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Implementation of Highly Reactive Pozzolans in the Key Royale Bridge Replacement

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PAGE 1

IMPLEMENTATION OF HIGHLY REACTIVE POZZOLANS IN THE KEY ROYALE BRIDGE REPLACEMENT By EDWARD K. ROSKE A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF ENGINEERING UNIVERSITY OF FLORIDA 2007

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2007 Edward K. Roske

PAGE 3

To my loving family (my mother Joyce Roske, my sister Tiere Roske, and my brother Dustin Roske) as they have offered their unyielding love and support.

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ACKNOWLEDGMENTS I thank my supervisory committee members for their ideas and assistance. My supervisory committee chair (Dr. H. R. Ha milton) provided his valuable time and knowledge of the subject, as well as financial support, to make this research successful. I thank Dr. Robert E. Minchin, Jr. and Dr Mang Tia for their guidance and knowledge. I thank Mike Bergin and Charles Ishee and their staff at the Florida Department of Transportation for contributing knowledge, assist ance, and funding. Special thanks go to Richard Delorenzo for his tremendous knowledge and assistance in the laboratory I would like to acknowledge Sal Depolis a nd Wayne Allick Jr. for their assistance in laboratory testing. I al so thank everyone in the Depa rtment of Civil and Coastal Engineering who contributed time and effort to my study. They include Mahir Dham, Christopher Ferraro, Samuel Smith, Tanya Reidhammer, Yu Chen, Beyoung Il Kim and Xiaoyan Zheng. My deepest appreciation goes to Stepha nie Lloyd for her co ntinual support and encouragement throughout the resear ch and writing of this thesis. iv

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TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iv LIST OF TABLES...........................................................................................................viii LIST OF FIGURES...........................................................................................................xi ABSTRACT.....................................................................................................................xiv CHAPTER 1 INTRODUCTION........................................................................................................1 2 LITERATURE REVIEW.............................................................................................3 Unhydrated Cement Chemistry....................................................................................3 Hydration Chemistry....................................................................................................5 Cement Hydration.................................................................................................5 Pozzolanic Reaction..............................................................................................6 Effect of Cement and Mineral Admixtures on Concrete Properties.............................6 Portland Cement....................................................................................................6 Fly Ash..................................................................................................................8 Ultrafine Fly Ash.................................................................................................12 Slag......................................................................................................................15 Metakaolin...........................................................................................................18 Silica Fume..........................................................................................................21 3 MIX DESIGN.............................................................................................................25 Materials.....................................................................................................................25 Basic Ingredients.................................................................................................25 Water............................................................................................................25 Fine aggregate..............................................................................................25 Coarse aggregate..........................................................................................26 Cement.........................................................................................................26 Mineral Admixtures.............................................................................................27 Fly ash..........................................................................................................27 Slag...............................................................................................................28 Ultra-fine fly ash..........................................................................................28 v

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Metakaolin....................................................................................................29 Silica fume....................................................................................................30 Chemical Admixtures..........................................................................................31 Air entrainer.................................................................................................31 Water reducer/retarder..................................................................................32 Superplasticizer............................................................................................32 Proportions..................................................................................................................33 Preparation of Concrete Mixtures...............................................................................39 Specimen Fabrication.................................................................................................41 Curing Conditions.......................................................................................................41 Additional Mixtures....................................................................................................42 4 LABORATORY TESTING.......................................................................................44 Plastic Properties Tests...............................................................................................44 Density (ASTM C 138).......................................................................................44 Slump (ASTM C 143).........................................................................................44 Air Content (ASTM C 173).................................................................................45 Bleeding of Concrete (ASTM C 232).................................................................46 Time of Setting (ASTM C 403)...........................................................................47 Temperature (ASTM C 1064).............................................................................47 Mechanical Tests........................................................................................................48 Compressive Strength (ASTM C 39)..................................................................48 Static Modulus of Elasticity a nd Poissons Ratio (ASTM C 469)......................53 Splitting Tensile Stre ngth (ASTM C 496)...........................................................55 Durability Tests..........................................................................................................56 Linear Shrinkage (ASTM C 157)........................................................................56 Volume of Voids (ASTM C 642)........................................................................57 Sulfate Expansion (ASTM C 1012)....................................................................57 Absorption (ASTM C 642)..................................................................................58 Corrosion of Embedded Steel Reinforcement (ASTM G 109)...........................59 Background Chloride Level (FM 5-516).............................................................62 Surface Resistivity (FM 5-578)...........................................................................62 Rapid Migration Test (NTBuild 492)..................................................................63 Water Permeability (UF Method)........................................................................65 5 RESULTS AND DISCUSSION.................................................................................68 Plastic Properties Tests...............................................................................................68 Mechanical Tests........................................................................................................71 Compressive Strength (ASTM C 39)..................................................................71 Flexural Strength (ASTM C 78)..........................................................................81 Modulus of Elasticity and Poissons Ratio (ASTM C 469)................................89 Splitting Tensile Strength of Cy lindrical Concrete (ASTM C 496)....................95 Durability Tests..........................................................................................................96 Linear Shrinkage (ASTM C 157)........................................................................96 Volume of Voids and Absorption (ASTM C 642)..............................................98 vi

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Sulfate Expansion (ASTM C 1012)....................................................................99 Corrosion of Embedded Steel Reinforcement (ASTM G 109).........................103 Surface Resistivity (FM5-578)..........................................................................103 Rapid Migration Test (NTBuild 492)................................................................111 Water Permeability (UF Method)......................................................................117 6 SELECTION OF MIX DESIGNS FOR PILES.......................................................118 Selection Approach...................................................................................................118 Selection Criterion I: Cost.................................................................................119 Selection Criterion II: Mechanical Properties...................................................119 Selection Criterion III: Durability.....................................................................120 Importance Factors............................................................................................121 7 CONCLUSIONS AND RECOMMENDATIONS...................................................123 APPENDIX A LABORATORY MI X TESTING DATA................................................................126 B LABORATORY MIX STATISTICAL DATA........................................................136 C LABORATORY MIX NORMALIZED DATA.......................................................140 LIST OF REFERENCES.................................................................................................142 BIOGRAPHICAL SKETCH...........................................................................................146 vii

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LIST OF TABLES Table page 2 1Typical Oxides and Th eir Shorthand Notation.............................................................4 2 2 Typical Chemical Compounds and Their Shorthand Notation...................................4 2 3 Typical Chemical Compositions and Properties of ASTM Type I to V cements.......8 2 4 Summary Table Comparing C ube Strength (Jones et al 2006).................................14 2 5 Percent Improvement of Ultraf ine Fly Ash vs. Ordinary Fly Ash............................14 2 6 Slag Activity Index (ASTM C 989)..........................................................................15 3 1 Proportions of Ceme ntitious Materials a)..................................................................36 3 2 Proportions of Ceme ntitious Materials b).................................................................36 3 3 Mix Designs a) (lb/yd3).............................................................................................37 3 4 Mix Designs b) (lb/yd3).............................................................................................37 4 1 Test Voltage and Duration for NTBuild 492.............................................................64 5 1 Plastic Properties....................................................................................................... 69 5 2 Average Compressive Strength at 365 days, Normalized 365 day Compressive Strength to CTRL2, and 91 to 365 day Slope..........................................................73 5 3 Modulus of Rupture, Compre ssive Strength, and Coefficient...................................88 5 4 Poissons Ratio.......................................................................................................... 95 5 5 Average Percent Length Change, COV, and Normalized (to CTRL1) Shrinkage Values at 32 Weeks of Age......................................................................................97 5 6 Average Percent Void and Absorption, COV, and Normalized (to CTRL1) Void and Absorption Values at 32 Weeks of Age............................................................99 5 7 Total Concrete and Mortar Expansion.....................................................................102 viii

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5 8 Increase in Surface Resistiv ity Between Test Ages (%).........................................105 5 9 Summary Table of Penetrability Ca tegory, Penetration Depth, Coulombs Passed and Surface Resistivity...........................................................................................110 5 10 Surface Resistivity (k -cm)..................................................................................111 5 11 Decrease in Migration Coefficient (%).................................................................113 5 12 RMT and RCP relationship...................................................................................115 5 13 RMT Values (mm/V*hr).......................................................................................116 5 14 Coefficient of Permeability...................................................................................117 6 1 Material Costs..........................................................................................................1 19 6 2 Normalized Mechanical Test Results......................................................................120 6 3 Normalized Durability Test Results........................................................................121 6 4 Summary of Normalized Results and Equation Values..........................................122 A 1 Plastic Properties Tests...........................................................................................126 A 2 Compressive Strength.............................................................................................126 A 3 Flexural Strength for In itial Series of Mixtures......................................................127 A 4 Flexural Strength for Second Series of Mixtures...................................................127 A 5 Averaged Flexural Strength....................................................................................128 A 6 Modulus of Elasticity..............................................................................................128 A 7 Poissons Ratio.......................................................................................................129 A 8 Splitting Tensile Strength.......................................................................................129 A 9 Linear Shrinkage, Volume of Voids, Absorption, and Permability.......................130 A 10 Sulfate Expansion.................................................................................................130 A 11 Surface Resistivity................................................................................................131 A 12 Rapid Migration Test............................................................................................131 B 1 Compressive Strength.............................................................................................136 B 2 Flexural Strength for In itial Series of Mixtures......................................................136 ix

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B 3 Flexural Strength for Second Series of Mixtures....................................................137 B 4 Splitting Tensile Strength.......................................................................................137 B 5 Linear Shrinkage, Volume of Voids, Absorption, and Permeability......................138 B 6 Sulfate Expansion...................................................................................................138 B 7 Surface Resistivity..................................................................................................139 B 8 Rapid Migration Test..............................................................................................139 C 1 Cost.........................................................................................................................140 C 2 Mechanical Tests....................................................................................................140 C 3 Durability Tests.......................................................................................................141 C 4 Summary.................................................................................................................141 x

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LIST OF FIGURES Figure page 3 1 Rotary Drum Mixer...................................................................................................40 4 1 DIAM-end Grinder....................................................................................................49 4 2 Test Mark Load Frame..............................................................................................50 4 3 Diagram of the Third-Point Loading Flexure Testing Apparatus.............................52 4 4 Instron Load Frame Testing Flexural Strength..........................................................52 4 5 Modulus of Elasticity and Poisson s Ratio Test Setup on the TEST MARK system.......................................................................................................................54 4 6 Splitting Tensile Strength Test on Forney Load Frame............................................55 4 7 ASTM G109 Specimen Molds containi ng the Reinforcing Bars and Reference Electrode...................................................................................................................60 4 8 ASTM G109 Specimen After The Epoxy Has Been Applied...................................60 4 9 Environmental Room Containing the Automated Monitoring Device and Corrosion Specimens................................................................................................61 4 10 Electrical Diagra m of Corrosion Specimens...........................................................61 4 11 Wenner Linear Four-P robe Array and Display.......................................................63 4 12 RMT Test Setup.......................................................................................................64 4 13 Cross-Section of Water Permeability Specimen Fixture.........................................67 4 14 Water Permeability Test Setup................................................................................67 5 1 Compressive Strength of All Mixtures......................................................................72 5 2 Average Early Strength of Slag Mixtures..................................................................74 5 3 Average Late Strength of Slag Mixtures...................................................................74 xi

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5 4 Average Early Strength of Metakaolin Mixtures......................................................76 5 5 Average Late Strength of Metakaolin Mixtures........................................................77 5 6 Average Early Compressive Stre ngth of Ultrafine Fly Ash Mixtures.......................78 5 7 Average Late Compressive Strength of Ultrafine Fly Ash Mixtures........................78 5 8 Compressive Strength of Silica Fume Mixtures........................................................79 5 9 Compressive Strength of Silica Fume Mixtures........................................................79 5 10 Modulus of Rupture of All Mixtures.......................................................................82 5 11 Average Modulus of R upture of Slag Mixtures......................................................83 5 12 Average Modulus of Rupt ure of Metakaolin Mixtures...........................................84 5 13 Average Modulus of Rupture of Ultrafine Fly Ash Mixtures.................................85 5 14 Average Modulus of Rupt ure of Silica Fume Mixtures..........................................86 5 15 Average Modulus of El asticity of All Mixtures......................................................90 5 16 Average Modulus of El asticity of Slag Mixtures....................................................91 5 17 Average Modulus of Elastic ity of Metakaolin Mixtures.........................................92 5 18 Average Modulus of Elasticity of Ultrafine Fly Ash Mixtures...............................93 5 19 Average Modulus of Elastic ity of Silica Fume Mixtures........................................94 5 20 Normalized Values of Sulfat e Expansion: Concrete Specimens...........................100 5 21 Normalized Values of Sulfat e Expansion: Mortar Specimens..............................101 5 22 Comparison of Mortar and Conc rete Sulfate Expansion Specimens....................103 5 23 Corrosion of Embedde d Steel Reinforcement.......................................................103 5 24 Average Surface Resistance of Slag Concrete Mixtures.......................................105 5 25 Average Surface Resistance of Metakaolin Concrete Mixtures............................107 5 26 Average Surface Resistance of U ltrafine Fly Ash Concrete Mixtures..................108 5 27 Average Surface Resistance of Silica Fume Concrete Mixtures...........................109 5 28 Average Migration Coefficient of Slag Mixtures..................................................112 xii

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5 29 Average Migration Coefficient of Metakaolin Mixtures.......................................114 5 30 Average Migration Coefficien t of Ultrafine Fly Ash Mixtures.............................114 5 31 Average Migration Coefficient of Silica Fume Mixtures......................................115 A 1 Relative Humidity in Dry Curing Room for a) 2005 and b) 2006..........................132 A 2 Temperature in Dry Curing Room for a) 2005 and b) 2006...................................132 A 3 Corrosion of Embedded Steel Reinforcement for a) CTRL1 and b) CTRL2.........132 A 4 Corrosion of Embedded Steel Reinforcement for a) SLAG1, b) SLAG2, and c) SLAG3...................................................................................................................133 A 5 Corrosion of Embedded Steel Reinforcement for a) META1, b) META2, and c) META3...................................................................................................................134 A 6 Corrosion of Embedded Steel Reinforcement for a) UFA1, b) UFA2, and c) UFA3......................................................................................................................135 A 7 Corrosion of Embedded Steel Reinforcement for a) SF1 and b) SF2....................135 xiii

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Abstract of Thesis Presen ted to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Engineering IMPLEMENTATION OF HIGHLY REACTIVE POZZOLANS IN THE KEY ROYALE BRIDGE REPLACEMENT By Edward K. Roske May 2007 Chair: H. R. Hamilton III Major: Civil Engineering The objective of our study was to assess th e use of alternative mineral admixtures to improve the service life of bridges constr ucted in severe marine environments. Our study evaluated the effects of highly reactive pozzolanic materi als in conjunction with fly ash on the plastic, mechanical, and durability properties of portland cement concrete. Additionally, mixtures using th ese highly reactive pozzolans we re designed for use in the precast, prestessed piling for the Key Royale bridge replacement project. Thirteen different trial mixtures were pr epared using varying proportions of several highly reactive mineral admixtur es. Two of the thirteen were control mixtures; one contained only portland cement and the othe r contained 18% fly ash. The remaining eleven mixtures contained 18% fly ash with varying proportions of slag, metakaolin, ultrafine fly ash, and silica fume. Plastic property tests were conducted on temperature, ai r content, slump, bleeding, and setting times. Mechanical test proce dures included compressive strength, flexural xiv

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strength, splitting tensile stre ngth, modulus of elasticity, and Poissons ratio. Several durability tests were performed including surface resistivity, rapid migration test, volume of voids, absorption, water permeability, shri nkage, sulfate expansion, and corrosion of embedded steel reinforcement. Using results from the laboratory testing, we created a decision matrix to select the relative mineral admixture proportions to be us ed to construct the piles. One mixture from each group of mineral admixtures was selected. The decision matrix included ratings for cost, mechanical properties, a nd durability. Although the costs of several mixtures were considerably higher than the controls, each mixture showed an overall improvement in mechanical and durability prope rties. Proportions determined to provide the most effective mixtures were 30% sla g, 10% metakaolin, 12% ultrafine fly ash, and 9% silica fume. Based on the decision matrix, each mixture showed consistent mechanical properties. The silica fume and metakao lin mixtures, however, performed the best overall in the durability tests. Silica fume mixtures showed improvement in durability over the cement only control ranging from 21 to 23%. Metakaolin also showed improvements of 17 to 20%. xv

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CHAPTER 1 INTRODUCTION The Florida Department of Transportation (FDOT) has set a goal to build bridges that will last at least 100 year s. Currently, the acceptance cr iteria consist of measuring the plastic properties, water-to-cementitious ratio and compressive strength. None of these acceptance criteria can be used to predict the ultimate service life of the structure. By performing more durability-related test s on local materials, the Department can develop a better understanding of how long a structure can be expected to last. Current design standards (2004 Structures Design Guidelines for Load and Resistance Factor Design ) allow only corrosion inhibitors or silica fume for reducing permeability of the concrete. Silica fume is currently specified in Florida concretes under certain conditions; when the e nvironmental classification is Extremely Aggressive due to the presence of chloride in the water, specify microsilica in the spla sh zone of all piles, columns or walls. Microsilica may be specified for the entire pile, column or wall but shall not be specified for drilled shafts. The splash zone is the vertical distance from 4 feet below MLW to 12 feet above MHW. Under new specifications proposed by AASHTO, other materials could be allowed in place of silica fume for concrete placed under such conditions. Mixtures containing highly-re active pozzolans such as metakaolin and superfine fly ash will provide similar strength as silica fume, while avoiding the detrimental workability issues. Currently, the availabil ity and cost of the highly reactive pozzolans designated in this study are both better than for silica fume. However, newer materials require investigation to determine which mixt ure design criteria should be implemented in order to provide the desired service life to FDOT structures. 1

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2 The present research evaluated the durability and mechanical properties of concrete made with highly reactive pozzo lans other than silica fume. Four of these concrete mixture designs were selected for use in fabricating piles for a bridge structure to be built in a severely aggressive environment. The field project was funded by the Federal Highway Administration through their Innov ative Bridge Research & Construction (IBRC) program. This investigation tested several alternativ e materials to provide the FDOT with the means to assess the applicability for utilization in the splash z one of a Florida concrete in a severely aggressive environment. Thes e materials include slag, metakaolin, and ultrafine fly ash. Research was conducted on the effects of implementing these highly reactive pozzolanic materials in conjunction wi th fly ash to the plastic, mechanical, and durability properties of portland cement conc rete. Additionally, this study provided the FDOT with a recommendation of the most effective mixtures containing various pozzolans for the utilization in the piling of the Key Royale bridge replacement project.

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CHAPTER 2 LITERATURE REVIEW Presently, the Florida Department of Tran sportation (FDOT) only allows the use of silica fume in the splash zone of concretes in a severely aggressive environment. There are, however, several other mineral admixtur es that provide an improvement in the mechanical and durability characteristics of a concrete. Many resear chers have presented data relating to the effects of mineral ad mixtures on the plastic, mechanical, and durability properties of a concrete. Therefore, this chapter presents a comprehensive review of the currently available literature. Unhydrated Cement Chemistry Portland cement is a hydraulic cement whic h is typically produced by initially heating limestone with clay in 2550 to 2900 F kiln to produce clinker (Mindess et al. 2003). The clinker is then ground to a specific fineness. Small amounts of gypsum is interground with the clin ker to control the hydration rate of the finished cement product. Shorthand notation used to represent the actual chemical formulas for oxides found in cements and mineral admixtures are shown in Table 2 1 Chemical compounds that are the major constituents in cement are formed from these oxides in the calcining process of cement manufacturing. The chem ical name, chemical formula and shorthand notation for the five most abundant compounds are found in Table 2 2 3

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4 Table 2 1 Typical Oxides and Their Shorthand Notation Common Name Cheula Shorthand Notation mical Form Lime CaO C Sili SiO S ca 2 Alumina Al2O3 A Ferric Oxide Fe2F O3 Magnesia MgO M Alkali K2O K Alkali Na2N O Sulfur Trioxide SO3 Carbon Dioxide CO 2 Water H2O H Tab al Cheomp ounds and Their Shorthand Notation Chemical Name Chemical Formula Shorthand Notation le 2 2 Typic mical C Tricicate 3CaOSiO2 C3S alcium Sil Dicalcium Silicate 2CaOSiO2 C2S Tric inate 2CaOAl2O3 3A alcium Alum C Tetracalcium Aluminoferrite 4CaO Al2O3Fe2O3 C4AF Callfate Dihyd (gy CaSO4H2O C H2 cium Su psum) rate ations of the quantity of thes e compounds can be made through Bogue equville 1995). Bogue equations are used to predict the properties of cement, such as rate of strength development and heat liberation. Moreover, manipulation of the cemd on results of these equations, c e made to modify certain properties to make it more appropriate to a pa rticular application (Mindess et al. 2003). The formula is as follows. Estim ations (Ne ent, base an b Case A: A/F 0.64 C 4.071C 7.600S 1.430F 2.3S = 6.718A 852 C2.867S 0.75443 C3A = 2.650A 1.692 C4AF = 3.043F Cas 4 C3S = 4.071C 7.600S 4.479A 2.859F 2.852 S = 2 C S F eB: A/F < 0.6 C 67S 0.7544 C3 C4AF = 2.100A + 1.702F 2S = 2.8 A = 0 C3S

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5 Each cement and mineral adm ixture is composed of so all of these com ides. A more detailed anal ysis of the typical compositions for each mat in the succeedi Hydration Chemistry The chemical reactions of poz ent hydration have been widely studied in which a few commonly accepted equati ons have been established (Mindess et 20 ation calcium hydroxide (CH) formed. C3S2H8 + 3CH (2-1) 2C2S + 9H C3S2H8 + CH (2-2) The composition of this calcium silicate hydr ate product can vary widelytypically in water content. Presented here, the product is in its saturated state. In contrast, CH has a fixed composition Another hydration reaction occurs in the pr esence of sulfate ions supplied by the dissolution of gypsum. These ions react with C3A to form a calcium sulfoaluminate hydrate. C3H2 + 26H C6A 3H32 (2-3) Thealcium sulfo only known as ettringite. Howev upply of sulfate ions present, the C3A will not be completely hydrated. Ettringite will then be reacted with C3A to form another me or pounds and ox erial is discussed ng section. zolans and cem al. 03). These equations are presented in th e subsequent sections for cement hydr and pozzolanic reactions. Cement Hydration The hydration of the calcium silicates in portland cement produces calcium silicate hydrate and calcium hydroxide. The C3S and C2S reactions are very similar, with the only difference being the quantity of 2C3S + 11H A + 3C c aluminate hydrate is a st able hydration product comm er, if there is an insufficien t s

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6 calcium sulfoalumrate with less sulfate, commonly known as monosulfoalumin 2C3A + C6A 3H32 + 4H 3C4A H12 (2-4) If a n gite is C6A 3H32 (2-5) Pozzolanic Reaction ith ozzolan is very high, a s econdary reaction will occur: S + 2S + 10.5H 3[CSH3.5] (2-7) When (2-8) Effect of C n Concrete Properties ortland Cement Portland cement mposition and fineness to ensure a tisfactory performance for a particular app lication, such as high early strength or low heat of hydration. ASTM created a cement clas sification to standardize cements so that a more consistent product can be manufact ured. These standardized cements are designated ASTM Types I, II, III, IV, and V. Before an explanation of how the st andardized ASTM cements are produced, knowledge of the hydration characteristics of cement compounds needs to be understood. inate hyd ate. ew source of sulfate ions comes in cont act this monosulfoaluminate, ettrin able to be reformed: C4A H12 + 2C H2 + 16H Pozzolan are not cementitious, but rather amorphous silica which will react w CH and water to form a cementious product, C-S-H: CH + S + H C-S-H (2-6) If the silica content in th e p C3 the pozzolan has large quantity of reactiv e alumina, the CH will react with alumina to form a calcium aluminate hydrate (C-A-H): CH + A + H C-A-H ement and Mineral Admixtures o P s are produced with a specifi c co sa

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7 It is u ent in a concrete. (Mindess et al. 2003) C3S react moderately to contribute early strength deve ute to ultimate strength. action of C3S liberates a moderate amount of heat. However, because of its high 2 2. 3re, its contribution ration is very high. The hydration of C4AF is moderate and is slowed by the pre The ASTM Type I is the most commonly used cement, as it is general purpose. It has average strength gain and heat of hydr ation. However, if a more specialized application, such as sulfate resistance or hi gh early strength development, is needed, a different type should be sele cted. Type V cements was developed to combat sulfate nvolves the hydration products formed from C3A. Therefore, lower strength concrete. This was accomplished by increasi r, more effectively, grinding th ement finer. However, much heat is gene rated during the hydration process because of h temperatures create rete, where thermal cracki ecome a problem. It is for this reason that Type IV was created. Type IV cement was seful to know how the chemical compounds listed in Table 2 2 affect strength development and rate of heat evolution. Calcium silicates provide most of the strength developm lopment. In later ages, C3S will contrib The re proportion in cement, its contribution to the overall heat libe ration is high. C S has a much slower reaction and a low heat ge neration. Therefore, at early ages, C S provides very little strength development. However, its contribution to ultimate strength is high The hydration of C A is a fast and highly exothermic reaction. Therefo to the overall heat libe sen ce of gypsum. attack. Sulfate attack i ing the percentage of C3A will serve to increase the sulfate resistance of a cement. Type III cement was developed to create a high early ng the proportions of C3S o e c the increase surface area of C3S. Therefore, this cement cannot be used where hig adverse effects, such as in mass conc ng can b

PAGE 23

8 developed to create a low h eat of hydration product. Th e proportions of the highly exothermic compounds, C3A and C3S, were reduced. However, there are problems associated with this cement also. Because of the lower C3S composition, this cement has slow strength gain; therefore, a Type II cement was developed. The C3S proportion remains t3ng fairly sulfate resistant. Table 2 3 was recreated from Mindess (et al. 2003), detailing typical chemi cal compositions and properties of ASTM Types I to V cements. Table 2 3 Typical Chemical Compositions and Properties of ASTM Type I to V I II III IV V a he same, while C A is slightly lowered. This cement has a better strength development, as well as bei cements C3S 55 55 55 42 55 C2S 18 19 17 32 22 C3A 10 6 10 4 4 C AF 8 11 8 15 12 4 C H2 6 5 6 4 4 Fineness (m2/kg) 365 375 550 340 380 he e a Class C has a mini mum of 50%. Derived from Fly ash Fly ash is precipitated from the exhaust ga ses of a coal burni ng power station. T majority of particles are spherical, glassy, a nd either hollow or solid in shape and have a high fineness. Typically, particle s have a diameter range of 1 m to 100 m and a specific surface between 250 to 600 m2/kg (Neville 1995). The main components in th composition of fly ash are oxides of silic on, aluminum, iron, and calcium. The varying calcium content in fly ash composition led to the creation of ASTM C 618. This standard created two classes of fly ashClass C and Class F. ASTM C 618 requires a Class F fly ash to be composed of a mini mum of 70% silicon oxide (SiO2) plus aluminum oxide (Al2O3) plus iron oxide (Fe2O3), while

PAGE 24

9 the bu water of a ugh For p the same workability for a concrete mixture. Neville (1995) ater demnd. The finer fly ash particle maecome electrically charged and cover the surface of the cement particles. He states that action deflo cculates the cement particles, rning of subbituminus coal or lignite Class C fly ash has a high lime (CaO) content. Because of this, it is also slightly cementitious. Problems arise with high demand, early stiffening, and rapid setting. Cla ss F fly ash is derived from the burning bituminous coal or anthracite. Its calcium content is lower than a Class C fly ash. Because fly ash is a pozzolan, the silica a nd alumina will react with CH to form cementitious compound, C-S-H and C-A-H, resp ectively. The reactions depend on the breakdown and dissolution of silica and alumina by the hydroxide ions and heat generated by the hydration of portland cement. The glass material in fly ash is only broken down when the pH value of the pore water is at least 13.2 (Neville 1995). In other words, the fly as will consume CH and form a hydration product as long as eno CH is present in the pore solution and th ere is sufficient void space present for the hydration product to fill. Fly ash influences the properties of a fr esh concrete in a variety of ways. Workability, bleeding, and time of setting are all affected by the addition of fly ash. the most part, the changes due to the addition of fly ash are because of the shape and size of the particles and it s chemical composition. A reduction in water demand and an increase is workability is attributed to the spherical shape of the particles. The part icle shape reduces the interparticle friction within the mixture, effectively increasing the workability. This also allows for a reduction in water to kee has found that another mechanism of fly ash may be dominant in decreasing the w a y b

PAGE 25

10 thus reducing the water demand for a given work ability. Another benefit of fly ash is the small particle size, whllows themack betwee cement particles. This is known as particle packing; it reduces bleeding, lowers the me an size of the capillary pores, and can reduce water requirements (Mindess et al. 2003). composition of fly ash also extends sett ing times and decreases the overall heat liberated during hydration. Dela yed setting times are ascrib ed to the w pozzolani reactions of fly ash. As mentioned above, the glassy fraction of fly ash will only breakdown when sufficient hydroxide ions are pr esethe pore so n. This pr takes place only after a certain amount of hydration of portland cement has taken place 995). A consequen ce of the delay in the cement hydration is the slow pattern of hea the is ich a to p en th The slo c nt in lu tio ocess (Neville 1 t evolution. Much of the heat is ge nerated during the early stages of hydration of the C3S and C3A within the paste. The delayed setti ng time allows the concrete to slowly liberate the heat generated. In addition, wh en fly ash is used a cement replacement, smaller quantities of the hi gh heat generating compounds, C3S and C3A, are present. Therefore, the overall heat of hydration is reduced. Fly ash influences the properties of a hardened concrete in a variety of ways. Compressive strength and rate of strengt h gain, modulus of elasticity, permeability, sulfate resistance, and drying shrinkage are all affected by the addition of fly ash. For most part, the changes due to the addition of fly ash are beca use of the shape and size of the particles and its chemical composition. The rate of strength gain is reduced by the addition of a Class F fly ash. As mentioned above, the pozzolanic reactions of fly ash depend on a high pH pores solution. Because this takes time to occur, the early hydration of mixtures containing fly ash

PAGE 26

11 slow. e oncrete gest characteristics will have a greater e ffect on modulus of elasti more ing fly ash is that the initial permeability is highe h ds in er ently, t al. Consequently, the early age compressive strengths are low. However, over time, the Class F fly ash will react to produce a stronger concrete than that of the same mixtur containing only portland cement (ACI 232.2R-03) Conversely, Class C fly ash c often exhibit higher rate of r eaction at early ages, but lower strength gain at late ages when compared to a Class F fly ash concrete (ACI 232.2R-03). ACI (232.2R-03) has found that the effects of fly ash on the m odulus of elasticity are not as significant as the effects on compre ssive strength. Furthermore, they sug that cement and aggregate city that the use of fly ash. Similar to modulus of elasticity, creep strain is affected by compressive strength than fly ash. Lower compressive strengths result in higher creep strains (ACI 232.2R-03). The consequence of using the slow react r than that of the same concrete c ontaining only portland cement (Neville 1995). However, over time the fly ash concrete wi ll develop a very low permeability throug pozzolanic reactions (ACI 232.2R-03). CH is susceptible to leaching, leaving voi which deleterious solution can ingress. Howe ver, fly chemically combines with CH to form a cementitious product, C-S-H. This action reduces the risk of leaching, and furth reduces permeability as the pore structure beco mes occupied with C-S-H. Consequ the durability of a concrete e xposed to aggressive environm ents containing sulfates and chlorides is improved because of the reduc tion in permeability (Neville 1995). In addition, sulfate resistance is further improve d through the removal of CH (Mindess e 2003).

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12 Ultra es h filters ior ased upon chemical composition and p e e particles increases water demand. There ash ultrafine fly ash and 30% ordinary fly ash mi xtures. Because of the retardation of C3A fine fly ash Ultrafine Fly ash, similar to ordinary fly ash, is precipitated from the exhaust gas of a coal burning power station. However, th e larger particles are removed throug or separators. The majority of particles are spherical, glassy, and either hollow or solid in shape and have a very high fineness. Boral (2003) states that the average particle diameter is 3 m and the distribution of par ticle size is as follows: Minimum of 50% of particle sizes less then 3.25 microns Minimum of 90% of particle sizes less than 8.50 microns. Little research has been conducted on the effects of ultrafine fly ash on the durability and mechanical properties of a concrete. However, estimations on the behav can be made through relations with ordinary fly ash b article size. The addition of ultrafine fly ash will influence the properties of a fresh concret similarly to ordinary fly ash. Differences in workability and bleeding from that of ordinary fly ash are attributed to the smaller average particle size. The higher surface area of the ultrafin fore, the addition of ultrafine fly as h reduces workability when compared to ordinary fly ash. However, workability is increased when compared to a cement only mixture (Boral 2003). Bleeding is also affected by the particle size. The ultrafine fly particles will pack between cement grains a nd aggregate. Consequently, the mixture is more cohesive and a reduc tion in bleeding is achieved. Jones (et al. 2003) conduced 72 hour h eat of hydration experiments on 30%

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13 hydration, the rate of heat e volution was impeded by 2 hours and 5 hours for the ordin fly ash and ultrafine fly ash mixtures, respec tively. They have sh ary own that both mixtures lower ize reactivity will increase. Consequently, the streng nd 91 ents of ordinary a nd ultrafine fly ash at a 0.50 w/ cm on cube strength. They ys, the control mi xture had the highest strength ( Table 2 4 ). At 90 and 1 the total heat of hydration when compar ed to the control. The ultrafine fly ash mixture showed the lowest total heat until 18 hours. Beyond 18 hours, the ordinary fly ash mixture had the lowest total heat. Because the mineral composition is the sa me, ultrafine fly ash will have similar chemical reactions to that of ordinary fly ash. However, beca use the average particle s of ultrafine fly ash is much smaller, the th and durability on the concrete will be higher at early ages. Boral (2003) has found that at 7 days there is an increase in strength activity index of 107% of the control, and 124% at 28 da ys. Furthermore, they have conducted compressive strength tests on 8% silica fume, 6% ultrafine fly ash, and 9% ultrafine fly ash mixtures with the following charact eristics: w/cm of 0.26 0.28, cement = 823 lb/yd3, and fly ash = 100 lb/yd3. They have shown that a 6% replacement of ultrafine fly ash has nearly equal compressive strength at 7 and 28 days, and roughly a 5% increase at 91 days when compared to an 8% silica fu me concrete. A 9% replacement showed increases over the 8% silica fume concrete of roughly 6%, 8%, and 11% at 7, 28, a days, respectively. Jones (et al. 2006) researched the effects of 15% and 30% replacem found that at 28 da 80 days, both ultrafine fly ash mixtures showed higher strength than the control, while both ordinary fly ash mixtures were lower.

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14 Table 2 4 Summary Table Comparing Cube Strength (Jones et al 2006) % of Control Mixture 28 day 90 day 180 day Control 100 100 100 15% Ordinary Fly Ash 75 85 87 30% Ordinary Fly Ash 54 30 64 15% Ultrafine Fly Ash 96 116 110 30% Ultrafine Fly Ash 87 102 104 At each age, the ultrafine fly ash m ixtures showed an improvement over the ordin f Fly Ash ary fly ash ( Table 2 5 ). Therefore, it is evident that the decreased particle size o the ultrafine fly ash increases the strength development at early ages. Table 2 5 Percent Improvement of U ltrafine Fly Ash vs. Ordinary % of Ordinary Fly ash Mixture 28 day 90 day 180 day 15% Ultrafine Fly Ash 27 36 39 30% Ultrafine Fly Ash 61 45 64 Research conducted by Boral (2003) has also shown that there is an improvement in a concrete against chloride penetration. They found chloride diffusion coefficients for 8% si ) at Jones (et al. 2003) researched the effects of 30% repla cement of ordinary fly ash and ultrafine fly ash on the total CH content wi thin a mixture. They found that from age lica fume, 8% ultrafine fly ash, and 12% ultrafine fly ash mixtures (0.40 w/cm 40 days and 2 years. At both ages, the ultrafine fly ash mixtures showed lower coefficients when compared to the control. It appears that the 12% replacement showed slightly better results that th e 8% mixture. However, neither ultrafine fly ash mixture had lower coefficients than the silica fume mixture.

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15 of 3 days to 90 days, the ultrafine fly ash mixtures showed a lower CH content when compared to the ordinary fly ash mixtures. Th is indicates that ultrafine fly ash is more reacti ent he raw slag is then dried ference Designation 7 day (%) 28 day (%) ve and has consumed more CH through pozzolanic reactions Slag Blast furnace slag is the residue wastes formed from the production or refinem of iron. Slag is removed from the molten meta l and rapidly cooled. T and ground to a specific fineness so that it can be used as a cement replacement. ASTM C 989 provides three grades for slag based upon its relati ve strength to a re mortar made with pure cement (Table 2 6 ). Table 2 6 Slag Activity Index (ASTM C 989) Grade 80 --75 Grade 100 75 95 Grade 120 95 115 5% mpound. re hat rb little water and act as slip planes in the pate. times at normal temperatures of typically 30 to 60 mi nutes. ACI (233R-03) has found that setting times of slag mixtures is significantly aff ected by portland cement setting characteristics Typically, silica, calcium, aluminum, ma gnesium and oxygen constitute over 9 of the chemical composition (ACI 233R-03). Because of the high lime content, slag is a hydraulic admixture, meaning it will react w ith water to form a cementitious co The addition of slag in a fresh concrete increases the workability, but make it mo cohesive. This is attributed to the better di spersion of cementitious particles and of the surface characteristics of the slag particles (Neville 1995). ACI (233R-03) has found t the smooth, dense surfaces of the slag particles ab so s Neville (1995) has suggested that slag l eads to retardation of setting

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16 andnt of pond cem withimixt ure. They state that setting times are delay when more tha% slag is used as a replacement. ng is red wheg is gd to a high fineness (Neville 1995). ACI (233R-03) supports this statement. They suggest that if slag is ground to a higher fineness than the cement particles and is replaced on an equal-mass basis, bleeding may be reduced; conversely, if the slag particles are larger, the rate and amount of bleeding may increase. addition of slag in a mixture increases the silica content and decreases the total lim -S-Hrod uced resulting in a microstructure that is denser than that of a cement only mixture (Nev ille 1995). However, the rate of strength gain is initially very slow b ecause of the presence of impervious coatings of amorphous silica and alumina on slag p les (Mess et al. 2003). These coatings are broken down in a slow process by hydroxyl ions that are released during the hydration of the portland cement (Neville 1995). 3R-03) fount whe mpared with a portland cement only concrete, the use of Grade 120 slag typically redu ces the strength at ages before 7 days; at 7 days and later, Grade 120 slag increases st rength. Grade 100 slag reduces strength at ages l e 80 ges beyond 7 days (ACI 233R-03). They suggest that the improvement in modulus of rupture is because of an increased density of the pa ste and improved bond at the aggregate-paste the amou rtla n 25 ent n the Bleedi uced n sla roun The e content. Consequently, m ore C is p the a rtic ind ACI (23 has d tha n co ess than 21 days, while producing equal or greater strength at later ages. Grad slag shows lower strength at ages less than 28 days, and comparable strength at 28 days and later. Modulus of rupture is generally increased with the addition of slag at a

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17 interface. Neville (1995) has s that corporation of slag does not significantly alter the usual relations between compre strength and modulus of rupture. ACI (233R-03) has suggested that water cu red slag concretes have do not have an effect of modulus of ticity rly ahowever, at later ages, modulus is increased. Conversely, air cured specimen exhibited reductions in modulus. This is attributed to inadequate curing. Mindess (et al. 2003) has found that modulus of elasticity is most dominantly affected by porosity. Therefore, prolonged moist curing is particularly important in a slag concrete in which the low early hydration results in a system of capillary pores which allow for the loss of water under dry conditions (Neville 1995). Consequently, hydration is halted, leaving a porous concrete. Cons equently, modulus of lasti will be er and more homogenous than that produ e tated th e in ssive el as at ea ges; e city is reduced. This compound adds to the strength of th e mix, while also increasing durability by decreasing the interconnectivity of the voids. In addition, the high silica and alumina content promote pozzolanic reactions. The CH produced from cement hydration consumed and transformed into more cemen titious compounds. These compounds are in the forms of C-S-H or C-A-H, depending on whether the reactive compound was silica or alumina. These new hydration products are dens ced by cement hydration alone. At early ages, the incorporation of slag in a mixture will increase shrinkage; however, at later ages shrinkage and creep are not adversely aff ected (Neville 1995). ACI (233R-03) supports the statement in whic h there is no significant affect on shrinkag or creep.

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18 The heat of hydration has been found by ACI (233R-03) to be lower in a 75% slag replac ). As a result, the permeability is slag content increases, the permeability decreases. Consequently, the resistance to sulf ate attack is increase d. The resistance to sulfate attack is further in creased through consumption of CH, the major component in sulf corros(Mindessl 2003). ACI (233R-03) found that 50% blends of slag with a Type I concrete had the same sulf ate resistance as a Type V cement concrete. Thed thatuse of sla we ll hydrated concrete reduces the penetrability of chloride ions and the de pth of carbonation. However, Neville (1995) has a conflicting opinio carbo n ts in a ement concrete than in a 30% fly as h concrete or cement only concrete. Slag reduced the early rate of heat genera tion and lowered the peak temperature. One benefit of the addition of slag into a concrete arises from the denser microstructure of hydrated cement paste in wh ich more of the pore sp ace is filled with CS-H than in a cement only paste (Neville 1995 decreased. ACI (233R-03) has found that as the oaluminate ion et a y have foun the g in a n in regards to improvements in depths of carbonation with th e addition of slag. He states that the slag can have a detrimental effect at early ages when there is very little CH present in the concrete. Because of the decreased pr esence, CH cannot react with n dioxide to form calcium carbonate in the pores. Conseque ntly, the depth of carbonation is significantly greater than in a conc rete containing only cement. Conversely, the reduced permeability of slag c oncrete at later ages prevents continued increases in depth of carbonation. Metakaoli Metakaolin is manufacture by calcining clay at high temper atures. This resul material that is largely composed of highly reactive amorphous aluminosilicates. Mindess (et al. 2003) has reporte d that, typically, the reactiv e silica and alumina content

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19 in metakaolin ranges from about 55% and 35 to 45%, respectively. The particles are plate-like and have an average size of 1 to 2 m, with a surface area of about 15 m2/g. ACI ( e homogenous than that pr oduced by cement hydration alone. (Mindess et al. 20 s over a cement only concrete. Conversely, a 10% replac the strength development of 0.4 w/ cm concrete with metakaolin replacements rates gth. n 232.1R-00) has reported an average size of highly reactive metakaolin to range from 1 to 20 m. Through pozzolanic reactions, CH will react with both silica and alumina to form a cementitious hydration product. These can be in the form of C-S-H or C-A-H, depending on whether the reactive co mpound is silica or alumina, which are denser and mor 03). Zongjin and Ding (2003) have found that a 10% blend of metakaolin reduces the fluidity of the mixture. They have s hown that the water demand was increased by roughly 11%, which is attribut ed to the plate-like particle shape and its tendencies to absorb water. Setting times were also show n to decrease by 26% a nd 36% for initial and final setting times. ACI (232.1R-00) has repor ted lower adiabatic temperatures for 15 and 30% metakaolin replacement ement showed higher temperatures when compared to the control. ACI (232.1R-00) has shown improvements in compressive strength of 0.3 and 0.4 w/cm concretes with blends of 8 and 12% metakaolin. At ages up to 45 days, each metakaolin mixture showed higher compre ssive strengths; compressive strength increased as proportion increased and w/cm decreased. Badogiannis (et al 2005) researched of 10% and 20%. Compressi ve strength was tested at ages of 1 to 180 days. They have shown that, at these ages, a 10% replacement will increase the compressive stren However, 20% replacement has shown that the compressive strength was not higher tha

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20 the control until ages of 7 days and later. In addition, the 20% replacement concrete showed lower compressive strength than the 10% blend at all ages. Kim (et al. 2007) conducted research on metakaolin bl ends of 5, 10, 15, and 20%. They have shown that there is no significant effect on the fl exural strength or splitting tensile strength for replacement levels of 5 to 15%. However, their appears to be slight decreases in strength in the 20% blends at ages less than 28 days. ACI (232.1R-00) has reported improvements in chloride penetration resistance both 0.3 and 0.4 w/cm concretes with an 8 and 12% blend of metakaolin. Furtherm they state that the 12% replacement improved the chloride penetration resistance more than reducing the w/cm from 0.4 to 0.3 in a concrete containing no metakaolin. By reducing the w/cm fro for ore, m 0.4 to 0.36, chloride permeability values for a 10% metakaolin concr l metakaolin can have a detrimental effect. Becau lcium owever, the reduced permeability of me takaolin concrete at later ages prevents continued increases in depth of carbonation. ete were reduced. Res earch conduced by Kim (et al. 2007) supports the findings by ACI, in which increasing metakaolin contents (5 to 20%), reduce chloride ion penetrability at 28, 60, and 90 days. They have also reported on the effects of increasing metakaolin contents on the depth of carbona tion. They have found that increasing metakaolin contents will increase the de pth of carbonation at age of 7, 14, 28, and 56 days. This data suggests that decreased in CH present in the concrete because of the pozzolanic reaction with the additiona se of the decreased presence, CH cannot react with carbon dioxide to form ca carbonate in the pores (Neville 1995). C onsequently, the depth of carbonation is significantly greater in the me takaolin concretes than in a concrete containing only cement. H

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21 Silica cement in concr s silicon e e ased by 5). 4R-06) has found that there is no significant delay in setting time. Howe s with Fume A by-product of producing silicon metals or ferrosilicone allo ys, silica fume is highly reactive pozzolanic material that is commonly used as a cement repla ete. Escaping gases condense to form a large quantity of highly amorphou dioxide, typically 85 to 98% by weight (ACI 234R -06). Its particle size is very small, typically 0.1 to 0.3 m with a surface area of 15 to 25 m2/g, and spherical in shap (Mindess et al 2003). Silica fume comes is four major forms: as produced, slurried, densified, and pelletized. Because of the large surface area, sili ca fume has a higher water demand which must be offset in low w/cm mixtures with a superplasticizer (Neville 1995). However, he has found that the effectivene ss of the superplasticizer is enhanced in a silica fume mixture. This is because of its spherical sh ape and small particle size which allow it to pack between cement particles and act as a lubricant (Mindess et al. 2003). Further benefit of the small silica fume particles pa cking between cement grains is the reduction in bleeding (Neville 1995). ACI (234R-06) has stated that bleeding is reduced as the content of silica fume is increased because th ere becomes very little free water availabl to bleed. Typically, air entraining admixture in a si lica fume concrete must be incre 125 to 150% than in a similar concrete with cement only (ACI 234R-06). This has been attributed to the high surface area of the particle (Neville 199 ACI (23 ver, they have shown that there is an increase in heat of hydration. Peak temperatures increase with higher contents of silica fume because of its interaction C3S. Silica fume tends to accelerate the e xothermic hydration of C3S; consequently,

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22 more CH is produced. In-tur n this action starts the pozzolanic reaction with the silica fume, which further increases the concrete temperature. However, they have also suggested that the tota l heat is somewhat decreased as the increase in s ilica fume dosa The effect of silica fume on the hardened properties is directly a function of th pore structure, cement paste-aggregate tran sition zone, and chemi cal composition (ACI 234R-06). As hydration continues, the por e structure becomes more homogenous and capillary pores sizes are re duced and become disconnected (Neville 1995). However, ACI (234R ge. e -06) has found that total porosity is largely unaffected by silica fume at all w/cm facial e t s of a fresh concr er ere is Mindess (et al.2003) has found that the cement paste-aggregate zone, or inter transition zone (ITZ), is composed of le ss C-S-H, has a higher localized w/cm and permeability, and contains large crystals of CH and ettringite. They have stated that silica fume greatly improves the ITZ by elimin ating large pores and making the structur more homogeneous, eliminating the growth of CH or transforming the already presen CH to C-S-H by pozzolanic reaction, and alte ring the rheological propertie ete by reducing internal bleed because the small size of the silica fume particles allow it to pack between cement particles and aggregate. ACI (234R-06) has found that concretes made with silica fume exhibit high compressive strengths at earlier ages, up to 28 days. They ha ve also found that th minimal contribution to compressive strength after 28 days. Neville (1995) has found that the behavior of silica fume beyond the age of 3 m onths depends on the moisture conditions. In wet cured condi tions, he supports ACI in whic h the silica fume concrete showed only a small increase in compressive strength for up to 3.5 years of age.

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23 Conversely, under dry conditions a retrogressi on of strength, typically 12% below the peak at 3 months, was observed. These findings indicate the tenden cies of a silica fume concr at of a cement only concr aste, but ACI r of 0% sion coefficient by a factor of seven. ete to self-desiccate. Therefore, adequa te curing is essential for a full development of strength. The trends of the development of compre ssive strength to flexural and splitting tensile strength of a concrete made with si lica fume is similar to th ete (ACI 234R-06). In other words, as compressive strength increases, the tensile strength also increases, but a decreasing ratio. They have found that a 20% silica fume had a compressive to flexural strength ra tio that ranged from 0.13 to 0.15. They have also found splitting tensile strength at vari ous ages to range from 5.8 to 8.2% of the compressive strength. As mentioned before, the use of silica fu me results in a refinement of the pore structure. Consequently, silica fume reduces the permeability of not only the p also the ITZ (Neville 1995). He found that a 5% replacement of silica fume resulted in a reduction of the coefficient of permeability by 3 orders of magnitude. Conversely, (234R-06) has found that a 5 to 12% silica fume replacement resulted in only a 1 orde magnitude reduction in permeability, in which no statement of w/cm was reported. However, they have also found that for a 0.20 w/cm concretes containing 10 and 2 silica fume, showed coefficient of permeability of 3*10-13 and 0.3*10-13, respectively. The control showed a hi gher permeability at 12*10-13. A consequence of reduced permeability is the greater resistance to chloride penetration (Neville 1995). ACI (234R-06) ha s found that an 8% substitution in a 0.40 w/cm concrete resulted in a reduction in diffu

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24 Furthermore, addition rates above 8% result ed in little additional improvement to resist in ance of chloride penetration. Redu ced permeability is the primary mechanism in which silica fume increases the resistance to sulfate attack by sodium sulfate (ACI 234R 06). However, an additional increase in sulfate resistance occurs from the pozzolanic reactions with silica fume as there is a larg e consumption of CH, the major component sulfoaluminate corrosion (Mindess et al 2003).

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CHAPTER 3 MIX DESIGN This chapter discusses the materials and proportions used in the concrete mixtures that were evaluated in this i nvestigation. Preparation of th e concrete mixtures, specimen fabrication, and curing cond itions are also described. Materials The materials used in the concrete mixtures are described in th e following sections. Admixtures, and Chemical Admixtures. aggregate in all concrete mixtu r d These constituents can be divided into thr ee categories: Basic Ingredients, Mineral Basic Ingredients There exist a few materials th at can be found within all of the concrete mixtures in this investigation. These ingr edients are water, fine aggr egate, coarse aggregate and cement. Water The water used in the concrete mixtures was obtained from the local city water supply. Fine Aggregate Silica sand from pit number 11-067 was used as fine res. The sand from this pit was test ed and passed the gradation requirements of Section 902 of the 2004 Florida Department of Transportation Standard Specification fo Road and Bridge Construction (FDOT Spec.). Additional testing of the sand determine a fineness modulus of 2.39 and a bulk specific gravity of 2.65, which were used in the mixture design to calculate yield. Specific te st results on the fine aggregate are provided in Appendix A. 25

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26 This sand was placed into cloth bags a nd dried in the oven until all moisture was removed. Prior to integration in the concrete mixtures, the sand was allowed to cool to the ambient temperature. Coarse Aggregate all gate was used in its approximate saturated surface dry (SSD) condi th each ed s. f the mineral admixtures and set retard Crushed limestone from pit number MX-411was used as the coarse aggregate in concrete mixtures. The aggregate from this pit was tested and passed the gradation requirement of Section 901 in the FDOT Spec. for a -in. maximum diam eter aggregate Additional testing of the limestone determ ined a bulk specific gravity of 3.61, which were used in the mixture design to calculate yield and adjust for moisture content. Specific test results on the fine aggr egate are provided in Appendix A. The coarse aggre tion. This SSD condition was obtained by filling woven polypropylene bags wi coarse aggregate. The bags were then subm erged in water for a minimum of 48 hours to fully saturate the aggregate. One day prio r to mixing, the coarse aggregate bags were removed from the water and allowed to drain for approximately one hour. Cement Type II portland cement manufactured by Holcim in the Theodore plant was used in mixture. This cement complied with Secti on 921 of the 2004 FDOT Spec. Tests show that the cement had an initial set time of 140 minutes, and a final set time of 215 minute This information is useful when determining the effects o ing chemical admixture on a mixture. Additional test results are provided in Appendix A.

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27 Mineral Admixtures Evaluating highly reactive mineral admixtures wa s an integral part of this researc The following sections describe the individual admixtures us ed along with its source and role in the modification of fresh and hardened concrete properties. General informatio was obtained from Mindess (et al. 2003). Fly ash h. n Fly ash is the waste product from the bur ning of pulverized coal in boiler furnaces used to generate electricit y at power stations. It is commonly used as a cement replacement in concrete. In addition to the obvious environmenta l advantages, use of concrete containing fly ash is advantageous because of the cost, particle size and shape and mineral composition. The cost of fly ash is typically slightly le ss than half that of portland cement. The spherical shape of fl y ash particles increases workability, which allows a lower water to cementious material (w/cm) ratio to be used. In addition, the small particle size increases the packing de nsity of the cementitious system. Thus, the permeability through interconnected voids is reduced, further improving durability. The mineral composition is also advantageous because of the high volume of reactive silica. This silica allows for a pozzolanic reacti on to consume calcium hydroxide (CH) and creates more calcium aluminate silicate hydrat es (C-S-H), which forms a denser paste structure. A class F fly ash meeting the requir ements of ASTM C 618, AASHTO M-321, and AASHTO M-295 was used in this investigation and was obtained from the Big Bend Power Station in Tampa, Florida. The fly ash also complied with Section 929-2 of the 2004 FDOT Spec. This class F fly ash sati sfies the requirements of ASTM C-618 and AASHTO M-295. Specific tests results are provided in Appendix A.

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28 Slag Blast furnace slag is the residue wastes formed from the production or refinement of iron. Slag is removed from the molten meta l and rapidly cooled. The raw slag is then dried and ground to a specific fineness so that it can be used as a cement replacement. Slag is advantageous for its chemical composition; it is rich in lime, silica, and alumina. Because of the high lime content, slag is a hydraulic admixture, meaning it will react with water to form a cementitious compound. This compound adds to the strength of the mix, while also increasing durabil ity by decreasing the interconne ctivity of the voids. In addition, the high silica and alumina conten t promote pozzolanic reactions. The CH produced from eactive compound was silica or alumina. These new ore homogenous than that produced by cement hydration alone. MCEM, produced by Civil and Marine (Holdings) Ltd., is a Grade 100 ground study. The slag complied with Section 929-5 of the 20 sults ly rease react ivity by increasing surface area resulting in higher early strengths and lower permeability than a standard fly ash mixture of the same proportions. cement hydration will be consumed and transformed into more cementitious compounds. These compounds are in the forms of C-S-H or C-A-H, depending on whether the r hydration products are denser and m CA granulated blast furnace slag used in this 04 FDOT Spec by meeting the requirement s of ASTM C 989. Specific tests re are presented in Appendix A. Ultra-fine fly ash Ultra-fine fly ash is the same material as regular fly ash. However, it has been sieved to greatly reduce the average particle si ze. The advantage of using an ultrafine f ash over a standard fly ash is because the partic le size is typically f our times smaller; the small particles inc

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29 In add ly ash used in this investigation was Micron3, a product of Boral Mater ed C-618, and AASH OT a cates. metakaolin is advantageous for use as a cement replacement because of this alone. he composition, the small partic le size of metakaolin is advantageous. ition, smaller particles have the abil ity to pack between the cement grains and aggregate creating a less permeable paste st ructure by reducing the interconnectivity of the voids. The ultra-fine f ial Technologies. The typical mean diameter of Borals Micron3, is 3.0 m. As certified by Boral Material Technologies Inc ., the distribution of pa rticle size measur by a laser particle size analyzer is as follows: Minimum of 50% of particle sizes less then 3.25 microns Minimum of 90% of particle sizes less than 8.50 microns. This class F fly ash satisfies the requ irements of AASHTO M-321, ASTM TO M-295. The ultra-fine fly ash comp lied with Section 929-2 of the 2004 FD Spec. Specific test data are presented in Appendix A. Metakaolin Metakaolin is manufacture by calcining clay at high temper atures. This results in material that is largely composed of highly reactive amorphous aluminosili Therefore chemical composition. Typicall y, the reactive silica and alumin a content in metakaolin is over 85%. Through pozzolanic reactions, CH w ill react with both silica and alumina to form a cementitious hydration product. These can be in the form of C-S-H or C-A-H, depending on whether the reac tive compound is silica or alum ina. These new hydration products are denser and more homogenous th an that produced by cement hydration In addition to t

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30 With a typical particle size of 1.4 m, particle packing will occur to create a less perme um of silica, iron, and alumina oxides was 87.9%. T ion. e small size, typically 0.1 to 0.3 m, allows the silica fume particles to pack betwe y able paste structure by decreasi ng the interconnectiv ity of the voids. The metakaolin used for this study was OPTIPOZZ, manufactured by Burgess. The requirements of ASTM C 618 Class N were met with a few modifications proposed by the FDOT Spec.: The s he loss on ignition was 0.8%. The percentage of available alkalis was negligible. The strength index at 7 days was 96%. Tests on the concrete containing metaka olin included ASTM C 39, ASTM C 157, ASTM C 1012, ASTM G 109, and FM 5-516. Therefore, the metakaolin complied with Section 929-4 of the 2004 FDOT Spec. Specific test results are presented in Appendix A. Silica fume Silica fume is the byproduct of producing silic on metals or ferrosilicon alloys. It is commonly used as a cement replacement in concrete because of its size, shape, and chemical composition. The spherical shape of silica fume decreases in terparticle frict This increases workability, thus allowing a lower w/cm while maintaining the same slump. Th en cement grains. These particles will pack between cement grains, and decrease segregation and bleeding while reducing permeability by re ducing the interconnectivit of the voids. In addition to the benefits re lated the shape and size of the particles, the chemical composition of silica fume is also advantageous. The extremely high reactive

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31 silica content, typically 85-98% will allow for large volumes of CH to be converted into C-S-H D ng admixtures are composed of an aqueous solution of neutralized resin acids mixture form ing a tiny, stable bubble that is disconnected The advantages of ha ving a disconnected air void structure is becau Also, because the silica content is so high, a secondary pozzolanic reaction will occur that converts tricalcium silicate (C3S ) to a C-S-H product. These reactions will create a stronger, more homogenous paste matrix. Force 10,000 D, produced by W. R. Grace & Co., was used as the silica fume in this investigation. It is a dry, densified microsilica powder made fr om silica fume. The silica fume is densified by air floatati on in silos. The tumbling action induces progressive entanglement of part icle to form dense clusters. These clusters allow for much easier transporting and handling, in cont rast to the original form. Force 10,000 complied with Section 929-3 of the 2004 F DOT Spec by meeting the requirements of ASTM C 1240. Specific test data is presented in Appendix A. Chemical Admixtures Air entrainer Air entraini and rosin acids in which the mol ecules have ends that are hydrophilic and hydrophobic. In other words, one end of the mo lecule is attracted to water, while the other end is repelled by water. This behavior causes the molecules to attach to air bubbles within a fresh concrete from other bubbles. se it will increase the resi stance of a concrete to freezing and thawing cycles, improve the workability and cohesiveness of a fresh concrete mixture, and reduce segregation and bleeding (Mindess et al. 2003). Because Florida concretes are not exposed to freezing and thawing cycles, the a ddition of air entraining admixture in this investigation was to increase work ability and decrease segregation.

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32 The air entrainer used in this study wa s Daravair 1000, produced by W. R. Grac Co. This admixture complied with Secti on 924 of the 2004 FDOT Spec by meeting the requirements of AASHTO M 154. e & Wate e by slowing down the rate of early d in this investigation ach mixture. By ixture used gation. WRDA 60 complied with Section 924 of the 2004 FDOT Spec by meeti Consequently, the strength and dur ability of a mixture is improved. r reducer/retarder Set retarding admixtures are typically composed of a polymer based aqueous solution of lignosulfonate, amine, and compound carbohydrates. These carbohydrates extend the setting time of fresh concrete mixtur hydration of C3S and C3A. A set retarding admixture wa s use because of the large number of test speci men fabricated from e increasing the setting time, all specimens were able to be properly consolidated before mixture began to harden. WRDA 60, produced by W. R. Grace & Co., wa s the set retarding adm in this investi ng the requirements of AASHTO M 194. Superplasticizer Surface charges on particles w ithin a fresh concrete will cause flocculation. A considerable amount of water is usually tied up in these agglomera tions, leaving little available to reduce the viscosity of the pa ste. The addition of a superplasticizing admixture, which is typically composed of an aqueous solution of carboxylated polyether, will serve to break up the bonds found between particles. This releases the available water within the mixture, there by increasing workability. This increase in workability then allows for a decrease in water to cementitious material ratio.

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33 The superplasticizer used in this st udy was ADVA 140, a product of W. R. & Co. It complied with Section 924 of the 2004 FDOT Spec. by meeting th Grace e requir mix proportions and othe r mix design parameter for bridges in ign Guidelines (July 2005) ent classification is a function of ressive environment and a more ing. he y ements of AASHTO M 194. Proportions Selection of the Florida is based on the local environment. The Structures Des defines three exposure conditions: Slightly Aggressive Moderately Aggressive Extremely Aggressive. For substructure elements, such as piling, th e environm the chloride content or pH level of the surrounding soil or water. Higher chloride content, lower pH, or both will result in a more agg restrictive rat If prestressed concrete piles are used in an extremely aggressive environment that is due to elevated chlorides in a marine environm ent, then silica fume must be used in t concrete mixture. The object of this rese arch was to evaluate the use of other highly reactive mineral admixtures on the fresh and hardened properties of concrete. These admixtures included slag, ultrafine fly ash, metakaolin, and fly ash. Prestressed concrete piling must use Class V (Special) or Class VI concrete for an environment. Class V (Special) is the mix design typically specified and has the following characteristics: Maximum water to cement ratio of 0.35

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34 Minimum total cementitious material content of a 752 lb/yd3 Air content range of 1 to 5% Target slump of 3 inches, which may be in creased to 7 inches when a water reducin admixture is used. g When ssive come fillers. this range caused no significant improvement in durability. he FDOT Spec. adopted this ra nge and now requires the use of fly ash in mode ed on % bility the piles are in a modera tely or extremely aggressive environment, the use of fly ash, slag, or both is required. Fly ash cement replacement rate is 18% to 22%, while slag is 25% to 70% for moderately aggressive and 50% to 70% for extremely aggre environments. Larsen and Armaghani (1987) found that the most effective addition rate of fly ash was between 18% and 22%. They found the rate in excess of this range caused the additional mineral admixture to stop react ing and essentially be Furthermore, rates below Consequently, t rately aggressive environments. The dosage rates in the current FDOT Sp ec for slag and metakaolin are bas the manufacturers recommendations. The suggested addition rate for slag is 25% to 70 by weight for moderately aggressive envi ronments, while metakaolin is 8 to 12% (Personal Communication with Mike Bergin 2005). At addition rates below the minimum, there were not significant improvements to mechanical properties and durability. Addition rates above the maxi mum will not react and become expensive fillers. The effect of Silica fume replacement rate s on modulus of rupture and permea were investigated by Tia (et al. 1990). They found that the most effective replacement

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35 rate w ot show any improvement in test data. pec. has adopted this range for silica fume replacement levels. OT als were weight. Theref ore, the proportion of fly ash used in every mixtu ineral admixtures, three mixtures t proportions of each admixture were designed. For example, three mixtu that d ining the placement rates for as in the range of 7% to 9% by we ight. Replacement rates below the minimum did not significantly improve the permeability and had little affect on the modulus of rupture while rates above the maximum did n Consequently, the FDOT S Although the ultrafine fly ash addition rates are not provided in the current FD Spec., the manufacturer has suggested that the range should be from 10% to 14% (Personal Communication w ith Charles Ishee 2005). Two control mixtures were designed. The first control mixture contained only Portland cement as the binder; no mineral admi xtures or other cementious materi used. A second control mixture was designed to contain Portland cement and fly ash at an addition rate of 18% by re was selected to be 18%. The FDOT Spec. minimum was selected because fly ash would be used in conjunction with other mineral admixtures. To thoroughly investigate th e effects of the m containing differen res containing metakaolin at proporti ons of 8%, 10%, and 12% were designed. These percentages were selected based on the metakaolin guidelines in the FDOT Spec The minimum and maximum proportions were se lected. In addition, a percentage was midway between the maximum and mini mum was selected to provide a broa distribution of data. The ultrafine fly ash mi xtures were also designed in this manner; proportions of 10%, 12%, and 14% were selected. Because the range of silica fume replacement rates in the FDOT Spec was narrow (7 to 9%), only mixtures conta minimum and maximum proportions were designed. The rang e of re

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36 slag i uld be too ause the proportion of cement would be too low. Neville (1995) found that for the highe m strength, the cement to ceme were used. The cementitious material proportions for in Table 3 1 and Table 3 2 ementitious Materials a) CTRL1 CTRL2 SLAG1SLAG2 SLAG3 n an extremely aggressive environment is 25 to 70% by weight. Because slag was being used in conjunction with fly ash, the maximum slag replacement rate wo high to create a durable concrete bec st medium ter ntitious material should be about 1:1. Therefore, smaller proportions of slag replacement in combination with 18% fly ash were selected to be investigated; slag proportions of 25%, 30%, and 35% all mixtures are presented Table 3 1 Proportions of C Cement 100% 82% 57% 52% 47% Fly Ash (FA) --18% 18% 18% 18% Slag ----25% 30% 35% Metakaolin ----------Ultrafine (FA) ----------Silica Fume ----------tions of Cementitious Materials b) META1 META2META3UFA1 UFA2 UFA3 SF1 SF2 Table 3 2 Propor Ceme nt 74% 72% 70% 72% 70% 68% 75% 73% Fly Ash (FA) 18% 18% 18% 18% 18% 18% 18% 18% Slag ----------------Metakaolin 8% 10% 12% ----------Ultrafine (FA) ------10% 12% 14% ----Silica Fume ------------7% 9% tracted from per in ACI 211.1-91. Th e fine aggregate content was determined rom the total aggreg ate volume. These The volume occupied by the cementious materials, water, and air was sub the total concrete volume to determin e the required aggregate volume. Proportions of coarse aggregate were selected from Table 6.3.6 (Volume of Coarse Aggregate Unit Volume of Concrete) by subtracting this coarse aggregate volume f

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37 proportions of fine and coar se aggregate were determined to be 35% and 65%, re designs are shown in Table 3 3 and Table 3 4 Table 3 3 Mix Designs a) (lb/yd ) L1 CTRL2 SLAG1SLAG2SLAG3 respectively. The resulting mixtu 3Material CTR Cement 752 617 429 391 354 Fly Ash 0 135 135 135 135 Slag 0 0 188 226 263 Micron3 0 0 0 0 0 Metakaolin 0 0 0 0 0 Silica Fume 0 0 0 0 0 Water 263 263 263 263 263 Fine Agg. 1055 1042 1035 1034 1032 Coarse Agg. 1078 1743 1736 1734 1734 Air Entrainer 3 oz. 3 oz. 3 oz. 3 oz. 4 oz Water Reducer 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. Superplasticizer 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. Additional 0 oz. 0 oz. 0 oz. 0 oz. 7 oz. Total 68 oz. 68 oz. 68 oz. 68 oz. 75 oz. Table 3 4 Mix Designs b) (lb/yd3) Material META1 META2 META3 UFA1 UFA2 UFA3 SF1 SF2 Cement 557 542 527 542 527 512 564 549 Fly Ash 135 135 135 135 135 135 135 135 Slag 0 0 0 0 0 0 0 0 Micron 0 0 0 75 90 105 0 0 3 Metakaolin 60 75 90 0 0 0 0 0 Silica Fume 0 0 0 0 0 0 53 68 Water 263 263 263 263 263 263 263 263 Fine Agg. 1030 1027 1024 1037 1037 1035 1032 1029 Coarse Agg. 1731 1728 1726 1739 1737 1737 1734 1731 Air Entrainer 5 oz 6 oz 6 oz 6 oz 7 oz 8 oz 8 oz 8 oz Water Reducer 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. Superplasticizer 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. Additional 20 oz. 30 oz. 41 oz. 0 oz. 0 oz. 0 oz. 0 oz. 0 oz. Total 88 oz. 98 oz. 109 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. Several chemical admixtures were used to control the fresh properties of the concrete, including air entraining, set re tarding, and high-range water reducer.

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38 Recommended addition rates for air entraining admixtures are not typically provided by the manufacturer because many factors affect the process of air entraining a concrete mixture. These factors included cement a nd mineral admixture, coarse and f aggregate, mixer type, mixing time, and vibr ation. Therefore, la boratory experience was ine used d dosage rate of 2.5 to 6 oz. per 100 lb of tly, slump was adjus he oo to determine the addition rate, whic h was 0.4 oz. per 100 lb of cementitious materials. The set retarder, WRDA 60, had a recomme nde cementitious materials. In this inve stigation, 2.5 oz. was used for each mixture. The lower end of the range was used because only a short delay in setting time was needed to ensure that all specimens could be fabricated before the mixture stiffened. To ensure consistency among the various mixes, the water content was held constant. It was deemed important, however, that the slump also remain consistent to ensure that the specimens were consolid ated similarly. Consequen ted with a high-range water reducer, rather than with additional mixing water. T manufacturers recommended dosage rate fo r the superplastici zer, ADVA 140, is 6 to 20 oz. per 100 lb of cementitious materials. Because each mineral admixture affects the mixture differently, the quantity of superplasticizer needed to get the desired slump was different for each mixture. An initial es timation of 9 oz per 100 lb of cementitious materials was used for each mixture. Sl ump readings were taken immediately after mixing was completed. If the slump was below the target range, additional superplasticizer was added at the lab managers discretion. Addition rates that were t large would cause segregation resulting in loss of strength and durability. This would be evident by large percentages of bleeding. Howe ver, the small variations in quantity of

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39 superplasticizer in each mixt ure of this investigation do not affect the durability or strength, but rather ensure consis tent consolidation among specimens. Preparation of Concrete Mixtures In preparation for mixing, the coarse a ggregate was placed in woven polypropylene bags which were submerged in water for a minimum of 48 hours to fully saturate the aggregate. One day prior to mixing, the coar se aggregate bags were removed from the water and allowed to drain for approximatel y one hour. The coarse aggregate was then batched and sealed for casting on the following day. This was done to keep the coarse aggregate in a saturated surface dry conditi on soouldt the requiremixture by absorbing or releasing water during m content was measured on representative sa mples taken from the batched material. Variations from saturated surface dr adjustduring m. The fine aggregate was placed in cotton sand bags. The bags were then dried in an oven to remove any in-situ moisture. One day prior to casting, batch quantities were weighed and sealed in plastic 5-gallon buckets. ixtures and cement were co llected from their receptacle one day prior to casting. The mials were wei ghed and sealed in plastic 5-gallon buckets. All thirteen concrete mixtures were produ ced in the two cubic feet rotary drum mixer shown in Figure 3 1 A buttexture, which is a small e replica o concrete mixture that contains no coarse aggregate, was used prior to mixing. This butter ace of the c oncrete mixer. This es int a te ve tsiste conix that it w not affec water ents of a m ixing. Moisture y were ed for ixing All mineral adm ater then r mi scal f a mixture was used to completely cover the in terior surf lim its chang paste con ent due to dhe rence to the in rior mixing surfaces; butter mixtures impro he con ncy of crete m tures.

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40 Figure 3 1 Rotary Drum Mixer cedure for mixing complied ASTM Initiae coarse fine aggregates were placed in the mixer wi th approximately half of the water and air entraining admixture. These constituents were then mixed for two minutes. Next, the cem ixtures, set retarding and superplasticizer admixtures, and remang water were added to the mixer and mixed for three minutes. The mixture was then allowed to rest for three minutes. A slump st was thennducted toaluate the mixture. If the slump was not within th e desired range, additional superplasticizing chemical admixture was integrated into the fresh concrete and mixed for an additional three m The pro with C 192 lly, th and ent, mineral adm ini te co ev inutes.

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41 Specimbricati various concrete specimens. These included cylinders, beams, prisms, and ASTM G 109 specimens. Each specimen was fabricated in accordance to the requirements of ASTM C 192. The 6-in. diameter x long cy were ccted in Other spe were placed in Spe were cated bs of ex ibration. Vibration continued until the surface of the concrete became smooth and large ce. Sp ecimen molds were then sealed to prevent evaTwenty-fou ter fa, all s wered frir molds and placed in the curing environment cal led for by the applicable test methods. Curing Conditions The curing condition of each specimen was di ctated by their respective test method. These conditions included fu ll submersion in aqueous solu tions containing aggressive agere in a controlle nvironment, wet cure in a controlled environment, and a wet cure in an elevated tempure water ception of tspecimens tested according to ASTM G 109, ASTM C 157, ASTM C 512, ASTM C 1556, and ASTM C 1012, curing procedures of ASTM C 511 were followed. This standard calls for demolding after 24 hours and placement into a curing environment that iolled at 3.0F a% humso tha wat d on the s at all sed for A G 109 wred for 2s in accce to A C 511. Upon removal from moist room, specimens were dry cured for two weeks in an environment controlled at a temperature of 73 3F and a relative humidity of 50 4%. en Fa on The desired testing schem e, discussed in chapter 4, required the fabrication of 12-in. li nders onstru 3 lifts. cimens two lifts cime ns onsolid y mean ternal v air bubbles ceased to break the surfa poration. r hours af brication pecimens e remov om the nts, dry cu d e erat bath With the ex he s contr 73.4 nd 100 idity, t free er is maintaine surface times. Specimens u STM ere cu 8 day ordan STM

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42 The epoxy barrier was then applied. Each sp ecimen was then return ed to the controlled dry nt for an additional eks. N speciere pn their exposure conditions. ASTM C 157 calls for specimens to be place in a curing environment that is maintained at 73 3F and a relative humidity of 50 4% immediately after demolding. ASTM C 512 also required that specimen be moved into a controlled dry cure after a 7-day initial cure For a portion of the specimens followed an accelera ted curing regime to simulate an older ge. This was accomplished by placing the appropriate specimens in a water bath osure When analyzing the data gathered from the testing regime, it became evident that there were errors and inconsistencies between specimens. This variability in test data prompted the recreation of specimens for seve ral test methods. The data gathered from these new specimens were used to supplem ent the existing data. Specimens were fabricated, cured, and tested identic ally to the initial mixtures. New specimens were created for the modulus of elasticity, Poi ssons ratio, splitting tensile strength, and flexural st rength tests. Errors in the testing apparatus for modulus of elasticity and Poissons ratio led to the full replacement of the existing data. The variability in the data gathered from splitti ng tension also prompted the full replacement of the existing data. Although the data from the flexural strength tests were consistent curing environme two w e ext, the mens w laced i in 100% hum idity room ASTM C 1556, a maintained at 105 5 F for 28 days. All specimens were then placed into their exp solutions. Specimens used for ASTM C 1012 had no curing period prior to testing. These specimens were demolded at 24 hours and immediately placed into an exposure solution. Additional Mixtures

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43 and showed low variability, the results were inconclusive. Additional test specimens were needed to be created to test at later ages than was originally designed to determin the long range effects on the flexural strength of the mineral admixtures. e

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CHAPTER 4 LABORATORY TESTING Evaluating the durability of concrete made with highly reactive pozzolans involved not only durability tests, but also plastic pr operties and mechanical properties. This chapter describes the test met hods used to evaluate these im portant properties. To the extent possible, standard test methods were used. However, in some cases it was necessary to deviate from standard pr ocedures or specimen configurations. Plastic Properties Tests The plastic properties tests were conduc ted to check the consistencies between bleed water, time of set, and temperature. often conducted because of its simplicity. tent procedure. From these e use of different mineral admixtures have ate ty pe and entrained air test that gives an estimate of concrete consistent workability and is lasticizer has been added to a mixture. xtures for the present research was 7 inches. Slump ixed. If the slump was less mixtures and evaluate the affects of the mine ral admixtures to the properties of the fresh concrete. The following plastic properties were measured: density, slump, air content, Density (ASTM C 138) The unit weight plastic property test is Typically, unit weight is measured as part of the air con results, yield estimation can be calculated. Th little affect on density as it is more greatly affected by aggreg (Mouli and Khelafi 2006). Slump (ASTM C 143) The slump test is a relatively simple field workability. This test is typically used to ensure a sometimes used to determine if sufficient supe rp The target slump of the design mi readings were taken immediately after the concrete was m 44

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45 than t s ction ver, ness er reducer dosages to maintain the target slump. Slag and metakaolin also decrease the slump because of th particles (Bai et al 2003). Air C t only air, rendering the chemical admixtu wever, the carbon levels of the miner he target, high range wa ter reducing admixture was added and slump was retested until the target slump was achieved. Because the recommended manufactures dosage were not exceeded, it is expected that th e physical characteristics of the hardened concrete remained unaffected. Because of the spherical shap e of the particles, fly ash reduces interparticle fri and increase slump (Neville 1995). Silica fume and ultrafine fly ash particles, howe because of their small size, have high surf ace areas and tend to increase the cohesive of the mixture (Mindess 2003). This results in a decrease in slump and a need for great high range water eir angular and plate like ontent (ASTM C 173) This test measures, by the volumetric method, the air contained in the mortar fraction of the concrete, without being affected by air contai ned within aggregate pores. This test method is unable to distinguish betw een entrapped and entrained air, as i measures total air content. However, it does provide the means of evaluating the effects of an air entraining admixture when a mixtur e is properly consolidated to remove all entrapped air. The addition of mineral admixtures will alter the effect of air entraining admixtures. High carbon content of some mineral admixtures will adsorb the entrained re less effective. Ho al admixture used in this investigati on are low enough so that air entrainment will be unaffected. The high surface areas also a lter the effectiveness of the air entraining admixture by requiring a larger dosage of air entrainer to reach the same air content

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46 (Nevi between bleeding and air content. Bleed to bility in a thus reducing bleeding segregation. Bleeding is also reduced by the use of mineral adm ume, ultrafine fly ash, and metak shown, however, that slag may increase bl eeding (Wainwright and Rey 2000). lle 1995). Therefore, if the same dos age of air entrainer was used for mixtures containing mineral admixtures as was with the control, the air content will be lower. Air entraining admixture was implemented to decrease the bleeding, as well as increase the workability and cohesiveness of the concrete mixtures. The measurements of air content were used to establish a co rrelation ing of Concrete (ASTM C 232) This test measures the percentage of bleed ing of a fresh concrete mixture. A metal beaker is filled with concre te and then consolidated. Af ter troweling the surface level, the bleed water is collected and measured. Bleeding is a form of segregation in whic h there is an upward movement of water after the concrete has been consolidated. Th is causes the upper layer of the concrete have a high water-to-cement ratio resulting in increased porosity and lower dura the cover concrete. Strength will also be reduced when large water pockets, caused by the upward movement of water during exce ssive bleeding, form under aggregate or reinforcing bars. Yet another ad verse affect of bleeding is la itance. This occurs when film of fine particle s are carried to the surface by the bl eed water. If the concrete is poured in lifts, this surface f ilm will create a poor bond to the next lift. (Mindess et al., 2003) Bleeding is reduced by using an air entr aining admixture. The entrained air increases the cohesiveness of the particles, ixtures. Silica f aolin have small particles that allo w it to pack between cement grains, thus reducing the porosity; consequently, bleeding is reduced (Neville 1995). Research has

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47 Time of Setting (ASTM C 403) The initial and final setting times of a fr eshly mixed concrete were determine measuring the stress needed to penetrate th e surface of a concret d by e. A stress of 500 lb/in2 and 4 setting lengthen the setting time (Brooks et al. 2000). Fly ash retards the early hydration of C3S (ACI 232.2R-03). Mixtures containing over 25% slag will see delays in setting time (ACI 233R-03). Conversely, metakaolin mixtures have shown increases in setting (Zongjin and Ding 2003). ACI (234R-06) have suggested that silica fume does not affect the setting times. Temperature (ASTM C 1064) Temperature measurements were taken immediately from fresh concrete, and completed within 5 minutes after obtaini ng the sample. The temperature of fresh concrete mixes becomes a critical factor when placing in hot or cold environments. In hot weather concreting, problems can occur wh en concrete temperatures become too high. High temperatures can cause plastic sh rinkage cracking, loss of workability and decreased setting times. In cold weather concreting, problems can arise if the fresh concrete temperatures becomes low enough to freeze early in its life. Therefore, a 000 lb/in2 determined the initial a nd final setting, respectively. Excessively long or short set times i ndicate possible problems with cement manufacturing, adverse chemical admixture r eactions, or excess gypsum. Specific time patterns can indicate which problem may be the cause. Time of setting is also an important measurement to predict maximum mixing and transit times and to gauge the effectiveness of set-controlling admixtures. The use of mineral admixtures affect th e setting times of concrete mixture. Research has shown that all mineral admixtur es used in this inve stigation

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48 measurement of fresh concrete temper ide an estimate on how it will perform in extreme temperature environments. Generally, low reactivity mineral admixtures as small cement replacements will result in lower mixture temperatures. Conversely, high reactivity admixtures will increase the fresh concrete temperature. Rese arch has shown that the incorporation of the low reactivity slag mineral admixture will result in a lower heat of hydration (Sioulas and Sanjayan 2000). On the other hand, Metakaolin additions ha ve been shown to increase the fresh concrete tem silica fume retarded the initial hydrat ion, resulting in lower temperatures. Mechanical Tests of the concrete. These characteristics are fre quently used in struct ural design to estimate the results of these mechanical tests, su ch as deflection and prestressing losses. The addition of mineral admixtures has a significant affect on the compressive strength of concrete. The early strength will be reduced if a low reactivity admixture, However, research by Jones (et al 2006) has sh own that there is still a reduction in early Conversely, early age strengths are typically higher than the control for high reactivity ature can prov perature (Frias et al 2000). Research has shown that, separately, fly and silica fume will also reduce the temperature of a fresh concrete mixture (Langan et al 2002). However, this research has also shown that the combination of fly ash and Standard test methods were conducted to determine the mechanical characteristics a variety of other concrete properties. Physi cal behavior also can be predicted based on Compressive Strength (ASTM C 39) such as fly ash and slag, are used in a mixture (ACI 232.2R-03 and ACI 233R-03). The increased fineness of ultrafine fly ash make s it more reactive than ordinary fly ash. strength development of ultr afine fly ash mixtures when compared to the control.

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49 pozzolans such as metakaolin and silica fume (Qian 2001 and ACI 234R-06). Late age strengths of concretes containing these mineral admixtures will be higher than the control. This is attributed to the stronge r, more homogenous paste matrix created pozzolanic reactions. by the The compressive strength of three 6 inch diameter x 12 inch long cylinder were tested at ages of 3, 7, 28, 91, and 365 days. In lieu of capping, the ends of each cylinder were ground smooth using a DIAM-end Gr inder manufactured by M&L Testing Equipment as shown in Figure 4 1 Figure 4 1 DIAM-end Grinder

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50 All cylinders were cured in a moist condition at a temperature of 73.4 3.0oF, s that free water was maintained on the surface at all times. Each test was completed o within in an hour of removal from the curing room on a Test Mark load frame as shown Figure 4 2 Cylinders were loaded continuously and without shock at 20 to 50 pounds per square inch per second. Figure 4 2 Test Mark Load Frame Because cracking is initiated in the tensil e region of the beam, the behavior of a concrete beam during a beam tests is governed by the tensile strength. Since the tensile strength of a concrete is largely a function of the aggr egate to paste bond, flexural strength is sensitive to the strength and si ze of the interfacial transition zone (ITZ). Mineral admixtures consume Calcium Hydroxi de (CH) and reduce ettringite formation,

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51 creating a stronger concrete ITZ. Therefore, the use of mineral admixtures will typically impro ures, silica fume and metak CI rdinary fly ash mixtures. At later ages, the miner the d re ously and without shock at a rate of 125 to 175 pounds per square inch per as shown in Figure 4 3 and Figure 4 4 ve the flexural strength of a concrete over time. Early strength development is reduced in the admixture with low reactivit y, such as fly ash and slag (ACI 232.2R-03 and ACI 233R-03). Conversely, the higher reacti vity mineral admixt aolin, will have higher modulus of rupt ure when compared to the control (A 334R-06 and Kim et al 2007). Research relate d to the effect of ultrafine fly ash on flexural strength seems to be unavailable. However, it is expected that because the surface area is increased, the ultrafine fly as h mixtures will show a larger flexural strength at early ages when compared to the o al admixtures will provide an increase in flexural strength when compared to control mixtures because of the improvement in the ITZ. Specimens were cast into 4 inch wide x 4 inch high x 14 inch long beams an tested at two ages day and 28 day. All b eams were cured in a moist condition at a temperature of 73.4 3.0oF, so that free water was maintained on the surface at all times. Each test was completed within an hour of removal from the curing room. Beams we loaded continu minute on an Instron load frame

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52 Figure 4 3 Diagram of the Third-Poin t Loading Flexure Testing Apparatus Figure 4 4 Instron Load Fram e Testing Flexural Strength

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53 Static Modulus of Elasticity and Poissons Ratio (ASTM C 469) Research has shown (Nassif et al. 2004) that the addition of mineral admix will increase the modulus of elasticity of the concrete at late ages. However, for high volume replacement of la tures ow rective mineral admi xtures such as fly ash and slag, early age m ineral arch that had been conducted shows no e addition of mineral admixtures. (Mirza et ke a definitive prediction of the affects variation to ASTM C 469. The Standard ate strength. However, slight s will exist in concrete at zero load due ent paste and the l expansion, as well as different responses to ate, little additional cracking increase at stresses above 30 to 40% of 2003) Therefore each specimen was only load ocedure was conducted in accordance to nd testing apparatus used to odulus of elasticity may be reduced. The amount of decrease will depend on the type and quantity of admixture implemented. Very little research has been conducted to find the relationship of various m admixtures to Poissons ratio. The rese discernable change in Poissons ratio with th al 2002) However, this data is not sufficient to ma of mineral admixtures. The procedure was performed in slight calls for the specimen to be loaded to 40% of its ultim damage may be induced at this level. Bond crack to differences in the elastic moduli be tween the hardened cem aggregates, different coefficien ts of therma moisture content. For stress levels up to 30% of the ultim will be observed. Bond microcracking begins to the compressive strength. (Mindess et al., to 25% of its ultimate strength. The rest of the pr the Standard. Figure 4 5 shows the instrumentation a measure the Modulus of Elasticity and Poissons Ratio.

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54 Figure 4 5 Modulus of Elasticity and Po issons Ratio Test S system Because of the low stress levels used to same 6 inch diameter x 12 inch long cylinders compressive strength tests. An initial te first cylinder from each set of three. Each of the two rem three times to measure the MOE. The initia l load gages, was ignored. The two subsequent loadin modulus of elasticity for that cy linder. An average was then two cylinders. Testing was conducted at 3, 7, 28, 91, and 365 day ages. etup on the TEST MARK test for Modulus of Elasticity (MOE), the that were used for MO E could be used for st of compressive strength was conducted on the a ining cylinders were loaded which was primarily for seating the gs were then used to calculate an average taken of the results from the ined when testing for MOE. The results from the secon s t Poissons Ratio was also obta d and third loading were averaged for each cylinder. The data from both cylinder were used to calculate an average Poissons ratio for each mix. Testing was conducted a 3, 7, 28, 91, and 365 day ages.

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55 Splitting Tensile Strength (ASTM C 496) ASTM has yet to adopt a standard test method to provide a direct measuremen tensile strength. This is because the probl ems with secondary stresses from gripping make it is very difficult to get consistent and reproducible results. However, a standard test, ASTM C 496, has been created to estimat e tensile strength through indirect tensio Because the failure of concrete in tension is governed by microcracking, the I will control the tensile strengt h of a concrete. (Mindess et al., 2003) The use of min admixtures will result in consumption of CH and reduction of ettringite formation, creating a stronger ITZ. As with flexural strength tests, the use of mineral admixtures in concrete used for splitting tensile strength tests will improve the tensile strength of a concrete as the pozzolani c reactions take place. t of n. TZ eral 28, Specimens cast into 4 inch diameter x 8 inch long cylinders we re tested at 3, 7 91, and 365 days of age. All cylinders were cured in a moist condition at a temperature of 73.4 3.0oF, so that free water was maintained on the surface at all times. Each test was completed within an hour of removal fr om the curing room on a Forney Load frame as shown in Figure 4 6 Figure 4 6 Splitting Tensile Streng th Test on Forney Load Frame

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56 Durability Tests The deterioration of concrete is the re sult of poor performanc components: reinforcement, paste, and aggreg ate. This can be the result of chemical or physical causes. The durability te sts performed in this investigation involve the assessment of each concrete mixs physical characteristics and respon attack. The use of mineral admixtures will a lter the concrete paste and pa e of the three major either se to chemical ste structure by e, and ined capillary pore structur eall of which result in an improvement to durability. ic expansion or cont raction of concrete the dominant factor in ction in capillary porosity, decreasing the porosity in a xtures exhibit a re duction in total linear ted that slag will reduce onducted by Akkaya (et al. 2007) has shown ease in total shrinkage compared to the also has little effect on total shrinkage. fly ash has no significant affect on linear CI 364R-06 and ACI 323.2R-03). Research on e unavailable. Linear shrinkage specimens were cast into 3 inch wide x 3 inch high x 11.25 inch long prism molds. Immediately after removal from the molds, the specimens were dry creating a stronger, more homogenous paste matrix, less permeable void spac ref Linear Shrinkage (ASTM C 157) The linear shrinkage test assesses volumetr due. Moisture loss through th e concrete pore structure is shrinkage (Mindess et al. 2003). Because of the typical redu the use of mineral admixtures will reduce linear shrinkage by concrete. Research has shown that metakaolin mi shrinkage (Brooks and Megat Johari 2001). ACI has sugges linear shrinkage (ACI 363R-03). Research c that fly ash and ultrafine fly ash show little decr control. ACI (364R-06) states that silica fume ACI also states that silica fume and shrinkage at small replacements levels (A the effects of ultrafine fly ash on linear shri nkage seems to b

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57 cured by placing them an environment controll ed at a constant temperature of 73 3 F and a 16, 32, and 64 weeks. Volum ed xtures will reduce the volume of voids through an increase denser hydra y 03; 234R-06) suggests that fly ash, slag, and silica fume increase a concretes resistance to sulfate attack. Research has shown that metakaolin also improves the resi stance to sulfate attack (Khatib and Wild constant relative humidity of 50 4% Due to mechanical problems with the environmental control system, temperature a nd relative humidity were slightly varied from that specified in ASTM C 157. The actual temperature and relative humidity readings are presented in Appe ndix A. Comparator readings were taken on all specimens at an age of 4, 7, 14, and 28 days, and after 8, e of Voids (ASTM C 642) This method was used to measure the pe rcentage of voids within a harden concrete. If exposed to a corrosive environm ent, these voids are su sceptible to becoming filled with deleterious chemicals. A reduction in void volume is therefore beneficial to a concrete. Mineral admi tion products produced fr om the pozzolanic reactions. Samples were cut from 2 inches below th e finished surface of a molded 4 inch diameter x 8 inch long concrete sample. Tests were conducted on each mixture at 28 days of age. Sulfate Expansion (ASTM C 1012) Length change measurements permit th e relative assessment of the sulfate resistance of concrete or mo rtar subjected to total immers ion in a sulfate solution. The sulfate ions in the solution combine with gypsum and CH to create an expansive reaction. This reaction, however, can be limited by the use of mineral admixtures. There are two means that mineral admixtures inhibit sulfat e expansion: a refine ment of the capillar porosity and a reduction in CH. ACI (232.2R03; 233R

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58 1998). Little research has been conducted on sulfate attack. It is expected, however, that ultrafine f ash concretes, because the smaller part icle si Specimens for the present research were inch long and 1 inch wide x 1 inch high x 11.25 inch long m respectively. Mortar was sampled from the fr through a 3/8 inch sieve to remove the coarse into a 5% SO4 solution at 24 hours after casting, imm the relations of ultrafine fly ash with ly ash will perform better than fly ze will further reduce permeability. cast into 3 inch wide x 3 inch high x 11.25 olds for concrete and mortar, esh concrete mix; fresh concrete was passed aggregate. All specimens were immersed e diately after their removal from the maintochemicals, such as chlorides and sulf n. Conseque ntly, the absorptivity of a concrete will be reduced. molds. The water temperature of the sealed tanks containing the sulfate solution was ained at 73.5 3.5 F. Readings were taken at 1, 2, 3, 4, 8, 13, and 15 weeks of exposure. Absorption (ASTM C 642) There are four transport mechanisms th at allow the penetration of deleterious chemicals into concrete. These mechanis ms are permeability, diffusivity, evaporative transport, and absorptivity. In an unsaturated concrete, absorption wi ll play a significant role in chemical transport. Absorption is controlled, in large part by the connectivity of the capillary pore system. Solution is draw n by capillary sucti on allowing harmful ates, to enter the concrete. This test method gives a means of assessing the capillary pores struct ure by measuring the absorptivity of an unsaturated concrete. The use of mineral admixtures will refine the capillary pore structure through pozzolanic reactio

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59 Specimens for the present research were pr epared using a 4 inch diameter x 8 inch long c of Corr of ng eans of assessing a c oncretes ability to inhibi ld containing three #4 deformed steel Figure 4 7 At an age of oist condition at a aintained on the surface at all times en was placed in an idity for a period of two weeks. inches wide x 3 inches high plastic dam ylinder molds. Each cylinder was cure d in a moist condition at a temperature of 73.4 3.0oF, so that free water was maintained on the surface at all times. From each these cylinders a 2 inch thick slice was cut from 6 inches below the finished surface. This test was conducted on each mixture at 28 days of age. osion of Embedded Steel Reinforcement (ASTM G 109) Corrosion is a particularly problemat ic phenomenon in reinforced concrete structures subjected to chloride ions. Becau se it is an expansive reaction, corrosion steel reinforcement leads to the cracking and spalling of the adjacent concrete. This will then lead to a direct, unobstr ucted path for additional elem ents to corrode the underlyi steel reinforcement. This method provides th e m t the corrosion of embedded steel reinforc ement. The use of mineral admixture will delay or even prevent the corrosion of th e embedded steel reinforcement by improving the surrounding concrete. The mineral admi xtures refine capillary porosity, reduce permeability, and improve the ITZ. Each of these effects will reduce the ingress of chloride ions. Each specimen was fabricated using a mo reinforcing bars and a titanium reference electrode as shown in 24 hours, each specimen was demolded and allowed to cured in a m temperature of 73.4 3.0oF, so that free water was m until they were 28-days of age. At th is time, each specim environmental chamber maintained at 50% rela tive hum Following this conditioning, a 6 inches long x 3

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60 was installed on the top of each specimen. All sides were then sealed, with the exception of the bottom and the inside of the d Sikadur 32 High Mod epoxy. Figur amned area, using e 4 8 shows the ASTM G109 specimen after the dam and epoxy seal was constructed. Reference Electrode Figure 4 7 ASTM G109 Specimen Molds containing the Reinforcing Bars and Figure 4 8 ASTM G109 Specimen After The Epoxy Has Been Applied Samples were then placed back into the environmental chamber until they were of 56 days of age. At this time, a non-standa rd testing procedure was followed. ASTM G

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61 109 states that samples should be ponded with a 3% NaCl, and stored at 73 5.0oF and a relative humidity of 50 5%. To accelerate corrosion, a 15% NaCl solution was use with the specimens exposed to 90 5oF. The specimens were connected to automated monitored device that measured current and potential once daily at the FDOT SMO photograph of this setup can be seen in Figure 4 9 Each specimen was subjected to a cycled regime of the 15% NaCl solution; the cycles were maintained d A at two weeks of d by two week s of drying. An electrical diagram of the te sealed continuous ponding, followe st setup is presented in Figure 4 10 taining the Automa ted Monitoring Device and Figure 4 9 Environmental Room Con Corrosion Specimens Figure 4 10 Electrical Diagram of Corrosion Specimens

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62 Background Chloride Level (FM 5-516) This method is used to determine the background levels of chloride in a concrete mixtu sistivity (FM 5-578) est measures the el ectrical resistivity across the face of a concr ce ater, 91, re. The results were used in calculations to determine the absolute level of chloride intrusion for ASTM C 1556. The use of minera l admixtures has no affect on this test, as their compositions do not contain chlorides. A concrete and paste sample was taken fr om the fresh concrete and allowed to hydrate for 3 days. Next, the hydrated concrete and paste was pulverized so that samples could be taken for chloride analysis. A chemical titration was performed to find the initial chloride content of each mix. Surface Re This non-destructive t ete specimen to provide an indication of its permeability. As the surface resistan increase, the correlated permeability decreases. The use of mineral admixture will increase the surface resistivity by lowering the permeability of the concrete. All specimens were water-saturated 4 inch diameter x 8 inch long molded cylinders. These samples were cured in a moist room containing no saturated lime w as this decreases the resistivity of the c oncrete. A Surface Resistivity meter with a Wenner linear four-probe array was implemented as shown in Figure 4 11 Surface resistivity was found in accordance with FM 5-578 for concrete cylinders at 3, 7, 28 and 365 days of age.

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63 Figure 4 11 Wenner Linear Four-Probe Array and Display Rapid diameter x 8 inch long conc rete cylinders. Cylinders were cured in a moist Migration Test (NTBuild 492) This procedure was used to determine the chloride migration coefficient in concrete from non-steady-state migration ex periments. A low mi gration coefficient effectively indicates that the porosity is low enough to limit th e migration of chloride ion into a concrete. The implementation of mineral admixtures will create a denser, less permeable concrete. The paste structure will be composed of a more homogenous C-S-H matrix, smaller ITZ, and less interconnectivity of pores. Therefore, the use of mineral admixtures will reduce chloride ion penetration. Samples for this research were cut from 4 inches below the finished surface of molded 4 inch condition at a temperature of 73.4 3.0oF, so that free water was maintained on the surface at all times. Tests were conducte d at 28, 56, and 91 days of age. At the appropriate test date, specimens were rem ove from the curing room and preconditioned by desiccating for three hours. Next, while maintaining vacuum, th e desiccation chamber was filled with a saturated Ca(OH)2 and vacuumed for an additional hour. The specimens were kept in the solution for 18 2hours. Each specimen was then placed in the test setup as shown in Figure 4 12 A 30V potential was applied to the sample to

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64 measure the initial current. From that reading the voltage was adjusted to the standardized value for each specimen. Table 4 1 details the test voltage and duration corrections given in NTBuild 492. The test was then conducted for 18 hours. Figure 4 12 RMT Test Setup Table 4 1 Test Voltage and Duration for NTBuild 492 Initial Curr Applied [Volts] Test Duration [hr] Expected Penetration [mm] V*t [Vhr] ent Voltage @ 30V [mA] < 5 60 96 < 23 5,760 5-10 60 48 12-20 2,880 10-15 60 24 10-15 1,440 15-20 50 24 12-16 1,200 20-30 40 24 12-18 960 30-40 35 24 15-21 840 40-60 30 24 18-27 720 60-90 25 24 22-33 600

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65 90-120 20 24 26-35 480 120-240 15 24 26-54 360 240-400 10 24 36-77 240 400-600 10 24 36-77 240 > 600 10 6 > 19 60 Immediately following the test, each specimen was removed and split longitudinally. A silver nitrate solution was then sprayed on exposed surface to highlight the chloride penetration. Measurements to the nearest 0.1 mm were then made using a ficient was calculated from digital caliper. From these measurements th e migration coef the following equation: D nssm 0.0239273T ()L U2 ()t x d 0.0238 273T ()L x d U2 (41) /s; U is the absolute value of the anolyte solution, C; L is the th ickness of the specimen, mm; xd is the average value of ised th rough direct intrusion of lfate. Therefore the concretes ability to l factor in the performance of a durable concrete. It is for this reason that permeability becomes an important where Dnssm is the migration coefficient, x 10-12 m2applied voltage, V; T is the average value of the initial and final temperature in the the penetration depths, mm; t is the test duration, hr. Water Permeability (UF Method) A concrete structure can be severely comprom deleterious chemicals, such as chloride and su resist sulfate or chlori de ion penetration is an essentia

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66 characteristic of a concrete. The implementation of mineral admixtures will create a less and hardened structure will be altered by the pozzo to rete a moist condition at a temperature of 73.4 3.0oF, on the surface at all times. From each of these cylinde y test. Sikad imilar in permeable concrete. The concrete rheology lans. Better consolidation and less bl eeding can be achieved. This creates a concrete with less capillaries and interconnected pores. Th e mature concrete is also affected; through pozzolanic reaction, a dens er and less permeable C-S-H product is produced. In previous research (Soongswang et al ., 1989) a testing method was developed directly measure the water permeability of a concrete sample. Permeability specimens were created for this method from molded 4 in ch diameter x 8 inch long molded conc cylinders. All cylinders were cured in so that free water was maintained rs a 2 inch thick slice was cut from 3 inches below the finished surface. Around each slice, a 2 inch wide impermeable e poxy (Sikadur 32 High-Mod ) ring was cast and allowed to cure for 24 hours. This epoxy ri ng serves to bond with the sides of the concrete so that a one-dimensional flow will be achieved during the permeabilit ur 32 High-Mod epoxy was utilized because it has a higher strength and a s coefficient of thermal expansion as the conc rete used in this investigation. The permeability testing specimens was then installed into the Plexiglas fixture as shown Figure 4 13

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67 Figure 4 13 Cross-Section of Water Permeability Specimen Fixture The specimen and fixture was then attached to the permeability testing apparatus as shown in Figure 4 14 A constant 80 pound per square inch water pressure was applied to each specimen. After steady state had b een achieved, the specimen was then removed from the apparatus. Figure 4 14 Water Permeability Test Setup

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CHAPTER 5 RESULTS AND DISCUSSION This chapter describes and discusses th e results obtained through experimental analysis. Inconsistencies in test data prompted the re-cre ation of test specimens for These changes are presented in the ts resented in Table 5 1 Each value average of individual tests, depending on the ixing and represents a single the extreme measured values. All partment of Transportations State s OfficSMO). MOE, Poissons ratio, and flexural strength tests. mechanical test section below. Plastic Properties Tes The results from the plastic properties tests are p represents either a single test result or an test method. Unit weight, for example, was taken during m test. The values differed by no more than 2% from plastic properties tests were performed at the Florida De Material e (FDOT 68

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69 Table 5 1 Plastic Properties Mi ity t3) Slu (i Air (%) Bleed Initial Set (min) Final (min) Mix Temp (oF) Air emp. (oF) x Dens (lb/f mp n) (%) Set T CTR5 5.75 2.0 0.00 300 81 75 L1 14 395 CTRL2 145 6.00 1.5 0.10 330 400 84 75 SLA4 6.50 1.1 0.19 340 81 75 G1 14 430 SLAG2 144 6.00 1.0 0.17 355 460 81 75 SLAG46 6.50 0.6 0.27 300 80 75 3 1 445 META1 144 6.25 1.4 0.00 375 435 84 75 META2 144 7.25 1.5 0.00 390 470 80 75 MET 75 A3 144 6.00 1.4 0.00 N/A N/A 80 UFA1 146 5.75 0.6 0.55 375 465 78 75 UFA2 145 6.75 1.8 0.00 385 485 78 75 UFA3 144 8.00 1.6 0.00 400 480 78 75 SF1 143 6.25 2.3 0.00 370 445 76 75 SF2 143 6.00 2.3 0.00 385 465 76 75 Density was measured and found to vary by 2% for all mixtures. This indicates that there are no large variati e among mixtures Slump measurements were between 5 .75 to 8 inches, indicating reasonably consistent results. Due to natural variability of concrete workability, a consistent concrete slump from mix to mix is difficult to obtain. For most mixtures, however, the consolidation among mixtures, thus minimi zing variation in test results due to however were within the acceptable range of 1 to 5% ex ons in entrapped air or aggr egate volum slump values were within 1 inch of the 7-in. target valu e. This allowed for consistent inconsistent specimen fabrication. Air content was found to range from 0.6% to 2.3%, which was below the target air content of 3%. The measured values cept for SLAG3 and UFA1, which had an air content of 0.6%. These lower air contents appeared to result in an increase in bleeding when comparing the results for SLAG3 and UFA1 of 0.27% and 0.55%, respectively. CTRL2, SLAG1, and SLAG2, however, also showed some bleeding, but without an extremely low air content

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70 Setting times conducted on the cement past e found that initial set was at 140 minutes and final set at 215 minutes. The c oncrete mixtures in this investigation had initial setting times that ranged from 300 to 400 minutes; final setting times ranged 395 to 485 minutes. These setting times are gr eater than that of the paste by 114% to 185% and 84% to 126% for initial and final setting times, respectively. For CTRL1, setting time from the increased by 114% for initial set and 84% for fina l set over the cement tests. This i e ETA1 articular crete temperatures ranged from 76 to 84 F, while the air temperature remained constant at 75 F. This temperature range is small; therefore, with this level of replacement, there was little a ffect on the fresh concrete temperature from the addition of the mineral admixtures. ndicates that the addition of the reta rder was successful in delaying the setting times. CTRL2 (18% fly ash) also shows extended setting times when compared to CTRL1 (cement only), revealing that the replacement of ceme nt with fly ash retards the setting times. In addition, all other mixt ures show an increase in setting times over CTRL2, indicating that the larg er quantity of mineral admi xtures further delays th setting times. The literature has suggested that metakaolin shortens the setting times, while silica fume has no affect (Zongjin a nd Ding 2003; ACI 234R-06). However, when looking at the mixtures with the same proporti ons of mineral admixtures, such as M (18% fly ash and 8% metakaolin) and SF1 ( 18% fly ash and 7% silica fume), little difference in setting times are noticed. This suggests that setting time is more greatly affected by the decreases in proportions of ceme nt, rather than the addition of a p admixture. Fresh con

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71 Mechanical Tests The mechanical test results for compressi Poissons ratio, and splitting tensile strength are presented below. Trends and relationships have been noted in the resu inconsistencies have been found in the results from This prompted the re-creation of duplicate test specim for testing at 7, 28, and 365 day ages and ve strength, flexural strength, MOE, lts of each test. However, errors and the MOE and Poissons ratio tests. ens. These specimens were created tested under the same conditions. st rength in the plot. In contrast, mi xtures made with silica fume and ent alone. At later ages, react and by 365 days, the es of just about 10.5 ksi. The lower result of errors in mixing that will be Compressive Strength (ASTM C 39) Figure 5 1 shows the strength gain curve for a ll the mixtures. Early compressive strength of concrete made with slower reac ting mineral admixtures, such as slag and fly ash, was less than that of the concretes made with portland cement alone, as seen in the lower values of early metakaolin exhibited a higher strength than with portland cem however, the low reactivity mi neral admixtures continued to compressive strength had converged to valu compressive strength of SLAG3 was likely the discussed subsequently.

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72 4 5 6 010020030040 7 8 9 11 0 Age (days) 10Compressive Strength (ksi) CTRL1 CTRL2 META SLAG UFA SFFigure 5 1 Compressive St rength of All Mixtures Although the strength gain curv e is not linear, it is also us eful to examine the rate of strength gain by considering the slopes of the lines between the 91 and 365 day strengths. These slopes presented in Table 5 2 show the average 365 day compressive streng for each mixture. The compressive strengths are also normalized to the CTRL1 strength to show the improvement and relative value. Disregarding SLAG3, the compssive strengths vary from CTRL2 by no more than 3%, indicating vary consistent values at late ages. The slopes of CTRL 1 and CTRL2, however, are nearly parallel, indicating that their rates of hydration are comparable ev en though CTRL2 contains fly ash. th re

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73 Table 5 2 Average Compressive Stre36, Nzedday ngCTnd 365Slo 365 ay Cress Sth (k Noized Cossiv Strength 1 tay Slope ksi* ay) ngth at RL2, a 9 5 days 91 to o 365 d ormali day 365 pe Compres d sive Stre th to rmal omp ive treng si) mpre e ( 105/d CRTL1 9.75 0.95 9.8 CTRL2 10.25 1.00 11.9 SLAG1 10.40 1.02 26.0 SLAG2 10.33 1.01 25.8 SLAG3 9.38 0.92 17.5 META1 10.17 0.99 19.1 META2 10.31 1.01 20.7 META3 10.59 1.03 28.8 UFA1 10.09 0.99 18.3 UFA2 10.09 0.98 22.3 UFA3 10.11 0.99 19.2 SF1 10.24 1.00 20.4 SF2 10.34 1.01 22.1 Furthermore, the slopes of the slag mixtures are parallel and are steeper than that the control mixtures, indicati ng a higher rate of hydration. Similarly, the metakaolin, of ultraf than n the e, in the prestressing industry, early compressive streng y tures. ine fly ash, and silica fume mixtures show steeper slopes than the control mixtures. Therefore, it is likely that these mixtures wi ll produce higher compre ssive strength the controls at later ages. However, becau se the strength gain curves are non-linear, accurate predictions of later comp ressive strengths cannot be made. At various ages, the compressive strength of a concrete plays at key role i selection of a mixture. For exampl th is needed to allow for the release of prestressed concrete member from the prestressing bed. Conversely, hi gher compressive strength at later ages is needed for piling to prevent damage during driving. Theref ore, a more refined analysis of the earl and late compressive strengths of each mixture is discussed. Figure 5 2 shows the early age strength development of the concrete mixtures containing ground granulated blast furnace slag compared to the two control mix

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74 Figur 1 of e 5 3 presents the late age strength develo pment. The control mixture, CTRL (cement only), had a higher early strength than CTRL2 (18% fly ash), which is typical low early strength developing mixtures cont aining low reactive mineral admixtures. Generally, a mixture with a sl ower initial hydration rate wi ll produce a denser calcium silicate hydrate (C-S-H ) matrix at a later age. It is th is C-S-H matrix that will have the largest contribution to a concretes compressive strength, pr oducing a higher strength later when compared to a high early strength mixture. 4 5 6 8 9 10 Age (days)Compssive Strength (ksi7 051015202530re ) CTRL1 CTRL2 SLAG1 SLAG2 SLAG3 Figure 5 2 Average Early Strength of Slag Mixtures 8.0 .5 Age (days) 8 9.0 20120220320Compressive St9.5 10.0 10.5 11.0rength (ksi) CTRL1 CTRL2 SLAG1 SLAG2 SLAG3 Figure 5 3 Average Late St rength of Slag Mixtures The data show that the average compressive strength of each slag mixture at 3 days and 7 days age is below that of the two contro l mixtures, which is a result of the further

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75 delay caused by the replacement of h slag. Generally, slag has low reacti t. have a th of both ower en tioned before, the higher mineral admixture conte e cimens increases. The data show that at 91 days of age, all slag mixtures are very close to having the same compressive strength. As mentioned before, ground granulated blast furnace slag generally has low reactivity at early ages and will begin to develop a dense C-S-H matrix as hydration continues. Therefore, the mixtures containing higher proportions of slag will exhi bit a low early strength. At later ages, however, the slag will begin to react and even tually develop a higher strength concrete in the mixtures containing higher volumes of slag. portland cement wit vity at early ages and therefore will not contribute to early strength developmen Indeed, it is not until around an age of 91 da ys when the slag mixtures begin to higher compressive strength than CTRL1. At 365 days, the compressi ve streng SLAG1 and SLAG2 show a strength well above that of CTRL1, and slightly higher than CTRL2. The data from Figure 5 2 and Figure 5 3 show that SLAG3 exhibits l strength than SLAG1 and SLAG2. As m nt in SLAG3 was expected to develop higher compressive strengths than SLAG1 and SLAG2. However, this did not happen. From Table 5 1 it is clear that SLAG3 shows a high bleed percentage when compared to other mixtures. This would suggest that there were problems with mixing. If the mixed proportions were incorrect, this may lead to a worse performing concrete than woul d be expected. Indeed, this trend of poor performance of SLAG3 is noted thro ughout subsequent test procedures. Figure 5 2 also shows that at early ages, the average compressive strength decreases as mineral admixture content is incr eased. In contrast, th is trend seems to b reversed as the age of spe

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76 Figure 5 4 shows the early age strength deve lopment of the mixtures containing metakaolin compared to the two control mixtures. Figure 5 5 presents the late age strength development. Because of its high reactivity, the metakaolin mixtures show a high early strength when compared to the control mixtures. As expected, all metakaolin mixtures have an average compressive streng th above that of CTRL2 for 3 day, 7 day and 28 day ages. The strength of the metakaolin mixtures then begin to overtake that of CTRL1 at an age of apparently 7 days. At an age of 91 days, however, CTRL2 has developed a higher strength than CTRL1 and a ll mixtures containing metakaolin. This is explained by the denser C-S-H matrix developed in slower hydration of the fly ash itself in CTRL2. By 365 days, however, the comp ressive strength of META1 and META2 are nearly equal to that of CTRL2. ME TA3 shows that highest strength. 4 6 7 8 051015202530 Age (days)pressive Strengt5 9 10Com h (ksi) CTRL1 CTRL2 META1 META2 META3 Figure 5 4 Average Early Streng th of Metakaolin Mixtures

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77 11.0) 8.0 8.5Co9.0mpressive St9.5 10.0 10.5 22 320 Age (dayth (ksi20 120 0 s)reng CTRL1 CTRL2 META 1 META 2 META 5 AvLate Streng Metakaolinures etakaolin incr eases, the data show a higher average ressive stat later agee highe r coof mineral admixture results in a larger th ultrafine fly ash have s, an e dration rate of fly ash. At 91 da 3 Mixt Figure 5 erage th of As the proportion of m comp rength s. Th ntent amount of available silicate oxide (S ) to react with calcium hydroxide (CH) to produce a denser matrix of C-S-H compounds. Figure 5 6 shows the early age strength deve lopment of the mixtures containing ultrafine fly ash compared to the two control mixtures. Figure 5 7 presents the late age strength development. The mixtures containi ng ultrafine fly ash have a similar streng development as the mixtures containing sla g. Because both slag and low reactivity, their early age strength ga in will be slow. At 3 day and 7 day age all mixtures containing ultrafine fly ash have a lower average compressive strength th both CTRL1 and CTRL2. At 28 day age, all three ultrafine fly ash mixtures have a higher strength than CTRL2, while CTRL1 remains at nearly the same strength. As th strength begins to develop, CTRL2 compressi ve strength becomes the highest. This again is due to the dense C-S-H matrix formed by the slow hy ys, CTRL2 continues to develop strengt h, while the ultrafine fly ash mixtures and CTRL1 have nearly the same compressive strength. However, by 365 days, the

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78 compressive strength of the ultrafine fly ash mixtures are only slightly lower than CTRL2. The strength of CTRL1 is still cons iderably lower than the other mixtures. 4 5 6 8 9 10Compssive Strength (ksi7 051015202530 Age (days)re ) CTRL1 CTRL2 UFA1 UFA2 UFA3 Figure 5 6 Average Early Compressive St rength of Ultrafine Fly Ash Mixtures 8.0 8.5Co9.0 9.5 10.0 10.5 11.0 20120220320 Age (days)mpressive Strength (ksi) CTRL1 CTRL2 UFA1 UFA2 UFA3 Figure 5 7 Average Late Compressive St rength of Ultrafine Fly Ash Mixtures It is apparent that the compressive strengt h increases as the dosage of ultrafine fly ash is increased. Due to the increase in S as mineral admixture is increased, a large quantity of CH is consumed. Thus, a denser matrix of C-S-H will form as proportions of ultrafine fly ash are increased. pment of the mixtures containing silica Figure 5 8 shows the early age strength deve lo fume compared to the two control mixtures. Figure 5 9 presents the late age strength development. Because of its high reactivity, the silica fume mixtures show a

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79 comparable early strength to the control mixtur es. At 3 day and 7 day tests, the strength of the silica fume is nearly the same as CT RL2 and only slightly less than CTRL1. At 2 days of age, the silica fume mixtures have gained strength and surpassed the average compressive strength of both CTRL1 and CTRL 2. At 91 days, the silica fume mixtures have continued to gain strength and re main higher than CTRL1. The compressive strength of 8 CTRL2, however, has increased co nsiderably and now is the highest. By 365 days, y both silica fume mixtures show a large increase in strength, and are now nearl equal to that of CTRL2. 4 5 6 8 9 10Compssive Strength (ksi7 051015202530re ) CTRL1 CTRL2 SF1 Age (days) SF2Figur e 5 8 Compressive Streng th of Silica Fume Mixtures 8.0 8.5 9.5 10.0 10.5 11.0 Age (days)rength (ksi)9.0 20120220320Compressive St CTRL1 CTRL2 SF1 SF2 Figure 5 9 Compressive Streng th of Silica Fume Mixtures

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80 From Figure 5 8 it is apparent that the mixture with the higher proportion of silic fume, SF2, has a higher strength at all ages when compared to SF1. This is explained the larger quantity of reactive silica, S, gained by increasi ng the proportion of the mine admixture. Again, a stronger, denser C-SH matrix is formed, thus increasing the compressive strength. Manufacturing of prestressed concrete pile s depends primarily on the early stre development of the concrete mixture. Pr estress cannot be tran fered until a minimum compressive strength is achieved. Conse quently, production is slowed and profits are reduced while the member remains in the form s. Consequently, it is likely that the manufactures would prefer a high early strength mixture. Typically, prestressed forces are transferred when the concrete has a co mpressive strength in the rang a by ral ngth e of 3,500 to ation exceeded this range. Therefore, in ineral admixtures did not portant during pile driving because the ge the piles. At levels above 30% of the develop; at about 70%, the cracks begin to hat develops will reduced the durability by providing a direct path for de leterious chemicals to enter the concrete. Therefore, a higher compressive strength will reduce the amount of damage caused by the pile driving process. Typically at around 28 days, the piles are removed from storage and driven. At this age, CTRL2 showed the lowest compressive st rength. The slag, metakaolin, and ultrafine fly ash mixtures ha d nearly the same compressive strength as 4,500 psi. At 3 days, all mixtures in this in vestig relation to early removal from prestressi ng forms, the m improve the mixture over the controls. The compressive strength also becomes im forces associated with driving damage may dama compressive strength, microcracking begins to propagate through the paste (Mindess et al. 2003). Cracking t

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81 CTRL1. The silica fume mixtures, howeve compressive strength over CTRL1. Therefore, provide the best resistance to damage caused by driving at this age. Flexural Strength (ASTM C 78) The number of flexural strength specimens cas and 28 day ages. A second mix was done so 365 days. The data presented in this secti on are the results from r, did show a slight improvement in it appears that the silica fume mixtures t in the first mix allowed testing at 7 that test could be conducted at 7, 28, and bot h the first and second set of e with the type of mineral admixture. From Figur mixtures. The early modulus of rupture (MOR) of c oncrete made with low reactivity mineral admixtures is usually less than that of por tland cement alone. The slower reaction tim results in a delay of strength gain, which varies e 5 10 the ultrafine fly ash and slag mixtures showed the lowest strength at early age. In contrast, concrete made with a highly reactive mineral admixture will gain strength faster, as seen with the metakaolin and silica fume mixtures. At 365 days, the silica fume and slag mixtures showed the highest MOR.

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82 1300 700 800 900 1000 1100 1200 0100200300400 Age (days)Modulus of Rupture (psi) CTRL1 CTRL2 SLAG META UFA SF Figure 5 10 Modulus of Rupture of All Mixtures Figure 5 11 shows the average MOR for the slag mixtures at 7, 28, and 365 days. The control mixture contai ning only cement, CTRL1, shows a higher MOR when compared with the control mixture containi ng cement and fly ash, CTRL2, for both 7 and 28 day ages. The low reactivity of fly ash aff ects the tensile strength similar to early age to produ compressive strength. By 365 days, however the fly ash in CTRL2 has reacted ce a higher MOR than that of CTRL1.

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83 700 800 1200 0100200300400 Age (days)uure (si900 1000 1100 1300Moduls of Ruptp) CTRL1 CTRL2 SLAG1 SLAG2 SLAG3 Figure 5 11 Average Modulus of Rupture of Slag Mixtures The 7 day MOR for all slag mixtures was lower than both the control mixtures. Because the reactivity of slag is also low, the combination of the two mineral admixtures, slag and fly ash, produces an even slower strength developing concrete than CTRL2 in the 7 day MOR tests. By 28 days, however, the MOR for all slag mixtures are nearly equal to both the control mixtures. This i ndicates that the fly as h and slag has started MOR to the CTRL1. At 365 es. The hydration products of the slag th of the paste at 365 days similar to metakaolin mixtures. At 7 days, ture has nearly the same MOR as the controls, with the exception of META1. The 28 day MOR for META1 was reacting prior to 28 days to produce a concrete with equal day age, SLAG1s MOR was slightly higher than CTRL1, while those of SLAG2 and SLAG3 were both well above both control mixtur and fly ash, have improved the tensile streng compressive strength. Figure 5 12 shows the MOR development of the the metakaolin mixtures show high early stre ngth. Each mix

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84 also lower than the other metakaolin and cont rol mixtures. Every other mixture at this age was nearly equal. At 365 days, META1 still has a lower MOR than the controls. META2 is equal to CTRL1, while M ETA3 is nearly equal to CTRL2. 700 800 1000 1100 0100200300400 Age (days)Modulus of Rupture (psi900 1200 1300) CTRL1 CTRL2 META1 META2 META3Figure 5 12 Average Modulus of Rupt ure of Metakaolin Mixtures Because of the calcining, metakaolin is mainly composed of amorphous aluminosilicates. These aluminosilicates are highly reactive, and will rapidly convert CH to a hydration product. Thus, the high early strength of the metakaolin mixtures is because of its highly reactive composition. Th e MOR data show that an increase in proportion of metakaolin results in a higher MOR, as seen at all ages in Figure 5 12 The average MOR for the ultrafine fly ash mixtures is presented in Figure 5 13 At 7 days, the MOR for all ultrafine fly ash mixtures were considerably lower than the control mixtures. By 28 days, there is a gain in MOR for the ultrafine fly ash mixtures; however, the MOR were below the control mixtures. The strength of the mixtures

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85 continues to increase at 365 days. UFA3 now has a modulus that is nearly equal of CTRL1, while UFA1 and UFA2 are slightly lower. to that 900 1 1300 700 800 0100200300400 Age (days) 1000 1100 200Modulus of Rupture (psi) CTRL1 CTRL2 UFA1 UFA2 UFA3 tio ns of fly ash relative to the mixtures with other more reactive mineral ad mixtures. Although the ultrafine fly ash has a higher surface area when compared to regu lar fly ash, making it more reactive, the reaction equations are still the same. The fly ash needs a high alkalinity in the pore water to continue the pozzolanic reaction. At 7 days of age, the high volumes of total fly ash in the ultrafine fly ash mixtures (28 to 32%) sl ow the hydration consid erably. By 28 days, however, the fly ash has begun to react, as show n in the significant MOR gain relative to the controls. At 365 days, the data shows a ge neral increase in MOR as the proportion of mineral admixture is increased. By this ag e, the alkalinity in the pore solution has stabilized to allow for reactions of the full quantity of fly ash. Consequently, the larger Figure 5 13 Average Modulus of Rupt ure of Ultrafine Fly Ash Mixtures These mixtures have the lowest averag e 7-day MOR of all mixtures in this investigation. This is likely due to the higher total propor

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86 proportions of mineral admixtur es increase the amount of ava ilable reactive silicate. From pozzolanic reactions, the CH is convert ed to C-S-H, creating a stronger paste. Figure 5 14 shows the MOR development for th e silica fume mixtures. At 7 days, the MOE of SF1 is practically equal to CTRL2; SF2 is nearly equal to CTRL1. However, by 28 days, the MOR in SF2 has increased more than all other mixtures, while SF1 remains close to CTRL2. By 365 days the MOR for SF2 has surpassed CTRL1. SF2 and CTRL2 had a substa ntial increase in MOR. 700 800 900 0100200300400 1000 1100 1200 1300 Age (days)Modulus of Rupture (psi) CTRL1 CTRL2 SF1 SF2Figure 5 14 Average Modulus of Rupture of Silica Fume Mixtures At 7 days, the MOR in SF1 is nearly the same as CTRL2. At the same age, however, SF2 showed an improvement in MO R over CTRL2. This illustrates that the larger replacement with silica fume has contri buted to the tensile strength of the paste. Generally, as the proportions of silica fume are increased, the MOR will increase, because there is a larger quantit y of reactive silica available to convert CH to a stronger C-S-H product. By 28 days, the additional silica content of SF2 increased the MOR over

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87 all other mixtures. By 365 days, the MOR in CTRL2 has increased over CTRL1 indicating that fly ash has begun to react. SF2 had continued to hydrate and shows the largest MOR. The MOR is an important parameter used to calculate the cr acking strength of reinforced and prestressed concrete member s. ACI (363R-92) has found that for both lightweight and normal weight high-strength concrete, the MOR falls in the range of 7.5* ( f`c ) to 12* ( f`c ) in psi. The following formul a is recommended as a prediction of the tensile strength of concrete as measured by the MOR from the compressive strength: cf RuptureofModulus `7.11 (psi) (5-1) where f`c is the compressive strength (psi). Table 5 3 shows the MOR and compressive strength data for all mixtures, along with a calculated coefficient based on the ( f` ). The average coefficient was calculated for each of the three test ages of 7, 28, and 365 days. c

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88 7 days 28 days 365 days Table 5 3 Modulus of Rupture, Co mpressive Strength, and Coefficient Mix r(psi) c(psi) rcr(psi) c(psi) rcr(psi) f f` f/ (f` )f f` f/ (f` ) f f`c (psi) fr/ (f`c) CTRL1 987 8,741 10.610498,78411.21,121 9,750 11.4 CTRL2 964 7,990 10.810248,28911.21,165 10,246 11.5 SLAG1 886 7,616 10.210338,72811.11,145 10,403 11.2 SLAG2 922 7,506 10.610438,64411.21,238 10,326 12.2 SLAG3 906 6,791 11.09978,69910.71,242 9,382 12.8 META1 901 8,860 9.69548,86010.11,060 10,171 10.5 META2 1,008 8,962 10.710298,84110.91,122 10,306 11.1 META3 964 8,962 10.210038,95910.61,180 10,594 11.5 UFA1 793 6,490 9.89748,46910.61,057 10,094 10.5 UFA2 834 6,770 10.19778,77510.41,088 10,090 10.8 UFA3 853 6,787 10.49848,72910.51,132 10,114 11.3 SF1 971 7,281 11.410228,95110.81,139 10,024 11.4 SF2 994 7,831 11.210919,17811.41,208 10,272 11.9 Average 10.5 10.8 11.4 The coefficients range from 9.6 to 12.8, with an average of 10.5, 10.8, and 11.4 for 7, 28, and 365 days, respectively. The actual coeffi cients are slightly lower than what is predicted in the ACI equation. Therefore, AC I has overestimated the tensile strength of the co ys. n than data le slag s uring transportation and driving of the piles. ncrete for all mixtures at 7 and 28 days, and nearly all mixtures at 365 da The data show that coefficients increa se with both age and higher volumes of mineral admixtures. In other words, the tens ile strength increased by a larger margi the compressive strength as age and proportion of mineral admixture increased. The also show that the silica fume mixtures had the highest coefficient at 7 days of age, whi hows the highest at 365 days of age; at 28 days, all mixtures had nearly the same coefficient. MOR is used to calculate the cracking st rength of reinforced and prestressed concrete members. In this investigation, the cracking st rength becomes important d

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89 Flexural stresses may develop at early ages during the handling and transportation of the piles from the prestress yard to the construction s ite. At 7 days, the slag and xtures, ag and e, e. nt in ability of the concr at a 9% nt ultrafine fly ash mixtures showed lower MOR when compared to the control mi while the metakaolin and silica fume mixtures we re nearly equal. Therefore, the sl ultrafine fly ash reduce the ability of a concrete to resist fl exural stresses at this ag while silica fume and meta kaolin have no affect. In addition to flexural stresses from handling, tensile stresses are created in the pile during driving as stress waves propagate through the concrete and re flect back. Because driving typically takes place at around 28 days, the MOR becomes important at this ag The ultrafine fly ash mixtures show lowe r MOR than the controls, while the slag mixtures and metakaolin, with the exception of META1, were nearly equal. SF1 also had nearly equal MOR to the control mixtures at 28 days. SF2 showed an improveme MOR over the controls. Therefore, the use of ultrafine fly ash reduces the ete to resist tensile stresses from drivi ng at 28 days of age, while silica fume replacement level show an improvement. All other mineral admixtures had no significa affect to the MOR. Modulus of Elasticity and Poissons Ratio (ASTM C 469) Due to testing errors it was necessary to prepare a second set of mixtures from which modulus of elasticity (MOE) specimens were fabricated. Detailed results from tests on both set of mixtures are included in Appendix A. The MOE at early ages for concretes made with low reactivity mineral admixtures will usually be less than that of portland cemen t alone; the slower reactions results in a delay of MOE gain. Conversely, concrete c ontaining highly reactive mineral admixtures will show higher MOE at early ages. This is apparent at 7 days, in which the metakaolin

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90 mixtures showed a higher MOE than the controls ( Figure 5 15 ). Subsequent ages showed nearly equal MOE to controls. Although silica fume is also a highly reactive pozzo lan, its interacti ons with fly ash decrease MOE at 7 and 28 days. By 365 days, however, the silica fume mixtures showed th e highest MOE of all mixtures. Generally each other mixture showed lower MOE than the controls because of their low reactivity. 4.5 5.0 5.5 6.0psi)050100150200250300350Age (days)Modulus of Elasticity (*106 CTRL1 CTRL2 SLAG META UFA SF Figure 5 15 Average Modulus of Elasticity of All Mixtures t 7 days of a, SLAG early ll 5 Figure 5 16 shows the change in MOE in the slag mixtures. A ge 1 and CTRL2 have a lower modulus th an CTRL1; SLAG2 a nd SLAG3 are n the same as CTRL1. At 28 days, both contro l mixtures have shown a large increase in modulus to place them well above each slag mi xture. Each slag mixture has shown sma gains. Both CTRL2 and CTRL1 have s hown almost no increase between 28 and 36 days of age, while the modulus in each slag mixture increased over this period.

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91 4.5 5.0 Age (days)Modu5.5 050100150200250300350lus of Elastiy psi)6.0 6.5cit(*106 CTRL1 CTRL2 SLAG1 SLAG2 SLAG3 Figure 5 16 Average Modulus of Elasticity of Slag Mixtures The slow gain in MOE for the slag mixtures is attributed to the low reactivity slag. At ea of rly ages, the breakdown of the silica with in the slag is minimal. As cement lag to be activated. A e sed presence of alkalis. The hydration of the fly ash requires a high alkalinity in e pore solution. However, slag hydration reduces the alkalinity. Therefore, the ydration of slag within mixtures reduces the reactivity of the fly ash. This is also seen rom the dramatic increase in modulus in CTRL2 over the slag mixtureswhich contain e same percentage of fly ash. The MOE for metakaolin mi xtures is presented in Figure 5 17 At 7 day, each ixture containing metakaolin has a higher MO E compared to the control mixtures. The igher early modulus of the metakaolin mixtures is attributed to th e high reactiv ity of the ineral admixture. At early ages, the metakaolin mixtures have high strength evelopment and low porosity. Therefore, when comparing the moduli to the controls, hydrates, the release of hydroxyl ions increases, allowing the s s these mixtures hydrate, the porosity of the pa ste decreases. This effect is seen in Figure 5 16 by the slow increase in the MOE over time. In addition to the lo w reactivity of slag the mixtures are somewhat retarded at early ag es from the interactions of fly ash with th decrea th h f th m h m d

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92 the metakaolin mixtures perform well at 7 days The modulus at 28 days for all mixtures is nearly the equal. There is almost no change in any mixture at 365 day age. 4.5 5.0us 5.5 Elast6.0y (*106.5 0 1 2 e (d 50 00150 Ag 00250 ays) 300 350Modul of ici t6 psi) CTRL1 CTRL2 META1 META2 META3 e 5 17aulula okaolxt re 5 shows the MOE of ultrafine fly as h ms. The day MOE of ultraf almos n a Figur Aver ge Mod s of E sticity f Meta in Mi ures Figu 18 ixture 7 the ine fly ash mixtures and CTRL2 are be low that of CTRL1, with the exception of UFA1. At 28 days, there has b een only little improvement in the moduli of the ultrafine fly ash mixtures. However, both control mi xtures have had a considerable gain in modulus and are nearly the equal. The resu lts at 365 days show that there has been t no increase for the control mixtures, while each ultrafine fly ash mix has show large improvement in MOE.

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93 4.5 5.0 6.0 .5Modulof Elasticity (*106 5.5 6 050100150200250300350us psi) CTRL1 CTRL2 UFA1 UFA2 UFA3 Age (days) e 5 18 Average Modulus of Elasti city of Ultrafine Fly Ash Mixtures Although the ultrafine fly ash has a higher surface area when compared to regular fly ash, making it more reactive, the reactions are still the same. The fly ash needs a high alkalinity in the pore water to continue the pozzolanic reaction. At 7 days of age, high volumes of total fly ash of UFA2 a nd UFA3, 30% and 32% respectively, slow the hydration. The slow hydration, at this age, leaves a more por ous concrete. Thus, MOE lower for these mixtures. The data from UF A1 seems a little high, and may be bad data. The results from 28 days further illustrate the previous statement; the higher proportions of total fly ash have reduced the hydration co mpared to the control mixtures. However, by 365 days, the ultr Figur the is afine fly ash mixtures have continued to hydrat e to form a denser, een in the large increa gure 5 19 The modulus result less permeable concrete when comp ared to the control mixtures. This is s se of the ultrafine fly ash mixtures in MOE between the ages 28 and 365 days, while the control mixtures have shown almost no increase. The MOE for silica fume mi xtures is presented in Fi s at 7 days for the silica fume mixtures are below that on the control mixtures. By 28 days, the silica fume and control mixtures have all had nearly the same increase in MOE. The results at 365 days show that th e control mixtures have not had any increase

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94 in modulus. The silica fume mixtures have c ontinued to increase; how ever, they are below that of the control mixtures. still 4.5 5.0 5.5 050100150200250300350 Age (days)Modulus of Elast psi)6.0 6.5icity (*106 CTRL1 CTRL2 SF1 SF2 Figure 5 19 Average Modulus of El asticity of Silic a Fume Mixtures It appears that the addition of silica fume in combination with fly ash lowers the MOE at 7 and 28 day ages. The reduction in modulus is attributed to the decreased reactivity of fly ash with silica fume. The alkalinity of the pore wate r is reduced with the pozzolanic reaction of silica fume, which cause s the fly ash to remain inactive until the alkalinity is high enough to cause activation. This effect is se en at 7 and 28 day ages. By 365 days, the MOE of the silica fume mixtures has surpassed the control mixtures. This shows that the silica fume and fly ash has had enough time to continue hydration. ACI (318R-02) has defined the concrete MOE for densities between 90 and 155 lb/ft3 as: c c cfwE ` 33 (lb/in. ) (5-2) where Ec is the secant modulus, wc is the density of the concrete in lb/ft3, and f`c is the compressive strength in lb/in2. Consequently, factors that af fect strength also influenc MOE. The most dominant factor is porosity as modulus will decrease markedly5.12e with the increase in porosity (Mindess et al. 2003). Therefore, the mixtures containing mineral

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95 admixtures will have higher moduli of elasti porosity through pozzolanic reaction. The results from Poissons ratio seem to appears to be about 0.25 (Table 5 4 ). Therefore, there is no could be drawn of the affects of different mineral adm Table 5 4 Poissons Ratio Mix 7day 28day365day city because of associated decreases in be inconclusive. At all ages, the ratio discernable conclusion that ixtures on Poissons ratio. CTRL1 0.26 0.28 0.27 CTRL2 0.18 0.28 0.18 SLAG1 0.26 0.26 0.20 SLAG2 0.28 0.26 0.31 SLAG3 0.25 0.26 0.30 META1 0.27 0.29 0.23 META2 0.26 0.26 0.21 META3 0.25 0.26 0.21 UFA1 0.24 0.24 0.26 UFA2 0.24 0.26 0.37 UFA3 0.24 0.25 0.22 SF1 0.23 0.26 0.28 SF2 0.25 0.26 0.22 Average 0.25 0.26 0.25 Splitting Tensile Strength of Cylindrical Concrete (ASTM C 496) The data show high variability for all testing ages (Appendix B). Although care was taken to limit errors from affecting the re sults, the fact remains that the level of variability within the sample set is large enough to influence the trend. These errors are largely attributed to the specim en shape; ma ny were not perfectly cylindrical through its entire length. Due to deformations in cylinder molds, the finished surface was oval shaped in many cylinders. This would allow a non-uniform load to be applied during the test, thus affecting the apparent tensile strength of the specime n. It is because of this high variability that no conclusions were able to be drawn from this set of data.

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96 Durability Tests The results obtained from tests of linear shrinkage, volume of voids, change in ngth due to sulfate exposure, absorption, surf ace resistivity, rapid migration tests, and and relationships in the results have been r a concrete age of 32 weeks is presented in nd CTRL2, have the highest levels of xtures. This shrinkage is attributed mostly to he largest shrinkage becau ores le water permeability are discussed below. Trends noted in the discussion for each test. Linear Shrinkage (ASTM C 157) The average percent length change fo Table 5 5 The two control mixtures, CTRL1 a length change when compare to al l other mi the interconnectivity of the specimen porosity. CTRL 1 expe riences t se it contains no mineral admixture. It s paste most likely contains a higher volume C-S-H porosity and larger capillary pore s. CTRL2 shows a less shrinkage when compared to CTRL 1 due to the addition of fl y ash. The fly ash has reacted with CH to form a denser C-S-H matrix as well as decr eased the amount and size of capillary p (Neville 1995).

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97 Table 5 5 Average Percent Length Cha nge, COV, and Norm Shrinkage Values at 32 Weeks of Age Mix Shrinkage (%) COV Normalized Shrinkage alized (to CTRL1) CTRL1 0.0360 12.1 1.00 CTRL2 0.0330 6.1 0.92 SLAG1 0.0307 13.2 0.85 SLAG2 0.0247 27.0 0.69 SLAG3 0.0270 6.4 0.75 META1 0.0243 8.6 0.68 META2 0.0210 20.2 0.58 META3 0.0227 3.1 0.63 UFA1 0.0330 4.6 0.92 UFA2 0.0207 43.4 0.57 UFA3 0.0193 36.7 0.54 SF1 0.0287 17.6 0.80 SF2 6.0 0.70 0.0253 Generally, as the proportion of minera l admixture is increased, the average shrinkage is decreased. The increased mine ral admixture provides a larger quantity of reactive silica that allows more CH to reac t, and thus forming a denser C-S-H matrix. The increased proportion of mineral admixtur e also reduces the quantity and size of capillary pores. The ultrafine fly ash mixtures performed the best. However, UFA1 shows a high level of shrinkage; in fact, this mixture show s the same change in length as CTRL2. The most likely cause is from a high volume of la rge capillary pores; th is mixture exhibited the highest level of bleeding, as shown in Table 5 1 The m etakaolin mixtures also perform restrained concrete exceeds the tensile strength of the concrete, cracking will occur. The ed well, followed by the si lica fume and slag mixtures. The importance of shrinkage in structures is related to cracking. The cracking tendency of a concrete is func tion of not only shrinkage but also the tensile strength and restraint from shrinkage defo rmation. If the stress created from the shrinkage in a

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98 limiting tensile strain ranges between 100 x 10-6 and 200 x 10-6 (Neville 1995). The linear shrinkage of all the mixtures ranged from 0.019% to 0.036%, s uggesting that each ng in a restrained system. However, the xtures. CTRL1 showed the highest nkage decreased as the proportion xtures showed the best performance. avera the ceme investigation. The higher w/cm produces a larger quantity and size of capillary pores (Mind ille (19 /cm below .38, capillary pores will no longer be present and voids will be sm all and disconnected within the hydrated cement paste. In this investig ation, a w/cm of 0.35 was used. Therefore, there were no capillary pores ava ilable for the hydration products to fill, which is the reason why the use of mineral admixt ures had no affect on the volume of voids and absorption characteristics of the concrete. mixture will begin to develop shrinkage cracki extent of shrinkage cracking will differ between mi level of linear shrinkage, while UFA3 showed the lowest, followed by UFA2 and META2. With each gr oup of mineral admixtures, shri increased. As a whole, the ultrafine fly ash mi Volume of Voids and Absorption (ASTM C 642) The volume of permeable pore space, voi ds, range from 13.1 to 15.5%, while the ge percent absorption ranges from 5.92 to 7.14% ( Table 5 6 ). META3 has the maximum absorption and void content, while SL AG2 exhibits the lowest. However, data are nearly equal for all mixtures. Ther efore, neither voids nor absorption appears to be affected by the use of mineral admixtur es. This is not supported by research by Parande (et al. 2006) and Gonen and Yazicioglu (2006) in which they have shown that use of metakaolin, fly ash, and silica fume each has resulted in a decrease in voids and absorption. However, this research wa s conducted on mixtures with water to ntitious material ratios (w/cm) of 0.45 and 0.50, which were higher that what was used in this ess et al. 2003). Nev 95) has found that at a w 0

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99 Table 5 6 Average Percent Void and Absorption, COV, and Normalized (to CTRL Voids 1) Void and Absorption Values at 32 Weeks of Age Absorption Mix (%) COV Normalized (%) COV Normalized CTRL 1 13.9 4.1 1.00 6.31 4.9 1.00 CTRL2 13.8 2.6 0.99 6.30 2.5 1.00 SLAG1 13.6 2.4 0.98 6.20 1.3 0.98 SLAG2 13.1 2.3 0.94 5.92 1.7 0.94 SLAG3 14.5 1.7 1.05 6.66 1.9 1.05 META1 15.0 2.4 1.08 6.92 1.8 1.10 META2 15.0 3.7 1.08 6.89 1.9 1.09 META3 15.5 4.1 1.12 7.14 2.0 1.13 UFA1 14.2 2.3 1.03 6.52 2.0 1.03 UFA2 13.9 2.6 1.00 6.34 1.4 1.00 UFA3 14.3 1.4 1.03 6.56 1.9 1.04 SF1 13.6 2.1 0.98 6.31 1.8 1.00 SF2 13.3 2.9 0.96 6.18 2.8 0.98 Sulfate Expa (AS 1012 ure depilot ofalized values of average sulfate expansion for the concrete specimens. Each mixture was normalized to CTRL1 to provide a means of asg thets of ineral atures of the sulfate resist ance of the concrete. enerally, as the proportion of mineral admixt ure is increased, the average expansion is decreased. This is attributed to an increase in reactive silica, S, as the mineral admixtures are increased. As a result, more CH is consumed and thus lowering the gypsum corrosion. nsion TM C ) Fig 5 20 cts a p norm sessin effec the m dmix G

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100 0.00 1. 1.25U UFA2 UFA3 SF1 SF2 ate ExpansionFigure 5 20 Normalized Values of Su lfate Expansion: Concrete Specimens presents the normalized values of the average sulfate expansion each ixture for mortar specimens that were sieved after mixing to remove the coarse aggregate. The data for each mortar specimen was also normalized to CTRL1 so that a lative comparison can be made for each mi xture. The first and most important dication is that mineral admixtures reduce sulfate expansion of the paste. As the roportion of mineral admixture is increased, the sulfate e xpansion is decreased. The increased proportions of mineral admixture in crease the total ava ilable reactive silica within the mixture. This in turns allows fo r more CH to be consumed, thus lowering the gypsum corrosion. 0.25 0.50 0.75 00Normalized Sulf CTRL1 CTRL2 SLAG1 SLAG2 TA1 TA2 TA3 FA1 ME ME ME SLAG3 was excluded from Figure 5 20 because its high expansive behavior that is most likely attributed to its higher permeability. The bleed water measurements presented in Table 5 1 for this mixture, show a high value when compared to other mixtures. This would indicate that SLAG3 had slight problems with segregation. This in turn increases the size and quantity of capillary pores, thus increasing the permeability. Therefore the more permeable concretes will allow a large ingress of sulfate, and eventually a higher average expansion. Figure 5 21 m re in p

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101 0.00 0.20ali0.40z0.60CTRL1 SLAG2 META1 META3 UFA1 UFA2 SF1 SF2 ate Expansion 2 ens xternte atta typifiedpa nsion of concrete, leading to cracking and ng. Skt al. 2 has found research that sugges ts several expansion limits ailure criterion for mr and con attack. A 0.1% expansion was proposed as th t as it ( Table 5 7 ). 0.80 1.00CTRL SLAG 2 1 ME TA 2 UFA3 Norm ed SulfFigure 5 1 Normalized Values of Sulfate Expansion: Mortar Specim E al sulfa ck is by ex spalli alany (e 002) as a f orta cre te samples exposed to an external sulfate e maximum acceptable criterion for failure for a moderate sulfate resist ant concrete, while a 0.05% expansion was the limit for a high sulfate resistant concrete when tests were performed according to ASTM C 1012. According to these limits, each mixture could be classified has highly sulfate resistan their expansion was well below the 0.05% lim

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102 Mixture Concrete Mortar Table 5 7 Total Concrete and Mortar Expansion Expansion Expansion CTRL1 20.9 12.0 CTRL2 18.1 11.7 SLAG1 15.9 10.7 SLAG2 24.3 6.3 SLAG3 10.6 18.3 META1 18.2 6.7 META2 30.8 20.7 META3 15.7 4.7 UFA1 27.0 4.1 UFA2 49.8 13.0 UFA3 35.6 10.8 SF1 16.9 8.9 SF2 29.4 17.7 The percent expansions in the concrete prisms are about half as much as the mortar prisms ( Figure 5 22 ). This is because the coarse aggr egate is not susceptible to sulfate attack and therefore is not e xpansive. In both the concre te and mortar prisms, CTRL1 showed the highest levels of sulfate expansion. As a whole, the silica fume and metakaolin mixtures performed the best. However, these improvements may not significantly extend the life of the concrete as each concrete is well below the 0.5% expansion limit proposed by Skalny (et al. 2002). Extended sulfate attack tests are needed to determine the attributes of each mixture at later ages.

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103 0.040 0.000 0.005 0.010Sulf0.015 0.020ate Expans0.02 0.03 5 0CTRL1 SLAG2 META1 UFA1 UFA2 SF2ion (%)0.035 Mortar ConcreteCTRL2 LAG S 1 META ET 2 A3 M UFA SF 3 1 5 22arisonortar an ncrete SuExpansioecimens ion oeddedl Reinforcement (ASTM G 109) A plot rent vss for UF shown in re 5 23 It is apparent that ut the test duration. This is typical of all mixtures in this Figure Comp of M d Co lfate n Sp Corros f Emb Stee of cur age A3 is Figu there in no change in current th rougho investigation. Therefore, at the present time, corro sion has yet to initiate in the specimens for the corrosion of embedded steel re inforcement tests. Plots of all mixtures are shown in Appendix A. G109 UFA3 0.75 1.25 1.75 2.00Currt ( A)0.00 0.25 0.50 1.00 1.50 050107157207257308358408 Age (Days)en Specimen A Specimen B Figure 5 23 Corrosion of Embedded Steel Reinforcement Surface Resistivity (FM5-578) Whiting and Mohammed (2003) have found th at the conductivity of a concrete is related to its permeability and diffusivity of ions through the concrete. Consequently, the

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104 electrical resistance can be used as an estima al. 2001). Research conducted by Chini (et al measurements to Rapid Chloride Penetration test interpretation of the surface The table categorizes the chloride ion penetrab measurements. tion of chloride ion penetrability (Hooton et 2003) relating the surface resistivity s produced a reference table to aid the resistivity results, which was later adopted by FM 5-578. ility of a concrete from surface resistivity ixtures. At the er, ity. 28%) CTRL1. The SR reading of CTRL1 had only increa e slag Figure 5 24 compares the surface resistivity (SR) of the control and slag m early ages of the contro l and slag mixtures of 3 and 7 days, there was not much of a difference in the SR values of all slag mixtures from the control mixtures. Howev beyond these early ages, there were noticeable in creases in the slag mixtures resistiv At the 28 day age, the slag mixtures had increased by roughly 150%, while the controls had only increased by about 50% ( Table 5 8 ). At the 91 day age, all slag mixtures had continued to increase, but at a slower rate. CTRL2 had shown a large increased (1 to about double the surface resistivity in se by 20%. At 365 day age, the SR of a ll slag mixtures had continued to increase. The resistivity of CTRL2 has also continued to increase but at a faster rate than th mixtures. By this age, the surface resistance of CTRL2 is nearly equal to that of the slag mixtures. CTRL1 has shown only a mini mal increase (8%) in surface resistance.

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105 0 Age (days) 20 40 60 80 100 120 140 160 180 200 0100200300400Resistance (KOhm-cm) CTRL1 CTRL2 SLAG1 SLAG2 SLAG3 Figure 5 24 Average Surface Resistance of Slag Concrete Mixtures Table 5 8 Increase in Surface Resistivity Between Test Ages (%) Age (days) Mix 3 to 7 7 to 28 28 to 91 91 to 365 CRTL1 8 46 20 8 CRTL2 15 58 128 127 SLAG1 70 142 71 86 SLAG2 91 164 90 68 SLAG3 101 150 50 70 META1 247 100 31 82 META2 309 80 54 89 META3 261 163 27 78 UFA1 34 250 200 126 UFA2 24 271 200 133 UFA3 27 332 200 109 SF1 107 461 79 43 SF2 154 501 89 14 As the proportion of mineral admixture is increased, larger volumes of reactive lica are available to chemically combine with CH to form more C-S-H. Consequently, a denser, less permeable concrete is produ ced. However, SLAG3 had the largest volume of mineral admixture, but was the worst performing slag mixture. This was most likely attributed to mixing problems. The bl eed water measurements presented in Table 5 1 si

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106 for this mixture, show a high value when compar ed to all others. This would indicate that adble segregation. This in turn in creases the size and quantity ry phus incg the permeability. However, SLAG3 still performed n botrol mi at all ages. m Table 5 1 it is clear that CTRL2 (18% fl y ash) showed the increases in R atd 365 days; the earlier dates showed only small gains. This shows the ivitye fly ash ixtur e. It isnt until beyond 28 day that the fly l begin to react andve the SR properties of the mixture. The slag mixture, e other hhowed r increases in the earlier ages than fly ash; the largest ns testing regime. This indicates that the slag is more reactive and will contribute more to the early properties of th e concrete than fly ash. concrete mixtures compared with the control mixtures. At 3 days of age, there was not a However, because of the high reactivity of metakaolin, the 7 day measurements showed a etakaolin mixtures had increased by 80% to 163% and now is about 3 to 4 times that of the control mixtures. By 91 day of age, the metakaolin mixtures had continued to show an increase in SR. At 365 days of age, the SR of a ll metakaolin mixtures had increased by about 80% and have a SR much higher than CTRL 1 and about 2 or 3 tim es that of CTRL2. SLAG3 h slight pro ms with of capilla ores, t reasin better tha th con xtures Fro surface S 91 an low react of th mineral adm ash wil impro on th and, s large gai were seen between 7 and 28 days, with a steady increase in SR throughout the Figure 5 25 shows a plot of the average surf ace resistance of the metakaolin noticeable difference between the metakaolin mixtures and the control mixtures. large increase (241% to 309%) in SR. At 28 days of age, the SR of the m

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107 0 20 40 60 80 100 120 140 160 180 200 0100200300400Resistance (KOhm-cm) CTRL1 CTRL2 META1 META2 Age (days) META3 y. This illustra tes the very high reactiv ity of metakaolin. SR betw een 3 and 7 days of all the pared with the control y, the ultrafine fly ash mixtures ixtures. However, by 28 large increases in SR ranging from 250% to 32%. At 91 days of age, the ultrafine fly ash mixtures continued to have substantially increases (200%) in SR; they were nearly 4 tim es that of the control mixtures. At 365 days of age, the resistance of the ultraf ine fly ash mixtures had increased by roughly 125%. The SR in the ultrafine fly ash mixt ures were nearly 10 times greater than Figure 5 25 Average Surface Resistance of Metakaolin Concrete Mixtures The largest gains in SR in the metakaolin mixtures were seen in the early ages. Each metakaolin mixtures showed an increa se of roughly 275% and a 125% increase at 3 days and 7 days, respectivel Indeed, the metakaolin showed the largest gain in mixtures in this investigation. The SR of ultrafine fly ash concrete mi xtures are com mixtures in Figure 5 26 At early ages, 3 day and 7 da show nearly equal resistance when compared to the control m days, the ultrafine fly ash mixtures showed 3

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108 CTRL1. The SR in the UFA2 and UFA3 may have been even larger because they had exceeded the measuring capabilitie s of the resistivity meter. 0 40 60 80 100 0100200300400 Age (days)Resistance (20 160Ohm-cm)120 140 180 200K CTRL1 CTRL2 UFA1 UFA2 UFA3 ed fineness of the ultrafine fly ash. The SR of silica fume mixtures are co mpared with the control mixtures in Figure 5 27 At 3 day ages, silica fume mixtures and co ntrol mixtures have nearly equal SR. At 7 days of age, the silica fume mixtures be gin to show an increase in SR (107% and 154%), while the control mixtures showed onl y a small increase (8 and 15%). At 28 day of age, the mixtures containing silica fume show a dramatic increase in SR (461% and Figure 5 26 Average Surface Resistance of Ultrafine Fly Ash Concrete Mixtures The ultrafine fly ash mixtures showed th e larges increases in SR beyond 7 days. The largest gains were seen between 7 and 28 days. The subsequent testing dates also showed significant gains of 200% and roughly 125% at 91days and 365 days, respectively. The later age SR gains show the low reactivity of the fly ash. However, when comparing the data from CTRL2 to the ultrafine fly ash mixtures, it can be seen that the SR increase at an earlier age than CTRL2. This is attributed to the increas

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109 501%). The silica fume mixtures have a SR of nearly 5 or 6 times greater than the control mixtures. At 91 days of age, all sili ca fume mixtures showed an increase in S about 85%. At 365 days of age, the silica fu me mixtures have surpassed the m capabilities of the resistivity meter. R of easuring 0 20 80 100 120 140 160 180 200 010 300400 Agays)KOhm-cm) CTRL1 CTRL2 SF1 40 60Resistance (0 200 d e ( SF2 27 Average Surface Resistance of Silica Fume Concrete Mixtures silica fixtures showed the larges eases in SR at the early ages. The creases was een 7 28 day fact, these mixtures showed the gains at thge of atures is invtion. Th is illustrates the high ty of the a fume en coing th in mixtures with the silica each show high early reactivity. Howeve r, the metakaolin seems to improve the SR at Figure 5 The ume m t incr largest in in SR be tw and s. In largest is a ll mix in th estiga reactivi silic Wh mpar e metakaol fume a slightly earl ier age than the silica fume. This suggests that the metakaolin is slightly more reactive than silica fume. Howe ver, later, the silica fume increase the SR much higher than the metakaolin mixtures, which is likely attributed to the higher reactive silica content in the silica fume.

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110 The research by Chini (et al. 2003) produced a reference table that was developed from their test data to aid the interpretation of the SR result. The table correlated SR with categories of chloride ion penetrability, which was established by Whiting (1981) based on the amount of coulombs passed from the rapi d chloride penetration (RCP) test results. The c ated Passed and Surface Resistivity Category (mm) (Coulombs) (k -cm) ategories of high, moderate, low, very low, and negligible penetr ability were rel to the depth of chloride penetr ation after a 90 day ponding test. Table 5 9 presents a summary of the chloride ion penetrability categories, chlo ride ion penetration depths, coulombs passed, and SR. Table 5 9 Summary Table of Penetrability Category, Penetration Depth, Coulombs Penetrability Penetration Depth Coulombs Passed Surface Resistivty High > 1.3 > 4,000 < 12 Moderate 0.8 1.3 0 12 21 2,000 4,00 Low 0.55 0.8 1,000 2,000 21 37 Very Low 0.35 0.55 100 1,000 37 254 Negligible < 0.35 < 100 > 254 Typically, concrete with RCP results of less than 1000 coulombs is specified by the engineer or owner for concrete elements under extremely aggressive environments (Pfeifer, McDonald and Krauss 1994). From on y other mixture showed lower SR. Therefore, based on the 1000 coulomb limit, only the metakaolin and silica fume mixtures are accep table for use in an extremely aggressive Table 5 9 this corresponds to a Very Low and Negligible category. Because the RCP resu lts are based on 90 day ponding tests specimen that were cured for 28 days, SR at 28 days will be evaluated for each mixture in this investigation. At 28 days, only the metakaolin and silica fume mixtures were in the Very Low category, corresponding to a RCP value less than 1000 coulombs ( Table 5 10 ). Ever

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111 environment. The mixtures that are below the limit are presented in bo However, this limit is somewhat flawed becau se of the early age at which m evaluated. The use of some mineral ad mixtures delays hydration beyond 28 days. Consequently, a mixture that has high SR at la ter ages will be reject early SR. For example, the ultrafine fly ash mixtures are deemed unacceptable based upon the 1000 coulomb limit at 28 days. Howeve r, they showed large increases in S after 28 days. Eventually, the ultrafine fly as h mixtures were comp silica fume and metakaolin mixtureswhich were both acceptable at a more refined approach that incorporates the reactivity of the mixture is ne ld typeface. ixtures are ed because of its low R arable to that of the 28 days. Therefore, ed for Table evaluation of chloride ion penetrability. 5 10 Surface Resistivity (k -cm) Mix 3 day 7 day 28 day 91 day 364 day CRTL1 8 9 13 16 17 CRTL2 7 8 13 30 69 SLAG1 6 10 25 43 80 SLAG2 6 11 29 55 92 SLAG3 6 11 28 42 72 META1 8 29 57 75 136 META2 8 34 61 94 177 A3 9 31 82 105 186 MET UFA1 5 7 25 75 169 UFA2 6 8 29 86 *200 UFA3 6 7 32 96 *200 SF1 7 14 78 140 *200 SF2 6 15 93 175 *200 Rapid Migration Test (NTBuild 492) Like surface resistivity tests, rapid migration tests (RMT ) are electrical tests that rely on estimating the concrete permeab ility based upon the electrical conductivity properties of a concrete. The RMT applies a pot ential to a concrete to force chloride ion to migrate through the concrete. After the test is complete, penetration depths are

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112 measured. Because the penetrability of the concrete is based on the interconnectivity of voids, the use of mineral admixtures will reduced the depth of chloride ion penetration by is clear that at 28 days, all ures. At this age, silica contained within xtures. Thus, the creating a denser, less perm eable paste structure through pozzolanic reactions. Figure 5 28 shows the average Non-Steady-Stat e Migration Coefficient of slag mixtures plotted against the contro l mixtures. From this plot it slag mixtures showed lower migration coefficien ts than the control mixt the slag within the concrete had started to hydrate. The reactive the slag particles is beginning to convert CH to C-S-H. This new CSH product is now much more dense and homogenous compared to that of the control mi migration coefficients are decreased. 0 20 40 50 Age (days)Dnssm (x110 30 60 70 90 100 20 40 60 801000-12 m2/ CTRL1 CTRL2 SLAG1 SLAG2 SLAG380s) At 56 days, CTRL2 shows a 49% decrease in migration coefficient, while CTRL1 only showed a 16% decrease ( Table 5 11 Figure 5 28 Average Migration Coefficient of Slag Mixtures ). The slag mixtures showed less of a decrease in migration coefficients when compared to CTRL2, however, each slag mixtures had a lower migration coefficients at this age. At 91 days, both control mixtures showed a decrease in migration coefficient of about 30%. Each slag mixture showed a larger decrease (39% to 49%) in migration coefficien t than the control mixtures. The migration

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113 coefficient in CTRL2 was about half that of CTRL1, while each slag mixture was CTRL1. Table 5 11 Decrease in Mi gration Coefficient (%) of Age (days) Mix 28-56 56-91 CTRL1 16 27 CTRL2 39 31 SLAG1 21 39 SLAG2 30 39 SLAG3 16 47 META1 25 49 META2 2 46 META3 32 32 UFA1 34 74 UFA2 49 37 UFA3 39 63 SF1 13 69 SF2 52 42 Figure 5 29 shows the average Non-Steady-St ate Migration Coefficient of metakaolin mixtures plotted against the cont rol mixtures. At all ages, each m etakaolin ixtures. At 28 da mixture showed a lower migrati on coefficient when compared to the control m ys, the migration coefficients in the me takaolin mixtures were roughly 25% of that of CTRL1. At ages of 56 and 91 days, the metakaolin mixtures showed a continual decrease in migration coefficients, ra nging from 2% to 32% and 32% to 49%, respectively. The migration coefficient for the metakaolin mixtures were again approximately 25% of CTRL1 at 56 days, and 17% at 91 days.

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114 0 20 40 60 80 20 40 60 80100 Age (days)Dnssm (x1-1s)10 30 50 70 90 10002 m2/ CTRL1 CTRL2 META1 META2 META3 Figure 5 29 Average Migration Coe fficient of Metakaolin Mixtures Figure 5 30 shows the average Non-Steady-St ate Migration Coefficient of ine e i w e control es. At 28 daysigration coef n the ultrafinesh mixtures were ly of that o t ages ays, the ufly ash mixtures ntinual d in migration ients, ranging4% to 49% and 37% t ultrafine fly ash mixtures plotted against the control mixtures. At all ages, each ultraf fly ash mixtur s showed a lower m gration coefficient hen compared to th mixtur the m ficien ts i fly a rough f CTRL1. A of 56 and 91 d ltrafine showed a co ecrease co effic from 3 o 74%, respectively. The migration coe fficient for the ultraf ine fly ash mixtures were approximately of CTRL1 at 56 days, and 1/6 at 91 days. 10 20 30 50 70 90Dnss m2/s40 60 80 100m (x10-12) CTRL1 CTRL20 20 40 60 80100 Age (days) UFA1 UFA2 UFA3 Figure 5 30 Average Migration Coefficient of Ultrafine Fly Ash Mixtures

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115 Figure 5 31 shows the average Non-Steady-State Migration Coefficient of sil fume mixtures plotted against the control mi xtures. At all ages, each mixture showed a lower migration coefficient when compared to the control mixtures. Indeed, both si fume mixtures show the lowest migration coefficients of all mixtures at all ages. At 28 days, the migration coefficients in the silica fu me mixtures were nearly a 10% of that o CTRL1. At ages of 56 and 91 days, the silica fume mixtures showed a continual decrea in migration coefficients, ranging from 13% to 52% and 42% to 69%, respectively. The migration coefficient for the metakaolin mi xtures were again a pproximately 13% of CTRL1 at 56 days, and 10% at 91 days. ica lica f se 0 10 20 30 40Dnssm (x150060-1702 m2/80s)90 4 60 8010 Age (da 100 20 0 ys) CTRL1 CTRL2 SF1 0SF2Figure 5 31 Average Migration Coefficient of Silume Mixtures ceptanceteria for T resulve not been estab. However, Stanish (et al 2005) has developed a relation between the result of RMT and RCP ( Table 5 12 ). (mm/ ica F Ac cri RM ts ha lished Table 5 12 RMT and RCP relationship RMT value RCP Value V*hr.) (Coulomb) 0.034 3000 0.024 2000 0.012 800 Typically, concrete mixtures that allow less than 1000 coulombs of charge to pass is specified by the engineer or owner for c oncrete elements in extremely aggressive

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116 environments (Pfeifer, McDonald and Krauss 1994). Through a linea r interpolation of the data in Table 5 12 a RMT value of 0.014 mm/V*hr. was found to correlate to an RCP value of 1000 coulombs. Based upon the maximum 1000 coulomb limit, an assess Mixture 28 56 91 ment of acceptable mixtures can now be made in Table 5 13 The mixtures that exceed the limit are illustrated in bold typef ace. The data leading to the 1000 coulomb limit was based on 90-day ponding tests that were cured for 28 days. Therefore, 28 day RMT values will be discussed. Table 5 13 RMT Values (mm/V*hr) CTRL1 0.029 0.029 0.021 CTRL2 0.025 0.020 0.014 SLAG1 0.016 0.014 0.010 SLAG2 0.016 0.015 0.009 SLAG3 0.017 0.017 0.010 META1 0.013 0.011 0.007 META2 0.008 0.009 0.006 META3 0.009 0.007 0.005 UFA1 0.019 0.014 0.006 UFA2 0.015 0.010 0.008 UFA3 0.017 0.012 0.005 SF1 0.009 0.007 0.006 SF2 0.008 0.005 0.004 It appears that only the metakaolin and silica fum e mixtures have RMT values r mixtures are not accep y lower than 0.014. Based upon the 1000 coul omb limit, all othe table mixtures to be used in extremely aggressive environments. However, this limit is somewhat flawed because of the earl y age at which mixtures are evaluated. The use of some mineral admixtures delays hydration beyond 28 days. Consequently, a mixture that has high RMT values at later ages will be rejected because of its low earl RMT. For example, the ultrafine fly ash mixtures showed a large increase in RMT values after 28 days. Eventually, the RMT values were comparable to that of the

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117 metakaolin and silica fume mixtureswhich we re both acceptable at 28 days. Therefor a more refi e, ned approach that incorporates the reactivity of the mixture is need for Water Permeability (UF Method) he re gatheredm the wate r permeability test are scattered and ive ( ). The most likely cause of variation in coefficients of lity is caused by poor bond between the concrete specimen and the epoxy etailest result provide in Appendix A. 14 Cicient of Permeability s Kp (ft/hr) turesKp (ft/hr) evaluation of chloride ion penetrability. T sults fro inconclus Table 5 14 permeabi barrier. D ed t s are Table 5 oeff Mixture Mix CRTL1 8.80 1 5.45E-10 9E-1 UFA CTRL2 8.90 2 8.03E-10 7E-1 UFA SLAG1 9.80 3 1.01E-09 1E-1 UFA SLAG2 3.77E-10 SF1 6.28E-10 SLAG3 4.97E-10 SF2 4.34E-10 META1 4.45E-10 META2 7.06E-10 META3 1.06E-09

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CHAPTER 6 SELECTION OF MIX DESIGNS FOR PILES The relative cost, mechanical properties, important factors in bridge construction. Ther ef determine the mixtures with the most favorab selected to determine the most feasible and e fficient m method and the rationale for choos ing the mixtures to be im and durability of a concrete are all ore, each of these factors was analyzed to le attributes. Cons equently, a method was ixtures. This chapter describes this Key R ay le actors to adjust for their relative lized to the CTRL1 mix (cement only) and tency, each of the normalized le results were less than 1.0. Scores were s of mineral admixture. The jor selection criteria along with the pl emented in the piles for the oyale bridge replacement project. Because of the approaching deadline for pile construction, final mixture designs were needed before later age testing could be completed. Consequently, ninety-one d data for the first series of specimens and 28 day data for the second series were availab for use in selecting the mixture designs. Selection Approach To rank the mixture designs, a decision matrix was generated using the data collected from both mechanical and durability tests. In addition, relative costs were included. Each set of results were assigned we ighting f importance. These results were then norma summed to result in a single score for that mix. For consis values was adjusted so that the more favorab ranked to aid in selection of the best mix design for each clas following sections describe each of the thre e ma rationale for the weighting factors. 118

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119 Selec ble 6 e mineral admixture to that of the cement tion Criterion I: Cost Although perhaps not the most important factor, materi al cost often plays a significant role in bridge design and construc tion. Because of this, cost was a major selection criterion in the decision matrix. Water, coarse aggregate and fine aggreg ate quantities are rela tively constant among the possible mixtures; consequently, only th e relative costs of th e cement and mineral admixtures were included. Market costs ($/to n) were collected for cement, fly ash, slag, metakaolin, ultrafine fly ash, and silica fu me from the appropriate manufacturers ( Ta 1 ). The relative costs are the ratio of th Table 6 1 Material Costs Cost ( $/Ton ) Relative Cost Cement 95 1.000 Fly Ash 42 0.442 Slag 90 0.947 Metakaolin 480 5.053 Ultrafine Fly Ash 1000 10.526 Silica Fume 600 6.316 Selection Criterion II: Mechanical Properties The mechanical tests included in the d ecision matrix were compressive strength, flexural strength, m nclusive. odulus of elasticity, and shrinkage ( Table 6 2 ). Because the data were highly variable, and splitting tensile strength tests were not included in the analysis. Results from Poissons ratio were also excluded because they were inco

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120 Table 6 2 Normalized Mechanical Test Results Strength Strength Elasticity Shrinkage Compressive Flexural Modulus of CRTL1 1.000 1.000 1.000 1.000 CTRL2 0.956 1.092 0.993 0.917 SLAG1 0.978 1.049 0.905 0.852 SLAG2 0.986 1.043 0.914 0.685 SLAG3 1.065 1.132 0.914 0.750 META1 0.983 1.086 0.951 0.676 META2 0.974 1.056 1.008 0.583 META3 0.967 1.041 1.006 0.630 UFA1 0.988 1.084 0.921 0.917 UFA2 1.000 1.081 0.871 0.574 UFA3 0.989 1.091 0.912 0.537 SF1 0.979 1.108 0.934 0.796 SF2 0.974 0.987 0.926 0.704 Tim e constraithaching construction deadlines for the field portion of tidi lo65 day age data. Therefore, 91 day age data for ig an. Comp lete testing data from the linear shrinkage le ecthanors in the testing setup for modulus of elasticity, ionalesroo retest these specimens. At the time the mixtures ere selected, only 28 day modulus of elasticity data were available to be used in the mixture determination process. Similarly, fl exural strength specimens were recreated and tested. Twenty-eight day data were available for analysis. Selection Criterion III: Durability The durability tests included in the decisi on matrix were surface resistivity, rapid migration test, volume of voids, absorption, and sulfate expansion of mortar specimens ( Table 6 3 ). Because of time constraints, results from the corrosion of embedded steel reinforcement and bulk diffusion tests, ASTM G109 and ASTM C1585 respectively, were not available to be used in the decision matrix. Water permeability results were also nts for e appro the inves gation d not al w for 3 compress ve stren th were alyzed tests were availab B ause of e mech ical err addit mixtur were p duced t w

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121 not included because it was determined that th e data were erroneous due to leaks in the bond between the concrete and epoxy. Table 6 3 Normalized Durability Test Results Surface T Voids Absorption Sulfate Expansion Resistivity RM CRTL1 1.000 1.0001.0001.000 1.000 CTRL2 0.511 0.5630.9930.997 0.886 SLAG1 0.360 0.3030.9770.982 0.963 SLAG2 0.285 0.3200.9410.938 0.874 SLAG3 0.369 0.2811.0461.054 0.977 META1 0.208 0.1671.0821.096 0.666 META2 0.167 0.1361.0781.092 0.609 META3 0.149 0.1171.119 1.131 0.715 UFA1 0.208 0.1411.0261.033 0.932 UFA2 0.18 0.9991.005 0.729 1 0.262 UFA3 0.16 1.0291.038 0.786 3 0.130 SF1 0.11 0.9801.000 0.540 1 0.143 SF2 0.08 0.9600.978 0.591 9 0.092 Importanc a calculated for each of the three major ,acaproperties, and durability. One c onsequence of this approach was that each test method result, within their own category, was weighted equally. Therefore, each category was also assigned an importance factor. Because the focus of this investigate was on the durability aspect of concrete mixtures, the durability test category was assigned an importance fact or of 50%. The mechanical test category was assigned a factor of 40%, while cost wa s assigned a value of 10%. The final score for each mixture design was calculated using the following equation: Score = 10%*Cost + 40%*Mechanical Properties + 50%*Durability (6-1) e Factors An verage norm alized test result was categories cost, mech ni l

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122 Because each value was normalized so favorable result was represented by a number less then 1.0, the mixture with the lowest score then indicated the mixture desig Mechanical Durability Tests Equation Value that th e more n with the most favorable attributes. Therefore, from each class of mineral admixtures, the mixture design with the lowest score was selected. Table 6 4 summarizes the normalized results for the selection criterion for each mixture with the final score. Table 6 4 Summary of Normali zed Results and Equation Values Mixture Cost Tests CRTL1 1.000 1.000 1.000 1.000 CTRL2 0.900 0.989 0.790 0.881 SLAG1 0.886 0.946 0.717 0.826 SLAG2 0.884 0.907 0.672 0.787 SLAG3 0.881 0.965 0.745 0.847 META1 1.224 0.924 0.644 0.814 META2 1.305 0.905 0.616 0.801 META3 1.386 0.911 0.646 0.826 UFA1 1.852 0.977 0.668 0.910 UFA2 2.043 0.881 0.635 0.874 UFA3 2.233 0.882 0.629 0.891 SF1 1.272 0.955 0.555 0.786 SF2 1.378 0.898 0.542 0.768 e From these data, CTRL1 and CTRL2 were se lected to be the control mixtures for the field investigation. SLAG2, META2, UFA2 and SF2 were selected because of they had the lowest final score within each class of mineral admixtures. For clarity, SLAG2 contained 30% slag, META2 contained 10% metakaolin, UFA2 contained 12% ultrafin fly ash, and SF2 contained 9% silica fume.

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123 CHAPTER 7 CONCLUSIONS AND RECOMMENDATIONS In order to provide sufficien t laboratory test data in wh ich the Florida Department of Transportation (FDOT) can utilize in assessing the implementation of alternative mineral admixtures in Florida Concretes, various plastic, mechanical, and durability testes were conducted. Thirteen mixtures we re investigated that contained fly ash in conjunction with varying proporti ons of slag, metakaolin, ul trafine fly ash, and silica fume. Plastic property tests were conducted on temperature, air content, slump, bleeding, and setting times. The mechanical test procedures included compressive strength, flexural strength, splitting tensile strength, m odulus of elasticity, and Poissons ratio. Several durability related test perfor med; these tests included, surface resistivity, rapid migration test, volum absorp tion, water permeabilit y, shrinkage, sulfate expansion, and corrosion of embedded steel reinforcement. Additionally, this research provided the FDOT with a recommendation of the most effective mixtures containing various pozzolans for the utilization in the piling of the Key Royale bridge replacement project. Conclusions are as follows: that the plastperties, voluoids, and absorption were not significantly affected by the implementati on of any of the mineral admixtures. In the compressive strengs, the metak xtures performed the best at ages of less than 28 days. At 28 days, each mi xture exhibited nearly equal compressive e mixtures show m e control mixture. However, at 365 days each mixture containing mineral admixtures were nearly equal. s were e of voids, It was found ic pro me of v th test a olin mi strength in which the silica fum ed the highest. At later ages, all ixtures displayed larger strength than th

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124 In the modulus of rupture (MOR) tests, th e ultrafine fly ash mixtures showed the lo s, h d that ACIs equation overestimated the MOR for nearly all mixtures. The 7 day test showed the greatest amount of overestima tion, while the 365 day tests showed the least amount of overestimation. odulus of elasticity (MOE), as they were nea e contr ges. The silica fume mixtures displayed the lowest MOE at 7 days, and the highest at 365 days. Poissons ratio appeared to be unaffected by the use of mineral admixtures, as the ratio was abo for all age f mineral admixtures improv resistance nkage; eacures lower linearage than t trol. The 1ltrafine flyixture ount of shrinkage, followed by the 12% ultrafine fly ash, then 10% metakaolin. In the sulfate attack experi ents, it was found that the expansion, when com l, was less t% for mo d 0.05% forete specim the silica fixtures sho he lowest at of expansllowed takaolin mixtures. However, the 14% ultrafine fly ash mixture showed the largest decrease (54%) in expansion from the control in the concrete specimens. west MOR at 7 days, while the metakaolin mixture showed the highest. At 28 day all mixtures showed nearly equal MOR as the control, excluding the ultrafine fly as mixturesas they were lower. At 365 days the slag mixtures displayed the highest MOR, while the ultrafine fly ash mixtures s howed the lowest. It was also foun The metakaolin mixture showed the best results for m rly equal to th ol at al l a average ut 0.25 s. The use o ed th e to shri h mixt exhibited shrink he c on 4% u ash m showed the lowest am m pared to the contro han 0.5 rtar an r conc ens. Generally ume m wed t moun ion, fo by the me

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125 face resistivityignificantl ted by the mineral adres. beyond 3 days, each mixture show ed higher surface re sistivity than the control mixture. The slag mixtures showed the lowest surface resistivity, with the exception of the control mixtures. The si lica fume mixtures showed the largest ce resistivity, fol by the ultrly ash, thekaolin. The chloride ion penetrability was also signi ficantly affected by mineral admixtures. At each age, all mixtures showed an improvement in migration coefficients when compared to the control. The silica fu me showed the best performance, followed closely by metakaolin. The ultrafine showed the least improvement of all the mineral admixtures at 28 days; however by 91 days the slag mixtures showed the least improvement. A relation to the 1000 coulomb limit was also made for RMT results. Again, only the metakaolin and silica fume mixtures were the only acceptable mixtures to be used in an extremely aggres sive environment at 28 days. However, at 91 days, all mixtures (excluding CTRL1) becomes acceptable. Based on results from the decision matrix, the most efficient proportions of mineral adm The sur was s y aff ec use of mixtu At ages surfa lowed afine f n meta ixtures to be used in conjunction with 18% fly ash were: 30% slag, 10% metakaolin, 12% ultrafine fly ash, and 9% silica fume.

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126 APPENDIX A ORATORY MIX TESTING DATA Table A 1 Plastics Tests Mix Density (lb/ft3) Slump Air (%) Bleed (%) Initial Set (min) Final Set (min) Mix Temp. (oF) Air Temp. (oF) LAB Propertie (in) CTRL1 145 5.75 2.0 0.00 300 395 81 75 CTRL2 145 6.00 1.5 0.10 330 400 75 84 SLAG1 144 6.50 1.1 0.19 340 430 81 75 SLAG2 144 6.00 1.0 0.17 355 460 75 81 SLAG3 146 6.50 0.6 0.27 300 445 80 75 META1 144 6.25 1.4 0.00 375 435 84 75 META2 144 7.25 1.5 0.00 390 470 75 80 META3 144 6.00 1.4 0.00 N/A N/A 80 75 UF146 5.75 0.6 0.55 375 465 75 A1 78 UFA2 145 6.75 1.8 0.00 385 485 78 75 UF144 8.00 1.6 0.00 400 480 75 A3 78 SF1 143 6.25 2.3 0.00 370 445 76 75 SF2 6.00 2.3 0.00 385 465 76 75 143 Table A 2 Compressive Strength Mix 3day (psi) 7day (psi) 28day (psi) 91day (psi) 365day (psi) CTRL1 7,760 8,740 8,780 9,480 9,750 CTRL2 6,830 7,990 8,290 9,920 10,250 SLAG1 6,160 7,620 8,730 9,690 10,400 SLAG2 5,750 7,510 8,640 9,620 10,330 SLAG3 4,890 6,790 8,700 8,900 9,380 META1 7,770 8,860 8,860 9,650 10,170 META2 7,050 8,960 8,840 9,740 10,310 META3 7,300 8,960 8,960 9,810 10,590 UFA1 5,310 6,490 8,470 9,590 10,090 UFA2 5,650 6,770 8,780 9,480 10,090 UFA3 5,680 6,790 8,730 9,590 10,110 SF1 6,170 7,280 8,950 9,680 10,240 SF2 6,230 7,830 9,180 9,730 10,340

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127 Table A 3 Flexural Strength for Initial Series of Mixtures Mix (psi) (psi) 3day 7day CTRL1 1,021 1,139 CTRL2 993 1,043 SLAG1 976 1,086 SLAG2 977 1,092 SLAG3 984 1,006 META1 991 1,049 META2 1,132 1,079 META3 1,079 1,094 UFA1 817 1,051 UFA2 872 1,054 UFA3 922 1,045 SF1 1,009 1,028 SF2 1,051 1,154 Table A 4 Flexural Strength for Second Series of Mixtures 3day (psi) 7day (psi) 365day (psi) Mix CTRL1 1,021 1,139 1,121 CTRL2 993 1,043 1,165 SLAG1 976 1,086 1,145 SLAG2 977 1,092 1,238 SLAG3 984 1,006 1,242 META1 991 1,049 1,060 META2 1,132 1,079 1,122 META3 1,079 1,094 1,180 UFA1 817 1,051 1,057 UF872 54 1,088 A2 1,0 UFA3 922 1,045 1,132 SF1 1,009 1,028 1,139 SF2 1,051 1,154 1,208

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128 Table A 5 Averaged Flexural Stren Mix 3day 7day (psi) 365day (psi) gth (psi) CT987 49 RL1 10 1,121 CTRL2 964 1024 1,165 SLA886 33 G1 10 1,145 SLAG2 922 1043 1,238 SLAG3 906 1,242 997 ME901 4 TA1 95 1,060 META2 1,008 1029 1,122 ME964 03 TA3 10 1,180 UFA1 793 974 1,057 UF834 7 A2 97 1,088 UFA3 853 1,132 984 SF1 971 1022 1,139 SF2994 91 10 1,208 Table A 6 Modulus of Elasticity Mix 7day 28day 365day (psi*106) (psi*106) (psi*106) CTRL1 5.10 5.855.82 CTRL2 4.91 5.805.85 SLAG1 4.82 5.295.49 SLAG2 5.11 5.345.72 SLAG3 5.16 5.355.71 META1 5.18 5.865.88 META2 5.36 5.895.93 META3 5.52 5.885.80 UFA1 5.14 5.385.95 UFA2 4.87 5.095.68 UFA3 4.67 5.335.58 SF1 4.63 5.465.90 SF2 4.77 5.465.97

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129 Table A 7 Poissons Ratio Mix 7day 28day365day CTRL1 0.258 0.278 0.273 CTRL2 0.179 0.281 0.183 SLAG1 0.260 0.261 0.204 SLAG2 0.282 0.256 0.313 SLAG3 0.253 0.263 0.297 META1 0.268 0.291 0.227 META2 0.259 0.255 0.212 META3 0.247 0.255 0.207 UFA1 0.242 0.243 0.263 UFA2 0.236 0.264 0.366 UFA3 0.243 0.252 0.219 SF1 0.227 0.259 0.276 SF2 0.247 0.259 0.219 Table A 8 Splitting Tensile Strength Mix 3day (psi) 7day (psi) 28day (psi)91day (psi) 365day (psi) CTRL1 1,227 1,184 987 1,007 1,192 CTRL2 1,041 916 1,035 1,196 1,214 SLAG1 951 980 1,248 1,153 1,302 SLAG2 969 949 1,197 989 1,251 SLAG3 1,021 848 892 962 1,058 META1 1,235 1,189 1,085 915 999 META2 1,191 1,259 1,300 1,304 966 META3 1,306 1,064 1,425 1,300 932 UFA1 936 757 812 1,015 794 UFA2 770 1,078 1,079 1,118 953 UFA3 572 1,040 1,057 1,026 819 SF1 1,213 1,131 987 1,107 749 SF2 1,224 1,208 977 1,193 834

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130 Table A 9 Linear Shrinkage, Volume of Voids, Absorption, and Permability (%) (%) (%) (ft*10-10/hr) Mix Shrinkage Voids Absorption Kp CTRL1 0.0360 13.9 6.31 8.89 CTRL2 0.0330 13.8 6.30 8.97 SLAG1 0.0307 13.6 6.20 9.81 SLAG2 0.0247 13.1 5.92 3.77 SLAG3 0.0270 4.97 14.5 6.66 META1 0.0243 15.0 6.92 4.45 META2 0.0210 15.0 6.89 7.06 META3 0.0227 15.5 7.14 10.63 UFA1 0.0330 14.2 6.52 5.45 UFA2 0.0207 13.9 6.34 8.03 UFA3 0.0193 14.3 6.56 1.01 SF1 0.0287 13.6 6.31 6.28 SF2 0.0253 13.3 6.18 4.34 Table A 10 Sulfate Expansion Mixture Concrete Expansion Mortar Expansion (%) (%) CTRL1 0.0179 0.0361 CTRL2 0.0143 0.0320 SLAG1 0.0158 0.0348 SLAG2 0.0147 0.0316 SLAG3 0.0260 0.0353 META1 0.0142 0.0254 META2 0.0137 0.0245 META3 0.0123 0.0250 UFA1 0.0167 0.0337 UFA2 0.0127 0.0297 UFA3 0.0083 0.0275 SF1 0.0102 0.0195 SF2 0.0100 0.0213

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131 Table A 11 Surface Resistivity Mixture 3 day 7 day 28 day 91 day 364 day CRTL1 8 9 13 16 17 CRTL2 7 8 13 30 69 SLAG1 6 10 25 43 80 SLAG2 6 11 29 55 92 SLAG3 6 11 28 42 72 META1 8 29 57 75 136 META2 8 34 61 94 177 META3 9 31 82 105 186 UFA1 5 7 25 75 169 UFA2 6 8 29 86 *200 UFA3 6 7 32 96 *200 SF1 7 14 78 140 *200 SF2 6 15 93 175 *200 Table A 12 Rapid Migration Test Mixture 28 56 91 CTRL1 0.029 0.029 0.021 CTRL2 0.025 0.020 0.014 SLAG1 0.016 0.014 0.010 SLAG2 0.016 0.015 0.009 SLAG3 0.017 0.017 0.010 META1 0.013 0.011 0.007 META2 0.008 0.009 0.006 META3 0.009 0.007 0.005 UFA1 0.019 0.014 0.006 UFA2 0.015 0.010 0.008 UFA3 0.017 0.012 0.005 SF1 0.009 0.007 0.006 SF2 0.008 0.005 0.004

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132 200520 40 60 70 0/11/3111 11/312/20tive Humid (%)0 10/11 10Rela30 50ity10/2110 /1011/20 012/10 12/30Date 200660 652/2 5/37/20 10/2812/17eRelative Humity (%)1tivedityry C Ror a) and006 70 301/135 40 45 50 55di04/11 1 9/8Data) b) Figure A Rela Humi in D uring om fo 2005 b) 2 2005 200676perat78ure (80oF)82 84 70 72 74 /110/ 11/20 3teTem10 1110/2110/3111/10Da11/3012/1012/2012/ 0 601/165 702/20 7/20DateTemperature (oF) 2 Teure in Drg Room005 and6 75 80 85 904/115/31 9/810/2812/17a) b) Figure A mperat y Curin for a) 2 b) 200 G109 CTR L1 -1.5 -1 -0.5 50107157207257308358408 Age (Days)Curr0ent0.5 ( A1 1.5) Spec 0 imen A Specimen B G109 CTRL2 -0.2 -0.1 0 050107157207257308358408 Age (Days)Current ( A)0.1 0.2 0.30.4 0.5 0.6 Specim en A Specim en Ba) b) Figure A 3 Corrosion of Embedded Steel Re inforcement for a) CTRL1 and b) CTRL2

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133 G 109 SL 52 592 310360410 Ag AG1 0 2 4Cu6nt (8 A)10 12 0 109 1 09259 e (Days)rre Specimen A Specimen B G109 SLAG2 0 20 40 60 80 100 120 140 052109159209259310360410 Age (Days)Current ( A) Specimen A Specimen Ba) b) G 109 S 140 160 50157 30808 AgCurreLAG3 Specimen A 180 0 20 40 60 80 100 120nt ( A)0 107 207257 3584 e (Days) Specimen B c) 4 sion inforcement for a) SLAG1, b) SLAG2, and c) SLAG3 Figure A Corro of Embedded Steel Re

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134 G109 META1 0 5 10rre15nt ( 20A)25 050 572 30808 Age 1071 07257 (Days) 3584CuSpecim en A Specimen B G109 META2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 050107157207257308358408 Age (Days)Current ( A) Specimen A Specimen Ba) b) G1 09 ME -4 -2 5 08 Age (DaysCurrentTA3 Specimen A Specimen 0 2 (mA)4 6 8 -8 -6 -10 0 0107157 2072573 358408 ) B c) 5 Con of Emded Stee nforcement for a) META1, b) META2, and c) META3 Figure A rrosio bed l Rei

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135 G109 UFA1 0 0.2 0.4Cu0.6nt ( 0.8A)1 1.2 0 50 72 308 Ag 10715 07257 e (Days) 358408rreSpecimen A Specimen B G109 UFA2 0 5 10 15 20 25 050107157207257308358408 Age (Days)Current ( A) Specimen A Specimen Ba) b) G 109 U1.00 1.25 501 20725738408 Age (Days)ent ( FA3 Specimen A Specimen0.00 0 0.25 0.50 0.75Curr1.50A)1.75 2.00 07157 0835 B c) 6 Con of Embedded Steel Rein forcement for a) UFA1, b) UFA2, and c) UFA Figure A rrosio 3 G109 SF1 0 2 4 6 050107157207257308358408 Age (Days)Curre8nt ( A)10 12 Specimen A Specimen B G109 SF2 -1 -0.5 0 050107157207257308358408 Age (Days)Current ( A)0.5 1 1.5 Specim en A Specim en Ba) b) Figure A 7 Corrosion of Embedded Steel Reinforcement for a) SF1 and b) SF2

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APPENDIX B LABORATORY MIX STATISTICAL DATA 1 ssive th 3 7day 28d91day day Table B Compre Streng Mix day ay 365 CTRL1 0.3 21.30.8 1.4 .2 CTRL2 1.5 04.32.4 4.6 .6 SLAG1 1.5 37.73.8 3.8 .6 SLAG2 1.1 56.74.7 1.8 .5 SLAG3 6.0 14.33.1 3.0 .3 META1 1.3 53.19.5 3.1 .2 META2 32.77.3 3.2 0.0 .3 META3 22.94.8 4.5 3.0 .1 UFA1 22.65.0 5.0 3.4 .8 UFA2 21.12.2 4.9 3.9 .4 UFA3 24.11.4 3.6 2.5 .4 SF11.2 8.2 2.1 3.1 3.9 SF2 2.4 6.4 5.4 3.8 1.8 Table B r itial Series of Mixtures Mix 3day 7d 2 Flexural St ength for In ay CTRL1 3.1 2.4 CTRL2 4.7 8.9 SLAG1 4.6 5.5 SLAG2 3.2 2.4 SLAG3 3.4 9.2 META1 3.8 4.9 META2 5.0 7.2 META3 2.5 6.5 UFA1 11.2 3.5 UFA2 8.1 6.0 UFA3 1.6 6.3 SF1 3.9 4.1 SF2 6.1 4.9 136

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137 Table B 3 Flexural Strength for Second Series of Mixtures M3day 7day 365day ix C1.4 4.2 7.0 TRL1 C2.1 4.8 4.6 TRL2 S1.6 6.7 3.3 LAG1 S3.0 5.5 1.7 LAG2 S0.7 6.1 2.9 LAG3 M5.8 10.8 5ETA1 .2 M0.6 2.1 0ETA2 .7 M4.5 5.7 2ETA3 .1 U3.4 6.0 5FA1 .0 U5.6 9.1 7FA2 .8 U1.4 4.1 5FA3 .9 S1.0 4.8 6F1 .3 S1.7 7.9 7F2 .9 h day day28day 91day 365day Table B 4 Splitting Tensile Strengt Mix 3 7 CTRL1 26.2 9 2.0 1.2 3.5 3. CTRL2 16.6 .8 1.9 11.7 5.5 11 1 SLAG1 10.1 .2 6.7 12.4 15 13.1 SLAG2 11.1 .3 3.7 12.4 20.3 16 1 SLAG3 13.3 4 17.4 23.9 8. 10.4 META1 13.1 7 27.2 18.5 7. 14.6 META2 27.5 .4 9.6 2.8 47.4 16 META3 30.0 .9 1.1 23.8 45.7 15 2 UFA1 22.0 4 6.4 9.7 45.5 2. UFA2 20.2 .9 5.6 18.0 34.6 16 2 UFA3 18.4 .3 9.1 15.8 16 20.1 SF1 24.4 4 6.6 3.6 33.3 3. SF2 18.0 .3 4.3 19.1 37.1 12 1

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138 Table B 5 Linear Shrinkage, Volume of Voids Absorption, and Permeability Mix Shrinkage Voids Absorption CTRL1 12.1 4.1 4.9 CTRL2 6.1 2.6 2.5 SLAG1 13.2 2.4 1.3 SLAG2 27.0 2.3 1.7 SLAG3 6.4 1.7 1.9 META1 8.6 2.4 1.8 META2 20.2 3.7 1.9 META3 3.1 4.1 2.0 UFA1 4.6 2.3 2.0 UFA2 43.4 2.6 1.4 UFA3 36.7 1.4 1.9 SF1 17.6 2.1 1.8 SF2 6.0 2.9 2.8 Table B 6 Sulfate Expansion Mixture Concrete Expansion (%) Mortar Expansion (%) CTRL1 0.0179 0.0361 CTRL2 0.0143 0.0320 SLAG1 0.0158 0.0348 SLAG2 0.0147 0.0316 SLAG3 0.0260 0.0353 META1 0.0142 0.0254 META2 0.0137 0.0245 META3 0.0123 0.0250 UFA1 0.0167 0.0337 UFA2 0.0127 0.0297 UFA3 0.0083 0.0275 SF1 0.0102 0.0195 SF2 0.0100 0.0213

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139 Table B 7 Surface Resistivity 3 day 7 day 28 day 91 day 364 day CRTL1 2.2 2.0 7.0 3.6 0.4 CRTL2 5.1 2.6 4.1 4.9 0.9 SLAG1 4.3 5.6 8.0 5.7 9.3 SLAG2 2.2 3.3 6.1 8.7 2.8 SLAG3 4.8 3.2 7.9 8.1 6.8 META1 4.0 5.3 9.8 8.1 5.3 META2 1.4 4.7 3.5 7.1 3.6 META3 3.5 5.7 4.0 2.8 5.7 UFA1 3.4 3.0 5.8 7.2 2.8 UFA2 4.5 6.1 5.8 2.4 *0.0 UFA3 3.5 3.5 10.7 7.7 *0.0 SF1 1.6 11.9 5.3 *0.0 4.6 SF2 7.2 5.1 7.1 2.5 *0.0 Table B 8 Rapid Migration Test Mixture 28 56 91 CTRL1 7.8 28.4 25.1 CTRL2 8.6 7.9 27.3 SLAG1 9.2 17.8 34.1 SLAG2 30.0 3.9 30.0 SLAG3 0.5 8.2 36.4 META1 27.6 9.1 31.1 META2 26.2 42.5 46.4 META3 13.0 8.7 15.6 UFA1 11.0 38.1 11.2 UFA2 19.0 4.3 25.1 UFA3 20.1 15.3 19.8 SF1 33.6 5.2 92.9 SF2 1.3 46.4 33.4

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APPENDIX C LABORATORY MIX NORM ALIZED DATA Relative Cost Table C 1 Cost Cost ( $/Ton ) Cement 95 1.000 Fly Ash 42 0.442 Slag 90 0.947 Metakaolin 480 5.053 Ultrafine Fly Ash 1000 10.526 Silica Fume 600 6.316 Table C 2 Mechanical Tests Compressive Strength Flexural Strength Modulus of Elasticity Shrinkage CRTL1 1.000 1.000 1.000 1.000 CTRL2 0.956 1.092 0.993 0.917 SLAG1 0.978 1.049 0.905 0.852 SLAG2 0.986 1.043 0.914 0.685 SLAG3 1.065 1.132 0.914 0.750 META1 83 1.086 0.9 0.951 0.676 META2 0.974 1.056 1.008 0.583 META3 1.041 1.006 0.630 0.967 UFA1 0.988 1.084 0.921 0.917 UFA2 1.000 1.081 0.871 0.574 UFA3 0.989 1.091 0.912 0.537 SF1 0.979 1.108 0.934 0.796 SF2 0.974 0.987 0.926 0.704 140

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141 Table C 3 Durability Tests Surface Resistivity RMT Voids Absorption Sulfate Expansion CRTL1 1.000 1.000 1.0001.000 1.000 CTRL2 0.511 0.563 0.9930.997 0.886 SLAG1 0.360 0.303 0.9770.982 0.963 SLAG2 0.941 0.285 0.320 0.938 0.874 SLAG3 1.046 0.369 0.281 1.054 0.977 META1 0.208 0.1671.0821.096 0.666 META2 0.167 0.1361.0781.092 0.609 META3 0.149 0.1171.1191.131 0.715 UFA1 0.208 0.1411.0261.033 0.932 UFA2 0.181 0.2620.9991.005 0.729 UFA3 0.163 0.1301.0291.038 0.786 SF1 0.111 0.1430.9801.000 0.540 SF2 0.089 0.0920.9600.978 0.591 Table C 4 Summary Mechanical Durability Equation Mixture Cost Tests Tests Value CRTL1 00 1.000 1.000 1.000 1.0 CTRL2 0.900 0.989 0.790 0.881 SLAG1 0.886 0.946 0.717 0.826 SLAG2 0.787 0.884 0.907 0.672 SLAG3 0.881 0.965 0.745 0.847 META1 1.224 0.924 0.644 0.814 META2 1.305 0.905 0.616 0.801 META3 1.386 0.911 0.646 0.826 UFA1 1.852 0.977 0.668 0.910 UFA2 2.043 0.881 0.635 0.874 UFA3 2.233 0.882 0.629 0.891 SF1 1.272 0.955 0.555 0.786 SF2 1.378 0.898 0.542 0.768

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144 Parande, A. K., Babu, B. R., Karthik, M. A., Kumar, D., Palaniswamy, N., Study on Strength and Corrosion Performance for St eel Embedded in Metakaolin Blended rials, 2006. Personal Communication with Ch arles Ishee, January 29, 2005. Pfe., McDonald, D.B., Krauss, P.D ., The raploride permeability test and its correlation to the 90-day chloride ponding test. PCI Journal, 1994, 41(4), pp. Qian, X., Li, Z., The Relationship Between Stress and Strain for High-performance te with Maolin, Cem and Concrete Research, 2001, V. 31, pp. 16071611. Saraswathy, V., Song, H,. El ectrochel Studies on Corrosion Performance of Steel Embedded in Activated Fly Ash Bl ended Concrete, Electrochimica Acta, 51, pp.1-4611. Skalny, J., Marchand, J.,and Odler, I. (2002). Sulfate Attack on Concrete Spon Press, ork, Newk. Sioulas, B., Sanjayan, J. G., Hydration Temperatures in La rge High-strength Cconcrete Columns Incorporating Slag, Cemnt and Concrete Research, 2000, V. 30, pp. 799. Soongswang, P., Tia, M., Bloomquist, D., Mele tiou, C., and Sessions, L., Efficient Test for Determg the Watermeability ofcrete, Transportation Research Record, 1988, V. 1204, pp. 77-82. Stanish, K., Hooton, R.D., Thomas, M.D.A., T he Rapid Migration Test for HPC, HPC Bridge Views, Jan.-Feb. 2005, V. 37, pp. 3. Stre.E., Alexa M.G., A C onduction Test for Concrete. Cement and Concrete Research,1995, V. 25, pp. 1284-1294. Tang, L., Nilsson, L., Rapid Determination of the Chloride Diffusivity in Concrete by plying an Electrical Field. ACI Materials Journal, 1992, V. 89, pp. 49-53. Tang, L. (1996). Chloride Transport In Conc rete Measurement and Prediction, PhD Dissertation, Chalmers Un iversity of Technology, 1996. ., S oongwang, P., Meletiou, C. A., Amornsrivilai, P., Dobson, E., Richardson, D., Field and Laboratory Study of Modulus of ture and Permeability of Structural Concre te in Florida, Florida Department of Transportation Technical Report, 1990. Concrete and Mortar, Construc tion and Building Mate ifer, D.W id ch 82. Concre etak ent mica th e 2006, V 460 New Y Yor e 1791-1 Setup inin -Per Con icher, P nder, hlo ride C Ap Tia, M., Bloomquist, D., Yang. M. C. K Rup

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145 Tia, M., Bloomquist, D., Meletiou, C. Amornsrivilai, Shih, C., Richardson, D., Dobson, E., Extension of Field and Labor atory Study of Modulus of Rupture and ability of Structural Concrete in Florida, Florida Department of ortatchnepor1. Wa P. J. N., Influ f GroGranullastfurnace Slag (GGBFS) Additions and Time Delay on th e Bleeding of Concrete, Cement & te Composites, 2000, V. 22, pp. 253-257. Whiting, D., Mohamad, N., Electrical Resistiv ity of Concrete-A L iterature Review. d CeAsso on, 20&D S No. 2 Zongjin, L., Ding, Z., Property Improvement of Portland Cement by Incorporating with olinlag,ent a ncretearch,, V. 33, pp. 579-584. ., A Perme Transp ion Te ical R t, 199 inwright, Rey, The en ce o und ated B Concre Portlan ment ciati 03, R erial 457. Metaka and S Cem nd Co e Res 2003

PAGE 161

BIOGRAPHICAL SKETCH e and Ed Roske. He graduated from Sebastian Rive r High School in June of 2000. He received his Associate of Arts degree in May of 2002 from Indian River Community College, and tran the Uniity of Flor engineering in the summer of 2002. While attend ing the University of Florida full time, Edward worked part time for the Department of Civil Engineering, for three year as a research assistant Dr. Reynaldo Roque and Dr Andrew Boyd. He received his Bachelor of Science in civil engineering in May of 2005, graduating with honors. continuis educatiy entering uate school to pursue a Master of Engineering in the Materials Group of the Ci vil and Coastal Engineering Department in May 2005. After graduating form the Univer sity of Florida w ith a Master of Engineering, Edward plans on working with URS Corporation as a bridge design engineer. Edward K. Roske was born May 17, 1982 in Vero Beach, Florida, to Joyc sferred to vers ida to pursue a Bachelor of Science in civil Edward ed h on b grad 146


Permanent Link: http://ufdc.ufl.edu/UFE0020963/00001

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Title: Implementation of Highly Reactive Pozzolans in the Key Royale Bridge Replacement
Physical Description: Mixed Material
Copyright Date: 2008

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Holding Location: University of Florida
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Material Information

Title: Implementation of Highly Reactive Pozzolans in the Key Royale Bridge Replacement
Physical Description: Mixed Material
Copyright Date: 2008

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
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IMPLEMENTATION OF HIGHLY REACTIVE POZZOLANS IN THE KEY ROYALE
BRIDGE REPLACEMENT















By

EDWARD K. ROSKE


A THESIS PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF ENGINEERING

UNIVERSITY OF FLORIDA


2007




























2007 Edward K. Roske
































To my loving family (my mother Joyce Roske, my sister Tiere Roske, and my brother
Dustin Roske) as they have offered their unyielding love and support.















ACKNOWLEDGMENTS

I thank my supervisory committee members for their ideas and assistance. My

supervisory committee chair (Dr. H. R. Hamilton) provided his valuable time and

knowledge of the subject, as well as financial support, to make this research successful. I

thank Dr. Robert E. Minchin, Jr. and Dr. Mang Tia for their guidance and knowledge.

I thank Mike Bergin and Charles Ishee and their staff at the Florida Department of

Transportation for contributing knowledge, assistance, and funding. Special thanks go to

Richard Delorenzo for his tremendous knowledge and assistance in the laboratory

I would like to acknowledge Sal Depolis and Wayne Allick Jr. for their assistance

in laboratory testing. I also thank everyone in the Department of Civil and Coastal

Engineering who contributed time and effort to my study. They include Mahir Dham,

Christopher Ferraro, Samuel Smith, Tanya Reidhammer, Yu Chen, Beyoung II Kim and

Xiaoyan Zheng.

My deepest appreciation goes to Stephanie Lloyd for her continual support and

encouragement throughout the research and writing of this thesis.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ................................................................................................. iv

LIST OF TABLES ....................................................... ............ .............. viii

LIST OF FIGURES ......... ....... .................... .......... ....... ............ xi

ABSTRACT .............. ............................................. xiv

CHAPTER

1 IN TR O D U C TIO N ......................................................................... .... .. ........

2 L ITER A TU R E R E V IEW .................................................................... ....................3

Unhydrated Cem ent Chem istry ............................................................................. 3
H ydration Chem istry ........................ .................. ..... .................. 5
Cem ent H ydration ........................ ............ ..................... .......5.
Pozzolanic Reaction ................................................ ........ .............6
Effect of Cement and Mineral Admixtures on Concrete Properties..........................6
P ortland C em ent ................................................................... ............... .. 6
F ly A sh .......................................................... ................ 8
U ltrafine F ly A sh .............................................................. .............. .... 12
S la g ....................................................................................................... 1 5
M e ta k a o lin ...................................................................................................... 1 8
S ilic a F u m e .....................................................................................2 1

3 M IX D E S IG N ...........................................................................................2 5

M a te ria ls ..............................................................................2 5
B a sic In g re d ien ts ............................................................................................ 2 5
W a te r ..................................................................................................2 5
F in e aggreg ate ...........................................................2 5
C oarse aggregate ............................................... ............... 26
C e m e n t .................................................................................................... 2 6
M in eral A dm ix tu res........................................................................................ 2 7
F ly a sh ................................................................2 7
S la g ...........................................................2 8
U ltra-fine fly ash ............................................... ............... 28


v









M e ta k a o lin .............................................................................................. 2 9
S ilic a fu m e .............................................................................................. 3 0
C hem ical A dm ixtures .................................................................................... 31
Air entrainer ................................... ......... .................... 31
Water reducer/retarder................... ......... ............................ 32
Superplasticizer ......... .. ........... ........ ......... 32
P proportions .........................................................................................................33
Preparation of Concrete M ixtures........................................ ........................... 39
Specim en F fabrication ............................. .... ...................... .. ...... .... ..... ...... 4 1
C during C onditions.......... ..... ............................................................ ......... ....... 4 1
A additional M fixtures .............. .................. ................... ..... .. ........ .... 42

4 L A B O R A TO R Y TE STIN G ............................................................ .....................44

P plastic P properties T ests ............................................................................. ... .........44
D density (A STM C 138) ............................................... ............................ 44
Slu m p (A S T M C 14 3) .............................................................. .....................44
A ir C content (A STM C 173)........................................... .......................... 45
Bleeding of Concrete (ASTM C 232) ...................................... ............... 46
Tim e of Setting (A STM C 403).................................... ......................... 47
Tem perature (A STM C 1064) ........................................ ......... ............... 47
Mechanical Tests .......................................... ........ 48
Compressive Strength (ASTM C 39) ....................................... ...................48
Static Modulus of Elasticity and Poisson's Ratio (ASTM C 469)..................... 53
Splitting Tensile Strength (ASTM C 496)................................ ............... 55
D u rab ility T ests ......................................................... ................. 56
Linear Shrinkage (ASTM C 157) .. ......... ............ ............. 56
Volume of Voids (ASTM C 642)........ .......................... 57
Sulfate Expansion (A STM C 1012) ....................................... ............... 57
A bsorption (A STM C 642)............................................................. ..................58
Corrosion of Embedded Steel Reinforcement (ASTM G 109) ...........................59
Background Chloride Level (FM 5-516)................................................62
Surface Resistivity (FM 5-578) ... ................. ......... ...............62
Rapid M igration Test (N TBuild 492)............................................................... 63
W ater Perm ability (UF M ethod).................................................. .................65

5 RESULTS AND DISCU SSION ........................................... .......................... 68

P plastic P rop erties T ests ..................................................................... .................... 6 8
Mechanical Tests .......................................... ........ 71
Compressive Strength (ASTM C 39) ...................................... ............... 71
Flexural Strength (ASTM C 78)....................................................81
Modulus of Elasticity and Poisson's Ratio (ASTM C 469) ..............................89
Splitting Tensile Strength of Cylindrical Concrete (ASTM C 496)....................95
D u rab ility T ests ......................................................... ................. 96
Linear Shrinkage (ASTM C 157) ............... .... .................. 96
Volume of Voids and Absorption (ASTM C 642) .............. .. ............ 98









Sulfate Expansion (ASTM C 1012) ................................................... 99
Corrosion of Embedded Steel Reinforcement (ASTM G 109) .........................103
Surface Resistivity (FM 5-578) ....................................................................... 103
Rapid Migration Test (NTBuild 492)............... .....................................111
W ater Perm ability (UF M ethod)...................................................................117

6 SELECTION OF MIX DESIGNS FOR PILES ......................................................118

S election n A p p ro ach ........................................................................ .......... .. .... 1 18
Selection Criterion I: Cost ....... ........ ......... .................................. .... ........... 119
Selection Criterion II: Mechanical Properties .............................119
Selection Criterion III: D durability ........................................ ............... 120
Importance Factors .................. ............................ .......................121

7 CONCLUSIONS AND RECOMMENDATIONS ........................ ............... 123

APPENDIX

A LABORATORY MIX TESTING DATA ..................................... .................126

B LABORATORY MIX STATISTICAL DATA....................................................... 136

C LABORATORY MIX NORMALIZED DATA...................................................... 140

L IST O F R E F E R E N C E S ...................................................................... ..................... 142

BIOGRAPHICAL SKETCH ............................................................. ............... 146
















LIST OF TABLES


Table page

2 1Typical Oxides and Their Shorthand Notation............... .............. ................4

2 2 Typical Chemical Compounds and Their Shorthand Notation .................................4

2 3 Typical Chemical Compositions and Properties of ASTM Type I to V cements .......8

2 4 Summary Table Comparing Cube Strength (Jones et al 2006) .............................14

2 5 Percent Improvement of Ultrafine Fly Ash vs. Ordinary Fly Ash ..........................14

2 6 Slag A activity Index (A STM C 989) ............................................... .....................15

3 1 Proportions of Cementitious M materials a)...................................... ............... 36

3 2 Proportions of Cementitious M materials b) ...................................... ............... 36

3 3 M ix D designs a) (lb/yd3) ................................................. ................................ 37

3 4 M ix D designs b) (lb/yd3) ................................................. ................................ 37

4 1 Test Voltage and Duration for NTBuild 492.................................. .....................64

5 1 Plastic Properties .................................... .. .. .. ..... .. ............69

5 2 Average Compressive Strength at 365 days, Normalized 365 day Compressive
Strength to CTRL2, and 91 to 365 day Slope ..................................... ...............73

5 3 Modulus of Rupture, Compressive Strength, and Coefficient ..................................88

5 4 P oisson 's R atio .........................................................................95

5 5 Average Percent Length Change, COV, and Normalized (to CTRL1) Shrinkage
V alues at 32 W eeks of Age .................. ......... ......... ...............................97

5 6 Average Percent Void and Absorption, COV, and Normalized (to CTRL1) Void
and Absorption Values at 32 Weeks of Age ....................... ................99

5 7 Total Concrete and M ortar Expansion........... ........... ...................... ............... 102









5 8 Increase in Surface Resistivity Between Test Ages (%) ......................................105

5 9 Summary Table of Penetrability Category, Penetration Depth, Coulombs Passed
and Surface Resistivity ........................................... ... ........... ... .. ........ 110

5 10 Surface Resistivity (kQ -cm ) ........................................................ ............... 111

5 11 Decrease in M igration Coefficient (% ) .............. ........................ .................. 113

5 12 RM T and RCP relationship ..................................................... ...................115

5 13 RM T V alues (m m /V *hr) ....................................................................... 116

5 14 C oefficient of Perm ability .......................................................................... .. 117

6 1 Material Costs .............. ............ ........... .. ........... .......... 119

6 2 Normalized Mechanical Test Results............................................ .. ...............120

6 3 N orm alized Durability Test Results ............................................. ............... 121

6 4 Summary of Normalized Results and Equation Values .......................................122

A 1 Plastic Properties T ests ......... ................. ...................................... ............... 126

A 2 C om pressive Strength...... .. .................. ........................................ ............... 126

A 3 Flexural Strength for Initial Series of Mixtures................................. ...............127

A 4 Flexural Strength for Second Series of Mixtures ................................................127

A 5 A averaged Flexural Strength ........................................................................ ... ... 128

A 6 M odulus of E lasticity .............................................................................. ............128

A 7 Poisson's Ratio ......................... ......... .. .... ....... ............... 129

A 8 Splitting Tensile Strength ....................................................................... 129

A 9 Linear Shrinkage, Volume of Voids, Absorption, and Permability .....................130

A 10 Sulfate Expansion .................. ............................ ........................ 130

A 11 Surface R esistivity ..................................... ......... .. ...... .. ........ .... 131

A 12 R apid M migration Test ................................................... .... .. ............... .131

B 1 C om pressive Strength ............................................................................. ..... .......136

B 2 Flexural Strength for Initial Series of Mixtures..........................................136









B 3 Flexural Strength for Second Series of Mixtures........................ ............... 137

B 4 Splitting Tensile Strength .............................................. ............................. 137

B 5 Linear Shrinkage, Volume of Voids, Absorption, and Permeability......................138

B 6 Sulfate Expansion .......................................... .. .. ............... ....... 138

B 7 Su rface R esistiv ity ........ ...................................................... ........ .. .................... 139

B 8 Rapid M migration Test ....... .. .. .......................... ..................... ............... 139

C- 1 Cost ..............................................................................................................................140

C 2 M mechanical Tests .............................................. ... ............. .. .... .. 140

C 3 D durability Tests....................... ...... ...................... .... ............. .. .... .. 141

C 4 Su m m ary ............ ........... .. .......... .. ......................................14 1




































x
















LIST OF FIGURES

Figure page

3 1 R otary D rum M ixer ................................................................... ..... .....................40

4 1 DIAM -end Grinder .................. ...................................... ..... ... ............49

4 2 Test M ark L oad Fram e ........................................... .................. ............... 50

4 3 Diagram of the Third-Point Loading Flexure Testing Apparatus .............................52

4 4 Instron Load Frame Testing Flexural Strength ............. ........................................52

4 5 Modulus of Elasticity and Poisson's Ratio Test Setup on the TEST MARK
sy ste m ...................................... ................................................... 5 4

4 6 Splitting Tensile Strength Test on Forney Load Frame .........................................55

4 7 ASTM G109 Specimen Molds containing the Reinforcing Bars and Reference
Electrode ............. ..... ... ..................................... ......... 60

4 8 ASTM G109 Specimen After The Epoxy Has Been Applied........................60

4 9 Environmental Room Containing the Automated Monitoring Device and
C orrosion Specim ens......... ...................................................... ...... .. .. .... .... 6 1

4 10 Electrical Diagram of Corrosion Specimens ................................. ............... 61

4 11 Wenner Linear Four-Probe Array and Display ................................................. 63

4 12 RMT Test Setup...................... ............... ..... ............ 64

4 13 Cross-Section of Water Permeability Specimen Fixture.......................................67

4 14 W ater Perm ability Test Setup ................................................... ..................67

5 1 Compressive Strength of All Mixtures ........................ ............... ............... 72

5 2 Average Early Strength of Slag M ixtures....................................... ............... 74

5 3 Average Late Strength of Slag M fixtures ....................................... ............... 74









5 4 Average Early Strength of M etakaolin M ixtures ..................................................76

5 5 Average Late Strength of Metakaolin Mixtures.....................................................77

5 6 Average Early Compressive Strength of Ultrafine Fly Ash Mixtures.....................78

5 7 Average Late Compressive Strength of Ultrafine Fly Ash Mixtures ........................78

5 8 Compressive Strength of Silica Fume Mixtures ..................................................79

5 9 Compressive Strength of Silica Fume Mixtures ..................................................79

5 10 M odulus of Rupture of A ll M fixtures ............... ...... ..................................... ......82

5 11 Average Modulus of Rupture of Slag Mixtures ................................. ...............83

5 12 Average Modulus of Rupture of Metakaolin Mixtures ..........................................84

5 13 Average Modulus of Rupture of Ultrafine Fly Ash Mixtures ..............................85

5 14 Average Modulus of Rupture of Silica Fume Mixtures ............................ ....86

5 15 Average Modulus of Elasticity of All Mixtures ........................ ............... 90

5 16 Average Modulus of Elasticity of Slag Mixtures ......... ....................................91

5 17 Average Modulus of Elasticity of Metakaolin Mixtures................. ............. ...92

5 18 Average Modulus of Elasticity of Ultrafine Fly Ash Mixtures.............................93

5 19 Average Modulus of Elasticity of Silica Fume Mixtures ..................................94

5 20 Normalized Values of Sulfate Expansion: Concrete Specimens.........................100

5 21 Normalized Values of Sulfate Expansion: Mortar Specimens...........................101

5 22 Comparison of Mortar and Concrete Sulfate Expansion Specimens ..................103

5 23 Corrosion of Embedded Steel Reinforcement........................... 103

5 24 Average Surface Resistance of Slag Concrete Mixtures................................ 105

5 25 Average Surface Resistance of Metakaolin Concrete Mixtures............................107

5 26 Average Surface Resistance of Ultrafine Fly Ash Concrete Mixtures.................. 108

5 27 Average Surface Resistance of Silica Fume Concrete Mixtures.........................109

5 28 Average Migration Coefficient of Slag Mixtures...............................................112









5 29 Average Migration Coefficient of Metakaolin Mixtures.................. ............114

5 30 Average Migration Coefficient of Ultrafine Fly Ash Mixtures...........................14

5 31 Average Migration Coefficient of Silica Fume Mixtures.................................... 115

A 1 Relative Humidity in Dry Curing Room for a) 2005 and b) 2006........................132

A 2 Temperature in Dry Curing Room for a) 2005 and b) 2006................................132

A 3 Corrosion of Embedded Steel Reinforcement for a) CTRL1 and b) CTRL2.........132

A 4 Corrosion of Embedded Steel Reinforcement for a) SLAG1, b) SLAG2, and c)
S L A G 3 ............................................................................ 13 3

A 5 Corrosion of Embedded Steel Reinforcement for a) METAl, b) META2, and c)
M E TA 3 ............................................................... ..... ..... ......... 134

A 6 Corrosion of Embedded Steel Reinforcement for a) UFA1, b) UFA2, and c)
U F A 3 .................................................................................... 1 3 5

A 7 Corrosion of Embedded Steel Reinforcement for a) SF1 and b) SF2 ..................135















Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Engineering

IMPLEMENTATION OF HIGHLY REACTIVE POZZOLANS IN THE KEY ROYALE
BRIDGE REPLACEMENT

By

Edward K. Roske

May 2007

Chair: H. R. Hamilton III
Major: Civil Engineering

The objective of our study was to assess the use of alternative mineral admixtures

to improve the service life of bridges constructed in severe marine environments. Our

study evaluated the effects of highly reactive pozzolanic materials in conjunction with fly

ash on the plastic, mechanical, and durability properties of portland cement concrete.

Additionally, mixtures using these highly reactive pozzolans were designed for use in the

precast, prestessed piling for the Key Royale bridge replacement project.

Thirteen different trial mixtures were prepared using varying proportions of several

highly reactive mineral admixtures. Two of the thirteen were control mixtures; one

contained only portland cement and the other contained 18% fly ash. The remaining

eleven mixtures contained 18% fly ash with varying proportions of slag, metakaolin,

ultrafine fly ash, and silica fume.

Plastic property tests were conducted on temperature, air content, slump, bleeding,

and setting times. Mechanical test procedures included compressive strength, flexural









strength, splitting tensile strength, modulus of elasticity, and Poisson's ratio. Several

durability tests were performed including surface resistivity, rapid migration test, volume

of voids, absorption, water permeability, shrinkage, sulfate expansion, and corrosion of

embedded steel reinforcement.

Using results from the laboratory testing, we created a decision matrix to select the

relative mineral admixture proportions to be used to construct the piles. One mixture

from each group of mineral admixtures was selected. The decision matrix included

ratings for cost, mechanical properties, and durability. Although the costs of several

mixtures were considerably higher than the controls, each mixture showed an overall

improvement in mechanical and durability properties. Proportions determined to provide

the most effective mixtures were 30% slag, 10% metakaolin, 12% ultrafine fly ash, and

9% silica fume.

Based on the decision matrix, each mixture showed consistent mechanical

properties. The silica fume and metakaolin mixtures, however, performed the best

overall in the durability tests. Silica fume mixtures showed improvement in durability

over the cement only control ranging from 21 to 23%. Metakaolin also showed

improvements of 17 to 20%.









CHAPTER 1
INTRODUCTION

The Florida Department of Transportation (FDOT) has set a goal to build bridges

that will last at least 100 years. Currently, the acceptance criteria consist of measuring

the plastic properties, water-to-cementitious ratio and compressive strength. None of

these acceptance criteria can be used to predict the ultimate service life of the structure.

By performing more durability-related tests on local materials, the Department can

develop a better understanding of how long a structure can be expected to last.

Current design standards (2004 Structures Design Guidelines for Load and

Resistance Factor Design) allow only corrosion inhibitors or silica fume for reducing

permeability of the concrete. Silica fume is currently specified in Florida concretes under

certain conditions; "when the environmental classification is Extremely Aggressive due

to the presence of chloride in the water, specify microsilica in the splash zone of all piles,

columns or walls. Microsilica may be specified for the entire pile, column or wall but

shall not be specified for drilled shafts. The splash zone is the vertical distance from 4

feet below MLW to 12 feet above MHW." Under new specifications proposed by

AASHTO, other materials could be allowed in place of silica fume for concrete placed

under such conditions.

Mixtures containing highly-reactive pozzolans such as metakaolin and superfine fly

ash will provide similar strength as silica fume, while avoiding the detrimental

workability issues. Currently, the availability and cost of the highly reactive pozzolans

designated in this study are both better than for silica fume. However, newer materials

require investigation to determine which mixture design criteria should be implemented

in order to provide the desired service life to FDOT structures.









The present research evaluated the durability and mechanical properties of concrete

made with highly reactive pozzolans other than silica fume. Four of these concrete

mixture designs were selected for use in fabricating piles for a bridge structure to be built

in a severely aggressive environment. The field project was funded by the Federal

Highway Administration through their Innovative Bridge Research & Construction

(IBRC) program.

This investigation tested several alternative materials to provide the FDOT with the

means to assess the applicability for utilization in the splash zone of a Florida concrete in

a severely aggressive environment. These materials include slag, metakaolin, and

ultrafine fly ash. Research was conducted on the effects of implementing these highly

reactive pozzolanic materials in conjunction with fly ash to the plastic, mechanical, and

durability properties of portland cement concrete. Additionally, this study provided the

FDOT with a recommendation of the most effective mixtures containing various

pozzolans for the utilization in the piling of the Key Royale bridge replacement project.









CHAPTER 2
LITERATURE REVIEW

Presently, the Florida Department of Transportation (FDOT) only allows the use of

silica fume in the splash zone of concretes in a severely aggressive environment. There

are, however, several other mineral admixtures that provide an improvement in the

mechanical and durability characteristics of a concrete. Many researchers have presented

data relating to the effects of mineral admixtures on the plastic, mechanical, and

durability properties of a concrete. Therefore, this chapter presents a comprehensive

review of the currently available literature.

Unhydrated Cement Chemistry

Portland cement is a hydraulic cement which is typically produced by initially

heating limestone with clay in 2550 to 29000F kiln to produce clinker (Mindess et al.

2003). The clinker is then ground to a specific fineness. Small amounts of gypsum is

interground with the clinker to control the hydration rate of the finished cement product.

Shorthand notation used to represent the actual chemical formulas for oxides found

in cements and mineral admixtures are shown in Table 2 1. Chemical compounds that

are the major constituents in cement are formed from these oxides in the calcining

process of cement manufacturing. The chemical name, chemical formula and shorthand

notation for the five most abundant compounds are found in Table 2 2.









Table 2 1 Typical Oxides and Their Shorthand Notation
Common Name Chemical Formula Shorthand Notation
Lime CaO C
Silica Si02 S
Alumina A1203 A
Ferric Oxide Fe203 F
Magnesia MgO M
Alkali K20 K
Alkali Na20 N
Sulfur Trioxide SO3S
Carbon Dioxide CO2
Water H20 H


Table 2 2 Typical Chemical Compounds and Their Shorthand Notation
Chemical Name Chemical Formula Shorthand Notation
Tricalcium Silicate 3CaO-SiO2 C3S
Dicalcium Silicate 2CaO-Si02 C2S
Tricalcium Aluminate 2CaO-A1203 C3A
Tetracalcium Aluminoferrite 4CaO- A1203-Fe203 C4AF
Calcium Sulfate Dihydrate CaS042H20 CSH2
(gypsum)

Estimations of the quantity of these compounds can be made through Bogue

equations (Neville 1995). Bogue equations are used to predict the properties of cement,

such as rate of strength development and heat liberation. Moreover, manipulation of the

cement, based on results of these equations, can be made to modify certain properties to

make it more appropriate to a particular application (Mindess et al. 2003). The formula is

as follows.

Case A: A/F > 0.64
C3S = 4.071C 7.600S 6.718A 1.430F 2.852S
C2S = 2.867S 0.7544 C3S
C3A = 2.650A 1.692F
C4AF = 3.043F

CaseB: A/F < 0.64
C3S = 4.071C 7.600S 4.479A 2.859F 2.852S
C2S = 2.867S 0.7544 C3S
C3A = 0
C4AF = 2.100A + 1.702F









Each cement and mineral admixture is composed of some or all of these

compounds and oxides. A more detailed analysis of the typical compositions for each

material is discussed in the succeeding section.

Hydration Chemistry

The chemical reactions of pozzolans and cement hydration have been widely

studied in which a few commonly accepted equations have been established (Mindess et

al. 2003). These equations are presented in the subsequent sections for cement hydration

and pozzolanic reactions.

Cement Hydration

The hydration of the calcium silicates in portland cement produces calcium silicate

hydrate and calcium hydroxide. The C3S and C2S reactions are very similar, with the

only difference being the quantity of calcium hydroxide (CH) formed.

2C3S + 11H -, C3S2H8 + 3CH (2-1)

2C2S + 9H -, C3S2Hs + CH (2-2)

The composition of this calcium silicate hydrate product can vary widely-typically in

water content. Presented here, the product is in its saturated state. In contrast, CH has a

fixed composition.

Another hydration reaction occurs in the presence of sulfate ions supplied by the

dissolution of gypsum. These ions react with C3A to form a calcium sulfoaluminate

hydrate.

C3A + 3CSH2 + 26H -, C6AS3H32 (2-3)

The calcium sulfoaluminate hydrate is a stable hydration product commonly known as

ettringite. However, if there is an insufficient supply of sulfate ions present, the C3A will

not be completely hydrated. Ettringite will then be reacted with C3A to form another









calcium sulfoaluminate hydrate with less sulfate, commonly known as

monosulfoaluminate.

2C3A + C6AS3H32 + 4H 3C4ASH12 (2-4)

If a new source of sulfate ions comes in contact this monosulfoaluminate, ettringite is

able to be reformed:

C4ASH12 + 2CSH2 + 16H -- C6AS3H32 (2-5)

Pozzolanic Reaction

Pozzolan are not cementitious, but rather amorphous silica which will react with

CH and water to form a cementious product, C-S-H:

CH + S + H -- C-S-H (2-6)

If the silica content in the pozzolan is very high, a secondary reaction will occur:

C3S + 2S + 10.5H -- 3[CSH3.5] (2-7)

When the pozzolan has large quantity of reactive alumina, the CH will react with alumina

to form a calcium aluminate hydrate (C-A-H):

CH + A + H -- C-A-H (2-8)

Effect of Cement and Mineral Admixtures on Concrete Properties

Portland Cement

Portland cements are produced with a specific composition and fineness to ensure a

satisfactory performance for a particular application, such as high early strength or low

heat of hydration. ASTM created a cement classification to standardize cements so that a

more consistent product can be manufactured. These standardized cements are

designated ASTM Types I, II, III, IV, and V.

Before an explanation of how the standardized ASTM cements are produced,

knowledge of the hydration characteristics of cement compounds needs to be understood.









It is useful to know how the chemical compounds listed in Table 2 2 affect strength

development and rate of heat evolution. Calcium silicates provide most of the strength

development in a concrete. (Mindess et al. 2003) C3S react moderately to contribute

early strength development. In later ages, C3S will contribute to ultimate strength. The

reaction of C3S liberates a moderate amount of heat. However, because of its high

proportion in cement, its contribution to the overall heat liberation is high. C2S has a

much slower reaction and a low heat generation. Therefore, at early ages, C2S provides

very little strength development. However, its contribution to ultimate strength is high.

The hydration of C3A is a fast and highly exothermic reaction. Therefore, its contribution

to the overall heat liberation is very high. The hydration of C4AF is moderate and is

slowed by the presence of gypsum.

The ASTM Type I is the most commonly used cement, as it is general purpose. It

has average strength gain and heat of hydration. However, if a more specialized

application, such as sulfate resistance or high early strength development, is needed, a

different type should be selected. Type V cements was developed to combat sulfate

attack. Sulfate attack involves the hydration products formed from C3A. Therefore,

lowering the percentage of C3A will serve to increase the sulfate resistance of a cement.

Type III cement was developed to create a high early strength concrete. This was

accomplished by increasing the proportions of C3S or, more effectively, grinding the

cement finer. However, much heat is generated during the hydration process because of

the increase surface area of C3S. Therefore, this cement cannot be used where high

temperatures create adverse effects, such as in mass concrete, where thermal cracking can

become a problem. It is for this reason that Type IV was created. Type IV cement was









developed to create a low heat of hydration product. The proportions of the highly

exothermic compounds, C3A and C3S, were reduced. However, there are problems

associated with this cement also. Because of the lower C3S composition, this cement has

a slow strength gain; therefore, a Type II cement was developed. The C3S proportion

remains the same, while C3A is slightly lowered. This cement has a better strength

development, as well as being fairly sulfate resistant. Table 2 3 was recreated from

Mindess (et al. 2003), detailing typical chemical compositions and properties of ASTM

Types I to V cements.

Table 2 3 Typical Chemical Compositions and Properties of ASTM Type I to V
cements
I II III IV V
C3S 55 55 55 42 55
C2S 18 19 17 32 22
C3A 10 6 10 4 4
C4AF 8 11 8 15 12
CSH2 6 5 6 4 4
Fineness
(m2/kg) 365 375 550 340 380
(m2/kg)__________________________________

Fly ash

Fly ash is precipitated from the exhaust gases of a coal burning power station. The

majority of particles are spherical, glassy, and either hollow or solid in shape and have a

high fineness. Typically, particles have a diameter range of 1 [tm to 100 [tm and a

specific surface between 250 to 600 m2/kg (Neville 1995). The main components in the

composition of fly ash are oxides of silicon, aluminum, iron, and calcium. The varying

calcium content in fly ash composition led to the creation of ASTM C 618. This standard

created two classes of fly ash-Class C and Class F. ASTM C 618 requires a Class F fly

ash to be composed of a minimum of 70% silicon oxide (SiO2) plus aluminum oxide

(A1203) plus iron oxide (Fe203), while a Class C has a minimum of 50%. Derived from









the burning of subbituminus coal or lignite, Class C fly ash has a high lime (CaO)

content. Because of this, it is also slightly cementitious. Problems arise with high water

demand, early stiffening, and rapid setting. Class F fly ash is derived from the burning of

bituminous coal or anthracite. Its calcium content is lower than a Class C fly ash.

Because fly ash is a pozzolan, the silica and alumina will react with CH to form a

cementitious compound, C-S-H and C-A-H, respectively. The reactions depend on the

breakdown and dissolution of silica and alumina by the hydroxide ions and heat

generated by the hydration of portland cement. The glass material in fly ash is only

broken down when the pH value of the pore water is at least 13.2 (Neville 1995). In

other words, the fly as will consume CH and form a hydration product as long as enough

CH is present in the pore solution and there is sufficient void space present for the

hydration product to fill.

Fly ash influences the properties of a fresh concrete in a variety of ways.

Workability, bleeding, and time of setting are all affected by the addition of fly ash. For

the most part, the changes due to the addition of fly ash are because of the shape and size

of the particles and its chemical composition.

A reduction in water demand and an increase is workability is attributed to the

spherical shape of the particles. The particle shape reduces the interparticle friction

within the mixture, effectively increasing the workability. This also allows for a

reduction in water to keep the same workability for a concrete mixture. Neville (1995)

has found that another mechanism of fly ash may be dominant in decreasing the water

demand. The finer fly ash particle may become electrically charged and cover the

surface of the cement particles. He states that action deflocculates the cement particles,









thus reducing the water demand for a given workability. Another benefit of fly ash is the

small particle size, which allows them to pack between the cement particles. This is

known as particle packing; it reduces bleeding, lowers the mean size of the capillary

pores, and can reduce water requirements (Mindess et al. 2003).

The composition of fly ash also extends setting times and decreases the overall heat

liberated during hydration. Delayed setting times are ascribed to the slow pozzolanic

reactions of fly ash. As mentioned above, the glassy fraction of fly ash will only

breakdown when sufficient hydroxide ions are present in the pore solution. This process

takes place only after a certain amount of hydration of portland cement has taken place

(Neville 1995). A consequence of the delay in the cement hydration is the slow pattern

of heat evolution. Much of the heat is generated during the early stages of hydration of

the C3S and C3A within the paste. The delayed setting time allows the concrete to slowly

liberate the heat generated. In addition, when fly ash is used a cement replacement,

smaller quantities of the high heat generating compounds, C3S and C3A, are present.

Therefore, the overall heat of hydration is reduced.

Fly ash influences the properties of a hardened concrete in a variety of ways.

Compressive strength and rate of strength gain, modulus of elasticity, permeability,

sulfate resistance, and drying shrinkage are all affected by the addition of fly ash. For the

most part, the changes due to the addition of fly ash are because of the shape and size of

the particles and its chemical composition.

The rate of strength gain is reduced by the addition of a Class F fly ash. As

mentioned above, the pozzolanic reactions of fly ash depend on a high pH pores solution.

Because this takes time to occur, the early hydration of mixtures containing fly ash is









slow. Consequently, the early age compressive strengths are low. However, over time,

the Class F fly ash will react to produce a stronger concrete than that of the same mixture

containing only portland cement (ACI 232.2R-03). Conversely, Class C fly ash concrete

often exhibit higher rate of reaction at early ages, but lower strength gain at late ages

when compared to a Class F fly ash concrete (ACI 232.2R-03).

ACI (232.2R-03) has found that the effects of fly ash on the modulus of elasticity

are not as significant as the effects on compressive strength. Furthermore, they suggest

that cement and aggregate characteristics will have a greater effect on modulus of

elasticity that the use of fly ash. Similar to modulus of elasticity, creep strain is more

affected by compressive strength than fly ash. Lower compressive strengths result in

higher creep strains (ACI 232.2R-03).

The consequence of using the slow reacting fly ash is that the initial permeability is

higher than that of the same concrete containing only portland cement (Neville 1995).

However, over time the fly ash concrete will develop a very low permeability through

pozzolanic reactions (ACI 232.2R-03). CH is susceptible to leaching, leaving voids in

which deleterious solution can ingress. However, fly chemically combines with CH to

form a cementitious product, C-S-H. This action reduces the risk of leaching, and further

reduces permeability as the pore structure becomes occupied with C-S-H. Consequently,

the durability of a concrete exposed to aggressive environments containing sulfates and

chlorides is improved because of the reduction in permeability (Neville 1995). In

addition, sulfate resistance is further improved through the removal of CH (Mindess et al.

2003).









Ultrafine fly ash

Ultrafine Fly ash, similar to ordinary fly ash, is precipitated from the exhaust gases

of a coal burning power station. However, the larger particles are removed through filters

or separators. The majority of particles are spherical, glassy, and either hollow or solid in

shape and have a very high fineness. Boral (2003) states that the average particle

diameter is 3 [tm and the distribution of particle size is as follows:

* Minimum of 50% of particle sizes less then 3.25 microns

* Minimum of 90% of particle sizes less than 8.50 microns.

Little research has been conducted on the effects of ultrafine fly ash on the

durability and mechanical properties of a concrete. However, estimations on the behavior

can be made through relations with ordinary fly ash based upon chemical composition

and particle size.

The addition of ultrafine fly ash will influence the properties of a fresh concrete

similarly to ordinary fly ash. Differences in workability and bleeding from that of

ordinary fly ash are attributed to the smaller average particle size.

The higher surface area of the ultrafine particles increases water demand.

Therefore, the addition of ultrafine fly ash reduces workability when compared to

ordinary fly ash. However, workability is increased when compared to a cement only

mixture (Boral 2003). Bleeding is also affected by the particle size. The ultrafine fly ash

particles will pack between cement grains and aggregate. Consequently, the mixture is

more cohesive and a reduction in bleeding is achieved.

Jones (et al. 2003) conduced 72 hour heat of hydration experiments on 30%

ultrafine fly ash and 30% ordinary fly ash mixtures. Because of the retardation of C3A









hydration, the rate of heat evolution was impeded by 2 hours and 5 hours for the ordinary

fly ash and ultrafine fly ash mixtures, respectively. They have shown that both mixtures

lower the total heat of hydration when compared to the control. The ultrafine fly ash

mixture showed the lowest total heat until 18 hours. Beyond 18 hours, the ordinary fly

ash mixture had the lowest total heat.

Because the mineral composition is the same, ultrafine fly ash will have similar

chemical reactions to that of ordinary fly ash. However, because the average particle size

of ultrafine fly ash is much smaller, the reactivity will increase. Consequently, the

strength and durability on the concrete will be higher at early ages.

Boral (2003) has found that at 7 days there is an increase in strength activity index

of 107% of the control, and 124% at 28 days. Furthermore, they have conducted

compressive strength tests on 8% silica fume, 6% ultrafine fly ash, and 9% ultrafine fly

ash mixtures with the following characteristics: w/cm of 0.26 0.28, cement = 823

lb/yd3, and fly ash = 100 lb/yd3. They have shown that a 6% replacement of ultrafine fly

ash has nearly equal compressive strength at 7 and 28 days, and roughly a 5% increase at

91 days when compared to an 8% silica fume concrete. A 9% replacement showed

increases over the 8% silica fume concrete of roughly 6%, 8%, and 11% at 7, 28, and 91

days, respectively. Jones (et al. 2006) researched the effects of 15% and 30%

replacements of ordinary and ultrafine fly ash at a 0.50 w/cm on cube strength. They

found that at 28 days, the control mixture had the highest strength (Table 2 4). At 90

and 180 days, both ultrafine fly ash mixtures showed higher strength than the control,

while both ordinary fly ash mixtures were lower.









Table 2 4 Summary Table Comparing Cube Strength (Jones et al 2006)
% of Control
Mixture 28 day 90 day 180
day
Control 100 100 100
15% Ordinary 75 85 87
Fly Ash
30% Ordinary 54 30 64
Fly Ash
15% Ultrafine
96 116 110
Fly Ash
30% Ultrafine
87 102 104
Fly Ash

At each age, the ultrafine fly ash mixtures showed an improvement over the

ordinary fly ash (Table 2 5). Therefore, it is evident that the decreased particle size of

the ultrafine fly ash increases the strength development at early ages.

Table 2 5 Percent Improvement of Ultrafine Fly Ash vs. Ordinary Fly Ash
% of Ordinary Fly ash
Mixture 28 day 90 day 180
day
15% Ultrafine 27 36 39
Fly Ash
30% Ultrafine 61 45 64
Fly Ash

Research conducted by Boral (2003) has also shown that there is an improvement

in a concrete against chloride penetration. They found chloride diffusion coefficients for

8% silica fume, 8% ultrafine fly ash, and 12% ultrafine fly ash mixtures (0.40 w/cm) at

40 days and 2 years. At both ages, the ultrafine fly ash mixtures showed lower

coefficients when compared to the control. It appears that the 12% replacement showed

slightly better results that the 8% mixture. However, neither ultrafine fly ash mixture had

lower coefficients than the silica fume mixture.

Jones (et al. 2003) researched the effects of 30% replacement of ordinary fly ash

and ultrafine fly ash on the total CH content within a mixture. They found that from age









of 3 days to 90 days, the ultrafine fly ash mixtures showed a lower CH content when

compared to the ordinary fly ash mixtures. This indicates that ultrafine fly ash is more

reactive and has consumed more CH through pozzolanic reactions

Slag

Blast furnace slag is the residue wastes formed from the production or refinement

of iron. Slag is removed from the molten metal and rapidly cooled. The raw slag is then

dried and ground to a specific fineness so that it can be used as a cement replacement.

ASTM C 989 provides three grades for slag based upon its relative strength to a reference

mortar made with pure cement (Table 2 6).

Table 2 6 Slag Activity Index (ASTM C 989)
Designation 7 day (%) 28 day (%)
Grade 80 --- 75
Grade 100 75 95
Grade 120 95 115

Typically, silica, calcium, aluminum, magnesium and oxygen constitute over 95%

of the chemical composition (ACI 233R-03). Because of the high lime content, slag is a

hydraulic admixture, meaning it will react with water to form a cementitious compound.

The addition of slag in a fresh concrete increases the workability, but make it more

cohesive. This is attributed to the better dispersion of cementitious particles and of the

surface characteristics of the slag particles (Neville 1995). ACI (233R-03) has found that

the smooth, dense surfaces of the slag particles absorb little water and act as slip planes in

the paste.

Neville (1995) has suggested that slag leads to retardation of setting times at

normal temperatures of typically 30 to 60 minutes. ACI (233R-03) has found that setting

times of slag mixtures is significantly affected by portland cement setting characteristics









and the amount of portland cement within the mixture. They state that setting times are

delay when more than 25% slag is used as a replacement.

Bleeding is reduced when slag is ground to a high fineness (Neville 1995). ACI

(233R-03) supports this statement. They suggest that if slag is ground to a higher

fineness than the cement particles and is replaced on an equal-mass basis, bleeding may

be reduced; conversely, if the slag particles are larger, the rate and amount of bleeding

may increase.

The addition of slag in a mixture increases the silica content and decreases the total

lime content. Consequently, more C-S-H is produced resulting in a microstructure that is

denser than that of a cement only mixture (Neville 1995). However, the rate of strength

gain is initially very slow because of the presence of impervious coatings of amorphous

silica and alumina on the slag particles (Mindess et al. 2003). These coatings are broken

down in a slow process by hydroxyl ions that are released during the hydration of the

portland cement (Neville 1995).

ACI (233R-03) has found that when compared with a portland cement only

concrete, the use of Grade 120 slag typically reduces the strength at ages before 7 days; at

7 days and later, Grade 120 slag increases strength. Grade 100 slag reduces strength at

ages less than 21 days, while producing equal or greater strength at later ages. Grade 80

slag shows lower strength at ages less than 28 days, and comparable strength at 28 days

and later.

Modulus of rupture is generally increased with the addition of slag at ages beyond

7 days (ACI 233R-03). They suggest that the improvement in modulus of rupture is

because of an increased density of the paste and improved bond at the aggregate-paste









interface. Neville (1995) has stated that the incorporation of slag does not significantly

alter the usual relations between compressive strength and modulus of rupture.

ACI (233R-03) has suggested that water cured slag concretes have do not have an

effect of modulus of elasticity at early ages; however, at later ages, modulus is increased.

Conversely, air cured specimen exhibited reductions in modulus. This is attributed to

inadequate curing. Mindess (et al. 2003) has found that modulus of elasticity is most

dominantly affected by porosity. Therefore, prolonged moist curing is particularly

important in a slag concrete in which the low early hydration results in a system of

capillary pores which allow for the loss of water under dry conditions (Neville 1995).

Consequently, hydration is halted, leaving a porous concrete. Consequently, modulus of

elasticity is reduced.

This compound adds to the strength of the mix, while also increasing durability by

decreasing the interconnectivity of the voids. In addition, the high silica and alumina

content promote pozzolanic reactions. The CH produced from cement hydration will be

consumed and transformed into more cementitious compounds. These compounds are in

the forms of C-S-H or C-A-H, depending on whether the reactive compound was silica or

alumina. These new hydration products are denser and more homogenous than that

produced by cement hydration alone.

At early ages, the incorporation of slag in a mixture will increase shrinkage;

however, at later ages shrinkage and creep are not adversely affected (Neville 1995).

ACI (233R-03) supports the statement in which there is no significant affect on shrinkage

or creep.









The heat of hydration has been found by ACI (233R-03) to be lower in a 75% slag

replacement concrete than in a 30% fly ash concrete or cement only concrete. Slag

reduced the early rate of heat generation and lowered the peak temperature.

One benefit of the addition of slag into a concrete arises from the denser

microstructure of hydrated cement paste in which more of the pore space is filled with C-

S-H than in a cement only paste (Neville 1995). As a result, the permeability is

decreased. ACI (233R-03) has found that as the slag content increases, the permeability

decreases. Consequently, the resistance to sulfate attack is increased. The resistance to

sulfate attack is further increased through consumption of CH, the major component in

sulfoaluminate corrosion (Mindess et al 2003). ACI (233R-03) found that 50% blends of

slag with a Type I concrete had the same sulfate resistance as a Type V cement concrete.

They have found that the use of slag in a well hydrated concrete reduces the penetrability

of chloride ions and the depth of carbonation. However, Neville (1995) has a conflicting

opinion in regards to improvements in depths of carbonation with the addition of slag.

He states that the slag can have a detrimental effect at early ages when there is very little

CH present in the concrete. Because of the decreased presence, CH cannot react with

carbon dioxide to form calcium carbonate in the pores. Consequently, the depth of

carbonation is significantly greater than in a concrete containing only cement.

Conversely, the reduced permeability of slag concrete at later ages prevents continued

increases in depth of carbonation.

Metakaolin

Metakaolin is manufacture by calcining clay at high temperatures. This results in a

material that is largely composed of highly reactive amorphous aluminosilicates.

Mindess (et al. 2003) has reported that, typically, the reactive silica and alumina content









in metakaolin ranges from about 55% and 35 to 45%, respectively. The particles are

plate-like and have an average size of 1 to 2 [tm, with a surface area of about 15 m2/g.

ACI (232.1R-00) has reported an average size of highly reactive metakaolin to range

from 1 to 20 [tm. Through pozzolanic reactions, CH will react with both silica and

alumina to form a cementitious hydration product. These can be in the form of C-S-H or

C-A-H, depending on whether the reactive compound is silica or alumina, which are

denser and more homogenous than that produced by cement hydration alone. (Mindess et

al. 2003).

Zongjin and Ding (2003) have found that a 10% blend of metakaolin reduces the

fluidity of the mixture. They have shown that the water demand was increased by

roughly 11%, which is attributed to the plate-like particle shape and its tendencies to

absorb water. Setting times were also shown to decrease by 26% and 36% for initial and

final setting times. ACI (232.1R-00) has reported lower adiabatic temperatures for 15

and 30% metakaolin replacements over a cement only concrete. Conversely, a 10%

replacement showed higher temperatures when compared to the control.

ACI (232.1R-00) has shown improvements in compressive strength of 0.3 and 0.4

w/cm concretes with blends of 8 and 12% metakaolin. At ages up to 45 days, each

metakaolin mixture showed higher compressive strengths; compressive strength

increased as proportion increased and w/cm decreased. Badogiannis (et al 2005)

researched the strength development of 0.4 w/cm concrete with metakaolin replacements

rates of 10% and 20%. Compressive strength was tested at ages of 1 to 180 days. They

have shown that, at these ages, a 10% replacement will increase the compressive strength.

However, 20% replacement has shown that the compressive strength was not higher than









the control until ages of 7 days and later. In addition, the 20% replacement concrete

showed lower compressive strength than the 10% blend at all ages.

Kim (et al. 2007) conducted research on metakaolin blends of 5, 10, 15, and 20%.

They have shown that there is no significant effect on the flexural strength or splitting

tensile strength for replacement levels of 5 to 15%. However, their appears to be slight

decreases in strength in the 20% blends at ages less than 28 days.

ACI (232.1R-00) has reported improvements in chloride penetration resistance for

both 0.3 and 0.4 w/cm concretes with an 8 and 12% blend of metakaolin. Furthermore,

they state that the 12% replacement improved the chloride penetration resistance more

than reducing the w/cm from 0.4 to 0.3 in a concrete containing no metakaolin. By

reducing the w/cm from 0.4 to 0.36, chloride permeability values for a 10% metakaolin

concrete were reduced. Research conduced by Kim (et al. 2007) supports the findings by

ACI, in which increasing metakaolin contents (5 to 20%), reduce chloride ion

penetrability at 28, 60, and 90 days. They have also reported on the effects of increasing

metakaolin contents on the depth of carbonation. They have found that increasing

metakaolin contents will increase the depth of carbonation at age of 7, 14, 28, and 56

days. This data suggests that decreased in CH present in the concrete because of the

pozzolanic reaction with the additional metakaolin can have a detrimental effect.

Because of the decreased presence, CH cannot react with carbon dioxide to form calcium

carbonate in the pores (Neville 1995). Consequently, the depth of carbonation is

significantly greater in the metakaolin concretes than in a concrete containing only

cement. However, the reduced permeability of metakaolin concrete at later ages prevents

continued increases in depth of carbonation.









Silica Fume

A by-product of producing silicon metals or ferrosilicone alloys, silica fume is

highly reactive pozzolanic material that is commonly used as a cement replacement in

concrete. Escaping gases condense to form a large quantity of highly amorphous silicon

dioxide, typically 85 to 98% by weight (ACI 234R-06). Its particle size is very small,

typically 0.1 to 0.33tm with a surface area of 15 to 25 m2/g, and spherical in shape

(Mindess et al 2003). Silica fume comes is four major forms: as produced, slurried,

densified, and pelletized.

Because of the large surface area, silica fume has a higher water demand which

must be offset in low w/cm mixtures with a superplasticizer (Neville 1995). However, he

has found that the effectiveness of the superplasticizer is enhanced in a silica fume

mixture. This is because of its spherical shape and small particle size which allow it to

pack between cement particles and act as a lubricant (Mindess et al. 2003). Further

benefit of the small silica fume particles packing between cement grains is the reduction

in bleeding (Neville 1995). ACI (234R-06) has stated that bleeding is reduced as the

content of silica fume is increased because there becomes very little free water available

to bleed.

Typically, air entraining admixture in a silica fume concrete must be increased by

125 to 150% than in a similar concrete with cement only (ACI 234R-06). This has been

attributed to the high surface area of the particle (Neville 1995).

ACI (234R-06) has found that there is no significant delay in setting time.

However, they have shown that there is an increase in heat of hydration. Peak

temperatures increase with higher contents of silica fume because of its interactions with

C3S. Silica fume tends to accelerate the exothermic hydration of C3S; consequently,









more CH is produced. In-turn this action starts the pozzolanic reaction with the silica

fume, which further increases the concrete temperature. However, they have also

suggested that the total heat is somewhat decreased as the increase in silica fume dosage.

The effect of silica fume on the hardened properties is directly a function of the

pore structure, cement paste-aggregate transition zone, and chemical composition (ACI

234R-06). As hydration continues, the pore structure becomes more homogenous and

capillary pores sizes are reduced and become disconnected (Neville 1995). However,

ACI (234R-06) has found that total porosity is largely unaffected by silica fume at all

w/cm.

Mindess (et al.2003) has found that the cement paste-aggregate zone, or interfacial

transition zone (ITZ), is composed of less C-S-H, has a higher localized w/cm and

permeability, and contains large crystals of CH and ettringite. They have stated that

silica fume greatly improves the ITZ by eliminating large pores and making the structure

more homogeneous, eliminating the growth of CH or transforming the already present

CH to C-S-H by pozzolanic reaction, and altering the theological properties of a fresh

concrete by reducing internal bleed because the small size of the silica fume particles

allow it to pack between cement particles and aggregate.

ACI (234R-06) has found that concretes made with silica fume exhibit higher

compressive strengths at earlier ages, up to 28 days. They have also found that there is

minimal contribution to compressive strength after 28 days. Neville (1995) has found

that the behavior of silica fume beyond the age of 3 months depends on the moisture

conditions. In wet cured conditions, he supports ACI in which the silica fume concrete

showed only a small increase in compressive strength for up to 3.5 years of age.









Conversely, under dry conditions a retrogression of strength, typically 12% below the

peak at 3 months, was observed. These findings indicate the tendencies of a silica fume

concrete to self-desiccate. Therefore, adequate curing is essential for a full development

of strength.

The trends of the development of compressive strength to flexural and splitting

tensile strength of a concrete made with silica fume is similar to that of a cement only

concrete (ACI 234R-06). In other words, as compressive strength increases, the tensile

strength also increases, but a decreasing ratio. They have found that a 20% silica fume

had a compressive to flexural strength ratio that ranged from 0.13 to 0.15. They have

also found splitting tensile strength at various ages to range from 5.8 to 8.2% of the

compressive strength.

As mentioned before, the use of silica fume results in a refinement of the pore

structure. Consequently, silica fume reduces the permeability of not only the paste, but

also the ITZ (Neville 1995). He found that a 5% replacement of silica fume resulted in a

reduction of the coefficient of permeability by 3 orders of magnitude. Conversely, ACI

(234R-06) has found that a 5 to 12% silica fume replacement resulted in only a 1 order of

magnitude reduction in permeability, in which no statement of w/cm was reported.

However, they have also found that for a 0.20 w/cm concretes containing 10 and 20%

silica fume, showed coefficient of permeability of 3*10-13 and 0.3*10-13, respectively.

The control showed a higher permeability at 12*10-13

A consequence of reduced permeability is the greater resistance to chloride

penetration (Neville 1995). ACI (234R-06) has found that an 8% substitution in a 0.40

w/cm concrete resulted in a reduction in diffusion coefficient by a factor of seven.






24


Furthermore, addition rates above 8% resulted in little additional improvement to

resistance of chloride penetration. Reduced permeability is the primary mechanism in

which silica fume increases the resistance to sulfate attack by sodium sulfate (ACI 234R-

06). However, an additional increase in sulfate resistance occurs from the pozzolanic

reactions with silica fume as there is a large consumption of CH, the major component in

sulfoaluminate corrosion (Mindess et al 2003).









CHAPTER 3
MIX DESIGN

This chapter discusses the materials and proportions used in the concrete mixtures

that were evaluated in this investigation. Preparation of the concrete mixtures, specimen

fabrication, and curing conditions are also described.

Materials

The materials used in the concrete mixtures are described in the following sections.

These constituents can be divided into three categories: Basic Ingredients, Mineral

Admixtures, and Chemical Admixtures.

Basic Ingredients

There exist a few materials that can be found within all of the concrete mixtures in

this investigation. These ingredients are water, fine aggregate, coarse aggregate and

cement.

Water

The water used in the concrete mixtures was obtained from the local city water

supply.

Fine Aggregate

Silica sand from pit number 11-067 was used as fine aggregate in all concrete

mixtures. The sand from this pit was tested and passed the gradation requirements of

Section 902 of the 2004 Florida Department of Transportation Standard Specification for

Road and Bridge Construction (FDOT Spec.). Additional testing of the sand determined

a fineness modulus of 2.39 and a bulk specific gravity of 2.65, which were used in the

mixture design to calculate yield. Specific test results on the fine aggregate are provided

in Appendix A.









This sand was placed into cloth bags and dried in the oven until all moisture was

removed. Prior to integration in the concrete mixtures, the sand was allowed to cool to

the ambient temperature.

Coarse Aggregate

Crushed limestone from pit number MX-41 lwas used as the coarse aggregate in all

concrete mixtures. The aggregate from this pit was tested and passed the gradation

requirement of Section 901 in the FDOT Spec. for a 34-in. maximum diameter aggregate.

Additional testing of the limestone determined a bulk specific gravity of 3.61, which

were used in the mixture design to calculate yield and adjust for moisture content.

Specific test results on the fine aggregate are provided in Appendix A.

The coarse aggregate was used in its approximate saturated surface dry (SSD)

condition. This SSD condition was obtained by filling woven polypropylene bags with

coarse aggregate. The bags were then submerged in water for a minimum of 48 hours to

fully saturate the aggregate. One day prior to mixing, the coarse aggregate bags were

removed from the water and allowed to drain for approximately one hour.

Cement

Type II portland cement manufactured by Holcim in the Theodore plant was used in each

mixture. This cement complied with Section 921 of the 2004 FDOT Spec. Tests showed

that the cement had an initial set time of 140 minutes, and a final set time of 215 minutes.

This information is useful when determining the effects of the mineral admixtures and set

retarding chemical admixture on a mixture. Additional test results are provided in

Appendix A.









Mineral Admixtures

Evaluating highly reactive mineral admixtures was an integral part of this research.

The following sections describe the individual admixtures used along with its source and

role in the modification of fresh and hardened concrete properties. General information

was obtained from Mindess (et al. 2003).

Fly ash

Fly ash is the waste product from the burning of pulverized coal in boiler furnaces

used to generate electricity at power stations. It is commonly used as a cement

replacement in concrete. In addition to the obvious environmental advantages, use of

concrete containing fly ash is advantageous because of the cost, particle size and shape

and mineral composition. The cost of fly ash is typically slightly less than half that of

portland cement. The spherical shape of fly ash particles increases workability, which

allows a lower water to cementious material (w/cm) ratio to be used. In addition, the

small particle size increases the packing density of the cementitious system. Thus, the

permeability through interconnected voids is reduced, further improving durability. The

mineral composition is also advantageous because of the high volume of reactive silica.

This silica allows for a pozzolanic reaction to consume calcium hydroxide (CH) and

creates more calcium aluminate silicate hydrates (C-S-H), which forms a denser paste

structure.

A class F fly ash meeting the requirements of ASTM C 618, AASHTO M-321, and

AASHTO M-295 was used in this investigation and was obtained from the Big Bend

Power Station in Tampa, Florida. The fly ash also complied with Section 929-2 of the

2004 FDOT Spec. This class F fly ash satisfies the requirements of ASTM C-618 and

AASHTO M-295. Specific tests results are provided in Appendix A.









Slag

Blast furnace slag is the residue wastes formed from the production or refinement

of iron. Slag is removed from the molten metal and rapidly cooled. The raw slag is then

dried and ground to a specific fineness so that it can be used as a cement replacement.

Slag is advantageous for its chemical composition; it is rich in lime, silica, and alumina.

Because of the high lime content, slag is a hydraulic admixture, meaning it will react with

water to form a cementitious compound. This compound adds to the strength of the mix,

while also increasing durability by decreasing the interconnectivity of the voids. In

addition, the high silica and alumina content promote pozzolanic reactions. The CH

produced from cement hydration will be consumed and transformed into more

cementitious compounds. These compounds are in the forms of C-S-H or C-A-H,

depending on whether the reactive compound was silica or alumina. These new

hydration products are denser and more homogenous than that produced by cement

hydration alone.

CAMCEM, produced by Civil and Marine (Holdings) Ltd., is a Grade 100 ground

granulated blast furnace slag used in this study. The slag complied with Section 929-5 of

the 2004 FDOT Spec by meeting the requirements of ASTM C 989. Specific tests results

are presented in Appendix A.

Ultra-fine fly ash

Ultra-fine fly ash is the same material as regular fly ash. However, it has been

sieved to greatly reduce the average particle size. The advantage of using an ultrafine fly

ash over a standard fly ash is because the particle size is typically four times smaller; the

small particles increase reactivity by increasing surface area, resulting in higher early

strengths and lower permeability than a standard fly ash mixture of the same proportions.









In addition, smaller particles have the ability to pack between the cement grains and

aggregate creating a less permeable paste structure by reducing the interconnectivity of

the voids.

The ultra-fine fly ash used in this investigation was Micron3, a product of Boral

Material Technologies. The typical mean diameter of Boral's Micron3, is 3.0 tm. As

certified by Boral Material Technologies Inc., the distribution of particle size measured

by a laser particle size analyzer is as follows:

* Minimum of 50% of particle sizes less then 3.25 microns

* Minimum of 90% of particle sizes less than 8.50 microns.

This class F fly ash satisfies the requirements of AASHTO M-321, ASTM C-618, and

AASHTO M-295. The ultra-fine fly ash complied with Section 929-2 of the 2004 FDOT

Spec. Specific test data are presented in Appendix A.

Metakaolin

Metakaolin is manufacture by calcining clay at high temperatures. This results in a

material that is largely composed of highly reactive amorphous aluminosilicates.

Therefore, metakaolin is advantageous for use as a cement replacement because of this

chemical composition. Typically, the reactive silica and alumina content in metakaolin is

over 85%. Through pozzolanic reactions, CH will react with both silica and alumina to

form a cementitious hydration product. These can be in the form of C-S-H or C-A-H,

depending on whether the reactive compound is silica or alumina. These new hydration

products are denser and more homogenous than that produced by cement hydration alone.

In addition to the composition, the small particle size of metakaolin is advantageous.









With a typical particle size of 1.4 atm, particle packing will occur to create a less

permeable paste structure by decreasing the interconnectivity of the voids.

The metakaolin used for this study was OPTIPOZZ, manufactured by Burgess.

The requirements of ASTM C 618 Class N were met with a few modifications proposed

by the FDOT Spec.:

* The sum of silica, iron, and alumina oxides was 87.9%.

* The loss on ignition was 0.8%.

* The percentage of available alkalis was negligible.

* The strength index at 7 days was 96%.

* Tests on the concrete containing metakaolin included ASTM C 39, ASTM C 157,

ASTM C 1012, ASTM G 109, and FM 5-516.

Therefore, the metakaolin complied with Section 929-4 of the 2004 FDOT Spec.

Specific test results are presented in Appendix A.

Silica fume

Silica fume is the byproduct of producing silicon metals or ferrosilicon alloys. It is

commonly used as a cement replacement in concrete because of its size, shape, and

chemical composition. The spherical shape of silica fume decreases interparticle friction.

This increases workability, thus allowing a lower w/cm while maintaining the same

slump. The small size, typically 0.1 to 0.3atm, allows the silica fume particles to pack

between cement grains. These particles will pack between cement grains, and decrease

segregation and bleeding while reducing permeability by reducing the interconnectivity

of the voids. In addition to the benefits related the shape and size of the particles, the

chemical composition of silica fume is also advantageous. The extremely high reactive









silica content, typically 85-98%, will allow for large volumes of CH to be converted into

C-S-H. Also, because the silica content is so high, a secondary pozzolanic reaction will

occur that converts tricalcium silicate (C3S) to a C-S-H product. These reactions will

create a stronger, more homogenous paste matrix.

Force 10,000 D, produced by W. R. Grace & Co., was used as the silica fume in

this investigation. It is a dry, densified microsilica powder made from silica fume. The

silica fume is densified by air floatation in silos. The tumbling action induces

progressive entanglement of particle to form dense clusters. These clusters allow for

much easier transporting and handling, in contrast to the original form. Force 10,000 D

complied with Section 929-3 of the 2004 FDOT Spec by meeting the requirements of

ASTM C 1240. Specific test data is presented in Appendix A.

Chemical Admixtures

Air entrainer

Air entraining admixtures are composed of an aqueous solution of neutralized resin

acids and rosin acids in which the molecules have ends that are hydrophilic and

hydrophobic. In other words, one end of the molecule is attracted to water, while the

other end is repelled by water. This behavior causes the molecules to attach to air

bubbles within a fresh concrete mixture forming a tiny, stable bubble that is disconnected

from other bubbles. The advantages of having a disconnected air void structure is

because it will increase the resistance of a concrete to freezing and thawing cycles,

improve the workability and cohesiveness of a fresh concrete mixture, and reduce

segregation and bleeding (Mindess et al. 2003). Because Florida concretes are not

exposed to freezing and thawing cycles, the addition of air entraining admixture in this

investigation was to increase workability and decrease segregation.









The air entrainer used in this study was Daravair 1000, produced by W. R. Grace &

Co. This admixture complied with Section 924 of the 2004 FDOT Spec by meeting the

requirements of AASHTO M 154.

Water reducer/retarder

Set retarding admixtures are typically composed of a polymer based aqueous

solution of lignosulfonate, amine, and compound carbohydrates. These carbohydrates

extend the setting time of fresh concrete mixture by slowing down the rate of early

hydration of C3S and C3A. A set retarding admixture was used in this investigation

because of the large number of test specimen fabricated from each mixture. By

increasing the setting time, all specimens were able to be properly consolidated before

mixture began to harden.

WRDA 60, produced by W. R. Grace & Co., was the set retarding admixture used

in this investigation. WRDA 60 complied with Section 924 of the 2004 FDOT Spec by

meeting the requirements of AASHTO M 194.

Superplasticizer

Surface charges on particles within a fresh concrete will cause flocculation. A

considerable amount of water is usually tied up in these agglomerations, leaving little

available to reduce the viscosity of the paste. The addition of a superplasticizing

admixture, which is typically composed of an aqueous solution of carboxylated

polyether, will serve to break up the bonds found between particles. This releases the

available water within the mixture, thereby increasing workability. This increase in

workability then allows for a decrease in water to cementitious material ratio.

Consequently, the strength and durability of a mixture is improved.









The superplasticizer used in this study was ADVA 140, a product ofW. R. Grace

& Co. It complied with Section 924 of the 2004 FDOT Spec. by meeting the

requirements of AASHTO M 194.

Proportions

Selection of the mix proportions and other mix design parameter for bridges in

Florida is based on the local environment. The Structures Design Guidelines (July 2005)

defines three exposure conditions:

* Slightly Aggressive

* Moderately Aggressive

* Extremely Aggressive.

For substructure elements, such as piling, the environment classification is a function of

the chloride content or pH level of the surrounding soil or water. Higher chloride

content, lower pH, or both will result in a more aggressive environment and a more

restrictive rating.

If prestressed concrete piles are used in an extremely aggressive environment that is

due to elevated chlorides in a marine environment, then silica fume must be used in the

concrete mixture. The object of this research was to evaluate the use of other highly

reactive mineral admixtures on the fresh and hardened properties of concrete. These

admixtures included slag, ultrafine fly ash, metakaolin, and fly ash.

Prestressed concrete piling must use Class V (Special) or Class VI concrete for any

environment. Class V (Special) is the mix design typically specified and has the

following characteristics:

* Maximum water to cement ratio of 0.35









* Minimum total cementitious material content of a 752 lb/yd3

* Air content range of 1 to 5%

* Target slump of 3 inches, which may be increased to 7 inches when a water reducing

admixture is used.

When the piles are in a moderately or extremely aggressive environment, the use of fly

ash, slag, or both is required. Fly ash cement replacement rate is 18% to 22%, while slag

is 25% to 70% for moderately aggressive and 50% to 70% for extremely aggressive

environments.

Larsen and Armaghani (1987) found that the most effective addition rate of fly ash

was between 18% and 22%. They found the rate in excess of this range caused the

additional mineral admixture to stop reacting and essentially become fillers.

Furthermore, rates below this range caused no significant improvement in durability.

Consequently, the FDOT Spec. adopted this range and now requires the use of fly ash in

moderately aggressive environments.

The dosage rates in the current FDOT Spec for slag and metakaolin are based on

the manufacturers recommendations. The suggested addition rate for slag is 25% to 70%

by weight for moderately aggressive environments, while metakaolin is 8 to 12%

(Personal Communication with Mike Bergin 2005). At addition rates below the

minimum, there were not significant improvements to mechanical properties and

durability. Addition rates above the maximum will not react and become expensive

fillers.

The effect of Silica fume replacement rates on modulus of rupture and permeability

were investigated by Tia (et al. 1990). They found that the most effective replacement









rate was in the range of 7% to 9% by weight. Replacement rates below the minimum did

not significantly improve the permeability and had little affect on the modulus of rupture,

while rates above the maximum did not show any improvement in test data.

Consequently, the FDOT Spec. has adopted this range for silica fume replacement levels.

Although the ultrafine fly ash addition rates are not provided in the current FDOT

Spec., the manufacturer has suggested that the range should be from 10% to 14%

(Personal Communication with Charles Ishee 2005).

Two control mixtures were designed. The first control mixture contained only

Portland cement as the binder; no mineral admixtures or other cementious materials were

used. A second control mixture was designed to contain Portland cement and fly ash at

an addition rate of 18% by weight. Therefore, the proportion of fly ash used in every

mixture was selected to be 18%. The FDOT Spec. minimum was selected because fly

ash would be used in conjunction with other mineral admixtures.

To thoroughly investigate the effects of the mineral admixtures, three mixtures

containing different proportions of each admixture were designed. For example, three

mixtures containing metakaolin at proportions of 8%, 10%, and 12% were designed.

These percentages were selected based on the metakaolin guidelines in the FDOT Spec.

The minimum and maximum proportions were selected. In addition, a percentage that

was midway between the maximum and minimum was selected to provide a broad

distribution of data. The ultrafine fly ash mixtures were also designed in this manner;

proportions of 10%, 12%, and 14% were selected. Because the range of silica fume

replacement rates in the FDOT Spec was narrow (7 to 9%), only mixtures containing the

minimum and maximum proportions were designed. The range of replacement rates for









slag in an extremely aggressive environment is 25 to 70% by weight. Because slag was

being used in conjunction with fly ash, the maximum slag replacement rate would be too

high to create a durable concrete because the proportion of cement would be too low.

Neville (1995) found that for the highest medium term strength, the cement to

cementitious material should be about 1:1. Therefore, smaller proportions of slag

replacement in combination with 18% fly ash were selected to be investigated; slag

proportions of 25%, 30%, and 35% were used. The cementitious material proportions for

all mixtures are presented in Table 3 1 and Table 3 2

Table 3 1 Proportions of Cementitious Materials a
CTRL1 CTRL2 SLAG1 SLAG2 SLAG3
Cement 100% 82% 57% 52% 47%
Fly Ash (FA) --- 18% 18% 18% 18%
Slag --- --- 25% 30% 35%
Metakaolin --- --- --- --- ---
Ultrafine (FA) -
Silica Fume --- --- --- ---

Table 3 2 Proportions of Cementitious Materials b)
METAl META2 META3 UFA1 UFA2 UFA3 SF1 SF2
Cement 74% 72% 70% 72% 70% 68% 75% 73%
Fly Ash (FA) 18% 18% 18% 18% 18% 18% 18% 18%
Slag --- --- --- --- --- --- --- ---
Metakaolin 8% 10% 12% --- --- --- --- ---
Ultrafine (FA) --- --- --- 10% 12% 14% --- ---
Silica Fume --- --- --- --- --- --- 7% 9%


The volume occupied by the cementious materials, water, and air was subtracted

from the total concrete volume to determine the required aggregate volume. Proportions

of coarse aggregate were selected from Table 6.3.6 (Volume of Coarse Aggregate per

Unit Volume of Concrete) in ACI 211.1-91. The fine aggregate content was determined

by subtracting this coarse aggregate volume from the total aggregate volume. These









proportions of fine and coarse aggregate were determined to be 35% and 65%,

respectively. The resulting mixture designs are shown in Table 3 3 and Table 3 4.


Table 3 3 Mix Designs a) (lb/yd3)
Material CTRL1 CTRL2 SLAG1 SLAG2 SLAG3
Cement 752 617 429 391 354
Fly Ash 0 135 135 135 135
Slag 0 0 188 226 263
Micron3 0 0 0 0 0
Metakaolin 0 0 0 0 0
Silica Fume 0 0 0 0 0
Water 263 263 263 263 263
Fine Agg. 1055 1042 1035 1034 1032
Coarse Agg. 1078 1743 1736 1734 1734
Air Entrainer 3 oz. 3 oz. 3 oz. 3 oz. 4 oz
Water Reducer 23 oz. 23 oz. 23 oz. 23 oz. 23 oz.
Superplasticizer 68 oz. 68 oz. 68 oz. 68 oz. 68 oz.
Additional 0 oz. 0 oz. 0 oz. 0 oz. 7 oz.
Total 68 oz. 68 oz. 68 oz. 68 oz. 75 oz.


Table 3 4 Mix Designs b) (lb/yd3)
Material METAl META2 META3 UFA1 UFA2 UFA3 SF1 SF2
Cement 557 542 527 542 527 512 564 549
Fly Ash 135 135 135 135 135 135 135 135
Slag 0 0 0 0 0 0 0 0
Micron3 0 0 0 75 90 105 0 0
Metakaolin 60 75 90 0 0 0 0 0
Silica Fume 0 0 0 0 0 0 53 68
Water 263 263 263 263 263 263 263 263
Fine Agg. 1030 1027 1024 1037 1037 1035 1032 1029
Coarse Agg. 1731 1728 1726 1739 1737 1737 1734 1731
Air Entrainer 5 oz 6 oz 6 oz 6 oz 7 oz 8 oz 8 oz 8 oz
Water Reducer 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. 23 oz. 23 oz.
Superplasticizer 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz.
Additional 20 oz. 30 oz. 41 oz. 0 oz. 0 oz. 0 oz. 0 oz. 0 oz.
Total 88 oz. 98 oz. 109 oz. 68 oz. 68 oz. 68 oz. 68 oz. 68 oz.

Several chemical admixtures were used to control the fresh properties of the

concrete, including air entraining, set retarding, and high-range water reducer.









Recommended addition rates for air entraining admixtures are not typically provided by

the manufacturer because many factors affect the process of air entraining a concrete

mixture. These factors included cement and mineral admixture, coarse and fine

aggregate, mixer type, mixing time, and vibration. Therefore, laboratory experience was

used to determine the addition rate, which was 0.4 oz. per 100 lb of cementitious

materials.

The set retarder, WRDA 60, had a recommended dosage rate of 2.5 to 6 oz. per 100

lb of cementitious materials. In this investigation, 2.5 oz. was used for each mixture.

The lower end of the range was used because only a short delay in setting time was

needed to ensure that all specimens could be fabricated before the mixture stiffened.

To ensure consistency among the various mixes, the water content was held

constant. It was deemed important, however, that the slump also remain consistent to

ensure that the specimens were consolidated similarly. Consequently, slump was

adjusted with a high-range water reducer, rather than with additional mixing water. The

manufacturers recommended dosage rate for the superplasticizer, ADVA 140, is 6 to 20

oz. per 100 lb of cementitious materials. Because each mineral admixture affects the

mixture differently, the quantity of superplasticizer needed to get the desired slump was

different for each mixture. An initial estimation of 9 oz per 100 lb of cementitious

materials was used for each mixture. Slump readings were taken immediately after

mixing was completed. If the slump was below the target range, additional

superplasticizer was added at the lab manager's discretion. Addition rates that were too

large would cause segregation resulting in loss of strength and durability. This would be

evident by large percentages of bleeding. However, the small variations in quantity of









superplasticizer in each mixture of this investigation do not affect the durability or

strength, but rather ensure consistent consolidation among specimens.


Preparation of Concrete Mixtures

In preparation for mixing, the coarse aggregate was placed in woven polypropylene

bags which were submerged in water for a minimum of 48 hours to fully saturate the

aggregate. One day prior to mixing, the coarse aggregate bags were removed from the

water and allowed to drain for approximately one hour. The coarse aggregate was then

batched and sealed for casting on the following day. This was done to keep the coarse

aggregate in a saturated surface dry condition so that it would not affect the water

requirements of a mixture by absorbing or releasing water during mixing. Moisture

content was measured on representative samples taken from the batched material.

Variations from saturated surface dry were adjusted for during mixing.

The fine aggregate was placed in cotton sand bags. The bags were then dried in an

oven to remove any in-situ moisture. One day prior to casting, batch quantities were

weighed and sealed in plastic 5-gallon buckets.

All mineral admixtures and cement were collected from their receptacle one day

prior to casting. The materials were then weighed and sealed in plastic 5-gallon buckets.

All thirteen concrete mixtures were produced in the two cubic feet rotary drum

mixer shown in Figure 3 1. A butter mixture, which is a small scale replica of a

concrete mixture that contains no coarse aggregate, was used prior to mixing. This butter

mixture was used to completely cover the interior surface of the concrete mixer. This

limits changes in paste content due to adherence to the interior mixing surfaces; butter

mixtures improve the consistency of concrete mixtures.



































Figure 3 1 Rotary Drum Mixer

The procedure for mixing complied with ASTM C 192. Initially, the coarse and

fine aggregates were placed in the mixer with approximately half of the water and air

entraining admixture. These constituents were then mixed for two minutes. Next, the

cement, mineral admixtures, set retarding and superplasticizer admixtures, and remaining

water were added to the mixer and mixed for three minutes. The mixture was then

allowed to rest for three minutes. A slump test was then conducted to evaluate the

mixture. If the slump was not within the desired range, additional superplasticizing

chemical admixture was integrated into the fresh concrete and mixed for an additional

three minutes.









Specimen Fabrication

The desired testing scheme, discussed in chapter 4, required the fabrication of

various concrete specimens. These included cylinders, beams, prisms, and ASTM G 109

specimens. Each specimen was fabricated in accordance to the requirements of ASTM C

192. The 6-in. diameter x 12-in. long cylinders were constructed in 3 lifts. Other

specimens were placed in two lifts. Specimens were consolidated by means of external

vibration. Vibration continued until the surface of the concrete became smooth and large

air bubbles ceased to break the surface. Specimen molds were then sealed to prevent

evaporation. Twenty-four hours after fabrication, all specimens were removed from their

molds and placed in the curing environment called for by the applicable test methods.

Curing Conditions

The curing condition of each specimen was dictated by their respective test method.

These conditions included full submersion in aqueous solutions containing aggressive

agents, dry cure in a controlled environment, wet cure in a controlled environment, and a

wet cure in an elevated temperature water bath.

With the exception of the specimens tested according to ASTM G 109, ASTM C

157, ASTM C 512, ASTM C 1556, and ASTM C 1012, curing procedures of ASTM C

511 were followed. This standard calls for demolding after 24 hours and placement into

a curing environment that is controlled at 73.4 3.00F and 100% humidity, so that free

water is maintained on the surfaces at all times.

Specimens used for ASTM G 109 were cured for 28 days in accordance to ASTM

C 511. Upon removal from moist room, specimens were dry cured for two weeks in an

environment controlled at a temperature of 73 30F and a relative humidity of 50 4%.









The epoxy barrier was then applied. Each specimen was then returned to the controlled

dry curing environment for an additional two weeks. Next, the specimens were placed in

their exposure conditions. ASTM C 157 calls for specimens to be place in a curing

environment that is maintained at 73 30F and a relative humidity of 50 4%

immediately after demolding. ASTM C 512 also required that specimen be moved into a

controlled dry cure after a 7-day initial cure in 100% humidity room. For ASTM C 1556,

a portion of the specimens followed an accelerated curing regime to simulate an older

age. This was accomplished by placing the appropriate specimens in a water bath

maintained at 105 5F for 28 days. All specimens were then placed into their exposure

solutions. Specimens used for ASTM C 1012 had no curing period prior to testing.

These specimens were demolded at 24 hours and immediately placed into an exposure

solution.

Additional Mixtures

When analyzing the data gathered from the testing regime, it became evident that

there were errors and inconsistencies between specimens. This variability in test data

prompted the recreation of specimens for several test methods. The data gathered from

these new specimens were used to supplement the existing data. Specimens were

fabricated, cured, and tested identically to the initial mixtures.

New specimens were created for the modulus of elasticity, Poisson's ratio, splitting

tensile strength, and flexural strength tests. Errors in the testing apparatus for modulus of

elasticity and Poisson's ratio led to the full replacement of the existing data. The

variability in the data gathered from splitting tension also prompted the full replacement

of the existing data. Although the data from the flexural strength tests were consistent






43


and showed low variability, the results were inconclusive. Additional test specimens

were needed to be created to test at later ages than was originally designed to determine

the long range effects on the flexural strength of the mineral admixtures.









CHAPTER 4
LABORATORY TESTING

Evaluating the durability of concrete made with highly reactive pozzolans involved

not only durability tests, but also plastic properties and mechanical properties. This

chapter describes the test methods used to evaluate these important properties. To the

extent possible, standard test methods were used. However, in some cases it was

necessary to deviate from standard procedures or specimen configurations.

Plastic Properties Tests

The plastic properties tests were conducted to check the consistencies between

mixtures and evaluate the affects of the mineral admixtures to the properties of the fresh

concrete. The following plastic properties were measured: density, slump, air content,

bleed water, time of set, and temperature.

Density (ASTM C 138)

The unit weight plastic property test is often conducted because of its simplicity.

Typically, unit weight is measured as part of the air content procedure. From these

results, yield estimation can be calculated. The use of different mineral admixtures have

little affect on density as it is more greatly affected by aggregate type and entrained air

(Mouli and Khelafi 2006).

Slump (ASTM C 143)

The slump test is a relatively simple field test that gives an estimate of concrete

workability. This test is typically used to ensure a consistent workability and is

sometimes used to determine if sufficient superplasticizer has been added to a mixture.

The target slump of the design mixtures for the present research was 7 inches. Slump

readings were taken immediately after the concrete was mixed. If the slump was less









than the target, high range water reducing admixture was added and slump was retested

until the target slump was achieved. Because the recommended manufacture's dosages

were not exceeded, it is expected that the physical characteristics of the hardened

concrete remained unaffected.

Because of the spherical shape of the particles, fly ash reduces interparticle friction

and increase slump (Neville 1995). Silica fume and ultrafine fly ash particles, however,

because of their small size, have high surface areas and tend to increase the cohesiveness

of the mixture (Mindess 2003). This results in a decrease in slump and a need for greater

high range water reducer dosages to maintain the target slump. Slag and metakaolin also

decrease the slump because of their angular and plate like particles (Bai et al 2003).

Air Content (ASTM C 173)

This test measures, by the volumetric method, the air contained in the mortar

fraction of the concrete, without being affected by air contained within aggregate pores.

This test method is unable to distinguish between entrapped and entrained air, as it only

measures total air content. However, it does provide the means of evaluating the effects

of an air entraining admixture when a mixture is properly consolidated to remove all

entrapped air.

The addition of mineral admixtures will alter the effect of air entraining

admixtures. High carbon content of some mineral admixtures will adsorb the entrained

air, rendering the chemical admixture less effective. However, the carbon levels of the

mineral admixture used in this investigation are low enough so that air entrainment will

be unaffected. The high surface areas also alter the effectiveness of the air entraining

admixture by requiring a larger dosage of air entrainer to reach the same air content









(Neville 1995). Therefore, if the same dosage of air entrainer was used for mixtures

containing mineral admixtures as was with the control, the air content will be lower.

Air entraining admixture was implemented to decrease the bleeding, as well as

increase the workability and cohesiveness of the concrete mixtures. The measurements

of air content were used to establish a correlation between bleeding and air content.

Bleeding of Concrete (ASTM C 232)

This test measures the percentage of bleeding of a fresh concrete mixture. A metal

beaker is filled with concrete and then consolidated. After troweling the surface level,

the bleed water is collected and measured.

Bleeding is a form of segregation in which there is an upward movement of water

after the concrete has been consolidated. This causes the upper layer of the concrete to

have a high water-to-cement ratio resulting in increased porosity and lower durability in

the cover concrete. Strength will also be reduced when large water pockets, caused by

the upward movement of water during excessive bleeding, form under aggregate or

reinforcing bars. Yet another adverse affect of bleeding is laitance. This occurs when a

film of fine particles are carried to the surface by the bleed water. If the concrete is

poured in lifts, this surface film will create a poor bond to the next lift. (Mindess et al.,

2003)

Bleeding is reduced by using an air entraining admixture. The entrained air

increases the cohesiveness of the particles, thus reducing bleeding segregation. Bleeding

is also reduced by the use of mineral admixtures. Silica fume, ultrafine fly ash, and

metakaolin have small particles that allow it to pack between cement grains, thus

reducing the porosity; consequently, bleeding is reduced (Neville 1995). Research has

shown, however, that slag may increase bleeding (Wainwright and Rey 2000).









Time of Setting (ASTM C 403)

The initial and final setting times of a freshly mixed concrete were determined by

measuring the stress needed to penetrate the surface of a concrete. A stress of 500 lb/in2

and 4000 lb/in2 determined the initial and final setting, respectively.

Excessively long or short set times indicate possible problems with cement

manufacturing, adverse chemical admixture reactions, or excess gypsum. Specific setting

time patterns can indicate which problem may be the cause. Time of setting is also an

important measurement to predict maximum mixing and transit times and to gauge the

effectiveness of set-controlling admixtures.

The use of mineral admixtures affect the setting times of concrete mixture.

Research has shown that all mineral admixtures used in this investigation lengthen the

setting time (Brooks et al. 2000). Fly ash retards the early hydration of C3S (ACI

232.2R-03). Mixtures containing over 25% slag will see delays in setting time (ACI

233R-03). Conversely, metakaolin mixtures have shown increases in setting (Zongjin

and Ding 2003). ACI (234R-06) have suggested that silica fume does not affect the

setting times.

Temperature (ASTM C 1064)

Temperature measurements were taken immediately from fresh concrete, and

completed within 5 minutes after obtaining the sample. The temperature of fresh

concrete mixes becomes a critical factor when placing in hot or cold environments. In

hot weather concreting, problems can occur when concrete temperatures become too

high. High temperatures can cause plastic shrinkage cracking, loss of workability and

decreased setting times. In cold weather concreting, problems can arise if the fresh

concrete temperatures becomes low enough to freeze early in its life. Therefore, a









measurement of fresh concrete temperature can provide an estimate on how it will

perform in extreme temperature environments.

Generally, low reactivity mineral admixtures as small cement replacements will

result in lower mixture temperatures. Conversely, high reactivity admixtures will

increase the fresh concrete temperature. Research has shown that the incorporation of the

low reactivity slag mineral admixture will result in a lower heat of hydration (Sioulas and

Sanjayan 2000). On the other hand, Metakaolin additions have been shown to increase

the fresh concrete temperature (Frias et al 2000). Research has shown that, separately,

fly and silica fume will also reduce the temperature of a fresh concrete mixture (Langan

et al 2002). However, this research has also shown that the combination of fly ash and

silica fume retarded the initial hydration, resulting in lower temperatures.

Mechanical Tests

Standard test methods were conducted to determine the mechanical characteristics

of the concrete. These characteristics are frequently used in structural design to estimate

a variety of other concrete properties. Physical behavior also can be predicted based on

the results of these mechanical tests, such as deflection and prestressing losses.

Compressive Strength (ASTM C 39)

The addition of mineral admixtures has a significant affect on the compressive

strength of concrete. The early strength will be reduced if a low reactivity admixture,

such as fly ash and slag, are used in a mixture (ACI 232.2R-03 and ACI 233R-03). The

increased fineness of ultrafine fly ash makes it more reactive than ordinary fly ash.

However, research by Jones (et al 2006) has shown that there is still a reduction in early

strength development of ultrafine fly ash mixtures when compared to the control.

Conversely, early age strengths are typically higher than the control for high reactivity







pozzolans such as metakaolin and silica fume (Qian 2001 and ACI 234R-06). Late age
strengths of concretes containing these mineral admixtures will be higher than the
control. This is attributed to the stronger, more homogenous paste matrix created by the
pozzolanic reactions.
The compressive strength of three 6 inch diameter x 12 inch long cylinder were
tested at ages of 3, 7, 28, 91, and 365 days. In lieu of capping, the ends of each cylinder
were ground smooth using a DIAM-end Grinder manufactured by M&L Testing
Equipment as shown in Figure 4 1.


I I


Figure 4 1 DIAM-end Grinder









All cylinders were cured in a moist condition at a temperature of 73.4 + 3.0F, so

that free water was maintained on the surface at all times. Each test was completed

within an hour of removal from the curing room on a Test Mark load frame as shown in

Figure 4 2. Cylinders were loaded continuously and without shock at 20 to 50 pounds

per square inch per second.




























Figure 4 2 Test Mark Load Frame

Because cracking is initiated in the tensile region of the beam, the behavior of a

concrete beam during a beam tests is governed by the tensile strength. Since the tensile

strength of a concrete is largely a function of the aggregate to paste bond, flexural

strength is sensitive to the strength and size of the interfacial transition zone (ITZ).

Mineral admixtures consume Calcium Hydroxide (CH) and reduce ettringite formation,









creating a stronger concrete ITZ. Therefore, the use of mineral admixtures will typically

improve the flexural strength of a concrete over time. Early strength development is

reduced in the admixture with low reactivity, such as fly ash and slag (ACI 232.2R-03

and ACI 233R-03). Conversely, the higher reactivity mineral admixtures, silica fume and

metakaolin, will have higher modulus of rupture when compared to the control (ACI

334R-06 and Kim et al 2007). Research related to the effect ofultrafine fly ash on

flexural strength seems to be unavailable. However, it is expected that because the

surface area is increased, the ultrafine fly ash mixtures will show a larger flexural

strength at early ages when compared to the ordinary fly ash mixtures. At later ages, the

mineral admixtures will provide an increase in flexural strength when compared to the

control mixtures because of the improvement in the ITZ.

Specimens were cast into 4 inch wide x 4 inch high x 14 inch long beams and

tested at two ages-7 day and 28 day. All beams were cured in a moist condition at a

temperature of 73.4 + 3.0oF, so that free water was maintained on the surface at all times.

Each test was completed within an hour of removal from the curing room. Beams were

loaded continuously and without shock at a rate of 125 to 175 pounds per square inch per

minute on an Instron load frame as shown in Figure 4 3 and Figure 4 4.








52



Ochine

optional Posilmns For One St.ll Rod
B One SiesH Bel?

SI- In. min.



Lodc-Olying W l upporl
blcks.



Boll '
'- L- HRigid loding struCture
or, if it iu a loading
acce////, Sitel Plat0
or Channel.


Wearing monw -- Span Length, L

Figure 4 3 Diagram of the Third-Point Loading Flexure Testing Apparatus


Figure 4 4 Instron Load Frame Testing Flexural Strength









Static Modulus of Elasticity and Poisson's Ratio (ASTM C 469)

Research has shown (Nassif et al. 2004) that the addition of mineral admixtures

will increase the modulus of elasticity of the concrete at late ages. However, for high

volume replacement of low reactive mineral admixtures such as fly ash and slag, early

age modulus of elasticity may be reduced. The amount of decrease will depend on the

type and quantity of admixture implemented.

Very little research has been conducted to find the relationship of various mineral

admixtures to Poisson's ratio. The research that had been conducted shows no

discernable change in Poisson's ratio with the addition of mineral admixtures. (Mirza et

al 2002) However, this data is not sufficient to make a definitive prediction of the affects

of mineral admixtures.

The procedure was performed in slight variation to ASTM C 469. The Standard

calls for the specimen to be loaded to 40% of its ultimate strength. However, slight

damage may be induced at this level. Bond cracks will exist in concrete at zero load due

to differences in the elastic moduli between the hardened cement paste and the

aggregates, different coefficients of thermal expansion, as well as different responses to

moisture content. For stress levels up to 30% of the ultimate, little additional cracking

will be observed. Bond microcracking begins to increase at stresses above 30 to 40% of

the compressive strength. (Mindess et al., 2003) Therefore each specimen was only load

to 25% of its ultimate strength. The rest of the procedure was conducted in accordance to

the Standard. Figure 4 5 shows the instrumentation and testing apparatus used to

measure the Modulus of Elasticity and Poisson's Ratio.



























Figure 4 5 Modulus of Elasticity and Poisson's Ratio Test Setup on the TEST MARK
system

Because of the low stress levels used to test for Modulus of Elasticity (MOE), the

same 6 inch diameter x 12 inch long cylinders that were used for MOE could be used for

compressive strength tests. An initial test of compressive strength was conducted on the

first cylinder from each set of three. Each of the two remaining cylinders were loaded

three times to measure the MOE. The initial load, which was primarily for seating the

gages, was ignored. The two subsequent loadings were then used to calculate an average

modulus of elasticity for that cylinder. An average was then taken of the results from the

two cylinders. Testing was conducted at 3, 7, 28, 91, and 365 day ages.

Poisson's Ratio was also obtained when testing for MOE. The results from the

second and third loading were averaged for each cylinder. The data from both cylinders

were used to calculate an average Poisson's ratio for each mix. Testing was conducted at

3, 7, 28, 91, and 365 day ages.









Splitting Tensile Strength (ASTM C 496)

ASTM has yet to adopt a standard test method to provide a direct measurement of

tensile strength. This is because the problems with secondary stresses from gripping

make it is very difficult to get consistent and reproducible results. However, a standard

test, ASTM C 496, has been created to estimate tensile strength through indirect tension.

Because the failure of concrete in tension is governed by microcracking, the ITZ

will control the tensile strength of a concrete. (Mindess et al., 2003) The use of mineral

admixtures will result in consumption of CH and reduction of ettringite formation,

creating a stronger ITZ. As with flexural strength tests, the use of mineral admixtures in

concrete used for splitting tensile strength tests will improve the tensile strength of a

concrete as the pozzolanic reactions take place.

Specimens cast into 4 inch diameter x 8 inch long cylinders were tested at 3, 7, 28,

91, and 365 days of age. All cylinders were cured in a moist condition at a temperature

of 73.4 + 3.0F, so that free water was maintained on the surface at all times. Each test

was completed within an hour of removal from the curing room on a Forney Load frame

as shown in Figure 4 6.


Figure 4 6 Splitting Tensile Strength Test on Forney Load Frame











Durability Tests

The deterioration of concrete is the result of poor performance of the three major

components: reinforcement, paste, and aggregate. This can be the result of either

chemical or physical causes. The durability tests performed in this investigation involve

the assessment of each concrete mix's physical characteristics and response to chemical

attack. The use of mineral admixtures will alter the concrete paste and paste structure by

creating a stronger, more homogenous paste matrix, less permeable void space, and

refined capillary pore structure-all of which result in an improvement to durability.

Linear Shrinkage (ASTM C 157)

The linear shrinkage test assesses volumetric expansion or contraction of concrete

due. Moisture loss through the concrete pore structure is the dominant factor in

shrinkage (Mindess et al. 2003). Because of the typical reduction in capillary porosity,

the use of mineral admixtures will reduce linear shrinkage by decreasing the porosity in a

concrete. Research has shown that metakaolin mixtures exhibit a reduction in total linear

shrinkage (Brooks and Megat Johari 2001). ACI has suggested that slag will reduce

linear shrinkage (ACI 363R-03). Research conducted by Akkaya (et al. 2007) has shown

that fly ash and ultrafine fly ash show little decrease in total shrinkage compared to the

control. ACI (364R-06) states that silica fume also has little effect on total shrinkage.

ACI also states that silica fume and fly ash has no significant affect on linear

shrinkage at small replacements levels (ACI 364R-06 and ACI 323.2R-03). Research on

the effects of ultrafine fly ash on linear shrinkage seems to be unavailable.

Linear shrinkage specimens were cast into 3 inch wide x 3 inch high x 11.25 inch

long prism molds. Immediately after removal from the molds, the specimens were dry









cured by placing them an environment controlled at a constant temperature of 73 3 F

and a constant relative humidity of 50 4%. Due to mechanical problems with the

environmental control system, temperature and relative humidity were slightly varied

from that specified in ASTM C 157. The actual temperature and relative humidity

readings are presented in Appendix A. Comparator readings were taken on all specimens

at an age of 4, 7, 14, and 28 days, and after 8, 16, 32, and 64 weeks.

Volume of Voids (ASTM C 642)

This method was used to measure the percentage of voids within a hardened

concrete. If exposed to a corrosive environment, these voids are susceptible to becoming

filled with deleterious chemicals. A reduction in void volume is therefore beneficial to a

concrete. Mineral admixtures will reduce the volume of voids through an increase denser

hydration products produced from the pozzolanic reactions.

Samples were cut from 2 inches below the finished surface of a molded 4 inch

diameter x 8 inch long concrete sample. Tests were conducted on each mixture at 28

days of age.

Sulfate Expansion (ASTM C 1012)

Length change measurements permit the relative assessment of the sulfate

resistance of concrete or mortar subjected to total immersion in a sulfate solution. The

sulfate ions in the solution combine with gypsum and CH to create an expansive reaction.

This reaction, however, can be limited by the use of mineral admixtures. There are two

means that mineral admixtures inhibit sulfate expansion: a refinement of the capillary

porosity and a reduction in CH. ACI (232.2R-03; 233R-03; 234R-06) suggests that fly

ash, slag, and silica fume increase a concrete's resistance to sulfate attack. Research has

shown that metakaolin also improves the resistance to sulfate attack (Khatib and Wild









1998). Little research has been conducted on the relations ofultrafine fly ash with

sulfate attack. It is expected, however, that ultrafine fly ash will perform better than fly

ash concretes, because the smaller particle size will further reduce permeability.

Specimens for the present research were cast into 3 inch wide x 3 inch high x 11.25

inch long and 1 inch wide x 1 inch high x 11.25 inch long molds for concrete and mortar,

respectively. Mortar was sampled from the fresh concrete mix; fresh concrete was passed

through a 3/8 inch sieve to remove the coarse aggregate. All specimens were immersed

into a 5% SO4 solution at 24 hours after casting, immediately after their removal from the

molds. The water temperature of the sealed tanks containing the sulfate solution was

maintained at 73.5 + 3.5F. Readings were taken at 1, 2, 3, 4, 8, 13, and 15 weeks of

exposure.

Absorption (ASTM C 642)

There are four transport mechanisms that allow the penetration of deleterious

chemicals into concrete. These mechanisms are permeability, diffusivity, evaporative

transport, and absorptivity. In an unsaturated concrete, absorption will play a significant

role in chemical transport. Absorption is controlled, in large part, by the connectivity of

the capillary pore system. Solution is drawn by capillary suction allowing harmful

chemicals, such as chlorides and sulfates, to enter the concrete. This test method gives a

means of assessing the capillary pores structure by measuring the absorptivity of an

unsaturated concrete. The use of mineral admixtures will refine the capillary pore

structure through pozzolanic reaction. Consequently, the absorptivity of a concrete will

be reduced.









Specimens for the present research were prepared using a 4 inch diameter x 8 inch

long cylinder molds. Each cylinder was cured in a moist condition at a temperature of

73.4 3.0F, so that free water was maintained on the surface at all times. From each of

these cylinders a 2 inch thick slice was cut from 6 inches below the finished surface.

This test was conducted on each mixture at 28 days of age.

Corrosion of Embedded Steel Reinforcement (ASTM G 109)

Corrosion is a particularly problematic phenomenon in reinforced concrete

structures subjected to chloride ions. Because it is an expansive reaction, corrosion of

steel reinforcement leads to the cracking and spelling of the adjacent concrete. This will

then lead to a direct, unobstructed path for additional elements to corrode the underlying

steel reinforcement. This method provides the means of assessing a concrete's ability to

inhibit the corrosion of embedded steel reinforcement. The use of mineral admixture will

delay or even prevent the corrosion of the embedded steel reinforcement by improving

the surrounding concrete. The mineral admixtures refine capillary porosity, reduce

permeability, and improve the ITZ. Each of these effects will reduce the ingress of

chloride ions.

Each specimen was fabricated using a mold containing three #4 deformed steel

reinforcing bars and a titanium reference electrode as shown in Figure 4 7. At an age of

24 hours, each specimen was demolded and allowed to cured in a moist condition at a

temperature of 73.4 3.0F, so that free water was maintained on the surface at all times

until they were 28-days of age. At this time, each specimen was placed in an

environmental chamber maintained at 50% relative humidity for a period of two weeks.

Following this conditioning, a 6 inches long x 3 inches wide x 3 inches high plastic dam









was installed on the top of each specimen. All sides were then sealed, with the exception

of the bottom and the inside of the damned area, using Sikadur 32 High Mod epoxy.

Figure 4 8 shows the ASTM G109 specimen after the dam and epoxy seal was

constructed.


igure 4 7 ASTM G109 Specimen Molds containing the Reinforcing Bars and
Reference Electrode


Figure 4 8 ASTM G109 Specimen After The Epoxy Has Been Applied

Samples were then placed back into the environmental chamber until they were of

56 days of age. At this time, a non-standard testing procedure was followed. ASTM G









109 states that samples should be ponded with a 3% NaC1, and stored at 73 5.0F and a

relative humidity of 50 5%. To accelerate corrosion, a 15% NaCl solution was used

with the specimens exposed to 90 50F. The specimens were connected to automated

monitored device that measured current and potential once daily at the FDOT SMO. A

photograph of this setup can be seen in Figure 4 9. Each specimen was subjected to a

cycled regime of the 15% NaCl solution; the cycles were maintained at two weeks of

sealed continuous ponding, followed by two weeks of drying. An electrical diagram of

the test setup is presented in Figure 4 10.


Figure 4 9 Environmental Room Containing the Automated Monitoring Device and
Corrosion Specimens


Figure 4 10 Electrical Diagram of Corrosion Specimens











Background Chloride Level (FM 5-516)

This method is used to determine the background levels of chloride in a concrete

mixture. The results were used in calculations to determine the absolute level of chloride

intrusion for ASTM C 1556. The use of mineral admixtures has no affect on this test, as

their compositions do not contain chlorides.

A concrete and paste sample was taken from the fresh concrete and allowed to

hydrate for 3 days. Next, the hydrated concrete and paste was pulverized so that samples

could be taken for chloride analysis. A chemical titration was performed to find the

initial chloride content of each mix.

Surface Resistivity (FM 5-578)

This non-destructive test measures the electrical resistivity across the face of a

concrete specimen to provide an indication of its permeability. As the surface resistance

increase, the correlated permeability decreases. The use of mineral admixture will

increase the surface resistivity by lowering the permeability of the concrete.

All specimens were water-saturated 4 inch diameter x 8 inch long molded

cylinders. These samples were cured in a moist room containing no saturated lime water,

as this decreases the resistivity of the concrete. A Surface Resistivity meter with a

Wenner linear four-probe array was implemented as shown in Figure 4 11. Surface

resistivity was found in accordance with FM 5-578 for concrete cylinders at 3, 7, 28, 91,

and 365 days of age.





















Figure 4 11 Wenner Linear Four-Probe Array and Display

Rapid Migration Test (NTBuild 492)

This procedure was used to determine the chloride migration coefficient in

concrete from non-steady-state migration experiments. A low migration coefficient

effectively indicates that the porosity is low enough to limit the migration of chloride ion

into a concrete. The implementation of mineral admixtures will create a denser, less

permeable concrete. The paste structure will be composed of a more homogenous C-S-H

matrix, smaller ITZ, and less interconnectivity of pores. Therefore, the use of mineral

admixtures will reduce chloride ion penetration.

Samples for this research were cut from 4 inches below the finished surface of

molded 4 inch diameter x 8 inch long concrete cylinders. Cylinders were cured in a

moist condition at a temperature of 73.4 + 3.0oF, so that free water was maintained on the

surface at all times. Tests were conducted at 28, 56, and 91 days of age. At the

appropriate test date, specimens were remove from the curing room and preconditioned

by desiccating for three hours. Next, while maintaining vacuum, the desiccation chamber

was filled with a saturated Ca(OH)2 and vacuumed for an additional hour. The

specimens were kept in the solution for 18 hours. Each specimen was then placed in

the test setup as shown in Figure 4 12. A 30V potential was applied to the sample to










measure the initial current. From that reading the voltage was adjusted to the

standardized value for each specimen. Table 4 1 details the test voltage and duration

corrections given in NTBuild 492. The test was then conducted for 18 hours.


Potential
(DC)

b

c

d h




a. Rubber sleeve e. Catholyte
b. Anolyte f. Cathode
c. Anode g. Plastic support
d. Specimen h. Plastic box
Figure 4 12 RMT Test Setup

Table 4 1 Test Voltage and Duration for NTBuild 492
Initial Applied Test Expected V*t

Current Voltage Duration Penetration [V-

@ 30V [Volts] [hr] [mm] hr]

[mA]

< 5 60 96 < 23 5,760

5-10 60 48 12-20 2,880

10-15 60 24 10-15 1,440

15-20 50 24 12-16 1,200

20-30 40 24 12-18 960

30-40 35 24 15-21 840

40-60 30 24 18-27 720

60-90 25 24 22-33 600









90-120 20 24 26-35 480

120-240 15 24 26-54 360

240-400 10 24 36-77 240

400-600 10 24 36-77 240

> 600 10 6 > 19 60


Immediately following the test, each specimen was removed and split

longitudinally. A silver nitrate solution was then sprayed on exposed surface to highlight

the chloride penetration. Measurements to the nearest 0.1 mm were then made using a

digital caliper. From these measurements the migration coefficient was calculated from

the following equation:


0.023(273+ T)-L (273 + T).L.d (4-
Dnssm = -- 0.0238--
nssm (U-2).t L U-2 1)





where Dnssm is the migration coefficient, x 10-12 m2/s; U is the absolute value of the

applied voltage, V; T is the average value of the initial and final temperature in the

anolyte solution, C; L is the thickness of the specimen, mm; Xd is the average value of

the penetration depths, mm; t is the test duration, hr.


Water Permeability (UF Method)

A concrete structure can be severely compromised through direct intrusion of

deleterious chemicals, such as chloride and sulfate. Therefore the concrete's ability to

resist sulfate or chloride ion penetration is an essential factor in the performance of a

durable concrete. It is for this reason that permeability becomes an important









characteristic of a concrete. The implementation of mineral admixtures will create a less

permeable concrete. The concrete rheology and hardened structure will be altered by the

pozzolans. Better consolidation and less bleeding can be achieved. This creates a

concrete with less capillaries and interconnected pores. The mature concrete is also

affected; through pozzolanic reaction, a denser and less permeable C-S-H product is

produced.

In previous research (Soongswang et al., 1989) a testing method was developed to

directly measure the water permeability of a concrete sample. Permeability specimens

were created for this method from molded 4 inch diameter x 8 inch long molded concrete

cylinders. All cylinders were cured in a moist condition at a temperature of 73.4 + 3.0F,

so that free water was maintained on the surface at all times. From each of these

cylinders a 2 inch thick slice was cut from 3 inches below the finished surface. Around

each slice, a 2 inch wide impermeable epoxy (Sikadur 32 High-Mod) ring was cast and

allowed to cure for 24 hours. This epoxy ring serves to bond with the sides of the

concrete so that a one-dimensional flow will be achieved during the permeability test.

Sikadur 32 High-Mod epoxy was utilized because it has a higher strength and a similar

coefficient of thermal expansion as the concrete used in this investigation. The

permeability testing specimens was then installed into the Plexiglas fixture as shown in

Figure 4 13.

















Steel bolts


25mm mm / / ounIow \ 25mm mm
(1 in.) wide 102mm (4 in.) (I in.) wide
epoxy collar diameter specimen epoxy collar
Figure 4 13 Cross-Section of Water Permeability Specimen Fixture

The specimen and fixture was then attached to the permeability testing apparatus as

shown in Figure 4 14. A constant 80 pound per square inch water pressure was applied

to each specimen. After steady state had been achieved, the specimen was then removed

from the apparatus.


Figure 4 14 Water Permeability Test Setup









CHAPTER 5
RESULTS AND DISCUSSION

This chapter describes and discusses the results obtained through experimental

analysis. Inconsistencies in test data prompted the re-creation of test specimens for

MOE, Poisson's ratio, and flexural strength tests. These changes are presented in the

mechanical test section below.

Plastic Properties Tests

The results from the plastic properties tests are presented in Table 5 1. Each value

represents either a single test result or an average of individual tests, depending on the

test method. Unit weight, for example, was taken during mixing and represents a single

test. The values differed by no more than 2% from the extreme measured values. All

plastic properties tests were performed at the Florida Department of Transportation's

State Materials Office (FDOT SMO).









Table 5 1 Plastic Properties
Initial Final Mix Air
M. Density Slump Air Bleed Set Set Temp. Temp.
Mix Qb/f'3) (in) Set Set Temp. Temp.
(lb/ft ) (in) (%) (%) min min) (F) (F)
(min) (min) (OF) (OF)
CTRL1 145 5.75 2.0 0.00 300 395 81 75
CTRL2 145 6.00 1.5 0.10 330 400 84 75
SLAG1 144 6.50 1.1 0.19 340 430 81 75
SLAG2 144 6.00 1.0 0.17 355 460 81 75
SLAG3 146 6.50 0.6 0.27 300 445 80 75
METAl 144 6.25 1.4 0.00 375 435 84 75
META2 144 7.25 1.5 0.00 390 470 80 75
META3 144 6.00 1.4 0.00 N/A N/A 80 75
UFA1 146 5.75 0.6 0.55 375 465 78 75
UFA2 145 6.75 1.8 0.00 385 485 78 75
UFA3 144 8.00 1.6 0.00 400 480 78 75
SF1 143 6.25 2.3 0.00 370 445 76 75
SF2 143 6.00 2.3 0.00 385 465 76 75

Density was measured and found to vary by 2% for all mixtures. This indicates

that there are no large variations in entrapped air or aggregate volume among mixtures.

Slump measurements were between 5.75 to 8 inches, indicating reasonably

consistent results. Due to natural variability of concrete workability, a consistent

concrete slump from mix to mix is difficult to obtain. For most mixtures, however, the

slump values were within + 1 inch of the 7-in. target value. This allowed for consistent

consolidation among mixtures, thus minimizing variation in test results due to

inconsistent specimen fabrication.

Air content was found to range from 0.6% to 2.3%, which was below the target air

content of 3%. The measured values, however, were within the acceptable range of 1 to

5% except for SLAG3 and UFA1, which had an air content of 0.6%. These lower air

contents appeared to result in an increase in bleeding when comparing the results for

SLAG3 and UFA1 of 0.27% and 0.55%, respectively. CTRL2, SLAG1, and SLAG2,

however, also showed some bleeding, but without an extremely low air content.









Setting times conducted on the cement paste found that initial set was at 140

minutes and final set at 215 minutes. The concrete mixtures in this investigation had

initial setting times that ranged from 300 to 400 minutes; final setting times ranged from

395 to 485 minutes. These setting times are greater than that of the paste by 114% to

185% and 84% to 126% for initial and final setting times, respectively. For CTRL1, the

setting time increased by 114% for initial set and 84% for final set over the cement tests.

This indicates that the addition of the retarder was successful in delaying the setting

times. CTRL2 (18% fly ash) also shows extended setting times when compared to

CTRL 1 (cement only), revealing that the replacement of cement with fly ash retards the

setting times. In addition, all other mixtures show an increase in setting times over

CTRL2, indicating that the larger quantity of mineral admixtures further delays the

setting times. The literature has suggested that metakaolin shortens the setting times,

while silica fume has no affect (Zongjin and Ding 2003; ACI 234R-06). However, when

looking at the mixtures with the same proportions of mineral admixtures, such as IMETAl

(18% fly ash and 8% metakaolin) and SF1 (18% fly ash and 7% silica fume), little

difference in setting times are noticed. This suggests that setting time is more greatly

affected by the decreases in proportions of cement, rather than the addition of a particular

admixture.

Fresh concrete temperatures ranged from 76 to 840F, while the air temperature

remained constant at 750F. This temperature range is small; therefore, with this level of

replacement, there was little affect on the fresh concrete temperature from the addition of

the mineral admixtures.









Mechanical Tests

The mechanical test results for compressive strength, flexural strength, MOE,

Poisson's ratio, and splitting tensile strength are presented below. Trends and

relationships have been noted in the results of each test. However, errors and

inconsistencies have been found in the results from the MOE and Poisson's ratio tests.

This prompted the re-creation of duplicate test specimens. These specimens were created

for testing at 7, 28, and 365 day ages and tested under the same conditions.

Compressive Strength (ASTM C 39)

Figure 5 1 shows the strength gain curve for all the mixtures. Early compressive

strength of concrete made with slower reacting mineral admixtures, such as slag and fly

ash, was less than that of the concretes made with portland cement alone, as seen in the

lower values of early strength in the plot. In contrast, mixtures made with silica fume and

metakaolin exhibited a higher strength than with portland cement alone. At later ages,

however, the low reactivity mineral admixtures continued to react and by 365 days, the

compressive strength had converged to values of just about 10.5 ksi. The lower

compressive strength of SLAG3 was likely the result of errors in mixing that will be

discussed subsequently.






72



11

0 10100 20

9 -9
8
C7


6

0E 5 -+-CTRL1 -+-CTRL2
*-META -- SLAG
4

0 100 200 300 400
Age (days)
Figure 5 1 Compressive Strength of All Mixtures

Although the strength gain curve is not linear, it is also useful to examine the rate

of strength gain by considering the slopes of the lines between the 91 and 365 day

strengths. These slopes presented in Table 5 2 show the average 365 day compressive

strength for each mixture. The compressive strengths are also normalized to the CTRL1

strength to show the improvement and relative value. Disregarding SLAG3, the

compressive strengths vary from CTRL2 by no more than 3%, indicating vary consistent

values at late ages. The slopes of CTRL1 and CTRL2, however, are nearly parallel,

indicating that their rates of hydration are comparable even though CTRL2 contains fly

ash.











Table 5 2 Average Compressive Strength at 365 days, Normalized 365 day
Compressive Strength to CTRL2, and 91 to 365 day Slope
365 day Normalized 91 to 365 day
Compressive Compressive Slope
Strength (ksi) Strength (ksi*105/day)
CRTL1 9.75 0.95 9.8
CTRL2 10.25 1.00 11.9
SLAG1 10.40 1.02 26.0
SLAG2 10.33 1.01 25.8
SLAG3 9.38 0.92 17.5
METAl 10.17 0.99 19.1
META2 10.31 1.01 20.7
META3 10.59 1.03 28.8
UFA1 10.09 0.99 18.3
UFA2 10.09 0.98 22.3
UFA3 10.11 0.99 19.2
SF1 10.24 1.00 20.4
SF2 10.34 1.01 22.1

Furthermore, the slopes of the slag mixtures are parallel and are steeper than that of

the control mixtures, indicating a higher rate of hydration. Similarly, the metakaolin,

ultrafine fly ash, and silica fume mixtures show steeper slopes than the control mixtures.

Therefore, it is likely that these mixtures will produce higher compressive strength than

the controls at later ages. However, because the strength gain curves are non-linear,

accurate predictions of later compressive strengths cannot be made.

At various ages, the compressive strength of a concrete plays at key role in the

selection of a mixture. For example, in the prestressing industry, early compressive

strength is needed to allow for the release of prestressed concrete member from the

prestressing bed. Conversely, higher compressive strength at later ages is needed for

piling to prevent damage during driving. Therefore, a more refined analysis of the early

and late compressive strengths of each mixture is discussed.

Figure 5 2 shows the early age strength development of the concrete mixtures

containing ground granulated blast furnace slag compared to the two control mixtures.










Figure 5 3 presents the late age strength development. The control mixture, CTRL1

(cement only), had a higher early strength than CTRL2 (18% fly ash), which is typical of

low early strength developing mixtures containing low reactive mineral admixtures.

Generally, a mixture with a slower initial hydration rate will produce a denser calcium

silicate hydrate (C-S-H) matrix at a later age. It is this C-S-H matrix that will have the

largest contribution to a concrete's compressive strength, producing a higher strength

later when compared to a high early strength mixture.

10





07
-- CTRL1
a6 CTRL2
a / SLAG1
E 5 -- SLAG2
U- SLAG3
4-
0 5 10 15 20 25 30
Age (days)
Figure 5 2 Average Early Strength of Slag Mixtures

11.0

S10.5

I 10.0

9.5

9.0
C-- -CTRL1 CTRL2
E 8.5
E 85-A-SLAG1 --SLAG2
C-X- SLAG3
8.0
20 120 220 320
Age (days)
Figure 5 3 Average Late Strength of Slag Mixtures

The data show that the average compressive strength of each slag mixture at 3 days

and 7 days age is below that of the two control mixtures, which is a result of the further









delay caused by the replacement of portland cement with slag. Generally, slag has low

reactivity at early ages and therefore will not contribute to early strength development.

Indeed, it is not until around an age of 91 days when the slag mixtures begin to have a

higher compressive strength than CTRL1. At 365 days, the compressive strength of both

SLAG1 and SLAG2 show a strength well above that of CTRL1, and slightly higher than

CTRL2.

The data from Figure 5 2 and Figure 5 3 show that SLAG3 exhibits lower

strength than SLAG1 and SLAG2. As mentioned before, the higher mineral admixture

content in SLAG3 was expected to develop higher compressive strengths than SLAG1

and SLAG2. However, this did not happen. From Table 5 1, it is clear that SLAG3

shows a high bleed percentage when compared to other mixtures. This would suggest

that there were problems with mixing. If the mixed proportions were incorrect, this may

lead to a worse performing concrete than would be expected. Indeed, this trend of poor

performance of SLAG3 is noted throughout subsequent test procedures.

Figure 5 2 also shows that at early ages, the average compressive strength

decreases as mineral admixture content is increased. In contrast, this trend seems to be

reversed as the age of specimens increases. The data show that at 91 days of age, all slag

mixtures are very close to having the same compressive strength. As mentioned before,

ground granulated blast furnace slag generally has low reactivity at early ages and will

begin to develop a dense C-S-H matrix as hydration continues. Therefore, the mixtures

containing higher proportions of slag will exhibit a low early strength. At later ages,

however, the slag will begin to react and eventually develop a higher strength concrete in

the mixtures containing higher volumes of slag.










Figure 5 4 shows the early age strength development of the mixtures containing

metakaolin compared to the two control mixtures. Figure 5 5 presents the late age

strength development. Because of its high reactivity, the metakaolin mixtures show a

high early strength when compared to the control mixtures. As expected, all metakaolin

mixtures have an average compressive strength above that of CTRL2 for 3 day, 7 day and

28 day ages. The strength of the metakaolin mixtures then begin to overtake that of

CTRL1 at an age of apparently 7 days. At an age of 91 days, however, CTRL2 has

developed a higher strength than CTRL1 and all mixtures containing metakaolin. This is

explained by the denser C-S-H matrix developed in slower hydration of the fly ash itself

in CTRL2. By 365 days, however, the compressive strength of METAl and META2 are

nearly equal to that of CTRL2. META3 shows that highest strength.

10




C7
-*-CTRL1
6 CTRL2
C- --META1
E 5 META2
U -X-.- META3
4
0 5 10 15 20 25 30
Age (days)
Figure 5 4 Average Early Strength of Metakaolin Mixtures










11.0

10.5

P 10.0

9.5
.Z +CTRL1
S9.0 CTRL2
C- / -AMETA1
E 8.5 META2
.Q- META3
8.0 ,
20 120 220 320
Age (days)
Figure 5 5 Average Late Strength of Metakaolin Mixtures

As the proportion of metakaolin increases, the data show a higher average

compressive strength at later ages. The higher content of mineral admixture results in a

larger amount of available silicate oxide (S) to react with calcium hydroxide (CH) to

produce a denser matrix of C-S-H compounds.

Figure 5 6 shows the early age strength development of the mixtures containing

ultrafine fly ash compared to the two control mixtures. Figure 5 presents the late age

strength development. The mixtures containing ultrafine fly ash have a similar strength

development as the mixtures containing slag. Because both slag and ultrafine fly ash

have low reactivity, their early age strength gain will be slow. At 3 day and 7 day ages,

all mixtures containing ultrafine fly ash have a lower average compressive strength than

both CTRL1 and CTRL2. At 28 day age, all three ultrafine fly ash mixtures have a

higher strength than CTRL2, while CTRL1 remains at nearly the same strength. As the

strength begins to develop, CTRL2 compressive strength becomes the highest. This

again is due to the dense C-S-H matrix formed by the slow hydration rate of fly ash. At

91 days, CTRL2 continues to develop strength, while the ultrafine fly ash mixtures and

CTRL1 have nearly the same compressive strength. However, by 365 days, the










compressive strength of the ultrafine fly ash mixtures are only slightly lower than

CTRL2. The strength of CTRL1 is still considerably lower than the other mixtures.

10





7
.Z -+-CTRL1
6 CTRL2
C. -- UFA1
S5 1- UFA2
0 )-.- UFA3

0 5 10 15 20 25 30
Age (days)
Figure 5 6 Average Early Compressive Strength of Ultrafine Fly Ash Mixtures

11.0

S10.5

I 10.0

9.5
Z. + CTRL1
9.0 -- CTRL2
Ca UFA1
E 8.5 -0- UFA2
o -- UFA3
8.0 I
20 120 220 320
Age (days)
Figure 5 7 Average Late Compressive Strength of Ultrafine Fly Ash Mixtures

It is apparent that the compressive strength increases as the dosage of ultrafine fly

ash is increased. Due to the increase in S as mineral admixture is increased, a large

quantity of CH is consumed. Thus, a denser matrix of C-S-H will form as proportions of

ultrafine fly ash are increased.

Figure 5 8 shows the early age strength development of the mixtures containing

silica fume compared to the two control mixtures. Figure 5 9 presents the late age

strength development. Because of its high reactivity, the silica fume mixtures show a







79


comparable early strength to the control mixtures. At 3 day and 7 day tests, the strength

of the silica fume is nearly the same as CTRL2 and only slightly less than CTRL1. At 28

days of age, the silica fume mixtures have gained strength and surpassed the average

compressive strength of both CTRL1 and CTRL2. At 91 days, the silica fume mixtures

have continued to gain strength and remain higher than CTRL1. The compressive

strength of CTRL2, however, has increased considerably and now is the highest. By 365

days, both silica fume mixtures show a large increase in strength, and are now nearly

equal to that of CTRL2.


0

Figure

11.0

S10.5

1 10.0

9.5

S9.0
0.
E 8.5
0


5


5 10 15 20 25 30
Age (days)
- 8 Compressive Strength of Silica Fume Mixtures


20 120 220 320
Age (days)
Figure 5 9 Compressive Strength of Silica Fume Mixtures


- CTRL1
-*CTRL2
--A-SF1
-SF2


--0- CTRL1
CTRL2
-A-SF1
+ SF2









From Figure 5 8, it is apparent that the mixture with the higher proportion of silica

fume, SF2, has a higher strength at all ages when compared to SF1. This is explained by

the larger quantity of reactive silica, S, gained by increasing the proportion of the mineral

admixture. Again, a stronger, denser C-S-H matrix is formed, thus increasing the

compressive strength.

Manufacturing of prestressed concrete piles depends primarily on the early strength

development of the concrete mixture. Prestress cannot be tranfered until a minimum

compressive strength is achieved. Consequently, production is slowed and profits are

reduced while the member remains in the forms. Consequently, it is likely that the

manufactures would prefer a high early strength mixture. Typically, prestressed forces

are transferred when the concrete has a compressive strength in the range of 3,500 to

4,500 psi. At 3 days, all mixtures in this investigation exceeded this range. Therefore, in

relation to early removal from prestressing forms, the mineral admixtures did not

improve the mixture over the controls.

The compressive strength also becomes important during pile driving because the

forces associated with driving damage may damage the piles. At levels above 30% of the

compressive strength, microcracking begins to develop; at about 70%, the cracks begin to

propagate through the paste (Mindess et al. 2003). Cracking that develops will reduced

the durability by providing a direct path for deleterious chemicals to enter the concrete.

Therefore, a higher compressive strength will reduce the amount of damage caused by the

pile driving process. Typically at around 28 days, the piles are removed from storage and

driven. At this age, CTRL2 showed the lowest compressive strength. The slag,

metakaolin, and ultrafine fly ash mixtures had nearly the same compressive strength as









CTRL1. The silica fume mixtures, however, did show a slight improvement in

compressive strength over CTRL1. Therefore, it appears that the silica fume mixtures

provide the best resistance to damage caused by driving at this age.

Flexural Strength (ASTM C 78)

The number of flexural strength specimens cast in the first mix allowed testing at 7

and 28 day ages. A second mix was done so that test could be conducted at 7, 28, and

365 days. The data presented in this section are the results from both the first and second

set of mixtures.

The early modulus of rupture (MOR) of concrete made with low reactivity mineral

admixtures is usually less than that of portland cement alone. The slower reaction time

results in a delay of strength gain, which varies with the type of mineral admixture. From

Figure 5 10, the ultrafine fly ash and slag mixtures showed the lowest strength at early

age. In contrast, concrete made with a highly reactive mineral admixture will gain

strength faster, as seen with the metakaolin and silica fume mixtures. At 365 days, the

silica fume and slag mixtures showed the highest MOR.









1300

m 1200

S1100
0.

W 1000
o
10
S900

o 800 --CTRL1 -- CTRL2
-r- SLAG META
-- UFA -SF
700
0 100 200 300 400
Age (days)
Figure 5 10 Modulus of Rupture of All Mixtures

Figure 5 11 shows the average MOR for the slag mixtures at 7, 28, and 365 days.

The control mixture containing only cement, CTRL1, shows a higher MOR when

compared with the control mixture containing cement and fly ash, CTRL2, for both 7 and

28 day ages. The low reactivity of fly ash affects the tensile strength similar to early age

compressive strength. By 365 days, however, the fly ash in CTRL2 has reacted to

produce a higher MOR than that of CTRL 1.










1300

'w 1200 -

ow o






0 100 200 300 400







Figure 5 11 Average Modulus of Rupture of Slag Mixtures

The 7 day MOR for all slag mixtures was lower than both the control mixtures.

Because the reactivity of slag is also low, the combination of the two mineral admixtures,

slag and fly ash, produces an even slower strength developing concrete than CTRL2 in

the 7 day MOR tests. By 28 days, however, the MOR for all slag mixtures are nearly

equal to both the control mixtures. This indicates that the fly ash and slag has started
reacting prior to 28 days to produce a concrete with equal MOR to the CTRL1. At 365
day age, SLAG's MOR was slightly higher than CTRL1, while those of SLAG2 and

SLAG3 were both well above both control mixtures. The hydration products of the slag
0 100 200 300 400










Agand fly ash, have improved the tensile strength of the paste at 365 days similar to












compressive strength.
Figure 5 1 Average Modulus of Ru2 shows the MOR development of the metakaolin mixtures. At 7 days,ures

the metakaolin mixtures show high early sty MOR for all slag mixtures wasngth. Each mixture has nearly the control mixtures.

MOR as the controls, wity of slag is also low, the combinaexception of METAl. The 28 day MOR for METAl was
slag and fly ash, produces an even slower strength developing concrete than CTRL2 in

the 7 day MOR tests. By 28 days, however, the MOR for all slag mixtures are nearly

equal to both the control mixtures. This indicates that the fly ash and slag has started

reacting prior to 28 days to produce a concrete with equal MOR to the CTRL1. At 365

day age, SLAGl's MOR was slightly higher than CTRL1, while those of SLAG2 and

SLAGW were both well above both control mixtures. The hydration products of the slag

and fly ash, have improved the tensile strength of the paste at 365 days similar to

compressive strength.

Figure 5 12 shows the MOR development of the metakaolin mixtures. At 7 days,

the metakaolin mixtures show high early strength. Each mixture has nearly the same

MOR as the controls, with the exception ofMETAL. The 28 day MOR for META1 was









also lower than the other metakaolin and control mixtures. Every other mixture at this

age was nearly equal. At 365 days, METAl still has a lower MOR than the controls.

META2 is equal to CTRL1, while META3 is nearly equal to CTRL2.

1300

'1200





1900 -


800 CTRL1 -- CTRL2
S-A-METAl -*-META2
--- META3
700 1 1
0 100 200 300 400
Age (days)
Figure 5 12 Average Modulus of Rupture of Metakaolin Mixtures

Because of the calcining, metakaolin is mainly composed of amorphous

aluminosilicates. These aluminosilicates are highly reactive, and will rapidly convert CH

to a hydration product. Thus, the high early strength of the metakaolin mixtures is

because of its highly reactive composition. The MOR data show that an increase in

proportion of metakaolin results in a higher MOR, as seen at all ages in Figure 5 12.

The average MOR for the ultrafine fly ash mixtures is presented in Figure 5 13.

At 7 days, the MOR for all ultrafine fly ash mixtures were considerably lower than the

control mixtures. By 28 days, there is a gain in MOR for the ultrafine fly ash mixtures;

however, the MOR were below the control mixtures. The strength of the mixtures









continues to increase at 365 days. UFA3 now has a modulus that is nearly equal to that

of CTRL1, while UFA1 and UFA2 are slightly lower.


1300

T1200




W1000--



M -*-CTRL1 ECTRL2
S800- -m-UFA1 -A-UFA2
-A- UFA3
700 i -
0 100 200 300 400
Age (days)
Figure 5 13 Average Modulus of Rupture of Ultrafine Fly Ash Mixtures

These mixtures have the lowest average 7-day MOR of all mixtures in this

investigation. This is likely due to the higher total proportions of fly ash relative to the

mixtures with other more reactive mineral admixtures. Although the ultrafine fly ash has

a higher surface area when compared to regular fly ash, making it more reactive, the

reaction equations are still the same. The fly ash needs a high alkalinity in the pore water

to continue the pozzolanic reaction. At 7 days of age, the high volumes of total fly ash in

the ultrafine fly ash mixtures (28 to 32%) slow the hydration considerably. By 28 days,

however, the fly ash has begun to react, as shown in the significant MOR gain relative to

the controls. At 365 days, the data shows a general increase in MOR as the proportion of

mineral admixture is increased. By this age, the alkalinity in the pore solution has

stabilized to allow for reactions of the full quantity of fly ash. Consequently, the larger