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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
King Saud University

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
King Saud University
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.

vi
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
4.3.2 Half-Cell Potential Results ..................................................................................... 68
4.3.3 Tafel Scan ............................................................................................................... 70
4.3.4 Scanning Electron Microscopy (SEM) Results ...................................................... 75
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
4.4.2 Half-Cell Potential Results ..................................................................................... 84

vii
4.4.3 Tafel Scan ............................................................................................................... 86
4.4.4 Scanning Electron Microscopy (SEM) Results ...................................................... 90
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

viii
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

ix
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(b) Comparison in NP solution ...... 70
Figure 4.11(c) Comparison in FA solution ...... 70
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(a) Comparison in Control solution ....... 74
Figure 4.13(b) Comparison in NP solution .. 74
Figure 4.13(c) Comparison in FA 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(a) Comparison in Control solution ....... 83
Figure 4.18(b) Comparison in NP solution ...... 83
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(a) Comparison in Control solution ....... 85
Figure 4.19(b) Comparison in NP solution ...... 85
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(a) Comparison in Control solution ....... 89
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
Half-Cell Potential (mV)
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)).

4.3.2 Half-Cell Potential Results

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

Half-Cell Potential (mV)


-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
Half-Cell Potential (mV)

-200

-100

0 A-NP

B-NP
100

200

300
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.11(b) Comparison in NP solution


-400

-300
Half-Cell Potential (mV)

-200

-100

0
A-FA

B-FA
100

200
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.11(c) Comparison in FA solution

69
-400

-300

Half-Cell Potential (mV)


-200

-100

0 A-SF

B-SF
100

200
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.11(d) Comparison in SF solution


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.

Corrosion Current Results

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
Corrosion Current (A/cm)

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
Corrosion Current (A/cm)

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)

Figure 4.13(b) Comparison in NP solution

73
0.12

0.10

Corrosion Current (A/cm)


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)

Figure 4.13(c) Comparison in FA solution


0.12

0.10
Corrosion Current (A/cm)

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(d) Comparison in SF solution

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).

4.3.4 Scanning Electron Microscopy (SEM) Results

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

The values of Rp were determined by using constant phase element best fitting method and

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)

Figure 4.18(a) Comparison in Control solution


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)

Figure 4.18(b) Comparison in NP solution

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)

Figure 4.18(c) Comparison in FA solution


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(d) Comparison in SF solution


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
4.4.2 Half-Cell Potential Results

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
Half-Cell Potential (mV)

-100

UP-C
0
P-C
100

200

300
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.19(a) Comparison in Control solution


-400

-300
Half-Cell Potential (mV)

-200

-100

UP-NP
0
P-NP
100

200

300
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.19(b) Comparison in NP solution

84
-400

-300

Half-Cell Potential (mV)


-200

-100
UP-FA
0
P-FA

100

200

300
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.19(c) Comparison in FA solution


-400

-300
Half-Cell Potential (mV)

-200

-100

0 UP-SF

P-SF
100

200

300
0 2 4 6 8 10 12 14 16
Time (Days)

Figure 4.19(d) Comparison in SF solution


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 Results


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

Corrosion Current (A/cm )


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
Corrosion Current (A/cm )

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

Corrosion Current (A/cm )


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
Corrosion Current (A/cm )

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
4.4.4 Scanning Electron Microscopy (SEM) Results

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

The values of Rp were determined by using constant phase element best fitting method and

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.

4.5.2 Half-Cell Potential Results

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)

Figure 4.26(a) Control

100
-400

-300

Half-Cell potential (mV)


-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
Half-Cell potential (mV)

-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
Half-Cell potential (mV)

-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

environments on the performance of SCMs

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.

Corrosion Current Results


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

Corrosion Current (A/cm)


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)

Figure 4.28(a) Control


0.40

0.35
Corrosion Current (A/cm)

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
Corrosion Current (A/cm)

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

Corrosion Current (A/cm)


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
environments on the performance of SCMs

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
Time (Days) Time (Days)

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
Time (Days) Time (Days)

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
Time (Days) Time (Days)

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
Time (Days) Time (Days)

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
Time (Days) Time (Days)

Figure A3(c) SF Figure A3(d) Comparison


Figure A3 Modulus variation with time of exposure for steel source A polished surface

123
-400 -400

-300 -300

Half-Cell Potential (mV)


Half-Cell Potential (mV)
-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
Time (Days) Time (Days)

Figure A4(a) FA Figure A4(b) NP


-400 -400

-300 -300
Half-Cell Potential (mV)

-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
Time (Days) Time (Days)

Figure A4(c) SF Figure A4(d) Comparison


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
Time (Days) Time (Days)

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
Time (Days) Time (Days)

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
Time (Days) Time (Days)

Figure B2(a) Control Figure B2(b) FA


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
Time (Days) Time (Days)

Figure B2(c) NP Figure B2(d) SF


Figure B2 Impedance variation with time for steel source comparison in mortar
-400 -400

-300 -300
Half-Cell Potential (mV)

Half-Cell Potential (mV)

-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
Time (Days) Time (Days)

Figure B3(a) Control Figure B3(b) FA

126
-400 -400

-300 -300

Half-Cell Potential (mV)


Half-Cell Potential (mV)
-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
Time (Days) Time (Days)

Figure B3(c) NP Figure B3(d) SF


Figure B3 Half-Cell variation with time for unpolished steel sources comparison in mortar
-350 -350

-300

-250 -250
Half-Cell Potential (mV)
Half-Cell Potential (mV)

-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
Time (Days) Time (Days)

Figure B4(a) Control Figure B4(b) FA


-350 -350

-300
-250 -250
Half-Cell Potential (mV)

Half-Cell Potential (mV)

-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
Time (Days) Time (Days)

Figure B4(c) NP Figure B4(d) SF


Figure B4 Half-Cell variation with time for polished steel sources comparison in mortar

127
-400 -400

-300 -300

Corroion Potential (mV)

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
Time (Days) Time (Days)

Figure B5(a) Control Figure B5(b) FA

-400 -400

-300 -300

Corroion Potential (mV)


Corroion Potential (mV)

-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
Time (Days) Time (Days)

Figure B5(c) NP Figure B5(d) SF


Figure B5 Corrosion penetration variation with time for steel source A surface condition
comparison in mortar

-400 -400

-300 -300
Corroion Potential (mV)
Corroion Potential (mV)

-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
Time (Days) Time (Days)

Figure B6(a) Control Figure B6(b) FA

128
-400 -400

-300 -300

Corroion Potential (mV)


Corroion Potential (mV)
-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
Time (Days) Time (Days)

Figure B6(c) NP Figure B6(d) SF


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

129