Sample Thesis PDF

Department of Civil Engineering,
College of Engineering,
King Saud University,
Riyadh, Kingdom of Saudi Arabia
EFFECT OF SUPPLEMENTARY CEMENTITIOUS MATERIALS ON THE

QUALITY OF PROTECTIVE PASSIVE LAYER DEVELOPED ON STEEL
REBARS
Submitted in partial fulfillment of the requirements for the Masters degree in the Department of
Civil Engineering at the College of Engineering at
King Saud University
Muhammad Shoaib Ashraf
Supervised by:
Prof. Abdulrahman M. Alhozaimy
Dr. Raja Rizwan Hussain
Jun 2014
KING SAUD UNIVERSITY

RIYADH, 11421 SAUDI ARABIA
DEANSHIP OF GRADUATE STUDIES
EFFECT OF SUPPLEMENTARY CEMENTITIOUS MATERIALS ON THE
QUALITY OF PROTECTIVE PASSIVE LAYER DEVELOPED ON STEEL
REBARS
By
Muhammad Shoaib Ashraf s/o Muhammad Ashraf
This thesis was defended and approved on 2nd Jun 2014 (4-Shaaban-1435H)
Supervisor Co-Supervisor
Prof. Abdulrahman M. Alhozaimy

Civil Engineering Department Assoc. Prof. Raja Rizwan
King Saud University Hussain
CoE-CRT, Civil Engineering
Department
Members of examination committee
Prof. Abdulaziz I. Al- Negheimish Prof. Muhammad Iqbal Khan

Civil Engineering Department Civil Engineering Department
King Saud University King Saud University
Prof. M. Jamal M. Al-Shannag

Civil Engineering Department
Authors Declaration
It is hereby declared that all the information in this manuscript has been gathered and presented
as per the academic rules and ethical conduct. It is also stated that the referred results and ideas
have been cited and referenced.
Muhammad Shoaib Ashraf
Signature:
i
Abstract
Corrosion of reinforcing steel is the leading cause of deterioration in concrete. When steel
corrodes, the resulting rust occupies a greater volume than the steel. This expansion creates tensile
stresses in the concrete, which can eventually cause cracking, delamination or spalling. It is well
established fact that a thin oxide passive layer in the nano-meter range forms on the steel rebars
and prevents the steel from corrosion. However, the severity in environment (chloride ions, hot
weather, high humidity, carbonation etc.) reduces the passiveness and corrosion resistance of steel
reinforced concrete. Supplementary cementitious materials (SCMs) are used as partial cement
replacement in concrete structures. Low permeability concrete can be attained by using SCMs.
They also increase the concrete resistivity, thus reducing the corrosion rate. However, there is
limited research on the effect of SCMs for the development and quality of passive film itself.
Electrochemical Impedance Spectroscopic (EIS) techniques are one of the most powerful and
reliable methods to investigate the state of passivation and for the corrosion studies of steel.
Therefore, this research covered the investigation of the formation of protective passive layer on
steel reinforcement bars embedded in mortar under the effect of the SCMs by using the EIS
technique. Two locally available steel rebar sources were used that are most commonly utilized in
the construction industry of the Kingdom of Saudi Arabia. Each of these two rebars was tested for
polished as well as unpolished surface conditions. Rebar passivation was investigated in simulated
concrete pore solution with the addition of varying dosages of SCMs. In addition to that, mortar
specimens were also cast using fly ash, silica fume and natural pozzolans. Steel rebras were
embedded in the mortar specimens and then EIS investigations were carried out.
Experiment results showed that natural pozzolans improved the quality of the passive layer by
filling the voids, depositing another film on the passive layer and increasing the thickness of the
passive layer. Whereas, addition of silica fume reduced the quality of the passive layer by
decreasing the pH value of the pore solution, and leaving voids and cracks in the passive layer. Fly
ash also improved the passive layer quality, however, the improvement was relatively less than
that of natural pozzolans.
ii

( )Passive Layer
( )SCMs
. SCMs
( )EIS
( )Passive Layer .
( )pH .
iii
iv
Dedication
I dedicate my work to
my loving parents,
Mr. & Mrs. Muhammad Ashraf,
respectable teachers,
siblings,
and friends.
Their continued efforts and prays have made me stand tall amidst the time of difficulties.
iv
Acknowledgments
All praises and thanks to Almighty Allah, the merciful, the only creator of the universe and source
of all knowledge and wisdom, who blessed me with health, thoughts, and nice teachers, helping
friends and the afforded opportunity to complete this study. I offer my humblest thanks to the Holy
Prophet Hazrat Muhammad (SAW) whos moral and spiritual teachings enlightened my heart,
mind and flourished my thoughts towards achieving high ideals of life.
I am pleased to express my cordial gratitude for the kindest efforts and supports of my supervisors,
Professor Dr. Abdulrahman M. Alhozaimy and Dr. Raja Rizwan Hussain. It was their precious
guidance and encouragement which made me through the procedure of completing this research.
I am indebted to them for good to make my path lit, particularly in harsh times.
The cooperation of my respectable teachers Dr. Muhammad Iqbal Khan and Prof.
Abdulaziz Ibrahim Al-Negheimish, especially at the crucial times, was vital to make the whole
thing into a success.
My gratitude extends to my brother Dr. M. Shafqat Ali and my friends Mr. Wasim Abbas and
Mr. Fahid Aslam for their help and guidance. They helped me to keep my spirit up and do justice
with the job. Their sincere efforts and support is invaluable to me for good.
It is also my privilege to take the opportunity to thank all the researchers and supporting staff,
including Engr. Zafarullah Qadri and especially Dr. Galal Faris at the Center of Excellence for
Concrete Research and Testing (CoE-CRT), for valuable help in this research.
Mr. Tufail, Mr. Alla-Ud-Deen, Mr. Sanaullah, and Mr. Muhammad Bakr in the lab as
technical associates made my work seem easier through their steady support and cooperation.
Finally and importantly, for the provision of all the facilities and commodities aiding to the
research work, I am thankful to the Department of Civil Engineering at College of Engineering,
King Saud University.
v
Table of Contents
Authors declaration .. i
Abstract ............ ii
........ iii
Acknowledgement ... iv
CHAPTER 1. INTRODUCTION ........................................................................................... 1

1.1 General .............................................................................................................................. 1
1.2 Problem Statement ............................................................................................................ 2
1.3 Research Objectives.......................................................................................................... 2
1.4 Thesis Outline ................................................................................................................... 2
CHAPTER 2. LITERATURE REVIEW ............................................................................... 4
2.1 General .............................................................................................................................. 4
2.2 Corrosion of Steel in Concrete ......................................................................................... 4
2.3 Supplementary Cementitious Materials (SCMs) .............................................................. 6
2.3.1 Fly Ash ...................................................................................................................... 7
2.3.2 Silica Fume ............................................................................................................... 9
2.3.3 Natural Pozzolan ..................................................................................................... 11
2.4 Steel Rebars .................................................................................................................... 12
2.4.1 Alloying Steel ......................................................................................................... 13
2.4.2 Quenched Steel (TM-PF Ring) ............................................................................... 13
2.5 Mill-Scale ....................................................................................................................... 14
2.6 Environment around Steel Rebars (SPS and Mortar) ..................................................... 15
2.7 Passive Layer .................................................................................................................. 17
2.8 Electrochemical Techniques to Monitor the Passive Film Formation ............................ 20
2.8.1 Potentiostat EIS Studies .......................................................................................... 22
2.8.2 Corrosion Potential ................................................................................................. 26
2.8.3 Tafel Scan ............................................................................................................... 27
2.9 Literature Review on Passive Layer using Electrochemical Techniques ....................... 30
2.10 Originality and Novelty of this Research ........................Error! Bookmark not defined.
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CHAPTER 3. EXPERIMENTAL PROGRAM, MATERIALS and METHODOLOGY
. 35
3.1 Experimental Program .................................................................................................... 35
3.2 Materials ......................................................................................................................... 37
3.2.1 Steel Rebars ............................................................................................................ 37
3.2.2 Cement and Sand .................................................................................................... 38
3.2.3 Supplementary Cementitious Materials (SCMs) .................................................... 39
3.3 Methodology & Testing Procedures ............................................................................... 40
3.3.1 Simulated Concrete Pore Solution Preparation....................................................... 40
3.3.2 Specimen Preparation ............................................................................................. 41
3.3.3 Electrochemical Studies .......................................................................................... 44
3.3.4 Field Emission Gun Scanning Electron Microscopy (FEG-SEM) Studies ............ 46
3.3.5 Energy Dispersive Spectroscopy/Energy Dispersive X-ray (EDS/EDX) ............... 47
CHAPTER 4. RESULTS AND DISCUSSIONS .................................................................. 48
4.1 General ............................................................................................................................ 48
4.2 Effect of SCMs on the Development of Passive Layer on Steel Rebars ........................ 48
4.2.1 EIS Results .............................................................................................................. 49
4.2.2 Half-Cell Potential Results ..................................................................................... 51
4.2.3 Tafel Scan Results................................................................................................... 53
4.2.4 Scanning Electron Microscopy (SEM) Results ...................................................... 57
4.2.5 Energy-Dispersive X-ray Spectroscopy (EDs) Results .......................................... 59
4.2.6 Discussion on Results of Effect of SCMs on the Passive Layer ............................ 62
4.3 Effect of SCMs on Passive Layer Developed on Different Steel Sources ..................... 65
4.3.1 EIS Results .............................................................................................................. 65
4.3.3 Tafel Scan ............................................................................................................... 70
4.3.5 Energy-Dispersive X-ray Spectroscopy (EDS) Results .......................................... 76
4.3.6 4.3.6 Discussion on Results of Effect of SCMs on Steel Sources .......................... 78
4.4 Effect of SCMs on Passive Layer Developed on Different Surface Conditions of Steel
Rebars ............................................................................................................................. 80
4.4.1 EIS Results .............................................................................................................. 81
vii
4.4.3 Tafel Scan ............................................................................................................... 86
4.4.5 EDS Results ............................................................................................................ 92
4.4.6 Discussion on the Results of Effect of SCMs on the Surface Condition ................ 93
4.5 Effect of Environment (Simulated Concrete Pore Solution and Mortar) on the
Performance of the SCMs on the Passive Layer Developed on Steel Reabrs ................ 96
4.5.1 EIS Results .............................................................................................................. 96
4.5.2 Half-Cell Potential Results ................................................................................... 100
4.5.3 Tafel Scan ............................................................................................................. 102
4.5.4 Discussion on the Results of Effect of Environment on the performance SCMs on
the Development of Passive Layer ...................................................................................... 106
CHAPTER 5. CONCLUSIONS AND RECOMMENDATIONS .................................... 110
5.1 Conclusions................................................................................................................... 110
5.2 Future Recommendations ............................................................................................. 111
References ..... 115
Appendices 124
Appendix A .... 124
Appendix B ........................................................................................ 127
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List of Tables
Table 3.1 Mechanical properties of steel rebar from both sources .. 38
Table 3.2 Compositional analysis of steel rebars . 38
Table 3.3 chemical composition of cement . 39
Table 0.4 Chemical properties of SCMs .. 39
Table 4.1 Elemental composition of passive layer developed on steel rebars in different solutions
from EDS analyses ... 61
Table 0.2 Rakings of passive layer quality immersed in different solutions ... 62
Table 0.3 pH values of solutions .. 64

Table 0.4 Rankings of passive layer quality developed on different steel sources .. 79
Table 0.5 Rankings of passive layer quality developed on different surfaces of rebar ... 95
Table 0.6 Rankings of passive layer quality developed in different SCMs ... 108
Table 0.7 Ranking of passive layer quality based on environment (SPS and mortar) ... 109
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List of Figures
Figure 2.1 Corrosion process of steel rebar 6
Figure 2.2 Protective passive layer on steel rebar embedded in concrete.... 18
Figure 2.3 The Randles equivalent circuit for a corroding interface ... 24
Figure 2.4 Example Bode plot . 25
Figure 2.5 Example Nyquist plot . 25
Figure 2.6 Classic Tafel analysis . 28
Figure 3.1 Experimental program .... 36
Figure 3.2 Nital solution treatment of two steel rebars .... 37
Figure 3.3 Particle size distribution curves of SCMs .. 40
Figure 3.4 Pore solution under continuous magnetic stirring ...... 41
Figure 3.5 Steel rebars used (polished and unpolished) .. 42
Figure 3.6 SPS specimen configuration and setup ... 43
Figure 3.7 configuration of the tested mortar specimen....... 44
Figure 3.8 Gamry potentiostat . 45
Figure 3.9 Field Emission Gun Scanning Electron Microscopy (FEG-SEM) . 47
Figure 4.1(a) Bode plot after 24 hours of exposure ..... 49
Figure 4.1(b) Bode plot after 15 days of exposure ...... 49
Figure 4.1 Bode plots after different time of exposure .... 49
Figure 4.2 Comparison of SCMs for impedance variation with time of exposure .. 51
Figure 4.3 Half-Cell Potential Variation with time of exposure .. 52
Figure 4.4(a) Tafel curve after 24 hours of exposure .. 54
Figure 4.4(b) Tafel curve after 15 days of exposure ... 54
Figure 4.4 Tafel scan curve for the SCMs at different time of exposures ... 54
Figure 4.5 Corrosion Current Variation with time of exposure ... 56
Figure 4.6(a) SEM image of steel sample in Control solution ........ 57
Figure 4.6 (b) SEM image of steel sample in NP solution .......... 58
Figure 4.6 (c) SEM image of steel sample in FA solution ...... 58
x
Figure 4.6 (d) SEM image of steel sample in SF solution ........... 58
Figure 4.6 SEM Image of different steel surfaces immersed in SCMs ....... 58
Figure 4.7(a) EDS analysis steel sample in Control solution .. 59
Figure 4.7(b) EDS analysis steel sample in NP solution . 60
Figure 4.7(c) EDS analysis steel sample in Control solution ...... 60
Figure 4.7(d) EDS analysis of SF .... 61
Figure 4.7 EDS analysis of different steel surfaces immersed in SCMs solutions ...... 61
Figure 4.8(a) Impedance .. 63
Figure 4.8(b) Half-cell potential .. 63
Figure 4.8(c) Corrosion current ... 63
Figure 4.8 Different electrochemical techniques results of effect of SCMs on development of
passive layer after 15 days .... 63
Figure 4.9(a) Bode plot after 24 hours of immersion ...... 66
Figure 4.9(b) Bode plot after 15 days of immersion ........ 67
Figure 4.9 Bode plot after different time of exposure for the Effect of steel source ... 67
Figure 4.10(a) Comparison in Control solution ... 67
Figure 4.10(b) Comparison in NP solution ...... 68
Figure 4.10(c) Comparison in FA solution ...... 68
Figure 4.10(d) Comparison in SF solution .. 68
Figure 4.10 Effect of SCMs on development of passive layer on different steel type .... 68
Figure 4.11(a) Comparison in Control solution ....... 69
Figure 4.11(d) Comparison in SF solution ...... 70
Figure 4.11 Potential variation with time of exposure for the effect of SCMs on development of
passive layer on different steel type .. 70
Figure 4.12(a) Tafel curve after 24 hours of exposure .... 72
Figure 4.12(b) Tafel curve after 8 days of exposure ....... 72
xi
Figure 4.12 Tafel scan curve after different time of exposure for the effect of SCMs on steel
source .... 72
Figure 4.13(b) Comparison in NP solution .. 74
Figure 4.13(d) Comparison in SF solution .......... 75
Figure 4.13 Corrosion current variation with time of exposure for the effect of SCMs on
development of passive layer on different steel type ........ 75
Figure 4.14(a) SEM Image of steel source A ... 76
Figure 4.14 (b) SEM Image of steel source B .. 76
Figure 4.14 SEM Image of different steel sources immersed in SCMs ... 76
Figure 4.15(a) EDS Image of steel source A 77
Figure 4.15 (b) EDS Image of steel source B ... 78
Figure 4.15 EDS Image of different steel sources immersed in SCMs ... 78
Figure 4.16 Schematic diagram of passivation of steel source A and B .. 80
Figure 4.17(a) Bode plot after 24 hours of immersion .... 83
Figure 4.17(b). Bode plot after 15 days of immersion .... 82
Figure 4.17 Bode plot after different time of exposure for the effect of SCMs on surface
condition ... 82
Figure 4.18(c) Comparison in FA solution .. 84
Figure 4.18(d) comparison in SF solution ........... 84
Figure 4.18 Impedance variation with time of exposure for the effect of SCMs on steel surface
condition.... 84
Figure 4.19(c) Comparison in FA solution .. 86
Figure 4.19(d) Comparison in SF solution ...... 86
xii
Figure 4.19 Potential variation with time of exposure for the effect of SCMs on steel surface
condition ... 86
Figure 4.20(a) Tafel curve after 24 hours of exposure .... 87
Figure 4.20(b) Tafel curve after 15 days of exposure ...... 88
Figure 4.20 Tafel scan curve after different time of exposure for the effect of SCMs on surface
condition of steel rebars..... 88
Figure 4.21(b) Comparison in NP solution .......... 89
Figure 4.21(c) Comparison in FA solution .............. 90
Figure 4.21(d) Comparison in SF solution .............. 90
Figure 4.21 Corrosion current variation with time of exposure for the effect of SCMs on steel
surface condition ....... 90
Figure 4.22(a) SEM Image in Control solution ....... 91
Figure 4.22(b) SEM Image in fly ash solution .... 91
Figure 4.22(c) SEM Image in natural pozzolans solution ... 92
Figure 4.22(d) SEM Image in silica fume solution ..... 92
Figure 4.22 SEM Image of different steel surfaces immersed in SCMs ..... 92
Figure 4.23(a) EDS analysis of Control solution ..... 93
Figure 4.23 (b) EDS analysis in NP solution ... 94
Figure 4.23 EDS analysis of different steel surfaces immersed in SCMs ... 94
Figure 4.24(a) Bode plot after 24 hours of immersion ........ 98
Figure 4.24(b). Bode plot after 15 days of immersion ......... 98
Figure 4.24 Bode plot after different time of exposure for different environments .... 98
Figure 4.25(a) Control ......... 99
Figure 4.25(b) NP ........ 99
Figure 4.25(c) FA ...... 100
Figure 4.25(d) SF ....... 101
Figure 4.25 Impedance variation comparison with time for exposure to mortar and SPS
environments on the performance of SCMs.... 101
Figure 4.26(a) Control ....... 102
xiii
Figure 4.26(b) NP .......... 102
Figure 4.26(c) FA ....... 103
Figure 4.26(d) SF ....... 103
Figure 4.26 Potential variation comparisons with time for exposure to mortar and SPS
environments on the performance of SCMs ....... 103
Figure 4.27(a) Tafel curve after 24 hours of exposure ...... 104
Figure 4.27(b) Tafel curve after 18 days of exposure ........ 105
Figure 4.27 Tafel scan curve after different time of exposure for the effect of environment on the
performance of SCMs ......... 105
Figure 4.28(a) Control ... 106
Figure 4.28(b) NP ...... 107
Figure 4.28(c) FA ....... 107
Figure 4.28(d) SF ........... 107
Figure 4.28 Corrosion current comparison with time for exposure to mortar and SPS
environments on the performance of SCMs ....... 107
xiv
CHAPTER 1. INTRODUCTION
1.1 General
Corrosion of reinforcing steel rebars in the concrete in severe environmental conditions, such
as severe hot weather conditions, is a major concern regarding the structural durability worldwide,
especially in Kingdom of Saudi Arabia. Chloride ions from the environment and already available
in the concrete components accelerate the deterioration process by depassivating the protective
film formed on the surface of steel rebar. Due to high pH value of concrete at the time of
construction, a thin oxide layer forms on the steel rebar surface, which prevents the steel rebar
from corrosion. This thin oxide film is called passive layer. The concrete pore solution is saturated
calcium hydroxide, containing small percentages of other alkali ions, such as sodium and
potassium ions, which maintain a pH value balance between 12.5 and 13.5. Under these pH levels,
the steel rebar attains a high potential that leads to passivity a condition of resistance for an active
steel rebar caused by the formation of a thin surface film on the steel rebar. The thickness of the
passive layer is normally very small (5 to 15 nanometers), and primarily composed of oxides of
iron. There is very limited literature available on the passive film and its chemical composition,
and structure, as well as its breaking process.
Supplementary cementitious materials (SCMs) are the additives added to the mixture of the
concrete, as a partial cement replacement to enhance fresh and hardened properties of the concrete
such as workability, compressive strength and durability. These materials are normally the
byproducts of the different industries, such as fly ash, silica fume and blast furnace slag. Other
SCMs are natural pozzolans, such as calcined clay, matakaoline, volcanic tuffs, etc. The influence
of these SCMs for the replacement of the ordinary Portland cement for the corrosion resistance of
1
the rebars is studied by several researchers (Thomas et al., 2012 and Muralidharan et al., 2008).
Many studies on this issue indicated that the use of SCMs reduces the rate of corrosion of rebars,
which could be due to the high density, low porosity and permeability resulted in resistance against
chloride penetration in the concrete (Al-Chaar et al., 2013 and Foroughi et al., 2012). However, a
very limited literature is available on the effect of these SCMs on the formation of the passive
layer.
1.2 Problem Statement
Supplementary Cementitious Materials (SCMs) are believed to increase the corrosion
resistance of the concrete structure by providing denser concrete and reducing the chloride
penetration from the environment. However, the effect of the SCMs on the passive layer is not yet
studied. So, in this research the effect of SCMs on the formation of passive layer is investigated.
1.3 Research Objectives
The main objective of this research program is to investigate the effect of SCMs on the
development and quality of passive layer formed on the steel rebars using electrochemical
techniques. The study covered the following parameters:
a. Three types of SCMs (fly ash, silica fume, and natural pozzolans) as the partial
cement replacement.
b. Two steel rebars sources (TMT steel and low alloy steel) most commonly used in
the kingdom of Saudi Arabia.
c. Two surface condition of the rebars (as received vs polished).
1.4 Thesis Outline
The thesis is divided into five chapters. A brief description of each chapter is given below:
2
Chapter 1: A brief discussion about the passive layer, corrosion and its effects on durability of
reinforced concrete is presented in this chapter. The objectives of the research are also defined.
Chapter 2: This chapter summarily presents the literature survey on the reinforced concrete
regarding passive layer, corrosion and SCMs.
Chapter 3: Description of the proposed research plan, methodology, process, specimens and
equipment used are described in this chapter.
Chapter 4: This chapter describes the results obtained from this research and detailed discussion
on the state-of-the-art analysis.
Chapter 5: This chapter consists of conclusions and future recommendations.
3
CHAPTER 2. LITERATURE REVIEW
2.1 General
In this chapter, a comprehensive literature review is presented about the passive layer, effect
of SCMs on the corrosion resistance of concrete, manufacturing process and chemical composition
of different steel types, mill scale, its composition and its effect on passivation. Electrochemical
techniques used to investigate the quality of passive layer are also discussed. Passive layer
development and corrosion of steel rebars can be investigated in simulated concrete pore solution
(SPS) or in actual concrete/ mortar and difference of both environmental conditions (SPS and
mortar) is also described.
2.2 Corrosion of Steel in Concrete
Corrosion of steel rebar is one of the major cause of deterioration in the reinforced concrete
structures. When steel rebars corrode, the resulting rust products occupy greater volume than the
steel rebars. This expansion due to increased volume creates tensile stresses in the concrete, which
can eventually cause cracking, delamination and spalling of the concrete cover (Diefenderfer,
1998).
For corrosion to occur, the following elements must be present:
1. There must be at least two metals (or two locations on a single metal) at different energy
levels
2. An electrolyte
3. A metallic connection
4
In reinforced concrete, the steel rebar may have many separate areas at different energy levels.
Concrete acts as an electrolyte, and the metallic connection is provided by wire ties, chair supports,
or the steel rebar itself (Jones, 1996).
Corrosion is an electrochemical process, involving the flow of charges (electrons and ions).
As shown in Figure 2.1, at active sites on the steel rebar, called anodes, iron atoms lose electrons
and move into the surrounding concrete as ferrous ions. This process is called as a half-cell
oxidation reaction, or anodic reaction, and is represented as in Equation 2.1:
2Fe 2Fe2+ + 4e- (2.1)
The electrons remain in the steel rebar and flow to sites called cathodes, where they combine with
water and oxygen in the concrete. The reaction at the cathode is called as a reduction reaction. A
common reduction reaction is (Equation 2.2):
2H2O + O2 + 4e- 4OH-- (2.2)
To maintain electrical neutrality, the ferrous ions migrate through the concrete pore water to these
cathodic sites where they combine to form iron hydroxides, or rust (Equation 2.3):
2Fe2+ + 4OH- 2Fe(OH)2 - (2.3)
This initial precipitated hydroxide tends to react further with oxygen to form higher oxides.
The volume increases as the reaction products react further with dissolved oxygen, leads to internal
circumferential stress within the concrete that may be sufficient to cause cracking and spalling of
the concrete cover.
5
Figure 2.1Corrosion process of steel rebar (Clear, 2000)
The corrosion of steel rebars in the concrete can be reduced by placing the high quality crack-
free concrete with low permeability and sufficient concrete cover. The low-permeability concrete
can be obtained by decreasing the water to cementitious materials ratio in the concrete mixture
and/or the use of SCMs. SCMs also increase the concrete resistivity against chloride ion
penetration, resulting in reduced the corrosion rate. ACI 318-2014 (Building Code Requirements
for Structural Concrete) suggests the minimum concrete cover requirements to help in protecting
the embedded steel rebars. Additional measures to mitigate the corrosion of steel rebars in the
concrete include the use of corrosion inhibiting admixtures, coating of reinforcement (such as
epoxy resin coating) and the use of sealers and impervious membranes on the concrete surface
(Clear, 2000).
2.3 Supplementary Cementitious Materials (SCMs)
Supplementary Cementitious Materials (SCMs) are the additives added in the concrete mix,
as a partial replacement of cement. These are normally byproducts of different industries, such as
fly ash, silica fume and blast furnace slag, etc. Other SCMs are natural pozzolans, such as calcined
clay, metakaoline, volcanic tuffs, etc. are also being used in the concrete construction industry.
6
Their judicious use in the concrete production is desirable both for environmental and energy
conservation, as well as for their technical benefits. SCMs also help to decrease the steel rebar
corrosion rates in concrete by improving the resistivity of concrete as compared to regular concrete
at same temperature and relative humidity. However, these findings are, in most of the cases, not
directly related to passivation of the steel rebars.
2.3.1 Fly Ash
Fly ash is a byproduct of electrical coal-fired power plants and can vary widely depending
on the source. It should meet the requirements of ASTM C 618 Standards, which classified fly ash
into two main classes - Class F and Class C. Fly ash particles are usually similar to cement particles
and most of the fly ash particles are spherical in shape. The Class C fly ash content of concrete
generally ranges from 15% to 40 % of the total cementitious material. Whereas, the Class F content
normally ranges from 15% to 25% of the total cementitious material. Addition of Fly ash in the
concrete usually reduces bleeding, increases initial and final setting time, improves workability,
reduces segregation in the plastic concrete, increases ultimate strength, reduces drying shrinkage,
lowers the heat of hydration, and reduces permeability and improve durability of concrete (Juenger
et al., 2006).
Extensive literature is available on the effect of fly ash on the corrosion of steel rebars
embedded in the concrete. Tae-Hyun et al. (2007) investigated the influence of fly ash on the
corrosion performance of steel in mortar and concrete. Electrochemical techniques, such as open
circuit potential measurements and anodic polarization studies were carried out. The fly ash
replacement levels namely 10%, 20%, 30% and 40% with respect to Ordinary Portland Cement
(OPC) was chosen for the study and the results were compared with OPC specimens without FA.
The results showed that the addition of fly ash decreases the pH of the concrete but still remains
7
above the threshold value (11.5) of the breakage of the passive film. It was concluded that 30 %
replacement of fly ash increases the corrosion resistance properties. Saraswathy and Song (2006)
used the electrochemical techniques, such as impedance linear polarization measurements, open
circuit potential, along with other techniques, such as mass loss and Scanning Electron Microscopy
(SEM) to evaluate the corrosion resistance of the concrete by replacing cement with fly ash from
10% to 40%. Results from this study confirmed that up to a critical level of 2030% replacement,
activated fly ash improved the corrosion resistance properties of the concrete.
Choi et al. (2006) investigated the effect of fly ash replacement in concrete on the
embedded steel rebars under the complete immersion in 3.5 % by weight NaCl solution. Three
techniques, open-circuit potential, polarization resistance measurement and electrochemical
impedance spectroscopy (EIS) were used to investigate the corrosion behavior of the steel rebar.
The results showed that the partial replacement of fly ash has led to an enhancement of the
corrosion resistance and a reduction of the corrosion rate because of a decrease in the permeability
of the concrete against chloride ions. Auger Electron Spectroscopy (AES) and X-ray Photoelectron
Spectroscopy (XPS) were used to study the effect of chloride ions (Cl) and fly ash on the behavior
of the passive film, formed on steel rebar in solutions simulating the concrete interstitial electrolyte
by Montemor (1998). Results showed the presence of fly ash and of Cl led to increase in the
amount of iron oxyhydroxide (FeOOH) in the outer layers of the passive film and to increase in
the thickness the passive film. Significant differences in the composition and thickness were
observed between the passive films formation in paste solutions and in calcium hydroxide (Ca
(OH) 2) solutions. In another research by Montemor (2000), during experimentation the corrosion
process of the steel rebars embedded in the concrete, with various amounts of fly ash (up to 50%
of the total binder), was tested for a complete and a partial immersion in the sodium chloride
8
(NaCl) solution. The corrosion process was followed by monitoring of the Open Circuit Potential
(OCP) and Electrochemical Impedance Spectroscopy (EIS). By adding Fly ash, the concrete
resistivity increased significantly and as a result of it the time for corrosion initiation also
increased, along with a decrease of corrosion rate
2.3.2 Silica Fume
Silica fume, also referred to as micro silica or condensed silica fume, is a byproduct
material used as a pozzolanic material. This byproduct is a result of the reduction of high-purity
quartz with coal in an electric arc furnace in the manufacturing of silicon or ferro-silicon alloy.
Silica fume is used to meet the requirements of a high strength and low permeable concrete. It has
been used to produce concrete with compressive strengths as high as 140 MPa. It should meet the
requirements of ASTM C 1240 Standards. Silica fume has spherical shape particles. It is extremely
fine with average particles size less the 1 m diameter. There are several benefits of using silica
fume in the concrete, such as reduced permeability of concrete, improves bonding within the
concrete, improves resistance to corrosion of steel rebars in concrete, can reduce alkali-silica
reactivity (ASR), increased compressive and flexural strengths, and increased durability
(concreteconstruction.net). The applications of the use of silica fume include; high-strength
structural columns, low permeable parking garage decks, and abrasion resistant hydraulic
structures.
Replacement of silica fume up to 8 percent by weight of Ordinary Portland Cement (OPC)
improved the corrosion resistance properties of steel in mortar and concrete (Muralidharan et al.,
2003). Silica-fume has both positive and negative effects on the different factors governing the
steel rebar corrosion. However, advantages are by far dominated over the disadvantages. Silica
fume has a positive effect like reduction in the risk of corrosion and rate of corrosion, provided
9
that normal good workmanship is carried out. Silica fume is not used in very low-quality concrete
to reduce the cement content (Muralidharan et al., 2008). Thomas et al. (2012) found that silica
fume reduced the chloride binding capacity of the binder, leaving more chlorides to attack the steel
rebars; however, silica fume improved the resistance against chloride ingress. Muralidharan et al.
(2003) conducted a study by varying replacement dosages of silica fume with cementitious
material i.e. from 2 % to 12% by weight of cement. They used open circuit potential and anodic
polarization techniques along with the mass loss technique and concluded that additions of silica
fume up to 8 percent by weight of Ordinary Portland cement (OPC) improved the corrosion
resistance properties of steel in mortar and concrete. According to Cao and Sirivivatnanon (2006),
use of 10 percent silica fume, as a cement replacement material in making 70 MPa concrete can
have beneficial effect to reduce the corrosion rate but there can be adverse effect if silica fume
used at a higher replacement level more than 20 percent.
The use of silica fume effects the pH of the concrete pore solution, as investigated in couple
of studies. Muralidharan et al. (2008) investigated the effect of the silica fume on the pH value.
Different dosages (from 2 % to 15 %) of silica fume were investigated and variation of pH was
measured and it was found that the silica fume reduces the pH value in the concrete mixture. The
reduction in pH was small when the dosage was up to 8 %; however, for 10% and higher, the
drastic changes in the pH value were observed. During the chemical reaction between silica fume
and components in the pore water, the content of components especially calcium hydroxide and
potassium keeping a high pH value reduced. The reason for pH reduction above 10 % silica fume
level could be due to gradual depletion of calcium hydroxide with higher silica fume contents
Silica fume has a much higher effect on pH reduction as compared with other mineral admixtures,
such as fly ashes and natural pozzolans. Byfors K. (1986) also investigated the effect of the fly ash
10
and silica fume on the pH of the pore solution. Experimentation was carried out for 10 %, 20 %
silica fume addition and fly ash was added 15% and 40%. The measurement of pressed out of the
cement paste (pore solution extracted from mortar by compressing) indicated that silica fume
reduces the pH by 0.7 units. This indicates that silica fume reacts with NaOH, KOH and Ca(OH)2.
Fly ash causes a small reduction in the pH by 0.3 units. It was concluded by the authors that the
alkalis included in the fly ash do not cause any noteworthy increase in the pore solution
concentration of alkali, thus, of the pH value. Nor does the fly ash appear to reduce the pH value
of the pore solution to any significant extent by chemically reacting with the hydration products,
at least not to the same extent as does silica fume
2.3.3 Natural Pozzolan
When the natural pozzolans materials are used in conjunction with Portland cement, they
contribute to the properties of the hardened concrete through hydraulic or pozzolanic activity, or
both. The major sources of natural pozzolans are volcanic ash, volcanic tuff, and pumicite
pozzolans. These are siliceous or aluminous materials, which possess little or no cementitious
value; but in finely divided form and in the presence of moisture, they chemically react with
calcium hydroxide (Ca(OH)2) to form compounds possessing hydraulic cementitious properties
(Al-Chaar et. Al ,2013). The pozzolonic reaction can be defined as:
Calcium Hydroxide+Silica+Water Calcium-Silicate-Hydrate (C-S-H)
C-S-H provides the hydraulic binding property of the material
Natural pozzolans, based upon their lime-reactive constituents, can be divided into four categories,
(a) unaltered volcanic glass (b) volcanic tuff (c) calcined clay or shale (d) raw or calcined opaline
silica (Mehta, 1987). However, this above proposed classification is not applicable to pozzolans
11
obtained from the category (a) and (b) volcanic origins, as the volcanic tuffs usually include both
altered and unaltered siliceous glass (Mehta, 1987). Mielenz et al., (1950) had also proposed
another classification for Natural Pozzolans (NP)s based on their identity of the pozzolanic
constituents. The materials in which the pozzolanic activity induced by calcination can be
classified as; (a) volcanic glass (b) opal, clays and Zeolites (c) hydrated oxides of aluminum. In
Kingdom of Saudi Arabia (KSA), natural pozzolans normally exist in consolidated rock-like
forms, such as volcanic tuffs and scoria (Khan and Alhozaimy, 2011).
Fajardo et al., (2009) used natural pozzolans as a partial substitute of normal Portland cement
in the reinforced mortar specimens. Compositions with substitution levels of 0%, 10% and 20%
by mass of normal Portland cement of natural pozzolans were investigated. The specimens were
exposed to penetration of chlorides for 100 days. Compressive strength, corrosion potential,
polarization resistance, electrical resistivity and chloride content of the mortars were determined
in order to characterize the physical, mechanical, electrical, and electrochemical behavior of the
mortar and the embedded steel. It was found that the use of pozzolan has resulted in a significant
increase in mortar resistivity and corrosion initiation time for the same cover depth of 30 mm, and
as a result, decreased the rate of corrosion of steel rebars once corrosion was initiated.
2.4 Steel Rebars
Mild steel or structural steel used in Reinforced Concrete (RC) structures are of two types;
Thermo Mechanically Treated (TMT) and low alloy steel. The manufacturing processes and
chemical composition for both the steel are different which are briefly explained below:
12
2.4.1 Alloying Steel
Alloy steel is a steel that is alloyed with a variety of elements in total amounts between
1.0% and 50% by weight to improve its mechanical properties. Alloy steels are broken down into
two groups: low-alloy steels and high-alloy steels. The difference between the two is somewhat
arbitrary: Smith (2001) and Hashemi (2007) define the difference at 4.0%, while Degarmo et al.
(2007) define it at 8.0%. Most commonly, the phrase alloy steel refers to low-alloy steels. Every
steel is truly an alloy, but not all steels are called "alloy steels". Even the simplest steels
are iron (Fe) (about 99%) alloyed with carbon (C) (about 0.1% to 1%, depending on type).
However, the term "alloy steel" is the standard term referring to steels with other alloying
elements in addition to the carbon. Common alloyants include manganese (the most common
one),nickel, chromium, molybdenum, vanadium, silicon, and boron. Less common alloyants
include aluminium, cobalt, copper, cerium, niobium, titanium, tungsten, tin, zinc, lead and
zirconium. The following is a range of improved properties in alloy steels (as compared to carbon
steel): strength, hardness, toughness, wears resistance, corrosion resistance, harden ability and hot
hardness. To achieve some of these improved properties the metal may require heat treating (Sami
et al., 2013).
2.4.2 Quenched Steel (TM-PF Ring)
In this process, the steel is heated to a temperature 760C, at holding time 60 min and then
cooled rapidly by removing the specimens from the furnace and quenching in water to room
temperature. Carbon steel quenched from these temperatures has a structure called martensite.
Martensite is supersaturated solid solution of carbon in -iron (greatly supersaturated ferrite). With
the quenching-hardening process the speed of quenching can affect the amount of marteniste
formed. Martensite plates are hard and brittle that it needs to be modified for practical applications.
13
To stabilize the structure, alleviate the brittleness and develop useful mechanical properties,
quenching is always followed by tempering. This process allows carbon atoms to diffuse out of
the distorted lattice structure associated with martensite, and thus relieve some of the internal
stresses. In this work tempering is done by heating the specimens to a temperature 500 C for 45
minutes and air cooling. Tempering process results in the formation of tempered martensite, which
consists of - iron and many dispersed particles of cementite (i.e., iron carbide, Fe3C). (Sami et
al., 2013)
2.5 Mill-Scale
Studies on the corrosion of steel rebars in the concrete have most frequently been
concentrated on polished steel surface prepared in laboratory works. However the natural oxides,
which are formed on the steel rebar during fabrication or exposure to the atmosphere, may affect
the corrosion behaviour of the steel rebar in the concrete. These superficial ferrous oxides are
generally known as mill scale and are composed of FeO, Fe2O3 and Fe3O4. The mechanism
whereby mill scale is formed is generally considered to be of dynamic nature so that alternate
formation and reduction of higher oxides of iron are occurred. The final result is a scale composed
of layers rich in oxygen at the scale surface and rich in iron at the metal.
In general, mill scale consists primarily of magnetite, Fe3O4, of characteristic blue-gray "steely"
colour. An extremely thin outer film of hematite, Fe2O3, is invisible to the naked eye.
The inner portion of the magnetite contains fine metal grains and sometimes, residual black FeO,
which contribute to the roughness of descaled metal. Mill scale is found on all hot-rolled steel
products unless processed in a protective atmosphere or descaled (e.g., for galvanizing). At hot
rolling temperatures, an inner layer of wstite, FeO, exists between the steel and magnetite. At
elevated temperatures, FeO constitutes about 85% of the scale thickness, Fe3O4 about 10 to 15%
14
and Fe2O3 about 0.5 to 2%. During slow cooling [below 1040 F] of hot-rolled coils or hot-rolled
strip (and heavy shapes), most of the FeO is transformed to Fe and Fe3O4, and the latter oxide is
predominant after cooling. The alloying metals form cations within the mill scale at about the
alloying proportions (unlike general heating or heat treatment scale, where Al, Cr, etc.
preferentially oxidize) due to the almost instantaneous oxidation of freshly exposed metal at high
temperature. Fe3O4 contains Fe+2 and Fe+3, and is sometimes written FeOFe2O3. Ni+2 substitutes
for Fe+2, Al+3 and Cr+3 substitutes for Fe+3. Thus, (Fe,Ni)O(Fe,Al,Cr)2O3. Cations of other
valences, e.g., Si+4 and Ti+4, are accompanied by cation vacancies to maintain overall electrical
neutrality. With very slow cooling, small grains of Si- and Ti-containing oxides may precipitate
within the scale. (United States Steel,2009).
2.6 Environment around Steel Rebars (SPS and Mortar)
Portland cement concrete pore solution is primarily consisted of saturated Ca(OH)2
(pH=12.6), but the presence of NaOH and KOH increases the pH to more than 13 (Andrade et
al.,1996). Under normal field conditions, in which reinforcing steel is embedded in the concrete
for many years before chlorides penetrate, this high alkalinity allows the steel to develop a stable
passive film. In laboratory studies, however, the steel is not generally given much time to passivate.
Indeed, there are many studies in which steel is embedded in concrete with admixed chlorides or
exposed to synthetic pores solution containing chlorides and, therefore, never has a chance to
passivate (Marcotte, 2001). While, there are many studies concerning the nature and the
composition of the passive film in pore solution and concrete (Foulkes et al., 1999), investigations
of the effect of SCMs and time required for steel to be passivated in concrete or in pore solution
in the presence of the SCMs is limited. This is particularly critical when the study is being done in
pore solution and there is an increasing tendency for such studies in order to obtain results in
15
shorter period of time. In couple of these studies (Moreno et al., 2004 and Zakroczymski, 1996),
it appears that insufficient time was provided for passivation before the steel was exposed to
chlorides and, in some cases the chloride was added to the pore solution at the beginning of the
experiment. Because of these unrealistic conditions, the application of such results, for example,
for the prediction of corrosion behaviour of steel in structures may be misleading.
Fajarado et al. (2009) examines the use of natural pozzolans as a partial substitute of normal
portland cement in reinforced mortar specimens. Compositions with substitution levels of 0%,
10% and 20% by mass of normal Portland cement of natural pozzolanas were investigated. The
specimens were exposed to penetration of chlorides. Compressive strength, corrosion potential,
polarization resistance, electrical resistivity, and chloride content of the mortars were determined
in order to characterize the physical, mechanical, electrical, and electrochemical behavior of the
mortar as well as the embedded steel. It was found that the use of pozzolans has resulted in a
significant increase in mortar resistivity and corrosion initiation time for the same cover depth, and
as a result, decreases the rate of corrosion of rebars once corrosion was initiated. Another
investigations was carried out by Oueslati and Duchesne (2012) in which the purpose of study was
to evaluate the effect of GBFS and MK on the corrosion performance of reinforced mortars. Mortar
cylinders were made with three cement types including ordinary Portland cement (OPC), GBFS
and MK cements at a fixed water/ cementitious material (w/cm) ratio of 0.65. It was found that,
blending the cement with 20% of MK is beneficial with regard to delaying the onset of the
corrosion by a factor of more than two. The corrosion of steel rebars in concrete and mortar is
studied by many researchers in the past for different variables like environmental condition,
chloride content, carbonation, corrosion under stress etc. However, the effect of SCMs on the
passive layer is not yet studied in mortar. This is the scope of work for this section of the research.
16
2.7 Passive Layer
Although steels natural tendency is to undergo corrosion reactions but the alkaline
environment of the concrete (pH of 12 to 13) provides protection against corrosion to the steel
rebars. Due to high pH value of concrete at the time of construction, a thin oxide layer forms on
the steel rebar surface, which prevents the steel rebar atoms from dissolving. The concrete pore
solution is saturated calcium hydroxide, containing small percentages of other alkali ions, such as
sodium and potassium ions, which maintain a pH value balance between 12.5 and 13.5. Under
these pH levels, the steel rebar attains a high potential that leads to passivity a condition of
resistance for an active steel rebar caused by the formation of a thin surface film in concrete. The
thickness of the passive layer is normally very small (a few nanometers), and primarily composed
of oxides of iron. There is very limited literature available on the passive film and its chemical
composition, and structure, as well as its breaking process. Most of the available techniques to
measure corrosion at a macro-scale but the growth and deterioration of the passive film takes place
at a nano-scale. The formation and breakage of the passive film is governed by the elemental
compositions and nano-microstructure of the steel rebar. The chemistry of the concrete and the
environment around the rebar also has a significant effect on the passive film. Figure 2.2 shows
the passive layer developed on a steel rebar embedded in the concrete.
17
Figure 2.2 Protective passive layer on steel rebar embedded in concrete (Clear et al. 2000)
Several researchers defined the passive layer and its composition in different ways.
According to Fontana's (1986), passivity can be defined as the loss of chemical reactivity
experienced by certain metals and alloys under particular conditions. Many metals, such as nickel,
silicon, iron, titanium, chromium, zinc, cadmium, tin, uranium, thorium and their alloys (e.g. steel),
may show passive behavior under particular conditions and act like noble metals, such as platinum
and gold (Revie 2000). In case of reinforced concrete, within the high pH environment and absence
of aggressive ions, soon after the start of hydration of cement, a thin passive layer develops on the
steel rebar. It is necessary to dissolve the metal that forms the passive layer. It consists of a film
laminated with magnetite (Fe3O4) adhered to the conductive surface of the steel covered by
insulating layer of molecules of ferric oxide, hematite (Fe2O3), impermeable to ions, and of ferrous
oxide (FeO), which are the stable products of corrosion. There may be the deposition of calcium
ferrite on outer side of the passive film, resulting from the reaction of Fe2(OH)3 with Ca(OH)2.
The presence of sodium hydroxide (NaOH) and potassium hydroxide (KOH), dissolved in the pore
water helps to maintain the high alkalinity i.e. the pH value remains above 11.5 due to that the
passive layer will remain stable, until the absence of chloride ions (Mehta and Monteiro, 1994. In
concrete, if the pH value remains between 12.5 and 13.5, the steel rebars would be in passive state
(Cascudo, 1997).
18
The published literature on kinetics and mechanism of formation of the passive film
suggested that formation of the film takes place only after steel comes in contact of the concrete
(Gan et al., 2011). Veleva et al. (2005) performed voltammetry and surface analysis of AISI 316
stainless steel in the chloride-containing simulated concrete pore solution environment and
concluded that more resistive passive film was found on the samples exposed to the cement
extracted solution as compared to saturated Ca(OH)2. Freire et al. (2009) studied the effect of the
pH on the formation of the passive film using direct current (D.C) potentiodynamic polarisation,
capacitance measurements and Electrochemical Impedance Spectroscopy (EIS). The chemical
composition was studied by X-Ray Photoelectron Spectroscopy (XPS). The analytical results
showed that the composition of the surface film changes with the pH value. The passive films
become enriched in Cr(III) and Fe(III) species and depleted in Fe(II) and Ni species, as the pH
decreases from 13 to 9. The results were consistent with the formation of a film, presenting a
bilayer structure, composed of an outer oxide/hydroxide layer, enriched in iron, and an inner
anhydrous layer, rich in chromium and nickel oxides. Ghods et al. (2009) studied the effect of the
concrete pore solution composition on the quality of passive oxide films on the black steel
reinforcement. The authors found that the pore solution composition has an effect on the protective
properties of the passive oxide films. Particular, sulfate ions have been shown to have a negative
influence on the film quality. Alhozaimy et al. (2012) investigated the passive layer formation
phenomenon for two types of steel rebars - TMT (thermo mechanically treated) bar produced by
quenching and tempering and alloying steel rebar produced by including multiple elements in the
rebar material. The passive layer thickness for the earlier and later steels was observed to be 7.8
and 6.7 nano-meter, respectively.
19
Despite the large number of studies that have been carried out on passive films, still the
nature and properties of different passive films, particularly on iron or carbon steel in the highly
alkaline environments, is a controversial subject (Frankenthal and Kruger ,1988; Sato and
Okamoto 1981; Kruger, 1988 and Heusler 1995).
2.8 Electrochemical Techniques to Monitor the Passive Film Formation
Electrochemistry is a branch of chemistry which deals with chemical reactions, take place in
a solution at the interface of an electron conductor. A metal or a semiconductor works as an
electrode and an ionic conductor as an electrolyte. These reactions involve electron transfer
between the electrode and the electrolyte or species in a solution. If the chemical reaction is driven
by an externally applied voltage, as in electrolysis, or if a voltage is created by a chemical reaction
as in a battery, it is an electrochemical reaction. In contrast, chemical reactions where electrons
are transferred between molecules are called oxidation-reduction (redox) reactions. In general,
electrochemistry deals with situations where redox reactions are separated in space or time,
connected by an external electric circuit. Some basic concepts of electrochemistry are discussed
below: (Dann, 2013)
Charge
Charge is the most fundamental electrical property. It derives from the charge inherent in the
electrons and protons that make up the atoms and molecules of metals, solutions, and gases that
we are concerned with. The unit of charge is the Coulomb, with the symbol C. The charge on the
electron is 1 .602176487x 1019C, and therefore, one Coulomb corresponds to 6.2 4151 x 1018
electrons (strictly, the charge on the electron is negative, and therefore, that should really be 1
C).
20
Current
Current is the flow of charge and a current of one Ampere corresponds to 1 C passing a given
point in an electrical circuit in 1 s.
Potential
The potential at a point is defined as the work done in moving unit positive charge to that point
from infinity. It is clearly a theoretical concept rather than anything that can really be used! The
unit of potential is volt, abbreviated as V, and the potential at a point is 1 V if 1 W is required to
move a positive charge of 1 C to that point.
Resistance
It is commonly found that the voltage across a component is proportional to the current passing
through the component. This behavior is known as Ohms Law, given by the well-known formula
V = IR, where V is the voltage (V), I the current (A), and R is the conventional symbol for the
resistance of the component, with the unit Ohm and the symbol .
Conductivity
In some situations, it is convenient to work in terms of the conductance of a component or the
conductivity of a metal or solution. These are simply the inverse of the resistance and resistivity
respectively. The unit of conductance is -1
Capacitance
A device that stores charge, the governing equation being Q = CV, where Q is the stored charge
(C), V the voltage across the capacitor (V). The unit of capacitance is Farads with the symbol F,
and a 1 F capacitor will store 1 C when 1 V is applied across it.
21
Inductance
As current flows along a conductor, it induces a magnetic field. When the current changes, this
magnetic field must also change and a voltage is required to cause this change. The inductance, L
(unit Henry, symbol H,), of a component is defined by
V =L dI/d t
While a capacitor can be thought of as storing charge, an inductor effectively stores current (i.e.,
once a current is flowing, the inductor tries to keep it flowing).
Impedance
Resistance, capacitance, and inductance all represent the response of a component to applied
voltage or current, and they can be combined into a single property, the impedance of the
component. Note that the resistance decreases with increasing area, whereas the capacitance
increases. The impedance of a resistor is independent of frequency and has a magnitude that is
equal to the resistance, and a phase shift of zero. The magnitude of the impedance of a capacitor
decreases with increasing frequency, and the phase shift is =- /2 radians (-90).
2.8.1 Potentiostat EIS Studies
Electrochemical Impedance Spectroscopy (EIS) is a recent tool in corrosion and solid state
laboratories that is slowly making its way into the service environment as units are decreased in
size and become portable. Impedance Spectroscopy is also called AC Impedance or just Impedance
Spectroscopy. The usefulness of impedance spectroscopy lies in the ability to distinguish the
dielectric and electric properties of individual contributions of components under investigation.
For example, if the behavior of a passive layer on steel rebar when embedded in concrete or pore
22
solution is required, by the appropriate use of impedance spectroscopy, a value of resistance and
capacitance for the passive layer can be determined through modeling of the electrochemical data.
The modeling procedure uses electrical circuits built from components such as resistors and
capacitors to represent the electrochemical behavior of the passive layer. Changes in the values for
the individual components indicate their behavior and performance. Impedance spectroscopy is a
non-destructive technique and so can provide time dependent information about the properties and
quality of passive layer.
Electrochemical impedance spectroscopy (EIS), extends the polarization resistance method by
measuring how the impedance varies with frequency. There are number of ways in which this
measurement can be made, but in essence the measurement consists in applying a series of AC
currents and measuring the AC potential response or applying a series of AC potentials and
measuring the current response. The impedance is then calculated by dividing the potential by the
current at each frequency (using complex arithmetic in order to maintain the phase information).
(Vadim, 2012)
Presentation of EIS Data
The EIS measurement produces a set of amplitude and phase values for a range of frequencies,
and there are two main ways of presenting these: The Bode plot presents log( amplitude) and phase
against log(frequency).Figure 2.4 presents a Bode plot for the equivalent circuit of Figure 2.3 (this
is known as the Randles equivalent circuit an d has three components : Rs is the resistance of the
pore solution, Rp is the polarization resistance of the steel rebar solution interface, and Cdl is the
double layer capacitance of the steel rebar solution interface ). On the Bode plot, a resistor
produces a horizontal line on the amplitude plot with amplitude equal to the resistance and a
constant phase of zero on the phase plot. A capacitor produces an amplitude that falls with a slope
23
of 1 as the frequency increases (the amplitude of the impedance is 1/(2 pfC ), where f is the
frequency and C the capacitance), and a constant phase of 90; as we are normally dealing with
resistors and capacitors, it is common to invert the phase axis (i.e., plotphase) so that capacitive
circuit elements give data above zero. The Nyquist plot normally plots the imaginary part of the
impedance against the real part (Figure 2.5). The Nyquist plot invariably inverts the imaginary
axis (i.e., it plots the imaginary component of impedance with increasingly negative values on the
y-axis), so that capacitive circuit elements plot above the x-axis. One weakness of the Nyquist plot
compared with the Bode plot is that it does not implicitly include the frequency of each
measurement point, so at least some points should have their frequency indicated.
Figure 2.3 The Randles equivalent circuit for a corroding interface (Ebrahimi et al., 2004).
24
Figure 2.4 Example Bode plot (Ebrahimi et al., 2004)
Figure 2.5 Example Nyquist plot (Ebrahimi et al., 2004)
Polarization resistance and phase angle can be calculated by analyzing Bode plot. By using these
parameters, the quality of the passive layer can be estimated, as higher the polarization resistance
25
better is the quality of passive layer. It is observed that, in passive state the modulus of impedance
of the passive film at the lowest studied frequency (10-2 Hz) increases with the exposure time. In
order to get quantitative values for the components of equivalent electrochemical circuit, the data
can be fitted with constant phase element model. It is well established in the literature that the
impedance behaviour of steel in contact with the concrete solutions do not follow an ideal faradaic
charge transfer reaction and multiple components in the reaction kinetics, including double layer
capacitance (Cdl) of reaction of metal with electrolyte, charge transfer resistance (RC) at metal
electrolyte interface, Cf (capacitance of the passive film), etc. take part in the reaction. (Vadim,
2012)
2.8.2 Corrosion Potential
Measurement of the corrosion potential is the starting point for many electrochemical
techniques, including the cyclic potentiodynamic polarization scan and Tafel scan. Understanding
its meaning and measurement are critical to proper scan generation. Electrochemical reactions
characteristic of the interaction between a surface and a solution govern the corrosion process of a
metal immersed in a solution. For example, when iron corrodes in acid, one half of the reaction
process is iron forming iron ions via the reaction Fe Fe+2 + 2e. The other half of the reaction is
hydrogen ions combining with the electrons generated by the dissolution of iron to form hydrogen
gas (2H+ + 2e H2). Since electrons are exchanged during such a corrosion process, the reactions
involved create an electrochemical potential. This potential is called the "corrosion potential"
(sometimes called the "open circuit potential"). This potential is a measure of all of the
electrochemical processes occurring at the surface and the environmental influence on those
processes. The corrosion potential is normally measured as the voltage difference between an
electrode made of the corroding material and an appropriate reference electrode, for example a
26
saturated calomel electrode, a silver-silver chloride electrode, or a mercury-mercurous sulfate
electrode. From the value of CP, an existence of the corrosion process and the stability of the
passive layer can be detected. If the current potential is less than -200mv, the passive film will be
stable, and there will be no corrosion (Jones, 1996).
2.8.3 Tafel Scan
Corrosion normally occurs at a rate determined by equilibrium between opposing
electrochemical reactions. The first is the anodic reaction, in which a metal is oxidized, releasing
electrons into the metal. The other is the cathodic reaction, in which a solution species (often O2
or H+) is reduced, removing electrons from the metal. When these two reactions are in equilibrium,
the flow of electrons from each reaction is balanced, and no net electron flow (electrical current)
occurs. The two reactions can take place on one metal or on two dissimilar metals (or metal sites)
that are electrically connected. Figure 2.6 diagrams this process. The vertical axis is potential and
the horizontal axis is the logarithm of absolute current. The theoretical current for the anodic and
cathodic reactions are shown as straight lines. The curved line is the total current. This is the
current that is measured when we sweep the potential of the steel rebar with potentiostat. The sharp
point in the curve is actually the point where the current changes signs as the reaction changes
from anodic to cathodic, or vice versa. The sharp point is due to the use of a logarithmic axis.
27
Figure 2.6 Classic Tafel Analysis (Jones, 1995)
The use of a log axis is necessary because of the wide range of current values that must be displayed
during a corrosion experiment. Because of the phenomenon of passivity, it is not uncommon for
the current to change by six orders of magnitude during a corrosion experiment.
The Tafel Scan technique is used by the electrochemists to get the corrosion information, such as
the corrosion rate, passivity and pitting susceptibility. The instrument is set to a series of pre-
defined scan limits. The starting point is set depending on the nature of the information required.
It is normal to start the scan at a potential close to that of the open circuit potential, which provided
by the software of the instrument. The limits of initial and final scan value are set to scan to provide
either anodic or cathodic information. The scan rate is typically expressed in mV/sec. At higher
scan rates the system under evaluation would not have time to stabilize at each potential. Scanning
at higher potentials would have the effect of pushing the readings (icorr, Ecorr) obtained to a more
positive value. The ASTM G59-97 Standards (Standard Test Method for Conducting
Potentiodynamic Polarization Resistance Measurements) recommended 0.1667 mV/sec (10
28
V/min) values as for the analysis of corroding systems. Scans are performed close to the open
circuit potential (-200mV for an anodic scan and +200mV for a cathodic scan). The corresponding
trace must have a point where the current measured is equal to zero. The Tafel plot extrapolated
to the zero current/potential gives a set of co-ordinates related to Ecorr (abscissa) and icorr (ordinate).
The icorr value could be calculated using the Tafel constants (a + c) and Rp. Where a and c are
the slopes of anodic and cathodic lines and Rp is the polarization resistance. The value of a can
be determined by taking the slope for the anodic portion of the curve and the values of c can be
determined for the corresponding cathodic part. Using the Rp value and the Stern-Geary equation,
the value of icorr can be determined. Using these parameters, the corrosion rate in mm per year can
be predicted for the steel rebars. (Jones, 1995)
Stern-Geary Equation
From the Ecorr value, it is possible to obtain a value for icorr, which is directly related to the
rate constant of the electrode reaction. The relation is given in Equation 2.4, which also termed as
Stern- geary equation.
()()
= 2.4
2.3 ()(+)
Where icorr = corrosion current (A cm-2)
EW = equivalent weight of the steel sample sample (g)
d = density of steel sample (g cm-3)
If the material density and surface area are known, it is also possible to compute the corrosion rate.
Plotting of different comparable metal electrodes, using the same physical/chemical environment,
provides information relating to general corrosion mechanisms and its rate. The techniques, such
29
as Tafel plots, cannot be used to provide information related to corrosion types, such as pitting and
crevice corrosion. However, this information is relatively easy to obtain using electrochemical
noise measurement, and the current and voltage are measured simultaneously in a static
(unperturbed) system. By analysing the Tafel plot corrosion current, mass loss and corrosion
penetration rate can be calculated. (Jones, 1995)
Corrosion Current
Armed with the Tafel equation and Tafel plots, it can be predicted that whether a particular
setup would result in corrosion and its rate. In order to initiate corrosion, there must be a suitable
anodic reaction and an appropriate cathodic reaction. This is manifested as an intersection of a
cathodic branch and an anodic branch on a Tafel plot. The point of intersection gives the corrosion
potential and the corrosion current (or, more accurately the log of the corrosion current density).
Generally, values of corrosion current varies from 0.1 A/cm to 1 A/cm. If the value of
corrosion current is lesser than 0.1 A/cm, it is an indication that there is negligible corrosion or
the specimen is in passive state. If the corrosion rate exceeds than 1 A/cm threshold, its mean
there is extensive corrosion is taking place. (Jones, 1995)
2.9 Previous Research on Passive Layer using Electrochemical Techniques
Electrochemical Impedance spectroscopy (EIS), Raman spectroscopy, Scanning Electron
Microscopy (SEM), Energy Dispersive X-ray Analysis (EDXA), X-Ray Diffraction analysis
(XRD) etc. were used by Ghosh and Singh (2007) to study the kinetics of the passive film
formation and understand the mechanism of the formation of the hydrozincite (HZ) passive layer
at the corroding interface. The techniques to develop an eco-friendly protective passive layer on
the galvanized coatings, prior to their embedding in concrete, was investigated in this study. Singh
and Ghosh (2003) also used electrochemical techniques and SEM along with XRD to study the
30
role of the surface condition (surface having black oxide, brown rust and bright & polished) of
thermo mechanically treated (TMT) low carbon mild steel rebars embedded in chloride
contaminated concrete mortars, on their corrosion resistance. It was found that the presence of
brown rust or black oxide scale on the steel rebars surface has an accelerating effect on the uniform
and localized corrosion rates. The mortar with descaled rebars cracked within 450 days of exposure
in the test environment whereas the mortars embedded with rebars having mill scale took 760 days
of exposure for cracking, The presence of black and brown oxides on the rebars surface and
embedded in concrete accelerated the corrosion which has been ascertained by weight loss,
electrochemical direct current polarization and alternating current impedance spectroscopy (EIS)
studies. A combination of electrochemical (cyclic voltammetry and electrochemical impedance
spectroscopy) and surface analysis techniques including AFM and XPS were used in the work in
order to analyze the changes that chlorides induce in those films as immersion time increases by
the Abreu et al. (2006). The results showed that the passive film evolves from mixed FeCr
magnetite-type structure, towards a more oxidized iron rich layer with different Cr distribution as
the immersion time in chloride solution increases. Samples having higher roughness show more
oxidized oxide layers at a given immersion time, which can indicate major oxygen availability at
the interface level. Moreover, chloride ions do not penetrate the film that dissolves in a very
heterogeneous way.
Veleva et al. (2005) used AFM and XPS to study the growth of the passive layer on AISI
316 stainless steel in simulate concrete pore solutions (SPS) contaminated with Cl- ions. 5 g/L of
NaCl was added to the SPS saturated with Ca(OH)2 and cement extract (CE). Cyclic voltammetry
(CV) shows different electrochemical responses of passive layers grown on samples immersed in
these solutions under open circuit potential. CE solution shows more resistive passive film as
31
compared to SPS. Sanchez et al. (2006) used Electrochemical Impedance Spectroscopy (EIS) and
Cyclic Voltammetry (CV) techniques to study the passive layer anodically grown on steel rebars
in SPS. Diffusional tail at low frequencies were found in Nyquist diagrams which recorded by EIS
at the different stabilization potentials.
Cyclic Voltammetry and Electrochemical Impedance Spectroscopy, Scanning Electron
Microscopy and X-ray powder Diffraction was used by the Abreu et al. (2007) to study the growth
and evolution of the passive layers formed on the tested electrodes. These techniques were used
for the chemical and morphological and characterization of the developed passive films. The
addition of Granite Cutting Slurries (GCS) in small amount s to alkaline solutions modify the
natural passive layer formed on carbon steel by decreasing the peak current of the magnetite
formation and by indicating a corrosion rate reduction. The GCS also showed the ability to inhibit
pitting of carbon steel in presence of chlorides.
To study the protective properties of passive film developed on the surface of a steel rebar
in two different media, Olga et al. (2008) used AFM and EIS. These two different media were the
alkaline chloride solution and the reinforced concrete used in the construction of bridges. For
corrosion performance characterization open circuit (corrosion) potential mapping and EIS were
used and AFM was used for surface morphology studies. The results observed under various test
conditions, the medium weight crystalline phosphate film composed of Zn and Ca phosphates
ensured the most effective protection of steel.
Aberu et al. (2004) studied the formation of the passive films on AISI 304L and duplex
stainless steel SAF 2205 in NaOH 0.1M using cyclic voltammetry, electrochemical impedance
spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). Main focus of the study was on
32
the effect of Mo in the generation of the films. Results showed that the stabilizing effect of the
molybdates on the surface of the film, enhancing the formation of a thin layer on the SAF 2205
with a higher Cr/Fe ratio. Ghods et al., (2009 and 2011) studied the effect of concrete pore solution
composition on the protective properties of the oxide films that form on black reinforcing steel.
Anodic polarization and Electrochemical Impedance Spectroscopy (EIS) were used for
investigation. Study was conducted on oxide films grown in saturated calcium hydroxide solutions
that included different representative amounts of NaOH, KOH, and Ca(SO4), to simulate the
concrete pore solution present in ordinary Portland cement concrete. The anodic polarization and
EIS tests clearly show that the SPS composition has an effect on the properties of the passive films.
The EIS and X-ray photoelectron spectroscopy was used by Feng et al. (2011) to investigate the
effect of stress on the passive behavior of steel bars in the concrete pore solution. In conclusion,
as the applied load increased, the passive ability of steel decreased and higher load had much
greater influence on passivation than repeated loading of small magnitude.
The literature review presented in this chapter has indicated that several researchers used
electrochemical techniques to investigate the passive film developed on the metals in different
alkaline solutions. A Few of them also investigated rebars for passive layer development in
simulated concrete pore solution (SPS). However, a very limited literature is available on topic of
the effect of SCMs on the development of the passive layer on steel rebar. Most of the studies
focused on the effect of SCMs on the quality of concrete, which improved the corrosion resistance
of the embedded steel rebars. Moreover, in the existing studies available in literature, SPS was
used for the investigation of the passive layer phenomena; however, the actual concrete or mortar
environment can be different in temperature, chemical reactions, alkalinity and rate of chemical
reaction that needs to be investigated. The effect of SCMs on the steel rebar chemistry and on the
33
steel rebar surface conditions for the development of passive layer is also not yet investigated. All
these points have been considered in this research as outlined below:
1. Effect of SCMs on the quality and protective properties of passive layer developed on steel
rebars under the simulated concrete pore solution environment and mortar by simultaneous
use of different electrochemical techniques for the study of passive layer properties.
2. Study of the growth rate of passive layer developed on steel rebar mounted in simulated
concrete pore solution and embedded in mortar.
3. Effect of SCMs on the rebar source for the development and quality of passive film.
4. Investigation for effect of SCMs on the surface condition (as received vs polished) for the
development of passive layer on steel rebar.
5. Investigation of the effect of SCMs on the composition and structure of passive layer.
34
CHAPTER 3. EXPERIMENTAL PROGRAM, MATERIALS &
METHODOLOGY
3.1 Experimental Program
A comprehensive experimental program was conducted to understand the effect of SCMs
on the passive layer development on the steel rebar surface in cement mortar and simulated
concrete pore solution. In this chapter, a general plan of experimental program is outlined
including the broad design and methodology adopted in this research. A clear description of the
experimental methods and procedures are also presented.
The experimental program was planned in the light of existing research and its shortcomings
so that the areas of research which were overlooked in the past and needed further study to achieve
targets, investigated in this research. Experimental program is shown in Figure 3.1. Three most
commonly used SCMs (fly ash, natural pozzolans and silica fume) were selected for the
investigation of their effect on the quality of passive layer developed on steel rebars. Fly ash and
natural pozzolans were replaced by 25 % and silica fume was replaced by 10 % of the quantity of
cement, as these replacements are common in practice. Two types of steel rebars with two surface
conditions were investigated for the effect of SCMs on the quality of passive layer. Steel rebars
were tested in simulated concrete pore solution and in mortar as well. Electrochemical
experimental testing techniques, comprising of Electrochemical Impedance Spectroscopy (EIS),
Tafel scan and corrosion potential with the nano-scale technique of Scanning Electron Microscope
(SEM) from the micro to nano-scale for the steel rebar passive layer, were employed.
Metallographic analysis on the steel rebars was also conducted to reveal the type and chemical
composition of steel rebar, which are very important for the passive layer characterization.
35
Experimental Program
SCMs
Control Natural Pozzolans Fly Ash Silica Fume
Steel Source "A" Steel Source "B"
As-Received Polished
Figure 3.1 Experimental program
36
3.2 Materials
3.2.1 Steel Rebars
Mild steel rebars procured from two different locally available sources were used. These
rebars are designated as steel source A and source B in this research and are shown in Figure
3.1. Both of these steel source are rolled by steels having different compositions; steel source B
is mild steel and source A is LAS (low alloy weathering type steel). The outer ring of steel source
B is Tempered Martensite (TM) and inner core is Pearlite Ferrite (PF), which can been clearly
observed in Figure 3.2. These phases can be seen in the rebars by fine polishing of their cross-
sectional surface and then etching in the Nital solution. The Tempered Martensitic (TM) ring tests
exhibit that only source B has TM-PF rings.
TM Ring
Alloy Steel
PF Core
Steel Source A Steel Source B
Figure 3.2 Nital solution treatment of two steel rebars
3.2.1.1 Mechanical Properties of Steel Rebars
The standard tension tests were performed on two coupons selected from each source of
steel rebars to determine the mechanical properties. The variability of these test results and their
37
mechanical properties, including yield strength, ultimate strength and percentage elongation are
summarized in Table 3.1.
Table 3.1 Mechanical properties of steel rebar from both sources
Yield strength Ultimate strength

Source Sample No.
MPa MPa
1 435 593
A
2 445 591
1 560 670
B
2 552 665
3.2.1.2 Chemistry of Steel Rebars
For measuring the properties of steel rebar samples, Photo-Electron Spectroscopy was
carried out. The results of Photo-Electron Spectroscopic analyses are presented in Table 3.2.
Table 3.2 Compositional analysis of steel rebars
Steel rebar
Steel Compositional analysis (%)
size
source
(mm) C Si Mn Cr S Ni Cu
A 16 0.32 0.41 0.80 0.01 0.04 0.05 0.17
B 16 0.35 0.48 0.50 0.02 0.01 0.03 0.05
3.2.2 Cement and Sand
White sand: procured from Saudi Ready Mix Company, North Riyadh. Bulk specific gravity
(OD basis) and fineness modulus was found 2.66 and 1.9 respectively.
Cement: procured from Al-Yammamah Cement Company, with chemical composition
accordance with ASTM C-150 (standard specification for Portland cement) for Type I cement.
Chemical composition of the cement is shown in Table 3.3.
38
Table 3.3 Chemical composition of cement
Oxides SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O L.O.I

% by weight 20.2 5.49 4.12 65.43 0.71 2.61 0.26 1.38
3.2.3 Supplementary Cementitious Materials (SCMs)
Chemical properties of fly ash, natural pozzolans and silica fume used in this research are
summarized in Table 3.4. Specific gravity of fly ash, natural pozzolans and silica fume was found
2.3, 2.78 and 2.27 respectively. Particle size distribution curves of SCMs are shown in Figure 3.3.
Table 3.4 Chemical properties of SCMs
%age by weight
Oxides Natural Silica fume
Fly ash
pozzolans
SiO2 55.83 43.31 93.2
Al2O3 26.95 15.41 <0.01
Fe2O3 10.17 12.48 0.05
CaO 4.32 9.26 0.72
MgO 0.31 10.1 0.14
SO3 0.18 0.06 <0.01
TiO2 - 2.19 -
Na2O 0.06 2.95 0.07
K2O 0.67 0.75 0.15
Cl 0.03 0.03 -
L.O.I 5.25 0.95 5.4
39
100
90
80
70
60
Passing %
50 PC
NP
40
SF
30 FA
20
10
0
0.01 0.1 1 10 100 1000 10000
Particle size (m)
Figure 3.3 Particle size distribution curves of SCMs

3.3 Methodology & Testing Procedures
3.3.1 Simulated Concrete Pore Solution Preparation
Simulated concrete pore solution (SPS) was prepared, which is normally used for the study
of the steel rebars corrosion properties. Simulated concrete pore solution was prepared by adding
NaOH, KOH and Ca(OH)2 as 4.0 g / liter, 9.8 g / liter and 2 g /liter respectively.
These chemical compounds were dissolved in distilled water. The solution was kept for 24 hours
under continuous magnetic stirring and then filtered using grade 15 Wattman filter paper (Figure
3.4). This step was necessary to remove insoluble CaO from the solution. The solution with the
above composition is used by several researchers to simulate the pore solution of the concrete to
study the passive film and corrosion behavior of steel rebars (Kitowski and Wheat, 1997 and
Andrade et al., 1995). The prepared solutions were stored in the air-tight plastic containers to avoid
40
diffusion of CO2 from the atmosphere, which could react with alkali and eventually bring down
the pH of the test electrolyte. To simulate the conditions of cement paste with a w/c of 0.5, fly ash
and natural pozzolans were added as 0.5 g/ml of SPS while for silica fume it was 0.2 g/ml. Manual
stirring was carried out twice a day throughout the duration of testing to avoid permanent
settlement of SCMs particles. Samples containing natural pozzolans, fly ash and silica fume are
designated in the legends by the symbols NP, FA and SF respectively. Simulated concrete
specimen without any SCMs is designated in the legends by the symbol C.
Figure 3.4 Pore solutions under continuous magnetic stirring
3.3.2 Specimen Preparation
Rebars Specimens
Steel Source A and B are commonly available in Kingdome of Saudi Arabia. These
rebars were tested for two types of surface conditions, including as-received with mill scale and
polished surface condition (Figure 3.5).
41
I. For unpolished steel rebar specimens, the surfaces of the specimens were rinsed
with acetone to degreased and then with distilled water to remove any residue from
the environment. They were then kept in desiccators until testing.
II. For the polished steel rebar specimens, the samples were cut, pickled and polished
with a grinder, followed by polishing with fine emery paper (1200 grade) to get a
scratch free surface. The specimens were then stored in a desiccators until testing.
Unpolished Polished
Figure 3.5 Steel rebars used (polished and unpolished/ as received)
The rebars were cut with a special grinder to avoid rebar surface burning due to the heat
generation during cutting process. The ordinary cutting process changes the microstructure of steel
rebars and affects their corrosion and passivation properties. To cut the smoother surface, the
automatic cutting machine was used, which cuts the samples very smoothly and without generation
of heat.
42
Rebars in SPS
To perform electrochemical tests on steel rebars in SPS, 10 cm long samples were cut from
the steel rebars. These samples were fixed in a glass cell containing 500 ml of simulated concrete
pore solutions. Configuration of specimen is shown in Figure 3.6.
Graphite Rod
Sense and counter

sense Electrodes
Pore Solution
Working Electrodes
Steel Rebar
Salt Bridge
Reference Electrode
Figure 3.6 SPS specimen Configuration and setup

The steel rebar specimens were the working electrodes .The saturated calomel electrode
(SCE) and pure graphite rod of 5 mm in diameter and 150 mm in length were used as reference
and auxiliary electrode, respectively. SPS specimens are designated by the symbol S in results
and discussions.
Rebars in Mortar
In addition to performing the tests in the simulated concrete pore solution, a set of
experiments was also performed on 150 mm long steel rebars embedded in mortar prepared by
mixing of cement, sand and water in the ratio of 1: 2.75: 0.5, respectively. The samples were also
prepared by replacing cement with fly ash, natural pozzolans and silica fume 25 %, 25 % and 10
43
% respectively by weight of cement (these replacements are commonly used in concrete industry).
Figure 3.7 presents configuration of the tested mortar specimen. Electric wire of 100 mm length
was connected with the steel rebar embedded in the mortar. This electric wire worked as working
electrode. Saturated calomel electrode worked as reference electrode and a graphite rod was used
to complete the current path. The pond reservoir was made and filled with same simulated concrete
liquid as used for the other tests. The purpose of the reservoir was to make connection between the
steel rebar embedded in mortar and the reference electrode. In the results and discussion mortar
specimens will be designated by the symbol M.
Graphite Rod
Mortar Specimen
Potentiostat
Reference Electrode
Electric Wire
Connected with
Embedded Steel Rebar
Working Electrode
Figure 3.7 Configuration of the tested mortar specimen
3.3.3 Electrochemical Studies
Gamry potentiostat / galvanostat was used to perform the electrochemical experiments (Figure
3.8). The electrochemical techniques used in this research can be divided in to two types,
Alternative Current techniques (AC) and Direct Current (DC) techniques. AC technique (EIS) was
used to investigate the quality of the passive layer developed on steel rebars was studied in the
simulated concrete pore solution, solutions containing SCMs and in mortar. DC techniques (half-
44
cell potential and Tafel scan) were used to determine the passive state of steel rebars.
Electrochemical tests were performed on the specimens, just after the contact of steel rebars with
pore solution and mortar to the complete formation of the passive film.
Figure 3.8 Gamry potentiostat

3.3.3.1 Potentiostate EIS Studies
EIS studies were performed to investigate the quality of passive layer developed on steel
rebar by using three electrode cells and by imposing sinusoidal voltage of 10-mV amplitude at the
open circuit potential of the working electrodes. No direct current (DC) potential was imposed on
the electrode surface during EIS studies. The frequency of applied Alternative Current (AC) was
varied between 100,000 Hz to 0.001 Hz. The data was collected by imposing sinusoidal voltage at
open circuit potential of the working electrode. The analysis of data was performed by the best
curve fitting methods, using the constant phase element and Randle models. CMS 300 software,
supplied by M/S Gamry Instrument, was used for data analysis.
45
3.3.3.2 Half- Cell Potential
Open circuit potential was measured with respect to time. These measurements were made
for the passivation properties of steel rebars, either immersed in the concrete pore solution or
embedded in the concrete. The results were analyzed according to ASTM C 876. The test was
performed for the duration of 30 minute which was sufficient for stabilization of open circuit
potential.
3.3.3.3 Tafel Scan
Tafel Scan was performed at a scan rate of 0.1667 mV/s as per ASTM G59-97(2009)
(Standard test method for conducting potentiodynamic polarization Resistance measurements).
The starting potential for the Tafel scan was the corrosion potential of the specimens. The Stern-
Gerry equation was used to analyze the Tafel scan. The outcome of the analysis was corrosion
current, which presents the state of passivation of protective passive layer developed on steel rebar.
3.3.4 Field Emission Gun Scanning Electron Microscopy (FEG-SEM) Studies
Characterization of passive layer developed on steel rebars under pore solution
environment was carried out using FEG-SEM technique. Samples of size 10mm long were cut
from the same steel rebars which were tested for electrochemical studies. After that the samples
were immersed in test solution for 15 days at room temperature for the formation and stabilization
of passive film. This time of exposure was chosen as it was observed during this study and also
reported by others that this period of exposure was good enough to form a stable passive film on
the surface of steel rebars. Field Emission Gun Scanning Electron Microscope (FEG-SEM) of FEI
microscope make (Model: JEOL JSM-7100FLV) was used as shown in Figure 3.9.
46
Figure 3.9 Field Emission Gun Scanning Electron Microscopy (FEG-SEM)
The images of the samples were acquired at the accelerating voltage of 15 keV and working
distance was kept 18 mm.
3.3.5 Energy Dispersive Spectroscopy/Energy Dispersive X-ray (EDS/EDX)
Energy Dispersive Spectroscopy/Energy Dispersive X-ray (EDS/EDX) analyses were carried out
for the elemental analysis, peak location and compound identification of passive layer. Field
Emission Gun Scanning Electron Microscope (FEG-SEM) of FEI microscope make (Model: JEOL
JSM-7100FLV) was used as shown in Figure 3.9. Steel samples of 10 mm length of 16 mm dia
rebar were cut from the steel rebar. These samples were mounted in the same test solutions, used
for the electrochemical tests. EDS tests were carried out on the steel samples after 15 days.
47
CHAPTER 4. RESULTS AND DISCUSSIONS
4.1 General
This chapter presents the results obtained from the experimental work on the investigation
of the effect of different parameters, including the types of SCMs used in the reinforced concrete
(silica fume, natural pozzolans and fly ash), types of steel rebars (source A and source B),
steel rebars surface conditions (as-received with mill scale and polished), and environmental
exposure conditions (simulated concrete pore solution and mortar), along with detailed discussion.
The quality of the protective passive layer was monitored using different electrochemical
techniques, and results of these techniques are presented in this chapter
4.2 Effect of SCMs on the Development of Passive Layer on Steel Rebars
In this section, the effect of SCMs on the development and quality of the protective passive
layer on the rebars is discussed in detail. As mentioned earlier, three types of the SCMs-silica
fume, natural pozzolans and fly ash were used in the SPS to study their effects on the passive layer
formation. The development of the passive layer was monitored by using the different
electrochemical techniques; SEM was also used to obtain the nano-scale images of the
phenomenon. Details of the test results are presented and discussed. In the results and discussion,
simulated concrete pore solution samples are designated in the legends by the symbol C and NP,
FA and SF stands for the samples mounted in the test solution with natural pozzolans, fly ash and
silica fume, respectively.
48
4.2.1 EIS Results
Electrochemical impedance studies, after different intervals of exposure of steel samples
in the simulated concrete pore solution, were performed and results are presented in Figure 4.1.
Figures 4.1(a) and (b) shows the comparison of the Bode plots after 24 hours and 8 days of
immersion of steel rebars in pore solutions respectively.
10000
1000
100
Impedance (Ohm)
C
FA
10
NP
SF
1
0.1
0.01
0.01 1 100 10000 1000000
Frequency (Hz)
Figure 4.1(a) Bode plot after 24 hours of exposure
10000
1000
Impedance (Ohm)
100
C
10
FA
NP
1 SF
0.1
0.01
0.01 1 100 10000 1000000
Frequency (Hz)
Figure 4.1(b) Bode plot after 8 days of exposure

Figure 4.1 Bode plots after different time of exposure
49
In Figure 4.1 the impedance values at higher and lower frequencies provided the pore
solution resistance (Rpore) and overall polarization resistance (Rp), respectively. It is observed that
the modulus of impedance of the passive film at the lowest studied frequency (10 -2 Hz) increased
with the exposure time. Significant changes were recorded only up to 8 days of the exposure time.
After this period, no substantial changes occurred. These results showed that with an increase in
the exposure time, the structure of the passive film transformed into relatively more protective
nature. In order to get quantitative values for the components of equivalent electrochemical circuit,
the data were fitted with constant phase element model shown in Figure 2.3.
The values of Rp were determined by using the constant phase element best fitting method
and are plotted in Figure 4.2. The results incorporated in Figure 4.2 show that the polarization
resistance of the samples increased with increased in the exposure time. These facts suggest that
the quality and protective properties of the initially formed film on the steel rebar surface gradually
transformed into a more protective passive and stronger film. The Rp values (impedance value at
lower frequency) are directly proportional to the thickness and quality of the passive layer
(alhozaimy et al. 2012). This phenomenon showed that higher the impedance values better would
be the quality of passive layer. The recorded values of impedance at lower frequencies of the plots
were another important observation made during this study. These values showed that samples
mounted in NP, at lower frequencies (< 10-2 Hz), after the exposure period of 8 days, exhibits
considerably higher impedance than of the control samples (Figure 4.2). It means that NP has a
better quality passive layer than the control samples.
50
4000
3500
3000
Impedance (Ohm)
2500
2000
1500
C
FA
1000
NP
500 SF
0
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.2 Comparison of SCMs for variation of impedance with time of exposure
Figure 4.2 shows the comparison of all the SCMs, it can be noted that the impedance values
of steel samples mounted in frequency test solution decreases from NP to SF. It reflects that the
natural pozzolans and fly ash improved the quality and increased the thickness of the passive film.
While, silica fume showed negative effect on the passivity of steel rebar. From Figure 4.2 it can
also be observed that passive layer stabilized after 8 to 10 days in all the solutions.
4.2.2 Half-Cell Potential Results
The results obtained from the open circuit potential tests are presented in Figure. 4.3. The
results were analysed according to ASTM C 876 (Standard Test Method for Corrosion Potentials
of Uncoated Reinforcing Steel in Concrete). In Figure 4.3 comparison of the different SCMs are
made with reference to the control.
51
-400
-300
-200
Half-Cell Potential (mV)
-100
C
FA
0
NP
SF
100
200
300
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.3 Half-cell potential variations with the time of exposure
In Figure 4.3 the film developed in the test solution containing natural pozzolans showed
lowest values of open circuit potential. Whereas, silica fume showed higher values than that of all
other samples. The results also showed that all steel samples were in a protective range (potential
> -200 mV), as per ASTM C-876 standard. Steel rebars immersed in test solutions showed very
high potential values at the beginning of the test as the passive layer initiated to develop. The
potential values decreased with the passage of exposure time and eventually it stabilized after 8 to
10 days of the exposure period. It can be concluded that the passive film took about 8 to 10 days
to develop and stabilize.
52
4.2.3 Tafel Scan Results
Tafel scan tests were performed on the steel rebar samples in pore solutions and the Tafel
plots are presented in Figure 4.4. The Tafel scan technique was used to obtain the information
regarding corrosion rate, passivity and pitting susceptibility. The test was analysed according to
ASTM G59-97 Standards (Standard Test Method for Conducting Potentiodynamic Polarization
Resistance Measurements). For each steel rebar in different test solution, the Tafel scan was carried
out frequently after 24 hours to 15 days of exposure time. The free-corrosion potential was
measured with the help of a Gamry PC4/300 Potentiostat/Galvanosatat/ZRA, relative to the
saturated calomel reference electrode. It took approximately one hour to take a measurement of
tafel scan, before the free-corrosion potential would no longer fluctuate significantly (fluctuations
were less than 1 mV/min). In the next step, Tafel curves were obtained starting the scan from 10
mV below the free potential and finishing at 800 mV SCE, using a scan rate of 0.166 mV/s, as
prescribed in ASTM G59-97 Standard. The choice of scan rate is a compromise between accuracy
and the time to complete the measurement. Tafel scan curves after 24 hours and 8 days of
immersion are shown in Figures 4.4(a) and (b) respectively. All of the Tafel scan curves have the
same general appearance. However, the curve for rebar immersed in the solution with natural
pozzolans is shifted to lower currents compared to the curves for other solutions. The inference is
that the passive films on the rebar specimens became relatively stable after eight days of immersion
in the pore solutions.
53
-0.80
-0.70
-0.60
-0.50
Potential (V)
C
-0.40 NP
FA
-0.30 SF
-0.20
-0.10
0.00
1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01
Current (A)
Figure 4.4(a) Tafel curve after 24 hours of exposure
-0.50
-0.40
-0.30
Potential (V)
C
NP
-0.20 FA
SF
-0.10
0.00
0.10
1.000E-08 1.000E-07 1.000E-06 1.000E-05 1.000E-04 1.000E-03 1.000E-02 1.000E-01
Current (A)
Figure 4.4(b) Tafel curve after 8 days of exposure

4.4 Tafel scan curve for the SCMs at different time of exposures
All of the corrosion currents occurring at the intersections of the cathodic line for the
reduction of oxygen which would all be vertical in accordance with the passive state conditions.
54
Oxides that are not as protective would passivate (become vertical on the Evans diagram) at higher
current densities and consequently the intersection of the oxygen reduction line with the passive
region occurs at lower potentials, in accord with the negative Tafel slope relating the reduction
over potential to the logarithm of the current density. Thus the polarization curves in Figure 4.4
moved down (to lower corrosion potentials) and to the right side (to higher current densities), as
the passive films become less protective. From the analysis of the Tafel scan plot corrosion current
can be obtain.
Corrosion Current Results
The corrosion current for all the specimens was calculated by analysing the Tafel scan plots
and results are presented in Figure 4.5. Armed with the Tafel equation and Tafel plots, it can be
predicted that whether a particular setup would result in corrosion and its rate. In order to initiate
corrosion, there must be a suitable anodic reaction and an appropriate cathodic reaction. This is
manifested as an intersection of a cathodic branch and an anodic branch on a Tafel plot. The point
of intersection gives the corrosion potential and the corrosion current (or, more accurately the log
of the corrosion current density).
Corrosion current density is one of the major indicator of the corrosion. In other words, it
indirectly represents the passive state of the steel rebar. In Figure 4.5 the corrosion current density
is plotted against the time of exposure of the steel rebar to the test solutions. Comparison of the
SCMs with the control sample is shown in Figure 4.5.
55
0.12
0.10
Corrosion Current (A/cm)
0.08
0.06
0.04
C
FA
0.02
NP
SF
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.5 Corrosion current variations with the time of exposure
In Figure 4.5 it can be observed that the natural pozzolans is helpful in reducing the
corrosion current density by reducing the corrosion current. On other hand, samples immersed in
other test solutions indicated higher values of the corrosion current. Fly ash decreased the current
density of the test samples more than that of control samples and this decrease is lesser than that
of natural pozzolans.
In Figure 4.5 it can also be concluded that the corrosion current for the silica fume
containing test solution was high up to 0.11 A/cm at the beginning of the exposure time. With
increase in the exposure period, the corrosion current density significantly decreased to 0.07
A/cm. After 8 days of exposure period, the corrosion current became almost constant at 0.07
A/cm, which indicates that that the passive layer took 8 to 10 days to form and stabilized. This
phenomenon of stabilization of the passive layer is almost the same for all other solutions as well.
56
All the specimens were in passive state as the corrosion current density was lesser than 0.1 A/cm
(Andrade et al., 2004 and Song, 2007).
4.2.4 Scanning Electron Microscopy (SEM) Results
After electrochemical tests, the microscopic images of the specimens were taken using
SEM and the results are presented in Figures 4.6(a) (d). To obtain these micrographs, 10 mm
specimens were cut from the rebar samples, which were previously used for electrochemical tests.
The specimens for SEM were immersed in the same test solutions. After 8 days of immersion,
when it was assured by the EIS test that the passive layer is stabilized, the specimens were scanned
with field emission scanning electron microscope (FE-SEM). The images of the samples were
acquired at the accelerating voltage of 15 keV and working distance was kept 12mm.
Smooth layer
with small
cracks
Figure 4.6(a) SEM image of steel sample in Control solution
57
Smooth and
solid layer
without cracks
Figure 4.6(b) SEM image of steel sample in NP solution
Smooth but little

porous layer
without cracks
Figure 4.6(c) SEM image of steel sample in FA solution
Layer with large

cracks
Figure 4.6(d) SEM image of steel sample in SF solution
Figure 4.6 SEM images of different steel surfaces immersed in SCMs
58
In Figure 4.6(a) the SEM image showed that there was a single film, with small thickness
with some cracks and voids, on the control specimen. The specimens immersed in natural
pozzolans, the SEM image showed that the surface of the steel rebar was very smooth, without
any crack, and relatively thicker as compared with the other samples (Figure 4.6(b)).Figure 4.6(c)
shows the image of a passive layer developed on the fly ash specimen, it can be observed that there
was a second protective layer; however, it is porous in nature. For the specimen mounted in the
silica fume solution, large cracks can be seen (Figure 4.6(d)).
4.2.5 Energy-Dispersive X-ray Spectroscopy (EDs) Results
EDS analysis for all specimens immersed in SPS is presented in Figures 47(a) (d). FEG-
SEM was used for analyses with a working distance of 16 mm and the current was 16kV for all
the specimens. The main purpose of this analysis was to obtain the elemental composition of the
passive layer. Comparison of EDS analysis is given in the Table 4.1.
Element Weight%
C 2.0
O 16.53
Na 0.8
Si 0.25
ca 0.19
Fe 80.23
Totals 100.00
Figure 4.7(a) EDS analysis steel sample in Control solution
59
Figure 4.7(b) EDS analysis steel sample in NP solution
Element Weight%
C 3.281
O 20.83
Na 0.9
Al 0
Si 0.39
Ca 0.25
Fe 74.3
Totals 100.00
Figure 4.7(c) EDS analysis of steel sample in FA solution

60
Figure 4.7(d) EDS analysis of steel sample in SF solution
Figure 4.7 EDS analysis of different steel surfaces immersed in SCMs solutions
Table 4.1 Table Elemental composition of passive layer developed on steel rebars in different
solution from EDS analysis
%age Present
Elements
CONT. NP FA SF
Fe 80.23 62.27 74.3 85.47
O 16.53 31.17 20.83 13.23
C 2.8 4.01 3.281 2
Si 0.25 0.49 0.39 0.23
Na 0.8 1.2 0.9 0.92
Ca 0.19 0.32 0.25 0.15
Mn 0 0 0 0.1
In Figure 4.7(b) and Table 4.1 it can be seen that the film developed on the rebar immersed
in the solution with natural pozzolans has high contents of oxygen and low contents of iron. This
may represent a higher quantity of the oxides of iron in the passive layer developed on steel rebar.
In passive state, higher oxide of iron may depict a higher quality of passive layer as more the iron
61
oxide, thicker would be the passive layer. Silica fume (Figure 4.7(d) and Table 4.1) shows the least
amount of iron oxides and the other favourable elements. From Table 4.1 it can be observed that
Si content is higher in the natural pozzolans, Si can react with iron and produce iron silicates
which are very resistive against corrosion.
4.2.6 Discussion on Results of Effect of SCMs on the Passive Layer
The quality of protective passive layer developed on the steel rebar immersed in the various
solutions can be ranked and summarized in Table 4.2.
Table 4.2 Raking of passive layer quality immersed in different solutions
Parameters
Ranking Impedance Half-cell Potential Corrosion Current
1 NP NP NP
2 FA FA FA
3 C C C
4 SF SF SF
The Tafel scan experiments suggested that high quality passive films had low passive current
densities and high corrosion potentials. The quality of the passive layers can be ranked from high
to low by ordering them according to low to high values of corrosion current. In addition, the EIS
correlations suggest that higher quality films have higher values of the real impedance at 0.01 Hz
and, hence, the quality of the films can be similarly ranked. In Table 4.2, these rankings of passive
layer for the quality and protectiveness are derived from both Tafel Scan and EIS techniques. It
can be seen that both techniques provide similar ranking for the passive layers. These measures
are not all independent, so it is not surprising that they lead to similar rankings; however, this
shows that any of the measures can be used to provide an estimate of the quality of the passive
layer.
62
Summary of results for Impedance, half-cell potential and corrosion current are shown in Figure
4.8 after the stabilization of passive layer. From the Figure 4.8(a) it can be seen that natural
pozzolans enhanced the quality of passive layer as compared to the control. Fly ash enhanced the
quality in comparison to control but increment is lesser than that of natural pozzolans. However,
the silica fume in the concrete pore solution has adverse effect on the protective properties of the
passive film. The Figure 4.8(b) shows that the passivity of natural pozzolan is significantly higher
than the control and that of silica fume and fly ash is comparable to the control. The Figure 4.8(c)
is reconfirming the trends obtained in Figure 4.8(b) with more precision.
4000 200
180
3500
160
3000
140 Control
Impedance (Ohm)
Control
2500
120
2000 100
80
1500
60
1000
40
500
20
0 0
NP FA SF NP FA SF
Figure 4.8(a) Impedance Figure 4.8(b) Half-cell potential
0.09
0.08
Control
0.07
Corrosion Current (A/cm )
0.06
0.05
0.04
0.03
0.02
0.01
0
NP FA SF
Figure 4.8(c) Corrosion current

Figure 4.8 Different electrochemical techniques results of effect of SCMs on development of
passive layer after 15 days
63
The results of anodic polarization tests and EIS tests, which were carried out after every 24
hours from immersion of rebar in the solutions to 15 days of immersion, suggest that eight days
are required for the oxides to stabilize. From the test results, it can be concluded that the protective
passive film can be categorized in this sequence NP>FA>C>SF in quality and protectiveness.
Silica fume reduces the pH of the concrete pore solution below 12 as summarized in Table 4.3.
Similar findings have also been obtained by a couple of other researchers in the past (Muralidharan
et al., 2008 and Byfors, 1986).
Table 4.3 pH values of solutions
Solution pH
Control 13.02
Natural pozzolans 12.85
Fly ash 12.65
Silica fume 11.52
During the chemical reaction between silica fume and components in the pore water, the
content of components especially calcium hydroxide and potassium keeping a high pH value
reduced. The reason for pH reduction could be due to gradual depletion of calcium hydroxide with
silica fume. Silica fume has a much higher effect on pH reduction as compared with other mineral
admixtures, such as fly ashes and natural pozzolans. It can be said that silica fume reacts with
NaOH, KOH and Ca(OH)2. Fly ash causes a relatively smaller reduction in the pH in comparison
to silica fume. It can be concluded that the alkalis included in the fly ash do not cause any
noteworthy increase in the pore solution concentration of alkali, thus, of the pH value. Nor does
the fly ash appear to reduce the pH value of the pore solution to any significant extent by
chemically reacting with the hydration products, at least not to the same extent as does silica fume.
Reduction in pH of concrete solution was one of the main reason for the lower quality and lesser
64
protectiveness of passive film developed on steel rebar immersed in silica fume contacting
solution.
Lastly, the SEM images also showed that the passive layer devolved on the specimens
immersed in the test solution contacting natural pozzolans is thicker, with less cracks. However,
the layer developed on the silica fume samples has micro-cracks on the surface. Fly ash helped to
deposit an additional layer but the quality of this layer was porous in nature. Elemental composition
attained by the EDS analysis also proved that the natural pozzolans have a positive effect on the
development, thickness and protectiveness of the passive layer. Oxides of iron were found higher
in the passive layer formed on steel rebars immersed in natural pozzolans than all other samples.
4.3 Effect of SCMs on Passive Layer Developed on Different Steel Sources
The effect of SCMs on steel rebars from two sources was investigated. Source A and
source B were selected since they have the major share in the market of Saudi Arabia. Source
B steel has tempered martensite ring indicating that the rebars are produced by thermo-
mechanical treatment. Source A rebar on the other hand, has no such tempered martensite ring.
To investigate the effect of SCMs on both sources of steel electrochemical tests were performed.
In this section the results are presented and discussed in detail.
4.3.1 EIS Results
Electrochemical impedance studies after different intervals of exposure of steel samples in
concrete pore solution were performed and plots are shown in Figures 4.9(a) (b). The impedance
values at higher and lower frequencies respectively provide pore solution resistance (Rpore) and
overall polarization resistance (Rp). It was observed that the modulus of impedance of the passive
film at the lowest studied frequency (10-2 Hz) increases with exposure time. The significant
65
changes are recorded only up to 8 days of exposure. Beyond this period, no substantial changes
were noted. These results show that with increase in duration of exposure, the structure of the
passive film transformed into more protective nature.
10000
1000
100
Impedance (Ohm)
A-NP
10
B-NP
0.1
0.01
0.01 1 100 10000 1000000
Frequency (Hz)
Figure 4.9(a). Bode plot after 24 hours of immersion

10000
1000
Impedance (Ohm)
100 A-NP
B-NP
10
0.1
0.01
0.01 1 100 10000 1000000
Frequency (Hz)
Figure 4.9(b). Bode plot after 8 days of immersion
Figure 4.9 Bode plot after different time of exposure for the Effect of steel source
The values of Rp were determined by using constant phase element best fitting method and
are plotted in Figure 4.10. Figures 4.10(a) (d) showed the comparison of both steel source for
control, NP, FA and SF. The results incorporated in these figures shows that polarization
66
resistance of the samples increase with exposure time. These facts suggest that the initially formed
film on the steel surface gradually transforms to a more protective passive film.
6000
5000
Impedance (Ohm)
4000
3000
2000
A-C
1000
B-C
0
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.10(a) Comparison of control

6000
5000
4000
Impedance (Ohm)
3000
2000
A-NP
1000
B-NP
0
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.10(b) Comparison in NP solution

6000
5000
Impedance (Ohm)
4000
3000
2000
A-FA
1000
B-FA
0
0 2 4 6 8 10 12 14 16
Time (Days)
67
Figure 4.10(c) Comparison in FA solution
6000
5000
4000
Impedance (Ohm)
3000
2000
A-SF
1000
B-SF
0
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.10(d) Comparison in SF solution

Figure 4.10 Effect of SCMs on development of passive layer on different steel type
Another observation that emerged during this study was the values of impedance recorded
at lower frequencies of the plots. These values showed that source B, after the exposure period
of 8 days exhibits considerably higher impedance than the source A. That means the steel source
B increases the quality and protectiveness of the passive layer. Source A showed lesser quality
and the passive layer developed on the rebar is off lesser thickness. Effect of SCMs can also be
seen on both the steel sources. Natural pozzolans helped to develop thicker and stronger passive
layer on both the steel rebar than of the silica fume and fly ash (Figures 4.10(a) (d)).
The results obtained from the open circuit potential tests are presented in Figure 4.11. The
test was analysed according to ASTM C876. The tests were performed from 24 hours of the
exposure period until the stabilization of the passive film. In Figures 4.11(a) (d), the comparison
of half potential values for control, natural pozzolans, fly ash and silica fume specimens are
presented for both steel sources.
68
-400
-300

-200
-100
0
A-C
B-C
100
200
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.11(a) Comparison in control solution

-400
-300
-200
-100
0 A-NP
B-NP
100
200
300
0 2 4 6 8 10 12 14 16
Time (Days)

-400
-300
-200
-100
0
A-FA
B-FA
100
200
0 2 4 6 8 10 12 14 16
Time (Days)
69
-400
-300

-200
-100
0 A-SF
B-SF
100
200
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.11 Potential variations with the time of exposure for the effect of SCMs on development
of passive layer on different steel type
From the Figure 4.11 it can be seen that the film developed on the steel source B in all
the solution showed lowest values of open circuit potential. Source A showed higher values in
all the solutions (Figures 4.11 (a) (d)). The steel rebars immersed in silica fume solution showed
higher values than the bars mounted in other solutions (-300 mV at the start and 120 mV after
stabilization). It also can be seen that all the steel samples are in protective range as described by
the ASTM C 876 (Potential > -200). Both steel sources rebars immersed in different pore solutions
showed very high potential values in the start, because at that time initiation of the development
of the passive layer took place. As time passes, the potential values start decreasing and after 8 to
10 days it get stabilize. It shows that passive film took almost 8 to 10 days to develop and stabilized
for both steel sources.
4.3.3 Tafel Scan
Tafel scan tests were conducted for both the steel rebars from 24 hours of immersion to the
stabilization of passive layer. Tafel scan curves are shown in Figure 4.12. All of the Tafel scan
70
curves have the same general appearance; however, the curve for rebar B immersed in the all
the solutions is shifted to lower currents compared to the curves for steel source A (Figures 4.12
(a) and (b)). Figure 4.12 (a) shows the Tafel scan plot for both steel sources after 24 hours of
immersion in pore solution. Figure 4.12 (b) shows the tafel scan plot after 8 days of immersion of
steel samples in pore solutions.
-0.6
-0.5
-0.4
Potential (V)
-0.3
-0.2
A-NP
-0.1 B-NP
0
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
Current (A)
Figure 4.12(a). Tafel scan curve after 24 hours of immersion
71
-0.6
-0.5
Potential (V) -0.4
-0.3
-0.2
-0.1
A-NP
B-NP
0
0.1
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
Current (A)
Figure 4.12(b). Tafel scan curve after 8 days of immersion

Figure 4.12 Tafel scan curve after different time of exposure for the effect of SCMs on steel
source
A simple Evans diagram description (plotting potential against log of the current density)
or Tafel scan curve of the present experiment would show all of the corrosion currents in Figure
4.12 occurring at the intersections of the cathodic line for the reduction of oxygen and the various
metal oxidation lines, which would all be vertical in accord with the passive state conditions. The
polarization curves in Figure 4.12 move down (to lower corrosion potentials) and to the right (to
higher current densities) as the passive films become less protective. Analysis of the tests results
was made according to ASTM G59-97 and corrosion current was calculated.
In Figure 4.13 the corrosion current density is plotted vs the time of exposure of steel rebar
to the solutions. Comparisons of the SCMs are made for both steel types in Figures 4.13(a) - (d).
By using Tafel equation and Tafel plots, it can be predicted that whether a particular setup would
72
result in corrosion and its rate. In order to initiate corrosion, there must be a suitable anodic reaction
and an appropriate cathodic reaction. This is manifested as an intersection of a cathodic branch
and an anodic branch on a Tafel plot. The point of intersection gives the corrosion potential and
the corrosion current (or, more accurately the log of the corrosion current density).Corrosion
current density was calculated by analysing the Tafel scan. Corrosion current density is one of the
major indicator of the corrosion. In other words, it indirectly represents the passive state of the
steel rebar.
0.12
0.10
0.08
0.06
0.04
A-C
B-C
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.13(a) Comparison in Control solution

0.12
0.10
0.08
0.06
0.04
A-NP
B-NP
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
73
0.12
0.10

0.08
0.06
0.04
A-FA
B-FA
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)

0.12
0.10
0.08
0.06
0.04
A-SF
B-SF
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.13 Corrosion current variations with the time of exposure for the effect of SCMs on
development of passive layer on different steel type
From the Figure 4.13 it can be observed that the source B in all the solution showed
lesser corrosion current density. On other hand, samples of steel source A immersed in all the
solutions shows higher values of the corrosion current. The effects of the SCMs are also very
prominent, although the effect is same on both the steel rebars. Natural pozzolans reduced the
corrosion current for both the steel sources. Silica fume increases the corrosion current. The other
74
conclusion that can be made from the Figure 4.13 is that in the start the corrosion current was
relatively high. As the time of exposure increased the corrosion current density decreased. After 8
days of immersion it became almost constant. This showed that passive layer took 8 to 10 days to
form and stabilized. For example corrosion current value of the steel source B specimen
immersed in solution contacting natural pozzolans was 0.06 A/cm in the initial stages. After 8
days it reduces to 0.035 A/cm and became constant. All the specimens were in passive state as
the corrosion current density was lesser than 0.1 A/cm (Andrade et al., 2004 and Song, 2007).
After the EIS tests and stabilization of the passive layer, SEM imaging was carried out and
results are represented in Figure 4.14. 10 mm pieces of 16 mm dia. steel rebar sources were placed
in the test solutions. Figure 4.14 (a) shows the SEM image of steel source A and Figure 4.14(b)
shows the SEM image of source B.
Broken
surfaces
overall
Figure 4.14(a) SEM image of steel source A
75
Small crack on the
surface
Figure 4.14(b) SEM image of steel source B

Figure 4.14 SEM images of different steel sources immersed in SCMs
From the SEM images it can be seen that in steel source A there are many irregularities
and bigger cracks (Figure 4.14(a)). From Figure 4.14(b) it can be seen that film developed on the
steel source B has a thicker surface and lesser cracks on the surface. The steel source B was
having TM ring, which has cracks and irregularities in it. When steel source B was immersed in
the alkaline nature solution containing SCMs, the voids and cracks get filled and showed lesser
cracks on the surface.
4.3.5 Energy-Dispersive X-ray Spectroscopy (EDS) Results
FEG-SEM was used for the EDS analysis of the samples and results of EDS are presented
in Figure 4.15. After performing the SEM imaging, the EDS analyses were performed to get the
information about the elements present in the passive layer. In Figure 4.15 (a) the EDS analysis of
source A is given and in Figure 4.15(b) the EDS analysis of source B is presented.
76
Element Weight%
C 2.80
O 17.53
Na 0.8
Si 0.25
Ca 0.19
C 2.98
Fe 81.23
Totals 100.00
Figure 4.15(a) EDS analysis of steel source A
Element Weight%
O 23.79
Na 1.11
Si 0.89
K 0.35
Ca 3.17
Mn 0.41
Al 0
Fe 71.8
C 2.0
Totals 100.00
Figure 4.15(b) EDS analysis of steel source B

Figure 4.15 EDS analysis of different steel sources immersed in SCMs
77
In Figure 4.15 EDS analysis of the control specimen for both steel sources is presented.
From the Figure 4.15 it can be seen that Si is more in the layer developed on steel rebar B (Si
=0.89) than that of the source A (Si=0.25). EDS analyses were carried out for all the specimens,
but only control is presented to avoid repetition. Remaining specimens showed the same trend for
both the steel surfaces. Source B showed better results than source A.
4.3.6 4.3.6 Discussion on Results of Effect of SCMs on Steel Sources
Rankings of the quality of the protective passive layer grown on rebar immersed in the
various solutions are shown in Table 4.4. Rank 1 is better than rank 2 in quality and protective
properties.
Table 4.4 Rankings of passive layer quality developed on different steel sources
Parameters
Ranking Impedance Half-cell Corrosion
Potential Current
1 B B B
2 A A A
It can be seen in Table 4.4 that these rankings of the passive layer developed on steel rebars,
derived from both Tafel scan and EIS techniques provided very similar rankings for the passive
layers. These measures are not all independent, so it is not surprising that they lead to similar
rankings; however, this shows that any of the measures can be used to provide an estimate of the
quality of the protective passive layer. This could prove useful in practical situations where some
measurements might be easier to make than others.
78
In general, the two most commonly used local rebars A and B are rolled by steels
having different compositions; steel source B is TMT steel and steel source A is LAS (low
alloy weathering type steel). The outer ring of steel source B is TM (tempered martensite) and
inner one is PF (pearlite ferrite). This ring is believed to have higher corrosion resistance but cracks
and irregularities could be present at the surface. When the steel rebar having TM ring is exposed
to the pore solution, these cracks are filled with the iron oxides and the already corrosion resisting
ring become stronger when passive film developed on it. On the other hand the steel source without
TM ring has the corrosion resistance only due to the passive film developed on it. Figure 4.16
represents the schematic diagram of this phenomenon.
Figure 4.16 Schematic diagram of passivation of steel source A and B

The pure iron is very reactive chemically and rapidly corrodes, especially in moist air or at
elevated temperatures. It has four allotropic forms or ferrites, known as alpha, beta, gamma, and
omega, with transition points at 700, 928, and 1530C. The alpha form is magnetic in nature, but
when transformed into the beta form, the magnetism disappears although the lattice remains
unchanged. The relations of these forms are peculiar. Alpha iron is the major chemical component
of martensite (Sami et al., 2013). When surface containing alpha oxide was exposed to alkaline
nature pore solution, alpha iron which is not fully stable elements reacts with the oxides and form
79
iron oxides. These iron oxides are the major part of the protective passive layer. That might be the
other reason, steel source having martensite (steel source B) had better and more protective
passive film. SEM and EDS results confirmed the phenomenon that the passive layer developed
on the steel rebar source B is better in protection and quality than source A. Iron oxides found
in the passive layer of source A are lesser than source B. Commonly used SCMs in concrete,
such as silica fume, natural pozzolans and fly ash do actually affect the passive layer formed on
common black reinforcing steel at the nano-scale. In particular, it has been observed by both Tafel
scan and EIS that the presence of silica fume in the concrete pore solution has a significant negative
effect on the protective properties of passive films developed on different steel types. The effects
of the SCMs were observed same for steel source A and B for the development of passive
layer on the steel rebars.
4.4 Effect of SCMs on Passive Layer Developed on Different Surface Conditions of Steel
Rebars
In this Section, the effects of mill scale on formation and stability of passive film on rebars
in the solutions having SCMs is presented. Studies were carried out on some electrochemical
parameters such as impedance, corrosion potential, corrosion current and corrosion penetration,
using EIS and Tafel scan tests. The experiments were performed in the simulated concrete pore
solution with different SCMs added to the pore solution. To compare the effect of mill scale the
tests were carried out for two surface conditions i.e. mill scale (unpolished or as-received) and
without mill scale (polished). Procedure of polishing is already explained in the sample preparation
section of Chapter 3. In all the results unpolished (with mill scale) specimens are symbolised in
the legends by UP and polished specimens are symbolised by P.
80
4.4.1 EIS Results
Electrochemical impedance studies after different intervals of exposure of steel samples in
concrete pore solution were performed and plots are shown in Figures 4.17 (a) (b).
10000
1000
100
Impedance (Ohm)
P-C
10
UP-C
0.1
0.01
0.01 1 100 10000 1000000
Frequancy (Hz)
Figure 4.17(a) Bode plot after 24 hours of immersion

10000
1000
100
Modulus (Ohm)
P-C
10
UP-C
0.1
0.01
0.01 1 100 10000 1000000
Frequancy (Hz)
Figure 4.17(b) Bode plot after 8 days of immersion

4.17 Bode plot after different time of exposure for the effect of SCMs on surface condition
are plotted in Figures 4.18(a) (d). The results incorporated in these figures show that polarization
81
resistance of the samples increase with exposure time. These facts suggest that the initially formed
film on the steel surface gradually transforms to a more protective passive film. This showed that
higher the impedance values better is the quality and thickness of passive layer. Another
observation that emerged during this study was the values of impedance recorded at lower
frequencies of the plots. These values showed that samples with mill scale mounted in NP, after
the exposure period of 8 days exhibits considerably higher impedance than the control samples, at
lower frequencies (< 10-2 Hz) (Figure 4.18 (a)).
4000
3500
3000
Impedance (Ohm)
2500
2000
1500
1000
UP-C
500 P-C
0
0 2 4 6 8 10 12 14 16
Time (Days)

4000
3500
3000
Impedance (Ohm)
2500
2000
1500
1000
500 UP-NP
P-NP
0
0 2 4 6 8 10 12 14 16
Time (Days)
82
4000
3500
3000
Impedance (Ohm)
2500
2000
1500
1000
UP-FA
500
P-FA
0
0 2 4 6 8 10 12 14 16
Time (Days)

4000
3500
3000
Impedance (Ohm)
2500
2000
1500
1000
UP-SF
500 P-SF
0
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.18 Impedance variations with the time of exposure for the effect of SCMs on steel
surface condition
Rebars with and without mill scale immersed in the solutions with the silica fume showed
the lowest values (Figure 4.18 (d)). That means the natural pozzolans increases the quality and the
thickness of the passive film. Silica fume has negative effect on the passivity of steel rebar. From
the Figures 4.18(a) (d) it can also be seen that in all the cases the steel reabrs with the mill scale
had given the higher quality. The polished bars showed lesser strength in other words lesser
thickness.
83
The results obtained from the open circuit potential test are presented in Figure 4.19. These
tests were performed from 24 hours of the exposure period until the stabilization of the passive
film. The test was analysed according to ASTM C 876 (Standard Test Method for Corrosion
Potentials of Uncoated Reinforcing Steel in Concrete).Comparison of control, NP, FA, SF is given
in Figures 4.19 (a) (d).
-400
-300
-200
-100
UP-C
0
P-C
100
200
300
0 2 4 6 8 10 12 14 16
Time (Days)

-400
-300
-200
-100
UP-NP
0
P-NP
100
200
300
0 2 4 6 8 10 12 14 16
Time (Days)
84
-400
-300

-200
-100
UP-FA
0
P-FA
100
200
300
0 2 4 6 8 10 12 14 16
Time (Days)

-400
-300
-200
-100
0 UP-SF
P-SF
100
200
300
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.19 Potential variations with the time of exposure for the effect of SCMs on steel surface
condition
From Figure 4.19 it can be observed that unpolished bars show lesser values of open circuit
potential than the polished bar for all the SCMs. That mean the passive layer developed on the
unpolished bar is more protective than the layer devoted on polished rebars. From Figure 4.19 it
can also be seen that the film developed in the solution having natural pozzolans showed lowest
values of open circuit potential with and without mill scale i.e. 200 mV and 130 mV respectively.
Silica fume solution for polished and unpolished surface bars showed higher values than all other
sample (120 mV for mill scale specimen and 80 mV for polished specimen). It also can be observed
85
that all the steel samples were in protective range as described by the ASTM C876 (Potential > -
200). Steel rebars immersed in different pore solutions showed very highly potential values in the
start because at that time initiation of the development of the passive layer takes place. For
example, specimen immersed in the test solution having silica fume with polished surface. The
initial potential was measured -390 mV and after 8 days it is observed that it is stabilized at 80
mV.
4.4.3 Tafel Scan
Tafel scan plots after 24 hours and after 15 days of immersion are shown in Figure 4.20.
Tafel curves were obtained by starting 10 mV below the free potential and finishing at 800 mV
SCE, using a scan rate of 0.166 mV/s, as prescribed in ASTM G59-97. The choice of scan rate is
a compromise between accuracy and the time to complete the measurement. Observed Tafel scan
curves are shown in Figure 4.20. Figure 4.20(a) represents the Tafel scan plot after 24 hours of
immersion and Figure 4.20(b) represents the Tafel plot after 15 days of immersion period.
-0.6
-0.5
-0.4
Potential (V)
-0.3
-0.2
UP-NP
-0.1 P-NP
0
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
Current (A)
Figure 4.20(a) Tafel scan curve after 24 hours of immersion

86
-0.5
-0.4
-0.3
Potential (V)
-0.2
-0.1
UP-NP
0 P-NP
0.1
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
Current (A)
Figure 4.20(b) Tafel scan curve after 15 days of immersion

Figure 4.20 Tafel scan curve after different time of exposure for the effect of SCMs on surface
condition of steel rebars
A simple Evans diagram description (plotting potential against log of the current density) or Tafel
scan curve of the present experiment would show all of the corrosion currents in Figure 4.20
occurring at the intersections of the cathodic line for the reduction of oxygen and the various metal
oxidation lines, which would all be vertical in accord with the passive state conditions. Thus the
polarization curves without mill scale in Figure 4.20 move down (to lower corrosion potentials)
and to the right (to higher current densities) as the passive films become less protective. From the
analysis of the Tafel scan plot the corrosion current can be calculated.

Corrosion current densities were calculated by analysing the Tafel scan and presented in
Figure 4.21. Corrosion current density is one of the major indicators of the corrosion. In other word
it is indirectly represent the passive state of the rebar. In Figure 4.22 the corrosion current density
87
is plotted vs the time of exposure of steel rebars to the solutions. Comparison of the surface
conditions for all the SCMs sample are shown in Figures 4.21(a) - (d).
0.14
0.12

0.10
0.08
0.06
0.04 UP-C
P-C
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.21(a) Comparison of Control

0.14
0.12
0.10
0.08
0.06
0.04 UP-NP
P-NP
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.21(b) Comparison of NP
88
0.14
0.12

0.10
0.08
0.06
0.04 UP-FA
P-FA
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.21(c) Comparison of FA

0.14
0.12
0.10
0.08
0.06
0.04 UP-SF
P-SF
0.02
0.00
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 4.21(d) Comparison of SF

Figure 4.21 Corrosion current variations with the time of exposure for the effect of SCMs on
steel surface condition
From the Figure 4.21 it can be observed that the natural pozzolans is helpful in reducing
the corrosion current density for both steel surfaces. On other hand, samples immersed in the other
solutions shows higher values of the corrosion current. In all the test solutions the polished bar
showed higher current densities than the unpolished bars. The other conclusion that can be made
from the Figure 4.21 is that in the start the corrosion current was high. As the time of exposure
increased the corrosion current density decreased. After 8 days of immersion it became almost
constant. This showed that passive layer took 8 to 10 days to form and stabilized.
89
SEM images for polished and unpolished steel rebar specimens are presented in Figure
4.22. Steel rebars specimens were immersed in all the test solutions. After 8 days of immersion
the test specimen were taken out from the solutions. After cleaning the specimens were dried and
tested with Field Emission Scanning Electron Micro scope (FE-SEM).
Small cracks
Bigger cracks
UP P
Spongy surface Figure 4.22(a) SEM image in Control solution
Cracked surface
UP P
Figure 4.22(b) SEM image in FA solution
90
Very smooth
Uneven surface
surface
UP P
Larger cracks on the surface

Figure 4.22(c) SEM image in NP solution
Broken surface
UP P
Figure 4.22(d) SEM image in SF solution
Figure 4.22 SEM Image of different steel surfaces immersed in SCMs

From the Figures 4.22(a) (d) it can be seen clearly that the unpolished surface has
smoother surfaces and cracks are visible in the polished surfaces. From Figure 4.22(a) it can be
seen that in control specimen, unpolished specimen showed smaller cracks but bigger hole/ pit can
be seen on the surface of polished specimen. In case of silica fume the unpolished surface showed
smooth surface but polished showed series of small holes on the surface (Figure 4.22(d). In fly ash
and natural pozzolans the same effect can also be observed (Figures 4.22(b) (c)).
91
4.4.5 EDS Results
After 15 days of the immersion EDS analysis was carried out and results are presented in
the Figure 4.23. EDS analyses were performed for the samples with and without mill scale to see
the elemental composition of the passive layer developed on the steel rebars. EDS analysis of
unpolished specimen in control solution is shown in Figure 4.23(a). Figure 4.23(b) represents the
EDS analysis of polished specimen in control.
Element Weight
%
C 2.80
O 17.53
Na 0.8
Si 0.25
ca 0.19
Fe 81.23
Totals 100.00
Figure 4.23(a) EDS analysis of unpolished specimen in control solution
92
Element Weight%
O 15.38
Na 0.75
Si 0.23
Ca 0.18
Mn 0.26
Fe 83.2
Totals 100.00
Figure 4.23(b) EDS analysis of polished sample in control solution

Figure 4.23 EDS analysis of different steel surfaces immersed in SCMs
From the above Figure 4.23 it can be revealed that the elemental composition of the passive
layer developed on unpolished bar is better than of the polished specimen. Iron oxides, silica
content and carbon are available in higher amount in unpolished surface. EDS analysis were
carried out for specimens immersed in all the solutions, but only the control specimen is presented
to avoid repetition of the results.
4.4.6 Discussion on the Results of Effect of SCMs on the Surface Condition
Rankings of the quality of the protective passive layer grown on polished and unpolished
rebar immersed in the pore solutions are shown in Table 4.5. The Tafel scan experiments suggested
that high quality passive layers have low passive current densities and high corrosion potentials;
93
hence the quality of the passive layer can be ranked from high to low by ordering them according
to low to high values of corrosion current. In addition, the EIS correlations suggest that higher
quality films have higher values of the real impedance at 0.01 Hz and, hence, the quality of the
films can be similarly ranked.
Table 4.5 Rankings of passive layer quality developed on different surfaces of rebar
Parameters
Rankings Impedance Half-cell Corrosion
Potential Current
1 UP UP UP
2 P P P
It can be seen in Table 4.5 that both Tafel scan and EIS techniques provided very similar
rankings for the passive layers developed on polished and unpolished steel rebar samples. These
measures are not all independent, so it is not surprising that they lead to similar rankings: However,
this shows that any of the measures can be used to provide an estimate of the quality of the
protective passive layer. This could prove useful in practical situations where some measurements
might be easier to make than others. The experiments in this research were designed to simulate
both in-service conditions of steel rebar and treated steel rebars in concrete.
In general, mill scale consists primarily of magnetite, Fe3O4, of characteristic blue-gray
"steely" colour. An extremely thin outer film of hematite, Fe2O3, is invisible to the naked eye.
The inner portion of the magnetite contains fine metal grains and sometimes, residual black FeO,
which contribute to the roughness of descaled metal. Mill scale is found on all hot-rolled steel
products unless processed in a protective atmosphere or descaled (e.g., for galvanizing). At hot
rolling temperatures, an inner layer of wstite, FeO, exists between the steel and magnetite. "At
94
elevated temperatures, FeO constitutes about 85% of the scale thickness, Fe3O4 about 10 to 15%
and Fe2O3 about 0.5 to 2%. During slow cooling [below 1040 F] of hot-rolled coils of hot-rolled
strip (and heavy shapes), most of the FeO is transformed to Fe and Fe3O4, and the latter oxide is
predominant after cooling. The alloying metals form cations within the mill scale at about the
alloying proportions (unlike general heating or heat treatment scale, where Al, Cr, etc.
preferentially oxidize) due to the almost instantaneous oxidation of freshly exposed metal at high
temperature. Fe3O4 contains both Fe+2 and Fe+3, and is sometimes written FeOFe2O3.
Ni+2 substitutes for Fe+2, Al+3 and Cr+3 substitute for Fe+3. Thus, (Fe,Ni)O(Fe,Al,Cr)2O3. Cations
of other valences, e.g., Si+4 and Ti+4, are accompanied by cation vacancies to maintain overall
electrical neutrality. With very slow cooling, small grains of Si- and Ti-containing oxides may
precipitate within the scale. (United States Steel, 2009).
Already available layer get stronger when it is exposed to the alkaline nature of simulated concrete
pore solution. The crakes (if present) in the mill scale were filled with the newly developed passive
layer as well as with the SCMs. That can be another reason of the better quality of layer developed
on the unpolished rebar. The effect of SCMs for the development of passive layer on steel rebar
was observed same for the polished and unpolished i.e. natural pozzolans increased the quality and
protectiveness of the passive layer and Silica fume reduces the quality of passive layer. The passive
layer developed on unpolished specimens showed about 35 % higher quality than that of polished
specimens for all the SCMs. These results may be contradicting to already available past literature.
It might be due to shorter duration of tests performed during the current studies. Also, the past
literature focused mostly on the effect of surface condition on corrosion of steel in concrete rather
than on the passive layer. For example, Singh et al. (2003) investigated the role of surface condition
(as received, polished and rusted) by embedding steel rebars in chloride contaminated mortar.
95
Weight loss, electrochemical direct current polarization and alternating current impedance
spectroscopy (EIS) studies were carried out to see the effect of black oxide on the rebars surface
embedded in mortar. They concluded that the presence of mill scale on rebars surface accelerates
corrosion in concrete. It was also observed that the mortars embedded with rebars having mill scale
cracked within 450 days of exposure in the test environment whereas the mortars with descaled
rebars took 760 days of exposure for cracking.
4.5 Effect of Environment (Simulated Concrete Pore Solution and Mortar) on the
Performance of the SCMs on the Passive Layer Developed on Steel Reabrs
The corrosion of steel rebars in concrete and mortar is studied by many researchers in the
past for different variables like environmental condition, chloride content, carbonation, corrosion
under stress etc. However, the effect of SCMs on the passive layer is not yet studied in mortar.
This is the scope of work for this section of the research.
In this research, the time required for steel reinforcing rebars to be passivated, quality and
protectiveness of passive layer in mortar and in simulated pore solution with SCMs has been
investigated. EIS, Tafel scan and half-cell potential techniques were used for determining the time
required for passivation and the quality of passive layer. In the legends of this section, symbol S
stands for the specimens immersed in the simulated concrete pore solution and symbol M stands
for the specimens embedded in the mortar.
4.5.1 EIS Results
Results of Electrochemical impedance studies are shown in Figure 4.24. During the
experimentation, it was observed that the modulus of impedance of the passive film at the lowest
96
studied frequency (10-2 Hz) increases with exposure time. The significant changes were recorded
only up to 8 days of exposure in SPS and 18 days in mortar. Beyond this period, no substantial
changes were noted. These results show that with increase in duration of exposure, the structure
of the passive film transformed into more protective nature.
10000
1000
Impedance (Ohm)
100
10
0.1
M-C
S-C
0.01
0.01 1 100 10000 1000000
Frequency (Hz)
Figure 4.24(a) Bode plot after 24 hours of immersion
10000
1000
Impedance (Ohm)
100
10
0.1 M-C
S-C
0.01
0.01 1 100 10000 1000000
Frequency (Hz)
Figure 4.24(b) Bode plot after 18 days of immersion

97
Figure 4.24 Bode plot after different time of exposure for different environments
are plotted in Figures 4.25 (a) (d). The results incorporated in these figures shows that
polarization resistance of the samples increase with exposure time. These facts suggest that the
initially formed film on the steel surface gradually transforms to a more protective passive film.
4000
3500
3000
Impedance (Ohm)
2500
2000
1500
M-C
1000
S-C
500
0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.25(a) Control

4000
3500
3000
Impedance (Ohm)
2500
2000
1500
M-NP
1000
S-NP
500
0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.25(b) NP
98
4000
3500
3000
Impedance (Ohm)
2500
2000
1500
M-FA
1000
S-FA
500
0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.25(c) FA
4000
3500
3000
Impedance (Ohm)
2500
2000
1500
M-SF
1000
S-SF
500
0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.25(d) SF
Figure 4.25 Impedance variation comparisons with time for exposure to mortar and SPS
environments on the performance of SCMs
Another observation that emerged during this study was the values of impedance recorded
at lower frequencies of the plots. These values showed that samples mounted in the SPS solutions
get stabilized after 8 days. On other hand the specimens embedded in the mortar took almost 18
99
days for the stabilization of the passive layer. From the Figure 4.25 it can be seen that the bars
immersed in the SPS initially showed higher impedance values but after getting stabilized the trend
became reverse. Rebars immersed in the solutions and mortar with the silica fume showed the
lowest values than the bars immersed in SPS and mortars other SCMs. That means the natural
pozzolans increases the quality and the thickness of the passive film. Silica fume reduces the
quality of passive layer and do have negative effect on the passivity of steel rebar although it has
positive effects on the concrete microstructure.
The results obtained from the open circuit potential test are presented in Figure 4.28. The
tests were analysed according to ASTM C 876 (Standard Test Method for Corrosion Potentials of
Uncoated Reinforcing Steel in Concrete). In Figures 4.26(a) (d), the comparison of the effect of
SCMs on the mortar and SPS specimens are made.
-400
-300
Half-Cell potential (mV)
-200
-100
0
M-C
100 S-C
200
300
400
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
100
-400
-300

-200
-100
0 M-NP
S-NP
100
200
300
400
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.26(b) NP
-400
-300
-200
-100
0
M-FA
100 S-FA
200
300
400
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.26(c) FA
-400
-300
-200
-100
0 M-SF
S-SF
100
200
300
400
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.26(d) SF
Figure 4.26 Potential variation comparisons with time for exposure to mortar and SPS
101
From the Figure 4.26(a) it can be seen that the film developed in the solution having natural
pozzolans showed lowest values of open circuit potential (300 mV). Silica fume showed higher
values than all other sample (200 mV). The steel rebars embedded in the mortar showed higher
protective properties of passive layer than the specimen mounted in simulated concrete pore
solution. It also can be seen that all the steel samples are in very protective range as described by
the ASTM C 876 (Potential > -200). Steel rebars immersed in different pore solutions and
embedded in mortar showed very highly potential values in the start because at that time initiation
of the development of the passive layer takes place. As time passes, the potential values start
decreasing and after 8 days it gets stabilized in pore solutions and 18 days in mortar. It shows that
passive film took almost 8 to 10 days to develop and stabilized in SPS and in mortar it requires 18
days.
4.5.3 Tafel Scan
Tafel scan curves for SPS and mortar specimens are shown in Figure 4.27. Tests were
performed from the first day of steel rebar exposure to SPS and mortar, until stabilization of the
passive layer. Figure 4.27(a) represents the Tafel plot after 18 hours of exposure and Figure 4.27(b)
shows the Tafel scan plot after 24 days of exposure.
102
-0.5
-0.4
-0.3
Potential (V)
-0.2
-0.1
S-SF
0 M-SF
0.1
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
Current (A)
Figure 4.27(a) Tafel scan curve after 24 hours of immersion

-0.5
-0.4
-0.3
Potential (V)
-0.2
-0.1
M-SF
0 S-SF
0.1
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
Current (A)
Figure 4.27(b) Tafel scan curve after 18 days of immersion

Figure 4.27 Tafel scan curve after different time for exposure to mortar and SPS environments
on the performance of SCMs
From the Figure 4.27 it is observed that after 24 hours the curve for the specimen immersed
in SPS showing lesser corrosion current and corrosion potential. After 18 days the curve for rebar
embedded in the mortar is shifted to lower currents compared to the curves for the specimen
immersed in the solution. The inference is that the passive layers on the rebar specimens became
103
relatively stable after eight days of immersion in the pore solutions but for bars embedded in the
mortar took 18 days.
A simple Evans diagram description (plotting potential against log of the current density)
or Tafel scan curve of the present experiment would show all of the corrosion currents in Figure
4.27 occurring at the intersections of the cathodic line for the reduction of oxygen and the various
metal oxidation lines, which would all be vertical in accord with the passive state conditions.
Oxides that are not as protective would passivate (become vertical on the Evans diagram) at higher
current densities and consequently the intersection of the oxygen reduction line with the passive
region occurs at lower potentials, in accord with the negative Tafel slope relating the reduction
over potential to the logarithm of the current density . Thus the polarization curves in Figure 4.27
move down (to lower corrosion potentials) and to the right (to higher current densities) as the
passive films become less protective. From the analysis of the Tafel scan plot, corrosion current
can be calculated.

In Figure 4.28 the corrosion current density is plotted against the time of exposure for the
steel rebar in the solutions and embedded in the mortar. A comparison of the effect of SCMS on
both environments is shown in Figures 4.28(a) - (d). Corrosion current density was calculated by
analysing the Tafel scan. Corrosion current density is one of the major indicator of the corrosion.
In other word it is indirectly represent the passive state of the rebar.
104
0.40
0.35

0.30
0.25
0.20
0.15 M-C
S-C
0.10
0.05
0.00
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)

0.40
0.35
0.30
0.25
0.20
0.15 M-NP
S-NP
0.10
0.05
0.00
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.28(b) NP
0.40
0.35
0.30
0.25
0.20
0.15 M-FA
S-FA
0.10
0.05
0.00
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.28(c) FA
105
0.40
0.35

0.30
0.25
0.20
0.15 M-SF
S-SF
0.10
0.05
0.00
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (Days)
Figure 4.28(d) SF
Figure 4.28 Corrosion current comparisons with time for exposure to mortar and SPS
Figure 4.28 showed that the natural pozzolans was helpful in reducing the corrosion current
density in both environments. The mortar specimen showed very higher current densities at the
beginning as compared to the SPS specimens. As cement hydrated with time, the formation of the
passive layer started gradually. Both lines (Mortar and SPS) starts coming closer to each other.
After 8 days of exposure, the corrosion current density became stable for the SPS. On the other
hand, the specimens exposed in mortar specimen took 18 days to stabilize the corrosion current
values. Effect of the SCMs is observed similar in both environments i.e. natural pozzolans samples
shows lower corrosion current as compared to silica fume samples.
4.5.4 Discussion on the Results of Effect of Environment on the performance SCMs on the
Development of Passive Layer
Rankings of the quality of the protective passive layer grown on the steel rebar immersed
in various solutions and embedded in mortar are presented in Table 4.6. The Tafel scan
experiments suggested that high quality passive layers have low passive current densities and high
corrosion potentials. As a result, the quality of the passive layers can be ranked from high to low
106
by ordering them according to low to high values of corrosion current. In addition, the EIS
correlations suggest that higher quality films have higher values of the real impedance at 0.01 Hz,
the quality of the films can be similarly ranked.
Table 4.6 Rankings of passive layer quality developed in different SCMs
Parameters
Ranking
Impedance Half-cell Potential Corrosion Current
1 NP NP NP
2 FA FA FA
3 C C C
4 SF SF SF
From Table 4.6 it can be observed that these measures derived from both Tafel scan and
EIS techniques provided very similar rankings for the passive layers. These measures are not all
independent, so it is not surprising that they lead to similar rankings. However, this shows that any
of the measures can be used to provide an estimate of the quality of the protective passive layer.
This could prove useful in practical situations where some measurements might be easier to make
than others.
On the bases of the environment (mortar and SPS), the passive layers developed on the
steel rebar can be ranked as better to poor on the basis of results obtained from different tests
performed. Table 4.7 summarizes these rankings.
Table 4.7 Ranking of passive layer qualitybased on environment (SPS and mortar)
Parameters
Ranking
Impedance Half-cell Potential Corrosion Current
1 M M M
2 S S S
107
Firstly, after 24 hours of exposure the SPS specimens showed lesser corrosion current,
corrosion potential and corrosion rate as compared to steel rebars embedded in mortar. In mortar
specimens, corrosion current, corrosion penetration and mass loss was higher in the beginning of
the test. Secondly, for EIS, the impedance/resistance was lesser for specimens embedded in the
mortar and was higher for the SPS specimens, which indicated that the passive layer developed on
the embedded specimens were weaker than of the layer developed on the SPS samples. After 18
days of exposure, the results showed that quality of passive layer became opposite i.e. mortar
specimens showed higher quality and protective properties of the passive layer as compared to the
SPS specimens. It can also be concluded that the formation of passive layer in mortar was slower
but stronger at the end. The reason behind this phenomenon could be the hydration of cement. In
SPS, the environment is simulated to the hydrated cement in which the pH value and alkalis are
simulated as per hydrated cement. However, in mortar, hydration process started after the addition
of water. The pH value and alkali formation in mortar specimens will be increased as the hydration
of cement goes on. It is well established fact that the formation of calcium hydro oxide is completed
70 % in first 7 days. After that the formation of passive layer accelerated in mortar specimens, as
the time passes and get stabilized after18 days.
In summary, commonly used SCMs in concrete, such as silica fume, natural pozzolans and
fly ash do actually affect the passive layer formed on common black steel rebar at the nano-scale.
In particular, it has been observed by both Tafel scan and EIS that the presence of silica fume has
a significant negative effect on the protective properties of passive films either it is immersed in
SPS or in mortar. The effect of SCMs for the development of the passive layer on steel rebars was
observed same for both specimens embedded in the mortar or placed in the SPS. From these results,
108
it can be concluded that the protective passive film can be categorized in this sequence
NP>FA>C>SF in quality and protectiveness for SPS and mortar specimens.
109
CHAPTER 5. CONCLUSIONS AND RECOMMENDATIONS
5.1 Conclusions
This research was aimed at investigating the effect of SCMs on the passive layer development
on the steel rebar. The effects of the SCMs on the passive layer were investigated experimentally
using the different electrochemical tests. SEM imaging and EDS analysis was also conducted for
the surface characterization of passive layer. From the test results, following conclusions can be
drawn:
1. Electrochemical techniques showed that SCMs used in SPS and mortar have a significant
influence on the quality of the passive layer developed on the steel rebars.
2. All SCMs reduce the pH value of the concrete pore solutions. Silica fume reduces the pH
value significantly as compared with natural pozzolans and fly ash.
3. The steel rebars immersed in SPS need 8 to days to fully develop and stabilize the passive
layer with and without SCMs. Whereas, in mortar, the passive layer needed three weeks to
get stabilized and fully developed.
4. During the initial age of the development of passive layer, mortar specimens showed lesser
quality in comparison to the passive layer developed in SPS specimens. However, once the
passive layer fully developed in mortar, the trend of passive layer in mortar became equal
or slightly higher than SPS.
5. Natural pozzolan improved the quality and protectiveness by depositing an overlay with
no voids or cracks on the passive layer. This improvement was about 38% compared to the
control.
110
6. Fly ash improves the quality of the passive layer by reducing the voids and cracks present
in the layer. This improvement was about 23% compared to the control.
7. Silica fume although good for concrete microstructure, it adversely affected the quality of
passive layer. This may be attributed due to the reduction in the pH of concrete pore
solution and formation of cracks and voids on the surface of passive layer.
8. Chemical composition of the steel rebar sources also have an effect on the formation of the
passive layer. The thermo mechanically treated steel rebars with TM-PF ring had stronger
and more protective passive layer in comparison to the micro alloyed steel.
9. The resistance of passive layer developed on unpolished steel rebar surface was stronger
than the passive layer developed on the polished surface of steel. This is in contradiction
to the earlier reported literature (Singh et al. (2003)). It might be due to the shorter duration
of tests performed during the current studies. Also, the focus of this research was on the
development of passive layer rather than on the corrosion of steel in concrete.
10. The EDS analysis indicates that the elemental composition of passive layer under the
influence of SCMs may play a role in defining the quality of passive layer, this needs
further study, especially on the role of Si deposition on the surface of steel rebar exposed
to SPS with SCMs.
5.2 Future Recommendations
Further research will help to improve future applications in the field of SCMs with respect
to the passive layer developed on steel rebars. In this research, the effect of SCMs on the quality
of the passive layer was studied using electrochemical techniques primarily. It should be
investigated at the nano-level using state of the art equipment such as XPS, Raman, and AFM etc.
111
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APPENDICES
Appendix A
4000 4000
3500 3500
3000 3000
Log Modulus (Ohm)

Log Modulus (Ohm)
2500 2500
2000 2000
1500 1500
1000 1000
A-C A-C
500 500
A-NP A-FA
0 0
0 5 10 15 20 0 5 10 15 20
Time (Days) Time (Days)
Figure A1(a) NP Figure A1(b) FA

4000 4000
3500 3500
3000 3000
Log Modulus (Ohm)
Log Modulus (Ohm)
2500 2500
2000 2000
1500 1500
1000 1000 A-C

A-C
A-FA
500 500 A-NP
A-SF
A-SF
0 0
0 5 10 15 20 0 5 10 15 20
Figure A1(c) SF Figure A1(d) Comparison

Figure A1 Modulus variation with time of exposure for steel source A
3000 3500
3000
2500
Log Modulus (Ohm)
Log Modulus (Ohm)
2500
2000
2000
1500
1500
1000
1000
A-C A-FA
500
500
A-P-C A-P-FA
0 0
0 5 10 15 20 0 5 10 15 20
122
Figure A2(a) Control Figure A2(b) FA
4000 2500
3500
2000
Log Modulus (Ohm) 3000
Log Modulus (Ohm)

2500
1500
2000
1000
1500
1000
A-NP 500 A-SF
500
A-P-NP A-P-SF
0 0
0 5 10 15 20 0 5 10 15 20
Figure A2(c) NP Figure A2(d) SF

Figure A2 Modulus variation with time of exposure for different surface
1400 1600
1200 1400
1200
Log Modulus (Ohm)
Log Modulus (Ohm)
1000
1000
800
800
600
600
400
400
A-P-C A-P-C
200 200
A-P-FA A-P-NP
0 0
0 5 10 15 20 0 5 10 15 20
Figure A3(a) FA Figure A3(b) NP

1200 1600
1400
1000
1200
Log Modulus (Ohm)
Log Modulus (Ohm)
800
1000
600 800
600
400
400 A-P-C
A-P-C
200 A-P-FA
200 A-P-NP
A-P-SF
A-P-SF
0 0
0 5 10 15 20 0 5 10 15 20

Figure A3 Modulus variation with time of exposure for steel source A polished surface
123
-400 -400
-300 -300

-200
-200
-100
-100 A-C
A-C
0
A-NP
0 A-FA
100
100 200
200 300
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Figure A4(a) FA Figure A4(b) NP

-400 -400
-300 -300
-200 Half-Cell Potential (mV) -200
-100 A-C
-100 A-FA
A-C A-NP
0
A-SF
0 A-SF
100
100 200
200 300
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16

Figure A4 Half-Cell potential variation with time of exposure for steel source A polished
surface
124
Appendix B
Effect of steel source (A and B) and surface conditions (as-received and polished) was also
investigated for the specimens embedded in mortar with all SCMs. As the results of mortar and
SPS specimens become similar after the development and stabilization of passive layer. Therefore,
experiment results for the comparison of steel source and surface conditions for mortar and SPS is
not presented in the chapter 4 (Results and Discussions) to avoid repetition and are presented in
the appendix of this dissertation.
1400 1400
1200 1200
1000 1000
Log Modulus (Ohm)
Log Modulus (Ohm)
800 800
600 600
400 400
A-P-C A-P-FA
200 200
S-P-C S-P-FA
0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
Figure B1(a) Control Figure B1(b) FA

1600 1200
1400
1000
1200
800
Log Modulus (Ohm)
Log Modulus (Ohm)
1000
800 600
600
400
400
A-P-NP 200 A-P-SF
200
S-P-FA S-P-SF
0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
Figure B1(c) NP Figure B1(d) SF

Figure B1 Impedance variation with time of steel source A for mortar and SPS
125
3000 3500
3000
2500
Log Modulus (Ohm) 2500
Log Modulus (Ohm)

2000
2000
1500
1500
1000
1000
A-Up-C A-UP-FA
500
500
B-Up-C B-UP-FA
0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

4000 4000
3500 3500
3000 3000
Log Modulus (Ohm)
Log Modulus (Ohm)

2500 2500
2000 2000
1500 1500
1000 1000
A-UP-NP A-UP-NP
500 500
B-UP-NP B-UP-NP
0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

Figure B2 Impedance variation with time for steel source comparison in mortar
-400 -400
-300 -300
-200 -200
-100 -100
0 0
100 100 A-FA

A-C B-FA
200 B-C 200
300 300
400 400
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
126
-400 -400
-300 -300

-200 -200
-100 -100
0 A-NP 0
B-NP
100 100 A-SF
B-SF
200 200
300 300
400 400
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

Figure B3 Half-Cell variation with time for unpolished steel sources comparison in mortar
-350 -350
-300
-250 -250
-200
-150 -150
-100
-50 -50
0 A-P-FA
A-P-C B-P-FA
50 50
B-P-C
100
150 150
200
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

-350 -350
-300
-250 -250
-200
-150
-150
-100
-50 A-P-NP
-50
B-P-NP
0
50 A-P-SF
50
B-P-SF
150 100
150
250 200
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

Figure B4 Half-Cell variation with time for polished steel sources comparison in mortar
127
-400 -400
-300 -300
Corroion Potential (mV)

-200 -200
-100 -100
0 0 A-UP-FA
A-UP-C
A-P-FA
100 A-P-C 100
200 200
300 300
400 400
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
-400 -400
-300 -300

-200 -200
-100 -100
0 A-UP-NP 0
A-UP-SF
A-P-NP
100 100 A-P-SF
200 200
300 300
400 400
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

Figure B5 Corrosion penetration variation with time for steel source A surface condition
comparison in mortar
-400 -400
-300 -300
-200 -200
-100 -100
0 0
B-UP-FA
B-UP-C
100 100 B-P-FA
B-P-C
200 200
300 300
400 400
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
128
-400 -400
-300 -300

-200 -200
-100 -100
0 B-UP-NP 0
B-UP-SF
B-P-NP
100 100 B-P-SF
200 200
300 300
400 400
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

Figure B6 Corrosion penetration variation with time for steel source B surface condition
comparison in mortar
129

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Department of Civil Engineering,

EFFECT OF SUPPLEMENTARY CEMENTITIOUS MATERIALS ON THE

Muhammad Shoaib Ashraf

Prof. Abdulrahman M. Alhozaimy

Dr. Raja Rizwan Hussain

KING SAUD UNIVERSITY

Muhammad Shoaib Ashraf s/o Muhammad Ashraf

Prof. Abdulrahman M. Alhozaimy

Members of examination committee

Prof. Abdulaziz I. Al- Negheimish Prof. Muhammad Iqbal Khan

Prof. M. Jamal M. Al-Shannag

have been cited and referenced.

Muhammad Shoaib Ashraf

Mr. & Mrs. Muhammad Ashraf,

CHAPTER 1. INTRODUCTION ........................................................................................... 1

Table 3.1 Mechanical properties of steel rebar from both sources .. 38

Table 3.2 Compositional analysis of steel rebars . 38

Table 3.3 chemical composition of cement . 39

Table 0.4 Chemical properties of SCMs .. 39

Table 0.3 pH values of solutions .. 64

and structure, as well as its breaking process.

1.2 Problem Statement

Supplementary Cementitious Materials (SCMs) are believed to increase the corrosion

1.3 Research Objectives

techniques. The study covered the following parameters:

the kingdom of Saudi Arabia.

c. Two surface condition of the rebars (as received vs polished).

1.4 Thesis Outline

regarding passive layer, corrosion and SCMs.

equipment used are described in this chapter.

on the state-of-the-art analysis.

Chapter 5: This chapter consists of conclusions and future recommendations.

mortar) is also described.

2.2 Corrosion of Steel in Concrete

For corrosion to occur, the following elements must be present:

or the steel rebar itself (Jones, 1996).

oxidation reaction, or anodic reaction, and is represented as in Equation 2.1:

2Fe 2Fe2+ + 4e- (2.1)

common reduction reaction is (Equation 2.2):

2H2O + O2 + 4e- 4OH-- (2.2)

2Fe2+ + 4OH- 2Fe(OH)2 - (2.3)

the concrete cover.

2.3 Supplementary Cementitious Materials (SCMs)

directly related to passivation of the steel rebars.

2.3.1 Fly Ash

techniques, open-circuit potential, polarization resistance measurement and electrochemical

increased, along with a decrease of corrosion rate

2.3.2 Silica Fume

(concreteconstruction.net). The applications of the use of silica fume include; high-strength

Replacement of silica fume up to 8 percent by weight of Ordinary Portland Cement (OPC)

used at a higher replacement level more than 20 percent.

at least not to the same extent as does silica fume

2.3.3 Natural Pozzolan

calcium hydroxide (Ca(OH)2) to form compounds possessing hydraulic cementitious properties

(Al-Chaar et. Al ,2013). The pozzolonic reaction can be defined as:

Calcium Hydroxide+Silica+Water Calcium-Silicate-Hydrate (C-S-H)

C-S-H provides the hydraulic binding property of the material

2.4 Steel Rebars

2.4.2 Quenched Steel (TM-PF Ring)

within the scale. (United States Steel,2009).

2.6 Environment around Steel Rebars (SPS and Mortar)

Portland cement concrete pore solution is primarily consisted of saturated Ca(OH)2

for the prediction of corrosion behaviour of steel in structures may be misleading.