Effect of A Newly Developed Lignosulphonate Superplasticizer On Properties of Cement Pastes and Mortars

EFFECT OF A NEWLY DEVELOPED
LIGNOSULPHONATE SUPERPLASTICIZER ON
PROPERTIES OF CEMENT PASTES AND
MORTARS
SUN DAO JUN
NATIONAL UNIVERSITY OF SINGAPORE
2008
EFFECT OF A NEWLY DEVELOPED
LIGNOSULPHONATE SUPERPLASTICIZER ON
PROPERTIES OF CEMENT PASTES AND
MORTARS
SUN DAO JUN

(B. Eng. (Hons.), NUS)
A THESIS SUBMITTED
FOR THE DEGREE OF MASTER OF ENGINEERING
DEPARTMENT OF CIVIL ENGINEERING
NATIONAL UNIVERSITY OF SINGAPORE
2008
Acknowledgements
The author would like to take this opportunity to express his sincere appreciation and
deep gratitude to his supervisor, Associate Professor Zhang Min-Hong for her
invaluable guidance, patience, kind encouragement and full support throughout the
entire course of this research.
The author’s heartfelt appreciation goes to Dr. Sisomphon Kritsada, Dr. Kåre Reknes
(Borregaard, Norway) and Mr. Philip Chuah (Borregaard, Singapore) for their useful
comments and constructive discussion.
This project would not have been successful without the kind assistance of the lab
technicians at Structural and Concrete Laboratory; special thanks to Mr. Ang Beng
Oon, who assisted the author to conduct some of the laboratory experiments. The
author also would like to deliver his gratefulness to his friends for their moral support;
special thanks to Mr. Lee Wah Peng and Wang Zengrong.
Sincere gratitude is extended to Borregaard Ligno Tech (Sarpsborg, Norway) for
providing the research grant.
Finally, the author dedicates this study to his dear parents who have given him fullest
support and unconditional love all these years.
i
Table of Contents
Acknowledgements .............................................................................................................. i
Table of Contents ................................................................................................................ii
Summary ...........................................................................................................................vii
List of Notations.................................................................................................................. x
List of Acronyms...............................................................................................................xii
List of Tables ....................................................................................................................xiv
List of Figures .................................................................................................................xvii
Chapter 1 Introduction ...................................................................................................... 21
1.1 Background.........................................................................................................21
1.2 Objectives ...........................................................................................................24
1.3 Scope...................................................................................................................25
Chapter 2 Literature Review ............................................................................................. 28
2.1 Nature of Water Reducing Admixtures ..............................................................28
2.1.1 Regular Water Reducing Admixtures (WRAs) ............................................29
2.1.1.1 Lignosulphonate....................................................................................29
2.1.1.2 Hydroxyl carboxylic acids and their salts.............................................30
2.1.1.3 Carbohydrates.......................................................................................31
2.1.1.4 Other compounds ..................................................................................31
2.1.2 Superplasticizers (SPs).................................................................................31
2.1.2.1 Modified lignosulphonate(MLS) ...........................................................33
2.1.2.2 Sulphonated melamine / naphthalene formaldehyde condensates
(SMF/SNF) ........................................................................................................34
2.1.2.3 Polycarboxylate based (PCE) ...............................................................34
ii
2.2 Mechanisms of Water Reduction ........................................................................36
2.2.1 Electrostatic Repulsion.................................................................................37
2.2.2 Steric Hindrance ...........................................................................................38
2.2.3 Solid-Liquid Affinity....................................................................................38
2.2.4 Mechanisms of WRA and SP of Different Natures......................................38
2.3 Portland Cement Hydration ................................................................................39
2.3.1 Chemistry of Portland Cement Hydration....................................................39
2.3.2 Heat Evolution of Portland Cement Hydration ............................................42
2.3.2.1 Measurement of heat evolution of cement hydration ............................42
2.3.2.2 Effect of the admixtures on heat evolution of cement hydration ...........42
2.4 Effect of the Admixtures on Cement Hydration .................................................43
2.4.1 Effect of LS Admixtures ..............................................................................44
2.4.2 Effect of SNF Admixtures............................................................................45
2.4.3 Effect of PCE Admixtures............................................................................47
2.5 Effect of the Admixtures on Workability............................................................48
2.5.1 Workability and Rheological Parameters .....................................................48
2.5.2 Effect of Admixtures on Initial Workability.................................................50
2.5.3 Effect of Admixtures on Workability Retention...........................................52
2.6 Effect of the Admixtures on Setting ...................................................................54
2.7 Effect of the Admixtures on Pore Structure & Strength Development...............55
2.7.1 Principle of Mercury Intrusion Porosimetry and Characterization of Pore
Structure ................................................................................................................55
2.7.1.1 Total porosity ........................................................................................56
2.7.1.2 Critical pore diameter...........................................................................56
2.7.1.3 Threshold pore diameter .......................................................................57
iii
2.7.1.4 Pore Size Distribtuion ...........................................................................57
2.7.1.5 Evaluation of MIP .................................................................................58
2.7.2 Effect of Admixtures on Pore Structure of Cement Paste ............................59
2.7.2.1 Effect of PCE Admixtures......................................................................59
2.7.2.2 Effect of SNF Admixtures ......................................................................60
2.7.2.3 Effect of LS Admixtures .........................................................................61
2.7.2.4 Comparisons of Effect of PCE, SNF and LS Admixtures......................61
2.8 Drying Techniques of Cement Paste and Testing Methods ................................62
2.8.1 Drying Techniques for Cement Paste...........................................................62
2.8.1.1 Oven drying ...........................................................................................62
2.8.1.2 D-drying ................................................................................................63
2.8.1.3 Vacuum drying ......................................................................................63
2.8.1.4 Solvent exchange ...................................................................................63
2.8.1.5 Freeze drying.........................................................................................64
2.8.2 X-Ray Diffraction (XRD) ............................................................................65
2.8.3 Thermogravimetric Analysis (TG) ...............................................................68
Chapter 3 Experimental Details ........................................................................................ 76
3.1 Introduction.........................................................................................................76
3.2 Materials .............................................................................................................76
3.2.1 Cement and Water ........................................................................................76
3.2.2 Aggregates....................................................................................................77
3.2.3 Water Reducing Admixtures ........................................................................77
3.3 Mix Proportions of Cement Pastes and Mortars.................................................79
3.4 Preparations for Cement Pastes and Mortars......................................................80
3.4.1 Preparation for Cement Pastes .....................................................................80
iv
3.4.2 Preparation for Mortars ................................................................................82
3.5 Test Methods and Analyses.................................................................................83
3.5.1 Heat Evolution of Cement Hydration ..........................................................83
3.5.2 Degree of Cement Hydration .......................................................................86
3.5.2.1 X-ray Diffraction (XRD)........................................................................86
3.5.2.2 Thermogravimety Analysis (TG) ...........................................................88
3.5.2.3 Non-Evaporable Water (NEW) Content................................................89
3.5.3 Workability Retention of Mortars ................................................................91
3.5.4 Setting Time of Mortars ...............................................................................94
3.5.5 Pore Structures of Pastes ..............................................................................94
3.5.6 Compressive Strength of Mortars ................................................................95
Chapter 4 Results and Discussion ................................................................................... 107
4.1 Heat Evolution of Cement Hydration ...............................................................107
4.2 Degree of Cement Hydration............................................................................113
4.2.1 Reduction of C3S in Cement Pastes ...........................................................113
4.2.2 Hydration Progress in the Cement Pastes ..................................................114
4.2.2.1 Calcium hydroxide (CH) in cement pastes..........................................114
4.2.2.2 Non-evaporable water in cement pastes .............................................117
4.2.3 Degree of Hydration in Cement Pastes ......................................................119
4.3 Workability Retention of Mortars with Time....................................................121
4.3.1 Change in the Yield Stress of Mortars with Time ......................................121
4.3.2 Change in Plastic Viscosity of Mortars with Time.....................................125
4.3.3 Change in Flow Value of Mortars with Time .............................................126
4.3.4 Relationship between the Yield Stress and Flow Value .............................127
4.4 Setting Times of Mortars ..................................................................................128
v
4.5 Pore Structure of Cement Pastes.......................................................................130
4.5.1 Total Porosity of Cement Pastes with Admixtures.....................................131
4.5.2 Pore Size Distribution of Cement Pastes with Admixtures........................132
4.5.3 Threshold and Critical Pore Diameters ......................................................135
4.6 Compressive Strength of Mortars .....................................................................137
Chapter 5 Conclusions and Recommendations............................................................... 163
5.1 Conclusions.......................................................................................................163
5.2 Recommendations.............................................................................................166
References ....................................................................................................................... 168
Appendix ......................................................................................................................... 181
vi
Summary
Lignosulphonate (LS) has been widely used in concrete as regular water reducers for
many decades due to its relatively low price. Significant advances have been made in
process and production of LS based admixtures. There is a wide range of
lignosulphonates available and their performance in concrete varies from regular
water reduction and strong retardation to high range water reduction. With the
development of a new modified LS superplasticizer (PLS), it is possible to produce
self-compacting concrete with such an admixture. However, there is not much
information available on the effect of the newly developed modified LS
superplasticizer on cement hydration, workability retention, and pore structure of
pastes in comparison to those of polycarboxylate, naphthalene and the other modified
LS superplasticizers and to those of regular LS water reducing admixtures. The
present research was, therefore, carried out.
Six admixtures were used which included four superplasticizers (one polycarboxylate
(PCE), one naphthalene (SNF), two modified lignosulphonates (PLS and UNA)) and
two regular water reducing admixtures (lignosulphonates (BCS and BCA)). Mortars
and cement pastes were designed to have similar workability. The dosages of
admixtures were determined to achieve an initial target yield stress of 75 ± 15 Pa for
mortars with w/c ratios of 0.34 and 0.40. This yield stress level will produce concrete
with slump ≥ 100 mm. For w/c of 0.40, all six admixtures were investigated; whereas
for w/c of 0.34, only four superplasticizers were investigated due to the difficulty in
achieving required initial yield stress by using regular water reducing admixtures.
vii
The results indicate that the water reducing admixtures and superplasticizers delayed
cement hydration for both w/c ratios at early ages, but did not have significant effect
on cement hydration at later ages from 7 to 91 days. The retardation of the pastes was
in the order of SNF < PCE < PLS < UNA < BCA < BCS.
The workability loss of the mortars with the LS superplasticizers was similar within
the first hour, but less than those with the SNF and PCE superplasticizers. The
workability loss of the mortars with the two regular water reducing admixtures was
more significant than those with the superplasticizers.
The order of setting times of mortars with admixtures agreed with the length of
induction periods in the heat curves of the respective pastes, i.e. SNF < PCE < PLS <
UNA< BCA < BCS. The admixtures had strong influence on the initial setting times.
However, once the mortars reached the initial setting, the final setting was not
significantly affected by the admixtures.
For the four superplasticizers, better workability retention corresponded to longer
setting time. However, the two regular LS based water reducing admixtures had
longer setting time, but poor workability retention which was probably related to their
acceleration for the cement hydration in the first hour according to the rate of heat
curves.
At 28 and 91 days, the porosity of the pastes with the LS superplasticizers at w/c of
0.34 was similar to that with the SNF superplasticizer, but higher than that with the
PCE superplasticizer. At w/c of 0.40, the total porosity of the pastes with different
viii
admixtures was not significantly different at 28 days. Pore size distribution of the
pastes changed with time due to cement hydration and they differed with respect to
w/c ratios and admixtures. In general, the proportions of small capillary pores in the
pastes investigated were not significantly different, and the differences were mainly
on the large and medium capillary pores. The pastes with LS superplasticizers had
similar large pores at 91 days compared to the paste with PCE superplasticizer, but
less large pores compared to the paste with SNF superplasticizer at both w/c ratios.
However, the pastes with LS superplasticizers had more medium pores compared to
the pastes with PCE and SNF superplasticizers. The pastes with the regular LS
admixtures (BCS and BCA) appeared to have less large capillary pores at 91 days
compared to those with the superplasticizers. The threshold and critical pore
diameters of the pastes were not significantly affected by the admixtures.
The chemical admixtures investigated affected early compressive strength of the
mortars due to their different retarding effects. However, the strength of the mortars
was not significantly affected by the admixtures beyond 7 days.
Keywords: cement hydration; compressive strength; lignosulphonate; naphthalene;
plastic viscosity; polycarboxylate; pore structure; setting times; superplasticizer; water
reducing admixture; workability retention; yield stress.
ix
List of Notations
A the first peak in heat curves
AFm monosulfoaluminate
AFt ettringite
B the second peak in heat curves
C2 S di-calcium silicate 2CaO.SiO2
C3 A tri-calcium aluminate 3CaO.Al2O3
C3 S tri-calcium silicate 3CaO.SiO2
C4AF tetra-calcium aluminoferrite 4CaO.Al2O3.Fe2O3
CH calcium hydroxide Ca(OH)2
C-S-H or C3S2H8 calcium silicate hydrates, 3CaO.2SiO2.8H2O
d spacing of the crystal planes or diameter
g flow resistance related to yield stress
h relative viscosity related to plastic viscosity
H height
I peak intensity in XRD spectrum
N rotational speed / velocity
n an integer
P pressure
Ri radius of inner cylinder
Ro radius of outer cylinder
t time
T torque
V volume
x
W weight fraction
w/c water-to-cement ratio
α degree of hydration of cement paste
γ surface tension
γ& shear rate
ε total porosity
θ angle of the diffraction peak
λ wavelength of radiation
µ plastic viscosity
τ shear stress
τo yield stress of fresh concrete
ωo angular velocity
xi
List of Acronyms
ASTM the American Society for Testing and Materials
HCP hardened cement paste
HRWRA high-range water reducing admixture
LOI loss on ignition
MIP mercury intrusion porosimetry
(M)LS (modified) lignosulphonate
NEW non-evaporable water
OPC ordinary Portland cement
PCE polycarboxylate
RH relative humidity
rpm rounds per minute
rps rounds per second
sbwc solid by weight of cement
SEM scanning electron microscopy
SMF/PMS sulfonated melamine formaldehyde condensates /
polymelamine sulfonate
SNF/PNS sulfonated naphthalene formaldehyde condensates /
poly-naphthalene sulfonate
SP superplasticizer
SRM standard reference material
SSD saturated surface dry
TG thermogravimetry
WRA water reducing admixture
xii
XRD X-ray diffraction or X-ray diffractometer
XRF X-ray fluorescence
xiii
List of Tables
Chapter 1
Table 1-1 Typical Effects of Water-Reducing Admixtures (Mindess et al, 2003)............. 27
Table 1-2 Classification of WRAs According to ASTM C494 ......................................... 27
Chapter 2
Table 2-1 Classification of Pores (information summarized from Mindess et al, 2003) .. 70
Table 2-2 Solvents and subsequent drying conditions used in solvent exchange ............. 70
Table 2-3 XRD powder pattern of a typical Portland cement (Taylor, 1997) ................... 71
Table 2-4 Summary of a typical cement paste TG graph .................................................. 71
Chapter 3
Table 3-1 Chemical & Mineral Compositions and Physical Properties of Cement Used
...............................................................................................................................96
Table 3-2 Physical properties and sieve analysis of sand.............................................96
Table 3-3 Characteristics of admixtures used in the project ........................................97
Table 3-4 Mix proportion of mortars to achieve an initial yield stress of 75 ± 15 Pa..97
Table 3-5 Mix procedures of mortars and pastes .........................................................98
Table 3-6 Analytical techniques and equipment used in this study..............................98
Table 3-7 Seven samples used to produce C3S calibration chart .................................99
Table 3-8 Process parameters set on BML Viscometer 3 for determination of the yield
stress and plastic viscosity.....................................................................................99
xiv
Chapter 4
Table 4-1 Times of peak appearance in heat curves of pastes......................................... 139
Table 4-2 Amount of CO2 from decomposition of CaCO3 in Fig. 4-9 TG curves .......... 139
Table 4-3 Times for C3S reduction & CH appearance in the cement pastes with and
without admixtures detected by XRD & TG............................................................ 139
Table 4-4 Degree of hydration of pastes at various ages (w/c = 0.34) ............................ 140
Table 4-5 Degree of hydration of pastes at various ages (w/c = 0.40) ............................ 140
Table 4-6 Flow values of mortars with time (w/c = 0.34)............................................... 141
Table 4-7 Repeatability of MIP on mortars with and without admixtures ...................... 141
Table 4-8 Critical and threshold pore diameters for pastes with w/c = 0.34................... 142
Table 4-9 Critical and threshold pore diameters for pastes with w/c = 0.40................... 142
Appendix
Table A-1 Intensity ratios of CH, C3S to anatase in pastes from XRD (w/c = 0.34) ...... 181
Table A-2 Intensity ratios of CH, C3S to anatase in pastes from XRD (w/c = 0.40) ...... 182
Table A-3 Non-evaporable water content in pastes from furnace burning (w/c = 0.34). 182
Table A-4 Non-evaporable water content in pastes from furnace burning (w/c = 0.40). 183
Table A-5 Calcium hydroxide content in pastes from TG (w/c = 0.34).......................... 183
Table A-6 Non-evaporable water content in pastes from TG (w/c = 0.34) ..................... 183
Table A-7 Calcium hydroxide content in pastes from TG (w/c = 0.40).......................... 183
Table A-8 Non-evaporable water content in pastes from TG (w/c = 0.40) ..................... 184
Table A-9 Yield stress, plastic viscosity and flow values of mortars with time (w/c =
0.34).......................................................................................................................... 184
Table A-10 Yield stress, plastic viscosity and flow value of mortars with time (w/c =
0.40).......................................................................................................................... 185
xv
Table A-11 Capillary pore size distribution and total porosity of pastes (w/c = 0.34).... 186
Table A-12 Capillary pore size distribution and total porosity of pastes (w/c = 0.40).... 187
Table A-13 Average and standard deviation of mortar compressive strengths (w/c =
0.34).......................................................................................................................... 188
Table A-14 Average and standard deviation of mortar compressive strengths (w/c =
0.40).......................................................................................................................... 188
xvi
List of Figures
Chapter 2
Fig. 2-1 (a) SMF condensate, (b) SNF condensate, (c) Repeating unit of
lignosulphonate (LS) molecule (d) Molecular structure of polycarboxylate ........72
Fig. 2-2 (a) Flocculation of cement particles resulting trapped water (b)
Deflocculation of cement particles upon adsorption of water reducing admixtures
(Law, 2004) ...........................................................................................................72
Fig. 2-3 Repulsion of cement particles by (a) electrostatic repulsion..........................73
Fig. 2-4 Rate of heat evolution during hydration of Portland cement (Mindess et al,
2003)......................................................................................................................73
Fig. 2-5 Structure of cement pastes (Illston and Domone, 2001) ................................74
Fig. 2-6 Effect of water, water-reducing and air-entraining admixtures ......................74
Fig. 2-7 Critical pore and threshold pore diameters of MIP analysis...........................75
Fig. 2-8 Comparison of MIP and image analysis pore size distribution for the same .75
Chapter 3
Fig. 3-1 Grading curve of fine aggregate (sand) used................................................100
Fig. 3-2 (a) Isothermal calorimeter (b) Sample loading and unloading .....................100
Fig. 3-3 Schematic diagram of an X-ray diffractometer ............................................101
Fig. 3-4 Calibration chart of C3S in materials of interest...........................................101
Fig. 3-5 Schematic diagram of a thermogravimeter...................................................102
Fig. 3-6 Determination of mass loss from a thermogravimetry curve (Haines, 2002)
.............................................................................................................................102
Fig. 3-7 Schematic diagram of a furnace ...................................................................103
xvii
Fig. 3-8 Schematic diagram of the BML-Viscometer (Source: ConTec Ltd., 2003) .103
Fig. 3-9 The relation between (a) torque - rotation speed and ...................................104
Fig. 3-10 A typical ramp down T-N curve from test on mortar by BML Viscometer 104
Fig. 3-11 Schematic diagram of flow table set-up .....................................................104
Fig. 3-12 Schematic diagram of a penetrometer ........................................................105
Fig. 3-13 Schematic diagram of a mercury intrusion porosimeter.............................106
Fig. 3-14 Schematic diagram of a compressive strength tester..................................106
Chapter 4
Fig. 4-1 Effect of SO3 content on heat of cement hydration ........................................... 143
Fig. 4-2 Rate of heat evolution of cement pastes (w/c = 0.34) ....................................... 143
Fig. 4-3 Rate of heat evolution of cement pastes (w/c = 0.40) ....................................... 144
Fig. 4-4 Cumulative heat evolution of cement pastes (w/c = 0.34) ................................ 144
Fig. 4-5 Cumulative heat evolution of cement pastes (w/c = 0.40) ................................ 145
Fig. 4-6 Rate and cumulative heat evolution of two control mixes ................................ 145
Fig. 4-7 C3S reduction in paste with time (w/c = 0.34)................................................... 146
Fig. 4-8 C3S reduction in paste with time (w/c = 0.40)................................................... 146
Fig. 4-9 A typical TG curve showing mass loss over time (w/c=0.40 control paste) ..... 147
Fig. 4-10 CH content in pastes increases with time from TG curves (w/c=0.34)........... 147
Fig. 4-11 CH content in pastes increases with time from TG curves (w/c=0.40) ........... 148
Fig. 4-12 Non-evaporable water content with time from furnace burning (w/c = 0.34). 148
Fig. 4-13 Non-evaporable water content with time from furnace burning (w/c = 0.40). 149
Fig. 4-14 Comparisons of non-evaporable water content ............................................... 149
Fig. 4-15 Average and standard deviation of the initial yield stresses of all mortars...... 150
Fig. 4-16 Yield stress response on mortars with time at 30 ± 3 °C (w/c = 0.34) ............ 150
xviii
Fig. 4-17 Yield stress response on mortars with time at 30 ± 3 °C (w/c = 0.40) ............ 151
Fig. 4-18 Responses of yield stresses of mortars at normalized time ............................. 151
Fig. 4-19 Plastic viscosity response on mortars with time (w/c = 0.34) ......................... 152
Fig. 4-20 Plastic viscosity response on mortars with time (w/c = 0.40) ......................... 152
Fig. 4-21 Change in flow value of mortars with time (w/c = 0.40) ................................ 153
Fig. 4-22 Relationship between yield stress and flow value .......................................... 153
Fig. 4-23 Initial and final setting times of prepared mortars (w/c = 0.34) ...................... 154
Fig. 4-24 Initial and final setting times of prepared mortars (w/c = 0.40) ...................... 154
Fig. 4-25 Relationship between the initial and final setting times of prepared mortars
and time to start the acceleration period in heat curves ........................................... 155
Fig. 4-26 A typical MIP graph (w/c = 0.40, paste with PCE superplasticizer) ............... 155
Fig. 4-27 Total porosity of pastes with w/c = 0.34 at various ages ................................. 156
Fig. 4-28 Total porosity of pastes with w/c = 0.40 at various ages ................................. 156
Fig. 4-29 Total porosities and pore size distributions of the pastes at 1 day................... 157
Fig. 4-30 Total porosities and pore size distributions of the pastes at 3 days ................. 158
Fig. 4-31 Total porosities and pore size distributions of the pastes at 7 days ................. 159
Fig. 4-32 Total porosities and pore size distributions of the pastes at 28 days ............... 160
Fig. 4-33 Total porosities and pore size distributions of the pastes at 91 days ............... 161
Fig. 4-34 Compressive strength of 50mm mortar cubes (w/c = 0.34) ............................ 162
Fig. 4-35 Compressive strength of 50mm mortar cubes (w/c = 0.40) ............................ 162
Appendix
Fig. A-1 TG curves of the control paste (w/c = 0.34) ..................................................... 189
Fig. A-2 TG curves of PCE paste (w/c = 0.34) ............................................................... 189
Fig. A-3 TG curves of SNF paste (w/c = 0.34) ............................................................... 190
xix
Fig. A-4 TG curves of PLS paste (w/c = 0.34)................................................................ 190
Fig. A-5 TG curves of UNA paste (w/c = 0.34) .............................................................. 191
Fig. A-6 TG curves of the control paste (w/c = 0.40) ..................................................... 191
Fig. A-7 TG curves of PCE paste (w/c = 0.40) ............................................................... 192
Fig. A-8 TG curves of SNF paste (w/c = 0.40) ............................................................... 192
Fig. A-9 TG curves of PLS paste (w/c = 0.40)................................................................ 193
Fig. A-10 TG curves of UNA paste (w/c = 0.40) ............................................................ 193
Fig. A-11 TG curves of BCS paste (w/c = 0.40) ............................................................. 194
Fig. A-12 TG curves of BCA paste (w/c = 0.40)............................................................. 194
Fig. A-13 MIP curves for PCE paste (w/c = 0.34) .......................................................... 195
Fig. A-14 MIP curves for SNF paste (w/c = 0.34) .......................................................... 195
Fig. A-15 MIP curves for PLS paste (w/c = 0.34)........................................................... 196
Fig. A-16 MIP curves for UNA paste (w/c = 0.34) ......................................................... 196
Fig. A-17 MIP curves for PCE paste (w/c = 0.40) .......................................................... 197
Fig. A-18 MIP curves for SNF paste (w/c = 0.40) .......................................................... 197
Fig. A-19 MIP curves for PLS paste (w/c = 0.40)........................................................... 198
Fig. A-20 MIP curves for UNA paste (w/c = 0.40) ......................................................... 198
Fig. A-21 MIP curves for BCS paste (w/c = 0.40) .......................................................... 199
Fig. A-22 MIP curves for BCA paste (w/c = 0.40).......................................................... 199
xx
Chapter 1 Introduction
1.1 Background
Over half of the concrete used worldwide contains chemical admixtures. Water
reducing admixtures (WRAs) are most commonly used. Water reducing admixture, as
its name suggests, reduces the water required to attain a given slump. They can be
utilized in the following three ways. Firstly, achieving a desired slump by reducing
the water content while keeping cement content unchanged means an effective lower
w/c ratio, resulting in a general improvement in strength, impermeability and
durability. Secondly, WRAs may be used to increase workability without increasing
water content and cement content, to ease the difficulty in placement. Lastly, they can
be used to reduce cement content either for economic (cement is the most expensive
ingredient in concrete) or technical reason (reduce the heat of cement hydration,
particularly for mass concreting) since a desired slump may be achieved by lowering
the cement content while keeping the w/c ratio unchanged.
Water reducing admixtures can be classified into low-range or regular (WRA, water
reducing capacity of 5% and above) and high-range (HRWRA, water reducing
capacity of 12-30%) (Table 1-1), according to ASTM C494. The HRWRA is
21
commonly referred to as superplasticizers (SPs). The ASTM Standard C494
categorizes several types of such admixtures according to their functions. Types A, D
(retarding) and E (accelerating) are regular water reducing admixtures (Table 1-2);
Types F and G (retarding) are both superplasticizers.
From composition point of view, there are four major categories of superplasticizers,
namely, sulfonated melamine formaldehyde condensate (SMF), sulfonated
naphthalene formaldehyde condensate (SNF), modified lignosulphonates (MLS), and
polycarboxylate (PCE) based superplasticizers. For decades, lignosulphonates (LS)
are one of the most commonly used regular WRAs in concrete industry worldwide
owing to their competitive prices and comparable performances.
The basic mechanisms of water reduction are through dispersion of cement particles
by electrostatic repulsion and/or steric hindrance. Fine particles such as cement grains
have a tendency to flocculate when mixed with water. When they flocculate, a certain
amount of water is often trapped inside agglomerates. Water reducing admixtures are
used to deflocculate and to free the trapped water. However, the effect of WRAs on
concrete performance depends on many influencing factors, such as cement type, mix
proportion, nature and dosage of WRAs, temperature, and time.
Basic LS based WRAs typically have water reduction capacity of 8-12%; modified
LS 15-25%; naphthalene formaldehyde condensed based superplasticizers (SNF)
22
typically 15-25%; and polycarboxylate based admixtures (PCE) more than 30%. Table
1-1 summarizes the water reduction capacity of the different types of water reducing
admixtures and their respective molecular structures and modes of action.
Lignosulphonate has been widely used in concrete for many decades due to its
relatively low price and is mainly regarded as basic water reducing admixture – at a
dosage of 0.05-0.1% they reduce the water requirement by 6 to 10% (Collepardi,
1993). In the past LS based admixtures are only used as normal WRAs since
excessive retardation and entrainment of air occur at high dosages (Ramachandran,
1995). However, significant advances have been made in process, production, and
application of LS based admixtures. There is a wide range of lignosulphonates
available and the performance in concrete varies from basic water reduction and
strong retardation to high range water reduction (Reknes, 2004). With the
development of a new modified lignosulphonate superplasticizer (PLS), it is possible
to produce self-compacting concrete (SCC) with such an admixture (Reknes and
Peterson, 2003).
With the modified lignosulphonate superplasticizers entering the market, its basic
performance, including workability, retardation and strength, have been researched.
However, there is not much information available in the literature on the effect of
these newly developed modified lignosulphonate superplasticizers on cement
hydration, workability retention and pore structure, in comparison to those of other
types of superplasticizers such as naphthalene and polycarboxylate based admixtures
23
and to those of traditional lignosulphonate water reducing admixtures. Therefore, the
current research was carried out.
1.2 Objectives
With limited literature on the earlier mentioned issues, the objectives of this research
project are as follows:
1. To determine the effect of water reducing admixtures and superplasticizers on
cement hydration based on heat evolution, reduction of clinker phase in
cement paste, and increased amount of hydration products;
2. To determine the workability retention of mortars incorporating different
admixtures by means of rheological parameters (yield stress and plastic
viscosity) and flow values changes with time;
3. To determine the retardation of cement hydration in terms of setting times of
prepared mortars and establish possible relationship between the setting times
and heat evolution of cement pastes;
4. To determine the pore structure of plasticized or superplasticized pastes and
the link between cement hydration and pore structure;
5. To determine the compressive strength development of mortars and possible
relations to hydration and pore structure; and
24
6. To evaluate and compare the performances of regular LS based water reducing
admixtures and modified LS based superplasticizers, with respect to fresh and
hardened pastes and mortars.
The focus of this study is on
1. Comparison of the newly developed LS superplasticizer (PLS) with
polycarboxylate (PCE), naphthalene (SNF), and the other modified
lignosulphonate (UNA) superplasticizers; and
2. Comparisons of the newly developed LS superplasticizer (PLS) with regular
lignosulphonate water reducing admixtures (BCS and BCA) and the other
modified lignosulphonate superplasticizer (UNA).
1.3 Scope
In practice, there are numerous situations in which concretes are designed to satisfy
specified workability and w/c requirements. The amount of the admixture may be
adjusted to achieve the requirements of workability and its retention at the specified
w/c. This opens up possibilities of using many different admixtures.
In this research, six admixtures were used which include four superplasticizers (one
polycarboxylate, one naphthalene, two modified lignosulphonates) and two regular
water reducing admixtures (lignosulphonates).
The dosages of admixtures were determined to achieve an initial target yield stress of
25
75 ± 15 Pa for mortars of w/c ratios of 0.34 and 0.40. This yield stress level will
produce concrete with slump of ≥ 100 mm. With w/c of 0.40, all six admixtures were
investigated; whereas for w/c of 0.34, only four superplasticizers were investigated
due to the difficulty in achieving the required initial yield stress by using regular
WRAs. The dosages obtained from mortars were kept the same for the respective
cement pastes.
Following parameters were determined to achieve the objectives:
1. Heat evolution of cement pastes up to 72 hours;
2. Reduction of C3S and increase in calcium hydroxide and non-evaporable water
content in cement pastes at various ages up to 91 days;
3. Changes on the rheological parameters (yield stress and plastic viscosity) of
mortars and flow values with time up to 60 minutes;
4. Setting times of mortars;
5. Pore structure of cement pastes at various ages up to 91 days; and
6. Compressive strength development up to 91 days.
Control pastes of both w/c ratios without admixtures were included in the
investigation of Items 1 and 2 above, but not in Items 3 - 6. The reason was that
setting times, pore structures, and compressive strength are strongly dependent on the
workability and compaction. Without admixtures, specified workability could not be
achieved. Hence, control mixes were not included in the investigation in Items 3 – 6.
26
Table 1-1 Typical Effects of Water-Reducing Admixtures (Mindess et al, 2003)
Water
Typical Increase in ASTM
Classification Common Name Reduction
Dosage#, % Slump, mm Specification
% w/c
Low-Range Regular 0.1 50 ~ 85 5-10 -0.05 C494
Mid-Range Mid-Range 0.5 50 ~ 100 10-15 -0.10
High-Range Superplasticizer 1.0 >100 15-30 -0.15 C494, C1017
#
Active ingreidnet by weight of cement, i.e. solid weight by cement (swbc)
Table 1-2 Classification of WRAs According to ASTM C494
Type of WRA Function of WRA

A Water Reducing Admixtures
D Water Reducing and Retarding Admixtures
E Water Reducing and Accelerating Admixtures
F Water Reducing, High Range Admixtures
G Water Reducing, High Range, and Retarding Admixtures
27
Chapter 2 Literature Review
An admixture is defined in ASTM C125 as “a material other than water, aggregates,
hydraulic cement and fiber reinforcement that is used as an ingredient of concrete or
mortar and is added to the batch immediately before or during its mixing”.
Admixtures, including water reducing admixtures (WRAs), have to fulfill
requirements for their use in concrete. Requirements for slump, water reduction,
setting times, compressive strengths and so on are specified in ASTM and other
relevant standards. For an understanding of the role of WRAs, mechanisms of the
action of the admixtures, workability, microstructure, durability and compatibility
between cement and admixtures, it is necessary to apply various research techniques.
2.1 Nature of Water Reducing Admixtures
Many different types of water reducing admixtures are available on the market.
According to ASTM C494, they are classified into categories based on their functions
in concrete as shown in Table 1-2. Based on the water reducing capacity,
28
these admixtures can be classified into three broad categories: regular WRAs, mid-
range WRAs and SPs. Regular WRAs can reduce water content by 5 to 10% whereas
SPs have water reducing capacity of 15 to 30% as shown in Table 1-1.
Polycarboxylate based SPs often have water reducing capacities of more than 30%.
2.1.1 Regular Water Reducing Admixtures (WRAs)
There are many different types of regular water reducing admixtures available on the
market. The main compounds used in the manufacture of water reducing admixtures
can be divided into four groups, namely, lignosulphonate, hydroxyl carboxylic acids
and their salts, carbohydrates and other compounds (Ramachandran, 1995).
2.1.1.1 Lignosulphonate
Lignosulphonates, first discovered in 1930s, are the most widely used raw material in
the production of water reducing admixtures (Ramachandran, 1993; Collepardi, 1993).
Lignosulphonate is a by-product from the production of paper-making from wood
whose composition includes about 20-30% lignin. It consists of non-uniform
polyelectrolyte with varying molecular weight distributions, approximately 20,000 to
30,000 with the molecular weights varying from a few hundreds to 100,000 (Rixom
and Mailvaganam, 1999).
In their crude form, lignosulphonates contain many impurities, such as pentose and
hexose sugars, depending on process of neutralization, precipitation and degree of
fermentation, as well as type and age of the wood used (Rixom and Mailvaganam,
1999). Sugars are known to be good retarders of cement hydration processes and the
29
presence of sugars in lignosulphonate may be accountable for its retarding effect in
cement hydration (Ramachandran et al, 1998). The two common types are calcium
(Ca2+) lignosulphonate and sodium (Na+) lignosulphonate based admixtures. Calcium
lignosulphonates are generally cheaper but less effective whereas sodium
lignosulphonates are more soluble and less liable to precipitation at low temperatures
(Hewlett, 1998).
Regular lignosulphonate at a dosage of 0.05 to 0.1% (solid by weight of cement, sbwc)
can reduce the water requirement in concrete by 6 to 10% (Malhotra, 1997). At higher
dosages, excessive retardation or excessive air entrainment may occur. To reduce air
entrainment, defoamer (commonly used is tributylphophate, TBP) may be added in
the production of these water reducing admixtures. Accelerating admixtures (such as
calcium chloride, calcium formate or triethanolamine) may be added to counteract the
retarding effect.
Because of the relatively low cost of lignosulphonates, there has been continued
interest in utilizing these products in concrete, even in the field of superplasticizers.
By special treatments such as ultrafiltration, desugarization and sulphonation,
modified lignosulphonate superplasticizers have been developed in recent years,
which can compete with melamine sulphonate (SMF) and naphthalene sulphonate
(SNF) based superplasticizers (Ramachandran, 1995).
2.1.1.2 Hydroxyl carboxylic acids and their salts
Salts of hydroxyl carboxylic acids were developed in 1950s. Although there is a
significant increase in their use, they are not used to the same extent as
30
lignosulphonates. As its name suggests, hydroxyl carboxylic acids have several
hydroxyl (-OH) groups and one or two terminal carboxylic acids (-COOH) groups
attached to a relatively short carbon chain.
They are normally used as an aqueous solution of sodium salts, or occasionally as
salts of ammonia (NH4+) or triethanolamine. Since they are usually synthesized
chemically, they have high purity.
2.1.1.3 Carbohydrates
Carbohydrates include natural compounds such as glucose and sucrose or
hydroxylated polymers obtained from hydrolysis of polysaccharides to form polymers
with a low molecular weight and containing different amounts of glycoside units.
These admixtures also have very strong retarding effects.
2.1.1.4 Other compounds
Quite a number of patents claim that other organic compounds could function as
WRAs. According to a summary on development of WRAs by Ramachandran (1993),
many formulations of WRAs are based on acrylate and methacrylate polymers to
improve workability and/or increase strength. Examples are polymers of alkoxylated
monomers and copolymerizable acid functional monomers.
2.1.2 Superplasticizers (SPs)
Superplasticizers, also known as high range water reducing admixtures, are high
molecular weight and water soluble polymers capable of achieving a given
31
workability at a much lower w/c ratio compared to that of low-range water reducing
admixtures. The superplasticizers can reduce water content by about 15 – 30% or
even higher.
Superplasticizers are adsorbed on cement particles and hydration products like
calcium hydroxide (CH) and calcium silicate hydrates (C-S-H) adsorb more SP
molecules than cement clinkers (Taylor, 1997). The adsorption rate of the
superplasticizers is affected by several factors such as the amount of tri-calcium
aluminates (C3A) present, the content of soluble sulphates, and the fineness of the
cement used.
Compared to regular WRAs, superplasticizers have lower air entrainment and less
retardation. The low air entraining ability is due to the repeating pattern of polar
groups which provide the molecules with no suitable hydrophobic region. As for the
weak retarding power, it can be attributed either to the assimilation of the
superplasticizers into the cement particles or the weak individual bonds between the
sorbent and sorbate which allow the sorbate to be displaced by ions added to the
product. The weak retarding power of superplasticizers allows the hydration products
to grow despite the presence of the sorbed material (Taylor, 1997).
Based on the main ingredient, there are four main types of superplasticizers, whose
molecular structures are shown in Fig. 2-1:
1. Modified lignosulphonate (MLS), essentially modified and/or purified
lignosulphonate plasticizers with the higher molecular weight fractions selected to
give greater efficiency
32
2. Sulphonated melamine formaldehyde condensates (SMF), also known as poly-
melamine sulphonate (PMS)
3. Sulphonated naphthalene formaldehyde condensates (SNF), also known as poly-
naphthalene sulphonates (PNS)
4. Polycarboxylate based superplasticizers (PCE), which include polyacrylates,
acrylic esters and sulphonated polystyrenes. These have been most recently developed,
and are sometimes referred to as ‘new generation’ superplasticizers.
2.1.2.1 Modified lignosulphonate(MLS)
Modified lignosulphonate is higher molecular weight lignosulphonate that is
considerably improved by the treatments of the crude by-product to remove
carbohydrate impurities. Though the refining process can enhance the performance of
lignosulphonate, it also causes the modified lignosulphonate to have greater tendency
of entraining air (Hewlett, 1998).
Ramachandran (1995) commented that tailored LS may qualify as a superplasticizer,
but problems associated with its use had to be resolved. He suggested that caution
should be exercised in the selection of deformers, which would be used to de-train air
when LS is at high dosage, as they may affect the aggregate-cement bond. He also
mentioned that concrete with highly dosed LS would show a lower early compressive
strength and would be offset by the use of compatible accelerators.
Typically the LS based admixtures have a more retarding effect than other types of
admixtures. Generally, larger sugar content in admixtures would result in longer
setting times (Ramachandran, 1995). The workability of concrete decreases with time,
33
known as slump loss; but the rates of slump loss are different for concrete made from
LS, SNF and PCE based admixtures. Hence, concrete made from different WRAs
have different setting times. Water reducing admixtures may also affect cement
hydration and temperature rise in concrete. These effects indicate that the
microstructure of cement paste and concrete may be influenced by the use of different
WRAs, which in turn would affect mechanical properties, permeability and durability
of concrete.
2.1.2.2 Sulphonated melamine / naphthalene formaldehyde condensates (SMF/SNF)
Sulphonated melamine formaldehyde condensates was first developed in Germany
and made commercially available in 1960s. Around the same time, SNF was first
developed in Japan. Both SMF and SNF based superplasticizers are linear anionic
polymers with sulphonate groups at regular intervals. Both types of superplasticizers
tend to give 16 to 25% water reduction. In comparison to SNF, SMF has a higher
molecular weight. Melamine based superplasticizers tend to reduce cohesion in the
mix with little or no retardation, making them effective at low temperatures or where
early strength is critical (Newman and Choo, 2003). On the other hand, less highly
polymerized SNF tends to increase air entrainment to provide cohesion and it also
poses greater retardation on the cement hydration than that of SMF (Newman and
Choo, 2003).
2.1.2.3 Polycarboxylate based (PCE)
Another common type of superplasticizer is polycarboxylate based. There are
polycarboxylates without graft chains, but their dispersing effect is usually limited
34
and this type of admixture is not widely used (Hanehara and Yamada, 2007). In this
study, only PCE with graft/side chains are discussed. Polycarboxylate based
superplasticizers are more effective complexants1 for divalent and trivalent metal ions
in comparison to the sulphonated polymers. They can reduce water by about 20 to
35% with little retardation and good workability retention. They are very powerful
water reducers and as such a lower dosage is normally used (Newman and Choo,
2003). They are essentially designed for high dispersing ability and their high
workability retention with a minimum setting retardation (Houst et al, 2005). The
PCE based superplasticizers could be further classified into homopolymer or
copolymer. This classification is related to the backbone of the polymer. For
homopolymer, the backbone is made up of only one type of monomer, whereas
copolymer consists of two types of monomers in the backbone. Both types of
polycarboxylate based superplasticizers have side chains made up of polyether. The
term ‘comb polymer’ has been used to describe this molecular structure. The
introduction of polyether side chains improves various performance of
superplasticizer which shows superior water-reducing at low dosage. When dosage
was 0.6%, the water reduction was as high as 36% in concrete and concrete slump
loss was very little in 90 min (He et al, 2005). Li et al (2005) also reported that the
high dispersing and flowing retention properties of PCE superplasticizers are mainly
affected by the length of side chains through steric repulsive force. Sugamata et al
(2003) found that the workability retention was a combination of the amount of PCE
superplasticizer adsorbed and the side chains of PCE molecules which extended out to
form a thick layer on cement particles, giving rise to greater repulsion.
1
Substances capable of forming a complex compound with another material in solution
35
The PCE superplasticizers are commonly used at a dosage up to approximately 1%
solid by weight of cement (sbwc). Instead of air entrainment, these superplasticizers
may actually decrease the amount of air entrained as a result of greater fluidity of the
mix (Taylor, 1997). When an overdose of superplasticizers is used, undesirable effects
such as excessive retardation and excessive slump loss may occur.
The dispersing action of the PCE superplasticizers is not only limited to ordinary
Portland cement. It can also be used together with other mineral admixtures to
produce higher quality concrete. Several different types of chemical and mineral
admixtures have been found compatible with these superplasticizers. These mineral
and chemical admixtures include fly ash, blast furnace slag, retarders, accelerators and
air entraining agents (Ramachandran et al, 1998).
It has been reported that PCE based superplasticizers ensured high plasticity concrete
mixes at dosages about one third that of conventional SNF based superplasticizer
(Faliman et al, 2005).
2.2 Mechanisms of Water Reduction
Water reduction by the regular WRAs and superplasticizers is achieved by
deflocculating the cement particles, thereby releasing the water trapped between the
cement agglomerates and making it available for mixing and workability. Without the
incorporation of these admixtures, the positively and negatively charged cement
particles will be attracted to each others, leading to flocculation as shown in Fig. 2-
2(a). Flocculation of these cement particles will trap part of the mixing water,
resulting in less water to be available for workability and cement hydration. With the
incorporation of these admixtures, flocculation of the cement particles is prevented or
36
minimized. These chemical admixtures are surface active agents which when
adsorbed by the cement particles will give them negative charges that cause repulsion
between particles. With the deflocculation of the cement particles, the trapped water
will be released and made available for workability and cement hydration. On top of
that, more surface areas of the cement particles will be exposed for the hydration
process. This is illustrated in Fig. 2-2(b). The water reducing capacity of these
admixtures allows a given workability to be achieved at a lower water requirement or
increase the workability for the same mix proportion, hence early strength gain.
There are basically three mechanisms to explain for the water reducing capability of
these admixtures. They are electrostatic repulsion, steric hindrance, and solid-liquid
affinity. Among the three mechanisms, electrostatic repulsion and/or steric hindrance
are dominating in deflocculation of cement particles. Besides all the three mechanism,
retardation of the cement hydration and air entrainment of these admixtures also aid
the deflocculation process, enhancing the water reducing capacity of these admixtures.
2.2.1 Electrostatic Repulsion
Electrostatic repulsion is generated as a result of increased magnitude of the zeta
potential. In the absence of these admixtures, the charges on the cement particles were
too small to determine the zeta potential. However, with the incorporation of the
admixtures, the zeta potential increases with the increase of the negative charges on
the cement particles. When all these cement particles carry sufficient magnitude and
same sign of surface charge, these particles will repel each others, resulting in
electrostatic repulsion as illustrated in Fig. 2-3(a).
37
2.2.2 Steric Hindrance
The steric hindrance effect, shown in Fig. 2-3(b), is due to the oriented adsorption of
the admixtures’ molecules which weaken the attraction between the cement particles.
One side of the admixtures’ molecules will be attached to the cement particles
whereas the other side to water. As a result of such attachment, a watery and
lubricating film is formed around the cement particles, weakening the attraction forces
between the cement particles. The mechanism of steric hindrance is exhibited mainly
by water reducing admixtures having branched molecular structures (Ramachandran
et al, 1998).
2.2.3 Solid-Liquid Affinity
The water reducing capacity of these admixtures could also be explained by the
increase in the solid-liquid affinity. When the solid-liquid infinity is increased with the
adsorption of these admixtures, the cement particles are attracted more to the water
rather than to each others. This will result in deflocculation of the cement particles.
2.2.4 Mechanisms of WRA and SP of Different Natures
The dispersing effect of LS based regular WRAs is due mainly to the mechanism of
electrostatic repulsion and to the mechanism of steric hindrance to some extent
(Uchikawa et al, 1997). Although LS based water reducing admixtures have a linear
molecular structure, the steric effect is caused by the very cross-linked molecules
taking up a relatively large volume on the cement surface (Ramachandran et al, 1998).
The mode action of superplasticizers is that they cause a combination of mutual
38
repulsion and steric hindrance between the cement particles. Opinions differ about the
relative magnitude and importance of these two effects with different superplasticizers.
For example, Yoshioka et al (2002) believed that the dispersing effect for PCE based
admixture is accountable by the steric hindrance effects, which was supported by
Uchikawa et al (1997) and Flatt et al (2000), while the dispersing effect is due solely
to electrostatic repulsion for SNF based admixtures. However, the general consensus
(Collepardi, 1998; Hewlett, 1998) is that
1. For SNF and modified LS superplasticzers, the dominant mechanism is
electrostatic repulsion;
2. For PCE superplasticizers, steric hindrance is equally if not more important than
electrostatic repulsion. This is due to a high density of polymer side chains on the
polymer backbone which protrude from the cement particle surface.
2.3 Portland Cement Hydration
2.3.1 Chemistry of Portland Cement Hydration
For an initial period after mixing, cement paste gradually loses the fluidity and starts
to stiffen at a much faster rate upon initial set. Strength gain does not start until after
the final set. The gain is rapid for the next few days, and continues for at least a few
months at a steadily decreasing rate.
The cement hydration reactions are exothermic, and the rate of heat evolution is a
direct indication of the rate of reactions. Figure 2-4 shows a typical curve of the rate
of heat evolution during hydration of Portland cement paste. Immediately after the
contact of the cement with water, there is a high peak (A), lasting only a few minutes.
39
This quickly declines to a low value for the induction (or dormant) period, when the
cement is relatively inactive. This may last for a few hours and the rate then starts to
increase rapidly, at a time corresponding roughly to the initial set, and reaches a broad
peak (B), some time after the final set. The reactions then gradually slow down,
sometimes with a narrow peak (C).
The main contribution to the short, intense first peak (A) is rehydration of calcium
sulphate hemihydrate, which is from gypsum decomposition during grinding process
(Coole, 1984). Additional contributions to this peak come from the hydration of the
free lime, the heat of wetting, heat of solution and the initial reactions of the
aluminate phases (Bensted, 1987).
In the early stages of hydration, C3A reacts very violently with water, resulting in
“flash set” of the paste if no gypsum is available in the system. Gypsum is added in
Portland cement to prevent the flash set because it reacts with C3A to produce
ettringite (AFt) and the reaction is much slower than that of the C3A alone. When
gypsum in the cement is depleted, ettringite is gradually transformed to calcium
monosulfoaluminate (AFm). If all the gypsum is consumed before all the C3A, the
direct hydrate C3AH6 is formed. The combined effect of AFt conversion to AFm and
direct hydration of C3A causes the short third peak C, which can occur 2 or 3 days
after hydration starts. Whether this peak occurs depends on the relative amount of
gypsum and C3A in the cement. The C4AF phase reacts over similar time scales, and
the reactions and products are both similar to those of C3A. The products contribute
little to the overall cement behaviour.
40
The two calcium silicates C3S and C2S form the bulk of anhydrated cement, and their
hydration products (calcium silicate hydrates and calcium hydroxide) give the
hardened cement paste most of its mechanical properties such as strength and stiffness.
Their reactions and reaction rates therefore dominate the properties of the hardened
cement paste and concrete. Their hydration reactions are shown in Eqs. 2-1 and 2-2.
2C 3 S + 11H → C 3 S 2 H 8 + 3CH (2-1)
2C 2 S + 9 H → C 3 S 2 H 8 + CH (2-2)
Figure 2-5 provides a visual illustration of cement hydration, where clinker phases
reduce in quantities and hydration products increase in volume with time. This leads
to the decrease in pore volume as the hydration products have lower specific gravity
than anhydrated cement particles, and thus occupy large volume in the paste.
The aluminate (C3A) phase is the most reactive, and therefore has the largest impact
on workability as it consumes large amounts of water upon hydration. The alite (C3S)
is the second most reactive phase, with strong impact on set and strength development.
Therefore the setting time is strongly affected by the free water content and by the
rate of reaction of both aluminate and alite (Sandberg, 2004).
In summary, cement hydration is a complicated process that includes a number of
exothermic chemical reactions. The characteristics of the heat of hydration are unique
for each concrete mix under each environmental condition. The hydration process also
directly influences paste/mortar/concrete workability, setting behavior, rate of
strength gain, and pore structure development.
41
2.3.2 Heat Evolution of Portland Cement Hydration
2.3.2.1 Measurement of heat evolution of cement hydration
Different test methods are available for measuring heat of hydration, including the
calorimeter method. There are four major calorimeters available: adiabatic, semi-
adiabatic, isothermal, and solution calorimeter. Isothermal conduction calorimetry has
been extensively used for monitoring the cement hydration and cement compounds.
Depending on the temperature, w/c ratio, nature and dosages of admixtures, the
intensity of the heat liberated varies with time. Much of the heat during cement
hydration is given off in the first few days. In conduction calorimeter, the rate of heat
evolution is recorded as a function of time. The area under the rate of heat curve gives
the total heat generated for a recorded period of time, varying from hours to days.
2.3.2.2 Effect of the admixtures on heat evolution of cement hydration
The measurement of the rate of heat evolution provides information on the rate of
cement hydration in the presence of WRAs. The hydration is generally delayed in the
case of cement hydration incorporated with WRAs. Bensted (1987) observed that the
first peak (A) was increased in cement paste with calcium LS admixture compared to
the control. The second peak (B) was delayed for the paste with WRA but the total
heat evolution was higher for plasticized paste. He further reasons that although the
calcium silicate hydration is delayed, the hydration of other cement phases (aluminate
and ferrite) increase and furthermore, once the delayed calcium silicate hydration
starts, it is effectively a delayed acceleration as indicated by the calorimeter heat
curve. Also, he comments that C3S can be either accelerated or retarded depending on
the types of superplasticizers used. Uchikawa et al (1995) found that the peak due to
42
C3S hydration (Peak B) was delayed by one hour when a SNF admixture was added
with the mixing water, and was shifted more to the right when addition of SNF was
delayed. Uchikawa et al (1995) observed that the second peaks (Peak B) in a heat
curve were similar for a sodium LS and a SNF based admixture, if other conditions
are the same. Pang et al (2005a) reported that a modified LS superplasticizer
remarkably delayed heat evolution of cement hydration. Peschard et al (2004)
suggested that the origin of retardation could be linked to an adsorption of admixtures
on the first hydrates forming a less permeable coating. On the other hand, Koizumi et
al (2007) found that SNF superplasticizer did not delay cement hydration at low
dosages based on the heat curves from calorimeter.
The use of superplasticizers reduces the heat generation during the setting period,
however, they do not affect the total heat of concrete (Wang et al, 2006). Aïtcin et al
(1987) also found that the total heat of hydration was not affected when SNF
superplasticizer was added in cement paste, even at a dosage as high as 1.45% sbwc.
2.4 Effect of the Admixtures on Cement Hydration
It is stated that water reducing admixtures do not change the kinetic laws, the Avrami-
Erofeev nucleation and growth law, and the three-dimensional diffusion involved in
the hydration processes (Ridi et al, 2003). However, hydrations of calcium silicates
and aluminates in cement may be affected by the presence of admixtures.
43
2.4.1 Effect of LS Admixtures
It is generally agreed that LS admixtures retards the hydration of C3S (Odler and
Becker, 1980; Bishop and Barron, 2006) or silicates (Ciach, 1971; Myrvold, 2006) or
cement (Mollah et al, 1995; Mikanovic et al, 2000; Carazeanu et al, 2002; Pang et al,
2005) at early ages. Modified LS superplasticizers also delayed cement hydration
(Pang et al, 2005a). Sakai et al (2006) found that the degree of C3S hydration in the
presence of refined LS superplasticizer at 3 days was smaller than that in other pastes
with SNF and PCE superplasticizers, and the degree of the hydration of C3S at 28
days was almost the same as that in pastes with the other superplasticizers.
Researchers have been investigating how the silicates are delayed. Khalil and Ward
(1973) attributed the delay of silicate hydration to an adsorption of the admixture on
the surface of cement particles. Bishop and Barron (2006) proposed that the calcium
ions (Ca2+) from LS based admixtures were involved in the formation of a semi-
permeable layer onto the cement grains, which acted as a diffusion barrier to delay the
cement hydration. Myrvold (2006) suggests that the ions released from the rapid
aluminates (C3A/C4AF) hydration may modify lignosulphonates and that the modified
lignosulphonates covers the silicate phases, which in turn slow down silicate
hydration.
In addition to the effect on the hydration rate, Odler and Becker (1980) found that the
amount of CH in pastes with the LS admixtures was distinctly lower than that in
control paste without the admixtures, and they suggest that the stoichiometric
composition of the C-S-H phase formed in the former may have higher Ca/Si ratio
than the latter without the LS admixtures. Dodson (1967) also found that the addition
of calcium LS admixture to C3S system could alter the morphology of calcium
44
hydroxide to form irregular crystals differing dramatically from the normal hexagonal
crystals. In addition, the LS admixtures seem to have an effect on the number of
calcium hydroxide crystals formed per unit volume of paste, although this can be
either increased or decreased depending on the type of material used (Rixom and
Mailvaganam, 1999).
The hydration of the silicates are delayed during early ages, however, it was reported
that both LS based (Bishop and Barron, 2006) and modified LS based (Pang et al,
2005a) admixtures accelerated ettringite formation at an early age. It was further
observed that the ettringite crystals in pastes with LS admixtures (Pang et al, 2005)
and modified LS admixtures (Pang et al, 2005a) were finer compared to those in
control paste without the admixtures. Odler and Samir (1987) reported otherwise.
They found that in the presence of a sodium LS, the hydration of C3A was also
retarded along with the C3S phase.
2.4.2 Effect of SNF Admixtures
Odler and Becker (1980) found that SNF admixtures retarded the hydration of pure
C3S and C3S component of Portland cement. The Ca/Si ratio of the C-S-H gel formed
in C3S hydration was distinctly increased by the admixtures. Koizumi et al (2007)
reported that a lower Ca/Si ratio at late age was observed. It was shown (Aïtcin et al,
1987) that SNF based superplasticizer, used at high dosage (1.45% sbwc) retarded the
hydration process of Portland cement. Based on the High Frequency Arc (HFA)
diameters obtained from AC impedance spectroscopy measurements and porosities
from mercury intrusion porosimetry (MIP), Gu et al (1994) concluded that SNF
superplasticizers had retardation effects at early ages (more evident after 7 hours), and
45
the effect was still notable at 28 days. The slower cement hydration reactions in the
presence of superplasticizers were confirmed by SEM examination and Ca(OH)2
content determined by thermal gravimetric (TG) method. The heat studies by Simard
et al (1993) supported this argument. On the other hand, Sakai et al (2006) and
Uchikawa et al (1992) found that SNF did not noticeably delay cement hydration.
Collepardi et al (1980) found that there were no substantial changes in the rate of C3A
hydration when 0.6% SNF was added. These different opinions presented are likely
related to the different dosages of the SNF admixtures used by researchers.
It is well known that SNF superplasticizer molecules are not only adsorbed on
anhydrated cement particles but also on some of their hydrates (Yilmaz and Glasser,
1989; Sarkar and Xu, 1992). It was found that the adsorbed SNF superplasticizer
molecules slowed down (Ramachandran, 1995; Hekal and Kishar, 1999; Mikanovic et
al, 2000; Mollah et al, 2000; Pourchet et al, 2006) or even stopped (Prince et al, 2002)
the growth of ettringite. However, normal growth of ettringite resumed when the
superplasticizer is consumed (Prince et al, 2002). The reasons for the slow down are
not clear. Prince et al (2003) found that the adsorption of SNF superplasticizer
molecules onto cement particles and their hydrates decreases the dissolution rate of
the constituents. Pourchet et al (2006) suggests that the slow down in the average rate
of ettringite precipitation may be linked to a decrease in C3A dissolution rate.
Roncero et al (2002), however, had different findings. The SNF superplasticizer they
investigated caused a lower C–S–H gel formation but the superplasticizer accelerated
formation of ettringite compared to the control paste where no admixture was added.
46
Not only the rate of ettringite precipitation may be altered, but the morphology of
ettringite may be modified as well. Hekal and Kishar (1999) studied a sodium salt of
SNF superplasticizer on the hydration of C3A with gypsum in a suspension. It was
found that the presence of the SNF superplasticizer caused a decrease in the size of
ettringite crystals, which agreed with the finding from Rößler et al (2007) that the
crystal size decreased as the dosage of superplasticizer increased. Prince et al (2002,
2003) also observed small massive ettringite clusters, rather than the usual needle-like
ettringite crystals, on an amorphous looking paste when an SNF superplasticizer was
added. However, when the SNF superplasticizer molecules were depleted, ettringite
crystals started to grow again in their usual shape (Prince et al, 2002).
2.4.3 Effect of PCE Admixtures
It is found that at early ages PCE admixtures retard cement hydration and the effect is
more pronounced at higher dosages (Kreppelt et al, 2002; Puertas et al, 2005). Based
on scanning electron microscope (SEM) observations, Kreppelt et al (2002) found that
very few hexagonal ettringite crystals were formed even after 24 hours of reaction
whereas Lothenbach et al (2007) did not observe distinct retardation of ettringite
formation. This may be due to the preferable adsorption of PCE onto C3A, observed
by Heikal et al (2006). Xu and Beaudoin (2000) also reported that PCE
superplasticizer reduced the rate of hydration during the first day. However, the
amount of C-S-H gel was similar after 28 days of hydration (Jolicoeur and Simard,
1998; Xu and Beaudoin, 2000; Puertas et al, 2005). In fact, Lothenbach et al (2007)
did not observe significant difference in the amount of hydrates formed after 6 days.
Although mineralogical analyses showed that the same hydration products were
47
formed in all pastes - mainly C–S–H gel (Puertas et al, 2005), it was revealed that a
few alterations in the structure and composition of C–S–H gel existed in the PCE
pastes. They found that pastes without admixtures had a somewhat higher Ca/Si ratio
than those containing 1% PCE superplasticizer at 2 days and that the Ca/Si ratio was
slightly lower in the control paste at 28 days. The lower Ca/Si ratio at a late age was
also reported by Koizumi et al (2007). Zhang et al (2006) found that PCE
superplasticizer molecule increased the crystallinity of C-S-H by intercalating into the
inner interlayer surface of the C-S-H.
2.5 Effect of the Admixtures on Workability
2.5.1 Workability and Rheological Parameters
Before discussing the effect of admixtures on workability and rheological parameters,
it is helpful to examine the basic principles of rheology. Rheology is a science dealing
with the deformation and flow of matter under stress. The simplest fluid is so-called
Newtonian fluid, which obeys Newton’s law (Eq. 2-3) of viscous flow.
τ = µγ& (2-3)
where τ = shear stress;
µ = coefficient of viscosity; and
γ& = rate of shear, or the viscosity gradient.
The relation of the shear stress vs shear rate of Newtonian fluids, which include very-
diluted suspensions of solid particles in liquid, is a straight line through the origin in a
48
shear stress τ - shear rate γ& graph. However, concentrated suspensions such as mortar
and concrete do not behave as Newtonian fluids. There is considerable evidence that
the flow behaviour of fresh mortar and concrete can be reasonably approximated by
Bingham Model (Eq. 2-4) (Mindess et al, 2003; Ferraris and de Larrard, 1998).
τ = τ o + µγ& (2-4)
where τ = shear stress;
τ o = yield stress or yield value;
µ = plastic viscosity; and
γ& = rate of shear, or the viscosity gradient.
They have to overcome a definite shear stress before flow can occur. This shear stress
is referred to as yield stress ( τ o ). Once the flow starts, the rate of flow is controlled by
the plastic viscosity (µ). For such materials, a single-point test such as slump or flow
table value may not be sufficient to describe their flow behavior.
Rheological parameters of fresh concrete are of great importance in understanding
workability of fresh concrete. The yield stress and plastic viscosity are two
rheological parameters, which are dependent on shear history, shear rate, and time of
measurement (Banfill, 2003). They are influenced by the use of chemical admixtures
such as air-entraining admixtures and water-reducing admixtures (Gjørv, 1994). The
general trends of the influences of regular water-reducing admixtures,
superplasticizers, and air entraining admixtures are shown in Fig. 2-6.
49
Most rotational rheometers are based on the principle that the material is stirred at a
controlled speed and the resulting torque is measured (Ferraris and Martys, 2003). In
the case of a Newtonian fluid, the viscosity is defined as the ratio between the shear
stress and shear rate (Mindess et al, 2003). Concrete and mortar are generally
accepted to be Bingham fluids (Ferraris and de Larrard, 1998). In such materials, the
plastic viscosity is defined as the slope of the shear stress versus shear rate once the
yield stress is overcome. Most rotational rheometers measure torque versus rotational
speed. Therefore, to obtain the true or absolute plastic viscosity, the slope of the curve
should be corrected by a function, f, which depends on the rheometer geometry and
experimental conditions.
2.5.2 Effect of Admixtures on Initial Workability
As shown in Fig. 2-6, regular WRAs and SPs generally reduce the initial yield stress
substantially compared to that of control mix. Gołaszewski and Szwabowski (2004)
found that PCE superplasticizers with the same dosage as SNF superplasticizer
considerably reduced g value (related to yield stress), but increased h values (related
to plastic viscosity) than those with SNF superplasticizer. It was reported that a
modified LS with an average molecular weight around 10,000 showed comparable
fluidity to SNF superplasticizer (Ouyang et al, 2006). For plain concrete with normal
w/c ratio of 0.40 or high w/c ratio of 0.5, the effectiveness of PCE and SNF
superplasticizers were similar (Gołaszewski and Szwabowski, 2004). This is quite
expected as superplasticizers are created for low w/c ratios.
At the same dosage, PCE superplasticized mixes are generally the most workable,
50
followed by those with SNF and LS admixtures. The performance of the modified LS
superplasticizers is dependent on the modification process and the sugar content,
counter-ions, and average molecular weight of the products. They may be comparable
to SNF superplasticizers in terms of their effect on the initial workability of mortar
and concrete.
There are few studies on plastic viscosity of mortars incorporating water reducing
admixtures. Some researchers studied apparent viscosity2 of cement pastes instead of
plastic viscosity due to their shear thinning effect. Odler and Becker (1980) found that
SNF and LS based admixtures lowered the apparent viscosity of both systems
compared with that of the control Portland cement paste.
Many factors can influence workability of cement paste, mortar and concrete, for
example, cement chemistry, nature and dosage of admixtures, temperature and age.
Lombois-Burger et al (2006) found that the yield stress level of cement pastes was
governed by the adsorption of superplasticizers, which was in competition with SO42-
to be adsorbed onto cement particles. They found that when cement containing mainly
hemihydrate was used, a rapid decrease of SO42- concentration with time resulted in
an increases in SNF adsorbed, which in turn led to less flow loss of cement paste.
Similar findings were reported by Hanehara and Yamada (1999) and Nakajima and
Yamada (2004). Zhor (2006) studied the effects of functional group of admixtures on
cement pastes and found that sulphonate had a very low correlation with dispersing
effect while carboxyl was the group most correlated to dispersing effect. The
2
It is defined as the ratio of shear stress to shear rate (at a given shear rate), as if the liquid
were Newtonian. If the liquid is actually non-Newtonian, the apparent viscosity depends on
the type and dimensions of the apparatus used and the shear rate.
51
workability of cement paste was also found to be dependent on counter-ions of WRAs,
with Na+ better than Ca2+ for SNF admixtures (Simard et al, 1993).
2.5.3 Effect of Admixtures on Workability Retention
Although water reducing admixtures are able to lower the initial yield stress, the
pastes with the admixtures also have workability loss with time just like the control
cement pastes. Björnström and Chandra (2003) reported that both yield stress and
plastic viscosity increased with time, from immediately after mixing to 45 min, for
cement pastes at w/c of 0.3 made with LS, SNF and PCE superplasticizers for two
cements with low and high C3A contents. However, neither the initial yield stresses
nor the admixture dosages were controlled at the same level as workability retention
is dependent on the initial workability.
It is generally agreed that concrete with SNF superplasticizer have very high slump
loss (Houst et al, 1999; Ouyang et al, 2006). Lim et al (1999) reported that SNF paste
lost over 50% of its initial slump at 120 min. Nawa et al (2000) found that SNF
superplasticizer had significant loss of flow but the loss decreased with an increase in
the dosage of SNF superplasticizer.
The rates of such loss may differ for admixtures of different natures. Chan et al (1996)
studied PCE and SNF superplasticizers at their respective saturation dosages, and
found that the workability retention of PCE was better than that of SNF. The
saturation dosage is defined as the dosage of water reducing admixtures beyond which
no significant increase in the workability is obtained. At the same dosage,
Gołaszewski and Szwabowski (2004) found the same workability retention of mortars
52
with PCE and SNF superplasticizers. The flow variations with time of pastes
(Uchikawa et al, 1995) and mortar (Houst et al, 1999) with PCE superplasticizer are
small.
Houst et al (2005) reported that a newly developed LS superplasticizer was much
more effective in terms of workability of concrete as a function of the dosage
compared to SNF superplasticizer. Chandra and Björnström (2002) observed that the
slump loss measured by flow value was higher with SNF compared with that with LS
admixtures when the initial flows were similar.
It has been recognized that flow and slump of concrete are related more to yield stress
than plastic viscosity. Thus, a lot of researches have been done on yield stress in the
last two decades. Plastic viscosity is not well studied. Gołaszewski and Szwabowski
(2004) found that PCE superplasticizer significantly reduced h values (related to
plastic viscosities) with time from 10 to 50 minutes while SNF one just slightly
decreased.
Reasons for workability loss are not yet quite understood. Bonen and Sarkar (1995)
concluded that the higher the ionic concentration in the pore solution of an SNF
superplasticized paste, the faster the slump loss. Hanehara and Yamada (1999)
suggested that slump loss and stiffness were caused by the production of large
amounts of ettringite based on their results of PCE, SNF, and LS admixtures. It was
reported (Uchikawa et al, 1983; Chandra and Björnström, 2002) that LS based
admixtures took up Ca2+ from the pore solution and thus the slump loss of mortars
with LS admixtures was lower than for those with SNF admixtures. Myrvold (2007)
53
suggests that workability retention of cement paste with LS admixtures may be
attributed to the adsorption of the LS on the silicate phases (C3S and C2S) and on the
hydration products (particularly CH, AFt) which causes retardation.
2.6 Effect of the Admixtures on Setting
Uchikawa et al (1984) found that when ion concentration (particularly Ca2+, SO42- and
OH-) was low, a large amount of needle-like ettringite crystals were produced, which
caused the stiffness and pseudo-setting of cement pastes. According to them, the PCE
superplasticizer seems to affect initial setting which was thought to correlate to C3S
hydration. Further, Uchikawa et al (1992) found that LS admixtures form complex
salts with Ca2+ in pore solutions more easily than SNF admixtures. Thus the LS
admixtures delayed the saturation of Ca2+ in the pore solutions which delayed the
setting of cement paste more than the SNF admixtures.
When SNF superplasticizer is added at small dosages, there is no or very little
retardation. However, Simard et al (1993) showed that the increase in the retardation
was roughly proportional to the SNF concentration (0.4-0.8% sbwc) in four cement
pastes with different C3S, C3A, and SO3 contents. Agarwal et al (2000) reported very
strong retardation of cement paste at SNF dosages of 1% and beyond.
Houst et al (2005) reported that the set retardation of a newly developed LS
superplasticizer was the same as traditional LS admixtures which retard the setting
more than SNF superplasticizer.
Vikan and Justnes (2007) suggest that the duration of the induction period is less
54
dependent on the silicate phases (C3S and C2S) than the aluminates (C3A and C4AF)
in cement pastes incorporating SNF and LS admixtures.
2.7 Effect of the Admixtures on Pore Structure & Strength
Development
2.7.1 Principle of Mercury Intrusion Porosimetry and Characterization of
Pore Structure
Mercury intrusion porosimetry (MIP) is a method often used to characterize the pore
structure of cement paste, mortar, and concrete in spite of its limitations. The MIP test
is governed by the Washburn (1921) equation, Eq. 2-5.
4γ cos θ
d =− (2-5)
P
where P = pressure, MPa;
γ = surface tension of the liquid, N/m;
θ = contact angle of the liquid with the solid, degree; and
d = diameter of the capillary, nm.
The following parameters are commonly obtained from the MIP test: (1) total porosity,
(2) critical pore diameter, (3) threshold pore diameter and (4) pore size distribution.
55
2.7.1.1 Total porosity
Porosity can be defined into two classes: total (or absolute) porosity and the effective
porosity. Total porosity, ε , including both open and closed pores, is the volume of
pores with respect to bulk volume of the material (often expressed in percentage), as
in Eq. 2-6:
V pore
ε= × 100% (2-6)
Vbulk
where V pore = the total pore volume in the bulk material; and
Vbulk = the bulk volume of the material.
Effective porosity is the fraction of open and interconnected pores with respect to bulk
volume of the material. The test with mercury intrusion porosimeter, therefore, can
only determine the open pores volume; hence effective porosity. The porosity
determined by MIP is defined as the ratio between the total injected mercury volume
and the total volume of the sample.
2.7.1.2 Critical pore diameter
The critical pore diameter (dc) is the pore size corresponding to the highest rate of
mercury intrusion. This is the point with the steepest slope of the cumulative intrusion
volume against pore diameter as shown in Fig. 2-7, therefore the point where
[dV/d(lnD)] is the maximum.
56
2.7.1.3 Threshold pore diameter
Winslow and Diamond (1970) defined threshold diameter (dt) of pores as that
corresponding approximately to the minimum diameter of channels that are
essentially continuous through the paste at a given age. The threshold diameter is the
diameter on the cumulative pore volume curve below which the pore volume rises
sharply. Above this value, there is comparatively little intrusion but immediately
below, the greatest portion of intrusion occurs.
2.7.1.4 Pore Size Distribtuion
At any stage of cement hydration, hardened cement paste (HCP) consists of solid
products such as calcium silicate hydrates, crystals of calcium hydroxide, calcium
sulphoaluminate hydrates, anhydrated cement, and pore space originally occupied by
water. The pores in the HCP can be classified into three categories, namely gel pores,
capillary pores, and air voids (see Table 2-1).
Gel pores do not play any significant role in the flow of water through concrete.
Capillary pores represent the space not filled by solid components in HCP and
therefore its volume and size depends on the distance between anhydrated cement
particles and degree of hydration (Parrott and Killoh, 1984). In well hydrated and low
w/c ratio pastes, the capillary pores may range from 10 nm to 50 nm (Mindess et al,
2003). Air voids in concrete are either entrapped during casting or intentionally
entrained using an air-entraining agent. The entrapped air may be as large as 3 mm
and the entrained air may be in the range of 50 – 200 µm. Both are larger than
capillary pores and have an effect on concrete permeation.
57
2.7.1.5 Evaluation of MIP
The microstructure of cement paste influences bulk properties such as compressive
strength, permeability and ion migration (Zhang and Glasser, 2000). The MIP
measurements also showed that the total volume as well as the distribution and
connectivity of pores significantly controlled various properties of concretes
(Diamond, 2000).
The MIP test has been used in the determination of microstructure for a long time as it
is one of the analytical techniques that permits an analyst to acquire data over such a
broad dynamic range using a single theoretical model (Webb, 2001).
However, the MIP method has limitations. Besides the required spherical pore shape
assumption, “ink-bottle” or “neck-bottle” (Diamond and Leeman, 1995) effect has
been found to have significant influences on the pore size distributions. As seen in
Fig. 2-8, large discrepancies were observed between pore size distribution determined
by the MIP method and that from image analysis, which are less affected by the
morphological features of the pore structure. Diamond (2000) criticized that the
features of pore structure characterized by the MIP method are not representative of
the real pore structure because of improper assumptions made on the shape of the
pores and their connectivity in concrete in the MIP method. Based on his study, he
further limited MIP credit only to threshold diameters and intruded pore space
measurements.
According to Cook (1991), the MIP method will indicate smaller than actual porosity
values where pores are too small or too isolated to be intruded by mercury. On the
other hand, MIP porosities may be closer to actual values than those indicated by
58
other techniques where mercury pressures can collapse small pores or break through
to isolated pores (Cook and Hover, 1999).
2.7.2 Effect of Admixtures on Pore Structure of Cement Paste
It is generally understood that the porosity of cement paste with or without admixtures
decreases with hydration time and that the greater the rate of hydration, the more
rapidly the porosity decreases. However, pastes with water reducing and retarding
admixtures may have different effects on the development in pore structures at a given
w/c ratio (Ramachandran et al, 1998).
2.7.2.1 Effect of PCE Admixtures
Puertas et al (2005) found that PCE admixtures used in the study modified
microstructure in the pastes which in turn reduced porosity and refined pore size. Xu
and Beaudoin (2000) found that PCE superplasticizer lowered overall porosity of
mortar at 28 days compared to the control mortar; however, the threshold pore
diameters were similar (around 70 nm) with or without the admixture. Xu and
Beaudoin (2000) also observed that the volume of pores ≥ 0.1 µm decreased while the
volume of pores < 0.1µm increased when PCE was added in the mortar.
Puertas et al (2005) observed that the presence of the PCE admixtures did not affect
paste strength at either 2 or 28 days. Nkinamubanzi and Aïtcin (2004) found that the
early age compressive strength of PCE concrete was less affected compared to
concrete with other superplasticizers due to the lower dosage required of PCE
admixtures to achieve similar slumps. Farrington (2007) found that PCE
59
superplasticizer retarded early cement hydration according to isothermal calorimeter
measurement, but it did not retard setting and early strength development when used
at the same dosage in concrete. It is important to realize that the effects of admixtures
on properties of cement paste, mortar and concrete may not be identical.
2.7.2.2 Effect of SNF Admixtures
Gu et al (1994) investigated effect of SNF superplasticizers (both calcium and sodium
SNF) on pore structure development of cement pastes at various ages from 1 to 28
days using MIP. The difference in the porosity between the pastes with the SNF
superplasticizer and the control paste were significant at early ages but relatively
small at late ages. They found that the superplasticized pastes had larger mean pore
sizes than that of the control paste at various ages up to 28 days. The porosity results
were supported by TG analysis, from which they found less CH in the pastes with the
SNF admixtures than the control one.
However, it was found that the addition of SNF superplasticizer to the cement pastes
led to pore narrowing (Khalil, 1999; Hwang and Lee, 1989). The total pore system of
cement pastes with SNF superplasticizer contained mainly small and/or medium
capillary pores at 28 days. Gu et al (1982) also found that SNF superplasticized pastes
reduced pore volume and capillary pore size when SNF was used to reduce the water
requirement, which effectively resulted in a lower w/c ratio. Apart from the
performance of SNF, the discrepancy may be related to different mix proportions and
to the purpose of superplasticizer addition.
60
2.7.2.3 Effect of LS Admixtures
Ramachandran (1995) reported that the total porosity of cement paste was increased
slightly in the presence of LS admixtures compared to that of the control paste. Pang
et al (2005a) found that the total pore volume of hydrated cement paste increased with
the increase in dosage of calcium LS. However, the average pore diameter of hydrated
cement paste with the calcium LS decreased, and the portion of pore with a diameter
over 30 nm decreased and the gel-pore with a diameter less than 10 nm increased
sharply. Pang et al (2005) investigated cement paste with a modified LS
superplasticizer and found that the results showed the same trend as that with the
calcium LS admixture - the portion of the gel pore increased and the average pore
diameter was refined. However, the incomplete growth of hydrate crystals and the
increase in pore volume in the cement led to reduction in the strength of cement paste
with the calcium LS within 28 days compared with the control cement paste.
2.7.2.4 Comparisons of Effect of PCE, SNF and LS Admixtures
Sakai et al (2006) observed that when SNF (without retardation effect) or LS (with
retardation effect) was added, almost similar pore structures were formed in the HCP.
They suggest that the difference in the pore structure of HCP with various types of
SPs is not related to the texture changes of the hydrates due to the retardation of
cement hydration, but related to the dispersion of the hydrates. Further, they found
that the volume of large pores of ≥ 0.1 µm in HCP with LS or SNF admixtures was
higher than that with PCE admixture cured for 28, 56 and 91 days. They suggest that
the size of the cluster of aggregated particles in the paste with PCE admixture may be
smaller than that with LS or SNF admixtures due to higher dispersing capacity of the
PCE admixture.
61
2.8 Drying Techniques of Cement Paste and Testing Methods
2.8.1 Drying Techniques for Cement Paste
In determination of the constitutional water associated with the C-S-H gel, it is
important to differentiate the free water from that bound by the gel. Since the interest
is in the chemically bound water, it is necessary to remove the free water in the
cement paste by some drying techniques. In all the drying methods presented below,
the samples must be crushed so that the drying can be achieved within a reasonable
period of time. (Hewlett, 1998)
There are five commonly used drying techniques for cement paste research. They are
conventional oven drying, D-drying, vacuum drying, solvent exchange and freeze
drying. Each has its advantages and disadvantages.
2.8.1.1 Oven drying
Oven drying is the most common drying technique. The sample is dried at an elevated
temperature, most commonly at 105oC. It was observed that at this temperature, it had
a destructive effect on microstructure and induced microcracking, consequently
leading to an overestimation of total porosity (Gallé, 2001). Balasubramanian et al
(1997) suggests a combination of 50oC followed by 105oC oven drying, and they
believe that this two-step drying would allow reasonably fast drying but cause less
alteration to the microstructure of the cement pastes.
62
2.8.1.2 D-drying
In D-drying procedure, samples are kept in a desiccator which is connected to a trap
cooled by a mixture of dry ice and ethanol at a temperature of -79 oC under vacuum
until the samples reach constant weights. The partial pressure of water vapor over the
ice precipitated in the trap is 5 x 10-4 torr (Hewlett, 1998). To put it simply, it is an
evacuation over dry ice (Ramachandran and Beaudoin, 1999).
2.8.1.3 Vacuum drying
Vacuum drying also has been used to dry the cement paste samples. However, vacuum
drying at low temperatures is a relatively slow process and therefore most suitable for
specimens older than 28 days, when not much free water is present in the paste
samples.
2.8.1.4 Solvent exchange
Solvent exchange is also known as solvent substitution or replacement. In this
technique, samples are to be immersed in a large volume of solvent, around 100:1,
due to the low solubility of water in most organic solvents (Ramachandran and
Beaudoin, 1999). The solvent immediately penetrates into the sample and replaces the
pore solution. The solvent should be renewed regularly. Normally, solvent exchange
is followed by oven drying (Ramachandran and Beaudoin, 1999). Researchers may
use different solvents and apply different temperatures. Some commonly used
solvents and references are summarized in Table 2-2.
This technique has been used by many researchers since it is simple and
63
straightforward. It is worth noting that it may partially dehydrate phases such as C-S-
H and ettringite; however, such dehydration probably has little effect on the outward
morphology of the hydration products (Scrivener, 1997).
Solvent replacement method can significantly affect the amount of calcium hydroxide
depending on the type of solvent used. Day (1981) reported that methanol altered
sample composition by reacting with CH to form a carbonate-like product. Taylor and
Turner (1987) reported that some organic liquids, including methanol and acetone,
may react with the hydration products and thus may affect the test results. Chemical
interactions between solvents such as isopropanol, methanol, and acetone, and the CH
surface were observed (Beaudoin et al, 1998). Marchand (1993) used isopropanol and
methanol as solvents and found that the amount of water replaced by methanol was
greater than the volume of the evaporable water in the pore solution of the sample. He
suggests that methanol molecules may be able to penetrate into C-S-H structure and
replace some of the structural water.
2.8.1.5 Freeze drying
The underlining principle of freeze-drying is to rapidly freeze cement paste samples in
the drying process to minimize the growth of ice crystals in the samples. The rapid
freeze can be achieved by immersing small samples in Freon cooled by liquid
nitrogen. Subsequently, the ice is to be sublimated into gas directly under vacuum.
This technique is fast and induces minimal damage to the microstructure of samples.
However, thermal shock of immersing samples in liquid nitrogen may shatter
specimens (Scrivener, 1997).
64
Gallé (2001) found that this technique did generate limited damage related to thermo-
mechanical stress; but it did not introduce capillary pores by the drying process.
Kjellsen and Diamond (2007) reported that freeze-dried and conventionally oven-
dried specimens at 60°C for more than 6 hours showed identical features on
microstructure.
2.8.2 X-Ray Diffraction (XRD)
X-ray diffraction is a powerful technique for identification of crystalline materials
because of the unique XRD patterns of individual crystalline phases. However, the
method is not useful for amorphous materials such as C-S-H in cement pastes.
In XRD spectra, the position of peaks is determined by the spacing of the
crystallographic planes according to Bragg’s law (Eq. 2-7) (1914):
nλ = 2d sin θ (2-7)
where n = an integer;
λ = wavelength of the radiation used;
d = spacing of the crystal planes; and
θ = angle of the diffraction peak.
The intensity of the peaks is affected by the types and positions of the atoms in the
crystal lattice according to the structure factor, which is beyond the scope of this
project. The peak intensity is also influenced by the quantity of a phase in a sample
and packing of the sample, and the latter is related to operators.
65
Quantitative analysis of samples from XRD spectra can be performed by measuring
the intensity of the peaks acquired in the scan in comparison to that of an internal
standard. In samples containing a mixture of phases, the intensity of a peak is
proportional to the mass fraction and the atomic number of the phase responsible for
that reflection. The derivation of the equations relating intensity and mass are
described by Nuffield (1966). To consider a simple mixture with two components (“a”
and “b”), the ratio of the intensities of the two components is given by Eq. 2-8.
Ia W K a ρb
=K a and K = = const. (2-8)
Ib Wb Kb ρa
where I a , I b = intensity of peak associated with components ‘a’ & ‘b’, respectively;
Wa , Wb = mass fraction of components ‘a’ & ‘b’, respectively;
K a , K b = constant dependent on the instrumental arrangements and the nature
of the components ‘a’ & ‘b’, respectively; and
ρ a , ρ b = density of components ‘a’ & ‘b’, respectively.
This equation shows that the intensity ratio of two peaks from the components in a
sample is proportional to the mass ratio of the two components. This equation is valid
for any two components in a mixture with two or more components.
If a standard of known mass fraction is added to a sample, and K is known, the mass
fraction of the second component can be determined.
If a constant amount of internal standard, for example anatase, was added in
calibration samples, Eq. 2-8 can further be simplified as in Eq. 2-9.
66
Wanatase I x
Wx = (2-9)
K I anatase
where Wx ,Wanatase = mass fraction of component x & anatase, respectively;
K = a constant, as in Eq. 2-8; and
I x , I anatase = peak intensity associated with component x & anatase, respectively.
The breadth of the peak is a function of instrumental parameters and the size of the
crystals in powder samples, but is constant for each sample (William et al, 2003).
Smaller crystals produce broader peaks, which in turn decrease the risk of preferred
orientation (William et al, 2003).
This is the simplest yet useful approach for semi-quantitative phase analysis of
cement and its paste (Mansoutre and Lequeux, 1996). It is possible to identify and
estimate anhydrated cement phases (e.g. C3S and C2S) and hydration products (e.g.
AFt and CH) in Portland cement pastes.
This method, however, has some limitations: (1) use of non-overlapping internal
standard for calibration makes the sample preparation tedious, (2) presence of
preferred orientation of crystals may affect results, and (3) overlapping peaks of
phases, e.g. alite and belite, makes the determination of the mass fraction of
individual phase difficult (Parrott et al, 1990; Mansoutre and Lequeux, 1996). The
C3S phase exhibits strong preferred orientation about the (001) 3 crystallographic
3
It is a representation of a plane in a structure, called Miller Index.
67
direction. This affects not only its own relative peak intensities, but also the derived
peak intensities of overlapping phases, especially C2S (Scarlett et al, 2001).
Other methods include the partially or fully computerized Rietveld method, which has
been used on XRD data analysis (Wiles and Young, 1981). The method consists of
fitting the complete experimental diffraction pattern with a calculated profile and
background. It requires the knowledge of the crystal structure of all phases in the
samples to be analyzed. By using Rietveld method, common problems associated with
quantitative phase analysis by XRD such as peak overlapping and preferred
orientation can be minimized (Scrivenera et al, 2004).
Table 2-3 presents XRD powder patterns of a typical Portland cement (Taylor, 1997).
It can be seen that alite (A) has some reasonably strong peaks at 29.4° 2θ) (I = 60) and
51.7°/51.8° (2θ) (I = 33-35) which do not overlap with those from other phases. For
belite (B), there is no strong distinguishable peak that does not overlap with others.
The peak at 29.4° was suitable to identify Alite in cements and cement pastes. The
51.7°/51.8° peak can be used to identify alite phase when there is a relative high
quantity in a sample. According to Taylor (1997), When a cement paste sample is 28-
day and older, care is needed to avoid errors by using the 51.7°/51.8° peak.
2.8.3 Thermogravimetric Analysis (TG)
In thermogravimetric analysis, the mass changes due to dehydration or decomposition
of compounds are determined as the sample is heated at a uniform rate to high
temperatures. By determining the mass loss at a given temperature range where a
material dehydrates or decomposes, the quantity of a component in the material
68
corresponding to the temperatures can be determined.
For a typical TG curve of a cement paste, the first mass loss, around 100-200 °C, is
mainly due to the dehydration of C-S-H and ettringite. The second major mass loss is
often observed at 450-550 °C which corresponds to the dehydration of CH. The third
mass loss is sometimes observed at 700-900 °C, corresponding to the decomposition
of calcium carbonate. The calcium carbonate can originate from Portland cements due
to the addition of limestone powder or from the carbonation of cement paste or a
combination of the two. Table 2-4 summarizes the temperature ranges in which
various reactions take place in cement paste samples.
69
Table 2-1 Classification of Pores (information summarized from Mindess et al, 2003)
Table 2-2 Solvents and subsequent drying conditions used in solvent exchange
Subsequent drying
Authors (Year of Publication) Organic liquid used
conditions
Taylor and Turner (1987) /
acetone and diethyl ether(#) -
Rickert and Thielen (2004)
Vacuum dried at room
Ftikos and Philippou (1990) / temperature for 24h /
acetone and diethyl ether
Lilkov et al (1997) Vacuum Oven dried at
105°C for 3h
Parrott et al (1990) AR Grade methanol -
Marchand (1993) 1)isopropanol 2)methanol -
Gu et al (1994) / Oven dried at 105 °C for
acetone
Gruskovnjak et al (2006) 24h / Oven dried at 40 °C
ethanol and diethyl ether
Chotard et al (2001) -
(1:1 by volume)
Peschard et al (2004) &
ethanol -
Govin et al (2006)
Note: - means unknown or not mentioned by the authors
#
Authors may have used the synonyms of diethyl ether (ether or ethyl ether).
70
Table 2-3 XRD powder pattern of a typical Portland cement (Taylor, 1997)
2θ° d (nm) Ipk Phases 2θ° d (nm) Ipk Phases

11.7 0.756 5 G 36.7 0.2449 6 A
12.1 0.731 6 F 37.4 0.2404 2 B
14.9 0.595 6 A 38.8 0.2321 12 A
20.7 0.429 7 G 39.5 0.2281 5 B
21.9 0.406 2 Al 41.3 0.2186 41 A, B
23 0.3867 7 A 41.6 0.2171 16 A, B
23.4 0.3802 3 B 44.1 0.2053 6 F
24.4 0.3648 3 F 44.5 0.2036 3 B
25.3 0.3520 4 A 44.7 0.2027 2 B
26.4 0.3376 2 B 45.8 0.1981 10 A, B
27.6 0.3232 2 B, A 47 0.1933 11 A
28.1 0.3175 4 A, B 47.4 0.1918 8 F
29.1 0.3069 5 G 47.8 0.1903 7 Al
29.4 0.3038 60 A 49.9 0.1828 5 A, F
30.1 0.2969 19 A 51.7 0.1768 33 A
31.1 0.2876 4 B, G 51.8 0.1765 35 A
32.2 0.2780 100 A, B, F 56 0.1642 2 A
2.6 0.2747 85 A, B 56.6 0.1626 18 A, B
33.2 0.2698 40 Al, A 58.7 0.1573 3 B, F
33.9 0.2644 23 F 59.4 0.1555 3 Al
34.4 0.2607 83 A, B 59.9 0.1544 6 A
Note: CuKα radiation; 2θ = diffraction angle; d = lattice parameter;
Ipk=relative peak intensity; A = Alite, C3S; B = Belite, C2S; Al = Aluminate,
C3A; F = Ferrite, C4AF; G = Gypsum; phases are given in decending order of
their major peak contributions.
Table 2-4 Summary of a typical cement paste TG graph
Authors, Year of Publication Temperature Observations

the evaporable water and part of the
Alarcon-Ruiz et al, 2005 30–105 °C
bound water escape
decomposition of gypsum and
Zhou and Glasser, 2001 110–170 °C
ettringite
Ramachandran and removal of loosely bound water and
< 200 °C
Beaudoin, 1999 firmly held water from C-S-H gel #
Khoury, 1992 180–300 °C the loss of bound water from C-S-H
General understanding 450–550 °C decomposition of calcium hydroxide
Grattan-Bellew, 1996 700–900°C decomposition of calcium carbonate
#
Note: DTA (differentitial thermal analysis) technique was used.
71
Fig. 2-1 (a) SMF condensate, (b) SNF condensate, (c) Repeating unit of
lignosulphonate (LS) molecule (d) Molecular structure of polycarboxylate
(References: (c), Hewlett, 1998; (a, b, d), Borregaard admixture handbook, 2006)
Fig. 2-2 (a) Flocculation of cement particles resulting trapped water (b)
Deflocculation of cement particles upon adsorption of water reducing admixtures
(Law, 2004)
72
Fig. 2-3 Repulsion of cement particles by (a) electrostatic repulsion

(b) steric hindrance (Ramachandran et al, 1998)
Fig. 2-4 Rate of heat evolution during hydration of Portland cement (Mindess et al,
2003)
73
Fig. 2-5 Structure of cement pastes (Illston and Domone, 2001)
Fig. 2-6 Effect of water, water-reducing and air-entraining admixtures

on rheological behaviors of concrete (adapted from Gjørv, 1994)
74
0.20
0.18
Cumulative Intrusion (ml/g)

0.16
Intrusion
0.14 dv/d(lnd)
0.12
0.10 dc
0.08
0.06
0.04
0.02
0.00 dt
0.001 0.01 0.1 1 10 100 1000
µm)
Pore Diameter (µ
Fig. 2-7 Critical pore and threshold pore diameters of MIP analysis
Fig. 2-8 Comparison of MIP and image analysis pore size distribution for the same
mix at 28 days with w/c = 0.40 cement paste (Diamond and Leeman, 1995)
75
Chapter 3 Experimental Details
3.1 Introduction
In the first part of this chapter, details of materials used in this project are described,
including but not limited to chemical, mineral compositions and physical properties of
cement, and the natures of various water reducing admixtures. Secondly, mix
proportions of cement paste and mortar are tabulated. Procedures of mix preparation
are also outlined. Finally, various test methods to achieve different objectives are
presented.
3.2 Materials
The materials used for all the experiments in this research project consist of cement,
water and fine aggregates, and six different water reducing admixtures (two regular
WRAs and four superplasticizers).
3.2.1 Cement and Water
Ordinary Portland cement (OPC) of ASTM Type I conforming to ASTM C150-02
requirements was used in the project. Table 3-1 summarizes its physical properties
and chemical and mineral composition. The chemical composition was determined by
76
ARL 9800 XP Sequential X-ray fluorescence spectroscopy (XRF), and oxide content
was calculated.
Deionized water, prepared by Barnstead Deionizer, was used for mixing cement
pastes. Normal tap water was used for mixing mortars.
3.2.2 Aggregates
Fine aggregate (sand) used in this project met the requirements of ASTM C136 -01,
and its grading curve is shown in Fig. 3-1. The fine aggregate sieve analysis was
conducted in accordance with ASTM C136-01 and the result is presented in Table 3-2,
together with the specific gravity and water absorption of the sand. The specific
gravity and absorption capacity of fine aggregate was determined according to ASTM
C128-97.
3.2.3 Water Reducing Admixtures
Six different admixtures including two regular WRAs and four superplasticizers were
investigated in this research project. Among these six admixtures, one was
polycarboxylate based (PCE), one was naphthalene based (SNF), and the other four
were lignosulphonate based (LS); and their characteristics are summarized in Table 3-
3. Polycarboxylate based admixture was obtained as solution with a concentration of
39.3%. The rest of the admixtures were initially in powder form and solutions were
made in laboratory.
The PCE and SNF based superplasticizers conform to requirements of ASTM C494
77
Type F high- range water-reducing admixtures (see Table 1-2). Lignosulphonate
admixture PLS is a highly purified sodium lignosulphonate product made from
modified softwood lignosulphonate. It has less than 0.5% of reducing substances.
Admixture UNA is a high molecular weight modified sodium lignosulphonate. It
contains approximately 1% of reducing substances, and has moderate set retardation.
Both the PLS and UNA admixtures can be used as ASTM Type F/G admixtures,
according to manufacturer.
Admixture BCS is a calcium lignosulphonate produced from hardwood. It contains
approximately 3% reducing substances. Admixture BCA is a calcium lignosulphonate
produced by fermentation of calcium lignosulphonate from softwood and contains
approximately 7% reducing substances. The raw material used for the production of
BCA is the same as that for the production of admixture UNA. Both BCS and BCA
admixtures are Type D water-reducing and retarding admixture.
For convenience and consistency, the powder admixtures were made into solution
before being added into mortar or cement paste. All powder admixtures were
dissolved in water to produce 30% solutions as recommended by the manufacturers
except for the PLS admixture. For the ease of handling, a solution of PLS admixture
with a concentration of 28% was made instead, due to the higher viscosity of PLS
solution at higher concentration.
The admixture powders were first dried in a 105 °C oven and cooled down to room
temperature in a desiccator. The admixture powder was then slowly added into
deionised water pre-heated to 50 °C, and stirred constantly for about 1 hour by a
78
magnetic stirrer to aid the dissolution of powder admixture until a uniform solution
was obtained. After admixture powder had been fully dissolved, tributylphosphate
(TBP, commonly known as defoamer) was added while stirring, at 0.5% by mass of
admixture powder, to the solution to control the air that may be entrained in pastes
and mortars. The admixture solutions were bottled with a tight cap and kept in a
refrigerator. Not to complicate the admixture solutions, no biocide was used to
lengthen the shelf life of the prepared admixture solutions. Instead, admixture
solutions were freshly made and kept in the refrigerator for no more than one month.
3.3 Mix Proportions of Cement Pastes and Mortars
Mix proportion of the cement pastes and mortars used for various tests was designed
to have similar workability. All the mixtures have the same proportions of cement,
water, and sand where used. Dosage of the admixtures was varied (Table 3-4) to
achieve yield stress of mortar at 75 ± 15 Pa. Based on tests on concrete, this yield
stress level of mortar will produce concrete with a slump of approximately 100 mm.
Two w/c ratios of 0.34 and 0.40 were used. For the w/c of 0.40, the effect of the six
admixtures were evaluated, whereas for the w/c of 0.34, only the effect of the four
superplasticizers were evaluated as the target yield stress was not achievable with the
regular water reducing admixtures at that low w/c. The air content of the concrete
measured right after mixing according to ASTM C138 ranged from 1.5 to 3%.
It is noted that the sand used in the project was oven dried to better control the
consistency of the mixtures. It is unlikely that full absorption will be achieved within
the time of mixing, but as the sand content is kept constant, the effective w/c ratio
remains similar for all mixes. The batching weight presented in Table 3-4 was in
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saturated surface dry (SSD) condition. The water was compensated for the dry sand
based on its water absorption capacity of 1.3%.
Two mortar/cement paste mixtures with the same w/c ratios as those with the
admixtures were included as controls for comparison in experiments to determine the
effect of the admixtures on cement hydration. Without water reducing admixtures or
superplasticizers, however, these two control mixtures would have lower workability
compared with the corresponding cement pastes or mortars with the admixtures.
Therefore, no control cement pastes and mortars were used for evaluation of
workability, setting time, pore structure, and compressive strength of the materials as
these properties are affected by their initial workability.
3.4 Preparations for Cement Pastes and Mortars
Mortars and cement pastes were cast in the procedures described in Table 3-5.
3.4.1 Preparation for Cement Pastes
Various test methods to determine degree of cement hydration and pore structure
demand very careful sample preparations. The methods used for monitoring the
cement hydration include X-ray diffraction, thermogravimetry, and non-evaporable
water content. The pore structure was determined by MIP test. Care should be
particularly taken on XRD and TG samples since the studies are related to curing ages
and samples may be carbonated if exposed to atmosphere for an extended period of
time.
80
The above mentioned tests to monitor the cement hydration were conducted at various
curing ages of 2, 4, 8, 12 hours and 1, 3, 7, 28, 91 days. The MIP tests were conducted
on cement pastes of 1 day and older. The procedure of cement paste sample
preparation comprises the following steps:
1. Pastes were cast in a 5-quart (4.7-liter) Hobart mixer, according to the
procedure described in Table 3-5. The amount of cement used for each mix
was 1000 g.
2. After mixing, small plastic bottles were filled with the cement pastes. Bottled
pastes were sealed with preheated wax and were capped to minimize possible
carbonation.
3. Sealed sample pastes were rotated for the first 12 hours to minimise
segregation/bleeding and to ensure homogeneity of the cement paste samples.
After that, the sample bottles were stored in the sealed condition at about 30
°C for curing.
4. For samples cured up to 12 hours, cement hydration was stopped by acetone
(solvent exchange) thoroughly for 3 – 5 times, and the samples were ground at
the same time. With great rate of evaporation and the help of a cold-wind hair
drier, acetone took water away from sample fairly quickly and most samples
were surface dry – the color changed from dark to grayish white - within about
one hour. Samples were further ground till the particles were not coarser than
150 µm, and oven-dried at 105 °C for 2 to 4 hours before being stored in
capped glass bottles in a desiccator.
5. For samples that were 1 day and older, the cement pastes were removed from
the bottles at specified ages. Top and bottom part of the paste together with
that in contact with inner wall of the bottle were removed by a chisel. The
81
remaining sample was crushed into small pieces, and the samples were divided
into three parts for the tests of
a. Thermogravimetry/X-ray diffraction: samples were crushed and ground
into powder so that particle sizes were not larger than 150 µm;
b. Non-evaporable water: samples were not larger than 2-3 mm;
c. Mercury intrusion porosimetry: samples were carefully chiseled into
pieces of approximately 10 mm x 5 mm x 2 mm.
6. Samples in 5) were then stored in a vacuum oven at 60 °C till constant weight
(usually about 1 week). The acceleration of cement hydration is believed to be
minimal when the relative humidity is way below 80%, at which hydration
will slow down significantly (Mindess et al, 2003). Finally they were bottled
and stored in the desiccators.
It should be noted that grinding small samples into fine powder was not that simple.
Ball mill grinding is not recommended due to the consideration of contamination and
partial decomposition of hydrates by the heat generated from high-speed grinding. In
this study, the samples were first crushed into small pieces, and then manually ground
in an agate mortar.
3.4.2 Preparation for Mortars
Mortars were mixed in a 30-quart (28.4-liter) Hobart mixer. Each casting had the
same batch weight and thus roughly the same batch volume was produced. The
mortars were used for the tests on yield stress, plastic viscosity, flow table value, and
setting times of fresh mortars, and compressive strength of hardened mortars.
82
3.5 Test Methods and Analyses
Cement hydration is a chemical reaction and it is exothermal. Therefore, it can be
evaluated from several different angles. First, the difference in original and remaining
reactants gives the amount of cement compounds (C3S, C2S) reacted. The cement
compounds can be monitored by XRD techniques. Second, the amount of hydration
products (CH, CSH) qualitatively indicates that the reactions, although clinker
reactions are extremely complex. The analytical techniques and equipments used in
this study have been summarized in Table 3-6.
3.5.1 Heat Evolution of Cement Hydration
Heat of cement hydration was directly measured using a TAM Air isothermal
calorimeter (Fig. 3-2) by monitoring the heat generated from cement hydration for
cement pastes with and without the chemical admixtures. Heat generated from cement
pastes with w/c of 0.34 and 0.40 were determined.
There were eight channels in the TAM Air calorimeter, and each channel was
constructed in twin configuration with one side for the sample and the other side for
an inert reference. In the current project, water was used as reference material. During
experiment, both the sample and reference materials were held in 20 ml sealed
ampoules. Each side of the calorimetric channel was then covered with a removable
cylindrical metal heat sink plug to prevent thermal disturbance from the circulating air.
The twin configuration of the sample and reference within a channel allowed the heat
flow from the active sample to be compared directly with the heat flow from the inert
reference. The voltage difference was a quantitative expression of the overall rate of
83
heat production in the sample. The rate of heat production, or heat flux, is defined as
the rate by which heat evolved by the sample. From the power output data and with
some appropriate conversions (Eqs. 3-1 and 3-2), the amount of heat produced in the
sample (energy output) could then be derived.
The data extracted from the calorimeter was power output (rate of heat evolution or
heat flux) generated from the cement hydration process. The differences in the sample
mass between the samples can be accounted for by normalizing the power output
generated from each channel with its respective sample mass. For every data point,
the normalized power output was calculated according to Eq. 3-1.
Pn = Po m (3-1)
where Pn = normalized power output (rate of heat evolution) obtained from cement
hydration, mW/g;
Po = power output from cement hydration obtained from calorimeter, mW; and
m = sample mass of the respective channel measured, g.
The energy curve represents the amount of heat liberated from the cement hydration
per gram of the sample. For every normalized data point, the energy conversion at that
point was calculated as Eq. 3-2.
E = Pn ⋅ t 1000 (3-2)
where E = normalized energy output (heat evolution) from cement hydration, J;
84
Pn = normalized power output from cement hydration, mW/g; and
t = time interval, seconds, in this case, t = 5 min = 300s.
The isothermal calorimeter was calibrated and conditioned at 30 °C for a day before
experiments and the amplifier range was set up to 600 mW. Before the experiments,
all the materials, mixing utensils, and sample ampoules were pre-conditioned in a 30
°C oven for at least 12 hours. The preconditioned cement was added into deionised
water, and hand mixed for about 1 minute. The cement paste sample of 10 ± 2 g
(sample masses were recorded) was then transferred into the sample ampoule. After
capping, the sample and reference ampoules were inserted into the calorimeter. The
calorimeter started to record heat 10 minutes after the cement was in contact with
water. Because of this procedure, the heat generated initially during mixing of the
cement and water was not captured.
The setting file defined the sampling interval and maximum number of samples
recorded at a specific temperature. In this project, the sampling interval was set at 5
minutes and the heat generated from the samples was monitored continuously for 3
days. It should be noted that machine sensitivity often limits the measurement to
about 7 days duration, beyond that the signal becomes virtually indistinguishable from
the background noise (NIST, 1996, online access 20074). Due to the background noise
and time required for the inserted sample ampoules to reach equilibrium with the
reference, the data extracted for the first 10 minutes was not used. In other words,
only the data collected 20 minutes after the cement in contact with water was used for
analysis.
4
http://ciks.cbt.nist.gov/bentz/phpct/database/thermal.html
85
3.5.2 Degree of Cement Hydration
There are many ways to determine the degree of cement hydration, either directly or
indirectly. The tests employed in this study were three commonly used ones, namely,
XRD analysis, TG analysis and non-evaporable water content. The XRD method was
used to monitor the reduction of cement clinkers such as C3S with the progress of
cement hydration. The TG method was used to monitor the increase in the calcium
hydroxide with the cement hydration. The non-evaporate water was used to monitor
the increase in the water associated with the formation of hydration products such as
calcium silicate hydrates and calcium hydroxide.
3.5.2.1 X-ray Diffraction (XRD)
The X-ray diffraction analyses were carried out using Shimadzu XRD-6000
o
diffractometer (Fig. 3-3) with Cu Kα ( λ = 1.54056 A ) radiation at 40 kV and 30 mA.
The XRD scan was between 5° to 60° (2θ) with a scan speed of 0.5°/min (0.02° step
and 2.4 seconds preset time or counting time). The range of 2θ was selected because it
contained major peaks of interested phases, including possible ettringite AFt and
monosulfoaluminate AFm (Yousuf et al, 1995; Williams et al, 2003). The X-ray
diffractometer was calibrated using 99.99% pure silicon. It was operated under the
following slit specifications: divergence slit 1°, scatter slit 1° and receiving slit 0.3
mm. Each sample was tested for three times consecutively and the average peak
intensities were taken for further analysis.
The results from XRD analyses were presented in terms of the intensity ratios
between the phases of interest and the reference material anatase (TiO2, 2θ = 25.3 o),
86
which was 10% by mass blended in the cement paste samples. The ratios indicate the
relative but not the actual amount of the phases of interest.
To link the X-ray diffraction peak intensity ratios to the actual C3S content in the
sample materials, a calibration chart of C3S content in materials of interest (Fig. 3-4)
was produced using the cement (Table 3-1) and mixtures of the cement with sodium
carbonate (Na2CO3, which has no overlap peaks with the cement). The C3S peak at 2θ
= 29.4 o was used for this calibration curve. The mixtures of the cement with sodium
carbonate were used so that the calibration chart would cover a wider range of C3S
content (Table 3-7) in the sample materials.
Seven data points were collected from the cement and its mixtures with sodium
carbonates. They were well spread across the range concerned. A linear function,
which exhibits the relationship between the XRD intensity ratio of C3S and the
reference anatase and the actual amount of C3S presented in the samples, is shown in
Eq. 3-3.
(I )
C3 S 2θ = 29.4°
C 3 S % = 68.575 ⋅ (3-3)
(I anatase )2θ = 25.3°
With the calibration chart, the approximate C3S content in the sample can be
calculated according to the XRD peak intensity. It is recognized that Bogue
calculation of C3S content is approximate, and possible errors may be introduced by
using this calibration chart. Also, XRD results have high variability depending on
particle size and sample packing. Nevertheless, this may serve as semi-quantitative
analyses for relative comparison.
87
3.5.2.2 Thermogravimety Analysis (TG)
Thermogravimetric analysis is used to monitor the increase in calcium hydroxide with
the progress of cement hydration. In a TGA (Fig. 3-5), the weight loss of a sample is
recorded while it is being heated at a uniform rate in a nitrogen environment. The
weight loss over specific temperature ranges provides information on the dehydration,
decomposition or phase changes of samples. Although the sample may be
decomposed at a temperature which is the characteristic of the compound, the shape
of the decomposition curve may be affected by many factors. Haines (2002)
recommended carrying out experiments with high thermal capacity furnaces, with
small and lightweight crucibles and using a low rate of heating, and small sample
sizes.
Calcium hydroxide decomposes at around 450 – 550 oC according to the chemical
reaction Eq. 3-4.
−
o
Ca(OH) 2 450 → CaO + H 2 O(g)
550 C
(3-4)
By determining the mass loss due to the loss of water in the decomposition of CH, the
amount of the CH and thus the degree of cement hydration can be determined
(Ramachandran, 2003).
Carbonation is a chemical reaction shown in Eq. 3-5.
Ca(OH) 2 + CO 2 → CaCO 3 + H 2 O (3-5)
The effect of carbonation on the amount of CH can be determined from the amount of
88
carbon dioxide given off at higher temperature according to Eq. 3-6.
o
−
CaCO 3 700 → CaO + CO 2
900 C
(3-6)
Samples used in the TG test were prepared as described earlier. The TG was carried
out using a Linseis L81-II thermogravimetric analyzer. For each test, approximately
100 mg of powdered sample was heated from room temperature to 950 oC at a rate of
10 oC/min in a nitrogen environment. A ‘‘blank test’’ (calibration without specimen)
showed that a fictitious mass gain (0.001 mg/°C) was recorded by the apparatus
during heating. It was recorded as a “zero” file. The final results presented in the
following chapter take this into account.
Figure 3-4 shows the calculation of mass loss from a TG curve (Haines, 2002). First,
two tangent lines corresponding to the initial and final baselines were drawn. Second,
after finding the largest slope between the temperatures before and after the mass loss,
a tangent line was drawn corresponding to this slope. This intersected with the earlier
two tangent lines. The difference between the two intersections was used as the mass
loss from the decomposition of a particular crystalline matter. It should be noted that
the above process is subjective and depends on the experience of the experimentalist
(Williams et al, 2003).
3.5.2.3 Non-Evaporable Water (NEW) Content
Non-evaporable water in cement paste samples includes chemically combined water
which is associated with hydration products such as CH, C-S-H etc. The NEW was
89
determined by mass loss determined by (1) igniting samples in a furnace at 950oC and
(2) thermalgravemetric analysis.
In the first method, clean crucibles weighing around 30g were burned in a muffle
furnace (Fig. 3-7) at 950 oC for 2 hours and left in the furnace till the temperature
went down to around 120 oC. The crucibles were then cooled to room temperature in a
desiccator. Burning the empty crucibles and handling them with tongs were to
minimize errors - some organisms that might be stuck on the crucible surfaces.
Approximately 50 g representative dried sample was weighed in the burned crucible.
The crucible containing the sample was ignited at 950 °C in the furnace for 3 hours.
After it was cooled down to around 120 oC, the crucible containing the sample was
placed in the dessicator and cooled to room temperature. The mass of the samples was
determined again. The mass loss was calculated from the difference before and after
the ignition. The non-evaporable water content was calculated according to Eq. 3-7.
W1 − W2
Wn = − LOI (3-7)
W1
where Wn = non-evaporable water content per gram of dried cement paste sample;
W1 = mass of the sample before the ignition;
W2 = mass of the sample after the ignition; and
LOI = loss on ignition of anhydrated cement in one gram of dried paste sample.
The TG curve provides mass loss during the heating, which is also associated with the
loss of water from the dehydration and decomposition of the hydration products. In
90
this thesis, the NEW determined from TG is referred to as NEW from TG, whereas the
NEW determined from the furnace ignition is referred to as NEW from furnace.
3.5.3 Workability Retention of Mortars
The workability retention of fresh mortars with and without WRAs was monitored by
the yield stress, plastic viscosity, and flow value. The initial test started at 10 minutes
from the addition of water into the mix, followed by tests at 30 and 60 minutes. The
flow table value was determined 2-3 minutes after the determination of the yield
stress and plastic viscosity.
The rheometer used to determine the yield stress and plastic viscosity of the mortars
in this study was a coaxial cylinder rheometer, ConTec BML Viscometer 3 (Fig. 3-8).
Sample container is placed on the plate during experiment and acts as the outer
cylinder. The inner cylinder has three components. The upper unit measures the torque.
The lower unit is used to eliminate the shear influence from the bottom of the outer
cylinder. The top ring is to keep a constant height where the torque is measured. The
ribs of both inner and outer cylinders are to reduce the tendency of slippage.
During the test, the outer cylinder rotates, at different rotation velocities N (angular
velocities ω 0 = 2π ⋅ N ). Torque (T) required to keep the inner cylinder stationary is
measured and registered.
Once torque-rotation speed relation (Eq. 3-8) is obtained from T-N curve, Reiner-
Riwlin Equation (Eq. 3-9) (Reiner, 1949) for coaxial cylinder viscometer can be used
91
to determine the yield stress τo (Eq. 3-10) and plastic viscosity µ (Eq. 3-11) for
Bingham Model. The effective shear rate γ& , which varies with the position r
measured from the center of the cylinders in the annulus, may be calculated from τ 0
and µ (Eq. 3-12). Assuming no plug flow occurs, Eqs. 3-9 and 3-12 may be combined
to yield Eq. 3-13. Figure 3-9 illustrates the transformation from torque-rotation speed
to shear stress-shear rate.
Equations 3-8 to 3-12 are summarized as follows (note that the symbols used in Eqs.
3-10 to 3-12 are the same as the ones defined in Eqs. 3-8 and 3-9):
T = g + hN (3-8)
where T = torque, Nm;
N = rotation speed, rps;
g = flow resistance, Nm; and
h = relative viscosity, Nm.s.
 Ro 
τ 0 ln  + ω 0 µ
R
 i
T = 4πH (3-9)
1 1
2
− 2
Ri Ro
where H = constant height between inner cylinder bottom and top ring bottom, m;
R0 = radius of the outer cylinder, m;
Ri = radius of the inner cylinder, m; and
ω0 = angular velocity = 2πN, rps.
92
 1 1 
 − 2
 Ri2
R o 
τ0 =  g (3-10)
 Ro 
4πH ln 
 Ri 
 1 1 
 − 2
 Ri2
R o 
µ= h (3-11)
8π 2 H
1 T 
γ& =  −τ 0  (3-12)
µ  2π ⋅ r H
2

−1
2  1 1   τ 0  Ro   τ
γ& = 2  2 − 2  ln  + ω 0  − 0 (3-13)
r R Ro  µ R   µ
 i   i 
The parameters used in the test (Table 3-8) were selected to produce smoothly the T-N
curve (Wallevik, 2003). Assume the position “r” in Eq. 3-13 equals the radius of the
inner cylinder; the shear rates experienced by the inner cylinder were in the range of 5
- 50 s-1. The rotation speed was from 0.5 rps to 0.1 rps, which means that yield stress
and plastic viscosity were determined from a ramp down T-N curve (see Fig. 3-10).
The rheological properties of cement paste, mortar, and concrete are strongly
dependent on the shear history (Wallevik, 2003). The mixing procedures described in
Table 3-5 were closely followed. Between any two tests using the BML viscometer,
the mortar mixture was left in the Hobart mixer bowl and was covered with a plastic
sheet to minimize water loss from evaporation. Before testing, the mortar was pre-
sheared at Speed 1 (139 rpm) for one minute to homogenize the samples.
Flow value of the same mortar was determined (see Fig. 3-11) according to ASTM
93
C230M-98 except that the value was measured after 10 drops instead of the standard
25 drops of the plate with the sample mortar. It was done to avoid overflow of the
mortars from the plate. The plate had a diameter of 250 mm. The flow cone used had
top diameter of 70 mm and bottom 100mm.
3.5.4 Setting Time of Mortars
The most widely used method for determining setting time of concrete (Fig. 3-12) is
ASTM C403 – Standard test method for time of setting of concrete by penetration
resistance (Lamond and Pielert, 2006). As the title suggests, the setting times are
determined from the changes in the penetration resistance of a sample as a function of
time. A sample of mortar is obtained either by sieving the fresh concrete on a 4.75 mm
sieve to remove the coarse aggregates or by preparing the mortar directly (Lamond
and Pielert, 2006). In this project, mortars were prepared directly to determine the
setting times. The sample mortar was placed into a 150-mm cubic steel mould and
stored in a room with a constant temperature at 30 °C. The mortars were covered with
a plastic sheet to prevent moisture loss, and excessive bleeding water on the top
surface was drawn carefully into a disposable syringe.
According to the ASTM standard, the initial and final setting times are defined when
the penetration resistance reached 3.5 MPa (500 psi) and 27.6 MPa (4000 psi),
respectively.
3.5.5 Pore Structures of Pastes
Mercury intrusion porosimetry test was used to determine total porosity and pore size
94
distribution of the cement pastes at 1, 3, 7, 28 and 91 days. The test was performed on
a Micromeritics Autopore WIN9400 Series mercury porosimeter (Fig. 3-13) with a
maximum pressure of 412.5 MPa. The minimum pore access diameter reached under
the maximum pressure was about 3.8 nm assuming a contact angle of 141.3° and a
mercury surface tension of 0.485 N/m (Ramachandran and Beaudoin, 1999)
Approximately 1.5 grams of hardened cement paste samples (2-3 pieces) were used
for each test. One MIP test was conducted on each sample. For each series of the paste
samples, one or two testing ages were randomly selected and samples were repeated
to ensure the repeatability of the test.
3.5.6 Compressive Strength of Mortars
The compressive strength of the mortars was determined at the ages of 1, 3, 7, 28 and
91 days in accordance with ASTM C109M. For each mortar mixture, fifteen 50 mm
cubes were cast, i.e. three cubes for each testing age. The cubes were covered with
plastic sheet and left in laboratory for the first 24 hours. They were demoulded after
that and cured in a fog room with a temperature of about 28 °C till their testing ages.
The loading rate employed for the test (Fig. 3-14) was 1670 N/s (100 kN/min), which
is within the range of 900 to 1800 N/s specified by the ASTM standard.
95
Table 3-1 Chemical & Mineral Compositions and Physical Properties of Cement Used
Properties ASTM C150

Initial Setting Time, min 180 ≥45
Physical Properties
Final Setting Time, min 210 ≤375
Blaine Fineness, m2/kg 363 ≥280
Calcium Oxide, CaO 63.19
Silica, SiO2 20.26
Aluminium Oxide, Al2O3 4.31
Iron Oxide, Fe2O3 3.61
Magnesia, MgO 3.25 ≤6.0
Chemical
Sodium Oxide, Na2O 0.25
Composition*, %
Potassium Oxide, K2O 0.30
Sulphuric Anhydride as SO3 2.06
Loss on Ignition (LOI) 2.53 ≤3.0
Insoluble Residue 0.26 ≤0.75
Total Alkalinity as Na2O+0.658K2O 0.35 ≤0.60
Mineral Tricalcium Silicate, C3S 63.2
Composition Dicalcium Silicate, C2S 10.4
According to Tricalcium Aluminate, C3A 5.3
Bogue Calculation,
% Tetracalcium Alumninoferrite, C4AF 11.0
* The chemical composition was determined by ARL 9800 XP Sequential X-ray
fluorescence spectroscopy (XRF), and oxide content was calculated.
Table 3-2 Physical properties and sieve analysis of sand
Sieve Size % retained by mass

4.75 mm 2.6
2.36 mm 11.2
1.18 mm 34.9
600 µm 72.4
300 µm 92.2
150 µm 98.5
Fineness Modulus 3.12
Absorption Capacity 1.30%
Specific gravity, SSD* 2.65
SSD* = saturated surface dry
96
Table 3-3 Characteristics of admixtures used in the project

Soluble Molecular Molecular
Reducing
Water SO4, % of Weight Weight
Type Notation substances,
Reduction dry Distribution, Distribution,
%
admixture Mw Mn
&
polycarboxylate PCE > 30% 0 N. A. N. A. N. A.
naphthalene SNF 15 ~ 25% 0 N. A. N. A. N. A.
purified
PLS 25% 0.5 0.2 41800 10650
lignosulphonate
modified
UNA 15 ~ 20% 1 0.7 47800 5800
lignosulphonate
Ca-
BCS 8 ~ 10% 3 0.2 5700 1600
lignosulphonate
Ca-
BCA 8 ~ 10% 7 0.5 21100 3050
lignosulphonate
&
N. A. = not available
Table 3-4 Mix proportion of mortars to achieve an initial yield stress of 75 ± 15 Pa

Sand
Concentr- Dosage, % Cement, Total
w/c Mix Admixture (SSD),
ation, % (sbwc^) kg water*, kg
kg
R# - - -
A PCE 39.3 0.13
B SNF 30 0.30
0.40 C PLS 28 0.28 8.50 3.400 14.97
D UNA 30 0.35
E BCS 30 0.60$
F BCA 30 0.45
&
V - - -
I PCE 39.3 0.17
0.34 II SNF 30 0.39 9.60 3.264 14.91
III PLS 28 0.35
IV UNA 30 0.45
R# = Control mix for w/c = 0.40 as reference
V& = Control mix for w/c = 0.34 as reference
sbwc^ = solid by weight of cement, %
0.60$ = maximum recommended dosage used, since even at 1% dosage it failed to
achieve the target yield stress
Total water* includes the water presented in admixture solutions
97
Table 3-5 Mix procedures of mortars and pastes
Time, Action
min Mortar (Speed 1 at 139rpm) Paste (Speed 1 at 139rpm)
dry mix of cement,
-1 dry mix of cement and sand
pour admixture solution into water
0 addition of water addition of water and admixture
1 addition of admixture -
3 idle for one minute to scrape deposit on the mixer walls
4 mix for another 1 min
5 start test seal in plastic bottles until specific ages
Table 3-6 Analytical techniques and equipment used in this study
Properties of paste or mortar investigated Techniques and equipment used

TAM Air Isothermal Calorimeter
Heat evolution
(multi-channel)
Calcium hydroxide, Shimadzu X-ray diffractometer (XRD-
Tricalcium / dicalcium silicate content 6000)
Calcium hydroxide and
Linseis L81-II Thermogravimetry (TG)
Non-evaporable water content
Mass loss at a high temperature of 950 oC
Non-evaporable water content
(Lenton Furnace)
Yield stress and plastic viscosity
ConTec BML Viscometer 3 (coaxial)
change with time
Flow value change with time Motorized flow table (H-3624)
Setting times Humboldt Penetrometer (H-4133)
Mercury intrusion porosimetry (MIP),
Porosity, pore structure
Micromeritics Autopore WIN9400 Series
Compressive strength Automax5 automatic compression tester
98
Table 3-7 Seven samples used to produce C3S calibration chart
% of the cement 100 95 80 65 50 35 20
% of Na2CO3 0 5 20 35 50 65 80
IC3S/ITiO2 (2θ=29.4°)* 0.96 0.84 0.75 0.60 0.44 0.31 0.18
C3S in sample 63.2** 60.0 50.6 41.1 31.6 22.1 12.6

* determined by XRD
** based on Bogue calculation
Table 3-8 Process parameters set on BML Viscometer 3 for determination of the yield
stress and plastic viscosity
Cylinder dimensions Run time Parameters

Height of inner cylinder, m 0.115 Max. rotation velocity, rps# 0.5
Radius of inner cylinder, Ri, m 0.085 Min. rotation velocity, rps 0.1
Radius of outer cylinder, Ro, m 0.1 No. of T/N points* 10
Beater control Transient interval, sec 2
Beater penetration time, sec 5 Sampling interval, sec 1
Penetration speed, 0.1-1 0.5 No. of sampling points 50
Note: rps# stands for rounds or revolutions per second
T/N point* was the average of the lowest 10 out of the 50 sampling points
99
100
ASTM Lower
90 ASTM Upper
Sand Used
80
70
% Passing by Mass
60
50
40
30
20
10
0
4.75 2.36 1.18 0.6 0.3 0.15
Standard Sieve Size, mm
Fig. 3-1 Grading curve of fine aggregate (sand) used
(a) (b)
Fig. 3-2 (a) Isothermal calorimeter (b) Sample loading and unloading
100
Fig. 3-3 Schematic diagram of an X-ray diffractometer
70
60
C3S % in material of interest
50
40
C3S = 68.575IC3S/Ianatase
2
R = 0.99
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
o
XRD intensity ratio, IC3S @29.4 /Ianatase
Fig. 3-4 Calibration chart of C3S in materials of interest
101
Fig. 3-5 Schematic diagram of a thermogravimeter
Fig. 3-6 Determination of mass loss from a thermogravimetry curve (Haines, 2002)
102
Fig. 3-7 Schematic diagram of a furnace
Fig. 3-8 Schematic diagram of the BML-Viscometer (Source: ConTec Ltd., 2003)
103
(a) (b)
Fig. 3-9 The relation between (a) torque - rotation speed and
(b) shear stress - shear rate (Bingham model)
Fig. 3-10 A typical ramp down T-N curve from test on mortar by BML Viscometer
Fig. 3-11 Schematic diagram of flow table set-up

(http://www.durhamgeo.com/testing/concrete/cement-flowtable.htm)
104
Fig. 3-12 Schematic diagram of a penetrometer
105
Fig. 3-13 Schematic diagram of a mercury intrusion porosimeter
Fig. 3-14 Schematic diagram of a compressive strength tester
106
Chapter 4 Results and Discussion
This chapter presents results and discusses effects of the admixtures on the cement
hydration, workability, setting time, pore structure, and strength development of
cement pastes and mortars. The dosages of the water reducing admixtures and
superplasticizers were determined so that the initial (at 10 min after the cement came
in contact with water) yield stress of the mortars was 75 ± 15 Pa for both w/c ratios of
0.34 and 0.40 with the exception of that with the BCS admixture as it failed to achieve
the target yield stress even though a dosage of 60% more than the maximum
recommended dosage was used. The same dosages of the admixtures based on solid
by weight of cement were correspondingly used for the cement paste mixtures.
Since the setting time (determined by penetration resistance), pore structure, and
compressive strength of the cement pastes and mortars are related to the compaction,
which is influenced by the workability of the cement pastes and mortars, the control
pastes and mortars were not included for comparison in Sections 4.3 – 4.6 as the
target yield stress of mortars could not be achieved without the admixtures.
4.1 Heat Evolution of Cement Hydration
As illustrated in Fig. 2-4, the heat curve of OPC generally exhibits one peak “A”
107
before induction and two peaks “B” and “C” after that. Peak “B” normally
corresponds to C3S hydration and peak “C” to C3A hydration, but they may be
switched depending on the SO3 content in OPC and w/c ratios (Sandberg, 2004).
The SO3 content of the cement used was 2.06%, and the heat curve of the cement
paste with w/c of 0.40 without any admixture was shown in Fig. 4-1. As mentioned
earlier in Chapter 3, Peak “A” was not obtained due to the limitation of the equipment
used. From Fig. 4-1, it can be observed that peak “C” was higher than peak “B”. In
order to confirm that peak “C” was indeed related to C3A reaction, SO3 in terms of
gypsum was increased in the cement paste, to 2.20%, 2.35%, 2.50%, 3.00% and
3.50% by the total weight of cement and additional gypsum. As seen in Fig. 4-1, the
position and magnitude of the peak “B” was relatively unchanged with the increase in
the SO3 content, whereas the peak “C” changed with the increase in the SO3 content,
and eventually flattened. This confirms that the peak “C” was related to C3A reaction.
As shown in Figs. 4-2 and 4-3, all the admixtures, regardless of regular water
reducing admixtures or superplasticizers, retarded cement hydration. However, the
degree of retardation varied with different admixtures. From the peak intensity and
time of peak occurrence in the heat curves, the cement paste mixtures may be
categorized into four groups, (1) control and SNF mixtures (little or no retardation); (2)
Mixture with PCE (weak retardation); (3) Mixtures with lignosulphonate
superplasticizers PLS and UNA (medium retardation) and (4) Mixtures with
lignosulphonate Water reducing admixtures BCS and BCA (strong retardation).
The heat curve of the mixtures with SNF did not differ from the control mixtures
108
significantly at both w/c ratios of 0.34 and 0.40. The hydration was delayed slightly,
shown by a small shift in the heat curves to the right.
For the mixtures with lignosulphonate-based admixtures (PLS, UNA, BCS and BCA),
the peak “C” was not visible in the heat curves shown in Figs 4-2 and 4-3. Although
the soluble SO3 contents in admixtures (Table 3-3) are not the same, the differences
are too small to cause a significant change in the total SO3 content available in the
system. These mixtures also showed reduction in the intensity of the silicate heat
peaks and delayed time of the peaks compared with the control mixtures.
It was observed that the peak intensities of the LS based admixtures were lower than
that of the control and the PCE/SNF superplasticized pastes. Various mechanisms of
set retardation have been proposed, which was summarized in a review paper by Zhor
and Bremner (1999).
1. Hansen (1959) proposed that the adsorption of LS molecules onto the surface of
anhydrated cement created a barrier to cement hydration.
2. Daughterty and Kowalewski (1968) proposed that chelation of functional groups of
admixtures to metal ions could be an important factor in the mechanism of retardation.
3. Watanabe et al (1969) proposed that the precipitation of calcium salts on
anhydrated cement caused the retardation.
4. In a review paper, Young (1972) presented a nucleation model which was proposed
by Greening. He reported that the nucleation of crystalline CH was inhibited by
soluble silica and thus proposed that this inhibition was a self-retarding feature of C3S
hydration. This principle was later supported by Berger and McGregor (1972). In their
109
paper, it was found that the morphology and number of CH crystals was clearly
influenced by LS admixtures.
5. Young (1972) further proposed a possible mechanism consolidating the earlier
proposed mechanisms.
From the results, it is unlikely to be the adsorption or precipitation mechanisms alone
as neither could explain the initial acceleration activity that occurred during the first
hour for these two admixtures. The observation probably can be explained by the
consolidated mechanism with a combination of (1) to (4). After the initial activity, the
admixtures were incorporated into the structures of the hydrates and removed from
the solution and the retardation of C3S predominates, which was governed by the
effect of admixture on CH nucleation. Based on the observation, it is quite reasonable
to attribute the peak suppression to the LS admixtures. However, the exact interaction
between LS molecules and CH is not clear.
The heat curves of the mixtures with PCE were between those with SNF and LS-
based admixtures.
Comparing the heat curves of the cement pastes with w/c ratios of 0.34 and 0.40, the
control mixture and mixtures with the PCE and SNF admixtures showed both Peaks
“B” and “C”. The two peaks may look quite the same in shape, but differed in the
time of appearance. Summarized in Table 4-1, it is found that for control and SNF,
PCE superplasticized pastes, the durations between the C3S and C3A peaks were
shorter for w/c of 0.34 than that for w/c of 0.40.
110
The length of induction period in the heat curves indicates the degree of retardation.
For both w/c ratios, the induction periods are in the ascending order of CTR < SNF <
PCE < PLS < UNA. For both w/c ratios, it shows that all admixtures delayed cement
hydration and that the four superplasticizers delayed cement hydration in the same
sequence, i.e. SNF < PCE < PLS < UNA. The SNF based SP had the least retardation
while the modified LS based SPs had the most significant retardation on cement
hydration among all the superplasticizers. The two regular WRAs delayed the onset of
acceleration period to as long as about 12 hours. Regardless of w/c ratios, all the LS
based admixtures induced a major reduction in the heat of hydration at an early age.
For w/c ratio of 0.40, their heat evolved had not reached that of the control mixture at
3 days. However, for w/c ratio of 0.34, they caught up with the control mixture after
48 hours and overtook it after that. The retardation effects of the admixtures were also
reflected in the cumulative heat curves shown in Figs. 4-4 and 4-5.
Figures 4-4 and 4-5 show that with the increase in the cement hydration and time, the
difference in the total heat released from the cement pastes with different admixtures
was reduced. Figure 4-4 shows that the differences of total heat evolved from
superplasticized cement pastes decreased with time, being 15.9% and 6.8% at 1 day
and 3 days. A similar trend is seen in Fig. 4-5, where the differences decreased from
54.2% at 1 day down to 12.3% at 3 days. This indicates that the total heat evolutions
for different mixes are getting closer with time, which would be the same eventually,
given the w/c ratio is the same for mixes. According to Ridi et al (2003), water
reducing admixtures only accelerate or delay cement hydration, but they did not
increase or decrease the total cement hydration.
111
It is interesting to note that the heat evolved from the cement pastes with the two
regular LS based admixtures BCA and BCS in the first hour was significantly higher
than that of the other mixtures. Tagnit and Sarkar (1990) reported that lignosulphonate
based water reducing admixtures may interfere with the dissolution of sulfates in
cements. The greater heat evolved at early ages for the mixtures with the BCA and
BCS might be related to the reduced SO42- in solution and thus increased the reaction
of C3A.
The 3-day total heat evolved (Fig. 4-6) for the two control mixtures were similar
although lower w/c ratio had a higher rate of hydration and heat evolution initially.
However, comparing the heat curves in Figs. 4-4 and 4-5, it seems that all the pastes
with the admixtures had higher heat evolution at w/c ratio of 0.34 before 4 hours and
after 48 hours. The pastes with the w/c ratio of 0.34 took a shorter time to accumulate
a given amount of heat at early hours. From 48 to 72 hours, it is very clear that
cumulative heat curves of lower w/c ratio pastes were above the control while those of
higher w/c ratio below the control. This is likely due to the fact that the amount of
cement used in w/c 0.34 was 12% more than that used in w/c 0.40. It is seen in Table
3-4 that more admixtures were dosed for w/c of 0.34 and all admixtures showed some
degree of retardation at the dosages used. One may think that the pastes having more
admixtures would produce less heat as cement hydration would be retarded, which
was contradictory to what was observed. On the other hand, higher cement content in
the pastes with w/c of 0.34 may affect the adsorption of the admixtures and thus the
amount of admixtures retained in pore solutions may also affect the heat evolution.
Further research is required to understand such behaviours better.
112
4.2 Degree of Cement Hydration
4.2.1 Reduction of C3S in Cement Pastes
Since C3S takes up more than 50% of the cement and hydrates from early age, its
reduction in quantity will provide information on the degree of cement hydration.
The C3S content will be reduced with cement hydration. In Figs. 4-7 and 4-8, it can be
seen that the C3S content in all the cement pastes was reduced with time, from the
earliest at 2 hours to 91 days. The chemical admixtures had significant effect on the
cement hydration at early age up to about 3 days. At 3 days and thereafter, the
differences in the C3S content in the paste samples with and without admixtures were
not significant at both w/c ratios. The results are consistent with the small differences
of the cumulative heat observed at 3 days (Figs. 4-4 and 4-5) for the various paste
samples. From Figs. 4-7 and 4-8, it is also observed that the influences of the
admixtures on the C3S hydration were dependent on the w/c ratio.
At a w/c of 0.34, the C3S in the control cement paste and the paste with the SNF
superplasticizer started to drop substantially as early as 2 to 4 hours. The C3S content
in the paste with PCE admixture began to decrease significantly at 4 to 8 hours. For
the pastes with PLS and UNA admixtures, the C3S began to reduce noticeably at 12
hours. The rate of reduction remained more or less the same till 3 days.
With a w/c of 0.40, the reduction in the C3S content was not noticeable in the control
paste and the paste with the SNF superplasticizer until 8 hours. This was more than 4
hours behind that with a w/c of 0.34. The C3S content in the cement pastes with PCE,
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PLS and UNA superplasticizers dropped noticeably at around 12 hours, whereas that
with the BCS and BCA admixtures had a noticeable drop 12 hours later.
The data of the C3S reduction and the cumulative heat both suggest that the cement
hydration of the pastes with the various admixtures was not delayed at 3 days and
beyond.
4.2.2 Hydration Progress in the Cement Pastes
The main hydration products from cement hydration are calcium silicates, calcium
hydroxide, and calcium sulphoaluminates (ettringite and monosulphoaluminate).
Since C-S-H is amorphous, XRD will not provide information for its formation. No
AFt and AFm phases were detected in the XRD analyses. This might be related to the
sample preparation in which the grinding of the dried cement pastes into powder
might have destroyed the calcium sulphoaluminate crystals. In this section, the
increases in the CH and the NEW content in the cement pastes are used as indicators
of the progress of cement hydration.
4.2.2.1 Calcium hydroxide (CH) in cement pastes
Both the C3S and C2S hydration produce calcium hydroxide. The C3S starts to hydrate
immediately after it comes in contact with water, whereas the C2S does not have
significant hydration at early age. The CH content in the cement pastes were
determined by TG analysis and the results are presented and discussed in this section.
Figure 4-9 shows TG curves of the control cement paste samples (w/c = 0.40) with the
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hydration ages from 2 hours to 91 days. The TG curves of the other dried cement
paste samples can be found in the appendix. From the curve, it is observed that the
drop around 500 °C, which corresponds to the decomposition of CH, occurred in the
paste sample after 4 hours hydration. This indicates that the CH appeared in the
cement paste after 4 hours of hydration. The drop became more substantial with the
increase in the curing age. It is seen in Fig. 4-9 that samples lost mass around 750 °C,
which corresponds to the decomposition of calcium carbonate (CaCO3). There are two
possible sources of calcium carbonate; either from the original cement in the form of
limestone powder or from the carbonation of CH. The average amount of CO2
released from decomposition of calcium carbonate of the same cement was 2.09%,
with sample size of 3 and standard deviation of 0.05%. The results presented in Table
4-2 show that the amount of CO2 released from the control paste at ages of 2 hours to
91 days were all not more than 2.16%. This confirms that carbonation of paste
samples was minimal and the calcium carbonate presented in the samples was mainly
from the cement. The current ASTM C150 allows the use of up to 5% limestone
(main composition is calcium carbonate) in Portland cements.
The increase in the CH content (determined from the TG analysis) with time of the
cement pastes with or without the admixtures is shown in Figs. 4-10 and 4-11 for the
pastes with w/c ratios of 0.34 and 0.40, respectively (data are presented in the
Appendix5). For both w/c ratios, it seems that the CH precipitation occurred at 4 to 8
hours in the paste with the SNF superplasticizer; at 8 to 12 hours in the paste with the
PCE admixture, and after more than 12 hours in the pastes with all LS based
admixtures except for paste with PLS admixture with a w/c ratio of 0.34 in which CH
5
The raw data can be found in the appendix wherever there is a figure plotted.
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precipitated at 8 to 12 hours. However, the overall CH produced in these pastes with
various admixtures at 91 days was similar to that of the corresponding control paste.
This indicates that the admixtures had significant influence on the cement hydration at
early age, but not at late age. At an early age from 2 hours to 1 day, the effect of the
admixtures on the time of occurrence and the amount of the CH in the cement pastes
were in an increasing order from the SNF < PCE < PLS < UNA < BCA < BCS.
The CH content was also monitored by X-ray diffractometer with 2θ = 18o, and the
time when the CH crystals precipitated in the pastes was determined and compared
with that from TG analysis in Table 4-3. However, the CH content was not determined
from the XRD spectrum due to the difficulty in quantitative XRD analysis.
Ramachandran (1979) also reported that XRD method underestimates CH by not
registering the presence of microcrystalline or near amorphous CH.
From Table 4-3, it is observed that the time of the CH appearance detected in the TG
analysis corresponded well to the time when significant C3S reduction was detected
for all the pastes at both w/c ratios. However, the XRD seemed to detect the CH
appearance earlier than the TG analysis.
Compared to the heat curves in Fig. 4-4, it is natural for CH to appear in the order of
SNF < PCE < PLS < UNA. But it is quite surprising that the control paste had the
lowest cumulative heat in the first 2 hours, yet it was the first to start CH precipitation.
This may be due to the flocculation effect when w/c was low and no admixture was
added, thus slower rate of ion dissolution and lower heat. In Fig. 4-5, the zoomed-in
graph clearly indicates the hydration rates were in the order of CTR > SNF > PCE >
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PLS > UNA > BCS > BCA within 12 hours.
It was reported by Chan et al (1996) and Chandra and Björnström (2002) that ion
concentrations in pore solutions at lower w/c were higher than at higher w/c so that
crystals could precipitate faster to stiffen the pastes of lower w/c. This indicates that
the cement hydration at the lower w/c ratio of 0.34 would be delayed less than that at
the higher w/c ratio of 0.40, which has been confirmed by the cumulative heat up to 3
days (Fig. 4-4) and C3S reduction and CH increase (Table 4-3).
4.2.2.2 Non-evaporable water in cement pastes
Figures 4-12 and 4-13 show the increase in the NEW content in the cement pastes
determined by ignition in a furnace with the hydration time. From the figures, it is
apparent that all the pastes with the admixtures had less NEW content than their
corresponding control pastes at earlier age up to 12 hours except for the paste with the
SNF admixture at the w/c of 0.34. This particular paste had NEW content similar to
that of the corresponding control paste from 2 hours to 28 days. It is clear that all the
admixtures used delayed cement hydration to certain extents.
It was also noted that the two cement pastes with the regular BCS and BCA always
had lower NEW contents than those with the superplasticizers at an early age up to 1
day. However, they had higher NEW contents than the control pastes and the pastes
with the superplasticizers at 28 and 91 days. Similar trend was also observed for the
pastes with the LS based superplasticizers at the w/c of 0.34. These two pastes had
lower NEW content at an early age up to about 8 to 12 hours, but had higher NEW
content than the pastes with the SNF and PCE superplasticizers at 91 days.
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The non-evaporable water in the cement pastes were also determined from the TG
curves. Figure 4-14 shows that the trend of the NEW determined from the ignition in
the Lenton furnace agreed well with that determined from the TG curves (R2 = 0.97).
However, the CH contents in the pastes determined from the former were lower than
those determined from the latter by about 3%. As mentioned in Chapter 3, the samples
used for both tests were vacuum-dried to constant weight and subsequently stored in
desiccators till the time of testing. However, there were some differences in the testing
conditions. The heating in both tests started from room temperature (around 30 °C)
with a constant heating rate of 10°C/min till 950 °C. However, in the TG analysis the
measurement of the mass was stopped immediately after the temperature had reached
950 °C, whereas the samples in the furnace stayed at 950 °C for another 3 hours, and
then were weighed after being cooled down. The other difference was that in the TG
test, the samples were heated in an environment with a flow of nitrogen gas (N2),
whereas the samples in the furnace were heated without N2 gas. It is very unlikely to
be caused by carbonation, which was confirmed in the earlier subsection. Moreover, if
it were due to carbonation, both the furnace and TG would have registered the
carbonation effect during the tests. No explanation has been found and further
research on this is required.
It is interesting to compare the data analyzed for CH and NEW contents of the pastes.
In Fig. 4-10, the pastes with PLS and UNA at w/c of 0.34 had lower CH contents at 7,
28, and 91 days compared to those with PCE and SNF superplasticizers. In Fig. 4-12,
all four superplasticized pastes had similar NEW contents at 7 and 28 days; but the
pastes with PLS and UNA showed higher contents at 91 days. Similar variations were
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also observed in the case of w/c of 0.40. The small variations at discrete ages for
independent test methods are believed to be normal experimental variability. This is
further supported by the C3S remaining in the pastes at 7, 28 and 91 days, shown in
Figs. 4-7 and 4-8. The independent testing methods suggest the water reducing
admixtures under investigation had insignificant effect on the hydration at later ages
from 7 till 91 days.
4.2.3 Degree of Hydration in Cement Pastes
The degree of hydration, α, is a measure of the extent of the reaction between the
cement and water. It is a function of time and it varies between 0% at the beginning of
hydration and 100% when complete hydration is reached. In reality, full hydration
may never be reached for concrete at jobsites, particularly for those with low w/c
ratios.
Generally, hydrated cement paste is assumed to be comprised of three components:
anhydrated cement, hydration product (gel) and capillary pores. According to Taylor
(1997), the water presented in the cement paste is categorized as evaporable and non-
evaporable water (wn). The degree of hydration (α) at a certain age (t) can be related
to the ratio of the amount of non-evaporable water at time t to that of complete
hydration denoted by the infinite sign ∞, as shown in Eq. 4-1.
(t )
w
α (t ) = n( ∞ ) (4- 1)
wn
The typical value for wn for complete hydration is 0.23 - 0.25 (Taylor, 1997).
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As mentioned earlier in Chapter 3, the non-evaporable water contents (Figs. 4-12 and
4-13) were determined as the relative mass loss between 105 and 1000 °C, corrected
for the loss on ignition (LOI) of the dry cement itself. Assuming that the ultimate
amount of non-evaporable water wn (∞) is 0.24, the degrees of hydration at various
times are shown in Tables 4-4 and 4-5.
Similar to Eq. 4-1, the degree of hydration also can be estimated from the chemical
reaction equations of calcium silicates, namely C3S and C2S. Shown in Eqs. 2-1 and
2-2, both silicates6 produce calcium hydroxide. Since we know the original amount of
C3S and C2S in cement from the Bogue calculations, the total calcium hydroxide may
be estimated at the time of complete hydration. The theoretical total CH content will
be about 24% for the cement paste samples. Therefore, the degree of hydration at
various time, t, can be estimated using Eq. 4-2.
CH (t )
α (t ) = (4- 2)
CH ( ∞ )
Based on this estimation, the degrees of hydration at various times are shown in
Tables 4-4 and 4-5.
From the estimated degrees of hydration of pastes with and without admixtures for
both w/c ratios, the behaviours are the same as the trends observed earlier in the NEW
and CH contents over the hydration time from 1 day to 91 days. However, the
differences between the two methods of degree of hydration are noticeably large for
both w/c ratios.
6
The relative molecular masses of C3S, C2S and CH are 228.32, 172.24 and 74.09
respectively.
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The ultimate degree of hydration, αu, is strongly affected by w/c ratio (Hansen, 1986).
According to Mindess et al (2003), the minimum w/c ratio should not fall below 0.42
for complete hydration if cement paste is cured under sealed condition, as shown in
Eq. 4-3.
(w / c )min = 0.42α (4-3)
It is noted that this is not affected by the curing temperature. Therefore the ultimate
degree of hydration is about 81% for w/c of 0.34 and around 95% for w/c of 0.40.
From Tables 4-4 and 4-5, the 91-day degrees of hydration for NEW method are quite
close to the ultimate degrees of hydration estimated from Eq. 4-3. It seems that the
NEW and CH contents were obtained through the laboratory tests to certain accuracy
and both can be used for estimation in terms of the degrees of hydration of pastes with
and without admixtures. Compared to the estimation of the CH method, NEW
estimation seems to be better. As discussed earlier in Section 4.2.2.2, it is most likely
related to the test methods.
4.3 Workability Retention of Mortars with Time
4.3.1 Change in the Yield Stress of Mortars with Time
With initial yield stress controlled at 75 ± 15 Pa for the mortars with the admixtures; it
makes comparison of the yield stress change with time meaningful. The mortar with
the BCS admixture failed to achieve the target yield stress even though a dosage of
60% more than the maximum dosage recommended by manufacturer was used. The
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initial yield stress of control mortar with the w/c ratio of 0.40 was 490 Pa. No control
mortar mixture was included as it was impossible to achieve the same initial target
workability without the admixtures. Figure 4-15 shows the average and standard
deviation of the initial yield stress of all the mortar mixtures with the admixtures.
Although the BCS admixture had the initial yield stress of 247 Pa which was not
comparable to that of the mortars with the other admixtures, it was still included in the
study to see its effect.
Regardless of the w/c ratios, the yield stresses increased (R2 ≥ 0.95) with time up to
60 minutes and the mortars stiffened with time (Figs. 4-16 and 4-17). Petit et al (2006)
reported linear relationship between the yield stresses and elapsed time up to the end
of the induction period (> 2 hours) of mortars with a SNF superplasticizer.
For both w/c ratios, the slopes of the yield stress are in the same order of SNF > PCE
> PLS > UNA for the four superplasticzers. This indicates that SNF has the least
workability retention and will experience greater loss of workability with time among
the four superplasticizers. The workability retention capability of the two LS based
superplasticizers (PLS and UNA) was better than that of the PCE and SNF
superplasticizers. The performance of the UNA and PLS superplasticizers was similar,
but the UNA admixture was slightly better than the PLS admixture on workability
retention.
The two regular LS based WRAs showed similar rate of yield stress increase and
workability loss. However, their rates of the yield stress increase were much higher
than those of the LS based superplasticizers, and even higher than the SNF
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superplasticizer (Fig. 4-17). This suggests that the cement in the mortars with these
two admixtures might have more hydration than that in the mortars with the other
admixtures during the first hour. For the paste with the BCS admixture, dispersing
capability of the admixture may also be an issue since the target yield stress was not
achieved. It is indeed shown in Fig. 4-4 that the cement pastes with the BCS and BCA
admixtures released heat much faster than the pastes with the other admixtures in the
first hour, and in Fig. 4-5 that the former ones had higher cumulative heat up to 4
hours than the latter ones.
It is well known that admixtures may be adsorbed not only onto the surface of the
cement particles but also onto the hydration products. Chen (2007) suggests that the
admixture molecules may even be covered by the hydration products. For the pastes
with the BCS and BCA admixtures, heat was released much faster than other pastes in
the first hour. It could probably be due to the accelerated C3A hydration. Because of
this rapid reaction, the admixtures may be removed from solution due to the
adsorption onto ettringite. This may explain the significant workability loss of the
mortars with the BCS and BCA admixtures based on the fact that the initial yield
stress was the same for mortars with admixtures. However, the results obtained from
the current studies only suggest but are unable to lead to definite conclusions. Further
research is needed.
Comparing Figs. 4-16 and 4-17, it is observed that the increase in the yield stresses of
the higher w/c ratio of 0.40 was less significant than those of the lower w/c ratio of
0.34, although the initial yield stresses were on the same level. The results are
consistent with the cumulative heat discussed in Section 4.1 and cement hydration
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discussed in Section 4.2.
The yield stresses were evaluated during the first hour which was in the induction
period of cement hydration from the heat curves obtained (Figs. 4-2 and 4-3). A
change in slope in the rate of heat curve can be easily detected for all the cement paste
mixes. This elapsed time corresponds to the end of the induction period (tf) and
reflects the beginning of the acceleration period of cement hydration (Lei and Struble,
1997). It is important to note that the end of the induction period is usually considered
as the point where the tangent lines of heat curves during the induction period and
acceleration period of cement hydration intersect (Lei and Struble, 1997). However,
instead of this conventional approach, the end of the induction period tf was
determined by the point corresponding to the lowest rate of heat before the
acceleration occurred in the rate of heat curve.
The normalized time t′ is defined as the ratio of any given elapsed time (e.g. BML and
flow table tests at 10 min, 30 min and 60 min) within the induction period to the final
time tf (t′ = t / tf). It is therefore a non-dimensional parameter and enables the
comparisons of variations in rheological parameters of the various mixtures at the
same relative scale of time, regardless of the length of the induction period.
As shown in Fig. 4-18, yield stresses increase linearly (R2 = 0.95) with the normalized
time, for superplasticized mortar mixes, being at w/c of 0.34 and 0.40. However, a
poor relationship exists for the two regular water reducing admixtures, due to their
extremely strong retardation, hence longer induction period.
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4.3.2 Change in Plastic Viscosity of Mortars with Time
Figures 4-19 and 4-20 show plastic viscosity changes with time for the mortars with
and without admixtures at the w/c of 0.34 and 0.40, respectively. At the lower w/c of
0.34, the initial plastic viscosities of the mortars (measured 10 minutes after the
cement came in contact with water) were 5.2 – 9.7 Pa.s, higher than those (3.3 – 4.4
Pa.s) at higher w/c of 0.40. At 60 minutes, the plastic viscosity of the mortars with the
w/c of 0.34 ranged from 6.3 to 9.8 Pa.s, and that with the w/c of 0.40 ranged from 2.6
to 4.3 Pa.s. It seems that the change in the plastic viscosity of the mortars with time
was not as significant as that in the case of yield stress.
It was noticed that for the mortars with the two modified LS based superplasticizers
(PLS and UNA), the initial plastic viscosities were higher than those with the PCE
and SNF superplasticizers, and they remain largely unchanged with time. In other
words, the modified LS superplasticizers had more effects on the yield stress τ 0 than
the plastic viscosity µ . This observation agreed with the results reported by Wallevik
(2003).
However, the other two superplasticizers behave differently for the two w/c ratios.
The plastic viscosity of the mortars with the PCE superplasticizer increased with time
at the w/c ratio of 0.34, but kept almost constant at the w/c ratio of 0.40. The plastic
viscosity of the mortars with the SNF admixture showed the opposite. It decreased at
the w/c of 0.34 but increased at the w/c of 0.40 with time.
For the two regular WRAs (BCS and BCA), the plastic viscosity of the mortar with
the BCS admixture increased substantially from 10 to 30 minutes, whereas that with
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the BCA decreased from 10 to 60 minutes. Due to the high initial yield stress and
plastic viscosity of the mortar with the BCS admixture and significant workability
loss, it was not possible to measure the yield stress and plastic viscosity after 60
minutes. .
4.3.3 Change in Flow Value of Mortars with Time
The flow value was reported in terms of the increase in average base diameter of the
mortar mass, expressed as a percentage of the original base diameter (100 mm) of the
flow cone after 10 drops of the flow table. For example, a mortar mass with a spread
of 150mm in diameter after 10 drops had a net flow of 50mm, and the flow value is
therefore 50%. Since the flow table has a diameter of 250mm, the term “overflow”
used in the Appendix (Table A-9) means a flow value of 150% or more.
Figure 4-21 show the change in the flow values of the various mortars at w/c ratios of
0.40 with time. The data for a w/c ratio of 0.40 were collected in the manner described
in Chapter 3 and presented in Fig. 4-21. The data for a w/c ratio of 0.34 were not
collected in the specified manner at 10 drops but at 25 drops because they even
overflowed at 30 minutes. The data of the latter were presented in Table 4-6.
Shown in Fig. 4-21, the flow values for the mortars were different at 10 minutes even
though their initial yield stress was controlled at 75 ± 15Pa except for the mortar with
the BCS admixture. For the two LS based superplasticizers, their mortars showed
similar flow values of about 140 % at both w/c ratios. Whereas for the PCE, SNF and
BCA admixtures, their mortars had roughly the same initial flow about 120 %. The
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mortar with the BCS admixture had the lowest flow of about 98% as expected.
It is seen in Table 4-6 that mortars with superplasticizers overflowed the flow table at
10 and 30 minutes when 25 drops were applied. It is shown that mortars with PCE
and SNF superplasticizers had similar flow values at 60 minutes and that mortars with
two modified LS superplasticizers also showed close flow values. These flow values
at 60 minutes supported the corresponding results of yield stress.
From Fig. 4-21, it seems that for a w/c of 0.40, the mortars had similar rate of
reduction in the flow values except for that with the PCE admixture. The mortar with
the PCE admixture had less than 5% reduction in the flow from 10 to 60 minutes,
which indicates that the PCE based superplasticizer was able to retain workability
well. This seems to contradict the results of the yield stress and plastic viscosity. This
suggests that the one-point flow value test may not sufficiently describe the
workability of mortars under the circumstance that their flow values fall within a
rather narrow range.
4.3.4 Relationship between the Yield Stress and Flow Value
As shown in Fig. 4-22, the yield stress is inversely proportional to the flow value with
an R2 value of 0.95, if the high flow values of 140 % (in the circle) are excluded.
These high flow values were not erratic. It merely suggests that the mortar was too
flowable to be properly measured by flow table, and the result was not proportional to
the yield stress. In fact, it is understood that when yield stress is sufficiently low, flow
should be infinite. The power fit in Fig. 4-22 thus is also reasonable, which has an R2
value of 0.91.
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This relationship is independent of w/c ratios, admixtures and time. Similar
relationships between yield stress and slump have been reported for concrete by
Ferraris and Brower (2001) and Emoto and Bier (2007).
Since the plastic viscosity of most mortars did not change significantly with time, no
definite relationship between the plastic viscosity and flow value was observed.
4.4 Setting Times of Mortars
Setting times of the mortars with and without the admixtures at w/c ratios of 0.34 and
0.40 are plotted in Figs. 4-23 and 4-24, respectively. The order of the setting times of
the superplasticized mortars agreed with the length of induction periods of the
corresponding pastes at w/c ratio of 0.34 (Fig. 4-2), i.e. SNF < PCE < PLS < UNA.
For w/c ratio of 0.40, it was noticed that paste with UNA superplasticizer had similar
length of induction period as that of BCA admixture (Fig. 4-3); however, the
corresponding mortar with UNA superplasticizer had 100 minutes shorter setting
times than those with BCA admixture. The magnitude of heat peak is another factor,
which indicates the admixture effect on set retardation. In the case of UNA and BCA
admixtures, paste with BCA admixture showed lower heat peak (Fig. 4-3). Hence, the
heat evolved from the pastes with the admixtures supported the order of the setting
times of the plasticized mortars, i.e. SNF < PCE < PLS < UNA < BCA < BCS.
Figure 4-25 shows the relationship between the initial and final setting time of the
mortars and the time when acceleration started after the induction period in the heat
curve. Generally, a later start of the acceleration period means that both the initial and
final setting times are longer, as indicated by the linear relationships with R2 ≥ 0.88
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for both w/c ratios. The result of the setting times is consistent with the time that CH
appeared in the pastes with different admixtures incorporated. The data shown in the
figure confirm that the setting times are affected by w/c ratio, besides the cement
hydration and dosages of admixtures. In other words, the heat curve itself is not
sufficient to determine the setting times of mortar or concrete.
Since the setting time was determined by the penetration resistance, the setting times
of the mortars with the lower w/c of 0.34 were generally shorter than those with the
higher w/c of 0.40 if no chemical admixture is used. However, the setting times are
also affected by the type and dosage of the admixtures, in addition to the w/c ratio.
For example, the setting times of the mortars with the PLS and UNA at w/c of 0.34
were higher than those at w/c of 0.40 because the formers had higher dosages of the
admixtures than those of the latter and the admixtures had retarding effects.
Comparing the setting times of superplasticized mortars with different w/c ratios, it is
interesting to note that, the difference between the initial and final setting times for the
mortars with the superplasticizers ranged from 65 to 100 minutes, despite the large
differences in their initial setting times. The differences in the initial and final setting
times for the mortars with BCA and BCS admixture were 160 and 300 minutes,
respectively, which were longer than those with the superplasticizers but the initial
setting times of the mortars with the two regular WRAs were also longer. This
indicates that admixtures may have a strong influence on the initial setting time but
less influence on the final setting time.
Sugar content in the LS admixtures is partly responsible for the retardation. However,
129
the sugar content may not be the only factor (Vikan, 2005). As seen in Fig. 4-24,
mortar with the BCS admixture had an initial setting time almost 4 hours longer and a
final setting time 6 hours longer than those with the BCA admixture. Yet the BCS
admixture from hardwood had a reducing matter of 3%, whereas the BCA admixture
from softwood had 7% reducing matter.
The PCE and SNF based superplasticizers were sugar free, but they also showed
retardation effect to certain extent.
It is important to note that the effect of the admixtures might not be the same for the
set retardation and for the workability retention. In other words, longer set retardation
may not always correspond to better workability retention. For the four
superplasticizers used in the mortars at both w/c ratios, it was found that the
workability retention determined by the yield stress was better when the setting times
were longer. However, for the two regular water reducing admixtures, it seems to be
otherwise.
For the two LS based superplasticizers, the mortar with the PLS had shorter setting
times than that with the UNA at both w/c ratios. This may be related partly to the
lower dosage of the admixture used in the former than the latter.
4.5 Pore Structure of Cement Pastes
Figure 4-26 shows typical curves7 of the intruded cumulative pore volume versus the
7
The curves for the cement pastes with other admixtures at w/c ratios of 0.34 and 0.40 are
included in the Appendix (Tables A-13 to A-24).
130
mean pore diameter of the cement paste with the PCE admixture at w/c of 0.40 at
various ages based on the mercury intrusion porosimetry. The total porosity of the
cement pastes with the w/c ratios of 0.34 and 0.40 cured for different periods are
shown in Figs. 4-27 and 4-28, respectively. In general, the cumulative pore volume in
the samples decreased with time due to cement hydration. The cumulative pore
volume of the cement pastes with the w/c ratio of 0.34 was smaller than that with the
w/c ratio of 0.40.
For the repeated MIP tests that were randomly selected for each series of pastes, it
was found that the variations (in terms of relative difference) in the total porosities
were within 2% for the pastes with w/c of 0.34, and 5% for those with w/c of 0.40
(Table 4-7). For example, for the paste with the PLS superplasticizer and w/c of 0.34
at 91 days, the total porosity of the repeat sample was 22.4%. Compared to the first
result of 22.7%, it has an absolute difference of 0.3%, and a variation of 1.3%. The
relatively small variations of the repeat samples indicate that the test results are
repeatable. Therefore, only one test was used for the remaining samples. For those
samples with duplicate tests, the first set of results was used in the analysis.
4.5.1 Total Porosity of Cement Pastes with Admixtures
For both w/c ratios, the differences in the porosity of the pastes with different
admixtures at early age are mainly associated with the retardation effect of admixtures.
The porosities of pastes with all admixtures were similar at 7 days with the given w/c
ratio.
For the w/c ratio of 0.34 (Fig. 4-27), the cement pastes with the PCE, SNF and PLS
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superplasticizers had similar porosities up to 3 days. The paste with modified LS
superplasticizer UNA had noticeably higher porosities at 1 day and 3 days, but its
porosity at 7 days were comparable to that of the other pastes. At 28 and 91 days, the
paste with the PCE superplasticizer had lower total porosity than those with the SNF
and LS superplasticizers, which may be due to the dispersion ability of the
superplasticizers. The pastes with the SNF and LS superplasticizers had similar total
porosity.
For the w/c of 0.40 (Fig. 4-28), the two LS based regular admixtures (BCS and BCA)
had slightly lower porosity at 1 day. This may be explained by the high rate of cement
hydration in the first 5 hours (related to C3A reaction) when these two admixtures
were incorporated in the cement pastes (Fig. 4-5). Having said that, it is noted that
mortar with BCS admixture had final setting time of nearly 23 hours and it had little
strength at 1 day. This suggests that its respective paste sample may not be strong
enough to produce reliable result. At 3 days, the pastes with PCE and SNF
superplasticzers appear to have lower porosity than those with the LS admixtures. The
total porosity of the pastes with different admixtures at 28 days was not significantly
different. At 91 days, however, the total porosities of the pastes with the BCS, BCA,
and UNA admixtures were lower than those of the paste with PCE, SNF, and PLS
superplasticizers. This might be related to the significant retardation effect of the
former on C3S hydration at early ages which might have resulted in more
homogenous distribution of hydration products in the cement pastes.
4.5.2 Pore Size Distribution of Cement Pastes with Admixtures
As discussed earlier, pores in cement paste can be either gel or capillary pores.
132
Capillary pores can be further divided into small, medium and large capillaries
according to their sizes. The MIP under study was able to detect capillary pores with
diameters as small as 3.8 nm. According to Table 2-3 (Mindess et al, 2003), the pores
were divided into small capillary pores with diameters from 3.8 to 10 nm (denoted as
G), medium capillary pores with diameters from 10 to 50 nm (denoted as M), and
large capillary pores with diameters from 50 nm to 10 µm (denoted as L). The small
capillary pores are part of the gel pores (Mindess et al, 2003).
Pore size distributions of the cement pastes with admixtures at various ages from 1 to
91 days are shown in Figs 4-29 to 4-33. The pore size distribution changed with time
due to cement hydration, and it also differed due to the differences in w/c ratios and
the admixtures used in the cement pastes. For the cement pastes with w/c ratios of
0.34 and 0.40 with various admixtures, their proportions of small capillary pores were
not significantly different, and the differences were mainly in the large and medium
capillary pores. At early ages, particularly at 1 day, the proportions of the large and
medium pores were mainly affected by the effect of admixtures on the retardation of
cement hydration. It is the pore size distribution at ages of 28 and 91 days that is of
importance since it affects permeability and resistance to the penetration of harmful
substances.
For the pastes with w/c of 0.34, it appears that the paste with SNF superplasticizer had
the lowest sum of small and medium capillary pores while pastes with other
superplasticizers had similar amount at 1 day (Fig. 4-29(a)). It also shows that paste
with UNA superplasticizer had the largest amount of large capillary pores. At 3 days
shown in Fig. 4-30(a), the paste with UNA superplasticizer still had the largest
133
amount of large capillary pores while it had slightly lower combination of small and
medium capillary pores than the other pastes which had similar pore size distributions.
At 7, 28, and 91 days (Figs. 4-31(a) to 4-33(a)) the two LS superplasticizers (PLS and
UNA) had less large pores but more medium pores compared with the paste with SNF
admixture. The pastes with the two LS and the PCE superplasticizers had similar large
pores at 28 and 91 days. However, the latter had less medium pores than the former.
Based on Figs. 4-31(a) to 4-33(a), it seems that at lower w/c ratio of 0.34, the two
modified LS, PLS and UNA, and PCE superplasticizers led to a significant reduction
in large and medium capillary pore volumes from 7 to 91 days and that SNF
superplasticizer was able to reduce medium capillary pore volume but not large ones.
The pastes with PLS and UNA superplasticizers at w/c ratio of 0.34 had lower CH
content (Fig. 4-10) compared to those with PCE and SNF ones at 7 and 28 days. This
confirms the general understanding that pore structure of paste with admixtures is
related to C-S-H produced from cement hydration, rather than the production of CH.
At w/c of 0.40, the pastes cured for 28 days (Fig. 4-32(b)) had similar medium and
large capillary pores except that the paste with PCE admixture had slightly less and
the paste with UNA admixture had slightly more large capillary pores. At 91 days
(Fig. 4-33(b)), the pastes with the LS admixtures had similar medium pores compared
with the pastes with PCE and SNF admixtures. However, the pastes with the LS
superplasticizers had less large capillary pores than that with the SNF admixture, but
similar large pores compared with the PCE paste. The pastes with the regular water
reducers (BCS and BCA) appear to have lower large capillary pores at 91 days
compared with those with the superplasticizers. This is probably also related to the
134
strong retardation of the regular water reducers that allowed a more even distribution
of hydration products and resulted in a more homogeneous microstructure. Overall,
the performances of the all the admixtures appear similar, and this suggests that the
effect of the admixtures on pore structures is not pronounced at high w/c ratios
compared with one another.
4.5.3 Threshold and Critical Pore Diameters
The threshold diameter is the first inflection point as shown in Fig. 4-26, and it
indicates the onset of percolation (Mindess et al, 2003). It corresponds approximately
to the minimum diameter of channels that are continuous through the paste at a given
age (Winslow and Diamond, 1970).
The critical pore diameter is the pore size corresponding to the highest rate of mercury
intrusion. This is the point where the slope of the curve of cumulative mercury
intrusion volume against pore diameter is the steepest. The critical pore diameter
represents the mean size of pore entryways that allows maximum percolation
throughout the pore system, and is also called continuous pore diameter (Mindess et al,
2003).
Both the threshold and critical diameters derived from pore size distribution curves
from the MIP tests are closely related to permeability and penetration resistance of the
cement pastes (Ramachandran and Beaudoin, 1999). The coefficient of permeability
increases with an increase in the threshold and critical diameters (Halamickova et al.,
1995; Ramachandran and Beaudoin, 1999). Similarly, the coefficient of chloride ion
135
diffusion varied linearly with the critical pore diameter as determined by the MIP
(Halamickova et al., 1995).
The threshold and critical pore diameters for the cement pastes with w/c ratios of 0.34
and 0.40 are presented in Tables 4-8 and 4-9, respectively. The results show that up to
28 days the cement pastes with a w/c of 0.34 generally had smaller threshold and
critical diameters than the corresponding pastes with a w/c of 0.40. At 91 days, no
definite trend was observed.
For the pastes with a w/c of 0.34, the threshold and critical diameters did not change
significantly with time. For the pastes with a w/c of 0.40, however, the threshold and
critical diameter reduced significantly with time at early age up to 7 days, with no
significant change after that.
For the cement pastes with a w/c of 0.34, the threshold and critical diameters of the
two modified LS superplasticizers were slightly smaller than those of the PCE and
SNF superplasticizers at 28 days. However, both the threshold and critical diameter of
the superplasticized pastes were of the same order.
For the cement pastes with a w/c of 0.40 and the four superplasticizers, their threshold
and critical diameters were similar at 28 days. The pastes with the BCS water reducer
had larger critical and threshold diameters, but that with the BCA admixture had
smaller critical and threshold diameters, compared to those of superplasticized pastes.
136
4.6 Compressive Strength of Mortars
The compressive strength development of the mortars with w/c ratios of 0.34 and 0.40
is shown in Figs. 4-34 and 4-35, respectively. The variations (in terms of standard
deviation calculated from three 50mm mortar cubes and indicated by the “I” bars) are
all below 10% of their respective average strength.
The compressive strengths of mortars with admixtures at 1 day were in a descending
order: SNF > PCE > PLS > UNA > BCA > BCS. This was exactly the opposite of the
setting times as the longer setting time means stronger retardation and less hydration,
hence lower strength at early ages.
For the w/c ratio of 0.34 (Fig. 4-34), the mortars with the PCE, SNF, and PLS
admixtures had similar compressive strength at 7 and 28 days. However, the lower
strength of the mortar with the UNA persisted. At 91 days, all the pastes had similar
strength.
For the w/c ratio of 0.40 (Fig. 4-35) the compressive strength at early ages,
particularly at 1 day, was also affected significantly by the retardation of the
admixtures. For the mortar with the BCS admixture, almost no strength was
developed at 1 day. At 7, 28, and 91 days, the compressive strength of the mortars
with various admixtures were not significantly different.
Compressive strengths of mortars are related to the mix proportions, w/c, degree of
cement hydration, particularly the hydration of calcium silicates C3S and C2S,
distribution of hydration products, porosity, pore structure, and bonding between the
137
sand and cement paste. The admixture will affect rate of cement reaction at early ages,
and consequently may affect the distribution of hydration products and later strength.
Since compressive strength is such a complex mechanical property of mortars, effect
of admixtures on individual factor may not be exactly in line with the strength. For
example, the paste with PCE superplasticizer with w/c of 0.34 had smaller total
porosity and similar small and medium capillary pores compared to the paste with
SNF superplasticizer at 28 and 91 days, however, this does not seem to be reflected in
the corresponding strengths as the corresponding mortar with SNF superplasticizer
showed higher strength.
138
Table 4-1 Times of peak appearance in heat curves of pastes

Mix Time to appear, min
w/c=0.34 Peak “B” Peak “C” Difference, min
CTR 375 430 55
PCE 650 700 50
SNF 440 515 75
w/c=0.40 Peak “B” Peak “C” Difference, min
CTR 450 555 105
PCE 750 805 55
SNF 540 650 110
Note: Peaks “B” and “C” overlap for pastes with other admixtures
Table 4-2 Amount of CO2 from decomposition of CaCO3 in Fig. 4-9 TG curves
Age, hours 0h* 2h 4h 8h 12h
CO2, % 2.09** 1.96 1.95 1.92 2.14
Age, days 1d 3d 7d 28d 91d
CO2, % 2.16 2.08 2.04 1.98 1.95
* This refers to the original cement which has not yet contacted with mixing
water.
** This was the average value of TG results (n = 3, σ = 0.05) for the same
cement.
Table 4-3 Times for C3S reduction & CH appearance in the cement pastes with and
without admixtures detected by XRD & TG
Significant C3S reduction (XRD) CTR PCE SNF PLS UNA BCS BCA
w/c = 0.34 2h 8h 4h 12h 12h - -
w/c = 0.40 8h 12h 8h 12h 12h >12h >12h
Ca(OH)2 appearance (TG) CTR PCE SNF PLS UNA BCS BCA
w/c = 0.34 4h 12h 8h >12h >12h - -
w/c = 0.40 4h 12h 8h >12h >12h >12h >12h
Ca(OH)2 appearance (XRD) CTR PCE SNF PLS UNA BCS BCA
w/c = 0.34 2h 4h 2h 8h 12h - -
w/c = 0.40 4h 8h 4h >12h >12h >12h >12h
139
Table 4-4 Degree of hydration of pastes at various ages (w/c = 0.34)
w/c = 0.34 1d 3d 7d 28d 91d

CTR 58.4 69.6 74.1 78.4 81.0
Estimation PCE 55.0 70.8 71.8 76.0 77.2
from NEW SNF 60.8 68.4 70.5 78.1 84.0
Content PLS 54.5 70.2 74.6 77.4 82.1
UNA 49.5 70.7 74.3 78.2 82.0
CTR 47.7 50.8 60.4 63.4 66.5
Estimation PCE 41.4 51.3 61.2 62.4 67.9
from CH SNF 45.7 56.6 58.7 61.4 69.6
Content PLS 44.6 52.8 55.9 59.0 64.6
UNA 43.5 53.8 55.0 58.4 61.0
Table 4-5 Degree of hydration of pastes at various ages (w/c = 0.40)
w/c = 0.40 1d 3d 7d 28d 91d

CTR 55.5 76.0 76.8 84.3 93.3
PCE 58.0 70.3 76.6 80.7 90.7
Estimation SNF 54.3 74.3 75.9 82.3 87.4
from NEW PLS 43.9 71.8 78.2 83.1 88.3
Content UNA 53.2 65.5 76.2 89.4 90.7
BCS 37.6 71.3 77.1 88.9 93.7
BCA 43.3 68.3 77.3 85.3 92.2
CTR 44.6 51.0 56.2 69.5 72.5
PCE 43.8 54.0 64.8 67.4 69.0
Estimation SNF 45.7 56.9 60.2 61.1 68.7
from CH PLS 36.8 58.8 64.8 66.0 70.2
Content UNA 28.3 50.5 63.6 67.4 71.7
BCS 21.8 57.3 60.7 71.7 72.2
BCA 24.0 52.0 56.3 64.5 71.5
140
Table 4-6 Flow values of mortars with time (w/c = 0.34)

Mortars with Flow Values, %
Age, minutes
Admixtures 10 drops 25 drops
10 n.m.* >150**
PCE 30 n.m. 120
60 n.m. 106
10 n.m. >150
SNF 30 n.m. 118
60 n.m. 100
10 n.m. >150
PLS 30 140 >150
60 102 132
10 n.m. >150
UNA 30 140 >150
60 112 144
* n.m. = not measured
** > 150% is used when an overflow of mortar occurs
Table 4-7 Repeatability of MIP on mortars with and without admixtures

Cement w/c = 0.34 w/c = 0.40
Age
pastes with Porosity, % Variation** Porosity, % Variation
PCE 28d 29.1(29.1) 0.0%
SNF 7d 33.3(34.3) 3.0%
PLS 91d 22.7(22.4) 1.3%
UNA 1d 40.3(40.3) 0.0%
28d 31.6(32.6) 3.2%
BCS 7d 32.9(32.4) 1.5%
91d 24.1(23.1) 4.3%
BCA 1d 42.7(41.4) 3.1%
* The repeated results are shown in parentheses.
** Variation is in percentage difference, not in absolute difference.
141
Table 4-8 Critical and threshold pore diameters for pastes with w/c = 0.34
Pore Diameter Paste with PCE admixture Paste with SNF admixture
(nm) 1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
Critical, dc 67.2 54.4 67.7 54.2 67.1 67.7 54.2 54.4 67.7 54.2
Threshold, dt 102.6 82.3 125.7 125.8 126.5 101.4 101.9 82.3 101.3 81.9
Pore Diameter Paste with PLS admixture Paste with UNA admixture
(nm) 1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
Critical, dc 54.4 54.1 54.6 43.8 67.5 67.4 54.4 43.6 43.8 43.7
Threshold, dt 126.3 82.6 67.5 82.3 124.7 127.2 101.8 82.3 82.1 82.8
Table 4-9 Critical and threshold pore diameters for pastes with w/c = 0.40
Pore Paste with PCE admixture Paste with SNF admixture
Diameter
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
(nm)
Critical,
197.0 82.8 67.9 68.0 54.3 299.9 128.3 68.1 67.0 54.3
dc
Threshold,
288.6 125.7 101.5 103.5 82.3 397.3 160.0 101.2 100.9 82.6
dt
Pore Paste with PLS admixture Paste with UNA admixture
Diameter
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
(nm)
Critical,
742.5 126.4 68.1 67.6 67.1 202.4 102.2 67.4 83.0 67.7
dc
Threshold,
1415.9 191.0 83.1 100.9 100.7 296.2 127.1 101.1 101.3 82.6
dt
Pore Paste with BCS admixture Paste with BCA admixture
Diameter
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
(nm)
Critical,
1421.2 158.3 67.7 83.0 53.8 473.0 82.9 54.2 43.5 53.8
dc
Threshold,
1744.0 196.2 100.4 125.9 82.9 907.0 157.2 82.3 82.3 82.9
dt
142
3.5
3
Rate of heat evolution, mW/g
W/C = 0.40
2.06% 2.20%
2.5
2.35% 2.50%
2 3.00% 3.50%
1.5
0.5
0
0 500 1000 1500 2000 2500
Time, minutes
Fig. 4-1 Effect of SO3 content on heat of cement hydration
4.0
PCE SNF
W/C = 0.34
PLS UNA
3.5 4.2 CTR
Zoom in
3.0
Rate of Heat Evolution, mW/g
2.5
3.7
2.0
1.5
3.2
250 450 650 850 1050
1.0
0.5
0.0
0 500 1000 1500 2000 2500 3000 3500 4000
Time, minutes
Fig. 4-2 Rate of heat evolution of cement pastes (w/c = 0.34)
143
4.0
3.5
3.0
W/C = 0.40
2.5 PCE SNF

PLS UNA
2.0 BCS BCA

CTR
1.5
1.0
0.5
0.0
0 500 1000 1500 2000 2500 3000 3500 4000
Time, minutes
Fig. 4-3 Rate of heat evolution of cement pastes (w/c = 0.40)
250
W/C = 0.34
PCE SNF
200 PLS UNA
CTR
Cumulative Heat Evolution, J/g
150
50
100
25
Zoom in
50
0
0 120 240 360 480
0
0 500 1000 1500 2000 2500 3000 3500 4000
Time, minutes
Fig. 4-4 Cumulative heat evolution of cement pastes (w/c = 0.34)
144
250
W/C = 0.40
PCE SNF
PLS UNA
200
BCS BCA
CTR
150
50
100
25
50 Zoom in
0
0 120 240 360 480 600 720
0
0 500 1000 1500 2000 2500 3000 3500 4000
Time, minutes
Fig. 4-5 Cumulative heat evolution of cement pastes (w/c = 0.40)
4.0 250
3.5
200

3.0
2.5
150
W/C = 0.40
2.0
W/C = 0.34
100
1.5
1.0
50
0.5
0.0 0
0 500 1000 1500 2000 2500 3000 3500 4000
Time, minutes
Fig. 4-6 Rate and cumulative heat evolution of two control mixes
145
70
63.2% C3S in the cement
60 W/C = 0.34
CTR PCE
C3S, % by mass of paste sample
50
SNF PLS
UNA
40
30
20
10
0
2h 4h 8h 12h 1d 3d 7d 28d 91d
Age
Fig. 4-7 C3S reduction in paste with time (w/c = 0.34)
70
63.2% C3S in the cement
60
W/C = 0.40
C3S, % by mass of paste sample
CTR PCE
50
SNF PLS
40 UNA BCS
BCA
30
20
10
0
2h 4h 8h 12h 1d 3d 7d 28d 91d
Age
Fig. 4-8 C3S reduction in paste with time (w/c = 0.40)
146
Fig. 4-9 A typical TG curve showing mass loss over time (w/c=0.40 control paste)
18
16
CH (TG) , % by mass of paste sample
14
12
10
W/C = 0.34
8
CTR PCE
6
SNF PLS
4
UNA
2
0
2h 4h 8h 12h 1d 3d 7d 28d 91d
Age
Fig. 4-10 CH content in pastes increases with time from TG curves (w/c=0.34)
147
18
16
CH(TG), % by mass of paste sample
14
12
10
W/C = 0.40
8
CTR PCE
6 SNF PLS
4 UNA BCS
BCA
2
0
2h 4h 8h 12h 1d 3d 7d 28d 91d
Age
Fig. 4-11 CH content in pastes increases with time from TG curves (w/c=0.40)
18
16
14
Non-evaporable water (furnace),
% by mass of paste sample
12
10
W/C = 0.34
8
CTR PCE
6
SNF PLS
4 UNA
0
2h 4h 8h 12h 1d 3d 7d 28d 91d
Age
Fig. 4-12 Non-evaporable water content with time from furnace burning (w/c = 0.34)
148
18
16
14
Non-evaporable water (furnace),
% by mass of paste sample
12
10
8 W/C = 0.40
CTR PCE
6
SNF PLS
4
UNA BCS
2
BCA
0
2h 4h 8h 12h 1d 3d 7d 28d 91d
Age
Fig. 4-13 Non-evaporable water content with time from furnace burning (w/c = 0.40)
25
Non-evaporeable water (TG), % by mass of paste sample
20
15
y = 1.06x + 2.86
2
R = 0.97
10
W/C 0.34
W/C 0.40
0
0 2 4 6 8 10 12 14 16 18 20
Non-evaporeable water (Furnace), % by mass of paste sample
Fig. 4-14 Comparisons of non-evaporable water content
149
125
100
Average Initial Yield Stress, Pa
W/C = 0.40 W/C = 0.34
75
50
25
0
PCE SNF PLS UNA BCS BCA PCE SNF PLS UNA
Fig. 4-15 Average and standard deviation of the initial yield stresses of all mortars
480
420
W/C = 0.34
360
PCE SNF
Yield Stress, Pa
300 PLS UNA
240
180
120
60
0 10 20 30 40 50 60
Time, min
Fig. 4-16 Yield stress response on mortars with time at 30 ± 3 °C (w/c = 0.34)
150
480
W/C = 0.40
420
PCE SNF
360 PLS UNA

Yield Stress, Pa
BCS BCA
300
240
180
120
60
0 10 20 30 40 50 60
Time, min
Fig. 4-17 Yield stress response on mortars with time at 30 ± 3 °C (w/c = 0.40)
500
450
PCE SNF
SP
400
PLS UNA
350
WRA BCS BCA
Yield stress, Pa
300
250
2
R = 0.95 (for SP)
200
150
100
50
0
0.00 0.05 0.10 0.15 0.20 0.25
Normalized time, t/tf
Fig. 4-18 Responses of yield stresses of mortars at normalized time
151
10
8
Plastic Viscosity, Pa.s
W/C = 0.34
PCE SNF
4
PLS UNA
2
0 10 20 30 40 50 60
Time, min
Fig. 4-19 Plastic viscosity response on mortars with time (w/c = 0.34)
10
W/C = 0.40
8
PCE SNF
Plastic Viscosity, Pa.s
PLS UNA
6 BCS BCA
2
0 10 20 30 40 50 60
Time, min
Fig. 4-20 Plastic viscosity response on mortars with time (w/c = 0.40)
152
150
PCE SNF
140
PLS UNA
130
BCS BCA
Flow Value, %
120
110
100
90
80
10 30 60
Time, minutes
Fig. 4-21 Change in flow value of mortars with time (w/c = 0.40)
150
PCE SNF
140
PLS UNA
130 -0.2319
Power: y = 349.19x BCS BCA
2
R = 0.91
Flow value, %
120
110
Linear: y = -0.1079x + 128.26

2
100 R = 0.95
90
80
0 50 100 150 200 250 300 350 400 450 500
Yield stress, Pa
Fig. 4-22 Relationship between yield stress and flow value
153
UNA 875 85
PLS 665 85
PCE 300 75
SNF 250 70 Initial

Final - Initial
0 240 480 720 960 1200 1440

Setting Time, min
Fig. 4-23 Initial and final setting times of prepared mortars (w/c = 0.34)
BCS 1075 300
BCA 850 160
UNA 745 95
PLS 560 100
PCE 330 90
Initial
SNF 260 75 Final - Initial
0 240 480 720 960 1200 1440

Setting Time, min
Fig. 4-24 Initial and final setting times of prepared mortars (w/c = 0.40)
154
1500
0.34, initial 0.40, initial

2
1200 R = 0.91
0.34, final 0.40, final 2
R = 0.88
Setting Times of Prepared Mortar, min
2
R = 0.88
2
R = 0.95
900
600
300
0
0 100 200 300 400 500 600 700 800
Time to Start Acceleration Period in a Heat Curve, min
Fig. 4-25 Relationship between the initial and final setting times of prepared mortars
and time to start the acceleration period in heat curves
0.30
1d
0.25
Cumulative Pore Volume (Intrusion) mL/g
0.20
3d
7d
28d critical
0.15 diameter, dc
91d
0.10
threshold
0.05 diameter, dt
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Pore Diameter, µm
Fig. 4-26 A typical MIP graph (w/c = 0.40, paste with PCE superplasticizer)
155
50
PCE SNF
PLS UNA
40
Total Porosity, %
30
20
10
0
1d 3d 7d 28d 91d
Age
Fig. 4-27 Total porosity of pastes with w/c = 0.34 at various ages
50
45 PCE SNF PLS
40 UNA BCS BCA

35
Total Porosity, %
30
25
20
15
10
0
1d 3d 7d 28d 91d
Fig. 4-28 Total porosity of pastes with w/c = 0.40 at various ages
156
50
(a) W/C = 0.34 G M L
40
30
Porosity, %
L, 27.2
L, 22.3 L, 24.7
L, 25.1
20
10
M, 11.0 M, 9.2 M, 10.8
M, 8.1
G, 1.5 G, 2.4 G, 2.9 G, 2.3

0
PCE SNF PLS UNA
50
(b) W/C = 0.40 G M L
40
30
Porosity, %
L, L, L,
32.9 35.8 L, 33.4
39.2 L,
L,
39.7
20 39.6
10
M, 9.2 M, 7.0 M, 8.0

M, 2.9
M, 0.8 M, 1.7
G, 1.5 G, 2.1 G, 3.0 G, 2.5
0 G, 1.2 G, 1.3
PCE SNF PLS UNA BCS BCA
Fig. 4-29 Total porosities and pore size distributions of the pastes at 1 day
157
50
(a) W/C = 0.34 G M L
40
30
Porosity, %
20 L, 19.0 L, 18.3 L, 22.6

L, 19.2
10
M, 8.6 M, 8.0 M, 7.4 M, 6.3
G, 2.3 G, 2.8 G, 2.3 G, 2.8

0
PCE SNF PLS UNA
50
(b) W/C = 0.40 G M L
40
30 L,
Porosity, %
L, L, 23.5
21.2 L, L, 26.6 L,
25.4 28.9 27.6
20
10 M, 11.9
M, 10.9
M, 10.1
M, 8.7 M, 6.9
M, 7.5
G, 4.0 G, 2.9 G, 3.2 G, 4.5

G, 2.7 G, 2.2
0
Fig. 4-30 Total porosities and pore size distributions of the pastes at 3 days
158
50
(a) W/C = 0.34 G M L
40
30
Porosity, %
20 L, 13.4 L, 13.1
L, 16.8
L, 15.8
10
M, 10.3 M, 11.1
M, 7.0 M, 6.4
G, 2.2 G, 3.2 G, 3.0 G, 3.2

0
PCE SNF PLS UNA
50
(b) W/C = 0.40 G M L
40
30
Porosity, %
L, L,
L, L, L, L, 19.2
18.9 21.5
19.4 21.8 20.2
20
10 M, 10.0 M, 11.3
M, 8.7 M, 9.0
M, 8.6 M, 9.8
G, 4.4 G, 4.4 G, 3.1 G, 2.8 G, 3.6 G, 3.9

0
159
50
(a) W/C = 0.34 G M L
40
30
Porosity, %
20
L, 13.4 L, 13.0
L, 16.1
L, 12.7
10
M, 9.1 M, 9.1
M, 4.8 M, 4.8
G, 2.3 G, 1.9 G, 3.0 G, 2.6
0
PCE SNF PLS UNA
50
(b) W/C = 0.40 G M L
40
30
Porosity, %
L, L, L, L,
L, 18.4 L,
14.1 16.5 15.8
20 16.9 16.8
10 M, 9.3
M, 9.8 M, 9.3
M, 9.5 M, 10.0 M, 8.6
G, 5.8 G, 4.5
G, 3.6 G, 3.1 G, 3.2 G, 3.8
0
160
50
(a) W/C = 0.34 G M L
40
30
Porosity, %
20
L, 12.5
L, 11.6
L, 16.2
L, 12.5
10
M, 8.1 M, 9.2
M, 4.1 M, 4.4
G, 2.9 G, 1.9 G, 3.0 G, 2.6
0
PCE SNF PLS UNA
50
(b) W/C = 0.40 G M L
40
30
Porosity, %
L, L, L, L,
20 16.1 L,
13.9 14.3 L, 12.5
13.2 12.8
10
M, 8.4 M, 9.8 M, 8.8
M, 9.0 M, 9.2 M, 8.4
G, 4.5 G, 3.3 G, 3.3 G, 2.9 G, 4.4

G, 2.7
0
161
80
PCE SNF
PLS UNA
60
Compressive Strength, MPa
40
20
0
1d 3d 7d 28d 91d
Age
Fig. 4-34 Compressive strength of 50mm mortar cubes (w/c = 0.34)
80
PCE SNF PLS

UNA BCS BCA
60
Compressive Strength, MPa
40
20
0
1d 3d 7d 28d 91d
Age
Fig. 4-35 Compressive strength of 50mm mortar cubes (w/c = 0.40)
162
Chapter 5 Conclusions and Recommendations
5.1 Conclusions
The focus of this study is a newly-developed LS based superplasticizer (PLS). The
main objectives are to investigate this LS superplasticizer (PLS) in comparison with
polycarboxylate (PCE), naphthalene (SNF) and the other modified LS (UNA) based
superplasticizers and with regular LS water reducing admixtures (BCS and BCA).
The mixtures were designed to achieve similar workability, thus the type and dosage
of the admixtures have influence on various properties. Based on the laboratory
results, the following conclusions may be drawn:
1. It is clear that the water reducing admixtures and superplasticizers delayed
cement hydration for both w/c ratios at early ages. However, the degree of
retardation is different for admixtures. The retardation of the pastes are in
the order of SNF < PCE < PLS < UNA < BCA < BCS based on the rate of
heat and length of the induction period. This retardation order of pastes
with admixtures at early ages is supported by cumulative heat, C3S
consumption and CH precipitation.
163
2. The test results, including C3S consumption, CH precipitation and non-
evaporable water content and compressive strength, suggest that the
admixtures did not have significant effect on the cement hydration at late
ages, from 7 to 91 days.
3. From yield stress determined by BML coaxial rheometer, the workability
loss of mortars with LS superplasticizers (PLS and UNA) were similar
within the first hour, but were less than those with SNF and PCE
superplasticizers. The workability loss of the cement pastes with two
regular water reducing admixtures (BCS and BCA) was more significant
than those with the superplasticizers in the same period of time. This
corresponds to the observation made from the heat development that the
BCS and BCA admixtures accelerated cement hydration at the very
beginning.
4. For the two modified LS based superplasticizers, plastic viscosities remain
relatively unchanged within the first hour for both w/c ratios whereas
mortars with PCE and SNF superplasticizers had some variation in plastic
viscosities. Nevertheless, the changes of plastic viscosity with time were
much less than those of the yield stress.
5. The order of setting times of the mortars with admixtures agree with the
length of induction periods in the heat curves of the respective pastes, i.e.
SNF < PCE < PLS < UNA< BCA < BCS. The admixtures have strong
influence on the initial setting times. However, once the mortars reached
the initial setting, the final setting was not significantly affected by the
admixtures.
6. For the four superplasticizers, better workability retention corresponds to
164
longer setting time. However, the two regular LS based water reducing
admixtures had longer setting time, but poor workability retention which is
probably related to their acceleration of cement hydration during the first
hour according to the rate of heat curves.
7. At 28 and 91 days, the porosity of the paste with the LS superplasticizers
at w/c of 0.34 was similar to that with the SNF admixture, but was higher
than that with the PCE admixture. At w/c of 0.40, the total porosity of the
pastes with different admixtures was not significantly different at 28 days.
8. Pore size distributions of the pastes changed with time due to cement
hydration and they differed with respect to w/c ratios and admixtures. In
general, the proportions of small capillary pores in the pastes investigated
were not significantly different, and the differences were mainly in the
large and medium capillary pores. The pastes with LS superplasticizers
had similar large pores at 91 days compared to the paste with PCE
admixture, but less large pores compared to the paste with SNF admixture
at both w/c ratios. However, the pastes with LS superplasticizers had more
medium pores compared to the pastes with PCE and SNF admixtures. The
pastes with the regular LS admixtures (BCS and BCA) appeared to have
less large capillary pores at 91 days compared to those with the
superplasticizers. The threshold and critical pore diameters of the pastes
were not significantly affected by the admixtures.
9. The chemical admixtures investigated affected early compressive strength
of the mortars due to their different retarding effects. However, the
strength of the mortars was not significantly affected by the admixtures
beyond 7 days.
165
10. The performances of regular and modified LS based admixtures were
different at the early ages but similar at 28 and 91 days. The regular LS
admixtures retarded cement hydration much more than the modified LS
superplasticizers. It was reflected on the heat generation of cement pastes
and setting times of respective mortars. On the other hand, the mortars
with regular LS admixtures had much higher rate of workability loss than
those with the modified LS superplasticizers.
5.2 Recommendations
Further studies are recommended in the following areas:
1. The current studies, including the heat evolution, C3S consumption, CH
production, NEW content; were concentrated on degree of hydration. It is seen
that water reducing admixtures delayed cement hydration and it also
demonstrated that these admixtures delayed C3S hydration to different degrees.
But it remains unclear how they influence the hydration rate of other clinker
phases, particularly C3A in cement at early age. Further studies of the
influences of these admixtures on the C3A and other relevant phases at early
age are recommended.
2. Microstructures of fresh cement paste with and without admixtures are of
great importance to understand cement hydration. Further study of the early-
age microstructures including the morphology – the shape and the size, would
provide a clear image of the anhydrated cement particles and hydration
products such as ettringite.
3. A study of the microstructures of hardened cement paste with and without
admixtures would be of great help to better understand cement hydration at
166
late ages. Microstructures at late stages include distribution of hydration
products and the pore structure of the paste samples.
4. Since the admixtures affect the pore structure of the cement pastes as
discussed before, it is important to determine how the differences in the pore
structure influence permeability and resistance of concrete to chloride ion
penetration, which affect long-term durability of reinforced concrete structures.
167
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180
Appendix
Table A-1 Intensity ratios of CH, C3S to anatase in pastes from XRD (w/c = 0.34)
I/Io CTR 2h 4h 8h 12h 1d 3d 7d 28d 91d

C3S 29.4° 0.75 0.71 0.48 0.39 0.25 0.19 0.17 0.15 0.15
C3S 51.7° 0.38 0.32 0.21 0.16 0.09 0.05 0.04 0.03 0.03
I/Io PCE 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.95 0.86 0.74 0.52 0.32 0.21 0.17 0.16 0.15
C3S 51.7° 0.48 0.39 0.34 0.24 0.12 0.06 0.05 0.04 0.03
I/Io SNF 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.86 0.70 0.58 0.43 0.28 0.21 0.18 0.17 0.14
C3S 51.7° 0.39 0.34 0.25 0.18 0.11 0.06 0.04 0.04 0.00
I/Io PLS 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.86 0.84 0.79 0.58 0.31 0.22 0.15 0.14 0.14
C3S 51.7° 0.39 0.39 0.38 0.26 0.10 0.05 0.04 0.03 0.00
I/Io UNA 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.85 0.84 0.81 0.66 0.35 0.19 0.18 0.17 0.16
C3S 51.7° 0.40 0.40 0.39 0.32 0.15 0.05 0.04 0.04 0.00
181
Appendix
Table A-2 Intensity ratios of CH, C3S to anatase in pastes from XRD (w/c = 0.40)
I/Io CTR 2h 4h 8h 12h 1d 3d 7d 28d 91d

C3S 29.4° 0.93 0.88 0.69 0.60 0.39 0.27 0.19 0.18 0.14
C3S 51.7° 0.48 0.46 0.33 0.22 0.15 0.07 0.04 0.02 0.00
I/Io PCE 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.95 0.88 0.85 0.72 0.38 0.22 0.16 0.15 0.14
C3S 51.7° 0.46 0.45 0.41 0.26 0.13 0.06 0.00 0.00 0.00
I/Io SNF 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.92 0.89 0.72 0.52 0.35 0.24 0.20 0.16 0.14
C3S 51.7° 0.46 0.44 0.36 0.21 0.13 0.06 0.04 0.00 0.00
I/Io PLS 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.88 0.86 0.84 0.62 0.44 0.23 0.17 0.15 0.14
C3S 51.7° 0.44 0.43 0.39 0.23 0.18 0.07 0.04 0.00 0.00
I/Io UNA 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.93 0.86 0.85 0.80 0.49 0.25 0.19 0.18 0.13
C3S 51.7° 0.44 0.42 0.41 0.42 0.21 0.07 0.04 0.00 0.00
I/Io BCS 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.86 0.81 0.79 0.77 0.52 0.24 0.18 0.16 0.13
C3S 51.7° 0.42 0.39 0.38 0.41 0.25 0.08 0.00 0.00 0.00
I/Io BCA 2h 4h 8h 12h 1d 3d 7d 28d 91d
C3S 29.4° 0.92 0.86 0.83 0.80 0.57 0.26 0.18 0.17 0.11
C3S 51.7° 0.42 0.39 0.39 0.38 0.26 0.07 0.03 0.00 0.00
Table A-3 Non-evaporable water content in pastes from furnace burning (w/c = 0.34)
2h 4h 8h 12h 1d 3d 7d 28d 91d

CTR 2.18 3.54 7.28 8.36 11.58 13.75 14.43 15.23 17.54
PCE 1.44 1.66 3.50 6.53 10.35 13.40 14.21 14.85 15.14
SNF 2.05 2.97 7.62 7.80 10.92 13.48 14.19 15.35 15.82
PLS 1.30 1.45 2.48 6.07 11.75 13.55 14.75 15.67 17.68
UNA 1.75 1.83 2.19 4.06 9.86 13.34 14.70 15.52 17.25
182
Appendix
Table A-4 Non-evaporable water content in pastes from furnace burning (w/c = 0.40)
2h 4h 8h 12h 1d 3d 7d 28d 91d

CTR 1.96 3.89 6.20 8.42 9.14 12.07 14.22 15.56 16.71
PCE 1.28 1.66 3.59 7.35 10.06 13.09 13.82 16.15 16.67
SNF 1.31 1.81 3.06 6.31 9.48 12.26 14.23 15.99 16.75
PLS 1.57 2.82 3.87 7.77 8.95 11.88 13.81 15.88 16.92
UNA 1.82 1.91 3.45 6.34 7.62 12.85 14.79 15.21 16.84
BCS 1.72 1.97 2.90 3.05 6.37 12.40 15.46 16.17 17.62
BCA 1.79 1.87 2.35 2.45 6.54 12.13 14.73 16.51 17.94
Table A-5 Calcium hydroxide content in pastes from TG (w/c = 0.34)
CH, % 2h 4h 8h 12h 1d 3d 7d 28d 91d

CTR 2.36 5.28 7.82 11.45 12.20 14.49 15.21 15.97
PCE 5.59 9.94 12.31 14.69 14.98 16.29
SNF 4.37 7.21 10.96 13.58 14.08 14.74 16.70
PLS 2.52 10.71 12.67 13.41 14.15 15.51
UNA 10.44 12.92 13.20 14.01 14.65
Table A-6 Non-evaporable water content in pastes from TG (w/c = 0.34)

NEW, % 2h 4h 8h 12h 1d 3d 7d 28d 91d
CTR 3.84 5.88 8.78 10.75 14.01 16.70 17.78 18.82 19.45
PCE 3.58 4.08 6.82 9.49 13.19 17.00 17.22 18.23 18.53
SNF 4.23 6.27 10.19 10.56 14.59 16.42 16.93 18.75 20.15
PLS 3.38 4.63 6.44 10.03 13.07 16.85 17.91 18.57 19.70
UNA 4.09 5.23 6.04 6.47 11.89 16.97 17.83 18.76 19.67
Table A-7 Calcium hydroxide content in pastes from TG (w/c = 0.40)
CH, % 2h 4h 8h 12h 1d 3d 7d 28d 91d

CTR 1.78 5.09 8.12 10.70 12.23 13.49 16.69 17.39
PCE 4.75 10.52 12.95 15.54 16.18 16.56
SNF 3.31 7.10 10.96 13.66 14.45 14.67 16.49
PLS 8.83 14.12 15.54 15.84 16.85
UNA 6.80 12.13 15.26 16.18 17.20
BCS 5.23 13.75 14.57 17.21 17.32
BCA 5.75 12.49 13.51 15.49 17.16
183
Appendix
Table A-8 Non-evaporable water content in pastes from TG (w/c = 0.40)

NEW % 2h 4h 8h 12h 1d 3d 7d 28d 91d
CTR 6.04 6.25 9.87 12.99 13.33 18.25 18.44 20.22 22.39
PCE 3.85 4.40 5.76 9.87 13.93 16.87 18.39 19.36 21.76
SNF 6.12 6.34 6.69 11.20 13.03 17.84 18.22 19.76 20.98
PLS 5.13 5.15 5.81 6.65 10.54 17.24 18.77 19.94 21.20
UNA 5.18 6.13 6.18 6.86 12.77 15.73 18.28 21.46 21.76
BCS 4.77 5.57 5.80 7.24 9.02 17.11 18.51 21.34 22.48
BCA 4.50 4.82 5.46 6.21 10.38 16.39 18.54 20.47 22.12
Table A-9 Yield stress, plastic viscosity and flow values of mortars with time (w/c =
0.34)
Rheological Parameters Flow Value
Yield Stress Plastic Viscosity 10 drops 25 drops
PCE τ0, Pa µ, Pa.s % %
10 min 70.5(1) ± 5.0(2) 7.0 ± 2.6 n.m.(3) Overflow
30 min 178 6.2 n.m. 120
60 min 264 7.2 n.m. 106
SNF τ0, Pa µ, Pa.s % %
10 min 68.5 ± 0.7 8.4 ± 0.5 n.m. Overflow
30 min 255 7.8 n.m. 118
60 min 470 6.3 n.m. 100
PLS τ0, Pa µ, Pa.s % %
10 min 77.0 ± 18.4 11.9 ± 3.2 n.m. Overflow
30 min 83 9.3 140 Overflow
60 min 147 9.5 102 132
UNA τ0, Pa µ, Pa.s % %
10 min 70.3 ± 17.0 11.1 ± 1.8 n.m. Overflow
30 min 79 9.3 140 Overflow
60 min 108 9.8 112 144
(1) (2) (3)
average value of the three data points standard deviation n.m. = not measured
184
Appendix
Table A-10 Yield stress, plastic viscosity and flow value of mortars with time (w/c =
0.40)
Rheological Parameters Flow Value

Yield Stress Plastic Viscosity 10 drops 25 drops
PCE τ0, Pa µ, Pa.s % %
(1) (2)
10 min 77.3 ± 6.1 4.1 ± 0.1 120 n.m.(3)
30 min 100 3.6 118 140
60 min 194 3.8 114 138
SNF τ0, Pa µ, Pa.s % %
10 min 73.7 ± 5.8 3.5 ± 0.2 116 n.m.
30 min 261 3.7 98 134
60 min 380 4.3 86 120
PLS τ0, Pa µ, Pa.s % %
10 min 76.0 ± 8.7 3.3 ± 0.2 144 n.m.
30 min 94 3 114 n.m.
60 min 162 3 112 142
UNA τ0, Pa µ, Pa.s % %
10 min 78.7 ± 6.8 4.7 ± 0.6 140 n.m.
30 min 97 3.5 122 146
60 min 148 3.5 110 140
BCS τ0, Pa µ, Pa.s % %
10 min 126 5.7 98 124
30 min 390 7.1 86 96
60 min n.m. n.m. n.m. n.m.
BCA τ0, Pa µ, Pa.s % %
10 min 75 ± 6.2 3.7 ± 0.2 122 n.m.
30 min 232 3.3 102 140
60 min 467 2.6 80 120
(1) (2) (3)
average value of the three data points standard deviation n.m. = not measured
185
Appendix
Table A-11 Capillary pore size distribution and total porosity of pastes (w/c = 0.34)
PCE SNF
Pore Volume,
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
mL/g
Gel
0.006 0.010 0.011 0.013 0.016 0.014 0.016 0.018 0.011 0.011
(3.8~10nm)
Medium
Capillary 0.047 0.038 0.033 0.027 0.022 0.047 0.045 0.036 0.027 0.025
(10~50nm)
Large
Capillary 0.095 0.084 0.075 0.071 0.068 0.146 0.104 0.093 0.090 0.092
(50~10µm)
Total Porosity
34.8 29.9 25.0 19.8 19.4 35.6 29.1 26.4 22.8 22.6
(%)
PLS UNA
Pore Volume,
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
mL/g
Gel
0.015 0.013 0.017 0.016 0.013 0.013 0.012 0.017 0.016 0.014
(3.8~10nm)
Medium
Capillary 0.048 0.043 0.057 0.049 0.035 0.063 0.028 0.061 0.054 0.049
(10~50nm)
Large
Capillary 0.129 0.110 0.074 0.072 0.050 0.158 0.099 0.072 0.076 0.066
(50~10µm)
Total Porosity
36.8 28.9 26.8 25.5 22.7 40.3 31.7 27.4 24.7 24.2
(%)
186
Appendix
Table A-12 Capillary pore size distribution and total porosity of pastes (w/c = 0.40)
PCE SNF
Pore Volume,
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
mL/g
Gel (3.8~10nm) 0.0097 0.0233 0.0249 0.0156 0.0172 0.0132 0.0146 0.026 0.0201 0.0182
Medium
Capillary 0.059 0.0638 0.0495 0.0251 0.0323 0.0431 0.0476 0.0588 0.0545 0.0498
(10~50nm)
Large Capillary
0.2118 0.1242 0.111 0.0382 0.0531 0.2212 0.1391 0.1113 0.0923 0.0892
(50~10000nm)
Total Porosity
43.6 36.1 32.4 29.1 26.8 44.9 36.7 33.3 29.9 28.4
(%)
PLS UNA
Pore Volume,
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
mL/g
Gel (3.8~10nm) 0.0167 0.0153 0.0221 0.0181 0.0165 0.0154 0.0169 0.0185 0.0194 0.0157
Medium
Capillary 0.0166 0.0526 0.0622 0.0555 0.0492 0.0492 0.0584 0.0641 0.0601 0.0535
(10~50nm)
Large Capillary
0.2214 0.202 0.1579 0.0982 0.0718 0.2062 0.1534 0.1411 0.1113 0.0769
(50~10000nm)
Total Porosity
45.1 38.6 33.5 29.5 27.3 43.9 39.6 34.1 31.6 25
(%)
BCS BCA
Pore Volume,
1d 3d 7d 28d 91d 1d 3d 7d 28d 91d
mL/g
Gel (3.8~10nm) 0.0075 0.0182 0.0212 0.0178 0.0181 0.0077 0.0254 0.0221 0.0271 0.0261
Medium
Capillary 0.0052 0.0388 0.0525 0.0407 0.0519 0.0103 0.0663 0.064 0.0558 0.0523
(10~50nm)
Large Capillary
0.2501 0.1549 0.1177 0.0791 0.0794 0.2382 0.1314 0.109 0.0948 0.0741
(50~10000nm)
Total Porosity
41.6 37.7 32.9 29.2 24.1 42.7 39.9 34.3 29.6 25.8
(%)
187
Appendix
Table A-13 Average & standard deviation of mortar compressive strengths (w/c = 0.34)
fcu* PCE SNF PLS UNA

1d 35.4 37.5 24.8 17.4
3d 53.2 54.1 49.7 45.7
7d 61.9 66.0 61.6 56.4
28d 69.7 72.6 70.7 64.8
91d 73.1 78.6 74.8 70.9
STD**
1d 0.0 0.4 0.5 0.6
3d 0.4 1.8 0.9 1.3
7d 0.3 0.3 1.0 1.4
28d 2.4 0.9 1.2 2.5
91d 3.8 3.3 4.6 1.5
* = average of compressive strength of three 50mm mortar cubes
** = standard deviation of the three fcu of the mortar cubes
Table A-14 Average & standard deviation of mortar compressive strengths (w/c = 0.40)
fcu* PCE SNF PLS UNA BCS BCA

1d 24.0 28.7 21.3 16.9 0.0 8.9
3d 45.3 47.0 43.0 40.2 40.5 40.0
7d 52.9 56.5 51.1 52.0 54.8 51.7
28d 70.8 67.9 62.9 66.7 73.0 67.0
91d 73.3 75.5 68.9 69.8 75.7 72.7
STD**
1d 0.3 1.1 0.8 0.2 0.0 0.6
3d 0.6 2.1 0.8 1.4 1.0 0.6
7d 1.1 1.3 2.0 0.8 0.5 1.3
28d 1.7 2.9 2.7 1.1 1.1 1.8
91d 0.6 2.2 1.6 2.3 1.3 1.0
* = average of compressive strength of three 50mm mortar cubes
** = standard deviation of the three fcu of the mortar cubes
188
Appendix
Fig. A-1 TG curves of the control paste (w/c = 0.34)
Fig. A-2 TG curves of PCE paste (w/c = 0.34)
189
Appendix
Fig. A-3 TG curves of SNF paste (w/c = 0.34)
Fig. A-4 TG curves of PLS paste (w/c = 0.34)
190
Appendix
Fig. A-5 TG curves of UNA paste (w/c = 0.34)
Fig. A-6 TG curves of the control paste (w/c = 0.40)
191
Appendix
Fig. A-7 TG curves of PCE paste (w/c = 0.40)
Fig. A-8 TG curves of SNF paste (w/c = 0.40)
192
Appendix
Fig. A-9 TG curves of PLS paste (w/c = 0.40)
Fig. A-10 TG curves of UNA paste (w/c = 0.40)
193
Appendix
Fig. A-11 TG curves of BCS paste (w/c = 0.40)
Fig. A-12 TG curves of BCA paste (w/c = 0.40)
194
Appendix
0.25
0.2
Cumulative Intrusion, mL/g
0.15 I-1d
I-3d
I-7d
0.1 I-28d
I-91d
0.05
0
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-13 MIP curves for PCE paste (w/c = 0.34)
0.25
0.20 II-1d
0.15 II-3d
II-7d
II-28d
II-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-14 MIP curves for SNF paste (w/c = 0.34)
195
Appendix
0.25
III-1d
0.20
0.15 III-3d
III-7d
III-28d
0.10 III-91d
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-15 MIP curves for PLS paste (w/c = 0.34)

0.25
IV-1d
0.20
IV-3d
0.15
IV-28d
IV-7d
IV-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-16 MIP curves for UNA paste (w/c = 0.34)
196
Appendix
0.30
A-1d
0.25
0.20
A-3d
A-7d
A-28d
0.15
A-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-17 MIP curves for PCE paste (w/c = 0.40)
0.30
B-1d
0.25
B-3d
0.20
B-7d
B-28d
0.15
B-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-18 MIP curves for SNF paste (w/c = 0.40)
197
Appendix
0.30
C-1d
0.25 C-3d
C-7d
0.20
C-28d
0.15 C-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-19 MIP curves for PLS paste (w/c = 0.40)
0.30
D-1d
0.25 D-3d
0.20 D-7d
D-28d
0.15
D-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-20 MIP curves for UNA paste (w/c = 0.40)
198
Appendix
0.30
E-1d
Cumulative Intrusion, mL/g 0.25
E-3d
0.20
E-7d
0.15 E-28d
E-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-21 MIP curves for BCS paste (w/c = 0.40)
0.30
F-1d
0.25
F-3d
0.20
F-7d
F-28d
0.15 F-91d
0.10
0.05
0.00
0.001 0.01 0.1 1 10 100 1000
Mean Diameter, µm
Fig. A-22 MIP curves for BCA paste (w/c = 0.40)
199

Effect of A Newly Developed Lignosulphonate Superplasticizer On Properties of Cement Pastes and Mortars

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Effect of A Newly Developed Lignosulphonate Superplasticizer On Properties of Cement Pastes and Mortars

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EFFECT OF A NEWLY DEVELOPED

SUN DAO JUN

NATIONAL UNIVERSITY OF SINGAPORE

SUN DAO JUN

entire course of this research.

comments and constructive discussion.

special thanks to Mr. Lee Wah Peng and Wang Zengrong.

Sincere gratitude is extended to Borregaard Ligno Tech (Sarpsborg, Norway) for

providing the research grant.

support and unconditional love all these years.

Table of Contents ................................................................................................................ii

List of Tables ....................................................................................................................xiv

List of Figures .................................................................................................................xvii

Chapter 1 Introduction ...................................................................................................... 21

1.2 Objectives ...........................................................................................................24

Chapter 2 Literature Review ............................................................................................. 28

2.1 Nature of Water Reducing Admixtures ..............................................................28

2.1.1 Regular Water Reducing Admixtures (WRAs) ............................................29

2.1.1.2 Hydroxyl carboxylic acids and their salts.............................................30

2.1.1.4 Other compounds ..................................................................................31

2.1.2 Superplasticizers (SPs).................................................................................31

2.1.2.1 Modified lignosulphonate(MLS) ...........................................................33

2.1.2.2 Sulphonated melamine / naphthalene formaldehyde condensates

2.1.2.3 Polycarboxylate based (PCE) ...............................................................34

2.2.1 Electrostatic Repulsion.................................................................................37

2.2.2 Steric Hindrance ...........................................................................................38

2.2.3 Solid-Liquid Affinity....................................................................................38

2.2.4 Mechanisms of WRA and SP of Different Natures......................................38

2.3 Portland Cement Hydration ................................................................................39

2.3.1 Chemistry of Portland Cement Hydration....................................................39

2.3.2 Heat Evolution of Portland Cement Hydration ............................................42

2.3.2.1 Measurement of heat evolution of cement hydration ............................42

2.3.2.2 Effect of the admixtures on heat evolution of cement hydration ...........42

2.4 Effect of the Admixtures on Cement Hydration .................................................43

2.4.1 Effect of LS Admixtures ..............................................................................44

2.4.2 Effect of SNF Admixtures............................................................................45

2.4.3 Effect of PCE Admixtures............................................................................47

2.5 Effect of the Admixtures on Workability............................................................48

2.5.1 Workability and Rheological Parameters .....................................................48

2.5.2 Effect of Admixtures on Initial Workability.................................................50

2.5.3 Effect of Admixtures on Workability Retention...........................................52

2.6 Effect of the Admixtures on Setting ...................................................................54

2.7 Effect of the Admixtures on Pore Structure & Strength Development...............55

2.7.1 Principle of Mercury Intrusion Porosimetry and Characterization of Pore

2.7.1.1 Total porosity ........................................................................................56

2.7.1.2 Critical pore diameter...........................................................................56

2.7.1.3 Threshold pore diameter .......................................................................57

2.7.1.5 Evaluation of MIP .................................................................................58

2.7.2 Effect of Admixtures on Pore Structure of Cement Paste ............................59

2.7.2.1 Effect of PCE Admixtures......................................................................59

2.7.2.2 Effect of SNF Admixtures ......................................................................60

2.7.2.3 Effect of LS Admixtures .........................................................................61

2.7.2.4 Comparisons of Effect of PCE, SNF and LS Admixtures......................61

2.8 Drying Techniques of Cement Paste and Testing Methods ................................62

2.8.1 Drying Techniques for Cement Paste...........................................................62

2.8.1.1 Oven drying ...........................................................................................62

2.8.1.2 D-drying ................................................................................................63

2.8.1.3 Vacuum drying ......................................................................................63

2.8.1.4 Solvent exchange ...................................................................................63

2.8.1.5 Freeze drying.........................................................................................64

2.8.2 X-Ray Diffraction (XRD) ............................................................................65

2.8.3 Thermogravimetric Analysis (TG) ...............................................................68