DETERMINATION OF TEST METHODS FOR THE

PREDICTION OF THE BEHAVIOR OF MASS CONCRETE

By

CHRISTOPHER C. FERRARO

A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL

OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

2009

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 UMI Number: 3400252

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© 2009 Christopher C. Ferraro

2
To Jennifer L. Clark, thanks for patience, support and Love

3
 ACKNOWLEDGMENTS

I would like to express my deepest gratitude to my advisor and committee chair, Dr. Mang

Tia. Thank you for all of your support, kind words, advice and direction during this research

process. After you inherited this project several years after its initiation, you guided me through

the complex process which involved the modification of this study to its finality. You were

always available to listen and offer advice, whether the subject matter was personal or

professional, which I most certainly appreciated.

I am also grateful for the assistance offered by Dr. Reynaldo Roque throughout this

process.. Your involvement in this research certainly prompted me to find the necessary focus

that this study required. Further, your input with respect to the fundamentals of laboratory testing

and the description of physical testing was a significant contribution to my growth as a

researcher.

I would like to express appreciation to Dr. H.R. Hamilton III for his assistance throughout

this project. Your availability to provide technical expertise and input in this study was of great

value to the process. Additionally, your willingness to offer professional, and career advice as

well as share your personal experiences with me were very welcome and helpful throughout this

endeavor. As the only person to serve on my masters and PhD committees, your presence offered

continuity throughout the atypical circumstances surrounding this process. The advice and

guidance offered by Dr. Peter Ifju of my committee is acknowledged and appreciated.

I would like to express gratitude to Dr. Andrew J. Boyd, Dr. Joseph W. Tedesco, and Dr.

Bjorn Birgisson. Your involvement in this research project was certainly beneficial and valuable.

Acknowledgement is expressed to Mr. John Gadja and Dr. Anton Schindler, both of whom

provided invaluable input with respect to the technical issues pertaining to mass concrete.

4
 Dr. Jonathon L. Poole, your experience and knowledge of calorimetry, apparent activation

energy and the general subject of mass concrete has been invaluable. Thank you for providing

technical advice, spreadsheet assistance, and personal encouragement throughout this process. I

certainly appreciate your willingness to consistently answer the phone despite your busy

schedule.

Thanks to Dr. Christos Drakos for his assistance with the preparation of the final exam

presentation, as well as the enormous support on the final exam day itself. The fact that you were

willing to travel from Europe to assist me with the final exam was invaluable part of the success

I achieved on that day. Your friendship and encouragement throughout this process will never be

forgotten.

I thank the following colleagues from the Florida Department of Transportation (FDOT)

who provided assistance with this project. Thomas Malerk, Michael Bergin, Mario Paredes,

Christine McDonald, Richard Delorenzo, Joseph Fitzgerald, Toby Dillow, Craig Roberts, Steven

Sauls, Fred Yon, Susan Blazo, Alfred Camps, Duane Robertson, Dr. H. Deford, Rahman

Henderson, Teresa Risher and Sue Rose. Mostly, I’d also like to thank Charles Ishee for

dedicating a great deal of personal time and interest to this project. The direct assistance with

experimental design, laboratory testing and general interest was extremely helpful, as well as

your personal insight and critical assessment of the details of this research. Johann Kepler said “I

much prefer the sharpest criticism of a single intelligent man to the thoughtless approval of the

masses”. Thanks for contributing your continuous critical assessment of every aspect of this

research entailed. Your knowledge of Portland cement concrete materials, and your friendship

throughout this process was an invaluable part of completing this research.

5
 I acknowledge the following colleagues from the University of Florida who assisted with

this project. Tony Murphy, Charles Broward, Hubert Martin. Additionally, I’d like to thank the

following graduate students for assistance; Adrian Lawrence, who was an excellent research

partner. Thanks for remaining so pleasant and positive for what could otherwise have been a

relatively unpleasant process. Additionally, I’d like to thank the Boris Haranki, John Emery and

who are fellow graduate students and good friends as well. Thanks for your assistance on the

project itself and for personal encouragement throughout this process. I also acknowledge the

following graduate and undergraduate students for assistance with this project; Eiji Ochiai,

Christopher Egan James Falls and Gustavo Morris.

I’d like to thank my friends and colleagues Marjorie Lynch and Thomas Howard who

spent an enormous amount of personal time editing this document for syntax, clarity and content.

Furthermore, I thank Marjorie for her mentorship and friendship throughout the years. Your,

knowledge of the engineering industry, construction practices and common hatred of the Georgia

Bulldogs and Florida State Seminoles football programs have always made conversations fruitful

and meaningful. I thank Thomas for being a trusted friend who’s availability for lunch at any

hour (especially within the final stages of this process) good conversation, and common hated of

the common hatred of the Georgia Bulldogs, Florida State Seminoles and Tennessee Volunteers

football programs have always made conversations fruitful and meaningful.

I’d like to thank the following friends and colleagues who were a great support system

throughout this process: Adam Smith, Richard Davis, Dr. Forrest Masters, Dr. David Prevatt,

Tanya Nash, Thomas Currie, Gregory Doig, Dr. Daniel Algernon, Dr. Alvaro Guarin, Dr. Ulas

Toros, James Hill, and Thomas Berke.

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 I thank my family for all of their support and encouragement throughout this process.

Thanks to my father Ronald Ferraro, my mother Victoria Ferraro, my brother Ronald Ferraro Jr.

my sister Alicia Ferraro, my sister-in-law Lucille Ferraro and my grandfather Charles Stokes.

Anthony Brandt said “other things may change us, but we start and end with family.”

Most importantly, I like to thank My Fiancé Ms. Jennifer L. Clark for her unyielding

patience, support, and love throughout this process. This research endeavor was a long, arduous,

stressful process which required attention and focus that words cannot describe. Your

selflessness as a partner and friend during this time of my personal, professional and academic

accomplishment will never be forgotten Thank you Belle… for everything. Mother Teresa said

“The greatest science in the world; in heaven and on earth; is love.” I’ve learned so much and yet

have so much to learn. I pray our primary topic of study in the days to come is the science of

love between you and I.

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 TABLE OF CONTENTS

page

ACKNOWLEDGMENTS.................................................................................................................... 4

LIST OF TABLES.............................................................................................................................. 12

LIST OF FIGURES ............................................................................................................................ 15

ABSTRACT ........................................................................................................................................ 25

CHAPTER

1 INTRODUCTION....................................................................................................................... 26

Background .................................................................................................................................. 26
Definition of Mass Concrete....................................................................................................... 26
Research Needs ........................................................................................................................... 28
Objectives of Research ............................................................................................................... 28
Hypothesis ................................................................................................................................... 29
Research Approach ..................................................................................................................... 29
Significance of Research ............................................................................................................ 30
Chemical Analysis of Cementitious Components..................................................................... 30
Outline of Dissertation ................................................................................................................ 32

2 LITERATURE REVIEW ........................................................................................................... 34

Mass Concrete Specifications..................................................................................................... 34

Tensile Stresses in Mass Concrete ............................................................................................. 39
Tensile Stresses Due to Thermal Gradients ....................................................................... 39
Tensile Stresses Due to Delayed Ettringite Formation ..................................................... 41

3 ISOTHERMAL CONDUCTION CALORIMETRY TESTING ............................................. 47

Introduction ................................................................................................................................. 47
Summary of Test Method ........................................................................................................... 48
Equipment and Procedure ........................................................................................................... 49
Mixing Procedure ........................................................................................................................ 49
External Mixing ................................................................................................................... 50
Internal Mixing .................................................................................................................... 50
Isothermal Calorimetry Testing Methodology .......................................................................... 51
Isothermal Calorimetry Testing Results .................................................................................... 52
Summary of Results .................................................................................................................... 55

8
4 MATURITY AND EQUIVALENT AGE ................................................................................. 57

Maturity Concept......................................................................................................................... 57
Equivalent Age Concept ............................................................................................................. 58
Arrhenius Equation and Activation Energy............................................................................... 59
Activation Energy Determination via Compressive Strength .................................................. 61
Apparent Activation Energy Determination as Per ASTM C 1074 ................................. 63
Activation Energy Determination Via Exponential Method............................................. 65
Activation Energy Determination via Isothermal Calorimetry ................................................ 69
Comparison of Strength Development Parameters ........................................................... 74
Summary of Results – Apparent Activation Energy ......................................................... 77
Summary of Findings Chapter 4 ................................................................................................ 79

5 SEMI-ADIABATIC CALORIMETRY TESTING .................................................................. 80

Introduction ................................................................................................................................. 80
Research Significance ................................................................................................................. 80
Equipment and Procedure ........................................................................................................... 81
Calibration Procedure .......................................................................................................... 81
Calculation of Adiabatic Temperature Rise ....................................................................... 83
Quadrel “IQ drum” test procedure .............................................................................. 83
University of Texas / Auburn University test procedure ........................................... 85
Semi-Adiabatic Calorimetry Testing Results ............................................................................ 85
Summary of Findings .................................................................................................................. 91

6 SURE CURE/ADIABATIC CALORIMETRY TESTING ...................................................... 92

Research Significance ................................................................................................................. 92

Equipment .................................................................................................................................... 93
Test Procedure ............................................................................................................................. 94
Sure Cure Calorimetry Testing Results ..................................................................................... 96
Limitations of the Test Method .................................................................................................. 98
Summary of Findings .................................................................................................................. 98

7 COMPARISON OF CALORIMETRY TESTING METHODS ............................................ 100

Introduction ............................................................................................................................... 100

Research Significance ............................................................................................................... 100
Calorimetry Testing Results ..................................................................................................... 101
Comparison of Sure Cure adiabatic calorimeter and semi-adiabatic calorimeter ......... 101
Comparison of semi-adiabatic calorimeter and the isothermal calorimeter................... 102
Comparison of cement and concrete ......................................................................... 103
Mortar testing ............................................................................................................. 108
Comparison of solution calorimetry to isothermal and semi-adiabatic calorimetry ..... 112
Summary of Findings ................................................................................................................ 114

8 LARGE-SCALE BLOCK EXPERIMENT - PHYSICAL TESTING ................................... 115

9
 Mixture Design .......................................................................................................................... 115
Concrete Specimen Creation and Curing ................................................................................ 116
Maturity and Equivalent Age ................................................................................................... 117
Maturity Calculation .......................................................................................................... 119
Equivalent age calculation ................................................................................................ 120
Physical Data and Results ......................................................................................................... 121
Compressive Strength Testing .......................................................................................... 121
Compressive strength vs. time................................................................................... 121
Compressive strength vs. maturity ............................................................................ 122
Compressive strength vs. equivalent age .................................................................. 124
Splitting Tensile Strength Testing .................................................................................... 129
Splitting tensile strength vs. time .............................................................................. 129
Tensile strength vs. maturity ..................................................................................... 130
Tensile strength vs. equivalent age ........................................................................... 130
Compressive Modulus of Elasticity .................................................................................. 134
Tangent modulus ........................................................................................................ 135
Secant modulus........................................................................................................... 136
Chord modulus ........................................................................................................... 136
Modulus of elasticity methodology ........................................................................... 136
Compressive modulus of elasticity vs. time ............................................................. 138
Compressive modulus of elasticity vs. maturity ...................................................... 139
Compressive modulus of elasticity vs. equivalent age ............................................ 140
Tensile Modulus of Elasticity ........................................................................................... 144
Tensile modulus of elasticity vs. time....................................................................... 145
Comparison of tensile and compressive modulus of elasticity ............................... 146
Summary of Findings ................................................................................................................ 149

9 LARGE-SCALE BLOCK EXPERIMENT – THERMAL TESTING .................................. 150

Coefficient of Thermal Expansion Testing ............................................................................. 150

Thermal Diffusivity Testing ..................................................................................................... 152
Specific Heat Capacity Testing ................................................................................................ 155
Summary of Findings ................................................................................................................ 157

10 RECOMMENDED TESTING PROGRAM FOR MASS CONCRETE ............................... 158

Recommended Laboratory Testing Method for Measurement of Heat Generation ............. 158
Recommended Laboratory Testing Method for Measuring Maturity/Equivalent Age ........ 159
Recommended Laboratory Testing Methods for Strength and Modulus of Elasticity ......... 160
Compressive strength ........................................................................................................ 160
Compressive Modulus of Elasticity .................................................................................. 161
Tensile Strength ................................................................................................................. 161
Recommended Laboratory Testing Method for Measurement of Coefficient of Thermal
Expansion ............................................................................................................................... 162
Recommended Physical Parameter for the Concrete Diffusivity........................................... 162
Recommended Physical Parameter for the Specific Heat Capacity....................................... 163
Summary of Testing Program .................................................................................................. 163

10
11CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE WORK............................. 164

Conclusions ............................................................................................................................... 164

Recommendations ..................................................................................................................... 164

APPENDIX

A METHOD OF TESTING FOR MEASURING THE HEAT OF HYDRATION OF

HYDRAULIC CEMENT USING ISOTHERMAL CONDUCTIVE CALORIMETRY .... 166

B RAW DATA-MORTAR CUBES AND APPARENT ACTIVATION ENERGY

CALCULATIONS .................................................................................................................... 172

C ISOTHERMAL CALORIMETRY RAW DATA AND ANALYSIS ................................... 185

Calorimetry Data of Cementitious Specimens ........................................................................ 185

Calorimetry Data of Mortar Specimens ................................................................................... 198

D SEMI ADIABATIC TEMPERATURE DATA ...................................................................... 207

E COMBINED CALORIMETRY DATA AND ANALYSIS .................................................. 211

F PHYSICAL DATA ................................................................................................................... 219

G CEMENTITIOUS MATERIAL DATA AND MILL CERTIFICATIONS .......................... 252

LIST OF REFERENCES ................................................................................................................. 267

BIOGRAPHICAL SKETCH ........................................................................................................... 277

11
 LIST OF TABLES

Table page

2-1 FDOT bridge environmental database results ...................................................................... 35

2-2 Cementitous material content for concrete materials ........................................................... 35

2-3 Mass concrete requirements per state agency ...................................................................... 36

2-4 Typical cementitous content used for mass concrete ........................................................... 38

4-1 Mortar cube mixture designs ................................................................................................. 62

4-2 Strength development parameters for each concrete mixture per ASTM 1074 ................. 65

4-3 Strength development parameters for each concrete mixture per exponential method ..... 68

4-4 Strength development parameters for each concrete mixture per isothermal
calorimetry / expoenential method ........................................................................................ 73

4-5 Strength development parameters for mixture 1 (100% Portland cement) per each
method of analysis.................................................................................................................. 74

4-6 Summary of Ea values per testing and analysis method ...................................................... 77

4-7 Percentage differences of Ea per testing and analysis method ............................................ 78

5-1 Mixture designs for concrete specimens ............................................................................... 86

5-2 Delivery temperatures for concrete mixes ............................................................................ 87

7-1 Comparison of energy rise values for each calorimetry method for each mix................. 113

8-1 Mixture designs for large-scale block specimens .............................................................. 115

8-2 Summary of apparent activation energy per testing and analysis method........................ 120

9-1 Specific heat for concrete material ...................................................................................... 156

A-1 Raw data sheet Mix 1 cubes 100% Portland cement ......................................................... 172

A-2 Raw data sheet Mix 1 cubes 100% Portland cement ......................................................... 172

A-3 Raw data sheet Mix 1 cubes 100% Portland cement ......................................................... 173

A-4 Raw data sheet Mix 2 cubes 50% Portland cement – 50% slag ........................................ 175

A-5 Raw data sheet Mix 2 cubes 50% Portland cement – 50% slag ........................................ 175

12
A-6 Raw data sheet Mix 2 cubes 50% Portland cement – 50% slag ........................................ 176

A-7 Raw data sheet Mix 3 cubes 65% Portland cement – 35% fly ash ................................... 178

A-8 Raw data sheet Mix 3 cubes 65% Portland cement – 35% fly ash ................................... 178

A-9 Raw data sheet Mix 3 cubes 65% portland cement – 35% fly ash ................................... 179

A-10 raw data sheet Mix 4 cubes 50%-30%-20% blend (Cement – slag – fly ash).................. 181

A-11 Raw data sheet Mix 4 cubes 50%-30%-20% blend (Cement – slag – fly ash) ................ 181

A-12 Raw data sheet Mix 4 cubes 50%-30%-20% blend (Cement – slag – fly ash) ................ 182

C-1 Mixture components, respective apparent activation energy and datum temperatures ... 185

D-1 Mixture designs for concrete specimens ............................................................................. 207

E-1 Mixture designs for mortar specimens used in the semi-adiabatic calorimeter ............... 211

F-1 Raw data compressive strength of cylinders- Mix 1 - 100% Portland cement ................ 219

F-2 Raw data compressive strength of cylinders- Mix 2 - 50% Portland cement – 50%
slag ........................................................................................................................................ 221

F-3 Raw data compressive strength of cylinders- Mix 2 - 65% Portland cement – 35% fly
ash.......................................................................................................................................... 223

F-4. Raw data compressive strength of cylinders- Mix 2 - 50% Portland cement – 30% slag
– 20% fly ash ........................................................................................................................ 225

F-5 Raw data splitting tensile strength of cylinders- Mix 1 - 100% Portland cement............ 228

F-6 Raw data splitting tensile strength of cylinders- Mix 2 - 50% Portland cement – 50%
slag ........................................................................................................................................ 230

F-7 Raw data splitting tensile strength of cylinders- Mix 2 - 65% Portland cement – 35%
fly ash .................................................................................................................................... 232

F-8 Raw data splitting tensile strength of cylinders- Mix 4 - 50% Portland - 30% slag -
20% fly ash ........................................................................................................................... 234

F-9 Raw data compressive modulus of elasticity of cylinders- Mix 1 - 100% Portland
cement ................................................................................................................................... 237

F-10 Raw data modulus of elasticity of cylinders- Mix 2 - 50% Portland cement – 50%
slag ........................................................................................................................................ 239

13
F-11 Raw data modulus of elasticity of cylinders- Mix 2 - 65% Portland cement – 35% fly
ash.......................................................................................................................................... 241

F-12 Raw data modulus of elasticity of cylinders- Mix 4 - 50% Portland cement - 30%
slag -20% fly ash .................................................................................................................. 243

F-13 Raw data tensile modulus of elasticity of cylinders- Mix 1 - 100% Portland cement ..... 246

F-14 Raw data tensile modulus of elasticity of cylinders- Mix 2 - 50% Portland cement –
50% slag ................................................................................................................................ 247

F-15 Raw data tensile modulus of elasticity of cylinders- Mix 2 - 65% Portland cement –
35% fly ash ........................................................................................................................... 248

F-16 Raw data tensile modulus of elasticity of cylinders- Mix 4 - 50% Portland - 30% slag
-20% fly ash .......................................................................................................................... 249

F-17 Raw data coefficient of thermal expansion testing ............................................................ 251

G-1 X-ray fluorescence data for Portland cement used in each mix ........................................ 254

G-2 X-ray diffraction data for Portland cement used in each mix ........................................... 254

14
 LIST OF FIGURES

Figure page

1-1 Behavior of mass concrete ..................................................................................................... 27

3-1 Isothermal conduction calorimeter test set up ...................................................................... 49

3-2 Mixing cell and ampoule used for internal mixing procedure ............................................ 50

3-3 Power vs. time for 0.50 w/c Portland cement at various temperatures ............................... 53

3-4 Energy vs. time for 0.50 w/c Portland cement at various temperatures ............................. 53

3-5 Fully hydrated specimen (23°C) vs. partially hydrated specimen (60°C) .......................... 54

3-6 Energy vs. time for 0.40 w/c Portland cement at various temperatures ............................. 55

4-1 Nurse-Saul maturity function (Carino, 2004) ....................................................................... 58

4-2 Compressive strength of mortar cubes vs. time for each temperature ................................ 64

4-3 Activation energy calculation for hyperbolic method ......................................................... 65

4-4 Compressive strength of mortar cubes vs. time for each temperature ................................ 68

4-5 Activation energy calculation for exponential method ........................................................ 69

4-6 Isothermal calorimetry data α vs. time for four temperatures ............................................. 72

4-7 Apparent activation energy calculation for exponential method ........................................ 73

4-8 Residual error vs. normalized time for hyperbolic curve fitting method (compressive
strength) .................................................................................................................................. 75

4-9 Residual error vs. normalized time for exponential curve fitting method (compressive
strength) .................................................................................................................................. 76

4-10 Residual error vs. normalized time for exponential curve fitting method (isothermal
calorimetry) ............................................................................................................................ 76

5-1 Heat flux sensor ...................................................................................................................... 82

5-2 Calculated losses for the water calibration test .................................................................... 83

5-3 Adiabatic temperature rise for Mix 1 .................................................................................... 87

5-4 Adiabatic temperature rise curves for Mix 1, delivered mix and lab mix .......................... 89

15
5-5 Adiabatic temperature rise for Mix 2, delivered mix and lab mix ...................................... 89

5-6 Adiabatic temperature rise for each mix ............................................................................... 90

6-1 Schematic of Sure Cure system with hydration chamber .................................................... 93

6-2 Photograph of the Sure Cure system with the computer, hydration chamber and
controller box.......................................................................................................................... 94

6-3 Sure Cure and semi-adiabatic temperature vs. time ............................................................. 96

6-4 Sure Cure and semi-adiabatic temperature vs. time ............................................................. 97

6-5 Sure Cure temperature rise for large scale block experiments ............................................ 97

7-1 Comparison of time-temperature histories between Sure Cure system and the IQ
drum for Mix 1 ..................................................................................................................... 101

7-2 Comparison of time-temperature histories between Sure Cure system and the IQ
drum for Mix 2 ..................................................................................................................... 102

7-3 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 1..................................................................... 104

7-4 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 2..................................................................... 105

7-5 Mortar cube compressive strength vs. time for Mix 2 ....................................................... 106

7-6 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 3..................................................................... 107

7-7 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 4..................................................................... 107

7-8 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and the IQ drum for mortar Mix 1 .......................................................................... 109

7-9 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and the IQ drum for mortar Mix 3 .......................................................................... 109

7-10 Cross section of isothermal calorimetry device ................................................................. 110

7-11 Cross section of semi-adiabatic device ............................................................................... 112

8-1 Large scale block testing configuration .............................................................................. 116

8-2 Thermocouple location for Sure Cure system .................................................................... 117

16
8-3 Time/temperature history of 4”x8” cylinder specimens .................................................... 118

8-4 Time/temperature history block – Sure Cure cylinder specimens .................................... 119

8-5 Compressive strength vs. time for each mix....................................................................... 121

8-6 Compressive strength vs. time for Mix 1 - 100% Portland cement .................................. 122

8-7 Compressive strength vs. maturity for Mix 1 - 100% Portland cement ........................... 123

8-8 Compressive strength vs. equivalent age for Mix 1 - 100% Portland cement ................. 124

8-9 Sure Cure specimen mold .................................................................................................... 125

8-10 Compressive strength vs. equivalent age for Mix 2 – 50% Portland cement - 50%
slag ........................................................................................................................................ 127

8-11 Compressive strength vs. equivalent age for Mix 3 – 65% Portland cement - 35% fly
ash.......................................................................................................................................... 128

8-12 Compressive strength vs. equivalent age for Mix 4 – 50% Portland cement- 30% slag
-20% fly ash .......................................................................................................................... 128

8-13 Splitting tensile strength vs. time for each mix .................................................................. 129

8-14 Splitting tensile strength vs. maturity for Mix 1 - 100% Portland cement ....................... 130

8-15 Splitting tensile strength vs. equivalent age for Mix 1 - 100% Portland cement ............. 131

8-16 Splitting tensile strength vs. equivalent age for Mix 2 - 50% Portland cement 50%
slag ........................................................................................................................................ 132

8-17 Splitting tensile strength vs. equivalent age for Mix 3 - 65% Portland cement 35% fly
ash.......................................................................................................................................... 133

8-18 Splitting tensile strength vs. equivalent age for Mix 4 – 50% Portland cement - 30%
slag -20% fly ash .................................................................................................................. 133

8-19 Typical stress-strain diagram for concrete, showing the different elastic moduli
(Mindess 2003) ..................................................................................................................... 135

8-20 Stress-strain diagram for concrete specimen ...................................................................... 137

8-21 Compressive modulus of elasticity vs. time for each mix ................................................. 139

8-22 Compressive modulus of elasticity vs. maturity for Mix 1- 100% Portland cement ....... 140

8-23 Compressive modulus of elasticity vs. equivalent age for Mix 1- 100% Portland
cement ................................................................................................................................... 141

17
8-24 Compressive modulus of elasticity vs. equivalent age for Mix 2 - 50% Portland
cement - 50% slag ................................................................................................................ 142

8-25 Compressive modulus of elasticity vs. equivalent age equivalent age for Mix 3 - 65%
Portland cement - 35% fly ash............................................................................................. 143

8-26 Compressive modulus of elasticity vs. equivalent age for Mix 4 – 50% Portland
cement - 30% slag -20% fly ash .......................................................................................... 143

8-27 Photo of tensile (flexural) modulus of elasticity test configuration .................................. 144

8-28 Tensile modulus of elasticity vs. time for each mix .......................................................... 145

8-29 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 1 ........................................................................................................................ 147

8-30 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 2 ........................................................................................................................ 148

8-31 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 3 ........................................................................................................................ 148

8-32 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 4 ........................................................................................................................ 149

9-1 Coefficient of thermal expansion vs. time for each mix .................................................... 151

9-2 Thermal diffusivity vs. time for each mix .......................................................................... 153

A-1 A schematic drawing of a heat conduction calorimeter ..................................................... 167

A-2 Steady state calibration plot ................................................................................................. 168

A-3 Cutaway of one of the 8 calorimetric channels showing the twin configuration ............. 171

B-1 Compressive strength vs. time - hyperbolic model for Mix 1 (ASTM C 1074) .............. 173

B-2 Compressive strength vs. time - exponential model for Mix 1 (Constant β) ................... 174

B-3 Compressive strength vs. time - exponential model for Mix 1 (constant αu, β) .............. 174

B-4 Compressive strength vs. time - hyperbolic model for Mix 2 (ASTM C 1074) .............. 176

B-5 Compressive strength vs. time - exponential model for Mix 2 (Constant β) ................... 177

B-6 Compressive strength vs. time - exponential model for Mix 2 (constant αu, β) .............. 177

B-7 Compressive strength vs. time - hyperbolic model – Mix 3 (ASTM C 1074) ................. 179

18
B-8 Compressive strength vs. time - exponential model for Mix 3 (Constant β) ................... 180

B-9 Compressive strength vs. time - exponential model for Mix 3 (constant αu, β) .............. 180

B-10 Compressive strength vs. time - hyperbolic model – Mix 4 (ASTM C 1074) ................. 182

B-11 Compressive strength vs. time - exponential model for Mix 4 (Constant β) ................... 183

B-12 Compressive strength vs. time - exponential model for Mix 4 (constant αu, β) .............. 183

B-13 Summary of time of set data ................................................................................................ 184

C-1 Power vs. time for Mix 1 ..................................................................................................... 186

C-2 Energy vs. time for Mix 1 .................................................................................................... 186

C-3 Power vs. maturity for Mix 1 .............................................................................................. 187

C-4 Energy vs. maturity for Mix 1 ............................................................................................. 187

C-5 Power vs. equivalent age for Mix 1 .................................................................................... 188

C-6 Energy vs. equivalent age for Mix 1 ................................................................................... 188

C-7 Power vs. time for Mix 2 ..................................................................................................... 189

C-8 Energy vs. time for Mix 2 .................................................................................................... 189

C-9 Power vs. maturity for Mix 2 .............................................................................................. 190

C-10 Energy vs. maturity for Mix 2 ............................................................................................. 190

C-11 Power vs. equivalent age for Mix 2 .................................................................................... 191

C-12 Energy vs. equivalent age for Mix 2 ................................................................................... 191

C-13 Power vs. time for Mix 3 ..................................................................................................... 192

C-14 Energy vs. time for Mix 3 .................................................................................................... 192

C-15 Power vs. maturity for Mix 3 .............................................................................................. 193

C-16 Energy vs. maturity for Mix 3 ............................................................................................. 193

C-17 Power vs. equivalent age for Mix 3 .................................................................................... 194

C-18 Energy vs. equivalent age for Mix 4 ................................................................................... 194

C-19 Power vs. time for Mix 4 ..................................................................................................... 195

19
C-20 Power vs. energy for Mix 4 ................................................................................................. 195

C-21 Power vs. maturity for Mix 3 .............................................................................................. 196

C-22 Energy vs. maturity for Mix 4 ............................................................................................. 196

C-23 Power vs. equivalent age for Mix 4 .................................................................................... 197

C-24 Energy vs. equivalent age for Mix 4 ................................................................................... 197

C-25 Power vs. time for Mortar Mix 1......................................................................................... 198

C-26 Energy vs. time for Mortar Mix 1 ....................................................................................... 199

C-27 Power vs. maturity for Mortar Mix 1 .................................................................................. 199

C-28 Power vs. maturity for Mortar Mix 1 .................................................................................. 200

C-29 Power vs. equivalent age for Mortar Mix 1 ........................................................................ 200

C-30 Energy vs. equivalent age for Mortar Mix 1 ...................................................................... 201

C-31 Power vs. time for Mortar Mix 3......................................................................................... 201

C-32 Energy vs. time for Mortar Mix 3 ....................................................................................... 202

C-33 Power vs. maturity for Mortar Mix 3 .................................................................................. 202

C-34 Energy vs. maturity for Mortar Mix 3 ................................................................................ 203

C-35 Power vs. equivalent age for Mortar Mix 3 ........................................................................ 203

C-36 Energy vs. equivalent age for Mortar Mix 3 ...................................................................... 204

C-37 Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 1 ............................................................................................................................... 204

C-38 Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 2 ............................................................................................................................... 205

C-39 Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 3 ............................................................................................................................... 205

C-40 Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 4 ............................................................................................................................... 206

D-1 Typical water calibration ..................................................................................................... 207

D-2 Semi-adiabatic temperature measurements for mix 1 (laboratory mix) ........................... 208

20
D-3 Semi-adiabatic temperature measurements for concrete mix 1 (lab and delivered)
mixes ..................................................................................................................................... 208

D-4 Semi-adiabatic temperature measurements for concrete mix 2 (lab and delivered)
mixes ..................................................................................................................................... 209

D-5 Semi-adiabatic temperature measurements for mix 3 (delivered) .................................... 209

D-6 Semi-adiabatic temperature measurements for mix 4 (delivered) .................................... 210

D-7 Semi-adiabatic temperature measurements for each mix .................................................. 210

E-1 Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 1 ................................................................................................................ 212

E-2 Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 2 ................................................................................................................ 212

E-3 Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 3 ................................................................................................................ 213

E-4 Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 4 ................................................................................................................ 213

E-5 Time-temperature histories obtained by the Sure Cure for each mix ............................... 214

E-6 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 1..................................................................... 214

E-7 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 2..................................................................... 215

E-8 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 3..................................................................... 215

E-9 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and isothermal calorimetry for Mix 4..................................................................... 216

E-10 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and the IQ drum for mortar Mix 1. ......................................................................... 216

E-11 Comparison of equivalent age – energy histories between semi-adiabatic calorimetry

system and the IQ drum for mortar Mix 3. ......................................................................... 217

E-12 Comparison of semi-adiabatic test and three different Sure Cure system offset
temperatures for a trial mix. ................................................................................................ 217

E-13 Comparison of semi-adiabatic test and four different Sure Cure system offset
temperatures for a trial mix. ................................................................................................ 218

21
F-1 Compressive strength vs. time for Mix 1 - 100% Portland cement .................................. 220

F-2 Compressive strength vs. maturity for Mix 1 - 100% Portland cement ........................... 220

F-3 Compressive strength vs. equivalent age for Mix 1 - 100% Portland cement ................. 221

F-4 Compressive strength vs. time for Mix 2 - 50% Portland cement – 50% slag ................. 222

F-5 Compressive strength vs. maturity for Mix 2 - 50% Portland cement – 50% slag .......... 222

F-6 Compressive strength vs. equivalent age for Mix 2 – 50% Portland - 50% slag ............. 223

F-7 Compressive strength vs. time for Mix 3 - 65% Portland cement – 35% fly ash ............ 224

F-8 Compressive strength vs. maturity for Mix 3 - 65% Portland cement – 35% fly ash ..... 224

F-9 Compressive strength vs. equivalent age for Mix 3 - 65% Portland cement – 35% fly
ash.......................................................................................................................................... 225

F-10 Compressive strength vs. time for Mix 4 – 50% Portland - 30% slag -20% fly ash........ 226

F-11 Compressive strength vs. maturity for Mix 4 – 50% Portland - 30% slag -20% fly ash . 226

F-12 Compressive strength vs. equivalent age for Mix 4 – 50% Portland - 30% slag -20%
fly ash .................................................................................................................................... 227

F-13 Compressive strength vs. age summary for each mix........................................................ 227

F-14 Compressive strength vs. equivalent age summary for each mix ..................................... 228

F-15 Tensile strength vs. time for Mix 1 - 100% Portland cement ............................................ 229

F-16 Tensile strength vs. maturity for Mix 1 - 100% Portland cement ..................................... 229

F-17 Tensile strength vs. equivalent age for Mix 1 - 100% Portland cement ........................... 230

F-18 Tensile strength vs. time for Mix 2 - 50% Portland cement – 50% slag .......................... 231

F-19 Tensile strength vs. maturity for Mix 2 - 50% Portland cement – 50% slag ................... 231

F-20 Tensile strength vs. equivalent age for Mix 2 - 50% Portland cement – 50% slag ......... 232

F-21 Tensile strength vs. time for Mix 3 - 65% Portland cement 35% fly ash ......................... 233

F-22 Tensile strength vs. maturity for Mix 3 - 65% Portland cement 35% fly ash .................. 233

F-23 Tensile strength vs. equivalent age for Mix 3 - 65% Portland cement 35% fly ash ........ 234

F-24 Tensile strength vs. time for Mix 4 – 50% Portland - 30% slag - 20% fly ash ................ 235

22
F-25 Tensile strength vs. maturity for Mix 4 – 50% Portland - 30% slag - 20% fly ash ......... 235

F-26 Splitting tensile strength vs. equivalent age for Mix 4 – 50% Portland - 30% slag -
20% fly ash ........................................................................................................................... 236

F-27 Compressive strength vs. age summary for each mix........................................................ 236

F-28 Tensile strength vs. equivalent age summary for each mix ............................................... 237

F-29 Compressive modulus of elasticity vs. time for Mix 1- 100% Portland cement .............. 238

F-30 Compressive modulus of elasticity vs. maturity for Mix 1- 100% Portland cement ....... 238

F-31 Compressive modulus of elasticity vs. equivalent age for Mix 1- 100% Portland
cement ................................................................................................................................... 239

F-32 Compressive modulus of elasticity vs. age for Mix 2 - 50% Portland cement 50%
slag ........................................................................................................................................ 240

F-33 Compressive modulus of maturity vs. age for Mix 2 - 50% Portland cement 50% slag . 240

F-34 Compressive modulus of elasticity vs. equivalent age for Mix 2 - 50% Portland
cement - 50% slag ................................................................................................................ 241

F-35 Compressive modulus of elasticity vs. age for Mix 3 - 65% Portland cement 35% fly
ash.......................................................................................................................................... 242

F-36 Compressive modulus of maturity vs. age for Mix 3 - 65% Portland cement 35% fly
ash.......................................................................................................................................... 242

F-37 Compressive modulus of elasticity vs. equivalent age equivalent age for Mix 3 - 65%
Portland cement 35% fly ash ............................................................................................... 243

F-38 Compressive modulus of elasticity vs. age for Mix 4 – 50% Portland cement - 30%
slag - 20% fly ash ................................................................................................................. 244

F-39 Compressive modulus of elasticity vs. maturity for Mix 4 – 50% Portland cement -
30% slag - 20% fly ash ........................................................................................................ 244

F-40 Compressive modulus of elasticity vs. equivalent age for Mix 4 – 50% Portland
cement - 30% slag -20% fly ash .......................................................................................... 245

F-41 Compressive modulus of elasticity vs. age for each mix................................................... 245

F-42 Compressive modulus of elasticity vs. age for each mix................................................... 246

F-43 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 1 - 100% Portland cement ............................................................................... 247

23
F-44 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 2 - 50% Portland cement 50% slag................................................................. 248

F-45 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 3 - 65% Portland cement 35% fly ash ............................................................ 249

F-46 Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 4 – 50% Portland - 30% slag -20% fly ash .................................................... 250

F-47 Tensile modulus of elasticity vs. time for each mix .......................................................... 250

F-48 Coefficient of thermal expansion vs. time for each mix .................................................... 251

G-1 Solution calorimetry data for Mix 1 – 100% Portland cement.......................................... 252

G-2 Solution calorimetry data for Mix 2 – 50% Portland cement – 50% slag ........................ 252

G-3 Solution calorimetry data for Mix 3 – 65% Portland cement – 35% fly ash.................... 253

G-4 Solution calorimetry data for Mix 3 – 50% Portland cement – 30% slag – 20% fly
ash.......................................................................................................................................... 253

G-5 Laboratory testing data of Portland cement used for Mix 1 .............................................. 255

G-6 Laboratory testing data of Portland cement used for Mix 1 .............................................. 256

G-7 Laboratory testing data of Portland cement used for Mix 2 .............................................. 257

G-8 Laboratory testing data of Portland cement used for Mix 2 .............................................. 258

G-9 Laboratory testing data of granulated blast furnace slag used for Mix 2 ......................... 259

G-10 Laboratory testing data of granulated blast furnace slag used for Mix 2 ......................... 260

G-11 Laboratory testing data of Portland cement used for Mix 3 .............................................. 261

G-12 Laboratory testing data of fly ash used for Mix 3 .............................................................. 262

G-13 Laboratory testing data of fly ash used for Mix 3 .............................................................. 263

G-14 Mill certification data for Portland cement used in each mix ........................................... 264

G-15 Mill certification data for granulated blast furnace slag cement used in each mix .......... 265

G-16 Mill certification data for fly ash cement used in each mix .............................................. 266

24
 Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

DETERMINATION OF TEST METHODS FOR THE

PREDICTION OF THE BEHAVIOR OF MASS CONCRETE

By

Christopher C. Ferraro

December 2009

Chair: Name Mang Tia

Co chair: Reynaldo Roque
Major: Civil Engineering

Hydration at early ages results from chemical and physical processes that take place

between Portland cement and water, and is an exothermic process. The resultant heat evolution

and temperature rise for massive concrete placements can be so great that the temperature

differentials between the internal concrete core and outer concrete stratum can cause cracking

due to thermal gradients. Accurate prediction of temperature distribution and stresses in mass

concrete is needed to determine if a given concrete mixture design may have problems in the

field, so that adjustments to the design can be made prior to its use.

This research examines calorimetric, strength, and physical testing methods in an effort to

predict the thermal and physical behavior of mass concrete. Four groups of concrete mixture

types containing different cementitious materials are examined. One group contains Portland

cement, while the other three groups incorporate large replacements of supplementary

cementitious materials: granulated blast furnace slag, fly ash, and a ternary blend (combining

Portland cement, fly ash, and slag).

25
 CHAPTER 1
INTRODUCTION

Background

The setting and hardening of traditional concrete are the result of chemical and physical

processes that occur when Portland cement and water are combined. This chemical reaction

(hydration) is an exothermic process which results in the evolution of heat, and the rise of

concrete temperature. For mass concrete elements, the heat evolution and resultant temperature

rise can be so great that the temperature differentials between the internal concrete core and outer

concrete stratum result in concrete cracking due to thermal gradients. Accurate modeling for the

prediction of temperature distribution and stresses in mass concrete is needed to determine if a

given concrete mixture design may have problems in real world applications, so that adjustments

to the mix design can be made prior to its adopted use.

Definition of Mass Concrete

Concrete cast in mass structures can develop excessive internal tensile stresses capable of

inducing significant cracking damage and possible failure. Such cracking can lead to reduced

structural capacity and certainly degrades concrete durability by permitting the ingress of

deleterious ionic species such as chlorides and sulfates. The American Concrete Institute (ACI)

currently defines mass concrete as “any volume of concrete with dimensions large enough to

require that measures be taken to cope with generation of heat from hydration from cement and

attendant volume change to minimize cracking” (ACI 207.1-R96). However, this definition is a

bit too vague for specification of concrete. State and local agencies typically define mass

concrete within their construction specification documents. Specification requirements vary with

the specifying organization and with local conditions.

26
Figure 1-1. Behavior of mass concrete

The primary reason mass concrete cracks is due to the heat evolution and resultant

temperature differentials between the internal concrete core and outer concrete stratum. Figure 1-

1 provides an illustration of evolution of cracking in concrete masses (Bamforth 1984). When

concrete is placed, it is a plastic material, uniform in temperature and has essentially no strength.

At early ages, the inner core of concrete will begin to develop heat and experience a resultant

temperature rise as illustrated in Figure 1-1a. However, the outer stratum will tend to experience

localized cooling (with the absence of adequate insulation) due to the dissipation of heat to the

colder environment. However, the inner core of the mass concrete will be insulated and the heat

will not be dissipated causing a localized temperature rise as illustrated I figure 1-1b. The hotter

27
concrete in the inner core experiences localized expansion shown by figure 1-1c. The resultant

cracking will be tensile in nature, typically initiating at the surface of the concrete and

propagating inward, shown by figure 1-1d.

Research Needs

For the modeling and prediction of temperature distribution in mass concrete structures,

knowledge of the following properties of concrete is needed:

• Heat generation rate

• Specific heat capacity
• Thermal diffusivity
• Coefficient of thermal expansion

For the prediction of stresses, strains and the resistance to cracking of mass concrete

structures, the following properties at early ages must also be known:

• Compressive strength
• Tensile and flexural strength
• Compressive modulus of elasticity
• Tensile modulus of elasticity

Complications and uncertainties in the determination of these properties arise since these

properties are functions of the hydration state of the cementitious materials and are therefore

dependent upon the curing history of the concrete. The industry needs a reliable and effective

testing regimen and analysis method so that the results from laboratory tests can be used in

thermal and stress analysis for the prediction of the behavior of mass concrete.

Objectives of Research

An accurate determination of physical and thermal properties of early-age concrete (as

functions of the maturity/hydration of concrete) is necessary in order to predict the physical

behavior a resulting from thermal distribution and corresponding stresses within mass concrete.

The current models available isolate specific properties of mass concrete in effort to predict

28
behavior. However, there are many parameters which influence mass concrete behavior and

these properties are interrelated and must be considered a system.

The main objective of this study is to develop a test regimen and analysis methodology to

provide these necessary input parameters. The specific objectives of this research are:

• Identify the appropriate test method for the prediction and measurement of heat of
hydration in cementitious materials.

• Analyze the results from heat of hydration testing which can be utilized for modeling and
predicting temperature development.

• Establish quantifiable relationships between temperature history and physical properties of

concrete materials.

• Develop a physical testing regimen which efficiently quantifies and characterizes the
characteristics which are related to the thermal cracking of mass concrete.

Hypothesis

The performance of mass concrete in its resistance to cracking is governed by a set of

critical field conditions which include heat of hydration of cementitious components resulting in

temperature rise, thermal characteristics, modulus of elasticity, and relative strength. Accurate

prediction of the behavior of a mass concrete structure depends on the accuracy of the

documentation of the thermal and mechanical properties used. In the past, these properties have

typically been determined with respect to time. Early-age thermal and mechanical properties of

cementitious materials are functions of the maturity/hydration history of these materials and must

be properly evaluated through laboratory testing and data analysis.

Research Approach

Separate physical and thermal testing programs were developed to investigate state-of-the-

art testing methods and to determine those methods which are suitable as input parameters for

analysis of the behavior of mass concrete.

29
The thermal testing regimen consisted of the following:

• Isothermal conduction calorimetry

• Semi-adiabatic calorimetry
• Sure Cure/adiabatic calorimetry
• Heat of solution calorimetry (ASTM C186)
• Thermal diffusivity (CRD C 36-73)
• Specific heat capacity

The physical testing regimen involved the following tests:

• Compressive strength (ASTM C39/109)

• Compressive modulus of elasticity (ASTM C469)
• Splitting tensile strength (ASTM C496)
• Flexural Strength (ASTM C-78)
• Tensile Modulus of elasticity
• Coefficient of thermal expansion (AASHTO TP60)

The program included testing on relatively small cement and concrete specimens. Large

scale block specimens were created in an effort to validate the measure the temperature and

strain of large scale specimens created in the lab. A portion of the project involved the creation

of a finite element model (Lawrence, 2009), and accordingly the results obtained from the

physical testing were used to validate the model upon its completion.

Significance of Research

Currently, there are no reliable and effective methods for determining the thermal and

physical/strength properties that predict thermal and physical behavior of mass concrete at early-

ages. Therefore, development of a testing regimen and analysis technique which can produce the

necessary thermal and physical properties of concrete used as model input parameters for mass

concrete would constitute a substantial contribution to science and the construction industry.

Chemical Analysis of Cementitious Components

Researchers often use cement chemistry to determine activation energy and total heat

available in a cementitious constituent as provided by X-ray fluorescence (XRF) or X-ray

30
diffraction (XRD) analysis (Schindler, 2004; Schindler and Folliard, 2005). The original

equations used for the conversion of chemical oxides to the cement phases were developed by

Bogue in the 1940’s (Bogue, 1947). However, it has been recently determined that the chemical

data obtained via XRF have relative bias and potential errors (Stutzman, 2007). Accordingly,

chemical analysis for the prediction of heat of hydration may be error prone.

The American Society of Testing and Materials (ASTM) and the American Association of

State and Highway Officials (AASHTO) recently harmonized their specifications for Portland

cement in an effort to create uniformity in the standards. As a result, ASTM C150 and AASHTO

M85 now have the same requirements regarding Portland cement. One of the major changes in

the standard is that both standards no longer require a limit on C3 S for type II (considered low

heat) cement (Melander, 2007). Prior to the change, ASTM C 150-04 table 2 limited the C3 S

content to be 58%. Currently, both standards require the type II cement to meet the following

requirement (ASTM, 2008d):

C 3 S + 4.75C 3 A ≤ 100% (1-1)

Typically, the components in Portland cement necessary for the calculation of equation 1-

1 are obtained via X-ray florescence (XRF) as per ASTM C-114, the standard test method for

the chemical analysis of Portland cement. Note 4 of ASTM C150-07 states “The limit on the

sum of C3 S +4.75 C3 A provides control on the heat of hydration of cement and is consistent with

a test method C 186 7-day heat of hydration limit of 335KJ/kg (80cal/g)” (ASTM, 2008d, p2).

However, the required quality assurance and quality control of cements used on FDOT projects,

has revealed that several type I/II cements which adhere to equation 1-1 per XRF analysis were

determined to have heat of hydration values at 7 days per ASTM C 186 above 335KJ/kg. Thus,

31
the concept of limiting the heat of hydration of cement via the use of chemical analysis is not

appropriate.

Considering the documented inconsistencies in the chemical analysis of Portland cement

components discussed in published documents, the use of chemical analysis for the prediction of

the heat of hydration of cementitious materials and Portland cement concrete does not yield

conservative results. Therefore, development of a finite element model which utilizes physical

testing (calorimetry) as opposed to chemical analysis for the determination of heat generation

and temperature rise of concrete is proposed.

Currently, no known analysis model predicts the heat rise in massive concrete structures

and also incorporates the results provided by isothermal conduction calorimetry for input

parameters. However, a model documented by Poole and Riding (Poole et. al, 2007 and Riding

et. al, 2007) utilizes semi-adiabatic calorimetry for the modeling of mass concrete. Both the

semi-adiabatic calorimetry test and the isothermal calorimetry test were investigated in this

study.

Outline of Dissertation

Chapter 2 is a review of the literature citing current specifications and sources for stresses

which result in cracking due to temperature rise in massive concrete structures. Chapter 3

addresses the details of the isothermal cement calorimetry test and its potential uses for mass

concrete.

Chapter 4 discusses maturity and equivalent age determination of cementitious and

concrete materials and the importance of determining their appropriate relationships. Chapters 5

and 6 discuss the semi-adiabatic and adiabatic calorimetry, respectively. The chapters within this

document discuss the thermal testing techniques that were studied in this project, with the

exception of thermal diffusivity and specific heat capacity testing regimens. Quantification of

32
thermal diffusivity and specific heat capacity of concrete composed of mixture components

typical for the state of Florida are reported by Ochiai (2009).

Chapter 7 addresses the maturity and equivalent age comparisons between isothermal

calorimetry and semi adiabatic and adiabatic calorimetry. Chapter 8 examines the results

obtained from the physical testing regimen performed on the large block specimens. Chapter 9

discusses the results of the large block experiment testing.

Recommendations for a testing program for the prediction of mass concrete behavior are

detailed in Chapter 10. Chapter 11 provides discussion, conclusions, and recommendations for

future research efforts.

33
 CHAPTER 2
LITERATURE REVIEW

Mass Concrete Specifications

More recently, ACI Specifications for Structural Concrete (ACI 301-05) has made

provisions pertaining to mass concrete within the Optional Requirements Checklist, which

identifies actions required by the Architect/Engineer to include the following; "Designate

portions of the structure to be treated as either plain mass concrete or reinforced mass concrete.

Whether or not concrete should be designated as mass concrete depends on many factors,

including weather conditions, the volume-surface ratio, rate of hydration, degree of restraint to

volume change, temperature and mass of surrounding materials, and functional and aesthetic

effect of cracking. In general, heat generation should be considered when the minimum cross-

sectional dimension approaches or exceeds 2-1/2 ft [760 mm] or when cement contents above

600 lb/yd ³ [356 kg/m ³] are used. The requirements for each project however, should be

evaluated on their own merits." (ACI 301-R05)

The ACI 301 document defines mass concrete by both a minimum dimension and a

minimum cementitious content. However, to consider any concrete with a total cementitious

content above 600 lb/yd3 to be mass concrete is not a practical requirement for concrete

construction in the state of Florida. Table 2.1 lists the structural classifications of concrete as per

Section 346 of the FDOT Road and Bridge Construction. Per Table 2.1, any structural concrete

with requirements above a Class II bridge deck is required to have a total cementitious content

above 608 lb/yd3. The FDOT Structures Manual states all structural elements exposed to a

moderately or severely aggressive environment must be made of Class IV, V or VI concrete.

A general survey of the FDOT’s bridge environmental database was used to determine the

approximate percentage of bridge structures which are located in moderately or severely

34
aggressive environments in the State of Florida. Table 2.1 provides the number of bridges in

Florida and the classification of each.

A survey of the FDOT’s Bridge Environmental Database was used to determine the

approximate percentage of bridge structures within the State of Florida which are located in

moderately or severely aggressive environments. Table 2.1 provides the total number and

environmental classification of each bridge within the State of Florida.

Table 2-1. FDOT bridge environmental database results

Total number of bridges in Florida* 11734
Number of bridges in the FDOT Bridge Environmental Database 6800
Number of bridges in severely or moderately aggressive environments 3262
Percentage of bridges in severely or moderately aggressive environments 48%
* Per National Bridge Inventory Records

According to the FDOT’s Bridge Environmental Database, the majority of bridges in the

State of Florida are considered to be located within a moderately or severely aggressive

environment. Therefore, if the construction industry within the state of Florida adopted the

Optional Requirements Checklist from ACI 301-R05, then a large percentage of the structural

concrete produced in the state would be considered mass concrete.

Table 2-2. Cementitous material content for concrete materials

Maximum Water
Minimum Total Cementitious
Class of Concrete Cementitious Materials
Materials Content (lb/yd3)
Ratio (lb/lb)
I (Pavement) 508 0.50
I (Special) 508 0.50
II 564 0.49
II Bridge Deck 611 0.44
III 611 0.44
III (Seal) 611 0.52
IV 658 0.41
IV (Drilled Shaft) 658 0.41
V (Special) 752 0.37
V 752 0.37
VI 752 0.37

35
 Many state DOTs define mass concrete with a minimum dimension or in a volumetric

manner similar to ACI 207. The Florida Department of Transportation Structures Manual defines

mass concrete to be the following:

1. “All Bridge components Except Drilled Shafts: When the minimum dimension of the
concrete exceeds 36-inches and the ratio of volume of concrete to the surface area is
greater than 12-inches, provide for mass concrete. (The surface area for this ratio includes
the summation of all the surface areas of the concrete component being considered,
including the full underside (bottom) surface of footings, caps, construction joints, etc.)
Note volume and surface area calculations in units of feet.

2. Drilled Shafts: All drilled shafts with diameters greater than 72-inches shall be designated
as mass concrete and a Technical Special Provision may be required.” (FDOT, 2009)

Seventeen out of the fifty State DOTs have requirements incorporated into the definition

and the conditions of mass concrete structural elements. Table 2.3 provides a summary of the

requirements for mass concrete regarding minimum dimension for the classification of mass

concrete elements, specifications for maximum placing temperature, maximum allowable curing

temperature and maximum allowable temperature differential (Chini et.al, 2003).

Table 2-3. Mass concrete requirements per state agency

Maximum Maximum
Maximum
Minimum Placement Curing
State Temperature
Dimension (ft.) Temperature Temperature
Differential (°F)
(°F) (°F)
Arkansas - 75 - 36
Specified by
thermal control
California 6.5 - 160
plan provided by
contractor
Colorado 5 - 165 45
First 48 hrs=
Determined on 40°F
Delaware - 160
project basis 2-7 days= 50°F
8-14 days= 60 °F
3 (structural) /
Florida - 185 35
6(drill shaft)
Georgia - - - 50
Illinois - - 160 35
Indiana - - - 35

36
Table 2-3. Continued
Maximum Maximum
Maximum
Minimum Placement Curing
State Temperature
Dimension (ft.) Temperature Temperature
Differential (°F)
(°F) (°F)
Iowa 3.9 65 160 35
Kentucky - - 160 35
Minnesota - - 160 35
Nebraska - - 176 27
North
- 75 - 36
Carolina
North
- - 160 50
Dakota
South
- 80 - 35
Carolina
Texas - 75 - 35
170°F (slag)
Virginia 5 - 35
160°F (fly ash)
West
4 - 160 35
Virginia

As per Table 2-3, the FDOT does not have requirements on the maximum placement

temperature nor the maximum allowable temperature in mass concrete. The FDOT requires that

a temperature control plan be submitted to and accepted by the SMO prior to the placement of

mass concrete on a given project. Therefore, the FDOT may decide not to accept a given

concrete mixture design as provided by the contractor.

A survey of mixes within the FDOT SMO database was performed to determine the

typical cementitious material type and content mass concrete mix design. The database contains

mass concrete mix design information for mixes used in the state of Florida between 1980 and

the present.

Table 2-4 provides a brief summary of 32 typical mix designs used for mass concrete. The

mix designs include the use of Type II cement, replacement of Portland cement with Grade 100,

granulated Blast Furnace Slag, or Type F fly ash. A search of the FDOT database revealed that

37
the FDOT has not accepted a mass concrete mix design which does not incorporate

supplementary cementitious materials since 1980. Type II Portland cement produces less heat

during the process of hydration than Type I cement (ASTM C 150). Supplementary cementitious

materials (as a replacement for Portland cement), generate less heat than concrete mixes which

utilize Portland cement alone (Malhotra and Mehta, 1996). The physical and chemical attributes

of supplementary cementitious materials are discussed in further detail in subsequent chapters.

Table 2-4. Typical cementitous content used for mass concrete

Fly Blast Blast
FDOT Cement Cement Fly
Name Ash Furnace Furnace
Class Type (lbs) Ash %
(lbs) Slag (lbs) Slag %
Mix #1 IV II 610 134 0 18.01 0
Mix #2 IV II 600 132 0 18.03 0
Mix #3 IV II 359 83 0 18.78 0
Mix #4 IV I 625 150 0 19.35 0
Mix #5 IV II 314 77 0 19.69 0
Mix #6 IV II 584 146 0 20 0
Mix #7 IV II 576 144 0 20 0
Mix #8 II II 457 115 0 20.1 0
Mix #9 II II 344 83 0 19.44 0
Mix #10 II II 329 0 115 0 25.9
Mix #11 IV II 500 200 0 28.57 0
IV
Mix #12 Drilled II 523 257 0 32.95 0
Shaft
Mix #13 IV II 500 260 0 34.21 0
Mix #14 IV II 428 230 0 34.95 0
IV
Mix #15 Drilled II 478 257 0 34.97 0
Shaft
Mix #16 II II 500 270 0 35.06 0
Mix #17 IV II 438 243 0 35.68 0
Mix #18 IV II 438 292 0 40 0
Mix #19 IV II 450 383 0 45.98 0
IV
Mix #20 Drilled II 440 390 0 46.99 0
Shaft
Mix #21 IV II 346 320 0 48.05 0
Mix #22 II II 296 274 0 48.07 0
Mix #23 II II 296 274 0 48.07 0

38
Table 2-4. Continued.
Fly Blast Blast
FDOT Cement Cement Fly
Name Ash Furnace Furnace
Class Type (lbs) Ash %
(lbs) Slag (lbs) Slag %
Mix #24 IV II 336 329 0 49.47 0
Mix #25 II II 196 0 196 0 50
Mix #26 IV II 450 450 0 50 0
Mix #27 IV II 330 0 330 0 50
Mix #30 V II 370 0 520 0 58.43
IV
Mix #31 Drilled I/II 290 0 436 0 60.06
Shaft
Mix #32 IV II 200 0 460 0 69.7

Tensile Stresses in Mass Concrete

As stated earlier, tensile stresses are the primary cause of failure of mass concrete

structures. Tensile stresses in mass concrete typically evolve from two primary sources: thermal

gradients throughout the concrete structure and delayed ettringite formation.

Tensile Stresses Due to Thermal Gradients

Thermal gradients are primarily induced by heat loss from the outer surface of the mass

concrete structure. As cement hydrates, it produces heat, increasing the temperature of the

concrete. Should the outer surface of the concrete be exposed to external temperatures lower than

those developed inside the structure by hydration, a temperature gradient will be created. Large

differences in temperature will lead to thermal stresses that can result in cracking. This

phenomenon is intensified by the use of cements high in C3 S and/or C3 A, as these compounds

are responsible for the majority of early heat development. It can also be intensified by cements

with higher fineness, resulting in faster reaction due to increased surface area (Price, 1974;

Poole, 2004; Neville, 1995; Woods et. al., 1933; Larsen, 1991; Higginson, 1970)

As shown in table 2-3, those DOTs which have requirements for mass concrete also

specify limitations on the maximum allowable temperature gradients for early-age mass

concrete. Most of these DOTs require a maximum temperature differential of 35 °F, which has

39
become the most commonly used temperature differential for mass concrete applications today.

This approach was based on the data collected from a project involving the construction of small

concrete dams in England more than 50 years ago (Fitzgibbon, 1976; Gajda, 2007). Although no

readily available laboratory data confirms the suitability of a maximum temperature differential

of 35 °F, it is nonetheless still required in many mass concrete specification documents today.

The exact magnitude of the temperature gradient depends on a number of factors, including

the initial concrete temperature, the ambient temperature around the structure, and the thermal

properties of the concrete itself. A number of early-age concrete properties affect the thermal

attributes of concrete, including heat development, tensile strength development, coefficient of

thermal expansion, thermal diffusivity, resultant strain gradients, temperature gradients, and the

chemistry of the cement paste. Supplementary cementitious materials can dramatically reduce

the amount of heat generated.

One of the principal difficulties in predicting cracking of concrete during hydration is that

the tensile stresses develop before the concrete has reached its ultimate strength. Under certain

conditions, such stresses can develop while portions of the concrete placement are still in the

plastic state, resulting in plastic shrinkage cracking. To model mass concrete performance

throughout the early hydration stage (wherein heat generation is maximized), it is first necessary

to characterize the development of stress-strain behavior of the concrete.

Stresses due to thermal gradients within a mass structure change over time, as does the

stress-strain behavior of the concrete. The relative magnitude of these two variables is important

when considering the potential for cracking. In at least one instance, published research has

claimed that thermal gradients can be mitigated by using faster hydrating cements, asserting that

tensile strength develops faster than the thermally induced tensile stresses (Lindstrom, 2003).

40
Though intriguing as a possibility, this research did not consider the rate of development of

tensile elastic modulus. While strength could very well develop more rapidly than the thermal

stresses, stiffness may possibly increase at an even faster pace. This would result in a lack of

strain capacity that would lead to cracking due to thermal expansion. To account for the effect of

these interrelated factors, the stress-strain behavior of concretes at different ages and

temperatures must be investigated.

Additionally, past research has focused on the compressive strength of the concrete when

determining its resistance to applied stresses. Though compressive strength is the primary design

parameter in mass concrete, thermal cracking is inherently a tensile phenomenon. Thus the

tensile strength properties are critically important in the modeling of mass concrete behavior.

Unfortunately, tensile strength of concrete can be very difficult to measure with traditional

techniques that are either extremely difficult to perform (direct tension) or insensitive to early

micro-cracking (splitting tension) (Bremner et. al, 1998; Boyd and Mindess, 2002; Boyd and

Mindess, 2004) An alternative method for determining tensile properties is to test the tensile

modulus of elasticity using flexural beam testing.

Tensile Stresses Due to Delayed Ettringite Formation

Delayed ettringite formation (DEF) is a form of internal sulfate attack on concrete that can

lead to severe cracking and damage and eventual material failure. During the hydration of

Portland cement under normal conditions, ettringite forms as a result of the chemical reaction

between C3 A and gypsum. The ettringite then further reacts with the remaining C3 A to produce

monosulfoaluminate, a relatively inert compound. Gypsum is added to cement in order to force

this ettringite formation and prevent flash set of the C3 A. As long as the ettringite forms while

the concrete is still plastic, it is essentially harmless.

41
 Under high temperatures, however, the ettringite is destroyed and its components sulfate

and aluminate are absorbed by the calcium-silicate-hydrate (C-S-H) in the hydrated cement

paste. After cooling, the sulfate is released and again becomes available to form ettringite.

Ettringite is an especially crystalline compound with a high aspect ratio that can form long

needle-like crystals. Once nucleation has occurred, ettringite crystals tend to grow lengthwise.

Even when the tips of the crystals encounter solid material, the growth continues, resulting in

very high localized stresses that lead to expansion and cracking of the hydrated cement paste

matrix.

The exact temperature required for the formation of DEF has been extensively debated.

The majority of available research reports 158 °F (70 °C) as the minimum temperature necessary

for the formation of DEF (Lawrence, 1998; Taylor, 1997; Gajda, 2007; Drimalas, 2004). Most of

the DOT specifications listed in table 2.2 require a maximum curing temperature of 160°F for

mass concrete structures in an effort to avoid the onset of DEF. However, there are specific

conditions necessary for the initiation of DEF. Even in the presence of high temperatures it only

occurs within cements with large amounts of SO3 (4%), alkalis, or MgO, and in the presence of

moisture. However, the exact effect of cement chemistries is not fully understood (Taylor, 1997).

The combination of high curing temperatures and moist environments is most common in

two situations: pre-cast concrete exposed to steam curing, and massive concrete members in a

damp environment (drilled shaft piles, foundations, abutments, etc.). To avoid DEF in mass

concrete, it is necessary to prevent the temperature rise in the concrete from exceeding the

threshold value at which ettringite nucleation occurs. The exact threshold temperature is affected

by several factors though little information is currently available concerning these parameters for

Florida concretes.

42
 DEF can be difficult to diagnose, especially at the early ages necessary for this research.

The minute scale of the crystals makes them impossible to find using optical microscopy, and

their formation does not change the chemical composition of the bulk hydrated cement paste,

thereby making traditional chemical analysis inadequate. The ettringite crystals themselves do

exhibit a unique chemical makeup from the rest of the paste, but they form due to chemical

realignment in the paste, and thus any reasonable sample size will exhibit the same chemical

makeup as it did before DEF formation.

Identification of ettringite alone is not sufficient to indicate DEF, since ettringite does form

during normal hydration and can be left over if the C3 A/gypsum balance of the cement is not

perfect. Small amounts of late-forming DEF are also harmless and could actually be beneficial

since they will initially fill in any voids in the hydrated cement paste, thus densifying the

microstructure and improving strength and permeability. This is commonly called Secondary

Ettringite formation (Skalny et. al, 2002). Only when sufficient ettringite forms to expand

beyond the allowable void space does it become a problem. Such incidents are evidenced by

cracks in the microstructure initiating from the ettringite crystals.

A rigorous literature search was performed in an effort to properly address the relevant

issues concerning DEF and mass concrete structures in Florida. As previously stated, DEF is a

form of internal sulfate attack which is a result of the high heat of hydration coupled with

sulfates in the cement paste and a relatively high C3 A content of the cement (Ghorab, 2002).

The FDOT permits the use of supplementary cementitious materials to replace Portland

cement in the construction of massive elements in which the core temperature of the concrete is

expected to exceed 165°F. FDOT specification allows use of 18%-50% Portland cement

replacement of fly ash and 50%-70% replacement of ground blast furnace slag to ensure lower

43
heats of hydration (FDOT, 2007). Currently, all of mass concrete construction in the state of

Florida utilizes Class F fly ash or slag as a major constituent of the cementitious material in the

concrete mix design. A significant portion of the literature review was dedicated to the effect of

fly ash and slag on DEF and sulfate attack of concrete materials and structures. It has been

shown that using 25% fly ash or 25% slag replacement in concrete mitigates the physical

mechanisms of DEF (Ramlochan et.al, 2003). Similar findings have been reported by other

researchers (Lane and Ozyildrum, 1999; Miller and Conway, 2003; Thomas et. al, 2008).

Despite the fact that the separate physiochemical mechanisms that cause internal sulfate

attack (DEF) and external sulfate attack are different, the expansive nature of the resultant

product (ettringite) is the same for both. Consequently, the literature review included the study of

external sulfate attack on ordinary and mass concrete and the effect of fly ash and slag on the

mitigation of sulfate attack. “The use of fly ash and blast furnace slag in making sulfate-resisting

concrete has frequently been reported” (Bhatty and Taylor, 2006). Other researchers have

reported similar findings (Skalny et. al, 2002; Malhotra and Mehta, 1996; Schlorholtz and

Bergeson, 1993).

Research has also been performed to evaluate massive concrete structures which have

shown deterioration due to sulfate attack. Several bridge structures in Europe were investigated

to determine the nature of sulfate attack and the possible mechanisms of the deterioration. The

study determined that the most likely cause of initial cracking was thermal expansion. The

sulfate attack which took place after the initial cracking was more likely to be due to an external

sulfate source rather than from within (Divet, L., and Pavione, 2002). The initial cracking of the

structure was attributed to a severe temperature differential between the outer concrete strata and

the internal core. Upon the initiation of the initial cracking, it was determined that the presence

44
of moisture and sulfate from the environment, rather than internal sulfate attack or DEF,

contributed to years of deterioration (Divet, L., and Pavione, 2002).

More recently, DEF has been found in a mass concrete bridge structure that is currently in

service. The bridge structure was diagnosed with alkali silica reaction (ASR) in some portions,

DEF in others, and some of the structure was considered to be free of significant damage. This is

the first well-documented case of DEF occurring in a concrete structure in which the temperature

rise of the concrete was due solely to internal hydration (i.e.- the structure was not steam cured).

Interestingly, the structure that sustained damage due to ASR and DEF was concrete which did

not contain supplementary cementitious materials. The portion of the structure that was free of

significant damage contained fly- ash. (Thomas et.al, 2008)

Research has been performed investigating the use of granulated blast furnace slag as a

partial replacement of Portland cement in mortars exposed to high temperatures. The results of

this research indicate that mortars which use 30% and 50% granulated blast furnace slag

experience damage due to expansion or DEF when exposed to curing temperatures of 208°F

(98°C) (Kelham, 2002). Thus, it is likely that mass concrete containing large replacements of

supplementary cementitious materials approved per the FDOT standard specification for Road

and Bridge Construction will not be subject to DEF due to the following reasons:

• The temperatures necessary to cause the dissolution DEF at early ages are less likely within
concrete structures containing supplementary materials

• The addition of supplementary materials mitigates the damage produced by DEF

• DEF in massive structures containing supplementary cementitious materials is less likely as

the near surface temperature is less than the core temperature. However, the core
temperature is less likely to be exposed to moisture due to the relatively large amount of
concrete cover.

As a result of the literature review as well as interviews conducted with FDOT personnel

and several onsite visits, it was determined that the factors most relevant to cracking in massive

45
structures are thermal stresses induced by a thermal gradients. Therefore, the DEF study was

altered to include a rigorous study of the components which are most likely to contribute to large

thermal gradients in massive concrete structures. The major components are as follows:

• High internal heats of hydration caused by the concrete mix design.

• Poor insulation of mass concrete at early ages.
• Mix designs which utilize too much cementitious material.
• The use of cements with high heats of hydration.

Along with FDOT personnel interviews, a review of the current practice of the

development of thermal control plans for mass concrete construction was conducted to determine

which issues contribute to thermal gradients in mass concrete. The majority of FDOT

construction using mass concrete involves bridge components in severely aggressive

environments. Per the FDOT standard specification, Type II Portland cement must be used on

projects constructed in aggressive environments. Consequently, this research will investigate the

chemical and physical properties of concrete mixes using primarily Type II cement enhanced

with Type F fly ash and/or Ground Blast Furnace Slag. Concrete with Type I Portland cement

will also be studied for comparison purposes.

46
 CHAPTER 3
ISOTHERMAL CONDUCTION CALORIMETRY TESTING

Introduction

Isothermal conduction calorimetry has gained much popularity throughout the building and

construction industry over the past two decades. As a result, ASTM C 1679, the standard

practice for measuring hydration kinetics of hydraulic cementitious mixtures using isothermal

calorimetry has been developed for measuring the relative differences in hydration kinetics of

hydraulic cementitious mixtures (ASTM, 2008b). Additionally, ASTM is currently in the process

of writing a standardized test method for the measurement of heat of hydration of cement with

heat conduction calorimetry (Robbins, 2007).

Isothermal conduction calorimetry measures the heat evolved from a relatively small

specimen over time. Therefore, this testing method is very useful for the testing of the

cementitious components to determine the heat evolved or the heat of hydration of the materials.

Currently, there is no analysis method which predicts the heat rise in massive concrete structures

that incorporates the results provided by isothermal conduction calorimetry for input parameters.

There is a model proposed by Poole et. al (2007) and Riding et. al ( 2007) that utilizes semi-

adiabatic calorimetry for the prediction of temperature rise of mass concrete.

Some researchers state that the semi-adiabatic calorimetry is not accurate for the

measurement of the heat of hydration / heat production at early ages (Wadso, 2003, Robbins,

2007). ASTM has not standardized either test method to date. However, a standard test method

for the use of isothermal calorimetry to measure heat evolution of cementitious materials will

more likely be available before a standardized test method for measuring heat evolution /

temperature rise of concrete using semi-adiabatic testing of concrete becomes available. The

reason for the potential publication of a standardized test method for the isothermal calorimetry

47
test is that there is currently a draft test method before ASTM committee C.1.09. (Robbins,

2007) However, the semi-adiabatic test method has not been presented to a standardization

committee for publication.

Isothermal calorimetry provides a direct measurement of heat generated for cementitious

materials. Several researchers have reported the use of cement chemistry to determine apparent

activation energy and total heat available in a cementitious constituent as provided by XRF or

XRD analysis (Ma et. al, 1994, Poole et. al, 2007, Schindler 2004, Schindler and Folliard, 2005).

Chapter 4 provides a detailed analysis of the determination of apparent activation energy using

several methods, including isothermal calorimetry data.

The original equations used for the conversion of chemical oxides to the cement phases

were developed by Bogue in the 1940’s (Bogue, 1947). Recently, it has been reported that the

chemical data obtained via XRF have relative bias and potential errors (Stutzman, 2007). Thus,

the use of chemical analysis for the prediction of heat of hydration could have errors accordingly.

Since isothermal calormetry provides a direct measurement of heat evolution from cementitious

materials, the potential errors per chemical analysis can be avoided accordingly.

Summary of Test Method

An isothermal heat conduction calorimeter consists of a constant-temperature heat sink

which two heat-flow sensors and sample holders are attached. One heat-flux sensor and sample

holder contains the test sample (with cementitious component). The other heat-flow sensor is

composed of a reference cell containing a sample that evolves no heat. The heat of hydration

released by the hydrating cementitious sample is passed across the sensor to the heat sink. The

output measured by the calorimeter is the difference in heat flow (thermal power) between the

sample cell and the reference cell. The physical measurement of heat flux is due to a small

temperature gradient that develops from the sample side to the heat-sink side. The temperature

48
difference is so small that for practical purposes, the sample is at a constant temperature

isothermal). The output from the heat-flow sensor is an mV signal that is proportional to the

thermal power from the sample. This output must be calibrated to a known thermal power. In this

method, this is accomplished by measurements on a sample that emits a constant and known

power level. The integral of the thermal power over the time of the test is the heat of hydration.

Equipment and Procedure

The FDOT SMO houses an isothermal conduction calorimeter made by Thermometric AB

called the TAM-Air isothermal calorimeter as shown in Figure 3-1. The calorimeter has eight

channels which allows for the monitoring of eight individual specimens at a time and an

operating temperature range of the calorimeter is from 5 °C to 60 °C. A detailed operating

procedure for the isothermal calorimeter is provided in Appendix A.

Figure 3-1. Isothermal conduction calorimeter test set up

Mixing Procedure

There are two acceptable methods for the introduction of the water into dry cementitious

materials for isothermal conduction calorimetry testing. The methods are referred to as

“external” and “internal” mixing.

49
External Mixing

External mixing is the process by which the water and cementitious materials are mixed in

a device, typically a high-speed blender outside the calorimeter. Researchers often use this

method because it requires less time for specimen preparation and does not require an internal

mixing calorimeter cell, which is relatively costly. The main limitation of the use of the external

mixing procedure for the measurement of heat of hydration of cemenitious materials is that this

procedure requires that the total heat of hydration calculation be corrected for the heat evolved,

prior to the introduction of the cementious specimen into the calorimeter (Poole, 2007). Due to

recent developments of the (unpublished) isothermal calorimetry test method, the precision and

bias statement regarding the corrections needed for the external mixing procedure have not been

developed.

Internal Mixing

The internal mixing procedure involves the use of a calorimeter cell filled with water,

attached to an ampoule filled with dry cement as show in Figure 3-2. The internal mixing

procedure is provided in detail in Appendix A.

Figure 3-2. Mixing cell and ampoule used for internal mixing procedure

50
 There are several main advantages for using the internal mixing procedure over the

external mixing procedure. The internal mixing procedure requires the calorimeter cell be placed

inside the calorimeter to establish the internal temperature conditions prior to initiation of

mixing. Unlike the external procedure, the specimen is known to be at the temperature of the

system prior to mixing. Another difference between the internal mixing and external mixing

procedure is that the internal mixing procedure allows for the more precise measurement of the

mass of the total cementitious product for mixing. The external mixing procedure tends to

require a relatively swift transfer of material (less than 5 minutes) from the mixer to the ampoule

at the time of mixing. The rapid nature of the transfer does not facilitate the accurate

proportioning of the mixed cementitious material. One other potential variable in the mixing

procedure can be attributed to the nature of the external mixer itself. As proposed by Poole

(2007), a high-speed blender should be used to mix the materials, which could potentially

introduce heat due to the friction of the mixing procedure. Another variable can be attributed to

external mixing procedure is the potential heat transfer from the operator to the specimen itself.

Since the external mixing procedure has more potential variables for the alteration of the

heat of the sample without quantification, it was decided to use the internal mixing procedure for

the isothermal cement calorimetry in this research. Most research to date using the Tam air

calorimeter (Poole, 2005, Wadso, 2003,) reports the use of isothermal calorimetry data with the

use of external mixing procedures. However, internal mixing has been reported for research on

cementitious materials as well (Evju, 2003).

Isothermal Calorimetry Testing Methodology

Isothermal conduction calorimetry has two main applications for the testing of

cementitious materials - determination of heat rise, and determination of activation energy. In

this chapter, the isothermal calorimetry testing results of a single Portland cement tested at

51
various temperatures and water to cementitious ratios are reported to discuss the reliability of

internal mixing procedure with regard to this test method, for the determination of heat rise. In

chapter 4, the results of isothermal calorimetry testing for the determination of activation energy

of cementitious mixtures is reported.

To determine the validity of the internal mixing procedure for the measurement of total

energy rise, testing was performed on two Portland cement mixes at temperatures of 15, 23, 38,

49 and 60°C, and water to cement ratios of 0.50 and 0.40. The Tam air isothermal conduction

calorimeter has an operating temperature range from 5°C to 60°C.

Isothermal Calorimetry Testing Results

The results from the isothermal calorimetry testing are typically reported in terms of power

per unit mass (W/g) vs. time and energy per unit mass (J/g) vs. time. Figure 3-3 shows the

resultant calorimetric curves for the 0.50 w/c ratio mix with regard to the power for each

isothermal temperature for the first 180 hours. The curves indicate that the larger temperatures

achieve larger total power at earlier ages than the lower temperatures. This result is consistent

with the findings of others (Ma et. al, 1994, Poole et. al, 2007, Broda et.al, 2002, Wadso, 2003).

The results are also consistent with the typical characteristics of the hydration of Portland cement

based materials (Mehta, 1986).

As discussed in Appendix A, the total heat of hydration of the sample is calculated by

integrating the power/g versus time data over the time interval of the test as shown in equation 3-

1 (Poole, 2007). Thus, the energy is calculated directly from the power.

(3-1)

52
 Figure 3-4 shows the resultant calorimetric curves for the 0.50 w/c ratio mix with regard to

the energy for each isothermal temperature for the first 180 hours. As to be expected, the curves

indicate that the higher temperatures evolve energy at faster rates than those of the lower

temperatures. However, the Portland cement tested at 60°C, did not obtain a higher energy as

compared with the specimens at lower temperatures.

Figure 3-3. Power vs. time for 0.50 w/c Portland cement at various temperatures

Figure 3-4. Energy vs. time for 0.50 w/c Portland cement at various temperatures

53
 This test result can be attributed to a limitation of the internal mixing procedure. Upon the

completion of the test, at the moment the specimen was removed from the calorimeter, the

ampoule was observed to have condensed water droplets distributed on the inside. This

phenomenon is most likely a result of incomplete hydration due to the evaporation of the mixing

water from the matrix which deposited onto the glass. The resultant hydration product appeared

to be an incompletely hydrated cementitious product. Figure 3-5 illustrates a side-by-side

comparison of a fully hydrated specimen tested at 23°C (left) with a partially hydrated specimen

tested at 60°C (right).

Figure 3-5. Fully hydrated specimen (23°C) vs. partially hydrated specimen (60°C)

As a result of the heat of the incomplete hydration of the cementitious product, as

indicated by the presence of the water droplets which collected on the ampoule, the resultant

power curve actually obtained negative readings at later ages (approximately 140 hours). This

results in the corresponding energy curve acquiring a slightly lower energy value. This

phenomenon is consistent with the conditions observed upon the removal of the ampoule from

the calorimeter. The water required energy input to maintain the isothermal temperature of 60°C

which resulted in a measured energy loss. The same phenomenon can be observed for the

cementitious specimens mixed with a lower w/c at 49°C as shown in Figure 3-6.

54
Figure 3-6. Energy vs. time for 0.40 w/c Portland cement at various temperatures

The specimen tested at 49°C for the 0.40 w/c does not behave exactly like that at 60°C, as

the results indicate that the 49°C specimen does not lose energy at later ages. However, the data

presented in Figure 3-6 shows the first 72 hours hydration. The testing regimen was shortened

for the investigation of the lower w/c mixture, as it was performed solely in an effort to

determine any potential effects of w/c on the internal mixing procedure and calorimetric results.

Summary of Results

The testing of the various Portland cement pastes with isothermal calorimetry resulted in

the following conclusions.

• Isothermal calorimetry preformed on mixes at higher temperatures provides larger rates of

energy rise with respect to time. This result is consistent with available literature. (Wadso,
2003, Ma et.al, 1994, Schindler 2003, 2004, Broda et.al, 2002 and Poole, 2007)

• The use of the internal mixing procedure for the isothermal calorimetry testing is a viable
method for the measurement of early-age energy rise.

• The isothermal calorimetry using the internal mixing procedure resulted in partially
hydrated specimens when tested at temperatures above 49°C. Therefore, isothermal
calorimetry testing for the specimens in this project would be limited to temperatures of
49°C and below.

55
• Due to some of the limitations of the internal mixing procedure, the use of a 0.50 w/c
mixture for the cementitious would be established for all of the concrete mix designs in this
project. This was decided because the mixes tested at a w/c below 0.50 did not provide a
typical energy profile at higher temperatures.

56
 CHAPTER 4
MATURITY AND EQUIVALENT AGE

As previously stated, the hydration of cement in concrete (an exothermic process- which

results in the evolution of heat) results in the rise of concrete temperature. The resultant product

of the hydration of Portland cement paste is the hardened cement paste matrix which, despite the

fact that the paste is initially fluid, becomes hard and strong as time passes (Young et. al, 1998).

This chapter discusses the maturity concept used to quantify the relative or equivalent age

of concrete with respect to time-temperature history. The investigation of various maturity and

equivalent age functions are investigated in this chapter. The maturity/equivalent age functions

established in this chapter are then used in each of the subsequent chapters for the analysis of the

respective physical or thermal properties.

Maturity Concept

The maturity method is one technique used for the estimation of the development of strength of

hardened concrete. Like many other chemical reactions, the rate of the reaction (hydration) of Portland

cement is influenced by the temperature of the reactants. Thus, the increase in concrete temperature will

result in a corresponding increase in the rate of the hydration reaction.

The first maturity functions for concrete were developed in the late 1940s by McIntosh, Nurse and

Saul (Carino, 2004). The term “maturity” and the Nurse-Saul maturity function originated from this

work, and the first widely accepted function was accepted by industry for the use of quantification of

time-temperature history of concrete. However, it was Saul that stated that under certain conditions, a

given mixture of concrete with the same maturity will have the same strength (Tank, 1988). As shown in

Figure 4-1, the maturity of concrete can be estimated by simply determining the area under the time-

temperature curve using the following equation:

57
Figure 4-1. Nurse-Saul maturity function (Carino, 2004)

M = (T − T0 )∆t (4-1)

Where:

M = maturity at age t
T = average temperature of the concrete during the time interval ∆t
To = Datum temperature

Per equation 4-1, the maturity of the concrete is quantified in units of time (hours) and

temperature (°C).e.g., (°C-hr). The datum temperature is considered to be the lowest

temperature at which the hydration reaction will occur (typically below 0°C). The standard

practice of estimating concrete strength by the maturity method (ASTM C1074) describes the

standardized procedure for calculating maturity and the datum temperature for concrete (ASTM,

2004c).

Equivalent Age Concept

The concept of equivalent age expresses the time temperature history of concrete in units

of time rather than using temperature-time units as described by the maturity method. ‘The

equivalent age of a concrete is defined as the number of days or hours at a specified standard

temperature required to produce a maturity value equal to the value achieved by a curing period

at temperatures different from the specified temperature. According to ASTM C1074, the actual

58
age of the concrete is transformed to its equivalent age at specified temperatures by means of a

maturity function’ (Tank, 1988 p.33).

There are a number of different equations that can be used to calculate the equivalent age

of concrete. For instance, it is possible to use the maturity function per equation 4-1 to create an

equivalent age as follows (Tank, 1988):

∑ (T − T )∆t 0
te = 0
(4-2)
(TS − T0 )

Where:

te = equivalent age at a standard temperature Ts(°C)

t = time (hours)
Arrhenius Equation and Activation Energy

Other equations have been developed for determining equivalent age (based on

temperature and time) which have been used for predicting the rate of strength gain in concrete.

The Arrhenius equation is nonlinear and describes temperature-dependent reactions as follows

(Glasstone et. al, 1941):

− Ea
k = Ae RT
(4-3)

Where:

k = the rate of heat evolution (W)

A= proportionality constant (W)
Ea = Activation Energy (J/mol)
R = Universal Gas Constant = 8.314 (J/mol/K)
T= Temperature (K)

Activation energy is defined as “the heat of activation or energy of activation of the

reaction; it represents the energy that a molecule in the initial state of the process must acquire

59
before it can take place in the reaction whether it be chemical or physical” (Glasstone et.al 1941.

p2)

Unlike the Nurse-Saul method, the Arrhenius equation requires the determination of the

apparent activation energy (Ea) for the calculation of maturity and equivalent age functions. Ea

represents the energy that the molecule in the initial state of the reaction process must acquire

before it can participate in the (hydration) reaction. The experimental Ea can be obtained from

the linear plot of reaction rate vs. the inverse of the temperature (Glasstone et. al, 1941). More

specifically, the experimental activation energy is determined by multiplying the negative value

of the universal gas constant (R) by the slope of the best fit line through ln(k) versus 1/(T*R) .

Glasstone discusses that the “experimental activation energy” is obtained via the best fit line

procedure, which is slightly different from the activation energy or the heat of activation,

depending upon the reactive species, energy liberated from reaction, and rate of reaction

(Glasstone et. al, 1941). The term “activation energy” for the purposes of this research is

interchangeable with “experimental activation energy” as defined by Glasstone. ‘The obtained

value of activation energy is used to characterize the reaction rate of cementitious materials at

various temperatures’ (Poole, 2007 p7).

The Arrhenius equation in the form presented in equation 4-3 is not suitable for the

calculation of equivalent age. The concept of using the Arrhenius equation for the description of

the hydration of Portland cement and concrete materials was first suggested by Freiesleben-

Hansen, and Pederson in the late 1970s (Freiesleben, et.al, 1977). The equation proposed by

Freiesleben-Hansen, and Pederson, is commonly referred to as the ‘Arrhenieus equation’ within

the Portland cement concrete industry, and is specifically used for the application of the

equivalent age concept with regard to concrete maturity:

60
 E 1 1 
t  − 
te (Tr ) = ∑ e
R  273+Tr 273+Tc 
∆t
0 (4-4)

Where:
te(Tr)= equivalent age at the reference curing temperature
Tc = average temperature of the concrete during the time interval ∆t
Tr = reference temperature (typically 22.8°C / 295.8°K)
E = activation energy, J/mol
R = universal gas constant, 8.3144 J/(mol °K)

ASTM C 1074 utilizes the Arrhenius equation as presented in equation 4-4 to determine

equivalent age for concrete materials as an alternative to the Nurse-Saul maturity function

(ASTM 1074 – 6.3) with some slight differences in the notation of the equation.

 1 1 
t −Q  − 
te = ∑ e
273+T 273+Ts
 a 
∆t (4-5)
0

Where:
te = equivalent age at a specified temperature T s, days or hours
Q = activation energy divided by the universal gas constant
Ta = average temperature (°C) of the concrete during the time interval ∆t
Tr = Specified Temperature, (typically 22.8°C / 295.8°K)

The equivalent age concept has been researched and applied to Portland cement concrete

materials by many researchers primarily for the estimation of the concrete strength properties

(Carino, 2002, Carino and Tank 1992, Carino and Lew, 1982, Carino et. al, 1982, Volz et. al,

1980, Voigt et, al, 2006, Tank, 1988).

Activation Energy Determination via Compressive Strength

On the day of concrete delivery for each large scale block specimen, Mr. Joseph

Fitzgerald, concrete mix design specialist from the FDOT State Materials office, visited the

Florida Rock Industries ready-mix plant in Gainesville, Florida, where the concrete was batched.

61
Mr. Fitzgerald obtained the dry Portland cement, sand, coarse aggregate and relevant

supplementary cementitious materials that were used in the concrete delivered to the State

Materials Office for laboratory specimen creation. This material was obtained for the creation of

laboratory specimens at a later date.

Table 4-1. Mortar cube mixture designs

mix Name Cement (g) Slag (g) Fly-Ash (g) w/c Water (g) Sand (g)
Lab mix
(100% Portland
Cement) 4086 0 0 0.5 2043 6570

Mix 1
(100% Portland
Cement) 4086 0 0 0.5 2043 6084

Mix 2
(50% Portland - 50%
Slag) 2046 2046 0 0.5 2046 6084

Mix 3
(65% Portland - 35%
Slag) 2658 0 1428 0.5 2046 6066

Mix 4 (50-30-20
Blend) 2046 1224 816 0.5 2046 6552

Some of this material was used to create mortar cubes with the same mixture proportions

as the large-scale block specimens in accordance with ASTM C 1074 for determination of Ea.

As shown in Table 4-1, the mortar cube mixes were proportioned with the appropriate Portland

cement, SCM (supplementary cement materials) (where applicable), 0.50 w/cm, and the

appropriate amount of sand per ASTM C109 for standard cube specimens. The specimen group

designated “lab mix” was created to perform laboratory tests for isothermal calorimetry testing.

Unlike the other specimen groups illustrated in Table 4-1, the lab mix does not correspond to the

mix used in the large block specimen, but has the same cement paste composition.

62
Apparent Activation Energy Determination as Per ASTM C 1074

ASTM C 1074 requires at least three sets of mortar cubes be created and exposed to three

different isothermal curing temperatures for the calculation of Ea. Temperatures of 8°C, 23°C,

and 38°C were chosen as the isothermal temperature groups for this research. The temperature of

23°C is considered to be standard curing temperature. The other specimen groups were stored at

15°C above and below the standard curing temperature. The mortar cubes were prepared in

accordance with ASTM C 109. However, to ensure isothermal conditions for the entire history

of the specimens, the cement, mortar and water and specimen molds were stored in an

environmental chamber at the isothermal temperature of 8°C or 38°C for 12 hours prior to the

fabrication of the specimens.

Upon the completion of the specimen fabrication, the molds were immediately returned to

their respective environmental chambers for 24 hours, after which the specimens were de-

molded and stored in a water bath at the appropriate temperature until compressive strength

testing was performed. The calculation of Ea per ASTM C 1074 requires the determination of

several parameters per equation 4-6 as follows:

k (t − t 0 )
S = Su (4-6)
1 + k (t − t 0 )

Where:
S = average cube strength at age “t” (psi)
t = test age (hours)
Su = limiting strength or ultimate strength (psi)
t0 = age when strength development is assumed to begin (hours)
k = rate constant.

Per ASTM C 1074 A1.1.8.1, ‘if the user has access to a computer program that will permit

the fitting of a general equation to a set of data… The computer program will calculate the best

63
fit values for Su , t0 and k. (ASTM, 2004c).” This can be performed by creating a simple

spreadsheet in a program such as Microsoft Excel into which the user programs equation 4-4 and

employs regression and the Excel Solver to find the best fit solution. Appendix B outlines the

methodology for the curve fitting procedure.

Figure 4-2 is a graphical representation of compressive strength versus time for both actual

values and the predicted values per equation 4-6 (hyperbolic / ASTM 1074) for mix #1. The

results of compressive strength versus time for each mortar mixture can be found in Appendix C.

Table 4-2 is a summary of the strength development parameters computed for each mortar

mixture.

Figure 4-2. Compressive strength of mortar cubes vs. time for each temperature

The observed data regarding compressive strength of cubes versus time compare relatively

well with the calculated data as per ASTM C1074A1.1.8.1. Table 4-2 is a data summary of the

curve fit / strength development parameters for each of the mortar mixes. The apparent

activation energy is calculated by determining the best fit straight line from the natural logarithm

of the k values versus the inverse of the absolute temperature. The negative slope of the line is

64
multiplied by the universal gas constant R (8.3144 J/mol-°K) to determine Ea, as shown in

Figure 4-4.

Table 4-2. Strength development parameters for each concrete mixture per ASTM 1074
Mix Name Temp (°C) Su (psi) k To (hr) R2 Ea (J/mol)
Mix 1 8 9330 0.004 17.6 0.9950
(100% Portland Cement) 23 9828 0.008 5.5 0.9998 35642
38 8327 0.019 1.9 0.9944
Mix 2 8 7064 0.002 15.8 0.9970
(50% Portland - 50% 23 8979 0.005 7.9 0.9997 33688
Slag) 38 11446 0.008 4.0 0.9981
Mix 3 8 6300 0.002 15.0 0.9747
(65% Portland - 35% 23 9018 0.004 7.5 0.9991 25757
Slag) 38 9290 0.005 3.2 0.9578
8 5529 0.002 9.0 0.9976
Mix 4 (50-30-20 Blend) 23 7152 0.005 7.7 0.9990 30013
38 11437 0.006 3.3 0.9939

Figure 4-3. Activation energy calculation for hyperbolic method

Activation Energy Determination Via Exponential Method

The determination of Ea via the exponential method is performed using the same

procedure for the ASTM C 1074 method. The difference between the method standardized by

ASTM and the exponential method is that the exponential method utilizes an exponential instead

65
of a hyperbolic equation to fit the strength versus time data. The calculation of activation energy

per the exponential method requires the determination of several curve fit parameters within each

equation per equation 4-7 as follows (Schindler, 2002):

 τ s β 
S = S u ⋅ exp −    (4-7)
  t  
 
Where:
S = average cube strength at age “t” (psi)
t = test age (hours)
Su = limiting strength or ultimate strength (psi)
β = shape constant
τ = time constant for strength prediction (hours)

Equation 4-7 is used to create a best fit equation for the evolution of strength vs. time in a

manner similar to the method outlined in ASTM C1074 (using a solver equation), which is then

used to calculate the Ea of the cementitious material. The primary difference between the

methods is the general form of the equation- hyperbolic vs. exponential. Schindler, (2002) states:

“If the experimental data are available at temperatures other than the reference temperature, the

best fit hydration parameters (τ) at each of the temperatures can be determined. When the

exponential equation is used, it is assumed that the slope parameter β is independent from the

curing temperature (Schindler, 2002 p.205). To create the exponential curve fit relationship,

Schindler used data provided by Kjellesten and Detwiler (1993) to Ea based on degree of

hydration rather than strength development incorporated into equation (4-8).

  τ s β 
α = α u ⋅ exp −    (4-8)
  t  
 
Where:
α = degree of hydration
t = test age (hours)
αu = ultimate degree of hydration
β = shape constant
τ = time constant for strength prediction (hours)

66
 The following procedure was used for the determination for the Ea using hydration

parameters per Schindler’s research:

• The best fit degree of hydration curve for the experimental data was obtained for the
reference temperature (23°C). The following parameters were determined:

τ = hydration time parameter at the reference temperature (hours)

β = hydration shape parameter

αu = ultimate degree of hydration

• The hydration shape parameter (β) and the ultimate degree of hydration (αu) were
determined at the reference temperature and were used as constants in the degree of
hydration curves at the other test temperatures.

• The best-fit hydration time parameters (τ) at all test temperatures are determined using a
solver / curve fitting software.

• The Arrhenius plot is constructed, by plotting the natural logarithm of the hydration
parameters (τ) for each temperature versus the inverse of the absolute curing temperature. “
(Schindler, 2002 p.207)

Figure 4-7 is a graphical representation of the compressive strength versus time results for

both actual values and the predicted values per equation 4-7 for Mix #1. The results of the

compressive strength versus time for each mortar mixture can be found in Appendix C. Table 4-3

is a summary of the strength development parameters computed for each mortar mixture.

The observed data from the compressive strength of cubes versus time compare relatively

well with the calculated data per the exponential method. Table 4-3 is a data summary of the

curve fit / strength development parameters for each of the mortar mixes. The Ea was

determined in the same manner by determining the best fit straight line from the natural

logarithm of the β values versus the inverse of the absolute temperature T. The negative slope of

the line is multiplied by the universal gas constant R (8.3144 J/mol-°K) as shown in Figure 4-6.

67
Figure 4-4. Compressive strength of mortar cubes vs. time for each temperature

Table 4-3. Strength development parameters for each concrete mixture per exponential method
Mix Name Temp (°C) Su (psi) β τ (hr) R2 Ea (J/mol)
Mix 1 8 9330 0.692 146.539 0.9980
(100% Portland Cement) 23 9828 0.692 76.563 0.9998 37401
38 8422 0.692 31.1063 0.9845
Mix 2 8 9762 0.475 559.113 0.9983
(50% Portland - 50% 23 10436 0.657 162.13 0.9999 39932
Slag) 38 14150 0.526 108.9 0.9972
8 6551 0.464 328.254 0.9992
Mix 3 23 10802 0.464 215.159 0.9999
(65% Portland - 35% 20643
Slag)
38 10971 0.464 139.866 0.9967
8 6307 0.508 348.302 0.9907
Mix 4 (50-30-20 Blend) 23 9395 0.508 197.126 0.9995 21158
38 13783 0.508 143.523 0.9895

The research presented by Schindler (2002) presents a mathematical inconsistency

regarding the calculation of apparent activation energy that is not well documented in his work.

Step 4 of the procedure for the calculation of activation energy states “ The Arrhenius plot can

now be constructed, by plotting the natural logarithm of the hydration parameters (τ) for each

temperature versus the inverse of the absolute curing temperature.“ (Schindler, 2002 p.207)

68
However, the τ parameters presented by Schindler (2002), are positive values greater than 1. The

natural logarithm positive numbers greater than 1 result in positive numbers. However, the k

value obtained via the exponential method per equation 4-7 which is developed from the ln(τ), is

negative. The reason for the negative value is not documented or resolved in the literature.

Regardless of the inconsistency in the presentation of the methodology for the calculation

of Ea using the exponential method, the method appears to calculate reasonable values.

Figure 4-5. Activation energy calculation for exponential method

Activation Energy Determination via Isothermal Calorimetry

The determination of Ea of concrete via the use of isothermal calorimetry testing has been

documented by several researchers (Ma et.al, 1994, Schindler 2003, 2004, Broda et.al, 2002,

Poole, 2007 and Poole et al 2007a). Similar to the methodology behind the determination of

apparent activation energy using the rate of strength gain over time, the determination of Ea via

the use of isothermal calorimetry utilizes the measured rate of heat generation of cementitious

materials at early-ages.

69
 Several researcher have used isothermal calorimetry for the determination of Ea in which

the rate of hydration (k) was determined from the linear portions of the heat conduction curves as

documented by (Ma et, al. 1994) and the use of the modified Arrhenius equation as documented

by (Schindler 2003, 2004, Broda et.al, 2002, Poole, 2007 and Poole et. al, 2007a).

The use of isothermal calorimetry data analyzed by the Arrhenius equation has gained

much favor in recent years. The calculation procedure outlined by Poole, 2007 is as follows:

Revisiting equation 4-2 (used to model equivalent age via compressive strength testing),

the calculation of Ea using isothermal calorimetry utilizes the same equation. Per equation 4-2

and the Arrhenius theory for rate processes, Ea is assumed to be independent of temperature.

E 1 1 
t  − 
te (Tr ) = ∑ e
R  273+Tr 273+Tc 
∆t (4-2)
0

The hydration of Portland cement is quantified by the degree of hydration (α) which is a

value between 0 and 1, with 0 being equivalent to no hydration having occurred and 1 indicating

complete hydration has taken place. Per this method, the degree of hydration is calculated to be

the ratio of the measured heat by the isothermal calorimeter at time t to the total heat available as

determined by chemical methods as shown in equation 4-7 (De Schutter and Taerwe, 1996,

D’Aloia, and Chanvillard, 2002, Schindler, A.K. 2002, Poole 2007).

H (t )
α= (4-7)
Hu

Where:
α = degree of hydration
H(t) = total heat evolved as measured by the isothermal calorimeter (J/gram)
Hu = total heat available (J/gram)
The total heat available for Portland cement is determined by equation 4-8.

Hcem=500 ·pC3 S + 260 ·pC2 S + 866 ·pC 3 A + 420 ·C4AF

(4-8)

70
 + 624 ·pSO3 + 1186 ·p FreeCa + 850 ·pMgO

Where:
Hcem = total heat available within Portland cement (J/gram) at α = 1,
p = the mass percentage of the cementitious component

A mathematical relationship used to model the degree of hydration development as

suggested by a number of researchers (Schindler and Folliard, 2005, Poole 2007a)

  τ s β 
α = α u ⋅ exp −    (4-6)
  t  
 

Where:
α = degree of hydration
t = test age (hours)
αu = ultimate degree of hydration
β = shape constant
τ = time constant for strength prediction (hours)

The following equation can be used to calculate apparent activation energy, Ea (Schindler,

2004, Poole, 2007)

 τ ref 
ln 
 τ c 
E=− ⋅R (4-9)
 1 1 
 − 
T 
 ref Tc 
Where:
E, Tref, Tc and R are previously defined

Apparent activation energy as outlined by Poole, 2007 is calculated as follows.

• Time and heat evolution data are recorded from the isothermal calorimetry testing of
cementitious material at 4 different temperatures: 15, 23, 38 and 49°C (59, 73, 100, 120°F)
for this study. Poole (2007) used 5 temperatures.

• The data are fit to equation 4-6 at each temperature by solving for αu, β, and τ using a least
squares fit for the exponential function

• αu and β, are presumed independent of (test) temperature, therefore all αu and β values are
equal to each other for a given sample.

71
• ln (τ) versus 1/Temperature (°K) is plotted. Ea is the slope of the best-fit line multiplied by
the negative of the universal gas constant R, as defined in equation 4-9.

The τ parameters presented by Poole (2007) akin to the values presented by Schindler

(2002), are positive values greater than 1. Thus, the exact procedure as presented above must be

altered to include the negative of ln(τ) for the calculation of Ea.

Figure 4-7 is a graph of isothermal calorimetry data with respect to degree of hydration (in

an effort to calculate apparent activation energy) over time, based on the curve fit parameters

developed in table 4-4.

Figure 4-6. Isothermal calorimetry data α vs. time for four temperatures

The observed data from the isothermal calorimetric data vs. time tests compare relatively

well with the calculated data per the exponential method. The Ea was calculated in the same

manner by determining the best fit straight line from the natural logarithm of the k values versus

the inverse of the absolute temperature. However this technique utilizes four temperature points

rather than three (per the compressive strength testing methods). Consistent with the Ea

72
calculation using compressive strength, the negative slope of the best-fit straight line is

multiplied by the universal gas constant R (8.3144 J/mol-°K) as shown in Figure 4-8.

Table 4-4. Strength development parameters for each concrete mixture per isothermal
calorimetry / expoenential method
Temp (°C) α β τ R2 Ea
Mix 1 15 0.716 0.943 22.1 0.9768
(100% Portland 23 0.716 0.943 19.9 0.9882
34235
Cement) 38 0.716 0.943 8.0 0.9943
49 0.716 0.943 5.5 0.9938
15 0.927 0.542 68.5 0.9677
Mix 2
23 0.927 0.542 47.4 0.9801
(50% Portland - 50400
50%Slag) 38 0.927 0.542 15.3 0.9580
49 0.927 0.542 7.9 0.9451
Mix 3 15 0.932 0.749 27.4 0.9835
(65% Portland - 35% 23 0.932 0.749 23.0 0.9816
32982
Slag) 38 0.932 0.749 11.8 0.9717
49 0.932 0.749 6.5 0.9866
15 1.000 0.523 56.7 0.9915
Mix 4
23 1.000 0.523 36.1 0.9880
(50-30-20 Blend) 37330
38 1.000 0.523 14.9 0.9640
49 1.000 0.523 11.6 0.9951

Figure 4-7. Apparent activation energy calculation for exponential method

73
Comparison of Strength Development Parameters

Many researchers consider the Arrhenius equation to be the most accurate description of

the hydration of concrete (Carino 2004, Poole et. al 2007a, Schindler, 2002). As previously

discussed, the ASTM 1074 method uses a rational asymptotic model to describe strength

development. One limitation of hyperbolic function is that it assumes zero gain in the property

under investigation until setting time is reached. Thus, the argument is that the hyperbolic

function as outlined in ASTM 1074 does not model the hydration behavior as well as an

exponential model. (Poole et.al, 2007).

A comparison of each of the methods used to model strength / rate of hydration per the

ASTM 1074 method (compressive cube strength) and exponential /Arrhenius method

(compressive cube strength) and the exponential/Arrhenius method using isothermal calorimetry

was performed.

Table 4-5. Strength development parameters for mixture 1 (100% Portland cement) per each
method of analysis
Compressive strength of mortar cubes
Method of Analysis Temp (°C) Su k To R2 Ea
8 9330 0.004 17.6 0.9950
Hyperbolic (ASTM 1074) 23 9828 0.008 5.5 0.9998 35642
38 8327 0.019 1.9 0.9944
Temp (°C) Su β τ R2 Ea
8 9330 0.692 146.539 0.9980
Exponential constant β 23 9828 0.692 76.563 0.9998 37401
38 8422 0.692 31.1063 0.9845
8 12771 0.447 274.092 0.9992
Exponential constant β & Su 23 12771 0.447 127.968 0.9999 30762
38 12771 0.447 77.2207 0.9967
Isothermal Calorimetry Testing
Temp (°C) αu β τ R2 Ea
15 0.630 0.997 17.3 0.9942
23 0.752 0.997 22.5 0.9938
Exponential constant β 30418
38 0.698 0.997 7.7 0.9948
49 0.712 0.997 5.7 0.9926
15 0.716 0.943 22.1 0.9768
23 0.716 0.943 19.9 0.9882
Exponential constant β & αu 34235
38 0.716 0.943 8.0 0.9943
49 0.716 0.943 5.5 0.9938

74
 Table 4-5 provides a summary of the strength development parameters, with R2 values and

calculated Ea for each method used. The hyperbolic method per ASTM 1074, Exponential

method constant b, constant β & αu strength testing), and exponential method constant β & αu

are the most widely accepted methods per the available research. The values of the Ea for the

Portland cement (mix 1) are 35642, 37401, and 34235 respectively, indicating that the three

methods of analysis are relatively comparable to each other, for mixes containing Portland

cement.

The data indicates that the “goodness of fit” for each of the curve parameters is relatively

strong, as the lowest per the R2 value obtained was 0.976 using the 15°C isothermal calorimetry

data. However, this measure of prediction estimation may not be the most accurate description of

the curve fitting abilities. A residual analysis may be a more appropriate method of describing

the error in the curve fitting. The residual is defined as the error or unexplained variation after

fitting a regression model. The residuals were calculated for each of the techniques used to

determine apparent activation energy.

Figure 4-8. Residual error vs. normalized time for hyperbolic curve fitting method (compressive
strength)

75
Figure 4-9. Residual error vs. normalized time for exponential curve fitting method (compressive
strength)

Figures 4-9 and 4-10 are graphical representations of the residual error vs. normalized time

for each compressive strength analysis technique. Despite the commonly accepted belief the

numerous accounts stating the exponential curve fitting method is more appropriate and more

accurate for the explanation of hydration, these two figures indicate that the hyperbolic method

has lower residuals, indicating a better fit than the exponential method.

Figure 4-10. Residual error vs. normalized time for exponential curve fitting method (isothermal
calorimetry)

76
 Figure 4-11 is a graphical representation of the residual error vs. normalized time results

for the isothermal calorimetry analysis techniques. The results clearly indicate that there is a

need for a higher order model (Ott, 1988) to properly describe the hydration of cement using

isothermal calorimetry. Despite the high R2 values calculated for each best fit curve, there is a

significant residual error which has not been reported by researchers in the past. Although the

curve fitting equations are able to estimate the hydration to a high degree of perceived accuracy,

the residuals have not been accounted for. It may be necessary to consider using higher order

equations for the accurate description of hydration curves.

Summary of Results – Apparent Activation Energy

Three Ea values for each mixture are summarized in Table 4-6. The values for each Ea

were calculated in accordance with the most widely accepted technique as previously discussed

therefore, each column in table 4-6 is arranged as follows (Ferraro and Tia, 2009):

• The first column is the mix name.

• The second column reports Ea calculated for each mixture using the hyperbolic method per
compressive strength of mortar cubes (ASTM 1074)

• The third column reports Ea calculated via the exponential method with constant β & αu
per the strength testing of mortar cubes.

• The third column reports Ea calculated via the exponential method with constant β & αu
per isothermal calorimetry testing.

Table 4-6. Summary of Ea values per testing and analysis method

Compressive strength of mortar cubes Isothermal Calorimetry
Hyperbolic calculation Exponential Exponential
Mix Name (ASTM 1074) calculation calculation
Mix 1 35642 37401 34235
Mix 2 33688 39932 50400
Mix 3 25757 20643 32982
Mix 4 30013 21158 37330

The values obtained for the Ea of mix 1 containing only Portland cement have a large

degree of variability regardless of the calculation method. However, the Ea values obtained for

77
the other mixes containing large amounts of supplementary materials vary significantly. Table 4-

7 provides a percentage difference of the Ea results presented in Table 4-6 between the ASTM

1074 hyperbolic calculation and the two exponential calculation methods obtained via

compressive strength of mortar cube testing and isothermal calorimetry testing, respectively.

Table 4-7. Percentage differences of Ea per testing and analysis method

Compressive Strength Isothermal
Mix Name of Mortar Cubes Calorimetry
Mix 1 4.94% -3.95%
Mix 2 18.53% 49.61%
Mix 3 -19.85% 28.05%
Mix 4 -29.50% 24.38%

The values calculated via the isothermal calorimetry testing for mixes with large amounts

of supplementary cementitious materials are consistently larger than those calculated using the

compressive strength of mortar cubes (with the exception of the mix containing Portland only).

The most plausible reason for the difference is due to the nature of the testing techniques. The

acquisition of the data for the compressive strength testing of mortar cubes is performed over a

time period of one day to 56 days. Isothermal calorimetry on the other hand, acquires the data

used to calculate Ea over a period of one minute to 14 days.

It has been stated by several researchers (Poole et. al 2007a; D’Aloia & Chanvillard 2007;

Kada-Benameur, 2000), that the Ea is dependent on degree of hydration of cement, and will tend

to be larger at the earlier stages of the cement hydration process which is reaction-rate limited as

opposed to the later stages of hydration where the reaction is diffusion related. Parrot and Killoh

(1984) indicate that the rate of hydration of Portland cement as represented by heat evolution by

which the rate was controlled by nucleation and growth. Thus, the Ea as calculated by the

acquisition of the heat of hydration via isothermal calorimetry testing is more dependent upon

the initial rate of the hydration reaction rather than at later ages. Therefore, the calculated Ea per

78
the isothermal calorimetry testing will tend to be larger for cementitious systems with large

replacements of Portland cement in which the temperature rate of reaction is disproportionally

dependent upon temperature. This concept is discussed in greater detail in Chapter Seven.

Summary of Findings Chapter 4

The investigation of the maturity and equivalent age parameters for the concrete in this

study results in the following:

1. The apparent activation energy is a critical parameter for the determination of equivalent
age of concrete. There are several different techniques available for the analysis of the
data obtained via compressive strength or isothermal calorimetry.

2. Despite the fact that there is some literature available stating the hyperbolic curve fitting
function is inferior to the exponential curve fitting function for the description of
hydration-strength parameters of concrete, this research determined the two curve fitting
techniques are equally effective (Ferraro and Tia, 2009).

3. The use of the Arrhenius equation for the prediction of early-age hydration parameters
may not be the best available equation as a higher order equation may be needed to
accurately describe early-age hydration of cementitious materials.

4. Ea obtained via isothermal calorimetry testing is more likely to provide larger values than
Ea obtained by compressive strength testing of mortar cubes.

79
 CHAPTER 5
SEMI-ADIABATIC CALORIMETRY TESTING

Introduction

The term “semi-adiabatic” has gained favor from the concrete industry over the last several

decades. The term adiabatic is defined as “no flow of energy between the system and the

surroundings due to heat, at each point of the process. It is common to model a process as

adiabatic because it occurs so rapidly that there is not enough time for appreciable heat transfer

to occur” (Gater, 1995, p2-11). In the study of thermodynamics, the term “semi-adiabatic” does

not exist. However, in 1997, the International Union of Laboratories in Construction Materials,

Systems and Structures (RILEM) wrote a technical recommendation (TC 119-TCE) which

defines a semi-adiabatic calorimeter as “a calorimeter where the maximum heat losses are less

than 100J/(K·h)” (RILEM , 1997, p451).

The purpose of performing semi-adiabatic testing of concrete materials is to obtain the

adiabatic temperature rise of the concrete at early ages. The concept of semi-adiabatic

calorimetry has gained favor over adiabatic testing of concrete because the equipment needed for

adiabatic testing is far more advanced, and requires the controlled supply of heat to the system

over time. Semi-adiabatic calorimetry is purely passive in nature, as it only requires the

monitoring of time, temperature and heat flux for the acquisition of temperature data. The

technique has also become more desirable because researchers have had success performing the

test in the field (Riding et al, 2007).

Research Significance

The purpose of the conducting research using the semi-adiabatic calorimetry device is to

determine its viability as an appropriate test method for the prediction of heat of hydration and

temperature rise in mass concrete. Some researchers state that semi-adiabatic testing is a viable

80
method for the determination of temperature rise of concrete (Schindler, 2003, Riding et al,

2007, Poole et al, 2007a), while other researchers state that the semi-adiabatic calorimetry

method does not adequately assess early age heat of hydration (Wadso, 2003, Brown, 1994).

This chapter presents the investigation on the use of semi-adiabatic calorimetry for the

determination of early-age heat of hydration of cement/concrete mixtures.

Equipment and Procedure

A semi-adiabatic calorimeter consists of an insulated cylinder which contains two

thermocouples and a heat-flux sensor. One of the thermocouples is embedded into the concrete

specimen in the center of the calorimeter as shown on the right of Figure 5-1, and the other

thermocouple is located on the on the exterior. The heat flux sensor is embedded within the

insulation of the semi-adiabatic calorimeter.

Calibration Procedure

Before using the semi-adiabatic calorimeter, it must be calibrated to account for the heat

loss as prescribed by Nordtest (NT Build 480, 1997), which requires a heated water specimen be

placed into the drum and allowed to cool. Deionized water is heated to the approximate

temperature the concrete is expected to reach within the calorimeter (typically 50°C), and is

monitored over time. The heat loss from the calorimeter is calculated as follows (Poole et al,

2007a):

dQ κ ⋅ A ⋅ (TInside − Toutside )
= (5-1)
dt d
where:
κ = thermal conductivity of instrument
A= area of heat transfer occurs, d = thickness of barrier;
T inside = the temperature on the inner side of the calorimeter
Toutside = the temperature on an outer point of the calorimeter

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 Equation 5-1 can also be measured by the heat flux sensor as shown in Figure 5-2 which

illustrates the principle of a heat flux sensor. In the same fashion, as the isothermal calorimetry

test, the heat flux is obtained by measuring the temperature difference (typically very small)

across a known thermal barrier and is expressed in terms of a voltage output. The resultant

voltage is used as dQ/dt as per equation 5-1 for the expression as a heat flux or heat loss from the

semi-adiabatic calorimeter (Poole et al, 2007a).

Figure 5-1. Heat flux sensor

The rate of heat loss from the semi-adiabatic calorimeter is non-linear in nature, especially

in the time near the commencement of the test. The correction factor in equation (5-2) for the

calibration as developed by Poole et. Al (2007) is the most appropriate for the description of heat

loss from the calorimeter as shown by Figure 5-3.

dQ
= q flux (C f 1 ⋅ ln(t ) + C f 2 ) (5-2)
dt
Where:
Q = Where: qflux = heat flux measured in terms of voltage,
Cf1 and Cf2 are correction factors,
t = time

82
Figure 5-2. Calculated losses for the water calibration test

It should be noted that the calculated adiabatic temperature slightly oscillates throughout

the test duration. As noted by Poole et al (2007), the use of time as the dependent variable in

equation 5-2 may not be the most accurate method for the calibration of the calorimeter because

heat loss is dependent on temperature difference rather than time. However, this research

investigated several heat loss equations which incorporated temperature difference rather than

time, but none were more accurate than the heat loss equation in equation 5-2.

Calculation of Adiabatic Temperature Rise

Once the calibration was completed, the loss equation was applied to the semi-adiabatic

testing results to obtain adiabatic temperature rise. For this research, two methods of the

calculation of the fully adiabatic temperature rise (ATR) as calculated from the semi-adiabatic

test were used and are described as follows:

Quadrel “IQ drum” test procedure

One method provides a result of the ATR with time as per the data and calculations

performed by Quadrel I service and equation 5-3. Quadrel is a testing company which

83
manufacturers the semi-adiabatic calorimeter, and software used for the calorimeter device used

in this study.

Q ⋅ Cm
ATR = (5-3)
U ⋅ CP
Where:
Q = the cumulative adiabatic heat of hydration at the equivalent maturity age (J/g)
Cm = total cementitious content per volume (kg/m3)
U = the unit weight of concrete (kg/m3)
CP = specific heat of concrete Mixture (J/kg/°C)

The total cementitious content of the concrete is typically a design parameter and is

inputted into the Quadrel software accordingly. The unit weight of concrete is typically measured

at the time of the concrete delivery when the other plastic properties of the concrete are measured

and the companion specimens are created (ASTM, 2008d). The value for the specific heat of

concrete is typically estimated by the equation 5-4 (Poole et.al, 2007). However, the “Q” term

for the cumulative heat of hydration is not provided by the Quadrel software. It is considered

proprietary by Digital Site Systems, Inc. (DSS) the makers of Quadrel I-Service. In order to run

the software, a Citrix client server is needed to login to the DSS website, after which the semi-

adiabatic heat drum can be programmed. Thus, in order to run any test, a connection with the

DSS server must be established before proceeding to raw data acquisition. Once the connection

to the server is established, a 6”x 12” cylinder is placed in the semi-adiabatic calorimeter and the

system monitors the cylinder temperature and heat flux to establish the ATR.

1
Cp = (WC αC ref + WC ⋅ (1 − α ) ⋅ C C + Wa C a + Ww C w ) (5-4)
γ
Where:
CP = Specific heat of concrete Mixture (J/kg/°C)
γ = unit weight of concrete (kg/m3)
Wc, Wa , Ww = weight of cement, aggregate and water per unit volume (kg/m3)
Cc, Ca, C w = specific heat of cement, aggregate and water (J/kg/°C)
Cref = specific heat of hydrated cement = 8.4xTc+339 (J/kg/°C)

84
University of Texas / Auburn University test procedure

The semi-adiabatic test procedure has been researched extensively at the University of

Texas and Auburn University for the purpose of predicting the temperature rise in concrete

(Schindler, 2002 , Poole, 2007). The method involves the same calibration and testing procedure

as the “IQ Drum” method. The only difference between the two methods is that the calculation

of the ATR is performed by an Excel spreadsheet in which all of the inputs and results can be

measured and calculated directly.

β
τ  β  E 1 1 
Qh = H u ⋅ WC ⋅   ⋅   ⋅ α (t e ) ⋅ exp  −   (5-5)
 
 te   te   R  273 + Tr 273 + TC 

Where:
Qh = rate of heat generation (W/m3)
Hu = total heat available (J/kg)
Wc, = weight of cementitious material content (kg/m3)
Tc = average temperature of the concrete
Tr = reference temperature (typically 22.8°C / 295.8°K)
E = activation energy, J/mol
R = universal gas constant, 8.3144 J/(mol °K)
α = degree of hydration
te = eqivalent age (hours)
β = shape constant
τ = time constant for strength prediction (hours)

Revisiting the derivation of the hydration parameters as presented in equations 4-2 – 4-7,

the heat evolution can be calculated using equation 5-5 (Poole et. al 2007). The calculation of the

ATR of concrete is an iterative procedure using equations 4-2, 4-6, 4-7, 4-8 and 5-5 which is the

same procedure used to calculate ATR used by Poole et al 2007. Appendix D provides a detailed

explanation of the spreadsheet used to calculate ATR per the Texas/Auburn method.

Semi-Adiabatic Calorimetry Testing Results

Semi-adiabatic tests were performed on each of the four mixes per the large block

specimens outlined in Chapters 8 and 9. Table 5-1 provides the mixture proportions for each mix

85
used in this research. Typically, mass concrete mixtures accepted by FDOT for use in

construction have contained granulated blast furnace slag, fly ash, or both, in addition to Portland

cement. As stated in Chapter 2, the supplementary cementitious materials are used to create a

concrete mixture which has a lower heat of hydration and ultimately a lower temperate rise. The

mixes were designed to characterize typical bridge substructure elements, which comprise the

majority of mass concrete placed in the State of Florida. This research incorporates the

investigation of several concrete mixture designs incorporating the following:

Mix 1 – 100% Portland cement

Mix 2 – 50% Portland cement and 50% granulated blast furnace slag
Mix 3 – 65% Portland cement and 35% class F fly-ash
Mix 4 – 50% Portland cement, 30% granulated blast furnace slag, and 20% class F fly ash

Table 5-1. Mixture designs for concrete specimens

Mix 3 Mix 4
Mix 1 Mix 2
65% Portland - 50-30-20
100% Portland Cement 50% Portland -50%
Material 35% fly ash blend
(lb/yd3) Slag (lb/yd3)
(lb/yd3) (lb/yd3)
Cement 681 341 443 341
Fly ash 0 0 238 136
GGBF Slag 0 341 0 204
Water 341 341 341 341
Fine Agg. 1095 1088 1036 1050
Coarse Agg. 1650 1668 1660 1650

A comparison the calculated ATR results for both the Texas / Auburn method of analysis

and the IQ-Drum method of analysis from Mix #1 is presented in Figure 5-4. The Texas /

Auburn method utilizes the “True Adiabatic” curve as the ATR, where the “IQ-Drum” curve is

denotes the ATR for the IQ-drum technique. The “measured” and “calculated” curves are the

observed temperature readings prior to analysis.

86
Figure 5-3. Adiabatic temperature rise for Mix 1

The results indicate that after 72 hours of age, Mixes are within 1.1% of each other.

However, the IQ drum does indicate a slightly larger ATR after 60 hours. Regardless, the two

techniques results indicate that the methods are comparable according to precision statements

made by (Moritabo, 1998 and Poole et.al, 2007).

Prior to the development of the Texas / Auburn method of analysis, the large-scale block

specimens were created and the semi-adiabatic calorimetry testing was performed on each of the

mixes delivered by the concrete supplier. The initial temperatures for each mix are listed in Table

5-2, which indicate that the delivery temperature of each mixture was higher than that of typical

laboratory temperatures of 23°C.

Table 5-2. Delivery temperatures for concrete mixes

Mix Name Delivery Temperature (°C)
Mix #1 35.0
Mix #2 32.2
Mix #3 30.6
Mix #4 28.3

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 Since temperature and heat flux logging equipment was not made available at the time of

the large-scale block specimen creation, the IQ drum method was used for the analysis.

However, at the time of delivery of mix 1, the FDOT computer server experienced a

communication failure with the DSS server and initiation of the semi-adiabatic test per the IQ

drum was delayed approximately 7 hours. The curves shown in Figure 5-3 indicate the

discrepancy of the ATR of the calorimetry specimens created in the lab (after the experiment)

and the specimen created with the concrete delivered to the laboratory with large scale block

specimen. The curves indicate that the absence of the first 7 hours of data logging as per the

delivered mix, will result in a curve that does not represent the true nature of the ATR of

concrete as indicated by the lower calculated ATR. Literature indicates that concrete mixes with

higher mixing temperatures will result in higher early age ATR (ACI 207.1, 2005). Subsequent

to the testing of Mix 1 delivered to the FDOT, the mixture was recreated in the laboratory at a

temperature of 23°C in an effort to get the ATR per the monitoring of the specimen for the entire

age of the specimen. The specimens delivered for the large-scale testing blocks experienced

approximately an hour of delay due to transportation from the concrete mixing plant. The ATR

was calculated via both methods as shown in Figure 5-4. The ATR for the concrete specimen

created from the delivered concrete (mix 2) and the mix recreated in the laboratory (mix 2 ) are

shown in Figure 5-5.

The ATR calculated for Mix 2 indicates ATR difference of approximately 18°C between

the delivered mix verses the mix created in the lab, despite the fact that the mixes had a

respective mixing temperature differential of 9°C. ACI 207.1 indicates that for a Type I Portland

cement, the ATR difference between the two mixes should be approximately 4.5°C. This

88
indicates that the ATR concrete created with blast furnace slag does not behave the same manner

as predicted by historical curves for concrete made with ordinary Portland cement.

Figure 5-4. Adiabatic temperature rise curves for Mix 1, delivered mix and lab mix

Figure 5-5. Adiabatic temperature rise for Mix 2, delivered mix and lab mix

The ATR for each of the mixes is presented in Figure 5-6, where each ATR was calculated

from the delivered mix in conjunction with the large scale specimens with the exception of Mix

89
1. The results indicate that Mix 1, which does not contain any supplementary cementitious

materials, has a significantly higher ATR than the mixes with supplementary cementitious

materials, (other than Mix #2) despite the fact the mixing temperature (only for Mix 1, mixed in

the lab) was lower than that of the other three mixes.

Mix 2 achieved a larger ATR than each of the other mixes. However, this result could

have been caused by the fact that Mix 2 had the highest delivery temperature of the mixes

(because Mix 1 was made in the lab). However, this is most likely not the case, since the large

scale block specimen for Mix 2 achieved the largest core temperature, per the data presented in

Chapter 9. Furthermore, the compressive strength of mortar data presented in table 4-2, indicates

that Mix 2, cured at 38°C, obtained the highest limiting strength of any of the mixes. Therefore,

the physical data indicates that the replacement of Portland cement with blast furnace slag will

result in continued hydration at later ages. Comparatively, the mixes without the addition of slag

(Mix 1 and Mix 3) have higher rates of hydration at earlier ages, based on the ATR.

Figure 5-6. Adiabatic temperature rise for each mix

90
 The data obtained from Mixes 3 and 4 indicates that the replacement of Portland cement

with fly ash will result in a lower ATR as well as a lower rate of hydration approximately 12

hours after mixing. This result is consistent with literature (Taylor 1997, Gajda, 2007).

Interestingly enough, Mix 4 (similar to Mix 2) demonstrates a lower rate of ATR at early ages;

yet, after approximately 12 hours, the rate of temperature increase is comparable or larger to that

of Mix 3 afterward. The ATR of Mix 4 becomes higher than Mix three at approximately 125

hours of age. One potential reason for the delay in reactivity or temperature rise of the Mixes

containing blast furnace slag is thought to be the impervious coatings of silica and alumina that

form on slag particles early in the hydration process. The presence of calcium hydroxide

(forming from the hydration of Portland cement) is a potential reason for the activation of the

slag particles which will potentially continue to hydrate after the initial activation (Mindess et.al,

2003).

Summary of Findings

The investigation of semi-adiabatic testing for the concrete in this study resulted in the

following :

• The calculation of adiabatic temperature rise of concrete can be performed using semi-
adiabatic calorimetry.

• The replacement of Portland cement with supplementary cementitious materials will result
in lower early age temperatures (48 hours or less), and lower ultimate temperatures.

• After 48 hours, the reaction rate of concrete containing large replacements of blast furnace
slag when combined with Portland cement will result in higher rates of temperature rise
when compared with concrete made with Portland cement alone, or Portland cement with
class-F fly ash.

91
 CHAPTER 6
SURE CURE/ADIABATIC CALORIMETRY TESTING

The Sure Cure device was designed to be used in concrete prestressed / precast facilities

for the simulation of high temperature curing of concrete cylinders used to make early-age

comparative determinations regarding formwork removal for larger steam cured structural

elements. It can also be used to determine temperature rise of concrete at early ages and

accordingly, it was used in this experiment for the simulation of adiabatic conditions for concrete

specimens.

Research Significance

The purpose of the conducting research using the Sure Cure adiabatic calorimetry device is

to determine its viability as a potential test method for the prediction of heat of hydration and

temperature rise in mass concrete. No published research is available regarding the use of the

Sure Cure device for adiabatic testing. Since there is research stating that the semi-adiabatic

calorimetry method does not adequately assess early age heat of hydration (Wadso, 2003,

Brown, 1994), this Chapter investigates the potential use of alternative calorimetry method for

the measurement of temperature rise in concrete. The isothermal calorimetry testing method has

shown promising results for the measurement of heat of hydration and temperature rise in

cement. However due to the small specimen size which can be accommodated by the isothermal

calorimeter (30g or less), it cannot be used on concrete specimens. Therefore, an alternative or

supplementary method could prove to be beneficial for the prediction of heat of hydration and

temperature rise of concrete.

Per RILEM TC 119-TCE, a calorimeter which can limit a concrete specimen’s

temperature loss to less than 0.02°K/hour or less, may be used for the calculation of ATR.

Referring to Gater (1995), it is common to model a process as adiabatic because it occurs so

92
rapidly that there is not enough time for appreciable heat transfer to occur” (Gater, 1995p2-11).

Thus, similar to the semi-adiabatic test method in Chapter 5, in the strictest of definitions the

term “adiabatic” testing of the temperature rise of concrete is not physically possible. However,

per the “adiabatic” definition per RILEM TC 119, similar to the research performed by Ng et.al

(2008), the loss of temperature per this method is prevented by the introduction of a controlled

quantity of heat into the system. This Chapter discusses the viability of using the Sure Cure

device for measurement of temperature and heat rise of concrete

Equipment

The Sure Cure system is designed to control the temperature of concrete specimens in

several ways. The system can receive temperature from an outside source such as a concrete

specimen, or it can be inputted into the computer controller to provide a user defined time-

temperature history.

Figure 6-1. Schematic of Sure Cure system with hydration chamber

The sure cure system used for the adiabatic testing in this research is essentially composed

of three major components as illustrated by Figure 6-1. The computer operates the software

which provides signals to the controller box. The controller box sends and receives temperature

signals to and from the hydration chamber. The hydration chamber contains insulation and

93
heating elements used to physically control the temperature. Additionally, the hydration chamber

contains two thermocouples, one in the center of the chamber acquires the temperature at the

center of the concrete mass, the other monitors the temperature within the center of the

insulation. The temperature within the insulation of the hydration is controlled by the

temperature of the concrete itself. The recorded time-temperature curve of the concrete is the

natural hydration curve. Figure 6-2 shows the orange hydration chamber and the micro computer

controller.

Figure 6-2. Photograph of the Sure Cure system with the computer, hydration chamber and
controller box

Test Procedure

Since the Sure Cure System has never been used to establish the relationship between the

temperature rise of concrete, it was necessary to perform a series of trial experiments to establish

the potential of using the sure cure system for the determination adiabatic temperature rise of

concrete. As per RILEM TC 119, “From the point of view of the reliability in determining the

adiabatic temperature increase… the temperature of the sample in an adiabatic calorimeter is at

94
any time very close to the temperature of the adiabatic temperature so the influence of the change

in the reactivity of the cement with temperature is taken into account” (RILEM , 1997 p.317).

The Sure Cure system can be programmed so that the hydration chamber temperature is the

same as, or offset from, the temperature of concrete within. As such, several trials of experiments

were performed prior to the large scale block experiments to establish a temperature

configuration in which the concrete would experience a true adiabatic temperature rise, rather

than gaining temperature at a faster or slower rate, due to the heat input as provided by the

hydration chamber. The experiments were designed to calibrate the temperature rise of the

concrete within the Sure Cure hydration chamber to match the temperature rise within the semi-

adiabatic calorimeter. Accordingly, the semi-adiabatic temperature of a 6”x12” concrete

specimen was obtained per the procedure outlined in Chapter 5. Afterward, the following

procedure was developed for acquisition of the adiabatic temperature rise for the Sure Cure

system:

• A 25 lb sample of fresh concrete was taken from each mix and placed in the hydration
chamber.

• A total of four hydration chambers (individual specimens) can be monitored for a single
concrete mix

• The concrete obtained for the Sure Cure and semi-adiabatic device was taken from the
same concrete mixture.

The initial calibration trial for the Sure Cure testing involved the programming of the sure

cure system to three offset temperatures. An offset temperature is defined as the temperature of

the concrete as recorded by the internal thermocouple, plus the temperature of the hydration

chamber. Thus, an offset of -1.0°F indicates that the temperature within the hydration chamber is

one degree Fahrenheit less than the concrete temperature (the offset temperature is presented in

Fahrenheit in this chapter in an effort to maintain consistency with the Sure Cure program).

95
 Sure Cure Calorimetry Testing Results

The calibration involved programming the hydration chamber to offset temperatures of

0.0°F, -0.5°F, and -1.0°F. The results from the initial calibration are presented in Figure 6-3,

where the offset chambers are presented in the legend and the semi-adiabatic result is denoted as

“Semi-Adiabatic”. The data indicates that the temperature offsets of 0.0°F, -0.5°F rise to a limit

of approximately 92°C and thereafter become constant. The limit was set in an effort to prevent

damage to the hydration chambers. The hydration chamber programmed with a -1.0°F offset

achieved a ATR curing history lower than that obtained by the semi-adiabatic testing device.

Figure 6-3. Sure Cure and semi-adiabatic temperature vs. time

Per the initial calibration testing, it was decided to set the hydration chambers to an offset

temperature between 0.5°F, and -1.0°F to better replicate the time-temperature history of the

semi-adiabatic test. Therefore the calibration procedure was repeated with offset temperatures of

-0.5°F, -0.6 °F, -0.7°F,and -0.8 °F. The results presented in Figure 6-4 indicate that the time-

96
temperature curves between an offset temperature of -0.7°F and the semi-adiabatic test are

relatively comparable.

Figure 6-4. Sure Cure and semi-adiabatic temperature vs. time

As a result of the calibration testing, it was decided to use an offset temperature of -0.7°F

for the Sure Cure testing for the large-scale block experiments and the testing results are

presented in Figure 6-5. The Sure Cure adiabatic test results indicate the test method does

replicate the ATR of concrete in a similar fashion as the semi-adiabatic test. A thorough

comparison of each of the calorimetry testing methods is presented in Chapter 7.

Figure 6-5. Sure Cure temperature rise for large scale block experiments

97
 Limitations of the Test Method

The Sure Cure testing system has several potential limitations which may not permit its use

for adiabatic testing of concrete. The Sure Cure computer programming is limited to a minimum

temperature offset of 0.1°F. Per Figure 6-4, the offset temperature of -0.7°F provides a

comparable time-temperature history as the semi-adiabatic temperature testing. However,

research indicates that the semi-adiabatic test does not replicate the true ATR of concrete

(Wadso, 2003). Additionally, Sure Cure test performed with an offset temperature of -0.6°F

resulted in a ATR of 13°C, approximately 20 percent higher than the concrete with an offset

temperature of -0.7°F/semi-adiabatic test. Results presented in Chapter 7 indicate that the energy

rise of cementitious materials tested via the semi-adiabatic calorimetry test is approximately 10%

lower than the energy rise of cementitious materials tested via isothermal calorimetry testing.

However, the smallest allowable increase in offset temperature via the sure cure test is 0.1°F.

Thus, the precision limitations of the Sure Cure system, do not easily resolve the differences in

the ATR produced for each offset temperature.

The concrete composed of Portland cement and cement with fly-ash tested via the Sure

Cure method showed a decrease in temperature after 100 hours of testing. This temperature

decrease may indicate a lack of necessary temperature or energy input with a hydration chamber

offset of -0.7 °F. Since a temperature offset between -0.6°F and -0.7°F cannot be programmed,

this method may not be suitable for the accurate calculation of ATR.

Summary of Findings

The investigation of Sure Cure-adiabatic testing for the concrete in this study resulted in

the following:

• The calculation of adiabatic temperature rise of concrete may be performed using Sure
Cure Adiabatic calorimetry.

98
• The replacement of Portland cement with supplementary cementitious materials will result
in lower early age temperatures (48 hours or less), and lower ultimate temperatures which
is similar to the results obtained via the semi-adiabatic testing method.

• The Sure Cure testing device may not be suitable for the accurate calculation of ATR due
to the limitations in the allowable temperature offsets.

• Further is testing is needed to establish the potential of the Sure Cure test method to be
used for ATR

99
 CHAPTER 7
COMPARISON OF CALORIMETRY TESTING METHODS

Introduction

The purpose of evaluating the three calorimetry testing methods in this research was to

determine the potential for each to serve as the method to provide the primary input parameter

for the modeling of the energy rise of cementitious materials and, ultimately, mass concrete. This

chapter discusses the comparison of the test results provided by each calorimetry testing method

and the potential implications for the use of each method as a predictor of physical properties of

cementitious materials.

Research Significance

There is currently insufficient research which compares adiabatic and semi-adiabatic

testing of concrete (Ng.et.al, 2009). Although RILEM TCE-119 (1998), and Morabito (1998)

address the specifications required to construct both types of equipment, there is presently no

known, published research available which compares commercially available equipment using

either of the two methods. The comparison of test data between the Sure Cure adiabatic test and

the Quadrel IQ Drum semi-adiabatic test has not yet been performed.

There is also little research available (Wadso, 2003) which compares the

energy/temperature rise of cementitious materials achieved between the semi-adiabatic

calorimeter and the isothermal calorimeter. This chapter, then, fills this research void by

presenting the results of mortar specimens tested using both test methods. The direct comparison

between isothermal calorimetry testing and semi-adiabatic testing of mortar has not yet been

performed.

The standard test method for the heat of hydration of hydraulic cement per ASTM C186

was performed on the cementitious materials for each concrete Mixture. The heat of hydration

100
test is the only standardized test method (per ASTM) and, therefore, it was decided to compare

the data obtained from the standardized test method and the other calorimetry tests performed for

this research.

Calorimetry Testing Results

Comparison of Sure Cure adiabatic calorimeter and semi-adiabatic calorimeter

The comparison of test data between the Sure Cure adiabatic calorimeter (hydration

chamber) and the Quadrel IQ Drum semi-adiabatic calorimeter was performed for each large

scale mix as per the procedures provided in Chapters 5 and 6. The results shown in Figures 7-1

and 7-2 indicate that concrete tested within the Sure Cure hydration chamber did not achieve the

same temperature increase as compared to that contained within the IQ-Drum semi-adiabatic

calorimeter.

Figure 7-1. Comparison of time-temperature histories between Sure Cure system and the IQ
drum for Mix 1

As discussed in Chapter 6, the Sure Cure system did not provide results which were

precise and accurate enough to be considered for the use in the calculation of ATR. Therefore,

the Sure Cure hydration chamber in its current configuration is not recommended for the

101
measurement of ATR of concrete. However, the incorporation of several small software and

hardware changes designed to increase the accuracy of the system which follows the

recommendations of RILEM TCE 119 or Ng et. al (1998) could make the Sure Cure a viable

testing technique. More research is accordingly needed to determine if the Sure Cure system is

viable for adiabatic testing.

Figure 7-2. Comparison of time-temperature histories between Sure Cure system and the IQ
drum for Mix 2

Comparison of semi-adiabatic calorimeter and the isothermal calorimeter

The energy rise for both the semi-adiabatic calorimeter and the isothermal calorimeter

was calculated for each test. As discussed in Chapter 3 and Appendix A, the isothermal

calorimetry test method measures power directly (from voltage measurements), and the

integration of the power as shown in Equation A-4 is used to calculate the energy rise (per mass).

The energy rise (per mass) using the semi-adiabatic calorimeter is determined by measuring the

adiabatic temperature rise, and, by applying the first law of thermodynamics, the principle of

energy conservation, to convert temperature rise to energy rise per Equation 7-1.

∆Q = m ⋅ C p ⋅ ∆T (7-1)

102
 Where:
ΔQ = the change in energy or energy rise (J)
m = mass of concrete (g)
Cp = Specific Heat Capacity (J/g°K)
ΔT = the change in energy or energy rise (°K)

As discussed in Chapter 5, the assumption that an adiabatic condition exists while using

the semi-adiabatic calorimeter is not a reliable one, since a known amount of heat is lost (and

measured) per the test method. Therefore, the assumption that the first law of thermodynamics

applies to the conversion of temperature rise to energy rise is not necessarily valid for the

conversion from adiabatic temperature rise to energy rise of concrete.

Comparison of cement and concrete

The isothermal conduction calorimeter is designed for use on relatively small specimens

(4-20g) and the semi-adiabatic calorimeter is primarily designed for use on specimens

approximately three orders of magnitude larger. The calculated energy with respect to equivalent

age for the isothermal test method as well as the semi-adiabatic test method is presented in

Figure 7-3 for Mix 1. The isothermal test was performed at temperatures of 15°C, 23°C, 38°C

and 49°C. The semi-adiabatic test was performed with an initial temperature of 23°C (laboratory

conditions).

The results indicate that the energy rise with respect to equivalent age is substantially

different with regard to each testing method. The semi-adiabatic test obtained a maximum energy

of (241J/g) at 250 hours where energy measured for each of the isothermal tests was above

305J/g. Thus, the calculated energy rise for the cementitious materials is relatively larger than

that measured by the isothermal calorimetry test.

103
Figure 7-3. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 1

Referring back to Figures 3-4 and 3-6, the energy increase with respect to time is

significantly larger at larger temperatures. However, Figure 7-3 indicates that the values for

energy increase for the isothermal calorimetry with respect to equivalent age is virtually equal

regardless of the test temperature. However, the energy rise at lower temperatures is slightly

larger with respect to equivalent age per Peng et. al (2009), the testing resulted in similar

findings regarding energy rise and equivalent age for isothermal calorimetry testing. These

findings are likely to be attributable to the hydration kinetics of Portland cement at higher

temperatures which are similar to the phenomenon discussed in Chapter 4, where the limiting

strength decreases as the curing temperature increases (Tank, 1988; Carino, 2004). At higher

temperatures, the hydration (strength evolution) of concrete takes place at a faster rate. However

the hydration at later ages (ultimate strength) will be reduced. This “crossover-effect” as

described by Verbeck and Helmuth (1968) and Carino (2004), is the concept that the hydration

104
products of Portland cement which have experienced high temperature do not become uniformly

distributed into the hardened cement paste matrix due to rapid product formation at early ages.

Escalante-Garcia and Sharp (2001) attribute the crossover-effect to an observed increase in

porosity for cements which are cured at higher temperatures.

Figure 7-4. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 2

The calculated energy with respect to equivalent age for the isothermal test method as well

as the semi-adiabatic test method is presented in Figure 7-4 for Mixture 2. The results indicate

that the energy rise with respect to equivalent age is substantially different with regard to each

testing method. The semi-adiabatic test showed a maximum energy of (210J/g) at 250 hours

whereas energy measured for each of the isothermal tests was above 325J/g (at temperatures of

38°C and 49°C). While similar to the results presented in Figure 7-3, the calculated energy rise

for the cementitious materials presented in Figure 7-4 is relatively larger than when measured by

the isothermal calorimetry test.

However, unlike the results obtained for Mixture 1, the results of the testing of energy rise

for the isothermal calorimetry for Mixture 2 (with 50% slag replacement) indicate dissimilar

105
values for each temperature with respect to equivalent age. The energy rise at higher

temperatures is larger with respect to equivalent age from testing.

Figure 7-5. Mortar cube compressive strength vs. time for Mix 2

There is insufficient research as to why this phenomenon occurs. However, the strength

testing results presented in Table 4-2 indicate that the ultimate/limiting strength is higher for the

specimens cured at higher temperatures for Mix 2. Therefore, the “crossover effect” is not

observed with regard to cements with large replacement of blast-furnace slag. Similar results are

observed with regard to compressive strength testing vs. age per the results presented in Figure

7-5 for isothermally cured cube specimens used calculate Ea. Chapter eight reports similar

results with respect to strength versus equivalent age test results. Additionally, similar results are

reported by Schindler (2003) and Brooks et. al (2007) for compressive strength verses time data.

All of the results indicate that the “crossover effect” does not occur when large amounts of

granulated blast furnace slag is incorporated into a mixture to replace Portland cement. To date,

there has not been a reported explanation as to why this phenomenon occurs. One potential

reason may be due to the formation of different reactants at higher temperatures in Portland

106
cement with large replacements of slag. Another possible reason for the phenomenon is that the

hydration of a blend of Portland and slag is not diffusion-controlled at later ages. In order to

ascertain the reason why Portland cement replaced with large portions of slag does not

experience the “crossover effect” at later age more research is needed.

Figure 7-6. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 3

Figure 7-7. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 4

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 The calculated energy with respect to equivalent age for the isothermal test method as well

as the semi-adiabatic test method is presented in Figures 7-6 and 7-7 for both Mixtures 3 and 4.

Both sets of results are consistent with the data in Figures 7-3 and 7-4 where the energy rise with

respect to equivalent age is substantially different between the semi-adiabatic test and the

isothermal calorimetry test.

Mixture 3 (which contains 35% fly ash) behaves in a manner similar to the Mixture

containing ordinary Portland cement in that the energy rise is larger at lower temperatures for a

given equivalent age. Mixture 4, however, behaves more like Mixture 2, lacking a demonstration

of the “crossover effect” per the energy rise curves. This behavior is most likely due to the

presence of blast furnace slag (20%) within the Mix.

Mortar testing

As stated earlier, the isothermal conduction calorimeter is designed for use on relatively

small specimens (4-20g) and the semi-adiabatic calorimeter is primarily designed for use on

specimens approximately three orders of magnitude larger. However, it is possible to create

mortar mixes which can be tested in each device. Thus, the best method of directly comparing

the results from both test methods is to obtain the energy rise data as measured by each device.

Mortar specimens consisting of cementitious materials used to create Mix 1 and Mix 3

were then created and tested in each calorimeter accordingly. Mixes 2 and 4 were not created for

this portion of the experiment since this portion of the testing was not anticipated and there was

not enough cementitious material available from those mixes to create specimens for semi-

adiabatic testing. The isothermal test was performed on mortar specimens at temperatures of

23°C, 38°C, and 49°C. The semi-adiabatic test was performed on mortar specimens with an

initial temperature of 23°C (laboratory conditions).

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Figure 7-8. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and the IQ drum for mortar Mix 1

Figure 7-9. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and the IQ drum for mortar Mix 3

Figures 7-8 and 7-9 indicate that the isothermal specimens cured at higher temperatures

experienced the crossover-effect similar to the ordinary Portland cement Mixture (without sand)

109
in Figure 7-3. The energy rise obtained by the semi-adiabatic calorimeter is lower than the

energy rise measured by the isothermal calorimeter. However, unlike the data presented in

Figures 7-3, 7-4, 7-6, and 7-7 the data presented in Figures 7-8 and 7-9, the material is the same

exact mortar Mix. Thus, potential discrepancies in the energy difference between isothermal

calorimetry and semi-adiabatic calorimetry are not due to differences in material behavior

between cement paste and concrete. These discrepancies are most likely due to the differences

within the testing equipment.

The isothermal calorimeter was designed to be a device to measure heat flux with a high

degree of precision and accuracy. The isothermal calorimeter was designed such that the entire

heat from the cement sample passes across the heat flux sensor to a heat sink on the other side as

illustrated by figure 7-10. Thus, the heat flux is one directional. The internal heat flux sensors,

presence of heat sinks, several layers of insulation a reference specimen (which produces no

heat) and the calibration technique itself all combine to facilitate the accurate, reliable and

repeatable test results.

Figure 7-10. Cross section of isothermal calorimetry device

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 The semi-adiabatic calorimeter was designed to obtain the temperature rise of the

concrete in the field. Thus, the semi-adiabatic device was never intended to serve as a high

precision instrument. However, it has been used with a satisfactory degree of success for the

prediction of temperature rise in concrete structures (Riding et. al, 2007).

One potential reason for the difference in the energy rise values between the isothermal

calorimetry test and the semi- adiabatic test may be attributed to the physical location of the flux

sensor in the semi- adiabatic calorimeter. As illustrated in Figure 7-11, the flux sensor does not

make direct contact with the concrete specimen. Although the configuration for the isothermal

calorimeter is somewhat similar (as illustrated by Figures in the A-4 and A-4 in Appendix A),

the primary difference between the two devices is that the isothermal calorimeter is equipped

with a heat sink where the semi-adiabatic calorimeter is not. Therefore, it is plausible that a

portion of the heat flux not measured by the semi-adiabatic calorimeter is measured by the

isothermal calorimeter. The illustration in figure 7-11 illustrated a loss of heat on all sides of the

concrete specimen, not just the side exposed to the flux sensor. Therefore, it is possible that the

heat loss is not measured, as there is potential for varying degrees of heat loss on each side.

Figures 7-3, 7-4, 7-6, 7-7, and 7-8 illustrate that the slopes shown on the energy vs.

equivalent age graphs are larger for the isothermal calorimetry test compared to the semi-

adiabatic test after the initial hydration curve (approximately 50 hours). Thus, the difference

discrepancy in the energy curves could be attributed to the inability of the semi-adiabatic

calorimeter to accurately and precisely measure lower quantities of heat loss or heat flux evolved

by Portland cement based materials at later ages.

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Figure 7-11. Cross section of semi-adiabatic device

Comparison of solution calorimetry to isothermal and semi-adiabatic calorimetry

The only standardized method currently used to determine the heat of hydration of

hydraulic cement is the solution calorimetry method as per ASTM C186. Since a portion of this

research was dedicated to the comparison of calorimetry methods, it was decided that a baseline

should be established which was incorporated into the standardized test method. The testing was

performed at the Construction Technology Laboratories Inc. (CTL) facility in Skokie, Illinois.

Prior to the shipment of the materials, appropriate proportions of the cementitious materials were

combined at the FDOT SMO.

Table 7-1 provides a summary of calorimetry values for each testing method. Isothermal

calorimetry data is reported for energy rise at 7 days of actual time and equivalent age for each

temperature. The calculated energy rise per the semi-adiabatic calorimetry testing is reported at 7

days of actual time and equivalent age. Solution calorimetry results are likewise reported.

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Table 7-1. Comparison of energy rise values for each calorimetry method for each mix
Mix 1 Mix 2 Mix 3 Mix 4
Energy (J/g) Energy (J/g) Energy (J/g) Energy (J/g)
Temperature °C Isothermal Calorimetry at 7 days (Time)
15 287 225 214 213
23 307 274 229 245
38 343 347 278 297
49 N/A N/A N/A N/A
Temperature° C Isothermal Calorimetry at 7 days (Equivalent Age)
15 323 258 235 241
23 307 274 229 245
38 295 288 222 256
49 289 299 221 276
Semi-Adiabatic Calorimetry at 7 days (Time)
252 255 194 200
Semi-Adiabatic Calorimetry at 7 days (Equivalent age)
227 236 153 151
Solution Calorimetry at 7 days
297 252 217 258

Of the various calorimetry test methods uses in this study, the isothermal calorimetry

testing at a temperature of 23°C and 7 days resulted in an energy increase most comparable to

the solution calorimetry for each of the testing methods and mixes performed. With the

exception of the ternary blended mix (Mix 4) the energy measured obtained by isothermal

calorimetry was slightly larger than the energy obtained by the solution calorimetry. This could

be attributed to the fact that the single operator precision of the solution calorimetry (as reported

by ASTM C186) has been found to be 14.8 J/g, indicating a lack of precision of the solution

calorimetry method. However, since the measured energy rise values obtained by the isothermal

calorimetry measurements are larger than those obtained by solution calorimetry, it may be

possible for the isothermal calorimetry method to measure heat of hydrations whereas the

solution calorimetry method cannot. These findings are consistent with those of Wadso (2003).

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 The semi-adiabatic testing resulted in an underestimation of the energy rise for each of the

mixes with the exception of Mix 2 which incorporated 50% slag replacement. This therefore

confirms the suggestion that the use of the semi-adiabatic method does not measure all of the

energy evolved from a cementitious system.

Summary of Findings

The comparison of the different calorimetry methods resulted in the following:

• The Sure Cure system does not have the necessary capabilities to accurately provide heat to
concrete to represent adiabatic conditions as per RILEM TCE 119. Therefore, the use of
the Sure Cure hydration chamber is not recommended for measuring the energy rise in
concrete.

• The semi-adiabatic test method does not measure as much of the energy evolved from a
cementitious system when compared with isothermal calorimetry and solution calorimetry.

• The Isothermal conduction calorimetry method allows the measurement of the largest
amount of energy evolved from a cementitious system. Accordingly, the isothermal
calorimetry method is the most conservative method for measuring the energy rise or heat
of hydration of cements.

• The total energy rise measured in Portland cement systems at cured higher temperatures is
lower than those systems cured at lower temperatures. Accordingly, the “cross over effect”,
the phenomenon in which Portland cements cured at higher temperatures will show a
decreased ultimate strength at later ages is observed via the energy rise in concrete as
measured by isothermal calorimetry.

• The “cross over effect” is not present in cementitious systems which have large
replacement of Portland cement with granulated blast furnace slag.

• The solution calorimetry method is acceptable for measuring the heat of hydration of a
system. However, it is limited because it only allows for a single point of measurement for
each sample. Isothermal calorimetry measures heat of hydration over time. Thus, the use of
isothermal conduction calorimetry is preferred for the potential modeling of the hydration
process of cementitious materials.

• The findings herein are similar to those by Wadso (2003) who concluded that the only
acceptable method for the calculation of temperature rise in concrete is the use of
isothermal calorimetry (when compared with semi-adiabatic and solution calorimetry).

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 CHAPTER 8
LARGE-SCALE BLOCK EXPERIMENT - PHYSICAL TESTING

The testing of the early-age concrete subsequent to the creation of the large scale block

specimens was performed using physical laboratory testing methods. The results obtained from

testing the large block specimens will serve as potential input parameters the prediction of the

behavior of mass concrete.

Mixture Design

Mass concrete mixtures that are accepted by FDOT for use in construction have typically

contain granulated blast furnace slag, fly ash, or both, in addition to Portland cement. The

purpose for using the supplementary cementitious materials is to create a concrete Mixture which

has a lower heat of hydration and, ultimately, a lower temperate rise. This research incorporates

the investigation of several concrete Mixture designs composed of the following:

Mix 1 – 100% Portland cement

Mix 2 – 50% Portland cement and 50% granulated blast furnace slag
Mix 3 – 65% Portland cement and 35% class F fly-ash
Mix 4 – 50% Portland cement, 35% granulated blast furnace slag, and 20% class F fly ash

Table 8-1. Mixture designs for large-scale block specimens

Mix 3 Mix 4
Mix 1 Mix 2
65% Portland - 50-30-20
100% Portland Cement 50% Portland -50%
Material 35% fly ash blend
(lb/yd3) Slag (lb/yd3)
(lb/yd3) (lb/yd3)
Cement 681 341 443 341
Fly ash 0 0 238 136
GGBF Slag 0 341 0 204
Water 341 341 341 341
Fine Agg. 1095 1088 1036 1050
Coarse Agg. 1650 1668 1660 1650

The mix designs for the large concrete blocks shown in Table 8-1 were designed with 0.50

water to cementitious material ratio in an effort to be compatible with isothermal calorimetry

testing. The coarse and fine aggregates were adjusted to reflect the volumetric differences due to

the density differences in each cementitious material. Cement has a specific gravity of

115
approximately 3.15 where fly ash and slag are approximately 2.5 and 2.9, respectively. The

approximate size of each large-scale specimen is 3.5’ x 3.5’ x 3.5’, with an approximate weight

of 5,800 lbs. Figure 7-1 is a photograph of the typical large block testing setup.

Figure 8-1. Large scale block testing configuration

Concrete Specimen Creation and Curing

The concrete used for the large-scale and small-scale specimens was not batched at

University of Florida or FDOT laboratories since approximately 100ft3 was required for each

Mixture. The maximum volume for a concrete mix the FDOT State Materials Office can create is

approximately 16ft3. As a result, the concrete was purchased from Florida Rock Industries

ready-Mix plant in Gainesville, Florida. At the time of delivery of the concrete for the large-scale

block specimens, companion cylinder specimens were also created for the physical testing. The

large-scale and companion specimens were cast in accordance with FDOT Standard specification

346, with the exception of 346-3, as the slump was higher than three inches (typically 8”).

Two sets of 8” high 4” diameter cylindrical specimens were created from the delivered

concrete. One set of the cylinder specimens was placed in a curing environment per ASTM C

116
192 and ASTM C 511. As second set of specimens was match cured with the temperature history

of the large-scale block (which remained in the laboratory), using a “Sure Cure” system

(discussed in Chapter 6)manufactured by Products Engineering, Inc. In an effort to create a

temperature history within the match cure cylinders identical to a single point within the large-

scale block specimen, the thermocouples from the Sure Cure system were positioned at the

midpoint between two corners along an edge of the non-insulated block specimen as shown in

Figure 8-2.

Figure 8-2. Thermocouple location for Sure Cure system

Thermocouples were located at the midpoint of the longitudinal-axis of the block two

inches below the concrete surface and two inches from the side wall of the formwork. This

location was chosen because it would provide an area of relatively low temperature history,

therefore providing a relative equivalent age lower than that of the inner core of the block.

Maturity and Equivalent Age

Concrete with lower temperature history will result in lower equivalent age, maturity, and

relative strength despite the fact that the actual age is the same (Tank, 1988; Carino, 2004).

Therefore, it was decided to monitor a portion of the block near the surface which would result in

117
relatively low strength and relatively high stresses as discussed in Chapter Two. The cylindrical

specimens were placed in the laboratory for 24 hours per ASTM C 192. The temperature at the

center of one of the cylindrical specimens was recorded to establish the exact 24 hour curing

history of the cylinder specimens themselves per ASTM C 1074 , after which the temperature of

the cylinders was assumed to be equivalent to the moist curing room at 23°C.

Figure 8-3. Time/temperature history of 4”x8” cylinder specimens

The early-age temperature data shown in Figure 8-3 and 8-4 provide the recorded

temperature history obtained from the 4”x8” cylinder specimens and Sure Cure specimens,

respectively. The temperature history for each mixture was used to calculate maturity and

equivalent age.

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Figure 8-4. Time/temperature history block – Sure Cure cylinder specimens

Maturity Calculation

The maturity of the concrete specimens for each mixture was calculated using the

temperature history provided in Figures 8-3 and 8-4 incorporated into the Nurse-Saul equation as

outlined in ASTM C 1074, which states:

t
M = ∑ (T − T0 )∆t (8-1)
0
Where:

M = maturity at age t
T = average temperature of the concrete during the time interval ∆t
To = Datum temperature

Equation 8-1 results in an increase of maturity only when the temperature of the concrete

is higher than that of the datum temperature. The standardized test method for the calculation of

the datum temperature is provided by ASTM C 1074 A1.1 and is discussed in detail in Chapter

4.

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Equivalent age calculation

The equivalent age for the concrete specimens for each mixture was calculated using the

temperature history, as provided in Figures 8-3 and 8-4 incorporated into the Arrhenius equation

as outlined in ASTM C 1074, which states:

−E 1 1 
t  − 
R  273+T 273+Tr
te = ∑ e 
∆t (8-2)
0
Where:

te = equivalent age
T = average temperature of the concrete during the time interval ∆t
Tr = reference temperature (typically 23°C)
E = activation energy, J/mol
R = universal gas constant, 8.3144 J/(mol °K)

Revisiting Table 4-6, three Ea values were obtained for each mixture. The calculated Ea

values are summarized in Table 8-2 and were used to calculate equivalent age for strength

properties for normal cure specimens as compared to specimens match-cured with the Sure Cure

System. Maturity calculations using ASTM 1074 (Nurse-Saul) are reported for normal versus

Sure Cure for test only as represented by the first column of Ea values in table 8-2 (Ferraro and

Tia, 2009).

Table 8-2. Summary of apparent activation energy per testing and analysis method
Compressive strength of mortar cubes Isothermal Testing
Hyperbolic calculation Exponential Exponential
Mix Name (ASTM 1074) calculation calculation
Mix 1 35642 37401 34235
Mix 2 33688 39932 50400
Mix 3 25757 20643 32982
Mix 4 30013 21158 37330

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 Physical Data and Results

Compressive Strength Testing

Compressive strength vs. time

Compressive strength data was obtained at ages of 1, 2, 3, 7, 14 and 28 days to establish a

rate of strength development over time which is often used to make determinations about the rate

of hydration of the cementitious materials. It is often used as a measure of the quality of the

concrete. Figure 8-5 is a graphical representation of strength vs. time for companion concrete

specimens cast for each mixture. The results are consistent with typical findings where concrete

with Portland cement alone gains strength fastest and where concrete with fly-ash gains strength

the slowest. Slag blend and ternary blend mixes gain strength at a rate between ordinary Portland

cement concrete and concrete with fly-ash, indicating that the partial replacement of Portland

cement with fly ash will reduce the initial rate of reaction of the concrete more than slag

assuming the quantities have been replaced by the same mass. Specimen testing within this

research was performed in accordance with ASTM C39.

Figure 8-5. Compressive strength vs. time for each mix

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 Concrete specimens subjected to higher temperatures will gain strength at a faster rate than

specimens that are exposed to lower temperatures (Carino and Tank, 1992; Carino, 2004;

Mindess et. al, 2003). The strength vs. time results for concrete cylinder specimens composed of

100% Portland cement subject to standard curing (Figure 8-3) and the cylinders subjected to the

Sure Cure / elevated temperature history (Figure 8-4) are shown in Figure 8-6.

Figure 8-6. Compressive strength vs. time for Mix 1 - 100% Portland cement

Compressive strength vs. maturity

The strength - maturity relationship was developed for the concrete specimens for each

Mixture. The strength vs. time data for concrete cylinder specimens composed from Mix 1

subjected to standard curing and the cylinders subjected to the Sure Cure is provided in Figure 8-

7. While a majority of the research comparing maturity and strength concludes that, for a given

maturity, the strength will be the same regardless of temperature history, the data indicates that

the maturity-compressive strength relationship is not suitable for the concrete specimens

composed of Portland cement.

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 Possible reasons for the difference in strength vs. maturity can be attributed to the fact that

research studying strength – maturity relationships typically involves the isothermal curing of the

concrete or mortar specimens prior to compressive strength testing. Another reason for the

inconsistencies with the strength-maturity relationship developed for the concrete blocks was

that testing was performed using mortar samples and there could be a slight difference between

the maturity results for mortar and concrete. However, the most likely reason for the difference

in the maturity results as shown in Figure 8-7 is the relatively unrefined nature of the Nurse Saul

equations.

Figure 8-7. Compressive strength vs. maturity for Mix 1 - 100% Portland cement

Carino outlines several constraints using the Nurse-Saul equation for the calculation of

concrete strength, which can be attributed to the possible deviation in the maturity-strength

relationships. However, each of the constraints are properly addressed in the temperature

histories for both sets of specimen curing history (Carino, 2004). In addition, Carino later states

that the maturity-strength relationship should only be considered an approximation, and that

123
concrete does not have a unique strength-maturity relationship. The application of the maturity

method for estimating in-place strength is often abused or oversimplified by the use of the

Nurse-Saul relationship alone. As shown in Figure 8-7, the Nurse-Saul relationship is not

accurate for the Sure Cure vs. normal cure specimens for Mix 1. Appendix B provides similar

inaccurate results for each of the four block mixes using the Nurse-Saul equation for the

comparison of normal cure vs. Sure Cure maturity-strength relationships.

Compressive strength vs. equivalent age

A more accurate way to describe the strength of concrete with the incorporation of

temperature history utilizes the concept of equivalent age. Using the Ea results provided by table

8-2 and the Arrhenius equation (8-2), the compressive strength versus equivalent age for the

normally cured concrete specimens as well as the Sure Cure specimens was calculated and is

shown in Figure 8-8 (Ferraro and Tia, 2009).

Figure 8-8. Compressive strength vs. equivalent age for Mix 1 - 100% Portland cement

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 Three Ea values obtained for Mix 1 using the different testing and calculation techniques

were used to create compressive strength versus equivalent age for the normal cure vs. Sure Cure

specimen groups (cured at significantly higher temperatures as experienced by the large block

specimen). The calculated results for compressive strength vs. equivalent age indicate there is

not a practical variation with respect to the method used to obtain Ea.

The compressive strength for the normal cure and the Sure Cure specimen groups are

essentially the same for the first 8 days of curing history. However, the Sure Cure specimens

exhibit higher compressive strength values after the 8 days. There are several factors

contributing to this deviation in strength. The normal cured specimens were placed in a moisture

room, which supplied additional curing water and also prevented water loss. However, the Sure

Cure specimens were cured in a sealed condition to prevent moisture loss. Figure 8-9 is a

photograph of a typical sure cure specimen mold.

Figure 8-9. Sure Cure specimen mold

The Sure Cure specimen molds are designed to provide insulation of the concrete as well

as provide additional heat to the match cure specimen as programmed by the computer system.

For this experiment, Sure Cure system was programmed to match the temperature produced by

the portion of the section of the block as discussed in Figure 8-2. Since the Sure Cure molds are

electrically powered, it is not feasible to add additional water to the Sure Cure specimens. Sealed

curing of specimens can lead to self-desiccation of the concrete as hydration progresses (Mindess

2003, Neville 1995).

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 Research has shown that specimens moist cured for 7 days then exposed to air will result

in an immediate strength gain when compared to specimens continuously moist cured (Price

1951). Assuming all other conditions are equal, the compressive strength of concrete cylinders of

dry concrete will be higher than saturated concrete (Kesler, 1966). Decreased strength in moist as

opposed to dry concrete has been attributed to the presence of moisture forcing the gel particles

apart (Ross et. al 1996). Therefore, it can be assumed that the higher 8 day compressive strength

associated with Sure Cure specimens is a result of the curing / saturation conditions rather than a

temperature/hydration effect.

The majority of the research regarding the maturity and equivalent age relationships

focuses primarily on the study of ordinary concrete and mortar which utilize ordinary Portland

cement as binder for compressive strength for specimens (Barnett et al., 2006). The study of the

replacement of Portland cement with supplementary cementitious materials such as ground

granulated blast furnace slag and fly ash has not been extensively researched.

The equivalent age concept was applied to Mix 2, which replaced 50% of the Portland

cement with granulated blast furnace slag. Using the data provided by table 8-2 and used in the

Arrhenius equation (8-2), the compressive versus equivalent age for the normally cured concrete

specimens as well as the Sure Cure specimens was calculated and is shown in Figure 8-10.

Unlike the compressive strength results obtained for Mixture 1, the normal cure and the Sure

Cure specimen groups differ significantly for the entire curing history of the specimens. The

observed difference is observed regardless of the testing method and calculation technique used

to obtain Ea. The difference is due to the maturity or equivalent age maturity functions increase

disproportionally at elevated temperatures and the increase depends upon the amount of

supplementary cementitious material, the water-to-cementitious material ratio, and the difference

126
in temperature between the normal cured specimen and the temperature history of the large scale

concrete. As a result, maturity relationships typically underestimate the strength development at

elevated temperatures (Gajda, 2007). The data obtained for each of the mixes which incorporate

supplementary cementitious materials clearly demonstrates this phenomenon.

Figure 8-10. Compressive strength vs. equivalent age for Mix 2 – 50% Portland cement - 50%
slag

The value of Ea calculated by the isothermal calorimetry testing was the highest for each

of the mixes with the exception of the Portland Cement only Mix. As a result, the strength-

equivalent age relationships between the regular cure and Sure Cure specimens were the most

accurate for the compressive strength for the samples with large replacement of Portland cement

with SCM. Figures 8-11 and 8-12 provide data showing the compressive strength versus the

equivalent age for Mix 3 (incorporating 35% replacement of Portland cement) and Mixture 4

which utilizes 30% slag and 20% fly ash as a replacement of Portland cement, respectively. The

127
slag blend and ternary blend Mixes gain strength at a rate between ordinary Portland cement

concrete and concrete with a high percentage replacement of fly-ash.

Figure 8-11. Compressive strength vs. equivalent age for Mix 3 – 65% Portland cement - 35%
fly ash

Figure 8-12. Compressive strength vs. equivalent age for Mix 4 – 50% Portland cement- 30%
slag -20% fly ash

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Splitting Tensile Strength Testing

Splitting tensile strength vs. time

Tensile strength is particularly important for the potential model inputs since mass

concrete failure typically takes place in tension. Tensile strength data was obtained at ages of 1,

2, 3, 7, 14 and 28 days to establish a rate of strength development over time, and Figure 8-13 is a

graphical representation of the tensile strength vs. time for each mixture. The results are

consistent with typical findings and compressive strength testing results, where concrete with

Portland cement alone gains strength fastest and concrete with fly-ash gains strength the slowest.

Slag blend, ternary Slag blend, and ternary blend mixes gain strength at a rate between ordinary

Portland cement concrete and concrete with a high percentage replacement of fly-ash. The tensile

strength testing of the cylinder samples within this research was performed in accordance with

ASTM C496.

Figure 8-13. Splitting tensile strength vs. time for each mix

129
Tensile strength vs. maturity

The tensile strength / maturity relationship was developed for the concrete specimens for

each Mixture. The strength vs. time data for concrete cylinder specimens composed from Mix 1

subjected to standard curing and the cylinders subjected to the Sure Cure is provided in Figure 8-

14. While similar to the results obtained for the compressive strength testing, the maturity-

splitting tensile strength relationship is not, however, suitable for the concrete specimens

composed of Portland cement. Appendix B provides similar inaccurate results for each of the

four block mixes using the Nurse-Saul equation for the comparison of normal cure vs. Sure Cure

maturity-strength relationships.

Figure 8-14. Splitting tensile strength vs. maturity for Mix 1 - 100% Portland cement

Tensile strength vs. equivalent age

A relationship between splitting tensile strength/equivalent age was created using the same

method used to create the compressive strength/equivalent age relationship. The splitting tensile

strength vs. equivalent age results for the normally cured concrete specimens as well as the Sure

Cure specimens was calculated and is shown in Figure 8-15 (Ferraro and Tia, 2009).

130
 The splitting tensile strength for the normal cure and the Sure Cure specimen groups is

essentially the same for the entire curing history. The splitting tensile strength does not deviate

between normal cure and Sure Cure after 8 days as observed during the compressive strength

testing. This is because the fracture mechanisms of splitting tensile test specimens are generally

the same regardless of moisture content. Research has shown that semi saturated and fully

saturated concrete has lower strength than unsaturated concrete (Ross et. al. 1996). Since the

normal cure concrete and Sure Cure concrete specimen groups were both at least semi-saturated,

it is probable that the fracture mechanics for both specimen groups were identical.

Figure 8-15. Splitting tensile strength vs. equivalent age for Mix 1 - 100% Portland cement

Since it is known that mass concrete will typically crack under tensile forces due to

thermal gradients, it is particularly useful to consider splitting tensile testing for the model input

parameters. The relationship between splitting tensile testing strength versus equivalent age for

concrete composed of Portland cement can be accurately predicted regardless of temperature

history.

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 The equivalent age concept was applied to Mix 2, which replaced 50% of the Portland

cement with granulated blast furnace slag. The strength versus equivalent age results for the

normally cured concrete specimens as well as the Sure Cure specimens was calculated and is

shown in Figure 8-16.

Figure 8-16. Splitting tensile strength vs. equivalent age for Mix 2 - 50% Portland cement 50%
slag

Unlike the compressive strength results obtained for Mixture 1, the normal cure and the

Sure Cure specimen groups differ significantly for the entire curing history of the specimens.

This observed result is consistent with the data obtained from compressive strength testing with

respect to equivalent age. Again, the equivalent age maturity functions increase disproportionally

at elevated temperatures (Gajda 2007). The data obtained for each of the Mixes which

incorporate supplementary cementitious materials clearly demonstrate this phenomenon. Figures

8-16 and 8-17 show the splitting tensile strength versus the equivalent age for Mix 3 (35%

replacement of Portland cement) and Mixture 4 which utilizes 30% slag and 20% fly ash as

replacement of Portland cement, respectively.

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Figure 8-17. Splitting tensile strength vs. equivalent age for Mix 3 - 65% Portland cement 35%
fly ash

Figure 8-18. Splitting tensile strength vs. equivalent age for Mix 4 – 50% Portland cement - 30%
slag -20% fly ash

The splitting tensile strength testing vs. equivalent age results for Mix 3 show relatively

similar values between the normal cure and Sure Cure specimens for the first 150 hours of

133
testing. However, at later ages the results deviate and the underestimation of strength with the

normal cure specimens occurs.

The value of Ea calculated by the isothermal calorimetry test was the highest for each of

the Mixes with the exception of the Portland Cement only Mix. Similar to the compressive

strength testing, the tensile strength-equivalent age relationships between the regular cure and

Sure Cure specimens were the most accurate per the Ea obtained by isothermal calorimetry for

the Mixes containing large replacements of SCM. Revisiting Figure 8-11, the results for the

compressive strength and equivalent age for Portland cement with fly ash are somewhat closer in

strength than the mix which incorporates blast furnace slag or the ternary blend (Figures 8-10

and 8-12). A possible reason for the relatively consistent result is that the percentage of Portland

cement replacement is lowest in Mixture 3 (35%) However, it is mostly likely that the

replacement of Portland cement with slag results in the disproportional increase in strength and

physical properties at elevated temperatures.

Compressive Modulus of Elasticity

Most structures are designed to undergo relatively small in-service deformations.

Typically, the primary failure mechanism of early age mass concrete is a result of thermal strain

exceeding the strain capacity. The cracking of the concrete occurs as a result. Therefore, it is

necessary to quantify the linear elastic properties of the concrete while under compression and

tension. The linear relationship between the stress and the strain of a material is known as

Hooke’s Law (Beer and Johnson 1992) and is expressed:

σ = Eε (8-3)
Where:

σ = the stress of the material

E = is Young's Modulus
ε = linear strain

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 However, concrete behaves as a nonlinear inelastic material in both compression and in

tension, therefore a single linear value modulus for elasticity does not accurately describe the

stress/strain behavior of concrete (Mindess et. al 2003). Figure 8-19 is an illustration of the

various points within the stress strain curve.

Figure 8-19. Typical stress-strain diagram for concrete, showing the different elastic moduli
(Mindess 2003)

Tangent modulus

Tangent modulus is defined as the slope of the stress/strain curve at any given point. It can

also be considered the instantaneous rate of change of the stress with respect to strain (Philleo,

1966). The closest approximation to the modulus of elasticity as described by Hooke’s law can

be described as the initial tangent modulus (also referred to as dynamic modulus), which is the

slope of the tangent to the stress-strain curve at the origin (Mindess et al 2003, Mehta 1986).

Both tangent and initial tangent moduli are depicted in Figure 8-19.

135
Secant modulus

The secant modulus is the slope of the secant between the origin and a given point on the

stress/strain curve. It is dependent upon the intersecting point on the stress/strain curve. The

secant modulus is considered to be the instantaneous rate of change of the stress with respect to

strain (Philleo, 1966). Typically, the secant modulus is determined to be the secant between the

origin and the point on the stress/strain curve which corresponds to 40% of the failure stress

(Mehta, 1986).

Chord modulus

The chord modulus is the slope of a line drawn between any two points on the stress/strain

curve. Research has shown that the initial tangent and secant moduli can produce errors in

measurement due to either initial loading seating effects or defects in the specimen both of which

result in non-linearity at the early portions of the stress/strain curve (Mindess et al, 2003). As

such, the Standard Test Method for Static Modulus of Elasticity of Concrete in Compression

(ASTM C 469) specifies the chord modulus be drawn between points corresponding to 50

microstrain and 40% of the ultimate strength.

Modulus of elasticity methodology

As concrete hydrates, the modulus of elasticity increases, and is analogous to the other

strength properties of concrete. However, the increase in elastic modulus of elasticity is

detrimental to early age mass concrete as the propensity for thermal cracking increases with

increased modulus. Therefore, the most conservative estimate of modulus of elasticity for mass

concrete is the highest calculated value per the stress/strain relationship.

The modulus of cylinder samples tested within this research was performed in accordance

with ASTM C469. Prior to the modulus of elasticity testing, the ultimate load was obtained using

the average compressive strength per ASTM C39. ASTM C 469 states that the specimens are to

136
be tested at stresses of up to 40% of ultimate load. Figure 8-20 is a stress-strain curve of a typical

concrete 4”x8” cylindrical specimen tested in accordance with ASTM C 469.

Figure 8-20. Stress-strain diagram for concrete specimen

Four different calculations for elastic modulus are presented in Figure 8-20: the initial

tangent modulus, the secant modulus, the chord modulus per ASTM C 496, and a truncated

secant modulus.

1. The initial tangent modulus was calculated as the best fit line between the first several
points of data. The modulus was obtained from the line drawn through the origin and a
point on the stress-strain curve at 2 microstrain. The initial tangent modulus is 4,551,135
psi for this specimen.

2. The secant modulus as prescribed by Mehta (1986) is a line between the origin and the
corresponding strain at 40% of the ultimate load. The secant modulus is calculated to be
1,933,840 psi using this technique.

3. The chord modulus per ASTM C 469 was calculated to be 1,897,142 psi.

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 Research has shown that microcracking can begin in concrete specimens when subjected to

loads of between 30% and 40% of ultimate load (Zheng, 2007, Bascoul 1996, Hsu et al, 1963).

The motivation behind the utilization of 40% of ultimate load for the standardized calculation of

chord modulus is to obtain a modulus of elasticity of concrete materials at design loads (Kesler

1966). The standard method for creep of concrete in compression (ASTM C 512, 2008) specifies

40% of the ultimate load for testing. Per this test method, it is expected that the concrete will

experience permanent deformations as a result of being subjected to such loads for long periods

of time. Therefore, it is appropriate to conclude that concrete will experience micro-cracking or

micro-damage at loads that are 40% of ultimate.

The onset of micro-cracking within the test specimen will result in permanent deformation

and lower modulus which- for the purposes of this research- is not conservative. Therefore, a

new method for the calculation of modulus of elasticity is being proposed by this research.

The “truncated secant modulus” is a line drawn between the origin and the corresponding

strain at 30% of the ultimate load. The truncated secant modulus shown in Figure 8-20 is

1,980,890 psi, which is the largest of the static moduli. The compressive modulus of elasticity

was calculated using the truncated secant modulus for each of the specimens used in this

research.

Compressive modulus of elasticity vs. time

Modulus of elasticity data was obtained at ages of 1, 2, 3, 7, 14 and 28 days to establish a

rate of modulus development over time for each of the concrete Mixtures. Figure 8-21 is a

graphical representation of the modulus of elasticity vs. time for companion concrete specimens

cast for each mixture. The results are consistent with typical findings where concrete with

Portland cement alone gains strength fastest and concrete with fly-ash gains strength the slowest.

138
Concrete mixes which replace Portland cement with slag, fly ash, or both (ternary blend Mixes)

gain strength at a rate between ordinary Portland cement concrete.

Figure 8-21. Compressive modulus of elasticity vs. time for each mix

Compressive modulus of elasticity vs. maturity

The modulus of elasticity / maturity relationship was determined for each mixture. The

modulus of elasticity vs. time result for Mix 1 subjected to standard curing and the cylinders

subjected to the Sure Cure is provided by Figure 8-22. These results are similar to those obtained

for the compressive strength and tensile strength testing. Thus, the maturity-modulus of elasticity

relationship is not suitable for the concrete specimens composed of Portland cement. Appendix B

provides similar inaccurate results for each of the four block Mixes using the Nurse Saul

equation for the comparison of normal cure vs. Sure Cure maturity – modulus relationships.

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Figure 8-22. Compressive modulus of elasticity vs. maturity for Mix 1- 100% Portland cement

Compressive modulus of elasticity vs. equivalent age

A relationship between modulus of elasticity and equivalent age was developed using the

same method as the modulus of elasticity equivalent age relationship. The modulus of elasticity

versus equivalent age for the normally cured concrete specimens as well as the Sure Cure

specimens was calculated and is shown in Figure 8-23.

The modulus of elasticity for the normal cure and the Sure Cure specimen groups are

essentially the same for the entire curing history. The modulus of elasticity does not deviate

between normal cure and Sure Cure after 8 days as observed with the compressive strength

testing. This can be attributed to the compressive loading for the modulus of elasticity testing

remaining below the threshold for micro cracking. By design, the loading remained in the elastic

range of the concrete. Therefore the fracture mechanics that apply to compressive strength

testing do not apply to modulus of elasticity testing.

140
Figure 8-23. Compressive modulus of elasticity vs. equivalent age for Mix 1- 100% Portland
cement

Since it is known that mass concrete will typically crack under tensile forces due to

thermal strains, it is particularly useful to consider modulus of elasticity testing for the model

input parameters. Modulus of elasticity versus equivalent age for concrete composed of Portland

cement as a relationship is accurately predicted regardless of temperature history.

The equivalent age concept was applied to Mix 2 which replaced 50% of the Portland

cement with granulated blast furnace slag. The equivalent age vs. strength result for the normally

cured concrete specimens as well as the Sure Cure specimens was calculated and is shown in

Figure 8-24.

Unlike the compressive strength results obtained for Mixture 1, the normal cure and the

Sure Cure specimen groups differ significantly for the entire curing history of the specimens.

This observed result is consistent with the data obtained from compressive strength- and tensile

strength testing with respect to equivalent age. Again, the equivalent age maturity functions

increase disproportionally at elevated temperatures (Gajda, 2007). The data obtained for each of

141
the mixes which incorporate supplementary cementitious materials clearly demonstrate this

phenomenon. Figures 8-25 and 8-26 show the modulus of elasticity versus the equivalent age for

Mix 3 incorporating 35% replacement of Portland cement and Mixture 4 utilizing 30% slag and

20% fly ash as replacement of Portland cement, respectively.

As with the results obtained from the splitting tensile strength testing, the modulus of

elasticity vs. equivalent age for Mix 3 shows relatively similar values between the normal cure

and Sure Cure specimens for the first 150 hours of testing. However, at later ages the results

deviate and the underestimation of strength with the normal cure specimens occurs. Revisiting

Figure 8-11, the equivalent age model for the compressive strength versus equivalent for the

mixes which do not contain large amount of slag replacement, more accurately model the

evolution of physical and strength properties than those mixes which incorporate blast furnace

slag. A possible reason for the relatively consistent data is that the percentage of Portland cement

replacement is lowest in Mixture 3 (35%). The relationships developed with respect to modulus

of elasticity equivalent age shown in Figures 8-24 and 8-25 are consistent with the relationships

developed for tensile strength testing.

Figure 8-24. Compressive modulus of elasticity vs. equivalent age for Mix 2 - 50% Portland
cement - 50% slag

142
 The value of Ea calculated by the isothermal calorimetry test was the highest for each of

the mixes with the exception of the Portland Cement only Mix. Similar to the results obtained by

the compressive and tensile strength testing, the modulus-equivalent age relationships between

the regular cure and Sure Cure specimens were the most accurate.

Figure 8-25. Compressive modulus of elasticity vs. equivalent age equivalent age for Mix 3 -
65% Portland cement - 35% fly ash

Figure 8-26. Compressive modulus of elasticity vs. equivalent age for Mix 4 – 50% Portland
cement - 30% slag -20% fly ash

143
Tensile Modulus of Elasticity

The primary failure mechanism of mass concrete can be attributed to the tensile stresses

induced by thermal gradients. Therefore, the tensile modulus is of the utmost importance when

considering the physical properties of concrete. There is very little research available which

compares tensile modulus to compressive modulus. The majority of tensile testing performed on

concrete materials is performed via indirect methods such as the splitting tensile test discussed

earlier in this chapter. There is no standardized method for the direct tensile testing of concrete

for strength or modulus. Therefore, it was decided to use the existing standardized flexural test

per ASTM C 78 to measure modulus of elasticity. The test was modified to incorporate linear

voltage displacement transducers (LVDTs) as shown in Figure 8-26. Equation 8-3 is a

calculation of modulus incorporating the measured load and deflection.

PL / 2
MOE = (8-3)
28∆I

Where:

MOE = Modulus of Elasticity (psi)

P= Load (lb)
∆ = Average deflection (in)
I = Moment of inertia = bh3 (in4 )

Figure 8-27. Photo of tensile (flexural) modulus of elasticity test configuration

144
 It may be more appropriate for the tensile testing presented herein to be considered flexural

modulus of elasticity testing. However, the stress-strain diagram produced for a concrete beam

subjected to a flexural load is due to tensile stresses. Furthermore, the third-point bending test

imparts a uniform moment across the loading area of the test specimen which facilitates

calculation of the modulus of elasticity.

Tensile modulus of elasticity vs. time

Compressive strength data was obtained at ages of 1, 2, 3, 7, 14 and 28 days to establish a

rate of strength development over time, which is considered to be analogous to the rate of

hydration of the cementitious materials over time. Figure 8-28 is a graphical representation of the

tensile modulus of elasticity vs. time for each mixture. The results are consistent with findings

per the compressive strength, splitting tensile strength and modulus of elasticity testing results,

where concrete with Portland cement alone gains strength fastest and concrete with fly-ash gains

strength the slowest. The slag blend and ternary blend Mixes gain strength at a rate between

ordinary Portland cement concrete and concrete with a high percentage replacement of fly-ash.

Figure 8-28. Tensile modulus of elasticity vs. time for each mix

145
Comparison of tensile and compressive modulus of elasticity

The moduli of elasticity / maturity relationships were not developed for the concrete

specimens for each mixture. The Sure Cure system is not capable of match curing the typical

prism specimens (6”x6”x22”) required for flexural/modulus testing. Appendix B provides a data

summary of the tensile modulus of elasticity results for each of the four block Mixes using the

Nurse-Saul equation.

Equivalent age relationships were developed for the laboratory cured specimens for both

the prism specimens and the cylinder specimens. The temperature history data for the 4”x8”

cylindrical specimens presented in Figure 8-3 was used to establish the equivalent age of the

specimens and was recorded to establish the exact curing history and equivalent age of the

cylinder specimens. Accordingly, the same procedure was performed on the prism specimens

used to establish the equivalent age.

There is little research available regarding the comparison of tensile and compressive

modulus of elasticity data, primarily because the determination of the modulus of elasticity in

tension is rarely performed. As previously discussed, tensile testing of concrete materials is

performed indirectly. Therefore, the modulus data obtained via an indirect test is difficult to

obtain and there is currently no standardized method available to acquire tensile modulus of

elasticity of concrete.

Balendran (1995) performed modulus of elasticity testing on concrete materials in direct

tension using a beam specimen in which the central portion had a reduced cross-sectional area. In

his experiment, Ballendran compared the tensile vs. compressive modulus of several

cementitious mixtures including concrete containing limestone coarse aggregate. However, the

experiment was limited in that the concrete was tested at an age of 28 days only. His results

indicated that the modulus of elasticity in compression is slightly larger (3%) than the modulus

146
of elasticity in tension. He concluded that “the modulus in tension is nearly equal to the modulus

in tension at a stress level of one-third the ultimate stress” (Balendran, 1995p 16).

The tensile and compressive modulus of elasticity vs. equivalent age for the four mixes are

presented in Figures 8-29 through 8-32. The results indicate that the compressive modulus of

elasticity is approximately equal to the tensile modulus for each of the mixes. However, data

obtained for the compressive modulus of elasticity is slightly lower than the tensile modulus at

earlier ages (one day). Conversely, the compressive modulus of elasticity is significantly larger

(15%) than the tensile modulus of elasticity at 28 days. This difference may be attributed to the

difference in testing equipment (stress and strain measurements). The stress- strain curves were

obtained in the same manner as Balendran, (using loads less than 33% of ultimate), and thus the

similarity in the results indicates the tensile and compressive stresses can be considered the same

value for prediction and modeling purposes.

Figure 8-29. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 1

147
Figure 8-30. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 2

Figure 8-31. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 3

148
Figure 8-32. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 4

Summary of Findings

The physical testing of properties the concrete in this study resulted in the following:

1. The application of Nurse-Saul maturity method is to determine physical and strength

parameters based on the time-temperature history of concrete. The Nurse-Saul per ASTM
1074 does not accurately model the physical and strength properties of concrete with
different time-temperature histories of concrete.

2. The equivalent age method per ASTM C1074 accurately models the evolution of physical
and strength parameters with different time-temperature histories time-temperature history
which can be used for the estimation of concrete created with Portland cement.

3. Neither the Nurse-Saul equation nor the equivalent age method per ASTM C1074
accurately models the hydration and strength evolution of Portland cement concretes with
large portions of supplementary cementitious materials with different curing histories.
Further research is needed to create maturity/equivalent age models for concrete using
large proportions of fillers (Ferraro and Tia, 2009).

4. The modulus of elasticity of concrete material is most accurately measured -with

comparable results- between different physical tests (compression, tension) at stress levels
equal to or less than 30% of ultimate.

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 CHAPTER 9
LARGE-SCALE BLOCK EXPERIMENT – THERMAL TESTING

The testing of the early-age concrete subsequent to the creation of the large scale block

specimens was performed using thermal laboratory testing methods. Results obtained from

laboratory testing of the concrete obtained from the same mixes as the large-scale block

specimens will serve as potential parameters the prediction of the behavior of mass concrete.

Coefficient of Thermal Expansion Testing

The coefficient of thermal expansion (CTE) is a very important thermal property with

regard to the prediction of the behavior of early-age mass concrete. Virtually all materials

experience volumetric changes when subjected to temperature change. Concrete behaves like

most other elastic materials in that it expands volumetrically when it is subjected to temperature

increase and shrinks volumetrically when it is subjected to temperature decrease. The magnitude

of the volumetric change is typically quantified by the CTE. The standardized test method for

CTE is defined as the linear change in material with respect to a change in temperature:

 ∆La 
 L 
CTE =  O 
(9-1)
∆T

Where:

∆La = actual length change of specimen during temperature change

LO = measured length of specimen at room temperature
∆Τ = measured temperature change

The coefficient of thermal expansion was obtained each of the four mixes at ages of 1, 2, 3,

7, 14 and 28 days. The testing was performed in accordance with AASHTO TP 60 with the

following exceptions:

1. 7.1 The early-age specimens (1, and 2 day) were not conditioned by submersion in lime
water for 48 hours prior to testing.

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 2. 8.3 Only two test segments for each test were performed at early ages because each test
segment required 8 hours (16 hours total). One segment was the 50°C temperature cycle;
the other segment was the 10°C temperature cycle

3. Individual specimens were tested once in an effort to avoid modifying the equivalent age
of specimens at each age

Figure 9-1 is a graphical representation of the coefficient of thermal expansion vs. time for

each mixture. The results indicate that the values of coefficient of thermal expansion obtained at

1,2, and 3 days of age were slightly lower than later age values for each mix. However, after

seven days, the values of coefficient of thermal expansion slightly increased for the blocks

containing supplementary cementitious materials. The increase of CTE values of the concrete at

early age per obtained in this study is similar to the findings by Cusson and Hoogeveen (2006),

where the CTE at early-ages is less than at later ages.

Figure 9-1. Coefficient of thermal expansion vs. time for each mix

Companion specimens for CTE testing using the “Sure Cure” system were not created due

to the limited number of 4”x8” specimen molds. CTE testing was performed primarily to obtain

151
values for use in potential analytical models and to record early age values of CTE vs. time for

concrete made with materials from Florida.

Currently, the standardized method for the measurement of CTE (AASHTO TP-60-2007)

has been withdrawn due to the potential concerns with the calibration factor (of stainless steel)

used to calibrate the test (Crawford, 2009). Therefore, the results obtained under this research

were calculated per the calibration testing performed at the FDOT SMO.

Thermal Diffusivity Testing

The quantification of the thermal diffusivity of concrete is necessary for the prediction of

the behavior of mass concrete. The thermal diffusivity is measure of the rate at which the

temperature changes within concrete (Mitchell, 1966). Knowledge of the rate at which concrete

is able to absorb or dissipate heat is important in determining the rate of cooling of mass

concrete, assuming an elevated early-age temperature has been obtained. The diffusivity is of

particular importance when calculating the temperature differential of concrete at early ages. The

equation used to calculate thermal diffusivity is determined from equation 9-2.

k
a=
Cp ⋅ρ

Where:

a= thermal diffusivity (m2 /day)

k = thermal conductivity (kJ/m·°C·h)
Cp = specific heat capacity (kJ/kg·°C)
ρ = concrete density (kg/m3)

The standardized test for the thermal diffusivity of concrete is outlined in CRD 36 (1973).

The test involves the temperature monitoring of a 6”x12” cylindrical concrete specimen as it is

placed from one high temperature water bath to another lower temperature water bath. The

testing method requires that the concrete be immersed in a water bath at 100°C until the center of

152
the specimen reaches temperature equilibrium; then the specimen is immersed in a low

temperature water bath while the time temperature history of the specimen is recorded.

The procedure for this research was slightly altered to accommodate the necessary

parameters per the testing of concrete specimens at early ages. In an effort to avoid heating (and

thereby artificially increasing the maturity of the concrete specimen) at early ages, the specimens

were left in the standard moist cure room at 23°C and immersed in a hot water bath for testing,

which is essentially the reverse of what the standard test method specifies. Ochiai (2009)

performed testing to determine the potential difference between concrete specimens initially hot

(CRD 36) and initially cold (modified CRD 36) and found the difference between the obtained

values was found to be negligible.

Figure 9-2. Thermal diffusivity vs. time for each mix

The early age thermal diffusivity results obtained by Ochiai for the concrete specimens for

each mix are presented in Figure 9-2. The results indicate that the thermal diffusivity increases

with respect to time for each of the concrete mixes. The concrete mixes that contain large

153
replacements of Portland cement with blast furnace slag or fly ash have a lower thermal

diffusivity. Accordingly, the concrete which contains large replacements of amounts of fly ash

and slag should be considered to have lower diffusivity values at early-ages.

ACI 207.2 lists the thermal diffusivity of concrete in which the values of thermal

diffusivity are reported. The diffusivity values for concrete made with limestone coarse

aggregate, reported by Table 3.1 of ACI 207.2 range from 0.029 – 0.054 (m2 /hour). The results

obtained from this study, are significantly lower than the values provided ACI 207.2. A potential

reason for the difference in diffusivity values between the concrete tested in this study and the

values published in ACI 207.2 can be attributed to the difference in coarse aggregate used in the

concrete.

The coarse aggregate used in this study was limestone produced from Florida, which is

more porous, less dense, and softer than limestone produced from other areas of the U.S. To

differentiate between limestone produced in Florida, and limestone produced elsewhere, Florida

limestone has been called Florida “limerock” by the local concrete industry. The porosity and

resultant density of the lime rock used for coarse aggregate used in this study is the cause for the

lower reported diffusivity values as compared to those reported by ACI 207. Tyner (1946)

reported lower thermal conductivity (which is similar to diffusivity) with concrete made with

Florida limerock as compared to concrete made with limestone from Minnesota.

The data obtained in this study per Figure 9-2 indicates that the thermal diffusivity

increases with concrete age. The results obtained in this study are similar to the results published

by Hansen et al (1982) and Morabito (2001). The results are contrary those reported by

DeSchutter and Taerwe (1995) who reported a decrease in thermal diffusivity of concrete with

154
respect to age. However, no consensus has been reached regarding the increase of decrease of the

thermal diffusivity at early ages (DeSchutter and Taerwe, 1995, Chirdon et. al 2007).

One potential explanation for the contrasting results between the diffusivity testing

performed in this study and the results reported DeSchutter and Taerwe is most likely due to the

different curing methods used in each respective experiment. The specimens used in this study

were moist cured in accordance with ASTM C192. However, DeSchutter and Taerwe sealed

their specimens which would allow for natural desiccation to take place. Therefore, the

diffusivity results over time would decrease proportionally. As concrete hydrates and the

microstructure becomes more dense, the absorptive, and diffusive properties decrease

accordingly. Since the thermal diffusivity test measures the rate of temperature change of a

concrete specimen submerged in water, a saturated sample (with available pore water in the

structure) would be more likely to conduct and transfer heat from than an unsaturated specimen.

Tyner (1946) found that the thermal diffusivity of concrete is dependent upon the moisture

content of concrete made with Florida lime rock. Therefore, the contrasting results obtained by

this study and DeSchutter in Taerwe is most likely due to specimen conditioning. A potential

reason for the increase in the thermal diffusivity of concrete per the results in this study could be

due to the formation of the concrete microstructure which would include the presence of a

saturated void system, as a result of the addition of curing water to the concrete.

Specific Heat Capacity Testing

The quantification of the thermal specific heat capacity of concrete is necessary for the

prediction of the behavior of mass concrete. The specific heat capacity is the measure of energy

or heat required to change unit mass by a unit temperature. As previously stated, the thermal

properties of Florida limerock are different than the values for limestone. Thus, in an effort to

155
obtain the specific heat of concrete which incorporates limerock, it was decided to measure the

specific heat of the materials used in this study.

Ochiai (2009) discusses in detail the testing procedure developed and performed for the

measurement of the specific heat capacity of the cement paste, coarse aggregate, fine aggregate

and concrete materials used in this study. Table 9-1 provides the results obtained for the average

specific heat capacity of the materials used in this study. The specific heat capacity of the cement

paste and concrete was measured at an age of 1 day.

Table 9-1. Specific heat for concrete material

Average Specific Heat
Material Type Capacity (kJ/ kg °C)
Cement Paste 1.10
Fine Aggregate 0.84
Coarse Aggregate 0.91
Concrete 1.19

The results indicate that the specific heat capacity testing method may have a potential

inconsistency because the results obtained for the concrete specimen are larger than any of the

constituent materials. However, another explanation for the larger value of the specific heat

capacity of concrete compared to its constituent materials could be attributed to the fact that

concrete has entrapped air and a different capillary system when compared to cement paste.

Therefore, the results obtained in this study are most likely accurate.

ACI 207.2 lists the values of the specific heat capacity of concretes made with various

coarse aggregates. The values of specific heat capacity of concrete made with limestone coarse

aggregate, reported by Table 3.1 of ACI 207.2 range from 0.920 – 1.033 (kJ/ kg °C). The value

of specific heat capacity of concrete measured in this study, (1.19 kJ/ kg °C) is significantly

larger than the values provided ACI 207.2. The most likely reason for the difference in

diffusivity values between the concrete tested in this study and the values published in ACI 207.2

156
is due to the difference in coarse aggregate used in the concrete. Referring to equation 9-1, the

thermal diffusivity is inversely proportional to the specific heat capacity.

Therefore, the values for the thermal diffusivity testing and the specific heat capacity

testing are consistent despite the fact that they were conducted independently. However, further

research should be performed which involves the measurement of specific heat capacity of

different concrete and constituent materials for the making of concrete.

Summary of Findings

The laboratory testing and of the thermal properties of concrete resulted in the following:

1. The coefficient of thermal expansion of concrete is lower at early ages than at later ages.

2. Concrete which contains large percentages of supplementary cementitious material

replacement of Portland cement has lower coefficient of thermal expansion values than
concrete made with Portland cement alone.

3. Concrete made with Florida limerock does not have the thermal properties as concrete
made with limestone not local to Florida.

4. The thermal diffusivity of saturated concrete increases at early ages.

5. The thermal diffusivity of concrete made with Florida limerock is lower than concrete.
made with limestone not local to Florida

6. The specific heat capacity of concrete made with Florida limerock is higher than concrete
made with limestone not local to Florida.

157
 CHAPTER 10
RECOMMENDED TESTING PROGRAM FOR MASS CONCRETE

The primary objective of this research was the development of a laboratory testing

program to predict the behavior of mass concrete. Accordingly, this research was performed to

determine which laboratory tests were most appropriate to be used as a predictor of the thermal

and physical behavior of concrete. Furthermore, conducting this research established some of the

physical properties necessary for the prediction of mass concrete and which, therefore do not

need to be evaluated for a given mixture design.

Recommended Laboratory Testing Method for Measurement of Heat Generation

The measurement of heat generation and resultant temperature rise of concrete is perhaps

the most important parameter for the prediction of the behavior of mass concrete. Temperature

rise, relative strength properties, and resultant maturity/equivalent age functions are all

dependent upon the heat generated by concrete. Three calorimetry methods were investigated for

the measurement of heat generation in concrete materials: isothermal conduction calorimetry,

semi-adiabatic calorimetry, and Sure Cure/adiabatic calorimetry.

Of the three methods investigated, the isothermal calorimetry method was determined to be

the most appropriate method for the quantification of heat generation of cementitious materials at

early ages. There are several reasons as to why the isothermal calorimetry method was favored

over the other calorimetry techniques. First, the isothermal calorimetry method provided the

most accurate and repeatable results for the measurement of the heat generation of cementitious

materials. Second, the results provided by the isothermal calorimetry are in units of power

(mW/g) and energy (J/g). Although this research established some baseline values for the

specific heat capacity of the ingredients used to make concrete, there are potential errors in those

values which could provide erroneous results in the conversion from temperature rise as

158
measured by semi-adiabatic and adiabatic calorimetry. Third, the isothermal conduction

calorimeter is commercially available and standardization of the test method for the

determination of energy rise of cementitious materials is imminent. Finally, there have been

some recent developments in modeling/prediction software programs which utilize the energy

rise data for cementitious materials for input parameters. Therefore, the use of the isothermal

conduction calorimeter is recommended for the measurement of heat/energy rise of concrete for

the purposes of prediction of the behavior of mass concrete.

Recommended Laboratory Testing Method for Measuring Maturity/Equivalent Age

The laboratory testing method for the establishment of maturity and equivalent age

relationships based on the time-temperature history falls under ASTM 1074. The relative

strength relationships developed by the maturity method (ASTM 1074-6.2) also known as the

Nurse-Saul maturity method did not yield accurate results. Therefore, it is not recommended to

use the Nurse-Saul method for the prediction of strength properties of mass concrete.

The standardized equivalent age method developed relative strength relationships per

ASTM 1074-6.3 (also known as the Arrhenius equation) which utilized a hyperbolic

mathematical model for the evolution of compressive strength of mortar cubes. This research

investigated a second equivalent age method (Schindler, 2003) which utilized the compressive

strength of mortar cubes as well, but developed an exponential mathematical model other than

the model than the one prescribed in ASTM 1074.6.3 (hyperbolic method) for the establishment

of Ea. A third method for the establishment of equivalent age (and Ea) was investigated utilizing

isothermal calorimetry of cementitious material in lieu of compressive strength testing of mortar

cubes. As previously stated, the isothermal calorimetry test is required for the determination of

the measurement of heat generation characteristics of the cementitious materials. Accordingly it

is possible to use the data obtained from isothermal calorimetry testing (for heat generation) to

159
determine the Ea of the cementtious material. Therefore, the compressive strength testing per

ASTM 1074 would not be needed for the determination of Ea, if the isothermal calorimetry

testing was used in its place.

Each of the three equivalent age techniques produced accurate results for the prediction of

the relative strength of concrete which utilized Portland cement as the only cementitious

material. However, initial testing indicated that the Ea results obtained by the isothermal testing

method were the most accurate for cementitious materials in which Portland cement was

replaced with a large percentage of supplementary cementitious material (35-50%). However,

the current models established for equivalent age relationships for concrete with large amounts

of supplementary cementitious materials do not adequately predict the behavior of relative

strength of concrete.

Therefore, the equivalent age relationships should be used to predict the strength behavior

of concrete. Following the results obtained in this research, the Ea as calculated via isothermal

calorimetry testing and the standardized test method may be used for the prediction of concrete

with large replacement of SCM. However, the models do not adequately predict the behavior of

relative strength of concrete with large replacements of SCM.

Recommended Laboratory Testing Methods for Strength and Modulus of Elasticity

Compressive strength

The most commonly measured property of hardened concrete is compressive strength. The

FDOT specification requires a standardized minimum compressive strength, at an age of 28 days

of all structural concrete used in the State of Florida. Thus, the compressive strength has become

the fundamental strength test for concrete. Despite the fact that mass concrete will rarely

experience failure in a compressive manner, it is recommended to perform compressive strength

testing of concrete for acceptance and comparative purposes.

160
Compressive Modulus of Elasticity

The modulus of elasticity is the most important strength parameter for the prediction of the

behavior of mass concrete. Near surface tensile strains (as predicted by CTE measurements) due

to the expansion of the hotter inner core of mass concrete can be used to calculate tensile stress if

the modulus of elasticity is known. Therefore, the modulus of elasticity is an important

parameter for the prediction of potential thermal/tensile cracking of mass concrete.

The compressive modulus of elasticity test is the only standardized test for measurement of

the modulus of elasticity for concrete. The findings of this research indicate that the compressive

modulus of elasticity is approximately the same as the tensile (flexural) modulus of elasticity

when tested at loads of 33% of ultimate. Therefore, the modulus of elasticity measured

compressively can be considered the same value for the tensile modulus of elasticity for

prediction and modeling purposes of mass concrete. Therefore, it is not necessary to determine

tensile/flexural modulus of elasticity via laboratory testing.

Tensile Strength

Tensile strength is particularly important for the prediction of mass concrete since the

failure of mass concrete at early ages is typically tensile in nature. Near surface tensile stresses

(as predicted by CTE) and modulus of elasticity measurements of mass concrete (as predicted by

modeling software) can be compared with tensile strength obtained via laboratory testing.

Accordingly, the prediction of cracking can be established with respect to the expansive nature

(due to temperature rise or temperature differentials) within the mass concrete. When the

predicted tensile stress exceeds the ultimate tensile stress of the concrete obtained by laboratory

testing cracking will occur.

161
 Recommended Laboratory Testing Method for Measurement of Coefficient of Thermal
Expansion

The coefficient of thermal expansion of concrete is perhaps the most important parameter

to accurately quantify with respect to mass concrete. Currently, the standardized method for the

measurement of CTE (AASHTO TP-60-2007) has been withdrawn due to the potential concerns

with the calibration factor (of stainless steel) used to calibrate the test (Crawford, 2009).

Therefore, the results obtained under this research were calculated per the calibration testing

performed at the FDOT SMO. Considering the recent developments and potential problems

regarding the CTE test method, it is recommended to perform CTE testing in the laboratory for

the prediction of mass concrete. Furthermore, it should be noted that early-age CTE is a

necessary parameter to properly establish and consider its variability in the prediction of the

behavior of mass concrete.

Recommended Physical Parameter for the Concrete Diffusivity

The thermal diffusivity testing reported in this research as performed by Ochiai (2009)

indicates that the thermal diffusivity values for concrete at early ages range from 0.513ft2 /day to

0.748ft2/day whereas the thermal diffusivity of concrete made with limestone aggregate as

reported by ACI 207.2 is 1.22ft2 /day. The reason for the difference in the diffusivity values

obtained in this research and those obtained by ACI 207.2 is due to the coarse aggregate within

the concrete. Therefore, the values for thermal diffusivity reported in this research should be

used for the prediction of mass concrete which incorporate coarse aggregate from Florida.

However, for concrete created with coarse aggregate from elsewhere, the values per ACI 207.2

should be considered for the prediction of the behavior of mass concrete.

162
Recommended Physical Parameter for the Specific Heat Capacity

The specific heat capacity testing reported in this research as performed by Ochiai (2009)

indicates that the specific heat capacity values for concrete at early ages range from 1.1 to 1.2

J/(g-°C), whereas the specific heat capacity of concrete made with limestone aggregate as

reported by ACI 207.2 is 0.91 to 1.05 J/(g-°C). The reason for the difference in the diffusivity

values obtained in this research and those obtained by ACI 207.2 is due to the coarse aggregate

within the concrete. Similar to the results obtained for thermal diffusivity, the specific heat

capacity values reported in this research should be used for the prediction of mass concrete

which incorporate coarse aggregate from Florida. However, for concrete created with coarse

aggregate from elsewhere, the values per ACI 207.2 should be considered for the prediction of

the behavior of mass concrete.

Summary of Testing Program

The laboratory testing program for the prediction of the behavior of mass concrete should

include the following tests:

1. Isothermal calorimetry for the measurement of heat generation rate

2. Compressive strength per ASTM 1074 or isothermal calorimetry testing for the
determination of Ea

3. Compressive strength of concrete cylinders

4. Splitting tensile strength of concrete cylinders

5. Compressive modulus of elasticity at 30% of ultimate strength (for the determination of

tensile modulus of elasticity)

6. Coefficient of Thermal Expansion

7. Thermal diffusivity and Specific heat capacity

163
 CHAPTER 11
CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE WORK

Conclusions

The following conclusions were drawn from this study as follows:

1. Isothermal conduction calorimetry is a viable testing method for the measurement of heat
of hydration of cementitious materials.

2. The calculation of Ea using isothermal calorimetry testing provides larger values when
compared with the calculation of Ea using the standardized test method per ASTM 1074.

3. Semi-adiabatic calorimetry does not measure as much energy evolved from a cementitious
system when compared with isothermal or solution calorimetry. Isothermal calorimetry
measured the largest amount of heat evolved from a cementitious system and therefore is
the most conservative method currently available for the measurement of heat of hydration
of cementitious systems.

4. The measured heat of hydration of Portland cement cured at higher temperatures is lower
than Portland cement cured at lower temperatures for the same equivalent age.

5. The measured heat of hydration of cementitious systems with large replacements of

Portland cement with blast furnace slag or fly ash cured at higher temperatures is higher
than the same cementitious systems cured at lower temperatures.

6. The Nurse-Saul maturity method (per ASTM 1074) does not accurately characterize
physical and strength parameters bases for concrete with different time-temperature
histories.

7. The equivalent-age method (per ASTM 1074) accurately models the evolution of physical
and strength parameters with different time temperature histories for concrete made with
Portland cement as the only cementitious material.

8. Neither the Nurse-Saul nor the equivalent age method accurately model the evolution of
strength and physical properties for cement concrete of cementitious systems with large
replacements of Portland cement with blast furnace slag or fly ash.

9. The tensile and compressive moduli of elasticity of concrete are approximately equal in
value for stresses below 30% of ultimate strength.

10. The thermal properties of concrete including the coefficient of thermal expansion,
diffusivity, and specific heat capacity which incorporates Florida limerock are different
than the published values of concrete using other limestones.

Recommendations

The following recommendations are based on the findings and conclusions from this study:

164
1. The laboratory testing program developed in this study should be implemented for the use
in finite element modeling of mass concrete structural elements.

2. Isothermal conduction calorimetry should be standardized for the measurement of the heat
of hydration of cementitious materials.

3. The standard practice for estimating concrete strength by the maturity method (ASTM C
1074) should be revised to include isothermal calorimetry testing for the calculation of
apparent activation energy which can then be used for the calculation of equivalent age per
equation 6.3

4. Accurate maturity/equivalent age models should be developed for cementitious systems

which have large replacements of Portland cement with blast furnace slag or fly ash.

5. The standard test method for the measurement of the compressive modulus of elasticity
(ASTM C469) should be revised to include comparative statements between tensile and
compressive modulus of elasticity at stress values 30% of ultimate strength.

6. Research should be performed which involves the measurement of specific heat capacity of
different concrete and constituent materials of concrete.

165
 APPENDIX A
METHOD OF TESTING FOR MEASURING THE HEAT OF HYDRATION OF
HYDRAULIC CEMENT USING ISOTHERMAL CONDUCTIVE CALORIMETRY

This test method was used to determine the rate of heat of hydration from hardened cementitious
materials by isothermal conduction calorimetry. This procedure was written in an effort to
conform to the procedure currently being developed by ASTM committee C01 for measurement
of heat evolution of cementitious materials at early ages using the internal mixing method.

Terminology
• Isothermal conduction calorimeter – A colorimeter that measures heat flow form a sample
maintained at a constant temperature by intimate thermal contact with a constant-
termperature heat sink.
• Thermal power – Heat production rate measured in watts (W) or joules per second (J/s),
and is the property measured by the calorimeter.
• Heat – Heat is the time intergral of thermal power measured in Joules (J).
• Baseline – The signal from the calorimeter when a sample of approximately the same mass
and thermal properties as a cement sample, but which is not undergoing any exothermic or
endothermic reactions.
• Reference cell – A heat-flow cell that is dedicated to outputting power from a sample that
is generating no heat. The purpose of the reference cell is to correct for certain errors
caused by drift and other systematic errors that can occur in heat-flow measuring
equipment.

Summary of Test Method

An isothermal heat conduction calorimeter consists of a constant-temperature heat sink to which
two heat-flow sensor and sample holders are attached with good thermal conductivity. One heat-
flow sensor and sample holder contains the sample of interest. The other heat-flow sensor is a
reference cell containing a blank sample (in this case glass beads) that evolves no heat. The heat
of hydration released by the reacting cementitious sample is passed across the sensor and into the
heat sink. The output from the calorimeter is the difference in heat flow (thermal power), the
sample cell and the reference cell. The heat-flow sensor actually senses a small temperature
gradient that develop from the sample side to the heat-sink side, however the heat is removed
from the hydrating sample fast enough that, for practical purposes, the sample is at a constant
temperature (isothermal).

The output from the heat-flow sensor is an mV signal that is proportional to the thermal power
from the sample. This output must be calibrated to a known thermal power. In this method, this
is accomplished by measurements on a sample that emits a constant and known power level. The
integral of the thermal power over the time of the test is the heat of hydration.

Significance and Use

This method is suitable for determining the total heat of hydration of hydraulic cement at
constant temperature at ages up to 7 days to confirm specification compliance. It gives test
results equivalent to ASTM C 186 up to 7 days of age.

166
Apparatus
• Balance – accurate to 0.001 g.
• Volumetric dispenser – device for measuring volume or mass of water, accurate to 0.1 mL.
This could be a syringe, pipette, weighting, etc.
• Sample holder – holds the cement paste and provides intimate contact with the colorimeter
heat sensing device and prevents evaporation of Mixing water.
• Resistance heater – frabricated from material with similar heat capacity and shape as the
test sample, but containing a resistor connected to a constant-voltage power supply such
that a stable output of 0.01 ± 0.0002 watt can be generated.
• Blank specimen – fabricated from material with similar heat capacity and shape as the test
sample.
• Multimeter – an instrument for measuring DC voltage and resistance to an accuracy of 1%
over the range of measurements required for calibration and execution of the test (Note 2).
This instrument is only required if the user is not following instrument specific calibration
procedures.
• Power supply – A constant voltage DC power supply with a voltage output range of at least
0 to 10 volts and a power rating of at least 0.25 watts.
• Calorimeter – The schematic design of a calorimeter is given in Figure A-1. It consists a
sample holder for the test and a reference sample, each thermally connected to heat flow
sensors, which are thermally connected to a constant-temperature heat sink. The minimum
sensitivity for measuring heat output is 100 μW.

thermostat
reference
sample

heat flow
sensors

heat sink

Figure A-1. A schematic drawing of a heat conduction calorimeter

• The baseline (the power output when no heat is being generated by the sample, U0 in the
calibration sequence) shall exhibit a low random noise level and be stable against drift. The
rate of change of the baseline measured during a time period of three days shall be less than
or equal to 20 μW per gram of sample, per hour and a baseline random noise level of less
than or equal to 10 μW per gram sample. In practive the baseline is measure for three days
and a straight line is fitted to the data using a linear least squares procedure. The long term
drift is then the slope in the line and the baseline noise level is the standard deviation
around this regression line.

167
• Data acquisition equipment – The data acquisition equipment used for this experiment was
capable of performing continuous logging of the calorimeter output measurement at a time
interval of 60 seconds. It is useful, for purposes of reducing amount of data, to have the
flexibility to adjust the reading interval up to 30 minutes when power output from the
sample is low.

Instrument Calibration and Operating Parameters

The objective of electrical calibration is to calculate a calibration constant for each individual
twin calorimetric channel. The calibration constant was entered into the PicoLog software as a
factor to correct the amplifier output to read the experimental results directly in mW. Each
channel has a permanent precision calibration heater on side A, the sample side. Side B, used for
the inert reference, does not need to be calibrated. The heater has a resistance of 100 ± 0.1 Ω and
a very low temperature coefficient. The eight calibration heaters are connected in series together
with a reference calibration resistor, also 100 ± 0.1 Ω. To provide the calibration power, an
internal power supply was turned on through a toggle switch, marked ‘Calibration Power’ on the
front panel of TAM Air. The calibration power applied was in the range of 35 mW, independent
on the measuring range. During the calibration, a digital voltmeter is connected to the two
sockets marked ‘Voltmeter’. This voltage measurement was used as part of the calculation of the
calibration constant.

Calibration was performed with empty calorimetric channels. Once a stable baseline has been
achieved, a known voltage is applied over the calibration heater by switching the toggle switch.
A stable signal, as shown below, indicates that the power input was leaving the measuring area at
the same rate as it was applied. This is called a ‘steady state’. Steady state calibration is simple to
evaluate and does not require any form of integration as shown in Figure A-2.

Figure A-2. Steady state calibration plot

The calibration was performed regularly, prior to performing each isothermal temperature for
example, once calibration was performed at 15 °C and 23 °C etc. Each channel was
independently calibrated.

168
Testing Procedure
• The calorimeter equipment and data acquisition unit was turned on. It was determined that
the calorimeter was at temperature equilibrium by verifying that the baseline (0.0V) was
stable over a period of a few minutes. The temperature of the heat sink during the test was
15.0, 23.0 ± 1.0 °C.

• Cement Specimens
o 4 grams of cementitious material was weighed the mass recorded to the nearest 0.001
grams, and was placed in the calorimeter cell. For each of the Mixes, 2.000 grams of was
used to provide a consistent water-cement ratio of at least 0.50 for each paste. After the
water and cement are weighted, the cell was placed in the calorimeter as shown in Figure
A-3.

o Allow any change in calorimeter output caused by this process to return to the baseline
level. Typically, a 24 hour interval is necessary for a return to the baseline level.

• Mortar Specimens
o 4 grams of cementitious material was weighed the mass recorded to the nearest 0.001
grams, and was placed in the calorimeter cell. For each of the Mixes, 2.000 grams of was
used to provide a consistent water-cement ratio of at least 0.50 for each paste.

o 6 grams of silica sand was weighted to the nearest 0.001g and added to the calorimeter
cell

o After the water and cement are weighted, the cell was placed in the calorimeter same
manner as the procedure used for the “cement specimens” noted above.

• After the baseline level was reached, the data collection was started and the water was
injected into the cementitious materials to form a uniform paste. Cementious paste
specimens were Mixed for 1 minute each. Mortar specimens were Mixed for 2 minutes
each.

• Data was collected on an interval of 1 minute for the duration of the test (72-336 hours).

Calculation or Interpretation of Results

The purpose of the evaluation is to calculate the heat produced during the first 4-14 days of
hydration. The evaluation method consists of the following steps:
Remove the baseline:
(A-1)

Here U raw is the signal from the calorimeter and Ubl is the measured baseline of the calorimeter.

Apply the calibration coefficients (A and B) and divide by the mass of cement (mc) in the sample
to get the specific thermal power P:
(A-2)

169
where P (J/s/g) is the power output per gram of dry cement, A and B are the calibration
coefficients determined during the calibration process, U(t) is the voltage output at each data
collection point, and m c is the mass of dry cement used in the test.

The total heat of hydration of the sample is calculated by integrating the power/g versus time
data over the time interval of the test (ti to te):

(A-3)

Where, Q (J/gcement) is the heat produced from the sample, ti is the time the sample was charged
into the calorimeter, and te is the time of the end of the measurement as calculated from the time
of Mixing cement and water.

Operationally, the integration is executed by averaging the power output from two consecutive
readings and multiplying by the time interval of the reading, giving an output for each time
increment in units of J/g. The heat so calculated in each time increment is then summed over the
duration of the test, as in the following equation.

(A-4)

Where P(ti) is the power output at time ti, and P(ti+1) is the power output at the next time interval
(ti+1). In this method (internally Mixed procedure), ti is taken as zero when water is added to the
cement.

170
Figure A-3. Cutaway of one of the 8 calorimetric channels showing the twin configuration

171
 APPENDIX B
RAW DATA-MORTAR CUBES AND APPARENT ACTIVATION ENERGY
CALCULATIONS

Table A-1. Raw data sheet Mix 1 cubes 100% Portland cement
Age
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test (hours)
1 4260 1065 9:58 AM
2
2 4360 1090 977 9:59 AM 49:10
Day
3 3100 775 10:01 AM
1 12630 3158 5:41 PM
4
2 12120 3030 3108 5:42 PM 129:03
Day
3 12540 3135 5:44 PM
1 15900 3975 11:39 AM
7
2 15360 3840 3856 11:42 AM 171:02
Day
3 15010 3753 11:44 AM
1 21800 5450 11:47 AM
15
2 21800 5450 5442 11:49 AM 363:10
Day
3 21700 5425 11:51 AM
1 28400 7100 1:39 PM
28
2 28700 7175 7025 1:42 PM 821:02
Day
3 27200 6800 1:44 PM
1 27900 6975 10:00 AM
56
2 32300 8075 7742 10:03 AM 1657:24
Day
3 32700 8175 10:07 AM
Temperature = 8°C
Time of Mix = 12/9/2008 8:49

Table A-2. Raw data sheet Mix 1 cubes 100% Portland cement
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 6730 1712 10:10 AM
1
2 6660 1695 1699 10:12 AM 24:57
Day
3 6640 1690 10:15 AM
1 11350 2888 10:14 AM
2
2 11190 2847 2864 10:16 AM 49:01
Day
3 11230 2858 10:18 AM
1 14400 3664 5:15 PM
3
2 13920 3542 3662 5:17 PM 80:02
Day
3 14850 3779 5:19 PM
1 19810 5041 11:10 AM
7
2 19650 5000 5069 11:12 AM 169:57
Day
3 20300 5165 11:15 AM
1 33950 8639 11:25 AM
28
2 30970 7880 8266 11:30 PM 678:15
Day
3 32540 8280 11:35 AM
Temperature = 23°C
Time of Mix = 6/18/2008 9:15

172
Table A-3. Raw data sheet Mix 1 cubes 100% Portland cement
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 6730 1712 10:10 AM
1
2 6660 1695 1699 10:12 AM 24:57
Day
3 6640 1690 10:15 AM
1 11350 2888 10:14 AM
2
2 11190 2847 2864 10:16 AM 49:01
Day
3 11230 2858 10:18 AM
1 14400 3664 5:15 PM
3
2 13920 3542 3662 5:17 PM 80:02
Day
3 14850 3779 5:19 PM
1 19810 5041 11:10 AM
7
2 19650 5000 5069 11:12 AM 169:57
Day
3 20300 5165 11:15 AM
1 33950 8639 11:25 AM
28
2 30970 7880 8266 11:30 PM 678:15
Day
3 32540 8280 11:35 AM
1 28000 7000 3:13 PM
14
2 29800 7450 7300 3:16 PM 4494:01
Day
3 29800 7450 3:19 PM
Temperature = 38°C

Figure B-1. Compressive strength vs. time - hyperbolic model for Mix 1 (ASTM C 1074)

173
Figure B-2. Compressive strength vs. time - exponential model for Mix 1 (Constant β)

Figure B-3. Compressive strength vs. time - exponential model for Mix 1 (constant αu, β)

174
Table A-4. Raw data sheet Mix 2 cubes 50% Portland cement – 50% slag
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 1676 419 10:03 AM
2
2 1694 424 429 10:04 AM 49:15
Day
3 1783 446 10:05 AM
1 5540 1385 5:46 PM
4
2 5460 1365 1338 5:48 PM 129:10
Day
3 5050 1263 5:53 PM
1 6640 1660 11:31 AM
7
Day 2 6800 1700 1710 11:34 AM 170:54
3 7080 1770 11:36 AM
1 10880 2720 11:53 AM
15
2 11570 2893 2760 11:55 AM 363:16
Day
3 10670 2668 11:57 AM
1 17580 4395 1:50 PM
28
2 17610 4403 4300 1:52 PM 821:13
Day
3 16410 4103 1:55 PM
1 22800 5700 9:50 AM
56
Day 2 22600 5650 5592 9:52 AM 1657:13
3 21700 5425 9:55 AM
Temperature = 8°C
Time of Mix = 12/9/2008 8:49

Table A-5. Raw data sheet Mix 2 cubes 50% Portland cement – 50% slag
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 1 1682 428 8:30 AM
Day 2 1466 373 401 8:33 AM 23:28
1 2090 532 1:30 PM
1
2 2100 534 534 1:35 PM 28:32
Day
3 2110 537 1:40 PM
1 4720 1201 9:15 AM
2
Day 2 4650 1183 1167 9:17 AM 48:14
3 4390 1117 9:19 AM
1 6960 1771 8:30 AM
3
2 6750 1718 1751 8:32 AM 71:29
Day
3 6930 1763 8:34 AM
1 15900 4046 8:20 AM
7
2 15270 3885 3997 8:27 AM 167:26
Day
3 15960 4061 8:40 AM
1 28400 7226 11:25 AM
28
Day 2 26600 6768 7031 11:31 AM 674:27
3 27900 7099 11:35 AM
Temperature = 23°C
Time of Mix = 7/22/2008 9:03

175
Table A-6. Raw data sheet Mix 2 cubes 50% Portland cement – 50% slag
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 1508 377 5:38 PM
12
2 1545 386 383 5:40 PM 9:01
Hour
3 1540 385 5:42 PM
1 6830 1708 8:34 AM
24
2 6920 1730 1714 8:35 AM 23:56
Hour
3 6820 1705 8:36 AM
1 8070 2018 6:15 PM
36
Hour 2 8960 2240 2228 6:19 PM 33:39
3 9710 2428 6:20 PM
1 16510 4128 3:41 PM
3
2 16790 4198 4166 3:44 PM 79:04
Day
3 16690 4173 3:44 PM
1 25300 6325 10:49 AM
7
2 24900 6225 6283 10:52 AM 170:12
Day
3 25200 6300 10:54 AM
1 32800 8200 3:24 PM
14
Day 2 32200 8050 8233 3:27 PM 318:48
3 33800 8450 3:30 PM
Temperature = 38°C
Time of Mix = 12/9/2008 8:39

Figure B-4. Compressive strength vs. time - hyperbolic model for Mix 2 (ASTM C 1074)

176
Figure B-5. Compressive strength vs. time - exponential model for Mix 2 (Constant β)

Figure B-6. Compressive strength vs. time - exponential model for Mix 2 (constant αu, β)

177
Table A-7. Raw data sheet Mix 3 cubes 65% Portland cement – 35% fly ash
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 2920 730 10:24 AM
2
2 2320 580 626 10:26 AM 49:47
Day
3 2270 568 10:27 AM
1 4820 1205 4:05 PM
4
2 4350 1088 1152 4:07 PM 103:41
Day
3 4650 1163 4:09 PM
1 7130 1783 10:45 AM
7
2 7920 1980 1853 10:46 AM 170:20
Day
3 7180 1795 10:48 AM
1 11340 2835 5:49 PM
15
2 9680 2420 2557 5:51 PM 369:25
Day
3 9660 2415 5:53 PM
1 13410 3353 2:41 PM
28
2 13190 3298 3200 2:43 PM 822:17
Day
3 11800 2950 2:45 PM
1 18460 4615 10:12 AM
56
2 19060 4765 4717 10:15 AM 1513:48
Day
3 19080 4770 10:17 AM
Temperature = 8°C
Time of Mix = 8:38 AM

Table A-8. Raw data sheet Mix 3 cubes 65% Portland cement – 35% fly ash
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 2720 692 8:29 AM
1 Day 2 3030 771 737 8:30 AM 22:46
3 2940 748 8:32 AM
1 5443 1385 9:09 AM
2 Day 2 5003 1273 1362 9:11 AM 47:26
3 5612 1428 9:12 AM
1 6681 1700 9:20 AM
3 Day 2 7066 1798 1819 10:20 AM 72:36
3 7703 1960 11:20 AM
1 11620 2957 9:13 AM
7 Day 2 10720 2728 2865 9:16 AM 127:31
3 11440 2911 9:18 AM
1 9710 2471 9:30 AM
14
Day 2 9040 2300 2533 9:35 AM 335:50
3 11110 2827 9:37 AM
1 20200 5140 11:04 AM
28
2 27400 6972 6234 11:09 AM 617:25
Day
3 25900 6590 11:14 AM
Temperature = 23°C
Time of Mix = 9:44 AM

178
Table A-9. Raw data sheet Mix 3 cubes 65% portland cement – 35% fly ash
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 3650 913 8:55 PM
12
2 3570 893 894 8:56 PM 12:30
Hour
3 3510 878 8:58 PM
1 5930 1483 8:29 AM
24
2 5570 1393 1448 8:31 AM 24:04
Hour
3 5880 1470 8:32 AM
1 6190 1548 7:31 PM
36
2 7430 1858 1684 7:33 PM 35:07
Hour
3 6590 1648 7:35 PM
1 9810 2453 5:35 PM
3 Day 2 11100 2775 2524 5:37 PM 81:10
3 9380 2345 5:38 PM
1 17130 4283 10:25 AM
7 Day 2 15990 3998 3976 10:27 AM 170:01
3 14590 3648 10:29 AM
1 23200 5800 10:59 AM
14
2 25100 6275 6163 11:02 AM 338:36
Day
3 24200 6050 11:05 AM
Temperature = 38°C
Time of Mix = 8:26 AM

Figure B-7. Compressive strength vs. time - hyperbolic model – Mix 3 (ASTM C 1074)

179
Figure B-8. Compressive strength vs. time - exponential model for Mix 3 (Constant β)

Figure B-9. Compressive strength vs. time - exponential model for Mix 3 (constant αu, β)

180
Table A-10. raw data sheet Mix 4 cubes 50%-30%-20% blend (Cement – slag – fly ash)
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 1473 368 10:28 AM
2
2 1535 384 380 10:29 AM 49:24
Day
3 1555 389 10:30 AM
1 4150 1038 4:12 PM
4
2 3930 983 968 5:12 PM 104:07
Day
3 3530 883 6:12 PM
1 5770 1443 10:40 AM
7
2 5860 1465 1442 10:41 AM 169:36
Day
3 5670 1418 10:43 AM
1 8870 2218 2:40 PM
15
2 8850 2213 2283 2:42 PM 365:37
Day
3 9680 2420 2:44 PM
1 14030 3508 2:47 PM
28
2 14200 3550 3505 2:49 PM 821:44
Day
3 13830 3458 2:51 PM
1 15380 3845 10:21 AM
56
Day 2 15200 3800 3818 10:23 AM 1513:18
3 15240 3810 10:25 AM
Temperature = 8°C
Time of Mix = 9:05:00 AM

Table A-11. Raw data sheet Mix 4 cubes 50%-30%-20% blend (Cement – slag – fly ash)
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 2180 555 9:13 AM
1
2 1950 496 528 9:15 AM 23:59
Day
3 2100 534 9:16 AM
1 4360 1109 9:09 AM
2
2 4560 1160 1137 9:11 AM 47:55
Day
3 4480 1140 9:12 AM
1 6650 1692 9:20 AM
3
2 6940 1766 1740 9:23 AM 72:08
Day
3 6930 1763 9:26 AM
1 13620 3466 9:21 AM
7
2 12110 3081 3228 9:24 AM 168:09
Day
3 12330 3137 9:27 AM
1 17310 4405 9:30 AM
14
2 17420 4433 4416 9:33 AM 336:18
Day
3 17340 4412 9:37 AM
1 31000 7888 11:04 AM
28
Day 2 30200 7684 7651 11:08 AM 673:52
3 29000 7379 11:11 AM
Temperature = 23°C
Time of Mix = 9:15:00 AM

181
Table A-12. Raw data sheet Mix 4 cubes 50%-30%-20% blend (Cement – slag – fly ash)
Age Specimen # Ultimate Load (lb) Strength (psi) Avg. Strength (psi) Time of Test Age (hours)
1 2580 645 9:00 PM
12
2 2600 650 640 9:03 PM 12:09
Hour
3 2500 625 9:05 PM
1 5420 1355 8:52 AM
24
2 6110 1528 1453 8:53 AM 24:00
Hour
3 5910 1478 8:54 AM
1 7420 1855 9:07 PM
36
2 7750 1938 1901 9:08 PM 36:15
Hour
3 7640 1910 9:10 PM
1 12730 3183 5:40 PM
3 Day 2 12050 3013 3169 5:42 PM 80:49
3 13250 3313 5:44 PM
1 21700 5425 10:33 AM
7 Day 2 22800 5700 5583 10:35 AM 169:42
3 22500 5625 10:38 AM
1 29700 7425 11:10 AM
14 Day 2 30700 7675 7292 11:13 AM 338:20
3 27100 6775 11:17 AM
Temperature = 38°C
Time of Mix = 8:53:00 AM

Figure B-10. Compressive strength vs. time - hyperbolic model – Mix 4 (ASTM C 1074)

182
Figure B-11. Compressive strength vs. time - exponential model for Mix 4 (Constant β)

Figure B-12. Compressive strength vs. time - exponential model for Mix 4 (constant αu, β)

183
Figure B-13. Summary of time of set data

184
 APPENDIX C
ISOTHERMAL CALORIMETRY RAW DATA AND ANALYSIS

Calorimetry Data of Cementitious Specimens

The data presented in this appendix are test results from isothermal calorimetry testing.

Each linear plot is an average plot of four individual specimens. The figures in this appendix

reflect various analysis techniques derived from the Power vs. Test duration curves. Maturity

calculations were performed using the Nurse-Saul technique using the datum temperatures

established per Table C-1. The apparent activation energy used to calculate equivalent age for

each respective graph was obtained per the ASTM C 1074 or hyperbolic calculation per the

testing as shown in Table C-1. The figures which display power vs. equivalent age include the

first 15 minutes of data (in logarithmic scale) where the other figures do not. The reason for this

display technique is the data appears as a vertical line at very early ages on a when viewed on a

typical time scale. Typically the data during the first 30 minutes of mixing results in larger

readings of power. Each specimen contained 4 grams of cementitious material and 2 grams of

water prior to mixing via the internal mixing method.

Table C-1. Mixture components, respective apparent activation energy and datum temperatures
Mix Datum
Mix Components Ea
Name Temperature (°C)

Mix 1 100 % Portland Cement 35642 -0.1

Mix 2 50% Portland- 50% Slag 33688 -0.4
Mix 3 65% Portland 35% Fly-Ash 25757 -0.45
Mix 4 50%-30%-20% Blend 30013 -9.63
Portland – Slag – Fly ash

185
Figure C-1. Power vs. time for Mix 1

Figure C-2. Energy vs. time for Mix 1

186
Figure C-3. Power vs. maturity for Mix 1

Figure C-4. Energy vs. maturity for Mix 1

187
Figure C-5. Power vs. equivalent age for Mix 1

Figure C-6. Energy vs. equivalent age for Mix 1

188
Figure C-7. Power vs. time for Mix 2

Figure C-8. Energy vs. time for Mix 2

189
Figure C-9. Power vs. maturity for Mix 2

Figure C-10. Energy vs. maturity for Mix 2

190
Figure C-11. Power vs. equivalent age for Mix 2

Figure C-12. Energy vs. equivalent age for Mix 2

191
Figure C-13. Power vs. time for Mix 3

Figure C-14. Energy vs. time for Mix 3

192
Figure C-15. Power vs. maturity for Mix 3

Figure C-16. Energy vs. maturity for Mix 3

193
Figure C-17. Power vs. equivalent age for Mix 3

Figure C-18. Energy vs. equivalent age for Mix 4

194
Figure C-19. Power vs. time for Mix 4

Figure C-20. Power vs. energy for Mix 4

195
Figure C-21. Power vs. maturity for Mix 3

Figure C-22. Energy vs. maturity for Mix 4

196
Figure C-23. Power vs. equivalent age for Mix 4

Figure C-24. Energy vs. equivalent age for Mix 4

197
 Calorimetry Data of Mortar Specimens

The data presented in this appendix are test results from isothermal calorimetry testing for

the specimens which contained mortar. Maturity calculations were performed using the Nurse-

Saul technique using the datum temperatures established per Table C-1. The apparent activation

energy used to calculate equivalent age for each respective graph was obtained per the ASTM C

1074 or hyperbolic calculation per the testing as shown in Table C-1. Each specimen contained 4

grams of cementitious material, 2 grams of water and 6 grams of Ottawa sand per the standard

specification ASTM C 778 prior to mixing via the internal mixing method.

Figure C-25. Power vs. time for Mortar Mix 1

198
Figure C-26. Energy vs. time for Mortar Mix 1

Figure C-27. Power vs. maturity for Mortar Mix 1

199
Figure C-28. Power vs. maturity for Mortar Mix 1

Figure C-29. Power vs. equivalent age for Mortar Mix 1

200
Figure C-30. Energy vs. equivalent age for Mortar Mix 1

Figure C-31. Power vs. time for Mortar Mix 3

201
Figure C-32. Energy vs. time for Mortar Mix 3

Figure C-33. Power vs. maturity for Mortar Mix 3

202
Figure C-34. Energy vs. maturity for Mortar Mix 3

Figure C-35. Power vs. equivalent age for Mortar Mix 3

203
Figure C-36. Energy vs. equivalent age for Mortar Mix 3

Figure C-37. Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 1

204
Figure C-38. Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 2

Figure C-39. Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 3

205
Figure C-40. Isothermal calorimetry data and plots used for the calculation of activation energy
for Mix 4

206
 APPENDIX D
SEMI ADIABATIC TEMPERATURE DATA

Table D-1. Mixture designs for concrete specimens

Mix 3 Mix 4
Mix 1 Mix 2
65% Portland - 50-30-20
100% Portland Cement 50% Portland -50%
Material 35% fly ash blend
(lb/yd3) Slag (lb/yd3)
(lb/yd3) (lb/yd3)
Cement 681 341 443 341
Fly ash 0 0 238 136
GGBF Slag 0 341 0 204
Water 341 341 341 341
Fine Agg. 1095 1088 1036 1050
Coarse Agg. 1650 1668 1660 1650

Figure D-1. Typical water calibration

207
Figure D-2. Semi-adiabatic temperature measurements for mix 1 (laboratory mix)

Figure D-3. Semi-adiabatic temperature measurements for concrete mix 1 (lab and delivered)
mixes

208
Figure D-4. Semi-adiabatic temperature measurements for concrete mix 2 (lab and delivered)
mixes

Figure D-5. Semi-adiabatic temperature measurements for mix 3 (delivered)

209
Figure D-6. Semi-adiabatic temperature measurements for mix 4 (delivered)

Figure D-7. Semi-adiabatic temperature measurements for each mix

210
 APPENDIX E
COMBINED CALORIMETRY DATA AND ANALYSIS

The data presented in this appendix are test results from isothermal, semi-adiabatic and

sure cure calorimetry testing for the specimens composed of cement, mortar and fly ash

respectively. Maturity calculations were performed using the Nurse-Saul technique using the

datum temperatures established per Table C-1. The apparent activation energy used to calculate

equivalent age for each respective graph was obtained per the ASTM C 1074 or hyperbolic

calculation per the testing as shown in Table C-1.Each isothermal calorimetry specimen

contained 4 grams of cementitious material, 2 grams of water and 6 grams of Ottawa sand per the

standard specification ASTM C 778 prior to mixing via the internal mixing method. The mortar

specimens tested via the semi-adiabatic calorimeter were composed of cementitious material,

water and Ottawa sand as per Table E-1.

Table E-1. Mixture designs for mortar specimens used in the semi-adiabatic calorimeter
Mix 3
Mix 1
65% Portland -
100% Portland Cement
Material 35% fly ash
(lb/yd3)
(lb/yd3)
Cement 1231 800
Fly ash 0 431
GGBF Slag 0 0
Water 615 615
Fine Agg. 1850 1850
Coarse Agg. 0 0

211
Figure E-1. Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 1

Figure E-2. Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 2

212
Figure E-3. Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 3

Figure E-4. Comparison of the time-temperature histories between the Sure Cure system and the
IQ drum for Mix 4

213
Figure E-5. Time-temperature histories obtained by the Sure Cure for each mix

Figure E-6. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 1.

214
Figure E-7. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 2.

Figure E-8. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 3.

215
Figure E-9. Comparison of equivalent age – energy histories between semi-adiabatic calorimetry
system and isothermal calorimetry for Mix 4.

Figure E-10. Comparison of equivalent age – energy histories between semi-adiabatic

calorimetry system and the IQ drum for mortar Mix 1.

216
Figure E-11. Comparison of equivalent age – energy histories between semi-adiabatic
calorimetry system and the IQ drum for mortar Mix 3.

Figure E-12. Comparison of semi-adiabatic test and three different Sure Cure system offset
temperatures for a trial mix.

217
Figure E-13. Comparison of semi-adiabatic test and four different Sure Cure system offset
temperatures for a trial mix.

218
 APPENDIX F
PHYSICAL DATA

The data presented in this appendix are physical coefficient of thermal expansion, compressive,

tensile and flexural strength testing as well as modulus of elasticity testing. The equivalent age for each

specimen was calculated regardless of the curing history of each cylindrical specimen. Two cylindrical

specimens were taken from each mix and monitored for temperature. Therefore, the laboratory cured

specimens have an equivalent age slightly larger than the actual age. The term “SC” denotes the

cylindrical specimen was match cured the Sure Cure system as explained in Chapter 8. Specimens subject

to the Sure Cure have substantially larger equivalent ages with respect to laboratory cured specimens. The

cylindrical specimens used in this research were 4” x 8” specimens, and were tested in compression,

splitting tension, modulus of elasticity, and for coefficient of thermal expansion in tested in accordance

with ASTM C39, ASTM C496, ASTM C469, and AASHTO TP-60 respectively.

Table F-1. Raw data compressive strength of cylinders- Mix 1 - 100% Portland cement
Age Specimen # Ultimate Time Equivalent Maturity Avg. Strength
Strength (psi) (hours) Age (hours) (°C-hr.) (psi)

1 Day 1 1480 25 28 578 1593

2 1630
1 2270
1 Day SC 25 57 623 2335
2 2400
1 2280
2 Day 2 2100 48 50 1109 2157
3 2090
1 3000
2 Day SC 48 116 1177 3035
2 3070
1 2510
3 Day 2 2630 72 74 1663 2567
3 2560
1 3550
7 Day 2 3460 168 170 3881 3527
3 3570
1 4440
7 Day SC 168 319 3949 4460
2 4480
1 3830
14 Day 2 4200 336 338 7762 3983
3 3920
1 4680
28 Day 2 4690 672 674 15523 4710
3 4760

219
Figure F-1. Compressive strength vs. time for Mix 1 - 100% Portland cement

Figure F-2. Compressive strength vs. maturity for Mix 1 - 100% Portland cement

220
Figure F-3. Compressive strength vs. equivalent age for Mix 1 - 100% Portland cement

Table F-2. Raw data compressive strength of cylinders- Mix 2 - 50% Portland cement – 50%
slag
Age Specimen # Ultimate Time Equivalent Maturity Avg. Strength
Strength (psi) (hours) Age (hours) (°C-hr.) (psi)
1 300
1 Day 2 280 24 25 562 283
3 270
1 1390
1 Day SC 24 45 588 1380
2 1370
1 870
2 Day 2 840 48 49 1123 860
3 870
1 3160
2 Day SC 48 103 1150 3175
2 3190
1 1380
3 Day 2 1240 72 73 1685 1363
3 1470
1 2450
7 Day 2 2560 168 169 3931 2543
3 2620
1 4710
7 Day SC 168 303 3958 4730
2 4750
1 3310
14 Day 2 3410 336 337 7862 3420
3 3540
1 4820
28 Day 2 4450 672 673 15725 4513
3 4270

221
Figure F-4. Compressive strength vs. time for Mix 2 - 50% Portland cement – 50% slag

Figure F-5. Compressive strength vs. maturity for Mix 2 - 50% Portland cement – 50% slag

222
Figure F-6. Compressive strength vs. equivalent age for Mix 2 – 50% Portland - 50% slag

Table F-3. Raw data compressive strength of cylinders- Mix 2 - 65% Portland cement – 35% fly
ash
Age Specimen # Ultimate Time Equivalent Maturity Avg. Strength
Strength (psi) (hours) Age (hours) (°C-hr.) (psi)
1 740
1 Day 2 730 25 27 586 720
3 690
1 1220
1 Day SC 25 45 612 1225
2 1230
1 1080
2 Day 2 990 48 51 1126 1057
3 1100
1 1750
2 Day SC 48 89 1175 1765
2 1780
1 1330
3 Day 2 1440 72 75 1688 1390
3 1400
1 1820
7 Day 2 1770 168 171 3940 1807
3 1830
1 2770
7 Day SC 168 270 3989 2800
2 2830
1 2310
14 Day 2 2530 336 339 7879 2297
3 2050
1 4680
28 Day 2 4690 672 675 15758 4710
3 4760

223
Figure F-7. Compressive strength vs. time for Mix 3 - 65% Portland cement – 35% fly ash

Figure F-8. Compressive strength vs. maturity for Mix 3 - 65% Portland cement – 35% fly ash

224
Figure F-9. Compressive strength vs. equivalent age for Mix 3 - 65% Portland cement – 35% fly
ash

Table F-4. Raw data compressive strength of cylinders- Mix 2 - 50% Portland cement – 30%
slag – 20% fly ash
Ultimate Avg.
Time Equivalent Maturity
Age Specimen # Strength Strength
(hours) Age (hours) (°C-hr.)
(psi) (psi)
1 260
1 Day 2 340 25 25 816 297
3 290
1 900
1 Day SC 25 35 846 810
2 720
1 860
2 Day 2 870 48 49 1566 867
3 870
1 1920
2 Day SC 48 73 1629 1780
2 1640
1 1280
3 Day 2 1170 72 73 2349 1213
3 1190
1 2360
7 Day 2 2220 168 169 5482 2257
3 2190
1 3700
7 Day SC 168 233 5545 3765
2 3830
1 3430
14 Day 2 2860 336 337 10964 3170
3 3220
1 3940
28 Day 2 4130 672 673 21927 4077
3 4160

225
Figure F-10. Compressive strength vs. time for Mix 4 – 50% Portland - 30% slag -20% fly ash

Figure F-11. Compressive strength vs. maturity for Mix 4 – 50% Portland - 30% slag -20% fly
ash

226
Figure F-12. Compressive strength vs. equivalent age for Mix 4 – 50% Portland - 30% slag -20%
fly ash

Figure F-13. Compressive strength vs. age summary for each mix

227
Figure F-14. Compressive strength vs. equivalent age summary for each mix

Table F-5. Raw data splitting tensile strength of cylinders- Mix 1 - 100% Portland cement
Age Specimen # Ultimate Time Equivalent Maturity Avg. Strength
Strength (psi) (hours) Age (hours) (°C-hr.) (psi)
1 137
1 Day 2 197 25 28 578 181
3 207
1 224
1 Day SC 25 57 623 222
2 221
1 252
2 Day 2 233 48 50 1109 241
3 239
1 359
2 Day SC 48 116 1177 340
2 320
1 222
3 Day 2 351 72 74 1663 280
3 268
1 321
7 Day 2 307 168 170 3881 320
3 332
1 395
7 Day SC 168 319 3949 410
2 425
1 493
14 Day 2 393 336 338 7762 431
3 407
1 466
28 Day 2 520 672 674 15523 479
3 451

228
Figure F-15. Tensile strength vs. time for Mix 1 - 100% Portland cement

Figure F-16. Tensile strength vs. maturity for Mix 1 - 100% Portland cement

229
Figure F-17. Tensile strength vs. equivalent age for Mix 1 - 100% Portland cement

Table F-6. Raw data splitting tensile strength of cylinders- Mix 2 - 50% Portland cement – 50%
slag
Age Specimen # Ultimate Time Equivalent Maturity Avg. Strength
Strength (psi) (hours) Age (hours) (°C-hr.) (psi)
1 34.7
1 Day 2 39.3 25 25 562 37
3 36.5
1 174
1 Day SC 25 46 588 163
2 152
1 107
2 Day 2 137 48 49 1123 117
3 108
1 367
2 Day SC 48 107 1150 365
2 364
1 178
3 Day 2 173 72 73 1685 179
3 188
1 319
7 Day 2 201 168 169 3931 335
3 257
1 489
7 Day SC 168 311 3958 449
2 410
1 381
14 Day 2 389 336 337 7862 356
3 299
1 399
28 Day 2 453 672 673 15725 434
3 450

230
Figure F-18. Tensile strength vs. time for Mix 2 - 50% Portland cement – 50% slag

Figure F-19. Tensile strength vs. maturity for Mix 2 - 50% Portland cement – 50% slag

231
Figure F-20. Tensile strength vs. equivalent age for Mix 2 - 50% Portland cement – 50% slag

Table F-7. Raw data splitting tensile strength of cylinders- Mix 2 - 65% Portland cement – 35%
fly ash
Age Specimen # Ultimate Time Equivalent Maturity Avg. Strength
Strength (psi) (hours) Age (hours) (°C-hr.) (psi)
1 99
1 Day 2 91 25 26 563 97
3 102
1 144
1 Day SC 25 38 612 147
2 150
1 131
2 Day 2 139 48 50 1126 135
3 134
1 194
2 Day SC 48 76 1175 190
2 185
1 183
3 Day 2 184 72 73 1688 185
3 186
1 259
7 Day 2 211 168 169 3940 236
3 238
1 338
7 Day SC 168 238 3989 310
2 282
1 288
14 Day 2 267 336 337 7879 277
3 276
1 466
28 Day 2 520 672 673 15758 479
3 451

232
Figure F-21. Tensile strength vs. time for Mix 3 - 65% Portland cement 35% fly ash

Figure F-22. Tensile strength vs. maturity for Mix 3 - 65% Portland cement 35% fly ash

233
Figure F-23. Tensile strength vs. equivalent age for Mix 3 - 65% Portland cement 35% fly ash

Table F-8. Raw data splitting tensile strength of cylinders- Mix 4 - 50% Portland - 30% slag -
20% fly ash
Age Specimen # Ultimate Time Equivalent Maturity Avg. Strength
Strength (psi) (hours) Age (hours) (°C-hr.) (psi)
1 61
1 Day 2 49 25 25 783 57
3 61
1 127
1 Day SC 25 34 846 139
2 151
1 117
2 Day 2 94 48 49 1566 111
3 121
1 194
2 Day SC 48 73 1629 187
2 181
1 150
3 Day 2 153 72 73 2349 147
3 138
1 280
7 Day 2 247 168 169 5482 264
3 265
1 431
7 Day SC 168 231 5545 350
2 270
1 275
14 Day 2 294 336 337 10964 319
3 387
1 327
28 Day 2 477 672 673 21927 414
3 438

234
Figure F-24. Tensile strength vs. time for Mix 4 – 50% Portland - 30% slag - 20% fly ash

Figure F-25. Tensile strength vs. maturity for Mix 4 – 50% Portland - 30% slag - 20% fly ash

235
Figure F-26 Splitting tensile strength vs. equivalent age for Mix 4 – 50% Portland - 30% slag -
20% fly ash

Figure F-27. Compressive strength vs. age summary for each mix

236
Figure F-28. Tensile strength vs. equivalent age summary for each mix

Table F-9. Raw data compressive modulus of elasticity of cylinders- Mix 1 - 100% Portland
cement
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 1.94E+06
1 Day 2 1.95E+06 25 25 783 1.95E+06
3 1.96E+06
1 Day SC 1 2.50E+06 25 34 846 2.50E+06
1 2.49E+06
2 Day 2 2.43E+06 48 49 1566 2.45E+06
3 2.41E+06
2 Day SC 1 2.97E+06 48 73 1629 2.97E+06
1 2.59E+06
3 Day 2 2.55E+06 72 73 2349 2.62E+06
3 2.73E+06
1 2.88E+06
7 Day 2 2.95E+06 168 169 5482 2.93E+06
3 2.97E+06
7 Day SC 1 3.22E+06 168 231 5545 3.22E+06
1 3.21E+06
14 Day 2 3.27E+06 336 337 10964 3.23E+06
3 3.21E+06
1 3.50E+06
28 Day 1 3.71E+06 672 673 21927 3.66E+06
1 3.76E+06

237
Figure F-29. Compressive modulus of elasticity vs. time for Mix 1- 100% Portland cement

Figure F-30. Compressive modulus of elasticity vs. maturity for Mix 1- 100% Portland cement

238
Figure F-31. Compressive modulus of elasticity vs. equivalent age for Mix 1- 100% Portland
cement

Table F-10. Raw data modulus of elasticity of cylinders- Mix 2 - 50% Portland cement – 50%
slag
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 1.43E+06
1 Day 2 1.25E+06 25 25 562 1.25.E+06
3 1.07E+06
1 Day SC 1 3.00E+06 25 46 588 3.00E+06
1 1.90E+06
2 Day 2 2.15E+06 48 49 1123 1.91.E+06
3 1.67E+06
2 Day SC 1 2.90E+06 48 107 1150 2.90E+06
1 2.29E+06
3 Day 2 2.09E+06 72 73 1685 2.16.E+06
3 2.11E+06
1 2.86E+06
7 Day 2 2.73E+06 168 169 3931 2.82.E+06
3 2.86E+06
7 Day SC 1 3.75E+06 168 311 3958 3.75E+06
1 3.08E+06
14 Day 2 3.05E+06 336 337 7862 3.12.E+06
3 3.21E+06
1 3.61E+06
28 Day 2 3.39E+06 672 673 15725 3.61.E+06
3 3.84E+06

239
Figure F-32. Compressive modulus of elasticity vs. age for Mix 2 - 50% Portland cement 50%
slag

Figure F-33. Compressive modulus of maturity vs. age for Mix 2 - 50% Portland cement 50%
slag

240
Figure F-34. Compressive modulus of elasticity vs. equivalent age for Mix 2 - 50% Portland
cement - 50% slag

Table F-11. Raw data modulus of elasticity of cylinders- Mix 2 - 65% Portland cement – 35% fly
ash
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 1.25E+06
1 Day 2 1.49E+06 25 26 563 1.42.E+06
3 1.51E+06
1 Day SC 1 1.39E+06 25 38 612 1.39.E+06
1 1.99E+06
2 Day 2 2.02E+06 48 50 1126 2.03.E+06
3 2.09E+06
2 Day SC 1 2.26E+06 48 76 1175 2.26.E+06
1 2.00E+06
3 Day 2 1.98E+06 72 73 1688 2.10.E+06
3 2.32E+06
1 2.41E+06
7 Day 2 2.54E+06 168 169 3940 2.40.E+06
3 2.26E+06
7 Day SC 1 2.87E+06 168 238 3989 2.87.E+06
1 2.76E+06
14 Day 2 2.73E+06 336 337 7879 2.75.E+06
3 2.77E+06
1 3.50E+06
28 Day 2 3.71E+06 672 673 15758 3.66.E+06
3 3.76E+06

241
Figure F-35. Compressive modulus of elasticity vs. age for Mix 3 - 65% Portland cement 35%
fly ash

Figure F-36. Compressive modulus of maturity vs. age for Mix 3 - 65% Portland cement 35% fly
ash

242
Figure F-37. Compressive modulus of elasticity vs. equivalent age equivalent age for Mix 3 -
65% Portland cement 35% fly ash

Table F-12. Raw data modulus of elasticity of cylinders- Mix 4 - 50% Portland cement - 30%
slag -20% fly ash
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 1.11E+06
1 Day 2 1.21E+06 25 25 783 1.12E+06
3 1.04E+06
1 Day SC 1 1.93E+06 25 34 846 1.93E+06
1 1.71E+06
2 Day 2 1.47E+06 48 49 1566 1.59E+06
3 1.59E+06
2 Day SC 1 2.22E+06 48 73 1629 2.22E+06
1 2.45E+06
3 Day 2 2.55E+06 72 73 2349 2.58E+06
3 2.73E+06
1 2.47E+06
7 Day 2 2.44E+06 168 169 5482 2.45E+06
3 2.45E+06
7 Day SC 1 3.28E+06 168 231 5545 3.28E+06
1 2.82E+06
14 Day 2 2.86E+06 336 337 10964 2.91E+06
3 3.04E+06
1 3.28E+06
28 Day 2 3.42E+06 672 673 21927 3.39E+06
3 3.47E+06

243
Figure F-38. Compressive modulus of elasticity vs. age for Mix 4 – 50% Portland cement - 30%
slag - 20% fly ash

Figure F-39. Compressive modulus of elasticity vs. maturity for Mix 4 – 50% Portland cement -
30% slag - 20% fly ash

244
Figure F-40. Compressive modulus of elasticity vs. equivalent age for Mix 4 – 50% Portland
cement - 30% slag -20% fly ash

Figure F-41. Compressive modulus of elasticity vs. age for each mix

245
Figure F-42. Compressive modulus of elasticity vs. age for each mix

Table F-13. Raw data tensile modulus of elasticity of cylinders- Mix 1 - 100% Portland cement
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 2.34E+06
1 Day 2 2.34E+06 25 25 783 2.33E+06
3 2.32E+06
1 2.61E+06
2 Day 2 2.46E+06 48 49 1566 2.46E+06
3 2.31E+06
1 2.64E+06
3 Day 2 2.47E+06 72 73 2349 2.54E+06
3 2.53E+06
1 2.76E+06
7 Day 2 2.81E+06 168 169 5482 2.79E+06
3 2.80E+06
1 2.83E+06
14 Day 2 3.19E+06 336 337 10964 2.99E+06
3 2.95E+06

246
Figure F-43. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 1 - 100% Portland cement

Table F-14. Raw data tensile modulus of elasticity of cylinders- Mix 2 - 50% Portland cement –
50% slag
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 1.25E+06
1 Day 2 1.21E+06 25 25 562 1.22E+06
3 1.20E+06
1 1.84E+06
2 Day 2 2.02E+06 48 49 1123 1.93E+06
3 No Data
1 2.10E+06
3 Day 2 2.08E+06 72 73 1685 2.15E+06
3 2.27E+06
1 2.58E+06
7 Day 2 2.50E+06 168 169 3931 2.56E+06
3 2.61E+06
1 2.81E+06
14 Day 2 2.99E+06 336 337 7862 2.92E+06
3 2.95E+06
1 3.30E+06
28 Day 2 3.35E+06 672 673 15725 3.33E+06
3 No Data

247
Figure F-44. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 2 - 50% Portland cement 50% slag

Table F-15. Raw data tensile modulus of elasticity of cylinders- Mix 2 - 65% Portland cement –
35% fly ash
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 1.67E+06
1 Day 2 1.67E+06 25 26 563 1.67E+06
3 1.67E+06
1 1.94E+06
2 Day 2 1.95E+06 48 50 1126 1.92E+06
3 1.88E+06
1 2.27E+06
3 Day 2 2.28E+06 72 73 1688 2.25E+06
3 2.20E+06
1 2.49E+06
7 Day 2 2.55E+06 168 169 3940 2.46E+06
3 2.35E+06
1 2.79E+06
14 Day 2 2.83E+06 336 337 7879 2.78E+06
3 2.72E+06
1 3.06E+06
28 Day 2 3.12E+06 672 673 15758 3.04E+06
3 2.95E+06

248
Figure F-45. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 3 - 65% Portland cement 35% fly ash

Table F-16. Raw data tensile modulus of elasticity of cylinders- Mix 4 - 50% Portland - 30% slag
-20% fly ash
Age Specimen # Modulus of Time Equivalent Maturity Avg. Modulus of
Elasticity (psi) (hours) Age (hours) (°C-hr.) Elasticity (psi)
1 1.18E+06
1 Day 2 1.28E+06 25 25 783 1.24E+06
3 1.25E+06
1 1.89E+06
2 Day 2 1.80E+06 48 49 1566 1.86E+06
3 1.88E+06
1 2.22E+06
3 Day 2 2.11E+06 72 73 2349 2.15E+06
3 2.12E+06
1 2.72E+06
7 Day 2 2.49E+06 168 169 5482 2.61E+06
3 2.61E+06
1 2.87E+06
14 Day 2 2.91E+06 336 337 10964 2.95E+06
3 3.07E+06
1 3.18E+06
28 Day 2 3.02E+06 672 673 21927 3.11E+06
3 3.15E+06

249
Figure F-46. Tensile modulus of elasticity and compressive modulus of elasticity vs. equivalent
age for Mix 4 – 50% Portland - 30% slag -20% fly ash

Figure F-47. Tensile modulus of elasticity vs. time for each mix

250
Table F-17. Raw data coefficient of thermal expansion testing
Mix 1 Mix 2 Mix 3 Mix 4
Age CTE Age CTE Age CTE Age CTE
(days) (in/in/ºC) (days) (in/in/ºC) (days) (in/in/ºC) (days) (in/in/ºC)
1 9.16E-06 1 1.11E-05 1 1.04E-05 1 9.39E-06
2 9.81E-06 2 1.11E-05 2 1.08E-05 2 9.92E-06
3 No data 3 No data 3 1.09E-05 3 1.00E-05
7 9.95E-06 7 No data 7 1.10E-05 7 1.01E-05
14 9.95E-06 14 1.20E-05 14 1.12E-05 14 No data
28 9.95E-06 28 1.17E-05 28 1.16E-05 28 No data

Figure F-48. Coefficient of thermal expansion vs. time for each mix

251
 APPENDIX G
CEMENTITIOUS MATERIAL DATA AND MILL CERTIFICATIONS

Figure G-1. Solution calorimetry data for Mix 1 – 100% Portland cement

Figure G-2. Solution calorimetry data for Mix 2 – 50% Portland cement – 50% slag

252
Figure G-3. Solution calorimetry data for Mix 3 – 65% Portland cement – 35% fly ash

Figure G-4. Solution calorimetry data for Mix 3 – 50% Portland cement – 30% slag – 20% fly
ash

253
Table G-1. X-ray fluorescence data for Portland cement used in each mix
Compound Mix 1 Mix 2 Mix 3 Mix 4
SiO2 20.53 20.61 20.26 20.10
Al2O3 4.85 4.94 5.02 4.96
Fe2O3 4.33 4.08 4.18 4.05
CaO 63.52 63.66 63.78 63.98
MgO 0.67 0.71 0.70 0.73
SO3 2.97 3.04 3.09 2.96
Na2O 0.146 0.155 0.149 0.156
K2 O 0.39 0.39 0.41 0.45
TiO2 0.25 0.25 0.25 0.25
P2O5 0.423 0.418 0.401 0.399
Mn2O3 0.020 0.019 0.017 0.019
C3A 5.509 6.180 6.245 6.303
C3S 55.341 54.828 57.16 60.093
C4AF2 13.188 12.423 12.708 12.316
C2S 17.415 18.038 15.278 12.626
Eq. Alkalies 0.402 0.412 0.417 0.453

Table G-2. X-ray diffraction data for Portland cement used in each mix
Phase Mix 1 Mix 2 Mix 3 Mix 4
Alite 48.81 51.76 54.20 54.91
Belite 28.94 26.05 23.69 21.92
Ferrite 13.70 12.35 13.15 13.07
Free Lime 0.40 0.17 0.38 0.30
Alum_cub 5.38 6.03 5.76 5.91
Alum_ortho 0.53 0.77 0.50 0.88
Periclase 0.17 0.25 0.00 0.20
Arcanite 0.00 0.58 0.60 0.54
Portlandite 0.83 0.49 0.36 0.78
Calcite 0.29 0.45 0.39 0.60
Quartz 0.00 0.00 0.00 0.00
Gypsum 0.00 0.00 0.00 0.00
Hemihydrate 0.95 0.85 0.85 0.78
Anhydrite 0.00 0.25 0.13 0.10

254
Figure G-5. Laboratory testing data of Portland cement used for Mix 1

255
Figure G-6. Laboratory testing data of Portland cement used for Mix 1

256
Figure G-7. Laboratory testing data of Portland cement used for Mix 2

257
Figure G-8. Laboratory testing data of Portland cement used for Mix 2

258
Figure G-9. Laboratory testing data of granulated blast furnace slag used for Mix 2

259
Figure G-10. Laboratory testing data of granulated blast furnace slag used for Mix 2

260
Figure G-11. Laboratory testing data of Portland cement used for Mix 3

261
Figure G-12. Laboratory testing data of fly ash used for Mix 3

262
Figure G-13. Laboratory testing data of fly ash used for Mix 3

263
Figure G-14. Mill certification data for Portland cement used in each mix

264
Figure G-15. Mill certification data for granulated blast furnace slag cement used in each mix

265
Figure G-16. Mill certification data for fly ash cement used in each mix

266
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 BIOGRAPHICAL SKETCH

Christopher C. Ferraro was born March 1, 1974, in Huntington, New York, to Ronald and

Victoria Ferraro. He graduated from Walt Whitman High School, in Suffolk County, N.Y.in

June of 1992. He received his Associate of Arts degree in December of 1994 from Palm Beach

Community College, and transferred to the University of Florida to pursue a Bachelor of Science

in Civil Engineering in the summer of 1995. While attending the University of Florida full time,

Christopher worked part time for the Department of Civil Engineering, for two years as a

teaching assistant and research assistant for Dr. Fazil T. Najafi. He received his Bachelor of

Science in Civil Engineering in May of 1998, graduating with honors.

Upon graduation, he relocated to Long Island, New York, and worked full time in

Manhattan, New York, as an Engineer Intern for Law Engineering Inc. After a year with Law, he

transferred to STV Incorporated where he worked on several inspection projects under the

supervision of Ms. Marjorie M. Lynch, P.E. who aided him in gaining expertise and knowledge

which inspired him to resume his education.

Christopher continued with his education, entering graduate school to pursue a Master of

Engineering in the Materials Group of the Civil and Coastal Engineering Department in August

2000 under the advisement of Dr. Andrew Boyd. After graduating from the University of Florida

with a Master of Engineering in 2003, Christopher continued his education and began work on a

PhD with the University of Florida, while simultaneously working full-time at the Florida

Department of Transportation State Materials Office (FDOT SMO), under the advisement of Dr.

Mang Tia. Upon the completion of this PhD Christopher intends to work as a post-doctorate

faculty member in the Department of Civil and Coastal Engineering at the University of Florida.

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