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PERFORMANCE OF EPOXY-BASED SELF-HEALING MORTAR
NUR FARHAYU BINTI ARIFFIN
UNIVERSITI TEKNOLOGI MALAYSIA
i
PERFORMANCE OF EPOXY-BASED SELF-HEALING MORTAR
NUR FARHAYU BINTI ARIFFIN
A thesis submitted in fulfilment of the
requirements for the award of the degree of
Doctor of Philosophy (Civil Engineering)
Faculty of Civil Engineering
Universiti Teknologi Malaysia
MAY 2016
iii
DEDICATION
Praise be to Allah s.w.t, the Lord of the Worlds
Who says (interpretation of the meaning):
“Give thanks to Me and to your parents. Unto Me is the final destination”
[Quraan, Luqmaan 31:14]
All glory and honor to Him
To my parents
Fadzillah Binti Idris and Ariffin Bin Sulaiman
To my greatest supporters
Nur Farhana, Mohd Syafiq Fauzan, Muhammad Syafiq Sazzuann, Nur Abyan
Nabilah, Alif Dzulfieka and Qaireen Nur Amani
And also to all who supported me by Doa and work. Thanks for everything. May
Allah bless you. Amin
iv
ACKNOWLEDGEMENT
Praise Be To Allah S.W.T, the Lord of the World
First and foremost, I like to express my sincere appreciation and profound
gratitude to my beloved thesis supervisors, Prof. Ir. Dr. Mohd Warid Hussin, Assoc.
Prof. Dr. Abdul Rahman Mohd Sam and Prof. Han Seung Lee, for encouragement,
guidance, critics and friendship. Without their continued support and interest, this
thesis would not have been the same as presented here.
I am thankful to Materials and Structures laboratory, Faculty of Civil
Engineering, Universiti Teknologi Malaysia and Hanyang University of South Korea
for providing the facilities for my research. My thanks also go to technicians and
staffs for their assistance in this research. The financial supports from Universiti
Teknologi Malaysia Research Management Centre, towards the research projects:
03H35 and 03H36, MyBrain15 and Ministry of Education, are appreciated.
Most importantly, I must thank my amazing family for their steadfast support,
love and encouragement. Mom and Dad, I cannot thank you enough for raising me
to be an independent thinker and instilling the traits of ambition and perseverance in
me from a young age. To my siblings, thank you for your constant support, for
always making me laugh, and for reminding me not to take life too seriously. I love
all of you with all my heart, and I am so lucky to call you my family.
My sincere appreciation also extends to all my colleagues and friends who
have provided assistance at various occasions. Your views and tips are useful indeed.
To all of you, thank you for everything.
v
ABSTRACT
Concrete is one of the oldest and versatile construction materials. After
water, it is the most utilised material in the world. However, due to various reasons,
the formation of micro-cracks can lead to a major problem such as corrosion of steel
reinforcement and further deterioration of the structure. The cost of repairing
deteriorated concrete structures is expensive as effective remedial requires special
repair materials and skilled labours. Thus, the development of new technologies and
material that can automatically repair cracks, consequently restore or even increase
the strength of both mortar and concrete to prolong the service life is highly needed.
Nowadays, the self-healing by using bacteria as a healing agent had gained interest
among researchers. However, limited study had been conducted on the use of
polymer as a healing agent. Thus, the aim of this study is to investigate the effects
and behaviour of epoxy resin without hardener as a self-healing agent in mortar. The
epoxy resin was used without hardener based on the understanding that it can harden
inside the mortar through the reaction between the epoxy resin and hydroxyl ions
produced from the cement hydration process. In this study, the mortar specimens
were prepared with mass ratio of 1:3 (cement: fine aggregates), water-cement ratio of
0.48 and 5% to 20% epoxy resin of cement content. Two types of curing regimes
were used namely dry-curing and wet-dry curing. Normal mortar was also prepared
as a control sample. Various tests were carried out to determine the characteristics of
materials including viscosity, Fourier transform infrared spectroscopy, X-ray
fluorescence and sieve analysis. The performance of the hardened mortar containing
epoxy resin without hardener was determined through compressive strength, flexural
strength, splitting tensile strength, initial surface absorption, water absorption,
apparent porosity, drying shrinkage and strength development. Furthermore, various
techniques including X-ray diffraction, scanning electron microscopy and
thermogravimetric analysis were used to study the microstructure of the hardened
epoxy-modified mortar. The ultrasonic pulse velocity, permeability, damage degree
and healing efficiency were conducted to determine the crack healing process by the
epoxy resin inside the cracked mortar specimens. The experimental results show that
the optimum percentage of epoxy resin used in the mix was 10% as it gives the
highest engineering properties compare to other percentage. The wet-dry curing
regime was found to give better performance of the sample containing epoxy resin
compared to dry curing. The epoxy resin without hardener as a healing agent was
found to perform effectively as the compressive strength, ultrasonic pulse velocity
and permeability of the cracked mortar samples regain the initial reading with
prolonged curing time. The microstructure study also revealed that the epoxy resin
reacts with the hydroxyl ions to heal the micro-cracks in the mortar specimen.
Overall test results together with microstructure study showed that epoxy resin
without hardener can be used as a self-healing agent in repairing the micro-cracks.
vi
ABSTRAK
Konkrit merupakan bahan binaan tertua dan serba boleh yang paling banyak
digunakan di dunia selepas air. Walau bagaimanapun, disebabkan faktor tertentu,
penghasilan retakan mikro boleh menyebabkan masalah seperti pengaratan tetulang
keluli dan kerosakan kepada struktur. Kos membaikpulih struktur konkrit adalah
mahal kerana kerja-kerja pemulihan memerlukan bahan terpilih dan tenaga kerja
mahir. Oleh itu, teknologi dan bahan yang dapat membaiki retakan secara automatik
dan mampu meningkatkan kekuatan mortar dan konkrit seterusnya memanjangkan
hayat perkhidmatan adalah sangat diperlukan. Pada masa ini, konkrit penyembuhan
automatik dengan menggunakan bakteria sebagai agen penyembuhan telah mendapat
perhatian para penyelidik. Walau bagaimanapun, kajian menggunakan polimer
sebagai agen penyembuhan masih tidak meluas. Oleh itu, tujuan penyelidikan ini
adalah untuk mengkaji kesan dan perlakuan resin epoksi tanpa pengeras sebagai agen
penyembuhan dalam mortar. Resin epoksi yang digunakan adalah tanpa pengeras
berdasarkan pemahaman bahawa ia boleh mengeras di dalam mortar melalui tindak
balas diantara resin epoksi dan ion hidroksil yang terhasil daripada proses
penghidratan simen. Dalam kajian ini spesimen mortar telah disediakan dengan
nisbah 1: 3 (simen: pasir), nisbah air-simen 0.48 dan 5% hingga 20% resin epoksi
daripada kandungan simen. Dua jenis pengawetan digunakan iaitu pengawetan
kering dan pengawetan basah-kering. Mortar biasa disediakan sebagai sampel
kawalan untuk perbandingan. Pelbagai ujian telah dijalankan untuk menentukan ciri-
ciri bahan termasuk ujian kelikatan, Fourier transform infrared spectroscopy, X-ray
Fluorescent dan analisis ayak. Prestasi mortar keras yang mengandungi resin epoksi
tanpa pengeras telah dikaji melalui kekuatan mampatan, kekuatan tegangan,
kekuatan lenturan, penyerapan air dipermukaan, penyerapan air, jumlah keliangan,
pengecutan kering and peningkatan kekuatan. Disamping itu, pelbagai teknik,
termasuk X-ray diffraction, scanning electron microscopy dan ujian
thermogravimetric telah digunakan untuk mengkaji mikrostruktur epoksi mortar.
Halaju denyutan ultrasonik, ketelusan, tahap kerosakkan dan keberkesanan
penyembuhan telah dilakukan untuk menentukan proses penyembuhan retakan oleh
resin epoksi dalam spesimen mortar yang telah diretakkan. Keputusan kajian
menunjukkan peratus optimum resin epoksi yang digunakan adalah 10% kerana ia
memberikan kekuatan mampatan mortar yang tertinggi. Pengawetan kering-basah
didapati telah memberikan prestasi yang lebih baik bagi spesimen yang mengandungi
resin epoksi tanpa pengeras berbanding pengawetan kering. Resin epoksi tanpa
pengeras juga didapati sangat efektif sebagai bahan penyembuh berasaskan kekuatan
mampatan, halaju denyutan ultrasonik dan ketelusan air spesimen mortar yang
diretakkan memberikan bacaan seperti bacaan awal pada jangkamasa pengawetan
yang lama. Kajian mikrostruktur juga menunjukkan resin epoksi bertindak balas
dengan ion hidroksil dan menyembuhkan keretakan mikro dalam spesimen mortar.
Keputusan keseluruhan beserta kajian mikrostruktur menunjukkan resin epoksi tanpa
pengeras boleh digunakan sebagai agen penyembuhan keretakan mikro.
vii
TABLE OF CONTENTS
CHAPTER TITLE PAGE
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES xiii
LIST OF FIGURES xv
LIST OF ABBREVIATIONS xx
LIST OF SYMBOLS xxi
LIST OF APPENDICES xxii
1 INTRODUCTION 1
1.1 Introduction 1
1.2 Problem Statement 3
1.3 Aim of the Study 5
1.4 Objectives of the Study 5
1.5 Research Question 6
1.6 Scope and Limitation of Study 6
1.7 Significance of Research 8
1.8 Thesis Outline 9
2 LITERATURE REVIEW 11
2.1 Introduction 11
viii
2.2 Problems of the Crack 14
2.3 Types of Repair 17
2.4 Cost Estimating For Structure Repairing 19
2.5 Self-Healing Concrete 22
2.6 Type of Healing Agent 25
2.6.1 Epoxy Resins 26
2.6.2 Cyanoacrylates 28
2.6.3 Alkali–silica Solution 29
2.7 Self-Healing Method 30
2.7.1 Encapsulation 30
2.7.2 Expansive Agent and Mineral Admixtures 32
2.7.3 Bacteria 32
2.8 Limiting Crack Width for Autogenic Self-Healing 35
2.9 Thermosetting Polymer 39
2.10 Polymer in Concrete 42
2.10.1 Epoxy Resin 44
2.10.2 Polymer-modified Concrete 47
2.11 Concluding Remarks 49
3 METHODOLOGY 51
3.1 Introduction 51
3.2 Experimental Programs 51
3.3 Materials 53
3.3.1 Epoxy Resin 54
3.3.2 Ordinary Portland Cement (OPC) 54
3.3.3 Fine Aggregates 55
3.3.4 Water 55
3.4 Mix Proportion 56
3.5 Mixing Procedure 57
3.6 Curing Conditions 57
3.7 Tests 58
3.7.1 Fresh Properties 59
3.7.1.1 Viscosity Measurement 59
ix
3.7.1.2 Flow Tests 60
3.7.1.3 Setting Time Test 61
3.7.2 Hardened Properties 62
3.7.2.1 Compressive Strength Tests 62
3.7.2.2 Flexural Test 63
3.7.2.3 Splitting Tensile Test 64
3.7.2.4 Initial Surface Absorption Test 64
3.7.2.5 Water Absorption Test 65
3.7.2.6 Apparent Porosity Test 66
3.7.2.7 Drying Shrinkage 67
3.8 Self-Healing Evaluation 68
3.8.1 Test Degree of Hardening 68
3.8.2 Pre-loading 70
3.8.3 Ultrasonic Pulse Velocity 72
3.8.4 Damage Degree of Concrete after Self-Healing 73
3.8.5 Permeability Test 74
3.9 Microstructure tests 75
3.9.1 Fourier Transform Infrared Spectroscopy 75
3.9.2 X-Ray Fluorescence 76
3.9.3 X-Ray Diffraction 77
3.9.4 Scanning Electron Microscopy 78
3.9.5 Thermogravimetric Analysis 79
4 ENGINEERING PROPERTIES OF EPOXY-MODIFIED
MORTAR
81
4.1 Introduction 81
4.2 Properties of Materials 81
4.2.1 Epoxy Resin 82
4.2.1.1 Viscosity 82
4.2.1.2 Fourier Transformation Infrared
Spectroscopy
83
4.2.2 Cement 85
4.2.2.1 X-Ray Fluorescence 85
x
4.2.2.2 X-Ray Diffraction 86
4.2.2.3 Fourier Transformation Infrared
Spectroscopy
87
4.2.3 Fine aggregates 89
4.2.3.1 Sieve Analysis 89
4.2.3.2 X-Ray Fluorescence 90
4.2.3.3 Fourier Transformation Infrared
Spectroscopy
90
4.3 Effect of Curing Regime 91
4.4 Fresh Properties of Epoxy-Modified Mortar 94
4.4.1 Flow Tests 94
4.4.2 Setting Time Test 94
4.5 Physical Properties of Epoxy-Modified Mortar 96
4.6 Mechanical Properties of Epoxy Modified Mortar 97
4.6.1 Compressive Strength 98
4.6.2 Flexural Test 100
4.6.3 Splitting Tensile Test 101
4.6.4 Relationship between Compressive, Flexural and
Tensile Strengths
103
4.6.5 Scanning Electron Microscopy Morphology 104
4.5.6 X-Ray Diffraction 107
4.5.7 Thermogravimetric Analysis 108
4.5.8 Initial Surface Absorption Test 113
4.5.9 Water Absorption Test 114
4.5.10 Apparent Porosity Test 115
4.5.11 Drying Shrinkage 117
4.7 Comparison between Optimum Epoxy-Modified Mortar
and Normal Mortar
119
4.7.1 Strength Development 119
4.7.2 Porosity 120
4.7.3 Scanning Electron Microscopy Morphology 122
4.7.4 X-Ray Diffraction 124
4.7.5 Fourier Transform Infrared Spectroscopy 125
xi
4.7 Summary 127
5 EVALUATION OF SELF-HEALING EPOXY-MODIFIED
MORTAR
128
5.1 Introduction 128
5.2 Visualization of Crack Formation after Pre-Loading 129
5.2.1 Normal Observation 130
5.2.2 UV-light Observation 131
5.3 Observation of Epoxy Resin without Hardener 132
5.4 Degree of Hardening 134
5.5 Self-Healing Mechanism of Epoxy resin without
hardener
135
5.6 Reaction between Epoxy Resin and Hydroxyl Ion 136
5.7 Self-Healing of Epoxy-Modified Mortar 139
5.7.1 Ultrasonic Pulse velocity 139
5.7.2 Compressive Strength 144
5.7.3 Relationship between Compressive Strength and
Pulse Velocity
149
5.8 Damage Degree of Concrete after Self-Healing 150
5.9 Permeability Test 152
5.10 Microstructure of Self-Healing Epoxy-Modified Mortar 154
5.10.1 Scanning Electron Microscopy Morphology 154
5.10.2 X-Ray Diffraction Analysis 159
5.10.3 Fourier Transformation Infrared Spectroscopy 160
5.11 Summary 163
6 CONCLUSIONS AND RECOMMENDATIONS 165
6.1 Introduction 165
6.2 Conclusions 165
6.2.1 Characterize the Properties of Materials 166
6.2.2 Optimum Mix Proportions of Epoxy-Modified
Mortar
166
6.2.3 Engineering Properties of Epoxy-Modified Mortar
xii
without Hardener 166
6.2.4 Self-Healing Mechanism of Epoxy Resin in
Hardened Mortar
167
6.2.5 Performance of Epoxy-Modified Mortar under
Microstructure Tests
168
6.3 Contribution of Presented Research Work 169
6.4 Recommendations for Future Research 170
REFERENCES 171
Appendices A-B 181-186
xiii
LIST OF TABLES
TABLE NO. TITLE PAGE
2.1 The advantages and disadvantages of self-healing agents 37
2.2 Advantages and disadvantages of thermosetting resins (Ray
and Rout, 2005)
41
3.1 Mix proportion of epoxy-modified mortar 56
3.2 The stages in producing the crack in epoxy modified and
normal mortars
71
3.3 Classification of the quality of concrete on the basis of
Pulse velocity (Levitt, 1970)
73
4.1 Properties of Diglycidyl Ether of Bisphenol A-type epoxy
resin
82
4.2 Composition and structure of raw epoxy resin 85
4.3 Chemical composition of cement by XRF analysis 86
4.4 Composition and structure of Portland cement 88
4.5 Chemical composition of fine aggregates 90
4.6 Composition and structure of fine aggregates 91
4.7 Compressive strength of epoxy-modified mortar 92
4.8 Optimum mix proportion of epoxy-modified mortar 99
4.9 Epoxy-modified mortar elements from XRD analysis 108
4.10 Result of thermogravimetric analysis 112
4.11 Percentage of gases decomposition 112
4.12 Comparison of composition and structure of normal and
epoxy-modified mortars
126
5.1 The crack generated to epoxy-modified and normal mortar 129
5.2 Velocity of epoxy and normal mortar after loaded at 28
xiv
days 141
5.3 Velocity of epoxy and normal mortar after loaded at 180
days
141
5.4 Velocity of epoxy and normal mortar after loaded at 365
days
142
5.5 Compressive strength of epoxy and normal mortar after
loaded at 28 days
146
5.6 Compressive strength of epoxy and normal mortar after
loaded at 180 days
146
5.7 Compressive strength of epoxy and normal mortar after
loaded at 365 days
147
5.8 Composition and structure of epoxy-modified mortars 162
5.9 Composition and structure of normal mortars 163
xv
LIST OF FIGURES
FIGURE NO. TITLE PAGE
1.1 Research Significant 8
2.1 Process of aggressive solution penetration (Interval,
2015)
12
2.2 Blood clotting in an injured vessel (Porter, 2006) 14
2.3 Cause of cracking (Kumar and Chandana, 2015) 16
2.4 Performance and cost comparison between normal
concrete material and self-healing material (Breugel,
2012)
20
2.5 Main mechanisms of autogenous healing (Tang et al.,
2015)
24
2.6 Hollow tube contains epoxy resin and hardener (Aïssa et
al., 2012)
28
2.7 Basic method of the microcapsule approach (White et al.,
2001)
31
2.8 Optical photomicrograph (1000×magnification) of
bacteria (Jonkers et al. 2010)
34
2.9 Research gap of the study 39
2.10 Classifications of polymer modifiers of cement paste
(Ohama and Ramachandran 1996)
40
2.11 System of classification of concrete-polymer composites 42
2.12 The cross-linking compound of epoxy resin (Zhengl et
al., 1995)
45
2.13 The global markets of epoxy resins (Massingill and
Bauer, 2000)
46
xvi
2.14 The reaction of epoxy resin with hydroxyl ion (Ohama et
al., 1993)
48
2.15 Number of publications per year containing the phrase
“self-healing polymer” (Scheiner et al., 2015)
48
3.1 Experimental Programme 53
3.2 Digital Brookfield Viscometer for epoxy resin viscosity
test
59
3.3 Type of spindle for viscosity test 60
3.4 The flow table and spreaded mortar 61
3.5 Initial surface absorption test equipment 65
3.6 Mechanical extensometer for drying shrinkage
measurement
68
3.7 Testing procedure of degree of hardening 69
3.8 The procedure to generating cracks 70
3.9 Different conditions that may be encountered when
testing an element
72
3.10 The apparatus and equipment for permeability test 74
3.11 (a) Pellet compress machine (b) FTIR analyser 76
3.12 X-Ray Diffraction machine at Hanyang University of
South Korea
77
3.13 Coating machine and the mortar sample after coating 78
3.14 Scanning Electron Microscopy and Energy-dispersive X-
ray machine at Hanyang University of South Korea
79
3.15 Thermogravimetric machine at Hanyang University of
South Korea
80
4.1 Formulation of epoxy resin with cement hydration
(Ohama et al., 1993)
83
4.2 Fourier transformation infrared spectroscopy of epoxy
resin
84
4.3 Scanning Electron Microscopy morphology of cement
hydrates without epoxy resin
86
4.4 X-ray diffraction of Portland cement 87
4.5 Fourier transformation infrared spectroscopy analysis of
xvii
Portland cement 88
4.6 Sieve analysis of fine aggregates 89
4.7 Fourier transformation infrared spectroscopy analysis of
fine aggregates
91
4.8 Relationship between curing condition and percentage of
epoxy in 28 days
92
4.9 Relationship between flow diameter and epoxy content 94
4.10 Relationship between setting time and epoxy content 96
4.11 Average density of epoxy-modified mortar 97
4.12 Compressive strength in wet-dry curing at 28 days 98
4.13 The visual different between 10% and 20% of epoxy-
modified mortar
100
4.14 Flexural strength and epoxy-modified and normal mortar 101
4.15 Relationship between splitting tensile strength and epoxy
content in 28 days curing
102
4.16 Relationship between compressive, flexural and splitting
tensile strengths in 10% epoxy content
103
4.17 Morphology of Scanning Electron Microscopy and
Energy-dispersive X-ray of epoxy-modified mortar
105
4.18 Calcium hydroxide present in 10% epoxy-modified
mortar
106
4.19 X-ray diffraction analysis of epoxy-modified mortar 108
4.20 Thermogravimetric analysis of 5% epoxy content 110
4.21 Thermogravimetric analysis of 10% epoxy content 110
4.22 Thermogravimetric analysis of 15% epoxy content 111
4.23 Thermogravimetric analysis of 20% epoxy content 111
4.24 Initial surface absorption of epoxy-modified mortar and
normal mortar
113
4.25 Relationship between water absorption and epoxy content 114
4.26 Relationship between apparent porosity and epoxy
content
116
4.27 Morphology of pores between (a) 10% epoxy content and
(b) normal mortar
117
xviii
4.28 Relationship between polymer content and drying
shrinkage of epoxy-modified mortars
118
4.29 Strength development after 485 days of curing 120
4.30 Relationship between apparent porosity and strength
development in 360 days
121
4.31 Correlation between apparent porosity and compressive
strength
122
4.32 The morphology of epoxy-modified mortar containing
calcium hydroxide and calcium silicate hydrate gel
123
4.33 Comparison of X-ray diffraction analysis between epoxy-
modified mortar and normal mortar at 365 days
specimens
124
4.34 Fourier transformation infrared spectroscopy for epoxy-
modified mortar and normal mortar
126
5.1 Epoxy-modified mortar before produce crack 130
5.2 Crack generated under 80% of ultimate load of epoxy-
modified mortar
130
5.3 Crack generated in epoxy-modified mortar observe under
UV-light
131
5.4 Unhardened epoxy resin after 28 days curing in epoxy-
modified mortar
131
5.5 Epoxy resin under microscopy observation (Guimard et
al. 2012)
132
5.6 Degree of hardening of epoxy resin 132
5.7 Self-healing mechanism by epoxy resin (Łukowski and
Adamczewski, 2013)
134
5.8 The bonding between hydroxyl ion and epoxy resin 137
5.9 The morphology of self-healing reaction 142
5.10 Velocity of self-healing epoxy-modified and normal
mortars after loaded at 28 days
142
5.11 Velocity of self-healing epoxy-modified and normal
mortars after loaded at 180 days
143
5.12 Velocity of self-healing epoxy-modified and normal
xix
mortars after loaded at 365 days 143
5.13 Compressive strength epoxy and normal mortar after
loaded at 28 days
147
5.14 Compressive strength of self-healing epoxy-modified and
normal mortars after loaded at 180 days
148
5.15 Compressive strength of self-healing epoxy-modified and
normal mortars after loaded at 365 days
148
5.16 Relationship between compressive strength and velocity
of epoxy-modified mortar
149
5.17 Relationship healing rate and velocity of epoxy-modified
mortar
150
5.18 Healing efficiency of epoxy-modified mortar 151
5.19 Relationship between degree of damage and healing
efficiency
152
5.20 Time measurement for water permeability of mortar for
crack produce at 28 days
153
5.21 Scanning Electron Microscopy morphology and Energy-
dispersive X-ray analysis of calcium silicate hydrate in
massive ball shape
155
5.22 Scanning Electron Microscopy morphology of calcium
silicate hydrate in fine granular shape
156
5.23 Scanning Electron Microscopy morphology of calcium
silicate hydrate in Rosette shape
157
5.24 Scanning Electron Microscopy morphology of calcium
silicate hydrate in Fibrous shape
157
5.25 Bonding between epoxy resin without hardener and
calcium hydroxide
158
5.26 X-Ray Diffraction analysis of self-healing epoxy-
modified mortar
159
5.27 Fourier Transform Infrared Spectroscopy analysis of self-
healing epoxy-modified mortar
161
5.28 Fourier Transform Infrared Spectroscopy analysis of
normal mortar
162
xx
LIST OF ABBREVIATIONS
50EM - 50% Epoxy-Modified
50NM - 50% Normal Mortar
80EM - 80% Epoxy-Modified
80NM - 80% Normal Mortar
ASTM - American Society For Testing And Materials
BS - British Standard
CSH - Calcium Silicate Hydrate
C3S - Tricalcium Silicate
C2S - Dicalcium Silicate
C3A - Tricalcium Aluminate
C4AF - Tetracalcium Aluminoferrite
Ca(OH)2 - Calcium Hydroxide
EDX - Energy Dispersive X-Ray
SEM - Scanning Electron Microscopy
ISAT - Initial Surface Absorption Test
TGA - Thermogravmetry Analysis
UPV - Ultrasonic Pulse Velocity
XRD - X-Ray Differaction
XRF - X-Ray Fluorescence
xxi
LIST OF SYMBOLS
σc Compressive strength
σf Flexural strength
σT Splitting tensile strength
P Load
A Area
t Time
L Length
b Width
d Thickness
H Height
D Diameter
3.142
xxii
LIST OF APPENDICES
APPENDIX TITLE PAGE
A List of Publications 181
B Example Calculation of TGA 186
1
CHAPTER 1
INTRODUCTION
1.1 Introduction
Polymer-modified mortar or concrete represents a modification technique or
concept that had been used in order to enhance the properties of normal mortar or
concrete. As in 1923, the first patent of polymer modified mortar and concrete had
been submitted by Cresson. That patent referred to the paving mixture containing
natural rubber latexes as a polymer addition and cement was used as filler. In
following year (1924), Lefebvre patented the first concept of polymer modification
(Ohama, 1998). Since then, the development of polymer modification for cement,
mortar and concrete have been conducted in various countries for almost 70 years or
more. Currently, many effective polymer modification systems for cement mortar
and concrete have been developed and are used in various applications in the
construction industry.
Concrete is a strong and relatively cheap construction material and is
therefore presently the most widely used material in the construction industry. The
main constituent that contributes to concrete strength is Portland cement. It is
estimated that cement (Portland clinker) production alone contributes about 7% of
2
the global carbon dioxide emissions due to the burning of limestone and clay at a
temperature of 1500°C. During this process, calcium carbonate (CaCO3) is
converted to calcium oxide (CaO) and carbon dioxide is released (Worrell et al.,
2001). From an environmental standpoint, concrete does not appear to be a
sustainable material (Gerilla et al., 2007). Moreover, improperly manufactured
concrete may experience shorter service life as it can easily develop cracks due to
excessive loading applied and other environmental causes. A good quality of
concrete is needed which not only prolongs its service life but would also reduce the
production of cement. The main focus in this study is to develop a maintenance-free
self-healing concrete that can curtail the need for cement production as well as
reduce the carbon dioxide gas emissions in the atmosphere.
The major problem of concrete structures is cracking. A cracking of concrete
can cause greater damage such as corrosion of steel reinforcement that can lead to
the collapse of the structure. A number of cracks with different morphology and size
will appear during the construction and the design life of the structure. In various
environmental conditions, including temperature and humidity changes, the
formation and expansion of the cracks will lead to reinforcement corrosion and
reducing the load carrying capacity of the structure (Zhang et al., 2011). The
allowable crack appears to be limited to micro-cracks with width of up to 0.1 to
0.2mm (Li and Yang, 2007).
Small cracks or micro-cracks need to be repaired before they become a major
crack. There are many types of repair materials and methods that can be selected and
used for repairing micro-cracks. However, in certain cases micro-cracks will still
occur in the concrete structure. If the micro-crack cannot be repaired effectively, the
performance of the structure is affected and service life will be shortened. The cost
of repairing concrete is expensive as it requires many raw materials such as cement
and skilled labour. Therefore, the development of new technologies and materials
that can automatically repair cracks and restore/increase the strength of concrete
giving longevity to the structure is essentially needed. Such concrete material will
eventually reduce maintenance costs as well as fulfil the need for sustainability.
3
1.2 Problem Statement
In many concrete structures, tensile forces can lead to cracks and these can
occur relatively soon after the structure is built. Repair of conventional concrete
structures usually involves applying mortar which is bonded to the damaged surface.
Sometimes, the mortar needs to be keyed into the existing structure with metal pins
to ensure that it does not fall off. The bonding property between host concrete and
new repair materials needs to be carefully checked to avoid another problem leading
to extra repair cost. Repairs can be particularly time consuming and expensive; often
it is very difficult to gain access to the structure to make repairs, especially if they are
underground or at a great height.
The occurrence of autogenous healing or self-healing of cracks in concrete
was recognized in a previous study by Reinhardt and Jooss (2003). In their study,
they develop a high-strength concrete and tested on permeability and self-healing
behaviour of cracked concrete. The self-healing performance was checked at the
temperature between 20 °C and 80 °C and crack width between 0.05 and 0.20 mm.
On the other hand, the research of Jonkers and Schlangen (2008) had developed a
microorganism that can heal the cracks automatically. The concrete that can repair
the crack automatically is called self-healing concrete. Self-healing concrete refers
to the ability of concrete to automatically repair the cracks without any external
intervention. This phenomenon has been adapted from the human skin healing
process.
The bacteria used in some studies are known as microorganism that can
survive in alkaline environment of concrete, as long as the air is available. In most
of these studies, an ureolytic bacterium of the genus Bacillus was used as a healing
agent for the biological production of calcium carbonate. The mechanism of calcium
carbonate formation from the bacteria is based on the enzymatic hydrolysis of urea to
ammonia and carbon dioxide (Hager et al., 2010). This reaction causes pH to
increase from neutral to alkaline conditions resulting in the formation of bicarbonate
4
and carbonate ions which precipitate in the presence of calcium ions to form calcium
carbonate minerals (Jonkers et al., 2010). This method proved promising for
repairing cracks in concrete, allowing the concrete to regain strength and decrease
permeability. Many research studies have been conducted using bacteria as a self-
healing agent. Bacteria is a good self-healing agent but the acceptance of using it in
the concrete is been a big issue among contractor. The perceptions of using bacteria
in the concrete become a serious concern due to the bacteria itself that have a
negative effect to human health.
The epoxy resin without hardener is introduced in this study as an additive
material and self-healing agent in the mortar. Epoxy resin has been used as one of
the repair materials to repair concrete for many decades. The use of epoxy resin
which is an external repair process entails the injection of epoxy resin solution
together with a hardener into existing concrete structure cracks. This method is well
known and usually used for concrete structure repair suffering from cracks. Epoxy
resin with different level of viscosity can repair cracks with different widths. Upon
injection, the pressure applied leads the epoxy to flow through the cracks. In
addition to using epoxy resin as a repair material, it can also be used as an additive or
replacement material in concrete mixtures. The main advantage of epoxy resin is its
amazing compressive strength, which can achieve 80 MPa or greater for most
concrete (Kanerva et al., 1991). Usually, the use of epoxy resin with the hardener
has been common practice. The hardener functions as hardening agent to the epoxy
which strengthens the binders in concrete.
However in this study, the epoxy resin is used without hardener based on the
understanding that epoxy resin can harden inside the concrete by reacting with
hydroxyl ion. Hydroxyl ion is produced from cement hydration and reacts with
epoxy resin to heal the cracks. The rationale for not using hardener was to let the
epoxy resin stay in the same state for later when cracks occurred. The unhardened
epoxy resin would then react with the hydroxyl ion to fill up the cracks. Quite
limited studies have been conducted by using epoxy resin without hardener in
concrete mixture and as a healing agent. This reported research focused on the
5
engineering properties and self-healing performance of epoxy resin without hardener
as an additive and self-healing agent as well as the microstructure studies.
1.3 Aim of the Study
The main aim of this research is to investigate the performance of epoxy resin
without hardener as a healing agent in mortar.
1.4 Objectives of the Study
Several objectives can be drawn according to the problem statement. The
objectives are as follow:
i. To characterize the properties of materials use in the study including epoxy
resin, fine aggregates and Portland cement.
ii. To determine the optimum mix proportions of mortar using various epoxy-
cement ratios.
iii. To investigate the engineering properties of self-healing epoxy-modified
mortar.
iv. To investigate the mechanism of self-healing process of epoxy resin in
hardened mortar.
6
v. To evaluate the self-healing performance of epoxy-modified mortar using
microstructure study.
1.5 Research Question
Four major questions needed to be answered from this research:
i. What are the mechanical properties of mortar by using epoxy resin without
hardener?
ii. How epoxy resin without hardener can contribute to the strength of the
mortar?
iii. How does the mechanism of epoxy resin as a self-healing agent work to heal
the cracks?
iv. What is the microstructure morphology of mortar with epoxy resin without
hardener?
1.6 Scope and Limitation of Study
An epoxy resin with high viscosity namely Diglycidyl ether of bisphenol A
type was used. Only one type of polymer was used since this polymer provides high
reactivity even without hardener. The amount of epoxy resin without hardener was
added in the mortar mixture was 5%, 10%, 15% and 20% of cement content in order
to select the best amount of epoxy resin that can corporate as a healing agent inside
7
the mortar specimens. The epoxy resin was added as an addition material in the
mortar mixture so the mortar was categorized as a polymer-modified mortar or in this
research was called epoxy-modified mortar. There are two types of curing regime
applied to the mortar specimens which is dry curing and wet-dry curing. Various
tests were carried out to determine the characteristics of materials including
viscosity, Fourier transform infrared spectroscopy, X-ray fluorescence and sieve
analysis. The performance of the hardened mortar containing epoxy resin without
hardener was determined through compressive strength, flexural strength, splitting
tensile strength, initial surface absorption, water absorption, apparent porosity,
drying shrinkage and strength development. Furthermore, various techniques
including X-ray diffraction, scanning electron microscopy and thermogravimetric
analysis were used to study the microstructure of the hardened epoxy-modified
mortar. The ultrasonic pulse velocity, permeability, damage degree and healing
efficiency were conducted to determine the crack healing process by the epoxy resin
inside the cracked mortar specimens.
The main function of epoxy resin without hardener was to serve as self-
healing agent while producing high mechanical properties. The production of cracks
was generated by 50% and 80% of the ultimate load and was checked by using the
Ultrasonic Pulse Velocity (UPV) together with compressive strength test. the crack
was produced in epoxy-modified self-healing mortar at the age of 28 days, 180 days
and 365 days. The cube specimen of 70 mm × 70 mm × 70 mm size was used for
compressive strength test, 100 mm × 100 mm × 100 mm for self-healing evaluation,
40 mm × 40 mm × 160 mm prism for flexural strength test and cylindrical specimen
of Փ70 mm × 150 mm for splitting tensile test. Normal mortar was cast as a control
specimen and water curing was applied. The tests were conducted based on
American Standard Testing Method (ASTM) standard and British Standard (BS).
Some testing methods such as degree of hardening of epoxy resin were adopted from
previous researchers, since it was not stated in any other established standard.
8
1.7 Significance of Research
The programme of research significant is summarised in the flow chart shown
in Figure 1.1. The significant findings of this study by using epoxy resin without
hardener as a self-healing agent are as followed:
i. Enhance the service life of concrete structure by repairing micro-cracks
automatically before the cracks become worse and as result, the service life of
the concrete/mortar structure will be increase.
ii. Reduce the cost of repairs by self-healing repair phenomenon.
iii. Minimize environmental impact by reducing materials used for repair work
especially the production of cement that produce carbon dioxide gases.
iv. Develop a self-healing agent by using existing materials instead of bacteria.
SELF-HEALING EPOXY-
MODIFIED MORTAR
APPROACH
Addition of epoxy resin (5% – 20%)
PROPERTIES
Mortar strength > 30 MPa
Good performance in repairing cracks
BENEFITS
Reduce maintenance cost
Reduce environmental pollution
Prolong service life
PRODUCT FEATURES
Using epoxy resin without hardener
Automatic cracks repair
AUTOMATIC SELF-HEALING
MORTAR
Figure 1.1 Research Significant
9
1.8 Thesis Outline
Chapter 1 (Introduction): Chapter 1 discusses the background of the research
comprising the statement of problem, research objectives, research scope, the
significance of the research, and limitations of study.
Chapter 2 (Literature Review): Chapter 2 initially discusses the past research
from various researchers all around the world. The main focus is to identify
important performance criteria and test parameters that had been done and compared
with current research. This chapter then discusses the history, studies, science and
different approaches of self-healing performance and evaluation. The differing self-
healing performance evaluation methods are discussed by looking at the different
healing agents that each researcher had reported.
Chapter 3 (Methodology): Chapter 3 focuses on testing method that had been
conducted in order to evaluate the performance of epoxy-modified mortar. The
methodology is separated into three parts: a) fresh properties of epoxy-modified
mortar, b) hardened properties, and c) self-healing evaluation. All the testing
methods and parameters are discussed in this chapter.
Chapter 4 (Engineering Properties of Epoxy-Modified Mortar): Chapter 4
reports and explains the analyses undertaken for achieving the first, second and third
objectives of this research. The results of material properties and engineering
performance of epoxy-resin without hardener are discussed in this chapter. Some
sections from objective 5 based on microstructure morphology are also included.
Chapter 5 (Evaluation of Self-Healing Epoxy-Modified Mortar): Chapter 5
discusses the self-healing performance of epoxy-modified mortar as to achieve the
10
Objectives 4 and 5. The correlation analysis was carried out in order to evaluate an
epoxy resin as a self-healing agent.
Chapter 6 (Conclusions and Recommendations): Chapter 6 concludes the
findings of the overall research work that was undertaken. The contribution and
implications of the findings toward the construction industry in general and
performance evaluation in particular are explained. The limitations and possible
improvements for future undertakings are also discussed. Suggestions for future
research are conveyed in the final part of this chapter.
171
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