate

163

4.82 SEM/EDX spectrum spot analysis for geopolymer mortar

(70% POFA+30% GGBS) after 6 months exposure to 8%

sodium sulfate

164



magnesium sulfate

165


GGBS) after 6 months exposure to 8% sodium sulfate

166


GGBS) after 6 months exposure to 8% magnesium sulfate

166

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sodium sulfate solution

167


(50% POFA+50% GGBS) after 6 months exposure to 8.0%

magnesium sulfate

168

4.88 FTIR Spectra for 100% POFA geopolymer mortar after 6

months exposure to sulfate attack

170

4.89 FTIR Spectra for geopolymer mortar (70% POFA+30%

GGBS) after 6 months exposure to sulfate attack

170

4.90 FTIR Spectra for geopolymer mortar (50% POFA+50%

GGBS) after 6 months exposure to sulfate attack

170

4.91 FTIR Spectra for Portland cement mortar after 6 months

exposure to sulfate attack

172

4.92 TGA results for 100% POFA geopolymer mortar after 6.0

months exposure to sulfate attack

173

4.93 TGA results for geopolymer mortar (70% POFA+ 30%

GGBS) after 6.0 months exposure to sulfate attack

173

4.94 TGA results for geopolymer mortar (50% POFA+ 50%

GGBS) after 6.0 months exposure to sulfate attack

174

4.95 TGA results for Portland cement mortar after 6 months

exposure to sulfate attack

175

4.96 DTG results analysis for Portland cement mortar after six

months of normal curing and six months of exposure to

sodium sulfate and magnesium sulfate

176

4.97 DSC thermograms for 100% POFA geopolymer mortar

after six months of normal curing and six months of

exposure to sodium sulfate and magnesium sulfate

177

4.98 DSC thermograms for geopolymer mortar (70% POFA+

30% GGBS) after six months of normal curing and six

months of exposure to sodium sulfate and magnesium

sulfate

177

4.99 DSC thermograms for geopolymer mortar (50% POFA+

50% GGBS) after six months of normal curing and six

months of exposure to sodium sulfate and magnesium

sulfate

178

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4.100 DSC thermograms for Portland cement mortar after six

months of normal curing and six months of exposure to

sodium sulfate and magnesium sulfate

179

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LIST OF ABBREVIATIONS AND ACRONYM

POFA Palm oil fuel ash

GGBS Ground granulated blast furnace slag

S/L Solid to liquid ratio

SS/SH Sodium silicate to sodium hydroxide ratio

SEM Scanning Electron Microscope

EDX Energy-dispersive X-Ray spectroscopy analysis

XRD X-Ray Diffraction

TGA Thermal Gravimetry Analyzer

DTG Derivative Thermogravimetry

DSC Differential Scanning Calorimetry

FTIR Fourier Transform Infra-Red

C-S-H Calcium Silicate Hydrate

C-A-S-H Calcium Aluminate Silicate Hydrate

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CHAPTER ONE

INTRODUCTION

1.1 Background

The development of alkali activated materials has been addressed by many researchers

as a competitive friendly alternative to ordinary Portland cement (OPC) (Provis and

Van Deventer, 2009; Provis and Van Deventer, 2014; Van Deventer et al., 2010; Li et

al., 2010). Alkali activated binders are classified as the third generation cements in

addition to lime and ordinary Portland cement (Shi et al., 2011; Li et al., 2010; Van

Davidovits, 2011). The alkali activation process is gaining a great recognition and

interest because of its low CO2 emissions where carbon footprint is of concern (Provis,

2014a). Recently, scientific and technological development being made at a rapid pace

due to their low energy consumption and qualities (Provis, 2014a; Villa et al., 2010;

Provis et al., 2012; Chindaprasirt et al., 2007; Provis and Van Deventer, 2009).

According to a recent rigorous and useful definition “Alkali activated materials are

produced through the reaction of an aluminosilicate-normally supplied in powder form

as an industrial by-product or other inexpensive martials-with an alkaline activator,

which is usually a concentrated aqueous solution of alkali hydroxide, silicate,

carbonate or sulfate” (Provis and Van Deventer, 2014; Provis, 2014a; Provis, 2009).

However, these materials, as new alternative binder to OPC in concrete technology,

are still at the beginning stages of development and need more investigations related

to the mechanisms of geopolymerization process (Pacheco-Torgal et al., 2012; Yip et

al., 2008). The activation methods, the type and dosage of alkali activators, curing

regime at the fresh state, and role of calcium in geopolymerization process are major

factors and still subjects of discussions for the researchers in this field (Nath and

Sarker, 2014; Nath and Kumar, 2013; Bernal et al., 2012; Bilim and Atiş, 2012; Yang

et al., 2012a; Liew et al., 2012a; Somna et al., 2011; Hajimohammadi et al., 2011).

The alkali activation process for an aluminosilicate source involves different

parameters. One of the governing factors on properties of the binding gel and its

formation is the type and dosage of alkali activators (Juenger et al., 2011). It has been

reported that different single activators were used in the activation process, such as

sodium hydroxide and sodium silicate (Somna et al., 2011; Rashad and Zeedan, 2011).

Combination of two different activators were also used in the alkali activation process

by using different liquid solutions (Luo et al., 2012; Altan and Erdoğan, 2012).

So far, a mix of liquid sodium silicate which is known as water glass and liquid sodium

hydroxide were the most used activating solutions in the geopolymers (Ryu et al.,

2013). This combination of activators were reported to have better performance in the

activation process comparing to single alkaline activators (Papa et al., 2014; Nath and

Sarker, 2014). The alkali hydroxide is required for dissolution of aluminosilicate

source while water glass solution acts as a binder, alkali activator and dispersant of

plasticizer (Komnitsas and Zaharaki, 2007). So far, different approaches have been

reported to measure the dosage of activators such as using sodium as a percentage of

the source material, or adding the total activator as a percentage of the binder (Bernal

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et al., 2012; Bilim and Atiş, 2012; Yang et al., 2012a). Nevertheless, previous works

have shown that solid to liquid (S/L) ratio and sodium silicate to sodium hydroxide

(SS/SH) ratio have tremendous effect on mechanical properties (Palomo et al., 1999;

Hardjito and Rangan, 2005a; Hardjito et al., 2004; Van Jaarsveld et al., 2002).

It has been reported that different factors affect the solid to liquid ratio and sodium

silicate to sodium hydroxide ratio in the alkali activation process. Firstly the shape and

particle size, and type of aluminosilicate precursor has an important effect on the

required quantity of the activator by which results in advanced dissolution (Kong et

al., 2007; Hardjito and Rangan, 2005a; Wang et al., 2005; Xu and Van Deventer,

2000b). The second factor affecting the geopolymerization process is the curing

regime at the fresh state of activation. In most cases the curing for alkali activated

materials is curried out at elevated temperatures ranging from 40 ºC to 90 ºC for a

period of 4 to 48 hours which is a limiting factor in construction industry (Lemougna

et al., 2013; Ryu et al., 2013; Rangan et al., 2005; Temuujin et al., 2009b). In order to

overcome the liming factors in geopolymerization process such as low reactivity, low

setting and slow strength development; calcium bearing materials or materials rich in

calcium oxide like GGBS were used to alter the reactivity of aluminosilicate precursors

(Oh et al., 2010; Guerrieri and Sanjayan, 2010; Yip et al., 2008; Nath and Sarker, 2014;

Kumar et al., 2010).

So far, different types of aluminosilicate materials such as Metakaolin (Yunsheng et

al., 2010; Liew et al., 2012b; Rashad, 2013; Pacheco-Torgal et al., 2011; Rovnaník,

2010), fly ash (Hardjito and Rangan, 2005b; Thomas et al., 2012; Provis et al., 2012)

and slag (Němeček et al., 2011; Luo et al., 2012; Fu et al., 2011; Bernal et al., 2011;

Bernal et al., 2010) were applied as alkali-activated cements.

Recently, researchers have incorporated palm oil fuel ash (POFA) as another potential

aluminosilicate source that can be used as an alkali activated cement. POFA is an agro-

waste produced in massive amounts from palm oil industry in South East Asia. POFA

has been used with a low content in binary mixes with other aluminosilicate materials

such as ground granulated blast furnace slag (GGBS), rice husk ash (RHA), and fly

ash in order to produce geopolymer paste, mortar and concrete while curing at oven

was the dominant regime in most of the studies.

This study intended to investigate the mechanisms by which calcium ions and

aluminum ions participate in the system in order to produce a high strength binder at

ambient temperature. It also studied the mechanism that governs the strength, chemical

composition, and microstructural change in the matrix after exposure to elevated

temperatures and sulfate attack.

1.2 Research Problem

The concept of alkali activated materials has been studied extensively as a promising

alternative to ordinary Portland cement (Provis, 2014a). However, the alkali activated

materials are still a complex class of binders (Provis and Van Deventer, 2009) and

there is still an increasing interest to improve the properties and microstructure of the

alkali activated binders. This is generated from the great need that is required to

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optimize the activation conditions in order to produce stronger, and more stable binder

(Bernal et al., 2014).

Furthermore, results from recent studies on the activation methods that being used in

alkali activation of different aluminosilicate sources have addressed the adverse effect

of oven curing as the dominant regime by which the production will be limited in the

real life situations comparing to Portland concrete.

There is also a consensus from some researchers regarding the use of Calcium bearing

materials or Calcium rich materials in binders with low calcium intake which results

in a better performance in terms of setting, hardening and also improving the load

bearing capacity of the gel; however, the mechanism of Calcium ion coupled with

Aluminum ion and their role in the system is still a complex subject.

Moreover, paucity has been noticed in the published studies and researches regarding

the behavior and degradation mechanism of alkali activated materials when exposed

to severe conditions such as heat exposure or sulfate attack. In this trend it is crucial

to investigate the change in compressive strength mechanism after exposure to such

environments.

Palm oil fuel ash (POFA) is one of the agricultural waste materials from the palm oil

industry in South East Asia. Malaysia is considered as the leading and the largest

producer of palm oil. It was estimated that only in Malaysia the wastes generated from

palm oil industry is 24.99 million tons per year (Hosseini and Wahid, 2013). The huge

amount of POFA is still a subject of wide criticisms and endless complaints because it

poses health hazard leading to various health problems. POFA needs large area to be

disposed which arising an environmental problem; in addition to the financial lost on

transportation of the waste and allocating hectares of lands for disposal. So far, some

studies have been conducted on low content POFA geopolymers although still a

comprehensive study on activation parameters, curing regime, its underlying

mechanism of geopolymerization, and its compatibility with other sources of

aluminosilicate is indispensable.

Recently, palm oil fuel ash (POFA) has been recognized as an aluminosilicate material

to be utilized in alkali activation technology. POFA was used as a supplementary

material in mixes with other aluminosilicate materials to produce geopolymer cement

paste, mortar and concrete. In all researches, a low content of POFA was kept to be

mixed with slag, fly ash and rice husk ash or other aluminosilicate materials to alter

POFA and increase its reactivity. Moreover, oven curing was associated to the

production process. Still, no study investigated the activation mechanism and the

microstructure of the resulted geopolymer binder from the activation of POFA as the

only aluminosilicate material source. Moreover, no study investigated the potential of

high volume of POFA to be activated with GGBS to produce high strength Geo-

polymerized paste and mortar at ambient temperatures.

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1.3 Hypothesis of the Research

The hypothesis that this study was built on is the role of calcium ions provided by

GGBS in developing the chemical composition and the microstructure of the gel. The

abundant quantity of calcium ions has the ability to develop the load bearing capacity

of the formed binding phase of POFA. This will lead to enhance the compressive

strength of the geopolymer binder to higher strength. Furthermore, Calcium ions will

participate in changing the setting and the hardening of the developed binder to

ambient temperature. In other words, calcium ions will develop the binding phase

structure to be stronger and eliminate the need for higher temperature for curing and

hardening.

1.4 Research Objectives

The main aim of this research was to study the ability of alkali activated materials to

produce high strength binder at ambient temperature from high volume POFA blended

with GGBS. This was assimilated by studying the mechanical and microstructural

properties of alkali activated paste and mortar through the following four objectives:

1. To identify activation parameters, Sodium Hydroxide concentration

(Molarity), Solid to Liquid ratio (S/L) and Sodium Silicate to Sodium

Hydroxide ratio (SS/SH) in production of a geopolymer binder with POFA as

a single aluminosilicate source.

2. To investigate the appropriate curing temperature in geopolymerization of

100% POFA.

3. To investigate the production of high strength geopolymer binder by using

binary mixing of GGBS and POFA.

4. To assess the durability performance of the proposed geopolymer mortar when

exposed to elevated temperatures and sulfate attack.

1.5 Research Questions

This study focused on the compressive strength, microstructural, chemical and thermal

characteristics of POFA geopolymer paste and POFA geopolymer mortar produced

from a binary mixture of POFA and GGBS in order to answer the following questions:

How do the solid to liquid ratio and sodium silicate to sodium hydroxide ratio

affect the geopolymerization process?

What is the mechanism by which calcium ions available in the aluminosilicate

material affect geopolymerization process and help the geopolymer binder to

set at ambient temperature and produce high strength binder and high strength

mortar?

How do thermal and microstructural analysis differentiate between C-S-H and

C-A-S-H as the main binding phases in alkali activated materials?

How do elevated temperatures and sulfate attack deteriorate the C-S-H, and C-

A-S-H in mortar?

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1.6 Research Contribution

Palm oil fuel ash (POFA) is designated with a moderate content of silicate and a low

content of aluminum which reportedly can produce a low strength geopolymer binder

(less than 18 MPa) when POFA is the only alkali activated material. In the same time

oven curing at 65 ºC to 75 ºC for 24 hours was associated as a curing regime in the

production process of this binder.

The aim of this study is to produce a high strength geopolymer binder using high

volume of palm oil fuel ash at ambient temperature. This study exploits the role of

calcium ions coupled with aluminum ions provided by GGBS to investigate the

mechanisms by which the strength of binding phase can be improved and allow to the

binder to harden without oven curing. Investigating the degradation mechanisms

governing the alkali activated mortar after exposure to elevated temperatures and

sulfate attack is another major contribution of the present study.

1.7 Significance of the Study

The overarching purpose of this study is to activate POFA albeit its very low content

of aluminum. The finding of this research will also explain the mechanism by which

aluminosilicate with low aluminum content are involved in the geopolymerization

process. Also, the results of this study may encourage and promote further research

on the use of POFA in geopolymer technology in mortar and concrete as well as the

use of other aluminosilicate materials with low aluminum content which will

ultimately lead to development of more environmentally friendly products with low

energy consumption and very low CO2 emissions.

Furthermore, there is no comprehensive study on the effect of curing temperature on

alkali activation of mixes with 100% POFA. So, the other purpose of this study is to

investigate the microstructure and chemical composition of POFA geopolymer paste

binder cured at ambient temperature (25-30) ºC and oven cured at 60 ºC, 70 ºC, and

80 ºC. This study proposes the applicability of ambient temperature as a curing regime

in POFA geopolymer binders. Investigating the use of ambient temperature to produce

a geopolymer binder from agro waste materials such as POFA will contribute to a

development of mix design to be used in structural sector. It can lower the cost and

energy consumption; meanwhile enhances construction pace.

Moreover, ground granulated blast furnace slag was used as a partial replacement of

POFA in order to enhance the load bearing quality (capacity) of the binder. The

purpose is to produce high strength binder as an alternative to ordinary Portland

cement in high strength concrete using ambient temperature curing regime. The

finding of this work may facilitate the development of high strength geopolymer

concrete using higher calcium alkali activated materials at ambient temperature.

The last but not least, this study investigates the durability of alkali activated binder

using the binary mix of POFA and GGBS after exposure to severe environment namely

elevated temperatures and sulfate attack. The findings of this study assess the

acceptability of the binder in terms of durability and also clarify on the deterioration

mechanism.

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1.8 Scope and limitations of the study

The main purpose of this study is to investigate new geopolymerization process to

produce high strength alkali activated binder from high volume of POFA cured at

ambient temperature. In order to achieve the established objectives, the scope and

limitations of this study are summarized as follows:

In this study, activation parameters are limited to Sodium Hydroxide concentration

(NaOH molarity), Solid to Liquid ratio (S/L), and Sodium Silicate to Sodium

Hydroxide ratio (SS/SH). Furthermore, a combination of liquid Sodium Silicate

(Na2SiO3) mixed with liquid Sodium Hydroxide (NaOH) was chosen as alkaline

activators and represented by SS/SH ratio. As for the curing regime only for

temperatures were assigned in the second objective which are namely; ambient

temperature at (25-30) ºC, and oven curing at three different temperatures of 60 ºC, 70

ºC, and 80 ºC. In order to study the effect of Ca ions and to develop a high strength

binder, GGBS was chosen and replaced with POFA at different levels of 10%, 20%,

30%, 40% and 50%.

The durability of geopolymer mortar produced from 100% POFA and POFA-GGBS

geopolymerized mortar was limited to the performance of the geopolymerised mortar

at elevated temperatures and in sulfate environments. The heat exposure was for one

hour within the rates of 100 ºC, 200 ºC, 300 ºC, 400 ºC, 500 ºC, 600 ºC, 700 ºC, and

800 ºC. Furthermore; the durability of geopolymer mortar were investigated by

exposing the mortars to Sodium sulfate and Magnesium sulfate. Geopolymer mortars

were exposed for 6 months to three different concentrations 3%, 5%, and 8%.

All the tests were conducted on geopolymer paste and mortars and aggregate with size

bigger than 4.75 mm were excluded from this study in order to eliminate the effect of

the volume concentration factor in the matrix and to minimize the effect of the thermal

conductivity and specific heat of the resulted matrix.

In this study, X-Ray fluorescence spectrometry scanning (XRF), setting time, flow

table test, compressive strength, X-Ray diffraction (XRD), Scanning Electron

Microscope (SEM) coupled with Energy-dispersive X-Ray spectroscopy analysis

(EDX), Thermogravimetric Analysis/Derivative Thermogravimetric Analysis

(TGA/DTG), Differential scanning calorimetry (DSC), and Fourier transform Infra-

Red (FTIR) were the main tests conducted to trace properties of the materials before

and after alkali activation in geopolymer paste and mortar.

1.9 Thesis Layout

In this study, an experimental work has been carried out to achieve the required

objectives. The work presented in this thesis is spread across five chapters.

Chapter one includes a general introduction about the alkali activated materials and

geopolymer technology as an alternative binder to ordinary Portland cement. The

studied objectives were illustrated in general in this chapter. Chapter two initially

illustrated the definition of alkali activated materials and the term geopolymer.

History, geopolymerization mechanisms, activation methods, activators,

aluminosilicate materials and tests that have been used in this technology were all

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illustrated. Chapter two is considered as a reference that can give all the required

information and details about alkali activation technology and geopolymers. Figures

and images were used to explain the way that the required tests were used in identifying

the changes before and after alkali activation, and the changes in the paste and mortar

with different parameters in the study. In chapter three, the methodology that used in

the experimental work was illustrated. This chapter showed the applied method for

alkali activation; moreover, the approach as a step by step method that being used to

identify the required parameters in alkali activation of an aluminosilicate material. The

designed methodology is considered as a reference for studying the alkali activation

for any aluminosilicate precursor. Chapter four discussed the test results for the used

method in alkali activation of POFA and POFA blended with GGBS. This chapter

tended to introduce the most effective parameters in the activation process. The

behavior of POFA geopolymer mortar and POFA blended with GGBS geopolymer

mortar after exposure to elevated temperatures and sulfate attack was also discussed.

Chapter five illustrated the conclusions of the study and recommendations for further

research.

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