Alkali Book

Effect of Alkalis and Sulfate on Portland Cement Systems
by
Mahmoud A. Halaweh
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A dissertation submitted in partial fulfillment
of the requirements for the degree of
Doctor of Philosophy
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Department of Civil and Environmental Engineering
College of Engineering
University of South Florida
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Major Professor: Abla M. Zayed, Ph.D.

Rajan Sen, Ph.D.
Ram Pendyala, Ph.D.
A. Sunol, Ph.D.
Hana Y. Ghorab, Ph.D.
Date of Approval:
December 8, 2006
Keywords: ettringite, expansion, durability, strength, alite content
© Copyright 2007, Mahmoud A. Halaweh

UMI Number: 3292555
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UMI Microform 3292555

Copyright 2008 by ProQuest Information and Learning Company.
All rights reserved. This microform edition is protected against
unauthorized copying under Title 17, United States Code.
ProQuest Information and Learning Company

300 North Zeeb Road
P.O. Box 1346
Ann Arbor, MI 48106-1346
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DEDICATION
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This work is dedicated in loving memory to my parents. Without their knowledge,
wisdom and guidance I would not have the goals I have, to strive and be the best to reach
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my dreams.
This and other achievements I may realize are dedicated to my loving wife and my
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wonderful family for their support and encouragement.

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ACKNOWLEDGEMENTS
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The author would like to express his appreciation to Dr. Abla M. Zayed, major
professor, for her support and guidance throughout this study. The author would like to
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extend his thanks to the supervisory committee for their help and support. In addition, the
author would like to thank Dr. A. Sunnol, Dr. Thomas Pichler and Mr. Anthony Greco
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for their assistance during the course of the study.

TABLE OF CONTENTS
LIST OF TABLES iv
LIST OF FIGURES v
LIST OF SYMBOLS AND ABREVIATIONS xv
ABSTRACT xvi
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CHAPTER 1 INTRODUCTION 1
1.1 Background on Sulfate Attack 1
1.2 Expansion Theories 4
1.2.1 Swelling Theory IE 4
1.2.2 Crystal Growth Theory 5
1.3 Factors Affecting Ettringite Formation and Expansion Potential 6
1.3.1 Effect of Curing Temperature 9
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1.4 Research Objective 11
1.4.1 Research Significance 13
1.5 Outline of Dissertation 13
CHAPTER 2 LITERATURE REVIEW 15

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2.1 Role of SO3 15

2.2 Role of C3A 19
2.3 Role of C3S 21
2.4 Role of Alkalis 22
2.4.1 Effect of Alkalis on Ettringite Formation 22
2.4.2 Effect of Alkalis on Hydration Process and Mechanical
Properties 23
2.4.2.1 Effect of Alkalis on the Hydration of Clinker Phases 23
2.4.2.2 Effect of Alkalis on Ions Availability in Solution 25
2.4.2.3 Effect of Alkalis on Mechanical Properties and
Microstructure 25
2.4.3 Effect of Alkalis on Expansion Potential 37
CHAPTER 3 EXPERIMENTAL METHODS AND PROCEDURE 39

3.1 Pure Clinker Minerals 39
3.2 X-Ray Diffraction (XRD) 39
3.3 Scanning Electron Microscopy (SEM) 40
3.3.1 Fractured Surfaces Preparation 40
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3.3.2 Polished Surfaces Preparation 41
3.4 Cement Analysis 41
3.4.1 Blaine Fineness 41
3.4.2 Oxide Chemical Analysis 42
3.4.3 Mineralogical Composition 42
3.4.3.1 Bogue Equations 42
3.4.3.2 Internal Standard Method (Calibration Curves) 42
3.4.3.3 The Rietveld Method 47
3.5 Chemical Analysis of Hydrating Cement 48
3.6 Porosity Measurements (BET) and Degree of Hydration 49
3.7 Mortar Preparation 49
3.7.1 Mortar Bars 49
3.7.2 Mortar Cubes 49
3.8 Paste Preparation 50
3.9 Heat of Hydration 50
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CHAPTER 4 MATERIALS SELECTION AND EXPERIMENTAL PLAN 52
4.1 Materials Used for Doping 52
4.2 Sand 52
4.3 Cement Selection IE 52
4.4 Experimental Plan and Philosophy 55
CHAPTER 5 ROLE OF SULFATES 63

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5.1 Expansion Results 63
5.2 Compressive Strength 67
5.3 XRD Results 70
5.5 Ionic Species Concentrations 79
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5.6.1 Fractured Surfaces 82
5.6.2 Polished Surfaces 83
CHAPTER 6 ROLE OF ALKALIS, PART I: EFFECT OF ALKALI SOURCE 84

6.3 XRD Results 87
6.6.1 Fractured Surfaces 101
CHAPTER 7 ROLE OF ALKALIS, PART II 103

7.3 XRD Results 112
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7.6.1 Fracture Surfaces 138
CHAPTER 8 CEMENTS MH3, MH4 AND ERD07 143

CHAPTER 9 DISCUSSION 153
CHAPTER 10 CONCLUSIONS 165
REFERENCES 166
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APPENDICES 174
Appendix A: Cement Dissolution Methods 175
A.1 Salicylic Acid-Methanol Extraction (SAM) 175
A.2 Potassium Hydroxide/Sugar Extraction (KOSH)
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Appendix B: XRD Scans 176
Appendix C: Schematic Representation of C3S Hydration 197
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ABOUT THE AUTHOR End Page
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LIST OF TABLES
Table 1: Mix Proportions for As-Received Cements (AR) 50
Table 2: Blaine Fineness 53
Table 3: Oxide Chemical Composition of As-Received Cements (weight %) 53
Table 4: Bogue Mineralogical Content 53
Table 5: Phase Composition of As-Received Cements
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Based on Calibration Curves 54
Table 6: Phase Composition of As-Received Cements (Rietveld Method) 54
Table 7: Mixes
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Table 8: Major Phases of All Cements 59

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Table 9: Mix Proportions for Cement C 61
Table 10: Mix Proportions for Cement E 61

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Table 11: Mix Proportions for Cement ERD07 61
Table 12: Mix Proportions for Cement MH3 62
Table 13: Mix Proportions for Cement MH4 62
Table 14: Mortar Flow Values for Cements C and E 128
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LIST OF FIGURES
Figure 1: Calibration Curve for C3A 44
Figure 2: Calibration Curve for C4AF 44
Figure 3: Calibration Curve for MgO 45
Figure 4: Calibration Curve for Alite 46
Figure 5: Effect of Sulfate Content on Expansion Behavior for Cement E 64
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Figure 6: Effect of Sulfate Content on Expansion Behavior for Cement C 64
Figure 7: Effect of Sulfate Content on Expansion Behavior for

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Cement ERD07 65

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Cement MH3 65

Cement MH4 66
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Figure 10: Effect of Sulfate Content on Strength Gain for Cement E 67
Figure 11: Effect of Sulfate Content on Strength Gain for Cement C 68
Figure 12: Effect of Sulfate Content on Strength Gain for Cement ERD07 68
Figure 13: Effect of Sulfate Content on Strength Gain for Cement MH3 69
Figure 14: Effect of Sulfate Content on Strength Gain for Cement MH4 69
Figure 15: XRD of Hydration products @ 24 hours for Cement E 70
Figure 16: XRD of Hydration Products @ 24 hours for Cement C 70
Figure 17: Effect of Sulfate Content on Ettringite Formation in Cement E 72
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Figure 18: Effect of Sulfate Content on Ettringite Formation in Cement C 72
Figure 19: Effect of Sulfate Content on C3S Hydration in Cement E 73
Figure 20: Effect of Sulfate Content on C3S Hydration in Cement C 74
Figure 21: Effect of Sulfate Content on C4AF Hydration in Cement E 74
Figure 22: Effect of Sulfate Content on C4AF Hydration in Cement C 75
Figure 23: Effect of Sulfate Content on Formation of Calcium Hydroxide

in Cement E 76
Figure 24: Effect of Sulfate Content on Formation of Calcium Hydroxide

in Cement C 76
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Figure 25: Effect of Sulfate Content on Formation of Amorphous
Content for Cement E 77
Figure 26: Effect of Sulfate Content on Formation of Amorphous

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Content for Cement C 77
Figure 27: Effect of Sulfate Content on Heat of Hydration for Cement E 78

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Figure 28: Effect of Sulfate Content on Heat of Hydration for Cement C 78
Figure 29: Effect of Sulfate Content on SO4-2 Concentration for Cement E 80

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Figure 30: Effect of Sulfate Content on SO4-2 Concentration for Cement C 80
Figure 31: Effect of Sulfate Content on Calcium ions Concentration for

Cement E 81
Figure 32: Effect of Sulfate Content on Calcium ions Concentration for

Cement C 81
Figure 33: SEM Micrographs for Cement E 82
Figure 34: SEM Micrographs for Cement C 83
Figure 35: SEM Micrograph on a Polished Section for

Cement E, Case AR-AR 83
Figure 36: Effect of Alkali Source on Expansion Behavior for Cement E 85
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Figure 37: Effect of Alkali Source on Expansion Behavior for Cement C 85
Figure 38: Effect of Alkali Source on Strength Gain for Cement E 86
Figure 39: Effect of Alkali Source on Strength Gain for Cement C 87
Figure 40: Effect of Alkali Source on Ettringite Formation for Cement E 88
Figure 41: Effect of Alkali Source on Ettringite Formation for Cement C 88
Figure 42: Effect of Alkali Source on C3S Hydration for Cement E 89
Figure 43: Effect of Alkali Source on C3S Hydration for Cement C 89
Figure 44: Effect of Alkali Source on C4AF Hydration for Cement E 90
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Figure 45: Effect of Alkali Source on C4AF Hydration for Cement C 91
Figure 46: Effect of Alkali Source on Formation of Calcium Hydroxide

for Cement E IE 91
Figure 47: Effect of Alkali Source on Formation of Calcium Hydroxide

for Cement C 92
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Figure 48: Effect of Alkali Source on Formation of Amorphous Content
for Cement E 92
Figure 49: Effect of Alkali Source on Formation of Amorphous Content

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for Cement C 93
Figure 50: Effect of Alkali Source on Heat of Hydration for Cement E 94
Figure 51: Effect of Alkali Source on Heat of Hydration for Cement C 94
Figure 52: Effect of Alkali Source on SO4-2 Concentration for Cement E 96
Figure 53: Effect of Alkali Source on SO4-2 Concentration for Cement C 96
Figure 54: Effect of Alkali Source on Aluminum Ions Concentration for

Cement E 97
Figure 55: Effect of Alkali Source on Aluminum Ions Concentration for

Cement C 97
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Figure 56: Effect of Alkali Source on Calcium Ions Concentration for
Cement E 98
Figure 57: Effect of Alkali Source on Calcium Ions Concentration for

Cement C 99
Figure 58: Potassium Ions Concentration for Cement E 100
Figure 59: Potassium Ions Concentration for Cement C 100
Figure 60: SEM Micrographs, Cement E, A) Case KH-CS, B) Case KS 101
Figure 61: SEM Micrograph on a Polished Section and EDX Spectra 102
Figure 62: Effect of Alkali on Expansion Behavior for Cement E-SO3=AR 104
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Figure 63: Effect of Alkali on Expansion Behavior for
Cement E-SO3=3.6% 104

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Figure 65: Effect of Alkali on Expansion Behavior for Cement C-SO3=AR 105
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Cement C-SO3=3.6% 106

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Figure 68: Cracked Mortar Bar of Case 5-3.8 for Cement E at 180 days 108
Figure 69: Effect of Alkali on Strength Gain for Cement E-SO3=AR 109
Figure 70: Effect of Alkali on Strength Gain for Cement E-SO3=3.6% 109
Figure 71: Effect of Alkali on Strength Gain for Cement E-SO3=5.0% 110
Figure 72: Effect of Alkali on Strength Gain for Cement C-SO3=AR 110
Figure 73: Effect of Alkali on Strength Gain for Cement C-SO3=3.6% 111
Figure 74: Effect of Alkali on Strength Gain for Cement C-SO3=5.0% 111
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Figure 75: XRD of hydration products for Case E-5-3.8 112
Figure 76: Effect of Alkali on Ettringite Formation for Cement E-SO3=AR 113
Figure 77: Effect of Alkali on Ettringite Formation for


Figure 79: Effect of Alkali on Ettringite Formation for Cement C-SO3=AR 115

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Figure 82: Effect of Alkali on C3S Hydration for Cement E-SO3=AR 117
Figure 83:
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Effect of Alkali on C3S Hydration for Cement E-SO3=3.6% 117
Figure 84: Effect of Alkali on C3S Hydration for Cement E-SO3=5.0% 118
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Figure 85: Effect of Alkali on C3S Hydration for Cement C-SO3=AR 118
Figure 86: Effect of Alkali on C3S Hydration for Cement C-SO3=3.6% 119
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Figure 87: Effect of Alkali on C3S Hydration for Cement C-SO3=5.0% 119
Figure 88: Effect of Alkali on Calcium Hydroxide Formation for

Cement E-SO3=AR 120



Cement C-SO3=AR 121

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Figure 94: Effect of Alkali on Amorphous Content Formation for

Cement E-SO3=AR 123



Cement C-SO3=AR 124
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Cement C-SO3=5.0% IE 125
Figure 100: Effect of Alkali on Heat of Hydration for Cement E-SO3=AR 126
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Figure 101: Effect of Alkali on Heat of Hydration for Cement E-SO3=5.0% 126
Figure 102: Effect of Alkali on Heat of Hydration for Cement C-SO3=AR 127
Figure 103: Effect of Alkali on Heat of Hydration for Cement C-SO3=5.0% 128
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Figure 104: Effect of Alkali on SO4-2 Concentration for Cement E-SO3 =AR 129
Figure 105: Effect of Alkali on SO4-2 Concentration for

Cement E-SO3 =3.6% 130

Figure 107: Effect of Alkali on SO4-2 Concentration for Cement C-SO3 =AR 131

Cement C-SO3 =3.6% 132

Cement C-SO3 =5.0% 132
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Figure 110: Effect of Alkali on Calcium Ions Concentration for
Cement E-SO3=AR 133



Cement C-SO3=AR 134

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Figure 116: Effect of Alkali on Aluminum Ions Concentration for

Cement E-SO3 =AR IE 136

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Cement C-SO3 =AR 137


Figure 122: SEM Images on Paste samples for Cements

C and E-Case 5-3.8 140
Figure 123: SEM Images for Paste 141
Figure 124: SEM Images for Mortar Bars 141
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Figure 125: SEM Polished and EDX Spectra for Case 5-3.8 of
Cements C and E 142

Cement MH3-SO3=AR 144

Cement MH3-SO3=3.6% 145

Figure 129: E Effect of Alkali on Expansion Behavior for

Cement MH4-SO3=AR 146
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Cement MH4-SO3=5.0% IE 147

Cement ERD07-SO3=AR 147
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Cement ERD07-SO3=5.0% 148
Figure 134: Effect of Alkali on Strength Gain for Cement MH3-SO3=AR 148
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Figure 135: Effect of Alkali on Strength Gain for Cement MH3-SO3=3.6% 149
Figure 137: Effect of Alkali on Strength Gain for Cement MH4-SO3=AR 150
Figure 140: Effect of Alkali on Strength Gain for Cement ERD07-SO3=AR 151
Figure 141: Effect of Alkali on Strength Gain for

Cement ERD07-SO3=5.0% 152
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Figure 142: Pore Size Distribution for Cement C 158
Figure 143: Photograph under Light Microscope for Cement C 159
Figure 144: XRD Pattern for Cement C-5-3.8, Case A in Fig. 143 159
Figure 145: XRD of Hydration Products, Case E-5-3.8 176
Figure 146: XRD of Hydration Products, Case E-3.6-3.8 177
Figure 147: XRD of Hydration Products, Case E-AR-3.8 178
Figure 148: XRD of Hydration Products, Case E-5.0-AR 179
Figure 149: XRD of Hydration Products, Case E-3.6-AR 180
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Figure 150: XRD of Hydration Products, Case E-AR-AR 181
Figure 151: XRD of Hydration Products, Case E-AR-1.5 182
Figure 152:
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XRD of Hydration Products, Case E-AR-2.0 183
Figure 153: XRD of Hydration Products, Case E-5.0-2.0 184

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Figure 154: XRD of Hydration Products, Case C-5.0-3.8 185

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Figure 156: XRD of Hydration Products, Case C-AR-3.8 187
Figure 157: XRD of Hydration Products, Case C-5.0-AR 188
Figure 158: XRD of Hydration Products, Case C-3.6-AR 189
Figure 159: XRD of Hydration Products, Case C-AR-AR 190
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Figure 166: Schematic Representation of C3S Hydration 197
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LIST OF SYMBOLS AND ABBREVIATIONS
ASTM American Society of Testing and Materials
SEM Scanning Electron Microscope
XRD X-Ray Diffraction
Cement Chemistry Nomenclature
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A Alumina, Al2O3
C Calcium Oxide, CaO
F Ferric Oxide, Fe2O3

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H Water, H2O
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S SiO2
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S Sulfur Trioxide, SO3
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C3A Tricalcium Aluminate, 3CaO. Al2O3
C4AF Tetracalcium AluminoFerrite, 4CaO. Al2O3. Fe2O3
C2S Dicalcium Silicate, 2CaO. SiO2
C3S Tricalcium Silicate, 3CaO. SiO2
CH Calcium Hydroxide, Ca(OH)2

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CSH2 Gypsum, Ca2SO4.H2O
C-S-H Calcium Silicate Hydrate
Na2Oe Alkali Content as Na2O
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EFFECT OF ALKALIS AND SULFATES ON PORTLAND CEMENT SYSTEMS
Mahmoud A. Halaweh
ABSTRACT
The effect of the sulfates and alkalis on the durability of Portland cement systems
was investigated through a series of cube and prism mixes. Durability was assessed using
expansion of mortar prisms and the compressive strength of mortar cubes. The study
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covered a large range of both alkali and sulfate contents using 5 different Portland
cements. The alkali contents ranged from 0.27 to 3.8%, the sulfate content (as SO3)
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ranged from 2.54 to 5%. Doping was done using Terra Alba gypsum and potassium
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hydroxide. In addition to physical measurements, SEM, XRD, chemical analysis and heat
of hydration calorimetry were used for further analysis. Mixing, curing and testing were
done at room temperature.

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The results show that sulfate contents up to the levels used in this study, at low alkali
contents and ambient temperature curing, did not adversely affect durability of Portland
cement mortars up to 360 days. A correlation was established between expansion and
ettringite formation.
Increasing the alkali content always resulted in loss of compressive strength, and in some
cases, excessive expansion. Excessive expansion was only experienced at the 3.8% level.
Alkali levels of up to 2% and sulfate levels of 5% did not result in excessive expansion at
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room temperature-cure up to the ages reported here. The effect of alkali depended on the
cement mineralogical composition, especially C3S content. The addition of alkalis seems
to impact the nature of the microstructure and the nature of other hydration products.
The addition of sulfates seems to counteract the effect of alkalis, especially on the loss of
compressive strength. However, these sulfates may result in other problems as they may
be available at any time to form ettringite which may, under certain conditions, result in
excessive expansion.
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It was concluded that sulfate levels on the order of 3-3.6%, did not pose any major
durability drawbacks under normal curing temperatures and low alkali contents (<1%).
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Alkali levels above 1% will adversely affect the durability of Portland cement systems.
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CHAPTER 1
INTRODUCTION
1.1 Background on Sulfate Attack
As concrete becomes increasingly used as a construction material, durability
issues become more and more important.
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Its availability and relative low cost compared to other building materials made it more
versatile. With less skilled labor required as compared to other construction techniques,
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the improvement in workmanship and quality control can only go so far, if the quality of
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the material used is not up to par, and as a one engineer once said, “The principles of
engineering have not changed throughout the history, but we can always improve the
materials”.
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One of the durability problems that may occur during the service life of a concrete
structure is sulfate attack. It may result in expansion, cracking, spalling and eventually
reduction of the strength of concrete. It can also subject the structure to other forms of
attack; corrosion, etc.
The ordinary Portland cement used in the manufacture of concrete consists mainly of
calcium silicates and aluminates; tricalcium silicates (C3S), dicalcium silicates (C2S),
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tricalcium aluminates (C3A), and tetracalcium aluminoferrites (C4AF) and of course other
minor phases. ASTM classifies Portland cement into five types according to the relative
amounts of these compounds. It should be noted, however, that although these
classification are based on chemical composition, the ASTM specifications are
performance based. That is, cements have to meet certain physical requirements.
Tricalcium silicate phase is responsible for the early strength gain in concrete and the
dicalcium silicate contributes to the late strength gain (beyond 28 days). Tricalcium
aluminate phase is very reactive and at the addition of water it would hydrate quickly and
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causes what is called “flash set”. This phenomenon will make it hard to place and finish
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the concrete in timely manner. To control the hydration, calcium sulfates (in one or more
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forms) are added, usually in the form of gypsum (CSH2), which reacts with C3A
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according to equation (1) and form an ettringite (tricalcium aluminate tricalcium sulfate
hydrate) coat around C3A grains.

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C3A + 3CSH2 +26H→ C6AS3 H32 ……………1
Ettringite formed during early hydration is referred to as ‘Primary Ettringite”. The
primary ettringite formed during the initial hydration does not cause damage, because of
its occurrence in a plastic matrix and the volume changes will be accommodated within
the matrix. The ettringite that forms after the concrete has hardened is called
“Secondary”, “Delayed” or “Late” ettringite, and this could be detrimental to concrete.
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In Type I Portland cement (ASTM specification), the Al2O3/SO3 ratio is mostly equal to
~ 1.6 and contains a maximum of 3.5 to 4% SO3 (US and European standards (1)) so at
the beginning of the hardening stage, primary ettringite will be converted to
monosulfoaluminate according to equation (2) since ettringite requires a Al2O3/SO3 ratio
of 3 to remain stable.
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C6AS3 H32 + 2 C3A +4H→ 3C4ASH12 …………….2
On subsequent exposure to a sulfate source in excess of that present in the MS, the
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monophase may reconvert to ettringite following equation (3)
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3C4ASH12 + 2CSH2 +16H→ C6AS3 H32 ………….3
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On the other hand, the monosulfate hydrate phase (C4ASH12) is known to be unstable at
room temperature and lower temperatures (1,2).

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Therefore, even in the absence of an external sulfate source, the monosulfate hydrate may
accept sulfate ions released from an internal source to reform ettringite. The later
phenomenon is called internal sulfate attack (ISA) which occurs usually in heat treated
concrete. The issue of internal sulfate attack started to receive more attention in the mid-
eighties when damage was reported in heat-cured prestressed concrete railway ties; it was
believed that this was due to the elevated heat-cure followed by ambient cure. However,
ISA is not limited to heat-cured concretes. ISA potential under ambient temperature cure
exists under certain circumstances; this notion was emphasized by Collepardi (3).
Collepardi proposed a model for the ISA to occur. The author called it a holistic
3

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Effect of Alkalis and Sulfate on Portland Cement Systems

Major Professor: Abla M. Zayed, Ph.D.

Keywords: ettringite, expansion, durability, strength, alite content

© Copyright 2007, Mahmoud A. Halaweh

UMI Microform 3292555

ProQuest Information and Learning Company

wonderful family for their support and encouragement.

for their assistance during the course of the study.

LIST OF SYMBOLS AND ABREVIATIONS xv

CHAPTER 2 LITERATURE REVIEW 15

2.1 Role of SO3 15

CHAPTER 3 EXPERIMENTAL METHODS AND PROCEDURE 39

CHAPTER 5 ROLE OF SULFATES 63

5.6 Scanning Electron Microscopy (SEM) 82

CHAPTER 6 ROLE OF ALKALIS, PART I: EFFECT OF ALKALI SOURCE 84

CHAPTER 7 ROLE OF ALKALIS, PART II 103

CHAPTER 8 CEMENTS MH3, MH4 AND ERD07 143

CHAPTER 9 DISCUSSION 153

CHAPTER 10 CONCLUSIONS 165

Table 1: Mix Proportions for As-Received Cements (AR) 50

Table 2: Blaine Fineness 53

Table 3: Oxide Chemical Composition of As-Received Cements (weight %) 53

Table 4: Bogue Mineralogical Content 53

Table 5: Phase Composition of As-Received Cements

Table 6: Phase Composition of As-Received Cements (Rietveld Method) 54

Table 8: Major Phases of All Cements 59

Table 10: Mix Proportions for Cement E 61

Table 11: Mix Proportions for Cement ERD07 61

Table 12: Mix Proportions for Cement MH3 62

Table 13: Mix Proportions for Cement MH4 62

Table 14: Mortar Flow Values for Cements C and E 128

Figure 1: Calibration Curve for C3A 44

Figure 2: Calibration Curve for C4AF 44

Figure 3: Calibration Curve for MgO 45

Figure 4: Calibration Curve for Alite 46

Figure 5: Effect of Sulfate Content on Expansion Behavior for Cement E 64

Figure 7: Effect of Sulfate Content on Expansion Behavior for

Figure 8: Effect of Sulfate Content on Expansion Behavior for

Figure 9: Effect of Sulfate Content on Expansion Behavior for

Figure 10: Effect of Sulfate Content on Strength Gain for Cement E 67

Figure 11: Effect of Sulfate Content on Strength Gain for Cement C 68

Figure 15: XRD of Hydration products @ 24 hours for Cement E 70

Figure 16: XRD of Hydration Products @ 24 hours for Cement C 70

Figure 17: Effect of Sulfate Content on Ettringite Formation in Cement E 72

Figure 19: Effect of Sulfate Content on C3S Hydration in Cement E 73

Figure 20: Effect of Sulfate Content on C3S Hydration in Cement C 74

Figure 21: Effect of Sulfate Content on C4AF Hydration in Cement E 74

Figure 22: Effect of Sulfate Content on C4AF Hydration in Cement C 75

Figure 23: Effect of Sulfate Content on Formation of Calcium Hydroxide

Figure 24: Effect of Sulfate Content on Formation of Calcium Hydroxide

Figure 26: Effect of Sulfate Content on Formation of Amorphous

Figure 27: Effect of Sulfate Content on Heat of Hydration for Cement E 78

Figure 29: Effect of Sulfate Content on SO4-2 Concentration for Cement E 80

Figure 30: Effect of Sulfate Content on SO4-2 Concentration for Cement C 80

Figure 31: Effect of Sulfate Content on Calcium ions Concentration for

Figure 32: Effect of Sulfate Content on Calcium ions Concentration for

Figure 33: SEM Micrographs for Cement E 82

Figure 34: SEM Micrographs for Cement C 83

Figure 35: SEM Micrograph on a Polished Section for

Figure 36: Effect of Alkali Source on Expansion Behavior for Cement E 85

Figure 38: Effect of Alkali Source on Strength Gain for Cement E 86

Figure 39: Effect of Alkali Source on Strength Gain for Cement C 87

Figure 40: Effect of Alkali Source on Ettringite Formation for Cement E 88

Figure 41: Effect of Alkali Source on Ettringite Formation for Cement C 88