ABSTRACT

Being the most widely used construction material, the long-term performance of concrete structures plays an important role in the economy of all nations. Concrete structures built using moderate strength concrete mixes are most often showing early signs of distress in the form of deterioration, poor long-term performance and inadequate resistance to the hostile environments. High-Performance Concrete (HPC) is simply concrete which is expected to provide superior performance in a particular application. The application may or may not require a higher compressive strength. Sea-water is one of the most wide-spread, natural, multi-component media in the form of a complex physico-chemical system containing electrolytes that are aggressive towards concrete. The salinity of seawater generally accounts at 34 to 35 g/l and the pH of seawater normally varies from 8.2 to 8.3. The destructive action of seawater on concrete has attracted attention in many countries and a very extensive literature is available on this subject. Engineers are making increasing use of HPC incorporating supplementary cementitious materials to enhance durability, also, leading to more efficient use of Portland cement. Chlorides in the exposure environment do not react with the cement hydration products, but on reaching the surface of the embedded steel reinforcement, depassivate the protecting layer and act as a catalyst in the corrosion process. The presence of chloride ions retards the swelling of concrete due to sulphate attack. Thus most of the literature discussing concrete in marine environment are studies on the individual effects of these aggressive ions. Not many studies have detailed on the effect of chemical composition of binders on the durability aspects of concrete incorporating supplementary cementing material. As the pozzolanic reaction potential of these materials and the oxide composition of total binders differ, the chemical resistance of concrete varies. A detailed laboratory scale experimental program is planned to study the effect of oxide composition in the binder and the curing/exposure conditions of concrete on the durability related characteristics of concrete. Concrete mixes made by binary blended (mixes with one supplementary cementitious material as partial replacement to cement) and ternary blended (mixes with two supplementary cementitious materials as partial replacement to cement) binders are investigated. The present investigation focuses on the strength deterioration, volume changes and weight losses due to exposure of concrete to a magnesium sulphate solution with a high sulphate concentration. The permeability, chloride diffusion characteristics and the corrosion of embedded steel reinforcement are also investigated to understand the behaviour of binary blended and ternary blended concrete mixes in marine environment. The present investigation is aimed to study the sulphate induced strength deterioration, volume expansion, and the permeation and diffusion of chloride ions through high performance concrete incorporating different pozzolanic cementitious materials in varying dosages and combinations. The parameters investigated include the effect of oxide composition of the binder materials used in concrete, the effect of initial moist curing given to concrete prior to the exposure to aggressive environment, and the effect of dosage of supplementary cementitious materials in the concrete mix.

In the present investigation, an attempt is made to compare the durability performance of binary blended mixes with a control mix (with cement as the only binder), and ternary blended mixes with few binary blends containing similar dosage of supplementary cementitious materials. The effects of initial moist curing and the dosage of pozzolanic material in the blends, on the durability performance of all binary and ternary blends are investigated. As the durability issues investigated in this thesis involves the chemical reactions between the products of cement hydration and pozzolanic reactions and the aggressive ions in the exposure medium, efforts are also made to correlate the durability parameters investigated in this study (such as strength loss, chloride ion diffusion and permeation) with the oxide composition of total binder used in the cementitious system. The results of the half-cell potential measurements taken on reinforced, highperformance concrete slabs in different exposure conditions over extended periods show that, use of binary blended concrete controls the de-passivation risk of embedded steel reinforcement in concrete exposed to seawater. Further improvement in this aspect is observed in case of ternary blended mixes.

Key words: high-performance concrete, marine environment, strength

deterioration, sulphate resistance, chloride attack, corrosion

ii

CONTENTS

ABSTRACT CONTENTS LIST OF FIGURES LIST OF TABLES NOMENCLATURE

i iii vi xiii xiv

1 HIGH-PERFORMANCE CONCRETE - AN INTRODUCTION 1.1 GENERAL 1.2 DURABILITY OF CONCRETE 1.3 SUPPLEMENTARY CEMENTITIOUS MATERIALS 1.4 HIGH-PERFORMANCE CONCRETE 1.4.1 NIST/ACI Workshop definition 1.4.2 University of Tokyo definition 1.4.3 Strategic Highway Research Program (SHRP) definition 1.4.4 Prestressed Concrete Institute definition 1.4.5 Civil Engineering Research Foundation definition 1.5 MARINE ENVIRONMENT 1.6 SUMMARY 1.7 ORGANISATION OF THE THESIS 2 LITERATURE REVIEW 2.1 CONCRETE IN MARINE ENVIRONMENT 2.2 SULPHATE ATTACK ON CONCRETE 2.2.1 Mechanism of Sulphate Attack 2.2.2 Testing for Sulphate Attack 2.2.3 Standard Specifications to Control Sulphate Attack 2.3 SULPHATE ATTACK STUDIES ON CONVENTIONAL CONCRETE 2.4 SULPHATE ATTACK STUDIES ON FLY ASH CONCRETE 2.5 SULPHATE ATTACK STUDIES ON SILICA FUME CONCRETE 2.6 SULPHATE ATTACK STUDIES ON METAKAOLIN CONCRETE 2.7 TRANSPORT MECHANISM THROUGH CONCRETE 2.7.1 Tests for Transport Mechanism through Concrete 2.8 STUDIES ON TRANSPORT PROPERTIES OF FLY ASH CONCRETE 2.9 STUDIES ON TRANSPORT PROPERTIES OF SILICA FUME CONCRETE 2.10 STUDIES ON TRANSPORT PROPERTIES OF METAKAOLIN CONCRETE 2.11 DURABILITY STUDIES ON TERNARY BLENDS 2.12 CORROSION OF STEEL IN CONCRETE

1 1 2 4 5 7 7 7 8 8 9 12 12 14 14 15 16 18 19 20 23 27 32 34 34 38 41 43 44 47

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2.12.1 Tests for Corrosion of Steel in Concrete 2.13 STUDIES ON CORROSION OF STEEL REBARS EMBEDDED IN CONCRETE 2.14 STUDIES OF CONCRETE IN MARINE ENVIRONMENT 2.15 PROBLEM IDENTIFICATION AND FORMULATION 2.16 OBJECTIVES OF THE RESEARCH WORK 2.17 SCOPE OF THE WORK 2.18 SUMMARY 3 MATERIALS AND METHODS 3.1 MATERIALS 3.1.1 Cement 3.1.2 Supplementary Cementitious Materials 3.1.3 Water 3.1.4 Aggregates 3.1.5 Steel Reinforcement 3.1.6 Superplasticiser 3.2 METHODOLOGY 3.2.1 Concrete Mix Design 3.2.2 Mixing Sequence 3.2.3 Preparation of Test Specimens 3.2.4 Specimen Curing and Exposure to Aggressive Environment 3.2.5 Testing 3.3 SUMMARY 4 CHEMICAL COMPOSITION RESULTS AND DISCUSSIONS 4.1 OXIDE COMPOSITION OF BINDERS 4.2 OXIDE COMPOSITION OF BINARY BLENDS 4.3 OXIDE COMPOSITION OF TERNARY BLENDS 4.4 SUMMARY

49 49 51 52 54 55 57 58 58 58 61 70 70 71 72 72 73 74 76 77 78 85 86 86 87 93 96

5 SULPHATE INDUCED DETERIORATION OF CONCRETE RESULTS AND DISCUSSIONS 98 5.1 GENERAL 98 5.2 COMPRESSIVE STRENGTH 98 5.2.1 Control Mix 99 5.2.2 PC-FA Blends 100 5.2.3 PC-SF Blends 106 5.2.4 PC-MK Blends 112 5.2.5 PC-FA-SF Blends 116 5.2.6 PC-FA-MK Blends 123 5.3 FLEXURAL STRENGTH 128 5.3.1 Control Mix 128 5.3.2 PC-FA Blends 129 5.3.3 PC-SF Blends 134 5.3.4 PC-MK Blends 139 5.3.5 PC-FA-SF Blends 143 5.3.6 PC-FA-MK Blends 149

iv

5.4

5.5

5.6

EXPANSION OF CONCRETE PRISMS 5.4.1 Control Mix 5.4.2 PC-FA Blends 5.4.3 PC-SF Blends 5.4.4 PC-MK Blends 5.4.5 PC-FA-SF Blends 5.4.6 PC-FA-MK Blends WEIGHT CHANGES IN CONCRETE CUBES 5.5.1 PC-FA Blends 5.5.2 PC-SF Blends 5.5.3 PC-MK Blends 5.5.4 PC-FA-SF Blends 5.5.5 PC-FA-MK Blends SUMMARY

155 155 156 159 162 165 168 171 171 171 174 174 174 178 179 179 179 179 181 184 186 188 190 190 193 195 196 200 204 204 204 205 209 209 212 218 218 220 222 223 236 238

6 CHLORIDE ATTACK - RESULTS AND DISCUSSIONS 6.1 GENERAL 6.2 RAPID CHLORIDE PERMEABILITY TEST 6.2.1 PC-FA Blends 6.2.2 PC-SF Blends 6.2.3 PC-MK Blends 6.2.4 PC-FA-SF Blends 6.2.5 PC-FA-MK Blends 6.3 BULK DIFFUSION TEST (Non-Steady State Diffusion) 6.3.1 PC-FA Blends 6.3.2 PC-SF Blends 6.3.3 PC-MK Blends 6.3.4 PC-FA-SF Blends 6.3.5 PC-FA-MK Blends 6.4 HALF-CELL POTENTIAL MEASUREMENTS ON REINFORCED CONCRETE SLABS 6.4.1 PC-FA Blends 6.4.2 PC-SF Blends 6.4.3 PC-MK Blends 6.4.4 PC-FA-SF Blends 6.4.5 PC-FA-MK Blends 6.5 SUMMARY 7 CONCLUSIONS AND SCOPE FOR FUTURE WORK 7.1 SULPHATE INDUCED DETERIORATION 7.2 CHLORIDE ATTACK 7.3 SCOPE FOR FUTURE WORK REFERENCES PUBLICATIONS FROM PRESENT RESEARCH WORK BRIEF RESUM

LIST OF FIGURES

Figure No. 2.1 2.2 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 4.1 4.2 4.3 4.4 4.5 4.6 5.1

Caption

Page No.

The University of Cape Town (UCT) chloride conduction test Set-up. 37 Tang and Nilsson Migration Cell. SEM Micrograph of Cement Particles. SEM Micrograph of Fly Ash Particles. SEM Micrograph of Silica Fume Particles. SEM Micrograph of Metakaolin Particles. Particle Size Distribution of Binder Materials. Mean Particle Size of Binder Materials. A schematic diagram of reinforcement arrangement in Slab. Rapid Chloride Permeability Test Set-up. Exposure set-up for Bulk Diffusion Test. Schematic of Half-cell Potential Measurement Major Oxide Compositions in Binary Blends. Basic Oxide Ratios of Binary Blends. Oxide Ratio Derivatives of Binary Blends. Major Oxide Compositions in Ternary Blends. Basic Oxide Ratios of Ternary Blends. Oxide Ratio Derivatives of Ternary Blends. Strength Development of Control Mix in Different Exposure Conditions. 99 37 61 64 66 67 69 69 72 80 82 83 88 91 92 94 95 97

5.2

Strength Development of PC-FA Mixes in Different Exposure Conditions. 101

5.3

Effect of Initial Moist Curing on Compressive Strength Loss of PCFA Mixes. 103

5.4

Effect of Fly ash Content on Compressive Strength Gain of PC-FA Mixes. 104

5.5

Variation of Compressive Strength Loss Against Oxide Composition

vi

of PC-FA Blends at 720 Days in Type I Exposure 5.6 Variation of Compressive Strength Loss against Fly ash Content of PC-FA Blends at 720 Days in Type I Exposure 5.7 Strength Development of PC-SF Mixes in Different Exposure Conditions. 5.8 Effect of Initial Moist Curing on Compressive Strength Loss of PCSF Mixes. 5.9 Effect of Silica fume Content on Compressive Strength Gain of PCSF Mixes. 5.10 5.11 Variation of 720 days Compressive Strength Loss with Silica Ratio Variation of 720 days Compressive Strength Loss with Silica fume Content 5.12 Strength Development of PC-MK Mixes in Different Exposure Conditions. 5.13 Effect of Initial Moist Curing on Compressive Strength Loss of PCMK Mixes. 5.14 Effect of Metakaolin Content on Compressive Strength Gain of PCMK Mixes. 5.15 Strength Development of PC-FA-SF Blends in Different Exposure Conditions. 5.16 Effect of Replacement of Fly Ash with Silica Fume on Strength Gain of PC-FA-SF Blends. 5.17 Effect of Partial Replacement of cement with Silica Fume on Strength Gain of PC-FA-SF Blends in Different Exposure Conditions. 5.18 Effect of Initial Moist Curing on Compressive Strength Loss of PCFA-SF Mixes. 5.19 Strength Development of PC-FA-MK Blends in Different Exposure Conditions. 5.20 Effect of Partial Replacement of Cement with Metakaolin on Strength Gain of PC-FA-MK Blends.

105

106

107

109

110 111

112

114

115

117

118

120

121

122

124

125

vii

5.21

Effect of Replacement of Fly Ash with Metakaolin on Strength Gain 126 of PC-FA-MK Blends.

5.22

Effect of Initial Moist Curing on Compressive Strength Loss of PCFA-MK Mixes. 127

5.23

Flexural Strength Development of Control Mix in Different Exposure Conditions. 129

5.24

Flexural Strength Development of PC-FA Mixes in Different Exposure Conditions. 130

5.25

Effect of Initial Moist Curing on Flexural Strength Loss of PC-FA Mixes. 132

5.26

Effect of Fly Ash Content on Flexural Strength Gain of PC-FA Mixes. 133

5.27

Effect of Fly Ash Content on Flexural Strength Loss of PC-FA Mixes at 720 Days in Type III Exposure. 134

5.28

Flexural Strength Development of PC-SF Mixes in Different Exposure Conditions. 135

5.29

Effect of Initial Moist Curing on Flexural Strength Loss of PC-SF Mixes. 137

5.30

Effect of Silica fume Content on Flexural Strength Gain of PC-SF Mixes. 138

5.31

Flexural Strength Development of PC-MK Mixes in Different Exposure Conditions. 139

5.32

Effect of Initial Moist Curing on Flexural Strength Loss of PC-MK Mixes. 141

5.33

Effect of Metakaolin Content on Flexural Strength Gain of PC-MK Mixes. 142

5.34

Effect of Metakaolin Content on 720 Days Flexural Strength Loss of PC-MK blends in Sulphate Environment. 143

5.35

Flexural Strength Development of FA40 and PC-FA-SF Mixes in Different Exposure Conditions. 144

5.36

Effect of Initial Moist Curing on Flexural Strength Loss of FA40 and PC-FA-SF Mixes. 146

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5.37

Effect of Silica Fume Content on Flexural Strength Gain of PC-FASF Mixes. 147

5.38

Effect of Replacement of Cement with Silica Fume on Flexural Strength Gain of PC-FA-SF Blends in Different Exposure Conditions. 148

5.39

Variation of 720 days Flexural Strength Loss with Silica Fume Content in PC-FA-SF Ternary Blend 149

5.40

Flexural Strength Development of FA40 and PC-FA-MK Mixes in Different Exposure Conditions. 150

5.41

Effect of Initial Moist Curing on Flexural Strength Loss of FA40 and PC-FA-MK Mixes. 151

5.42

Effect of Metakaolin Content on Flexural Strength Gain of PC-FAMK Mixes. 153

5.43

Effect of Replacement of Cement with Metakaolin on Flexural Strength Gain of PC-FA-MK Blends in Different Exposure Conditions. 154 with Metakaolin 154

5.44

Variation of 720 days Flexural Strength Loss Content in PC-FA-MK Ternary Blends

5.45

Sulphate Induced Expansion of Control Mix in Different Exposure Conditions. 155

5.46

Sulphate Induced Expansion of PC-FA Mixes in Different Exposure Conditions. 157

5.47

Effect of Fly Ash Content in PC-FA Mixes on Expansion of Concrete in Different Exposure Conditions. 158

5.48

Sulphate Induced Expansion of PC-SF Mixes in Different Exposure Conditions. 159

5.49

Effect of Silica Fume Content in PC-SF Mixes on Expansion of Concrete in Different Exposure Conditions. 161

5.50

Sulphate Induced Expansion of PC-MK Mix in Different Exposure Conditions. 162

5.51

Effect of Metakaolin Content in PC-MK Mixes on Expansion of Concrete in Different Exposure Conditions. 164

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5.52

Sulphate Induced Expansion of FA40 and PC-FA-SF Mixes in Different Exposure Conditions. 166

5.53

Effect of Silica Fume Content in PC-MK-SF Mixes on Expansion of Concrete in Different Exposure Conditions. 167

5.54

Sulphate Induced Expansion of FA40 and PC-FA-MK Mixes in Different Exposure Conditions. 169

5.55

Effect of Metakaolin Content in PC-FA-MK Mixes on Expansion of Concrete in Different Exposure Condition. 170

5.56

Gain in Weight of Control mix and PC-FA Mixes in Different Exposure Conditions. 172

5.57

Gain in Weight of Control Mix and PC-SF Mixes in Different Exposure Conditions. 173

5.58

Gain in Weight of Control and PC-MK mixes in Different Exposure Conditions. 175

5.59

Gain in Weight of FA40 and PC-FA-SF mixes in Different Exposure Conditions. 176

5.60

Gain in Weight of FA40 and PC-FA-MK Mixes in Different Exposure Conditions. 177 180 181 182 183 184 185

6.1 6.2 6.3 6.4 6.5 6.6 6.7

Variation of Charge Passed for Various PC-FA Blends. Total Charge Passed versus Fly Ash Content in PC-FA Blends. Variation of Charge Passed for Various PC-SF Blends. Total Charge Passed versus Silica Fume Content in PC-SF Blends Variation of Charge Passed for Various PC-MK Blends. Total Charge Passed versus Metakaolin Content in PC-MK Blends Variation of Charge Passed for Various PC-FA-SF Ternary Blends and Comparable Binary Blends.

186

6.8

Chloride ion permeation in PC-FA-SF Ternary Blends Effect of increasing replacement of Fly ash with Silica fume 187

6.9

Variation of Charge Passed for Various PC-FA-MK Ternary Blends and Comparable Binary Blends. 188

6.10

Chloride ion Permeation in PC-FA-MK Ternary Blends Effect of Increasing Replacement of Fly ash with Metakaolin 189

6.11 6.12

Diffusion Coefficient of PC-FA Mixes at Different Ages of Testing Effect of Fly Ash Content on 90 day Diffusion Coefficient of PC-FA Mixes Initially Cured for 3 days.

191

192 192 193

6.13 6.14 6.15

D90 versus Lime Saturation Factor for 3 day Cured PC-FA Blends. Diffusion Coefficient of PC-SF Mixes at Different Ages of Testing Diffusion Coefficient of PC-SF Mixes at 90 day versus Lime Saturation Factor.

194 195

6.16 6.17

Diffusion Coefficient of PC-MK Mixes at Different Ages of Testing. Diffusion Coefficient of PC-FA-SF Mixes at Different Ages of Testing.

197

6.18

Effect of Silica Fume Content on 28 day Diffusion Coefficient of PCFA-SF Mixes Initially Cured for 3 days. 198

6.19

Comparison of D90 Estimated with Silica Fume Content as Variable (Eqn. 6.15) with Observed Values for PC-FA-SF Mixes. 199 Effect of Calcium Oxide Content on 28 day Diffusion Coefficient of PC-FA-SF Mixes Initially Cured for 3 days. 199

6.20

6.21

Comparison of D90 Estimated with CaO Content as Variable (Eqn. 6.17) with Observed Values for PC-FA-SF Mixes. 200 Diffusion Coefficient of PC-FA-MK Mixes at Different Ages of Testing. 201

6.22

6.23

Effect of Metakaolin Content on 28 day Diffusion Coefficient of PCFA-MK Mixes Initially Cured for 3 days. 203

6.24

Comparison of D90 Estimated with Metakaolin Content as Variable (Eqn. 6.19) with Observed Values for PC-FA-MK Mixes. 203

6.25

Variation of Potential Gradient with Age for PC-FA Blends in Different Exposure Conditions. 206

6.26

Variation of Potential Gradient with Age for PC-SF Blends in Different Exposure Conditions. 207

6.27

Variation of Potential Gradient with Age for PC-MK Blends in Different Exposure Conditions. 208

6.28

Variation of Potential Gradient with Age for PC-FA-SF Blends in Different Exposure Conditions. 210

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6.29

Variation of Potential Gradient with Age for PC-FA-MK Blends in Different Exposure Conditions. 211 213 214 215 216 217

6.30 6.31 6.32 6.33 6.34

Equi-potential Lines for Control Mix and PC-FA Binary Blends. Equi-potential Lines for Control Mix and PC-SF Binary Blends. Equi-potential Lines for Control Mix and PC-MK Binary Blends. Equi-potential Lines for FA40 and PC-FA-SF Binary Blends. Equi-potential Lines for FA40 and PC-FA-MK Binary Blends.

xii

LIST OF TABLES

Table Title No. 1.1 Average Chemical Combination of Seawater. 1.2 2.1 3.1 3.2 3.3 Equivalent Salt Content in Seawater. Dosage of SCM for Different Binary and Ternary Blends. Physical Properties of Cement. Chemical Composition of Cement. Physical Properties and Chemical Composition of Supplementary Cementitious Materials. 3.4 3.5 3.6 4.1 Particle Size Distribution of Coarse Aggregate. Particle Size Distribution of Fine Aggregate. Details of Concrete Mix Proportions. Oxide Composition of Binders.

Page No. 10 10 56 59 60

68 70 71 75 86

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NOMENCLATURE

Abreviations AR CH CSE C-S-H FA HM HPC LC LSF MK PC RCPT SCM SEM SF SR ss UCT Notations (CaO) (SiO2) (t) c Mass percentage of calcium oxide Mass percentage of silicon dioxide Testing age of concrete Period of initial moist curing (days), or a factor depending on period of initial moist curing D D0 Diffusion coefficient, m2/s Diffusion coefficient of control mix, m2/s Alumina Ratio Calcium Hydroxide, Portlandite Copper Sulphate Electrode Calcium Silicate Hydrate Fly Ash Hydraulic Modulus High-Performance Concrete Least Count Lime Saturation Factor Metakaolin Portland Cement Rapid Chloride Permeability Test Supplementary Cementitious Material Scanning Electron Microscope Silica fume Silica Ratio solid solution University of Cape Town

xiv

D90,3 Fa fcu L0 Ln m Mk PC-FA PC-FA-MK PC-FA-SF PC-MK PC-SF Q Qm Ra Rf Ri Sf T Xd a

90-days diffusion coefficient of 3-day moist cured specimen, m2/s Percentage of fly ash in the mix Cube compressive strength of concrete, MPa Strength loss in control mix, % Natural Logarithm Percentage of metakaolin in PC-MK mix Percentage of metakaolin in mix Binary blend of cement and fly ash Ternary blend of cement fly ash and metakaolin Ternary blend of cement fly ash and silica fume Binary blend of cement and metakaolin Binary blend of cement and silica fume Total charge passed, Coulombs Total charge passed through PC-MK blends, Coulombs Demac gauge reading at any age Resistance factor Initial Demac gauge reading Percentage of silica fume in mix Duration of exposure Average penetration depth, m Strain at any age

xv