properties of cement-based materials in the presence of nano and microparticle additives

232 Pages·2013·4.17 MB·English

PROPERTIES OF CEMENT-BASED MATERIALS IN THE
PRESENCE OF NANO AND MICROPARTICLE ADDITIVES

A Dissertation
Presented to
The Academic Faculty

by

Amal Raj Puthur Jayapalan

In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy in the
School of Civil & Environmental Engineering

Georgia Institute of Technology
August 2013

COPYRIGHT 2013 BY AMAL RAJ PUTHUR JAYAPALAN
PROPERTIES OF CEMENT-BASED MATERIALS IN THE
PRESENCE OF NANO AND MICROPARTICLE ADDITIVES

Approved by:

Dr. Kimberly Kurtis, Advisor Dr. Michael Bergin
School of Civil and Environmental School of Civil and Environmental
Engineering Engineering, School of Earth and
Georgia Institute of Technology Atmospheric Sciences
Georgia Institute of Technology

Dr. Lawrence Kahn Dr. John Crittenden
School of Civil and Environmental School of Civil and Environmental
Engineering Engineering
Georgia Institute of Technology Georgia Institute of Technology

Dr. Arun Gokhale
School of Materials Science and
Engineering
Georgia Institute of Technology

Date Approved: June 24, 2013
ACKNOWLEDGEMENTS

I would like to express my deepest gratitude to my advisor, Dr. Kimberly Kurtis
for her continuous support and guidance throughout my M.S. and Ph.D at Georgia Tech. I
truly appreciate her patience and encouragement and am fortunate to have worked with
such a great advisor and mentor. I would also like to thank Dr. Lawrence Kahn for his
guidance and insightful comments throughout my graduate studies at Georgia Tech. I
want to thank Dr. Michael Bergin, Dr. John Crittenden and Dr. Arun Gokhale for being
part of my thesis committee and for their time and support for my research.
I would like to thank National Science Foundation for funding my research
project under Grant No. CMMI-0825373. I am grateful for the financial support provided
by the American Concrete Institute (ACI) Georgia Chapter and Georgia Institute of
Technology.
I want to thank Bo Yeon Lee for being an integral part of the research project. I
am grateful for the assistance provided by Eva Land, David Tanner and Dr. Greg Huey
with the photocatalytic experiments, Arka Pandit and Liz Minne for their help with the
life cycle analysis and Nortey Yeboah for assistance with the surface area analysis. I
would also like to thank Andy Udell for his help with fabrication of experimental setups.
Undergraduate and graduate research assistants Sarah Fredrich, Melinda Jue, Justin Bel,
Daniel Glass, Theau Conte, Chen Chris Wenhao, Matthew Treager are thanked for their
valuable contributions to this research.
All my current and past research group members have made graduate school life
fun and enjoyable at Georgia Tech and I greatly appreciate their friendship and thank
iii
them for all the insightful as well as light-hearted discussions. My sincere thanks goes to
Dr. Robert Moser, Dr. Victor Garas, Dr. Jun Chen, Lisa Lindquist Hoeke, Jonah Kurth,
Dr. Andrea Mezencevova, Chris Shearer, Dr. Bo Yeon Lee, Sarah Fredrich, Passarin
Jongvisuttisun, Nathan Mayercsik, Bradley Dolphyn, Elizabeth Nadelman, Marc Knapp
and Alvaro Paul. I also want to thank Dr. Andrew Bechtel, Dr. Benjamin Kosbab, Dr.
Jonathan Hurff, Dr. Kennan Crane, Andrea Rose, Falak Shah, Dr. J. Ben Deaton, and
countless others for their friendship and for being an invaluable part of my life at Georgia
Tech. I would also like to thank my friends Dr. Rakesh Nambiar, Dr. Subodh Jagtap,
Rishiraj Bheda, Pawan Moradia, Debesh Bhatta and Sidharth Oommen for their
camaraderie and for making life outside graduate school enjoyable.
Most importantly, I would like to express my heartfelt gratitude to my father
Jayapalan P.R and mother Lekshmi C.S., as well as my brother Reghuraj Jayapalan and
sister-in-law Aathira Prasad for being there for me every step of the way. I will always be
indebted to you for your love, encouragement and unconditional support.

iv
TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES x
LIST OF FIGURES xii
LIST OF SYMBOLS xv
LIST OF ABBREVIATIONS xvii
SUMMARY xix
CHAPTER 1: INTRODUCTION 1
1.1 Background 1
1.2 Fillers in Cement 6
1.2.1 Nanoparticles and TiO in Cement 8
2
1.2.2 Microparticles and Limestone in Cement 10
1.3 Research Motivation 12
1.4 Purpose and Objective 13
1.5 Organization of Dissertation 15
CHAPTER 2: LITERATURE REVIEW 17
2.1 Properties of Cementitious Materials in Presence of Inert Fillers 17
2.2 Early Age Properties in Presence of Inert Fillers 18
2.2.1 Temperature Sensitivity and Activation Energy in Presence of Inert
Fillers 23
2.2.2 Model for Quantification of Cement Hydration Data and Calculating
Activation Energy 28
2.3 Long-term Properties in Presence of Inert Fillers 31
2.4 Photocatalytic Properties 34
v
2.4.1 Review of Current Test Methods for Photocatalytic NO Conversion36
X
2.4.1.1 JIS R 1701-1 37
2.4.1.2 ISO 22197-1 38
2.4.1.3 UNI 11247 38
2.4.1.4 Other NO tests 39
X
2.5 Sustainability of TiO and Limestone Cement Mixes 40
2
2.5.1 Sustainability Matrices and Life Cycle Analysis 40
CHAPTER 3: EARLY AGE HYDRATION STUDIES 45
3.1 Introduction 45
3.2 Experimental Procedure 46
3.2.1 Materials 46
3.2.2 Test Methodology 47
3.2.2.1 Setting Time 47
3.2.2.2 Flow Characteristics 47
3.2.2.3 Isothermal Calorimetry 48
3.2.2.4 Chemical Shrinkage 48
3.2.2.5 Autogenous Shrinkage 49
3.2.2.6 Microscopy 50
3.2.2.7 Activation Energy of Cement-Nanoparticle Mixes 50
3.2.2.8 Powers’ Model for Cement Hydration 54
3.3 Results and Discussion 55
3.3.1 Setting Time 55
3.3.2 Flow Characteristics 57
3.3.3 Isothermal Calorimetry 57
3.3.3.1 Calorimetry Studies of TiO –Cement Mixes 57
2
vi
3.3.3.2 Calorimetry Studies of Limestone-Cement Mixes 61
3.3.4 Hydration of Cementitious Mixtures at Different Temperatures 64
3.3.5 Chemical Shrinkage 65
3.3.6 Autogenous Shrinkage 69
3.3.7 Microscopy 71
3.3.8 Activation Energy Using Single Linear Approximation Method 73
3.3.9 Activation Energy Using Modified ASTM C1074 Method 76
3.3.10 Powers’ Model for Cement Hydration 83
3.4 Summary 89
CHAPTER 4: LONG TERM PROPERTIES OF CEMENTITIOUS MATERIALS WITH
NANO AND MICROPARTICLE ADDITIVES 91
4.1 Introduction 91
4.2 Experimental Procedure 92
4.2.1 Materials 92
4.2.2 Test Methodology 93
4.2.2.1 Strength Test 93
4.2.2.2 Pore Size Distribution 94
4.2.2.3 Rapid Chloride Permeability Test 95
4.2.2.4 Surface Resistivity Test 96
4.3 Results and Discussion 97
4.3.1 Strength Development 97
4.3.2 Pore Size Distribution 101
4.3.3 Rapid Chloride Permeability Test 105
4.3.4 Surface Resistivity Test 108
4.4 Summary 110
vii
CHAPTER 5: PHOTOCATALYTIC PROPERTIES 112
5.1 Introduction 112
5.2 Methodology 116
5.2.1 Materials 116
5.2.2 Specimen Preparation 117
5.2.3 NO Exposure Chamber 119
X
5.2.4 Concentration and Flow Rate of NO 120
X
5.2.5 Characterization of Photocatalytic Efficiency 123
5.3 Results and Discussion 126
5.3.1 Photocatalytic Activity of TiO -Cement Paste Samples 127
2
5.3.2 Effect of Variation of Input Gas Concentration on Photocatalytic
Activity 131
5.3.3 Photocatalytic Efficiency Factor (PEF) for TiO -Cement Mixes 133
2
5.4 Conclusions 136
CHAPTER 6: SUSTAINABILITY OF CEMENT MIXTURES WITH TITANIUM
DIOXIDE AND LIMESTONE PARTICLE ADDITIVES 139
6.1 Introduction 139
6.2 Methodology Used in Life Cycle Analysis 141
6.2.1 Scope and Functional Unit of LCA 141
6.2.2 Stages of Life Cycle Analysis 143
6.3 Life Cycle Analysis Results 145
6.3.1 Life Cycle Inventory Analysis Results 146
6.3.2 Life Cycle Impact Assessment Results 146
6.3.3 Life Cycle Analysis – Interpretation – Results 149
6.4 Pathways for Use of Nano and Micro Particles - Do We Need Nano Particles?
151
viii
6.5 Economic Cost Analysis 156
6.6 Summary of Life Cycle Analysis 156
CHAPTER 7: CONCLUSIONS AND FUTURE RESEARCH 159
7.1 Conclusions 159
7.1.1 Early Age Hydration Studies 159
7.1.2 Long Term Properties 160
7.1.3 Photocatalytic Properties of TiO -Cement 161
2
7.1.4 Sustainability of cementitious mixtures with TiO and limestone 162
2
7.2 Recommendations 163
7.2.1 Early Age Properties 163
7.2.2 Long Term Properties 164
7.2.3 Photocatalytic Properties 164
7.2.4 Sustainability of TiO and Limestone Cement Mixes 165
2
7.3 Future research 166
APPENDIX A: EFFECT OF PARTICLE DISPERSION ON HYDRATION 170
APPENDIX B: LIFE CYCLE INVENTORY DATA 174
REFERENCES 196

ix
LIST OF TABLES
Page
Table 1.1: Maximum prescriptive limits on limestone addition to cement-based materials
10
Table 2.1: Comparison of testing, sample and analysis parameters of various tests for
testing NO conversion performance of photocatalytic materials 36
X
Table 3.1: Properties of TiO (T) and limestone (L) powders added to cement 46
2
Table 3.2: Reaction rate of ordinary portland cement and 5% T3 mix using single linear
approximation method 75
Table 3.3: Activation energy calculated according to linear approximation method 76
Table 3.4: Activation energy (Ea) and parameters of three parameter model (α , τ and β)
u
cement mixes calculated according to modified ASTM C 1074 method 80
Table 3.5: Chemical shrinkage of cement mixes at 100% hydration obtained using
Powers’ model and experimental data (extrapolated) 85
Table 4.1: Concrete mix design used for chloride permeability and surface resistivity tests
(for 1 cu. yd. concrete) 93
Table 4.2: Results from analysis of variance (ANOVA) of strength data 99
Table 4.3: Results from specific surface area nitrogen adsorption-desorption experiments
(28 day results) 101
Table 4.4: Rapid chloride permeability test results for TiO and limestone concrete mixes
2
at 0% and 5% replacement rate 106
Table 5.1: Comparison of testing, sample and analysis parameters of various tests for
testing NO conversion performance of photocatalytic materials 115
X
Table 5.2: Properties of TiO added to cement, as provided by manufacturers 117
2
Table 6.1: Environmental impact factors considered in the BEES model 142
Table 6.2: Environmental impact factors considered in the EcoIndicator 99(E) model 143
Table 6.3: Life cycle impact assessment results based on BEES impact assessment 147
Table 6.4: Life cycle impact assessment results based on EcoIndicator 99(E) impact
assessment 147
x