Seeding For CSH Growth

New Advanced Admixtures
for UHPC
Vietnam Concrete Association (VCA)
Hanoi, 13 March 2019
Prof. Dr. Johann Plank

Chair for Construction Chemicals
Technische Universität München, Germany
PCE Effectiveness and Time of Addition
➢ Generally, superplasticizers should be added to concrete
as late as possible
➢ Delayed addition can save up to 50 % in dosage
PCEs can introduce significant amounts of air into concrete

© Prof. Plank 2019
Content …..
….. PCE – the basis for UHPC
….. Admixtures for fast flowing concrete
….. Non-adsorbing flow enhancers
….. Phosphate ester superplasticizers
….. Early strength
enhancing admixtures
….. Conclusion
Strength Development From Clinker Phases
C3S responsible for early strength of concrete:
© Prof. Plank 2019

The Difference Between C3S and C2S
Ca3(SiO4)O (triclinic) Ca2(SiO4)
O2-
C3S is tricalcium oxy silicate
© Prof. Plank 2019

Admixtures For High Early Strength
Conventional accelerators
Ca(NO3)2, Ca(HCOO)2
Alkaline accelerators
Na2SiO3, NaAl(OH)4
Alkali-free accelerators
Al(OH)SO4, Al(OH)2(HCOO),
Al(OH)3 amorphous
Disadvantage: they all reduce final strength !

© Prof. Plank 2019
C-S-H Foils as Nuclei for C-S-H Needles
C-S-H foils C-S-H needles
1. I.G. Richardson, The calcium silicate hydrates, Cement and Concrete Research, 38 2008, 137-158.
2. E.T. Rodriguez, I.G. Richardson, L. Black, E. Boehm-Courjault, A. Nonat, J. Skibsted,

Composition, silicate anion structure and morphology of calcium silicate hydrates (C-S-H) synthesized by silica-lime
reaction and by controlled hydration of tricalcium silicate, Advances in Applied Ceramics, 114, 2015, 362-371.
© Prof. Plank 2019
Seeding Effect of C-S-H-PCE Nanocomposites
Preparation of Nano C-S-H Seed Crystals using PCE :
PCE
Na2SiO3 + Ca(NO3)2 C-S-H - PCE
Thin foils, dispersed by PCE
• C-S-H seed crystals accelerate C-S-H formation
Source: BASF
© Prof. Plank 2019

Early Strength Enhancement with C-S-H-PCE
• Nanofoils of C-S-H - PCE composite produce significantly
higher early strengths
500 nm
TEM image of C-S-H – PCE Mortar testing according to DIN EN 196-1

nanocomposite after 6 and 10 h; CEM I 52.5 R, w/c = 0.5
© Prof. Plank 2019

Metamorphosis of C-S-H – PCE
2h 2h 4h
Foils
Foils
50 nm PCE shell 50 nm 50 nm
Nanofoils form inside the metastable C-S-H droplets

Recrystallisation of C-S-H
5h 4,5 h 4h
50 nm 50 nm 50 nm
© Prof. Plank 2019

Acceleration of CEM II /B-V by C-S-H – PCE
OPC Clinker + 35 % fly ash + 2,0 % C-S-H – PCE:
Portlandite reflection
Earlier consumption of Portlandite (Ca(OH)2) signifies

that pozzolanic reaction starts earlier
Kanchanason V., Plank J.,
"Effectiveness of a calcium silicate hydrate – Polycarboxylate ether (C-S-H-PCE) nanocomposite on early strength
development of fly ash cement",
Construction and Building Materials 169 (2018) 20 – 27.
Acceleration of CEM II /B-S by C-S-H – PCE
OPC Clinker + 35 % Slag + 2,0 % C-S-H – PCE:
Portlandite
Strength exceeding
that of OPC !
Hemicarbonate
© Prof. Plank 2019

Acceleration of CEM II /B-V by C-S-H – PCE
OPC Clinker + 35 % Calcined clay + 2.0 % C-S-H – PCE:
Portlandite
Strength exceeding
that of OPC !
Hc
Hemicarbonate
© Prof. Plank 2019

C-S-H-PCE Accelerator Improves Durability of Concrete
C-S-H - PCE initiates C-S-H crystallization also in the pore solution

between cement particles
normally, C-S-H crystallizes only on the surface of cement particles
decreased porosity and permeability increase durability

→ more ecological concrete !
Valentini L., Ferrari G., Russo V., Stefancic, M., Serjun V.Z., Artioli G.,
„Use of nanocomposites as permeability reducing admixtures“,
Journal of the American Ceramic Society 101(2018) 4276.- 4284.
© Prof. Plank 2019
C-S-H-PCE Produces More Dense Microstructure
© Prof. Plank 2019

TECHNISCHE UNIVERSITÄT MÜNCHEN
Lehrstuhl für Bauchemie
A Comprehensive Study on Calcium Silicate Hydrate –

Polycarboxylate Superplasticizer (C-S-H – PCE) Nanocomposites
as Accelerating Admixtures in Cement
Vipasri Kanchanason
Vollständiger Abdruck der von der Fakultät für Chemie der

Technischen Universität München
zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften (Dr. rer. nat.)
genehmigten Dissertation.
Vorsitzender: Univ.‐Prof. Dr. Michael Schuster

Prüfer der Dissertation: 1. Univ.‐Prof. Dr. Johann P. Plank
2. apl.Prof. Dr. Anton Lerf
Die Dissertation wurde am 23.01.2018 bei der Technischen Universität München

eingereicht und durch die Fakultät für Chemie am 12.03.2018 angenommen.
“The moon and the stars reside up high,
one must climb a long ladder to reach them”
The Royal Guidance of His Majesty the King Bhumipol Adulyadej

Acknowledgements
I would like to express my deepest gratitude to my supervisor, Prof. Dr. Johann Plank, who
has provided me the great opportunity to conduct my doctoral study here at the Chair for
Construction Chemistry, Technische Universität München, and who has given me the
valuable guidance, encouragement, motivation, and immense knowledge throughout my Ph.D
work. Without his continuous support and patience it would not be possible to achieve this
research. I greatly appreciate the precious opportunities he has offered to improve my soft
skills via working as an assistant in lab courses and oral presentations at international
conferences.
I would also like to gratefully thank SCG Cement-Building Materials for financial support of
my study at TUM.
I would like to acknowledge Prof. Dr. Sevil Weinkauf, Dr. Peter Carsten and Dr. Marianne
Hanzlik from the center of Electron Microscopy at TUM’s Chemistry department for their
technical support with TEM. A special “thank you” is also extended to Florian Weigl and
Jasmin Haberl from department of Analytical Chemistry at TUM for conducting the ICP-
OES measurements.
Special thanks go to my senior Ph.D. colleagues Salami Taye, Constantin Tiemeyer, Nan
Zou, Thomas Pavlitschek, Stefan Baueregger, Ahmad Habbaba, Alex Lange, Julia
Pickelmann, Markus Meier, Teresa Pique, Teepakorn Napharatsamee, Huiqun Li, Michael
Kaul, Lei Lei, Johanna de Reese, Laura Severin and Thomas Hurnaus for their help and
suggestions. Also, I would like to express my gratitude to Dr. Oksana Storcheva for her help
-I-
regarding the 29Si NMR and TEM measurements. Thanks to our secretaries Anke Kloiber and
Liu Jingnu for all their administrative work.
I owe my deepest gratitude to my other colleagues for their friendly assistance, cheerfulness,
and creative suggestions: Somruedee Klaithong, Timon Echt, Maike Müller, Manuel Ilg,
Markus Schönlein, Johannes Stecher, Mouala Moumin, Stefanie Gruber, Claudia Chomyn,
Marlene Schmid, Alexander Engbert, My Linh Vo, Florian Hartmann, Michael Spörl,
Magdalena Strobl, Christopher Schiefer, Johann Mekulanetsch, Haijing Yang, Dr. Theau
Conte, Eileen Quek Ee Ling, Nabisha Syed Ali, Wenjun Li and Dagmar Lettrich.
The great appreciation also goes to the Analytical and Testing Lab of Siam Research and
Innovation Company (SRI) for providing the XRF measurements and for conducting the
concrete tests. I truly thank my colleagues at the Admixture and Advanced Materials
Research group of SRI for their technical support and valuable discussions.
I am grateful to TUM English Writing Center for consulting in English writing of my thesis.
And finally I would like to thank my mother Kruewun Kanchanason, my father Somboon
Kanchanason, my sister Kanchana Puangjit and her family, my brother Kittipong Rakchuay,
and my beloved Thai friends here and in Thailand for their love, support and encouragement
over all these years. Without all of you, this work would have not been successful.
- II -
List of Publications
This thesis includes the following publications:
Peer reviewed SCI(E) journal:
1) V. Kanchanason, J. Plank
Role of pH on the structure, composition and morphology of C-S-H – PCE
nanocomposites and their effect on early strength development of Portland cement
Cement and Concrete Research, 102, 2017, 90-98.
Effectiveness of a calcium silicate hydrate – polycarboxylate ether (C-S-H–PCE)
nanocomposite on early strength development of fly ash cement
Construction and Building Materials, 169, 2018, 20-27.
Non-review conference papers:
Early nucleation and crystal growth of C-S-H – PCE nanocomposites used as strength
enhancers in cement
The 12th International Conference on Superplasticizers and Other Chemical Admixtures
in Concrete, Beijing, China, October 28 - October 31, 2018, accepted
- III -
Relationship between the structure and morphology of C-S-H – PCE nanocomposites and
their accelerating effect in cement
Tagung Bauchemie, Bauhaus-Universität Weimar, Tagungsband 1, Weimar, Germany,
GDCh-Monographie, 52, 2017, 36-40.
Effectiveness of C-S-H – PCE Nanocomposites Possessing Globular and Foil-Like
Morphology on Early Strength Development of Portland Cement
2nd ICCCM International Conference on the Chemistry of Construction Materials,
Technische Universität München, Munich, Germany, GDCh-Monographie, 50, 2016, 85-
88.
C-S-H – PCE nanocomposites for enhancement of early strength of cement
19. ibausil, Bauhaus-Universität Weimar, Tagungsband 1, Weimar, Germany, 2015, 759-
766.
C-S-H – PCE Nanocomposites for Enhancement of Early Strength of Portland Cement
Proceedings of the 14th ICCC International Congress on the Chemistry of Cement,
Abstract book p. 326, Proceedings CD, Section 4: Admixtures, Beijing, China 2015.
- IV -
List of abbreviations
General abbreviations:
APEG -allyl--methoxy or -hydroxy poly(ethylene glycol)

API American Petroleum Institute
bwoc By weight of cement
CEM I Portland cement with maximum 5 wt. % of minor constituents
CEM II Portland composite cement
d50 Average particle size (50 % of particles by number are below that
value)
DEA Diethanol amine
DEIPA Diethanolisopropanol amine
DI water Deionized water
DIN The German national standards organization
DLS Dynamic Light Scattering
EO Ethylene oxide
eq/g Equivalent amount per gram of polymer
FT-IR Fourier-transform infrared
g gram
GGBFS Ground granulated blast furnace slag
hr Hour
HPEG -methallyl--methoxy or -hydroxy poly(ethylene glycol)
IPEG Isoprenyl oxy poly(ethylene glycol)
Ip C-S-H inner product in hardened cement
J Joule
LOI Loss on ignition
m Meter
MA Methacrylic acid
MAS Magic angle spinning
MCL Mean chain length
min Minute
mL Milliliter
Mn Number average molecular weight
MPEG Methoxy poly(ethylene glycol)
MPEG-MA -methoxy poly(ethylene glycol) methacrylate ester
-V-
Mw Weight average molecular weight
nm Nanometer
NMR Nuclear magnetic resonance
Op C-S-H outer product in hardened cement
OPC Ordinary Portland cement
Pa Pascal
PAAM Polyamidoamine
PCE Polycarboxylate (ether)
pH Pondus hydrogenii
PDI Polydispersity index
PEG Polyethylene glycol
PEO Polyethylene oxide
Poly-DADMAC Poly diallyl dimethylammonium chloride
PVA Polyvinylalcohol
rpm Rotations per minute
SCC Self-compacting concrete
SCM Supplementary cementitious material
sec Second
TEA Triethanol amine
TEM Transmission electron microscopy
TIPA Triisopropanol amine
TOC Total organic carbon
UHPC Ultra-high strength concrete
W Watt
wt. % Weight percent
w/b ratio Water-to-binder ratio
w/c ratio Water-to-cement ratio
VPEG -vinyl--hydroxy poly(ethylene glycol)
XRD X-ray diffraction
XRF X-ray fluorescence
 Micro
- VI -
Notation in cement chemistry:
Notation Chemical formula Mineral name
A Al2O3 Aluminium oxide
C CaO Calcium oxide
F Fe2O3 Iron oxide
H H2O Water
S SiO2 Silicon dioxide
$ SO3 Sulfur trioxide
C3 S Ca3(SiO4)O Tricalcium silicate
C2 S Ca2(SiO4) Dicalcium silicate
C3 A Ca9Al6O18 Tricalcium aluminate
C4AF Ca4Al2Fe2O10 Tetracalcium alumino ferrite
C$H2 CaSO4·2H2O Gypsum
C6A$3H32 (C3A·3C$·H32) [Ca6Al2(OH)12](SO4)3·26H2O Ettingite
C4A$H12 (C3A·C$·H12) [Ca4Al2(OH)12](SO4)·6H2O Monosulfoaluminate
C-S-H xCaO·ySiO2·zH2O Calcium silicate hydrate
- VII -
Contents
1 Introduction………………………………………………………………...1
2 Aims and scope……………………………………………………………..3
2.1 Influence of different PCE structures on the strength enhancing effect
of C-S-H particles………………………………………………………....…...…..3
2.2 Effect of synthesis conditions on the effectiveness of C-S-H – PCE
nanocomposites as accelerators in Portland cement………..………………….…...4
2.3 Application of the C-S-H – PCE nanocomposite as an accelerator in
blended cements………………………………………………………………..…..4
2.4 Nucleation and growth of C-S-H – PCE nanocomposites…………...……….…....4
3 Theoretical background and state of the art………………………….…..5
3.1 Calcium silicate hydrate (C-S-H)..……………………………………….….….….5
3.1.1 Formation of calcium silicate hydrate………………………….....……..…5
a) Nucleation theories..……………………………………….……….…..5
b) Formation of C-S-H in cement…………………....……….……….…..8
- Dissolution…...……………………………………………….…..…..9
- Nucleation……………………………………………………...……10
- Growth of C-S-H……..………….……………….…………..……..10
c) Synthetic C-S-H…………….…………………....…………..….……11
3.1.2 Types of calcium silicate hydrate……….....………………...………...…12
a) Crystalline C-S-H………………...……………..………………….....12
b) Less crystalline C-S-H…………………………………..…………....13
- C-S-H gel….………………………………………………..……....13
- VIII -
- Synthetic C-S-H…..…………………………………………..……15
3.1.3 Structure of C-S-H...…………………….....…………………….….……20
a) Structural models for C-S-H……………...………………………......20
b) Molecular models for C-S-H……………………..………………......22
3.2 Polycarboxylate based superplasticizer………………………………….……….24
3.2.1 Molecular structure of PCEs…………………………..………......…..…24
3.2.2 Preparation of PCEs………………………...…………………......…..…26
3.2.3 Impact of PCE structure on adsorption and dispersion.………......…..….28
3.3 C-S-H-based nanocomposites……………………………….…….…….….……..33
3.3.1 Mode of interaction between C-S-H and organic compounds......…....…..33
a) Surface adsorption via calcium complexation...…………….....…...…33
b) Grafting at the defect sites on the silicate chains……..……...…..........34
c) Intercalation into the interlayer galleries of the C-S-H…...….…..........35
d) Covalent bonding of organic compounds with C-S-H…………..….....36
3.4 Hydration kinetics of Portland cement…………………………….…….……..…38
3.5 Hardening accelerators...…………….…………………………….…….….….…41
3.5.1 Accelerating chemicals...………………………………………...….....…41
3.5.2 C-S-H as an accelerator..………………………………………...….....…43
4 Materials and methods………………………………………………..…..47
4.1 Materials………………………………………………………………….……….47
4.1.1 Chemicals for the synthesis of C-S-H…………………………...…….….47
4.1.2 Polycarboxylate superplasticizers (PCEs)..……………………...….....…47
4.1.3 Cement…………………………………....……………………...…....….50
4.2 Methods………………………………………………………………….….....….53
4.2.1 Preparation and characterization of C-S-H – PCE nanocomposites......….53
- IX -
4.2.2 Principal techniques…………...…………………………………...........57
- Specific charge amount….……………………………………………57
- Particle size analysis…….……………………………………………58
- X-ray diffraction……..….……………………………………………58
- Fourier-transform infrared spectroscopy…..…………………………59
- Nuclear magnetic resonance spectroscopy...…………………………60
- Total organic carbon content…………………………………………61
- Transmission electron microscopy...…………………………………61
- Isothermal heat flow calorimetry..…………………………………...62
- Mortar testing………...….………………………………………...…63
- Concrete testing……...….……………………………………………65
5 Results and discussion…………………………………………………..67
5.1 Influence of different PCE structures on the strength enhancing effect of
C-S-H particles……………………………………………………………......….69
5.1.1 Effect of the side chain length of PCE…………………………...…..…69
5.1.2 Effect of the grafting density of PCE…………….……………...…...…83
5.2 Effect of synthesis conditions on the effectiveness of C-S-H – PCE
nanocomposites as accelerators in Portland cement………………………..…...95
5.2.1 Effectiveness of C-S-H – PCE nanocomposites in Portland cement...…95
5.2.2 Effect of pH on the composition, structure and morphology of
C-S-H – PCE nanocomposites…..……………….……………...…..….99
5.3 Application of the C-S-H – PCE nanocomposite as an accelerator in
blended cements…………………………………………….………………….123
5.3.1 Fly ash blended cement………………………………………….....….123
5.3.2 Slag blended cement……………..……………….……………...…….132
-X-
5.3.3 Calcined clay blended cement.…..……………….……………...…….137
5.4 Nucleation and growth of C-S-H – PCE nanocomposites…………...………...141
6 Summary and outlook………………………………………………….159
7 Zusammenfassung und Ausblick……………………………………...163
References…………………………………………………………………..167
- XI -
CHAPTER 1. INTRODUCTION
1 Introduction
CO2 emissions from cement production are generated from the decarbonation of limestone
(CaCO3), the calcination, and the milling process. About 900 kg of CO2 are released for every
ton of clinker produced, thus producing approximately 5 - 7 % of global anthropogenic
carbon dioxide emissions [1-3]. In order to reduce the environmental impact of CO2
emissions from cement production, a part of the clinker can be substituted with
supplementary cementitious materials (SCMs) such as fly ash, blast furnace slag, limestone,
etc. These are known as blended cements (CEM II/III) that are more environmentally more
friendly than Portland cement. However, the disadvantage of blended cements is their slow
early strength development, owing to a reduced rate of cement hydration and the slow
pozzolanic reaction of SCMs.
Generally, calcium based salts such as calcium chloride, nitrate or formate are used as
accelerators to increase the rate of hydration and to boost the early strength of Portland
cement [4]. In blended cements, many reports showed an increase of early strength through
addition of accelerating admixtures, such as calcium chloride, calcium formate, sodium
sulfate, sodium thiocyanate, alkanolamines, and glycerol [5-8]. However, those admixtures
sometimes lead to a decreased final strength.
Calcium silicate hydrate (C-S-H) is well-known as the main hydration product of ordinary
Portland cement. The layered structure of C-S-H consists of linear silicate chains which are
aligned in “dreierketten” sequences and share oxygen atoms with calcium ions in plane [9].
Recently, synthetic C-S-H has been introduced as a seeding material for acceleration of
cement hydration [10-12]. However, only a minor acceleration can be observed from C-S-H
due to rapid agglomeration and/or OSTWALD ripening of the initially formed nanofoils. In
order to maximize acceleration, the size of the C-S-H particles has to be controlled to their
-1-
CHAPTER 1. INTRODUCTION
original nanoscale by adding polymeric dispersants such as polycarboxylate (PCE)
superplasticizers [13-16].
PCE copolymers are known as high-range water-reducing admixtures for concrete. They
are structured in a comb-like shape that consists of a backbone grafted with side chains. The
backbone contains carboxylate anchor groups that are negatively charged and responsible for
the adsorption onto the positively charged surface of e.g. cement particles. The non-ionic side
chains made of polyethylene glycol (PEG) promote dispersion via a steric hindrance effect.
Based on this specific molecular structure, PCEs can be applied to adsorb on freshly formed
C-S-H and to produce C-S-H particles of particularly large surface area which is very
beneficial for effective acceleration of cement hydration [17,18].
In this thesis, C-S-H – PCE nanocomposites were synthesized and used as seeding
materials for the purpose of early strength enhancement in Portland cement and blended
cements. Four main studies were carried out to obtain the superior C-S-H – PCE crystal seeds
and to understand their mode of action. First, the influence of different molecular structures
of PCEs, such as the side chain lengths and the grafting density, on the size of the C-S-H
particles and their ability to accelerate the early strength development of mortar was
investigated. Second, the impact of composition, structure and morphology of the synthesized
C-S-H – PCE nanocomposites on their strength enhancement in Portland cement was studied
mechanistically. Third, the effectiveness of the C-S-H – PCE nanocomposite on the early
strength development of mortar and concrete made from fly ash and slag blended cements
was determined. Based upon these investigations, a model for the interaction between PCE
and C-S-H was proposed and the mechanism of the C-S-H – PCE seeding admixture in
cement was revealed. Finally, the nucleation and crystallization of C-S-H in the presence and
absence of a PCE superplasticizer were investigated.
-2-
CHAPTER 2. AIMS AND SCOPE
2 Aims and scope
This PhD work aims to study and optimize C-S-H – PCE nanocomposites as seed crystals
for the hydration of silicate phases in cement; to achieve the strongest seeding effect in
cement hydration, as demonstrated by the largest gain in early strength of mortar and
concrete; and to measure the key parameters controlling the size and the characteristics of the
C-S-H – PCE nanocomposites.
Therefore, the process variables during the synthesis of C-S-H – PCE, such as the
molecular structure of PCE, pH value, Ca/Si ratio, temperature and ageing time, were looked
at. The characteristics of the synthesized C-S-H – PCE nanocomposites were determined in
the context of their ability to accelerate the early strength development of mortar and concrete
made from Portland or blended cements. Moreover, the mode of action of the C-S-H – PCE
nanocomposite in cement was elucidated. Finally, the study on the nucleation and
crystallization of C-S-H in the presence and absence of PCE is of relevance to understand the
development of C-S-H in actual cement.
2.1 Influence of different PCE structures on the strength enhancing effect of C-S-H
particles
The aim of this part is to use PCE superplasticizers of different molecular structures to
stabilize and control the size of the C-S-H particles. This part describes the effect of side
chain length and grafting density of MPEG PCEs on the size and characteristics of C-S-H
particles. The effectiveness of the synthesized C-S-H – PCE nanocomposites in Portland
cement was determined by 16 hour mortar strength tests. The impact of the C-S-H ‒ PCE
29
nanocomposites in cement was investigated based on heat flow calorimetry and Si MAS
NMR spectroscopy.
-3-
CHAPTER 2. AIMS AND SCOPE
2.2 Effect of synthesis conditions on the effectiveness of C-S-H – PCE nanocomposites as
accelerators in Portland cement
The impact of several process parameters during the C-S-H synthesis on the characteristics
and performance of the C-S-H – PCE nanocomposites was investigated. A design of
experiments (DOE) was used to determine the relationship between process parameters (e.g.
pH value, Ca/Si ratio and temperature) and early strength of mortar. After that, the dominant
parameter impacting the early strength of mortar was identified with regard to the structure,
29
composition and morphology of C-S-H – PCE nanocomposites by using XRD, FT-IR, Si
MAS NMR, TOC, TEM, etc. measurements. Additionally, a structural model for the C-S-H –
PCE nanocomposite was proposed.
2.3 Application of the C-S-H – PCE nanocomposite as an accelerator in blended
cements
Blended cements have a relatively slow early strength development. The first objective of
this section was to study the effectiveness of the C-S-H – PCE nanocomposite on early
strength development of mortar and concrete made from fly ash, slag and calcined clay
blended cements. Secondly, the behavior of the C-S-H – PCE seeding admixture in the
blended cements was studied via in-situ XRD and calorimetric measurements.
2.4 Nucleation and growth of C-S-H – PCE nanocomposites
The very early nucleation and subsequent crystallization of C-S-H in the presence and
absence of an IPEG PCE was monitored via transmission electron microscopy (TEM).
Moreover, the effectiveness of C-S-H – PCE nanocomposites prepared at different ageing
times on the early strength development of mortar was determined.
-4-
CHAPTER 3. THEORETICAL BACKGROUND AND STATE OF THE ART
3 Theoretical background and state of the art
3.1 Calcium silicate hydrate (C-S-H)
Calcium silicate hydrates (C-S-H) consist of CaO, SiO2 and H2O in different
stoichiometry. Their structures are variable in the range from crystalline to semicrystalline
and nearly amorphous [9,19]. Generally, more than 30 crystalline minerals of C-S-H are
known such as tobermorite, jennite, wollastonite, xonolite, etc. The semicrystalline phases
have been reported as imperfect forms of 1.4-nm tobermorite; C-S-H (I) and jennite; C-S-H
(II). Poorly ordered C-S-H (which mistakenly is also called “C-S-H gel”) is the main
hydration product of Portland cement. It forms up to 60 % of hardened cement and presents
the binding phase which is responsible for the strength properties and durability in hardened
cement.
3.1.1 Formation of calcium silicate hydrate
a) Nucleation theories
Nucleation is the most important stage to create the first tiny solid aggregates. It includes
the conglomeration of atoms, ions or molecules to form the first sub-microscopic cluster or
nucleus of the solid crystal [20,21].
i. The classical nucleation theory (CNT) distinguishes between two main processes:
primary and secondary nucleation. Primary nucleation involves the formation of the
first nucleus which occurs in the absence of a solid interface in the solution
(homogeneous nucleation) or in the presence of a solid interface of a foreign seed
(heterogeneous nucleation). Opposite to this, crystal nuclei produced from a pre-
existing crystal is known as secondary nucleation [21].
The classical nucleation theory considers the formation of a molecular or ionic
-5-
cluster [22]. The rate of nucleation (J) is given by a simple Boltzmann approach
(Equation 1).
−𝛥𝐺𝑇
𝐽 = 𝐾 exp( ) Equation 1
𝑘𝑇
where k is the Boltzmann constant, ΔGT is the change in Gibbs free energy, and K
is the kinetic prefactor.
The Gibbs free energy change (barrier height) resulting from cluster formation is
expressed in the CNT as the sum of surface and volume energies (Equation 2). It is
associated with the formation of a spherical cluster of radius “r” that is given by
Equation 3.
𝛥𝐺𝑇 = 𝛥𝐺𝑆 + 𝛥𝐺𝑉 Equation 2
4 𝑟 3
𝛥𝐺𝑇 = 4𝑟 2  − 𝛥 Equation 3
3 𝑉𝑚
where  is the interfacial free energy based on a unit surface area between the
forming phase and the metastable phase, and Δ is the difference in the specific free
energy between liquid and solid.
The growth of a cluster to achieve a stable nucleus depends on the competition
between the surface and volume energies. The surface term, which hinders the
formation of a new phase, increases with r2 whereas the volume energy term which
typically drives nucleation decreases with r3. The net free energy change (ΔGT)
increases with the increase in the cluster size until it reaches a maximum, then the net
free energy decreases at further growth (Figure 1). The size of the cluster
corresponding to the maximum free energy change is known as the critical nucleus
-6-
size (r*) that is the smallest crystalline unit capable of growing further into a larger
crystal. From the critical nucleus size the clusters can overcome the nucleation barrier
energy, form a stable crystal nucleus and grow further. Therefore, at a high level of
supersaturation the rate at which clusters reach the critical nucleus size increases and
nucleation occurs more rapidly.
Figure 1: Graphical representation of the free energy change of a cluster as a function of its
radius (redrawn after [22])
ii. Non-classical nucleation theory
This concept presents that the morphology of the precritical clusters can differ
significantly from that of the final bulk crystal (Figure 2) [23-25]. The mechanisms
can involve formation of liquid droplets [26,27] or amorphous nanoparticles (possibly
formed after aggregation of stable prenucleation clusters) as precursors [28,29]. The
nucleated amorphous solid phase subsequently crystallizes to generate the final stable
crystal product.
-7-
Figure 2: Known pathways to crystallization by particle attachment (from [24])
b) Formation of C-S-H in cement
Ordinary Portland cement (OPC) consists of four main compounds including the two
silicate phases; tricalcium silicate (C3S) and -dicalcium silicate (C2S); and two aluminate
phases; tricalcium aluminate (C3A) and tetracalcium aluminoferrite (C4AF) [9]. Yet, the main
component of cement is C3S representing ~ 50 - 70 %.
When the cement grains make first contact with water, C-S-H is produced together with
Portlandite (Ca(OH)2) as a by-product during the hydration of the C3S and C2S phases via
dissolution-precipitation reaction, as originally proposed by Le Chatelier [30]. This reaction
proceeds in several steps (Equations 4-6 for C3S hydration), including the dissolution of the
silicate phases, the nucleation of metastable and stable forms of C-S-H, and the growth of the
stable C-S-H precipitates [31-33]. So far, it was believed that the C-S-H precipitation follows
a classical nucleation process [34].
-8-
C3S dissolution
Ca3SiO5 + 3H2O → 3Ca2+ + 4OH- + H2SiO42- Equation 4
C-S-H precipitation
1.7Ca2+ + 1.4OH- + H2SiO42- → (CaO)1.7( SiO2)(H2O)1.7 Equation 5
Ca(OH)2 precipitation
1.3Ca2+ + 2.6OH- → 1.3Ca(OH)2 Equation 6
- Dissolution
The reaction between C3S and water starts immediately after wetting. At first, Ca2+ ions
are extracted from the surfaces of C3S and C2S while the silicate anions remain in the solid
phases, thus signifying a rare incongruent dissolution behavior. After several hours (~ 2 - 3
hrs), the silicate anions start to dissolve as well until the concentrations of calcium and
silicate in the pore solution reach an equilibrium (Equation 4). The dissolution rates can be
monitored by analyzing the evolution of the ionic concentrations in the pore solution over
time. The dissolution rate of C3S at undersaturated condition has been tracked by analyzing
the Si concentration in the pore solution [35-38]. Generally, the dissolution rate in
undersaturated condition depends on the solubility of the ionic species, specific surface area,
structure of the crystalline lattice, temperature, ionic concentration in solution [39], and
crystallographic defects [40-42]. Over time, the solution gets more enriched with calcium and
silicate ions and then supersaturated with respect to C-S-H which consequently precipitates.
However, the formation of a protective layer of hydration products [43,44], or the presence of
aluminum [42] on the surface of the C3S particles limit the dissolution, leading to delayed
nucleation and growth of C-S-H.
-9-
- Nucleation
Currently it is believed that the precipitation of C-S-H in cement follows a classical
nucleation process (heterogeneous nucleation). C-S-H can nucleate and grow on the C3S
grains after the concentrations of calcium and silicate in solution increase until reaching the
level of supersaturation. It has been reported that the lime (Ca(OH)2) concentration in
solution is the most important parameter to control the heterogeneous nucleation process
during the hydration of C3S and C2S [34]. The number of C-S-H nuclei formed in the first
minutes controls the hydration kinetics of the induction period. It depends on the dissolution
rate of C3S, the volume of the solution (w/c ratio) and the initial concentration of calcium,
silicate and hydroxide in the solution. A higher number of precipitated C-S-H nuclei implies a
faster hydration [45,46].
- Growth of C-S-H
The growth mode of C-S-H mainly controls the acceleration period of cement hydration.
Nuclei of stable C-S-H continue to grow around the alite grains until complete coverage of
the surface is reached. The C-S-H growth is anisotropic which occurs at two different rates
parallel and perpendicularly to the surface [46]. The rate of growth depends on the number of
active growth sites on the cement grains and the lime concentration in solution [47]. The
growth mechanism of C-S-H has been described via two structural developments such as the
defective sheets of silicate and aggregation of nanoparticles. In the first scenario, Gartner et
al. [48,49] proposed a mechanism whereby C-S-H grows as branching sheets from localized
nanocrystalline regions of existing C-S-H (Figure 3). These sheets grow in two dimensions
and can build a defect into the layer. This leads to a distorting of the sheets and a disordering
of the crystalline structure. According to the second model, the initial C-S-H nanoparticles
aggregate. As such, the growth of C-S-H is limited until their size reaches a few nanometers.
- 10 -
These C-S-H nanoparticles can provide new sites for further heterogeneous nucleation or the
agglomeration with previously precipitated C-S-H nanoparticles [50-54].
Figure 3: Schematic representation of the nanocrystalline region in C-S-H (from [49])
c) Synthetic C-S-H
C-S-H can be synthesized via a silica-lime reaction, co-precipitation and other processes.
The precipitation of C-S-H from aqueous supersaturated solution is described as a sequence
of nucleation and growth processes. First, the nucleation of C-S-H in aqueous solution
(Equation 7) occurs at conditions in which the degree of supersaturation exceeds a critical
value. Once the C-S-H nucleus has reached the supercritical size, it can grow.
Ca2+(aq) + H2SiO42-(aq) → CaH2SiO4(s) Equation 7
The homogeneous nucleation of C-S-H has been studied from different supersaturated
solutions by mixing solutions of lime and silica, or – more preferably – calcium salts (e.g.
Ca(NO3)2) with a soluble silicate (e.g. Na2SiO3·5H2O). The degree of supersaturation is the
main parameter to control the homogeneous nucleation rate. High levels of supersaturation
lead to a reduction in the time required to induce C-S-H nucleation (induction time);
however, nucleation at very low supersaturation becomes heterogeneous [34]. Moreover, it
- 11 -
has been reported that the pH value plays an important role in the kinetics relative to the
formation of C-S-H precipitates. An increase in pH value (e.g. from 10 to 12) at constant
supersaturation can slow down the rate of precipitation and produces C-S-H crystallites of
larger size [55].
3.1.2 Types of calcium silicate hydrate
a) Crystalline C-S-H
Among the various crystalline calcium silicate hydrates, the structures of 1.4-nm
tobermorite and jennite are best characterized.
The crystal structure of 1.4-nm tobermorite, Ca5Si6O16(OH)2·8H2O, consists of a central
Ca–O layer with attached linear silicate chains on both sides. These silicate chains are aligned
in sequences of “dreierketten” which present a repeating unit of three silica tetrahedra. Two
of the silica tetrahedra (pairing tetrahedra) are linked to the calcium oxide layer, while the
third silica tetrahedron is bridged two pairing tetrahedra (Figure 4). 1.4-nm tobermorite
exhibits a layered structure which has a layer thickness of 1.4 nm, as determined by XRD.
The interlayer spaces of tobermorite contain water molecules and additional calcium cations
[9,19,56,57].
Figure 4: Schematic diagram of dreierketten chains present in 1.4-nm tobermorite

(redrawn after [19])
- 12 -
The layered structure of jennite, Ca9(Si6O18)(OH)6·8H2O, contains ribbons of edge-sharing
calcium octahedra flanked on both sides by silicate tetrahedra (Figure 5). These main layers
are linked by additional calcium octahedra on inversion centers. The hydroxyl groups are
bonded to three calcium cations while no SiOH groups are observed [58]. Thus, jennite has a
much higher Ca/Si ratio of ~ 1.5 vs. 0.83 in tobermorite and its layer thickness is 1.05 nm.
Figure 5: Schematic diagram of the silicate chains present in jennite (from [58])
b) Less crystalline C-S-H
- “C-S-H gel”
The C-S-H present in hardened Portland cement is poorly crystalline. Many reports have
described the structure of C-S-H in hardened cement using a defect tobermorite structure
[9,19,59] where some of the silicate tetrahedra are missing.
Generally, C-S-H is composed of silicate tetrahedra which are aligned in a dreierketten
structure [60-63]. These silicate tetrahedra share oxygen atoms with calcium in plane and are
stacked in a layer structure (Figure 6). The mean silicate chain length of C-S-H obtained
during the hydration of Portland cement is in the range of 5-8 tetrahedra only [61,64]. The
- 13 -
interlayer of C-S-H is also occupied by water, calcium ions and other ions which influence
the distance of the interlayer space.
Figure 6: Schematic structure of C-S-H (from [9]). Triangles: silica tetrahedra; black circles:
calcium atoms/ions in CaO planes and calcium ions; empty circles: species in the
interlayer (water). Qn: n represents the number of SiO4 units attached to an
individual silicate tetrahedron, p: pairing units, b: bridging sites
The composition of C-S-H in hardened cement is variable and depends on the water-to-
cement (w/c) ratio, ageing time, concentration of calcium and silicate in solution, etc.
Moreover, Ca2+ is the main parameter controlling the hydration kinetics, stoichiometry and
structure of C-S-H. Generally, the Ca/Si molar ratio of C-S-H formed in cement hydration is
greater than 1.5, with a mean of ~ 1.7 [62,63,65-69]. In hardened cement, C-S-H occurs in
various morphologies, namely as small globular particles with diameters of ~ 6 - 8 nm in the
inner product (Ip), and with fibrillar morphology in the outer product (Op) (Figure 7)
[19,65,70,71].
- 14 -
Ip
Op
Ip-Op boundary
Ip Op
Figure 7: TEM micrograph showing the inner product (Ip) and the outer product (Op) of
C-S-H present in a hardened C3S paste (from [71])
- Synthetic C-S-H
Most studies focus on the variations of composition, structure and morphology of
synthetic C-S-H produced by controlled C3S hydration, silica-lime reaction, co-precipitation,
etc.
Synthetic C-S-H has been categorized in several systems including semicrystalline C-S-H
which exhibits an intermediate structure between 1.4-nm tobermorite, jennite and C-S-H gel.
The semicrystalline C-S-H formed at room temperature has been classified as C-S-H (I) and
- 15 -
C-S-H (II) [9,72,73]. They are known as an imperfect version of 1.4-nm tobermorite and
jennite, respectively. Additionally, Nonat et al. have proposed three types of C-S-H including
C-S-H (), C-S-H () and C-S-H () [74,75].
Composition
The composition of C-S-H is typically characterized by the molar ratio of calcium to
silicon in its structure (Ca/Si ratio). The Ca/Si ratio can vary from 0.7 to 2.0 [70]. Generally,
specific compositions of C-S-H can be found in crystalline phases such as 1.4-nm tobermorite
(Ca5Si6O16(OH)2·8H2O; Ca/Si = 0.83) and jennite (Ca9(Si6O18)(OH)6·8H2O; Ca/Si = 1.5) [9].
For semicrystalline C-S-H, the Ca/Si ratios of the C-S-H (I) vary in the range from 0.67 to 1.5
while the Ca/Si ratios of C-S-H (II) are nearly 2.0 [9,72,73]. Furthermore, for C-S-H () a
Ca/Si ratio of 0.7 - 1.0, for C-S-H () a Ca/Si of 1.0 - 1.5 and for C-S-H () a Ca/Si > 1.5
have been reported [74,75].
The Ca/Si ratios depend on several factors such as the initial mixture of raw materials, the
activity of the ions in the equilibrium solution, pH value, temperature, synthesis approach,
etc. Also, the correlation between the concentrations of calcium and silicate ions in the
solutions and the Ca/Si ratio has been highlighted [76]. There, a decreased silicate
concentration and rise in the calcium concentration in solution led to an increased Ca/Si ratio
of the C-S-H products. The lowest and highest Ca/Si ratios found in C-S-H were at ~ 0.7 and
~ 1.45, respectively. Amorphous silica and calcium hydroxide were also detected in C-S-H
with Ca/Si ratios lower than 0.7 and greater than 1.45, respectively. Recently, a uniform C-S-
H (without contamination by calcium hydroxide phase) possessing controlled Ca/Si ratios up
to 2.0 was produced using a micro mixer system [77]. Moreover, strongly alkaline solutions
led to an increase in the Ca/Si ratios in the C-S-H [78-81].
- 16 -
Composition of the silicate chain
29
Si MAS NMR presents a very useful technique for the characterization of silicate chains
present in C-S-H precipitated during cement hydration or in synthetic C-S-H. Evidence from
29
Si NMR spectroscopy suggests linear silicate chains for the synthetic C-S-H arranged in
dreierketten. The silicate chains generally contain terminal silicate groups (Q1,  = -79 ppm)
and chain members linked to two neighboring silicate units (Q2), as shown in Figure 8. The
Q2 silica tetrahedra positioned in the middle of the chains can arrange in a “dreierketten”
structure whereby a dimer of silicate tetrahedra (paring tetrahedra; Q2p,  = -85 ppm)
connects to the bridging tetrahedron (Q2b,  = -83 ppm) [82-87]. It has been shown that the
number of bridging tetrahedra decreases when the Ca/Si ratio increases [80,88,89].
Figure 8: Schematic representation of a pentameric silicate chain of the type present in the
dreierketten-based model for the structure of C-S-H
Deconvolution of the spectrum in terms of three resonances allows an estimation of the
mean chain length (MCL) that can be calculated by following Equation 8 [89]. It has been
observed experimentally that the silicate chain in C-S-H contains 3n-1 tetrahedra, where n is
an integer [19]. When all bridging tetrahedra are missing in the silicate chain, then the chain
represents a series of dimeric anions thus giving the shortest MCL.
- 17 -
2 (Q1 +Q2b +Q2p +Q3 )

MCL = Equation 8
Q1
The MCL of silicate chains in C-S-H depends on the degree of polymerization (Q2/Q1). An
increase in the mean chain length reflects a higher degree of polymerization. Moreover, the
mean chain length increases with decreasing Ca/Si ratio, particularly Ca/Si ratios of
~ 1.1 - 1.3 [80,84,88-94]. High pH conditions lead to an increase in Q1 units and a decrease in
the MCL of the silicate chains [80,81,86,95,96]. Furthermore, several reports have revealed
that the substitution of Si by aluminium Al(IV) in the bridging positions of the silica
dreierketten structure [97-103] increases the mean chain length of the silicate chain [95].
Surface charge of C-S-H
Generally, the external surfaces of C-S-H contain silanol groups attached to the bridging
tetrahedra (Q2b) and the end-chain tetrahedra (Q1) (Figure 8). These silanol groups are
ionized in highly alkaline condition and result in a negatively charged surface (Equation 9).
However, most often this charge is changed via complexation by dissolved calcium ions
(Equation 10). Consequently, in cement the surfaces of C-S-H exhibit a slightly positive
charge as determined by zeta potential measurement [104-106]. Several factors affect the
surface charge of C-S-H such as Ca/Si, pH value, calcium concentration, type of alkaline
cations, etc. A negative zeta potential of C-S-H is measured at very low calcium
concentrations and low Ca/Si ratios. While at higher calcium concentrations and high Ca/Si
ratios, sorbed calcium overcompensates the negatively charged surface, resulting in an
apparent charge reversal [105,107,108]. Moreover, a reduction in the zeta potential of C-S-H
in the presence of various alkaline cations such as Na+, K+, Cs+, etc. has been reported. This
indicates that these monovalent ions partially replace the calcium ions in the interlayer and on
the surfaces of C-S-H (Equation 11) [95,105,109,110].
- 18 -
SiOH  SiO- + H+ Equation 9
SiO- + Ca2+  SiO Ca+ + H+ Equation 10
SiO- + M+  SiOM + H+ Equation 11
(where M is a monovalent ion)
Morphology
The morphology of C-S-H has been studied via transmission electron microscopy (TEM).
Various morphologies have been reported for synthetic C-S-H (Figure 9) which depend on
the Ca/Si ratio, pH value, synthesis method, and temperature.
The morphology of C-S-H changes from foils at low Ca/Si ratio to fibres at high Ca/Si
[89,111]. At high Ca/Si ratios, a mixture of C-S-H and a fibrous lime-rich phase is observed
[112]. At low Ca/Si ratio of 1.0, a globular-like morphology of C-S-H is found at low pH
values < 10.9 while a foil-like morphology of C-S-H is always observed at pH values  11.7
[81].
The synthetic C-S-H fabricated via silica-lime reaction attains a foil-like morphology at
Ca/Si ratios of ~ 0.7 - 1.5, whereas a fibrillar morphology is observed at higher lime
concentrations of CaO > 22 mmol/L and Ca/Si ratios > 1.58 in the controlled C3S hydration
method [89]. Additionally, the C-S-H samples prepared by mechano-chemical reaction show
a coarser foil-like morphology when compared to the C-S-H obtained from the silica-lime
reaction. Under hydrothermal conditions of the silica-lime reaction, the morphologies of C-S-
H can vary from sheet to long reticular fibers as the Ca/Si ratios increase from 1.0 to 1.7
[114,115].
- 19 -
Figure 9: TEM images of various morphologies of synthetic C-S-H observed at ambient
temperature (from [81,89])
3.1.3 Structure of C-S-H
a) Structural models for C-S-H
Several papers have presented models for the mesostructure of C-S-H. These concepts rely
on two different theories, namely the colloidal model and the layer model.
The first model was developed by Power and Brownyard which is known as the P-B
model [116]. They assumed that the C-S-H gel is as a colloidal structure made of small bricks
with interstitial gel pores.
On the other side, Feldman and Sereda (F-S) presented a model of the C-S-H network as
formed by irregular C-S-H layers with adsorbed and interlayered water molecules (Figure
10). They suggested that the interlayered water can be reversibly removed upon drying, thus
instead of using water as a medium in the sorption isotherms, they studied the diffusion of
helium into the C-S-H structure to provide evidence for the layered structure of the C-S-H gel
[117].
- 20 -
Figure 10: Schematic representation of the Feldman and Sereda model (from [118])
Afterward, the colloidal model I (CM-I) which combined the F-S and P-B concepts was
developed by Jennings. This model defines the size, density, and packing efficiency of C-S-H
basic building blocks. Moreover, the structure of calcium silicate hydrate between 1 and 100
nm was described through a series of SANS and SAXS analyses. The basic units of C-S-H
are small spheres with a diameter of ~ 2.2 nm that flocculate to form larger globules (= basic
building block) of ~ 5.6 nm diameter. The globules pack together to form low density (LD)
and high density (HD) C-S-H depending on the packing densities [119]. The combination of
these units leads to a formation of the microstructure of C-S-H.
According to Jennings’ colloidal model-II (CM-II) [120], the nanostructure of C-S-H can
be described based on the analysis of water sorption isotherms. The C-S-H gel is assumed as
a fractal structure consisting of an assembly of C-S-H flocs formed as globules (not identical
with the globules shown later in this work here) with a cross section of ~ 5 nm. These
“globules” are multilamellar objects and contain interlayer spaces and intraglobular spaces
(IGP) in which water can be located. The stacking of the “globules” can create two types of
pores: the small gel pores (SGP) of 1 - 3 nm and the large gel pores (LGP) of 3 - 12 nm.
- 21 -
Figure 11: Schematic presentation of the nanoscale structure of C-S-H according to the
CM-II model (from [120])
b) Molecular models for C-S-H
Most models proposed for the nanostructure of C-S-H are based on linear silicate chains,
similar to those which are present in 1.4-nm tobermorite, the known dreierkette-based
models.
The first dreierkette-based model for C-S-H was proposed by Bernal et al. [121]. The
crystallographic tests were performed on two synthetic C-S-H products; C-S-H (I) and C-S-H
(II) produced by hydration of C3S. It was found that C-S-H (I) had a layer structure, similar to
the natural mineral 1.1-nm tobermorite (Ca/Si = 0.83) that contains infinite linear silicate
chains of dreierketten (bridging tetrahedron which link to paired tetrahedra) in which the
paring silicate tetrahedra share O–O edges with the CaO plane.
The structure of poorly crystalline and amorphous C-S-H phases is described as a layered
structure built up from CaOx polyhedra sandwiched between two dimeric or polymeric
- 22 -
silicate chains [122]. The layers of C-S-H are separated by an interlayer which contains H2O,
Ca2+, OH-, and other ions.
Taylor’s model [61] revealed that the structures of C-S-H containing Ca/Si ratios above
0.83 are characterized by the removal of some bridging tetrahedra which are substituted by
calcium ions. The Ca/Si ratios of the C-S-H gels were in the range of 0.83 - 2.25 as present in
1.4-nm tobermorite and jennite at low and high Ca/Si ratios, respectively. The silicate chains
in their structures are aligned in dreierketten with the length of 3n-1 tetrahedra (where n = 1,
2, 3, ...). The dimeric structural units representing the shortest silicate chains are obtained
from omission of all bridging tetrahedra from the tobermorite and jennite structures.
Richardson and Groves proposed models for C-S-H which were classified into two
different combinations of structures such as the T/J (tobermorite/jennite) and T/CH
(tobermorite/calcium hydroxide) structure [123]. These models have been applied to describe
the nanostructure of C-S-H in real cement pastes. There, the Ca/Si ratios of C-S-H were
extended to the range of 0.67 - 2.5. The tobermorite-like core is the part of the braces which
consists of a highly disordered layer structure containing finite silicate chains at a length of
3n - 1. The Ca2+ ions are in the main layer and the interlayer which is required for charge-
balance. The position of Ca2+ ions in the T/J and T/CH structures is different: in the T/J
structure, the Ca2+ ions form part of the main jennite-based layers, as Si–O–Ca–OH, while on
the T/CH structure the Ca2+ ions are present in layers of CH which occupy the space between
the silicate layers of the tobermorite-like structure. Moreover, the model was also applied to
the C-S-H structure present in blended cements [124] where bridging Si4+ was substituted by
Al3+ in the silicate chains, resulting in C-A-S-H.
- 23 -
3.2 Polycarboxylate based superplasticizers
Polycarboxylate (PCE) superplasticizers are known as high-range water-reducing
admixtures in concrete [125], such as ready-mix concrete, self-compacting concrete (SCC),
ultra-high strength concrete (UHPC) [126-128], etc. PCEs improve the rheology of concrete
through the dispersion of particles [129,130]. Consequently, the water consumption in the
mix proportion of concrete is reduced, leading to an improvement of compressive strength
and durability of hardened concrete [131,132].
3.2.1 Molecular structure of PCEs
The structure of comb-like PCE copolymers generally consists of a main chain (backbone)
to which side chains are attached. The backbone carries carboxylate anchor groups (COO)
that have a negative charge and are responsible for adsorption of the polymer onto the
positively charged surface sites of cement particles and hydration products like ettringite
[133-136]. The non-ionic side chains grafted to the backbone of PCEs are normally made
from polyethylene glycol (PEG) which is accountable for the dispersing ability via a steric
hindrance effect [130,137,138].
Currently, several types of PCE superplasticizers are used in the concrete industry,
including MPEG-type PCEs, APEG-type PCEs, VPEG-type PCEs, HPEG-type PCEs, IPEG-
type PCEs, and PAAM-type PCEs [139] (Figure 12).
- 24 -
Figure 12: Chemical structures of various PCE superplasticizers
- 25 -
3.2.2 Preparation of PCEs
There are two main synthetic routes used for producing PCEs (Figure 13) [139,140]:
(a) Esterification of carboxylic groups in polyanionic trunk chains with poly(ethylene
glycol) can be used to synthesize MPEG-based PCEs. This procedure produces a
highly uniform PCE with statistical distribution of the side chains along the backbone.
However, this method is less popular in the industry because of high cost, long
reaction time, and low conversion rate.
(b) Free radical copolymerization of a monomer carrying carboxylic groups and a
monomer bearing the side chain (macromonomer) is normally used in the industry
due to its simpler procedure and higher cost-effectiveness. This process produces a
gradient polymer with non-homogeneous distribution of the side chains along the
main chain. Recently, reversible addition-fragmentation chain-transfer or RAFT
polymerization technique has been used for the production of specific gradient
polymers such as MPEG PCEs with a well-controlled structure [141], and MPEG
PCEs with large anionic blocks that can adsorb more strongly on cement [142].
Several kinds of PCE can be synthesized via free radical copolymerization such as:
- MPEG-type PCEs are prepared from -methoxy poly(ethylene glycol)
methacrylate ester macromonomer with methacrylic acid [143].
- APEG-type PCEs are made from -allyl--methoxy or -hydroxy poly(ethylene
glycol) ether and maleic anhydride or acrylic acid [144].
- VPEG-type PCEs are synthesized by aqueous free radical copolymerization of 4-
hydroxy butyl-poly(ethylene glycol) vinyl ether and maleic anhydride or acrylic
acid [145].
- HPEG-type PCEs are made from the macromonomer -methallyl--methoxy or
-hydroxy poly(ethylene glycol) with e.g. acrylic acid [146].
- 26 -
- IPEG-type PCEs (also called TPEG-PCE) are prepared from isoprenyl oxy
poly(ethylene glycol) ether as macromonomer by copolymerization with e.g.
acrylic acid [147].
Figure 13: Two synthetic methods for producing MPEG-type PCEs
- 27 -
3.2.3 Impact of PCE structure on adsorption and dispersion
The adsorption of PCE copolymers on the surfaces of cement particles is one of the most
important parameters influencing the rheological properties such as fluidity and slump loss of
concrete. The charged surfaces of the particles, as measured by zeta potential, are a key factor
for PCE adsorption via electrostatic interaction. A highly positive zeta potential leads to a
high PCE adsorption [135,136,148].
The various architectural structures in PCE superplasticizers control their adsorption and
dispersing effect [139,149-155] which include:
- length of the backbone
- chemical composition of the backbone (acrylic, methacrylic, maleic etc.)
- length of side chains
- grafting density of side chains (polyether/ester to carboxylate ratio)
- distribution of the side chains along the backbone (random, gradient)
The density of ionic groups in the polymer backbone relates to the anionic charge density
of a PCE which can be determined experimentally by titration with a cationic polyelectrolyte
such as polydadmac, etc. The anionic charge density of the PCE plays a vital role for its
adsorption behavior and, consequently, its dispersing power. Generally, PCE adsorption
increases with an increase in the density of ionic groups on the backbone [149,154].
However, a decreased PCE adsorption can be observed for PCE copolymers possessing a
long side chain at the same grafting density [149,152]. Moreover, the pH value of the
aqueous solution and calcium ions present in the cement pore solution affect the anionic
charge of the PCE [156]. The anionic charge of PCEs increases with increasing pH values
due to a deprotonation of the carboxylate (–COO-) groups in the polymer backbone.
However, a reduction in anionic charge results from the presence of calcium ions that can
coordinate with the carboxylate groups, both through complexation and counter-ion
- 28 -
condensation. Generally, the –COO- groups can coordinate Ca2+ as a monodentate or
bidentate ligand (Figure 14) which depends on the architecture of the PCE. In PCEs
possessing a high side chain density, the –COO- group is shielded by the side chains and
preferably coordinates with Ca2+ as bidentate ligand, producing a neutral Ca2+–PC complex.
Consequently, this type of PCE shows almost no anionic charge in cement pore solution.
PCEs exhibiting a high density of –COO- possess anionic character in pore solution due to
monodentate complexation of Ca2+.
Figure 14: Schematic illustration of monodentate (left) and bidentate (right) complexation of
Ca2+ by PCEs possessing different molecular structures (redrawn after [156])
The different side chain lengths (nEO) of PCE copolymers lead to different molecular
conformations in solution such as flexible backbone worm (FBW), stretched backbone worm
(SBW), stretched backbone star (SBS), etc. which are derived from the model of Gay and
Raphäel [157] (Figure 15).
- 29 -
Figure 15: Behavior of a non-ionic comb-like polymer in a good solvent (from [157])
The molecular conformations of PCEs affect the adsorbed amount of PCE on cement
particles [152,153]. There, the worm-like copolymers with nEO  7 adsorb flat (“train type”)
and form a densely packed layer leading to higher adsorbed amounts of the copolymer.
Whereas star copolymers possessing long side chains (nEO  34) prefer perpendicular
adsorption on the cement surfaces (“tail” type) resulting in the higher surface occupancy via
their extended graft chains (Figure 16). Consequently, a lower amount of PCE adsorbed can
be observed.
Figure 16: Adsorbed conformations of PCEs on a cement grain (redrawn after [152])
- 30 -
The different distribution of the negatively charged groups and side chains along the PCE
backbone like in gradient or random copolymers influences the dispersing behavior of these
comb copolymers. A gradient polymer can adsorb on cement surfaces stronger than the
random polymer, leading to a higher dispersing effect [142].
The PEG side chain is the most important part to disperse cement particles via a steric
hindrance effect (Figure 17). It has been reported that the steric repulsion originating from
the graft chains correlates to the adsorbed layer thickness (ALT) of the adsorbed polymer.
Generally, the steric repulsion originating from PCEs increases with increased adsorbed layer
thickness of the PCE [137,158,159]. Moreover, assuming full coverage of the cement surface
by PCEs, the dispersive power of PCEs possessing long side chains is higher than that from
PCEs having short side chains [160].
Figure 17: Illustration of the dispersion mechanism via steric hindrance effect of PCEs
Several authors have also studied PCE adsorption on supplementary cementitious
materials and inert materials such as calcite, fly ash, silica fume, clays, slag, etc. [148,161-
167]. Moreover, PCEs are applied in other significant applications such as iconic concrete
structures, shotcrete for high speed railway tracks, gypsum wallboard, cement grinding agent,
etc. [139]. Recently, another attractive application of PCEs includes their use for the
preparation of C-S-H – PCE nanocomposites as seeding materials to enhance the early
- 31 -
strength development of concrete [13,17,18,168]. To better understand the role and the
relevance of PCE adsorption on C-S-H to achieve a superior seeding material, the effect of
PCE superplasticizer structure on properties of the C-S-H – PCE nanocomposites was
investigated. This topic will be discussed in the next section.
- 32 -
3.3 C-S-H-based nanocomposites
The improvement of properties (e.g. modulus of elasticity and compressive strength) and
durability of concrete have been studied for a long time via the modification of C-S-H by
using organic compounds such as anionic, cationic, non-ionic polymers etc. Moreover, PCE
superplasticizers present essential components and are widely used to improve the fluidity of
concrete. So far, only few reports have described the interaction between PCE copolymers
and C-S-H. Importantly, the mode of interaction between C-S-H and the organic component
depends on the characteristics of C-S-H and type of the organic compound.
3.3.1 Mode of interaction between C-S-H and organic compounds
a) Surface adsorption via calcium complexation
As presented before, C-S-H formed at Ca/Si ratios above 1.0 attains a positively charged
surface due to an overcompensation of the deprotonated silanol groups by adsorbed calcium
ions (Equation 9) [110,111,169]. This way, anionic organic compounds such as PCEs, amino
acids, PAAm-co-PAA; poly(acrylamide-co-acrylic acid) are able to adsorb on these surfaces
via the complexation of calcium ions [13,81,170-174].
In such a PCE copolymer, the carboxylate groups present on the backbone of the polymer
can coordinate via monodentate complexation of calcium species in solution (Figure 18)
[81,172,173]. The various architectural structures of PCEs [13-16,175,176] control their
adsorption on the C-S-H surfaces. The PCEs possessing low grafting density show an
increased anionic charge density leading to a higher amount of adsorbed PCE on C-S-H
particles. However, a lower adsorbed amount of PCE on C-S-H can be observed at low pH
values such at pH = 10.4 as a result of a lower specific anionic charge density of PCE and a
less positively charged surface of C-S-H [81]. The molecular structure of PCEs also affects
the conformation and the layer thickness of adsorbed PCEs on C-S-H [159]. It was observed
- 33 -
that the conformation of PCEs with very long side chains corresponds to a flexible backbone
star (FBS). Furthermore, the layer thickness of PCEs adsorbed onto C-S-H surfaces increases
with increased side chain length and the grafting ratio (C/E; carboxylate to ester groups) of
the PCE copolymer.
The surface chemistry of C-S-H also depends on the Ca/Si ratio and the pH value. It has
been reported that at low Ca/Si ratio of 0.66 and pH = 10.3, the zeta potential value of C-S-H
is negative because the silanol groups on the C-S-H surfaces are partially deprotonated and
poorly compensated by calcium ions. Thus, electrostatic interactions between the
deprotonated silanol groups and positively charged organic compounds are favored [171].
Figure 18: Model illustrating the electrochemical double layer formed on the surface of
C-S-H at high pH value resulting from interaction between PCE, Ca2+ and the
chains of C-S-H
b) Grafting at the defect sites on the silicate chains
The number of missing bridging silica tetrahedra on the silicate chains of C-S-H generally
increases with an increase in Ca/Si ratio (Ca/Si > 1.0). These defect sites can provide the
possibility of adsorption of organic compounds such as poly(ethylene glycol), poly(acrylic
acid), methylene blue, hexadecyltrimethylammonium, etc. [177-180] via H-bonds or Van der
- 34 -
Waals interactions (Figure 19). These evidences have been investigated via 29Si MAS NMR
spectroscopy which indicated a rise in the number of Q2 sites leading to an increase in the
Q2/Q1 ratio and the mean chain length of the silicate chains in the structure of C-S-H
modified with organic/polymer molecules.
Figure 19: Schematic representation of an organic compound adsorbed at a defect site of the
C-S-H surface
c) Intercalation into the interlayer galleries of the C-S-H
Generally, the interlayer spaces of C-S-H contain water molecules and additional calcium
ions which balance the negatively charged sites of the C-S-H. The distance between the
interlayers of C-S-H can be retrieved from the basal spacing (d002) as evidenced in the XRD
pattern [9].
Charged linear polymers can intercalate into the interlayer spaces of C-S-H (Figure 20)
leading to an increase in the interlayer spacing. The degree of expansion depends on several
factors such as chemical composition and structure of C-S-H, type of polymer, concentration
of used polymer, etc. [181-185].
It has been reported that the Ca/Si ratio of C-S-H limits the extent of intercalation of
polymer. Anionic polymers such as poly(methacrylic acid), poly(acrylic acid) and nonionic
- 35 -
polymers like poly(vinyl alcohol) preferably intercalate into C-S-H structures containing
Ca/Si ratios  0.7 [181,183-185], whereas the intercalation of cationic polymers into the
galleries of C-S-H such as poly(diallyl dimethylammonium chloride), poly(4-vinylbenzyl
trimethylammonium chloride), etc. were favored at Ca/Si ratios  1.0 [182,183]. Moreover, a
shift of the d002 basal spacing to smaller angles (larger d-spacing) was found in the C-S-H
synthesized at high concentrations of polymers.
Figure 20: Schematic representation of the intercalation of cationic, anionic or nonionic
polymers into the C-S-H nanostructure
d) Covalent bonding of organic compounds with C-S-H
Novel hybrid organic-inorganic calcium silicate hydrate materials were synthesized via a
sol-gel process from a mixture of organo trialkoxy silane and tetraethoxy silane with calcium
salt in alkaline media. The organic compounds covalently bonded at the end and in the
middle of the C-S-H chains (Figure 21) as evidenced by NMR measurements. Moreover, the
organic compounds can incorporate into the interlayer space of C-S-H depending on the
length of the alkyl chains. In the case of highly hydrophobic organic groups, a phase
separation was observed [186,187].
- 36 -
Additionally, some reports have described the interaction via covalent bonds between
PCEs containing silyl functionalities (PCE-Sil) and the surfaces of C-S-H. This covalent
bond occurs through siloxane bridges between silanol groups of silylated PCE and the silanol
groups in dimers of C-S-H [173,188].
Figure 21: Schematic representation of polymers bonded to silicate tetrahedra in C-S-H
- 37 -
3.4 Hydration kinetics of Portland cement
Ordinary Portland cement contains four major components including C3S, C2S, C3A, and
C4AF. The chemical reactions between anhydrous cement, or one of its constituent phases,
and water begin immediately after wetting, which is known as hydration. The rate of
hydration of Portland cement can be tracked by using isothermal heat flow calorimetry. The
overall progress of hydration at ambient temperature is divided into five stages (Figure 22),
which include pre-induction, induction, acceleration, deceleration, and final hydration period
[31,32,189-192].
Figure 22: Rate of cement hydration as a function of time as evidenced by isothermal
calorimetry measurement
- 38 -
I. Pre-induction period (Initial dissolution and nucleation)
The first, highly exothermic signal in isothermal calorimetry signifies the rapid dissolution
of the anhydrous phases in clinker such as C3A and C3S, and the precipitation of hydration
products such as ettringite and metastable C-S-H. This period lasts only slowly (a few
minutes) and is then followed by induction period.
C3A is the most reactive phase in cement leading to flash set. For this reason, calcium
sulfate like gypsum is always added to Portland cement clinker during the grinding process.
The high heat release from the hydration of C3A in the presence of calcium sulfate indicates
the dissolution of C3A and the rapid precipitation of ettringite (C6A$3H32) on the anhydrous
grains (Equation 12). It has been reported that the rate of C3A dissolution can be slowed
down by adsorption of sulfate ions on reactive sites [192].
C3A + 3C$H2 → 26H + C6A$3H32 Equation 12
The rapid dissolution of C3S contributes an increase of the Ca2+, H2SiO42-, and OH-
concentrations in the liquid phase and a thin, metastable layer of C-S-H precipitates on the
cement grains. After that, the dissolution rate of C3S decelerates. The mechanism of this early
deceleration of C3S hydration has been discussed. For its explanation, two hypotheses
including the metastable barrier hypothesis and the slow dissolution step hypothesis have
been proposed [31,32].
II. Induction period
In this stage, the hydration of all clinker phases is very slow. For the hydration of C3S, the
metastable C-S-H phases still form during the induction period. The termination of this
- 39 -
period can be detected once the C-S-H nuclei reach a certain critical size and start to grow
[193].
III. Acceleration period
The main peak of heat release stems from a heterogeneous nucleation and growth of the
C-S-H, and the precipitation of Portlandite. Moreover, the calcium sulfate completely
dissolves and the concentration of sulfate decreases due to the formation of AFt and possibly
the adsorption of sulfate on the C-S-H surfaces. Accelerating admixtures or mineral
admixtures such as limestone powder, clay minerals etc. [194-196] can affect the hydration
kinetics of cement; for example, by shifting the onset of the acceleration period to earlier
times, and increasing the total heat released during the accelerating period.
IV. Deceleration period
Here, the hydration rate slows down and is controlled by a diffusion process. The C-S-H
phase continuously precipitates at the interface between non-hydrated cement grains and
originally formed C-S-H. Moreover, a second peak representing the sulfate depletion point
occurs during this deceleration. This peak corresponds to a higher dissolution of C3A and a
faster precipitation of AFt.
V. Final hydration period
The last stage of heat release shows a low activity due to the slow diffusion of species in
the hardened cement. Furthermore, a third peak corresponding to the precipitation of
monosulfoaluminate (AFm; C4A$H12) from the reaction between ettringite and C3A is
observed (Equation 13).
2C3A + C6A$3H32 → 4H + 3C4A$H12 Equation 13
- 40 -
3.5 Hardening accelerators
An accelerating admixture is a material that is normally used in concrete for improving the
development of early strength and increasing the rate of cement hydration at early ages
[4,194]. Various admixtures are used in various applications such as in blended cements,
urgent repair works, concrete works performed in cold climates, or speeding up the
production in precast concrete plants etc.
3.5.1 Accelerating chemicals
The American Concrete Institute (ACI) Manual of Concrete Practice (Committee 212.3R-
10) [197] has divided accelerators into four groups as follow:
i. Soluble inorganic salts such as chlorides, bromides, fluorides, carbonates,
thiocyanates, nitrites, nitrates, thiosulfates, silicates, aluminates, and alkaline
hydroxides can accelerate the setting of Portland cement.
ii. Soluble organic compounds consisting of triethanol amine (TEA), calcium formate,
calcium acetate, calcium propionate, and calcium butyrate.
iii. Quick setting admixtures are used in shotcrete applications which promote setting in
a few minutes. These admixtures contain sodium silicate, sodium aluminate,
aluminum chloride, sodium fluoride, and calcium chloride.
iv. Miscellaneous solid admixtures include calcium aluminate, silicate minerals, finely
ground magnesium carbonate and calcium carbonate.
Among those admixtures, calcium chloride (CaCl2) is most widely used in concrete
because of its ready availability, low cost, and high performance. However, it is not
recommended for use in reinforced or prestressed concrete because of its tendency to
promote the corrosion of steel. According to the mechanism of acceleration with calcium
chloride [198], it acts as catalyst and mainly affects the hydration of C3S phase leading to an
- 41 -
increase in the rate of C-S-H formation, thus increasing the early strength. While a minor
accelerating effect on early hydration is obtained from the reaction between C 3A and calcium
chloride is observed. In the presence of gypsum, calcium chloride has an accelerating effect
on the reaction between C3A and gypsum resulting in a series of hydration products. The
sequence of reactions possible in the system C3A/CaCl2/CaSO4/H2O is shown in Equations
14-16.
C3A + 3CaSO4 + 32H2O → C3A · 3CaSO4 · 32H2O Equation 14
CaCl2 + C3A + 10H2O → C3A · CaCl2 · 10H2O Equation 15
C3A · 3CaSO4 · 32H2O + 2C3A · Ca(OH)2 · 12H2O
→ 3C3A · CaSO4 · 12H2O + 20H2O + 2Ca(OH)2 Equation 16
Non-chloride accelerating admixtures have been commercially used such as calcium
formate, calcium nitrate, sodium aluminate, triethanol amine, etc. Calcium formate
(Ca(HCOO)2) acts as an accelerator [199] in the same manner as calcium chloride, but higher
dosages (~ 3 - 5 times) are required and its solubility is limited. Calcium nitrate (Ca(NO3)2)
can also be used for shortening the time of setting and hardening for concrete, and it is also a
very effective corrosion inhibitor for metal imbedded in concrete [200]. Furthermore, there
have been many studies on alkanolamine-based additives such as triethanol amine (TEA),
triisopropanol amine (TIPA), etc. TEA is well-known as an effective grinding aid, and also
used as an accelerator in cement [201,202]. It accelerates the hydration of C3A and the
formation of ettringite during the induction period. However, higher dosages of TEA (> 0.5
% by weight of cement) lead to retardation of the C3S phase. Recently, binary and ternary
hardening accelerating admixtures have been studied in Portland cement and blended
- 42 -
cements; for example, calcium nitrate and TEA, CaCl2 and diethanol-isopropanol amine
(DEIPA), sodium thiocyanate (NaSCN), diethanol amine (DEA) and glycerol, etc. [203-205].
However, the gain in early strength by using those admixtures is limited and sometimes leads
to a decreased final strength.
3.5.2 C-S-H as an accelerator
Several authors have reported that synthetic C-S-H particles can be used as an accelerator
in cement [10-12,206]. C-S-H can serve as a seeding material to reduce the activation energy
barrier which needs to be overcome to initiate the nucleation of C-S-H gel in hydrated cement
(Figure 23).
Figure 23: Schematic illustration of the reduction of the energy barrier height (ΔG*original)
after adding conventional accelerators (ΔG*salt) and seed crystals (ΔG*seed)
C-S-H seeds can provide new nucleation sites in the capillary pores of the cement paste for
generating the C-S-H gel (Figure 24) [10]. This way, hydration of the silicate phases C3S and
- 43 -
C2S is initiated much earlier and leads to an increase in the degree of hydration, as detected
29
via isothermal heat flow calorimetry and Si NMR spectroscopy [10,11]. The influence of
addition of the synthetic C-S-H particles on the acceleration effect on cement depends on the
particle size, surface area, composition and the dosage of C-S-H, the characteristics of
cement, etc. Importantly, a high surface area of the C-S-H seeds is necessary to provide a
massive number of seeds for the formation of C-S-H. This promotes the nucleation of C-S-H
and accelerates the rate of hydration in cement. However, the C-S-H seeds produced
according to [206] produce only a minor accelerating effect, owed to their relatively large
size, possibly due to agglomeration and/or OSTWALD ripening. To avoid these effects, the
size of the C-S-H seeds must be stabilized to their original nanosize by addition of polymeric
dispersants such as polycarboxylate (PCE) based superplasticizers [13-16,207].
Figure 24: Schematic illustration of the hydration of C3S or cement particles with and
without C-S-H seeds (from [10])
In 2011, BASF invented finely dispersed C-S-H particles that have been commercialized
under the trade name of X-SEED® [168,208-211]. In this product, the C-S-H particles are
- 44 -
stabilized by the addition of PCE comb copolymers. These C-S-H particles exhibit a high
surface area and low aggregation and turned out to be a highly effective cement hardening
accelerator [17,18,212-214]. However, intensive scientific studies are still required to
improve the effectiveness of this admixture, and to further understand how the accelerating
mechanism relates to the material characteristics. These are resolved by this thesis.
- 45 -
CHAPTER 4. MATERIALS AND METHODS
4 Materials and methods
This chapter provides an overview of all materials and essential techniques used in this
thesis. The preparation steps to obtain C-S-H – PCE nanocomposites and the principals of the
techniques used in this work are also described.
4.1 Materials
4.1.1 Chemicals for the synthesis of C-S-H
The starting materials used in the synthesis of C-S-H were Ca(NO3)2  4H2O (PanReac
AppliChem, Germany) and Na2SiO3  5H2O (VWR Prolabo BDH Chemicals, Germany).
Moreover, HNO3 65 wt. % (VWR Prolabo BDH Chemicals, Germany) and NaOH (Merck
KGaA, Germany) were used to adjust the pH value during the synthesis.
4.1.2 Polycarboxylate superplasticizers (PCEs)
MPEG PCEs
A series of methacrylate based polycarboxylate superplasticizers with varying side chain
lengths and molar ratio of methacrylic acid (MAA) to -methoxy polyethylene glycol
methacrylate ester (MPEG-MA) were used for the synthesis of the C-S-H – PCE
nanocomposites (Section 5.1). Their general chemical structure is shown in Figure 25.
Five methacrylic acid‒co‒‒methoxy poly(ethylene glycol) (MPEG) methacrylate ester
polymers possessing different side chain lengths were synthesized by aqueous free radical
copolymerization [133]. The samples were denoted as xPC6, whereby 6 refers to the molar
ratio between methacrylic acid and ‒methoxy poly(ethylene glycol) methacrylate ester,
- 47 -
while x corresponds to the side chain length which varied from 8, 17, 25, 45 to 114 ethylene
oxide (EO) units.
Furthermore, another three MPEG PCEs were synthesized with side chains made of 45
ethylene oxide (EO) units and molar ratios of methacrylic acid (MAA) to -methoxy
polyethylene glycol methacrylate ester (MPEG-MAA) between 2:1, 6:1 and 8:1. The
properties of all synthesized MPEG PCE samples are listed in Table 1.
a =2-8
b =1
nEO = 8 - 114
Figure 25: Chemical structure of the methacrylic acid‒co‒‒methoxy poly(ethylene glycol)
(MPEG) methacrylate ester based PCE superplasticizers used in the study
IPEG PCE
A commercial isoprenyl oxy poly(ethylene glycol) based superplasticizer (IPEG PCE) was
employed in the synthesis (Section 5.2 and 5.3). The solid content of this PCE solution was
40 % by weight and the chemical structure of this PCE polymer is presented in Figure 26. Its
molecular properties and anionic charge amount measured at different pH values are
summarized in Table 2.
- 48 -
Table 1
Molecular properties and specific anionic charge density of the MPEG PCE samples
PCE Property
polymer
MAA : Ethylene oxide Molar mass, Molar mass, Polydispersity Specific anionic Solid
sample
MPEG-MA (EO) units Mw Mn index charge density content
(a : b) (nEO) (g/mol) (g/mol) (PDI) in NaOH (µeq/g) (%)
8PC6 6:1 8 14,250 6,425 2.2 9,014 31.7
17PC6 6:1 17 15,290 7,601 2.0 5,119 35.3
25PC6 6:1 25 16,820 8,750 1.9 4,036 37.5
45PC6 6:1 45 26,060 14,900 1.7 3,641 18.4
114PC6 6:1 114 65,730 35,390 1.9 1,734 36.0
45PC2 2:1 45 43,410 23,020 1.9 1,320 36.4
45PC6 6:1 45 26,060 14,900 1.7 3,641 18.4
45PC8 8:1 45 28,860 15,130 1.9 4,098 20.2
Figure 26: Chemical structure of the isoprenyl oxy poly(ethyleneglycol) (IPEG) based PCE
superplasticizer used in the study
- 49 -
Table 2
Molecular properties and pH-dependent specific anionic charge density of the IPEG PCE
sample used in the study
Molar masses Polydispersity Specific anionic charge density in NaOH Solid content
(g/mol) index (µeq/g) at pH value (%)
Mw Mn (PDI) 10.4 11.7 12.4 13.8
35,100 15,700 2.2 1,800 2,750 2,140 -* 40.0
*No stable value obtained
4.1.3 Cement
Ordinary Portland cement
An ordinary Portland Cement (OPC) sample (Type CEM I 42.5R) obtained from Schwenk
Cement Company (Allmendingen, Germany) was used in this study. Its phase composition
was determined by quantitative XRD including Rietveld refinement and thermogravimetric
analysis of the calcium sulfate hydrates. The results are listed in Table 3. Its specific surface
area (Blaine) and mean particle size (d50 value) were found at 2,990 cm2/g and 17 μm,
respectively.
A slowly hydrating Ordinary Portland Cement (OPC) sample (API Class G oil well
cement, corresponding to a CEM I 32.5N) obtained from Dyckerhoff GmbH (Germany) was
used for testing the early strength development of mortars. This cement was selected for its
particularly slow development in early strength. Its phase composition was determined by
quantitative XRD including Rietveld refinement and thermogravimetric analysis of the
calcium sulfate hydrates. The results are listed in Table 3. Its specific surface area (Blaine)
and mean particle size (d50 value) were found at 3,000 cm2/g and 17 μm, respectively.
- 50 -
Table 3
Phase composition of the OPC samples as determined by quantitative XRD using Rietveld
refinement and thermogravimetry
Phase CEM I 42.5 R cement API Class G cement

(wt.%) (wt.%)
C3 S 54.7 59.3
C2 S 16.2 19.5
C3 A 6.7 1.7
C4AF 11.3 14.1
free CaO 0.8 < 0.3
*
CaSO4 · 1/2H2O 0.1 0.2
CaSO4 · 2H2O * 4.7 4.6
Anhydrite 1.4 < 0.1
Arcanite < 0.1 < 0.1
Calcite 1.7 -
Dolomite 3.1 -
Quartz 4.0 -
Total 99.3 99.7

*
Determined by thermogravimetry
Blended cement
A fly ash-blended cement (Type IP according to ASTM C595, corresponding to a CEM
II/B-V) containing 35 wt. % of fly ash Class F was used in the tests. Oxide composition
(determined by XRF), density and specific surface area (Blaine) of this cement are listed in
Table 4.
The slag-blended cement was prepared from 35 wt. % of ground granulated blast-furnace
slag (GGBFS) that was obtained from Schwenk Cement Company, Karlstadt, Germany.
Mineralogical composition of the slag sample was investigated by XRD measurement and the
XRD spectrum is exhibited in Figure 27.
- 51 -
The calcined clay-blended cement was prepared from 35 wt. % of a calcined clay that was
obtained from Bavaria/Germany. The oxide composition (determined by XRF), specific
surface area (Blaine), mean particle size (d50 value) and density of the slag and calcined clay
samples are listed in Table 4.
Table 4
Chemical composition and physical properties of fly ash-blended cement, GGBFS and
calcined clay samples
Composition (%) Fly ash-blended cement GGBFS Calcined clay

SiO2 24.9 35.9 52.6
CaO 50.8 42.8 5.7
Al2O3 9.9 11.4 22.2
MgO 1.7 6.4 2.2
TiO2 0.3 0.8 1.0
K2O 0.9 0.3 2.8
Na2O 1.1 0.3 0.3
Fe2O3 7.1 0.5 8.4
Mn3O4 - 0.3 -
SO3 2.4 2.4 1.4
SrO - 0.1 -
ZrO2 - < 0.1 -
BaO - 0.1 -
LOI* 0.9 - 2.9
Blaine value (cm2/g) 4,100 4,000 -
d50 value (m) 12.0 13.2 14.2
Density (g/cm3) 3.0 2.9 2.6
*Loss on ignition
- 52 -
Figure 27: XRD spectrum of the GGBFS used in the slag-blended cement
4.2 Methods
This section, the preparation of the C-S-H – PCE nanocomposites, their characterization,
performance testing, and investigations relating to their mode of action in cement are
described.
4.2.1 Preparation and characterization of C-S-H – PCE nanocomposites
An overview of the preparation and characterization of the C-S-H – PCE nanocomposites
is presented in Figure 28.
The C-S-H  PCE nanocomposites were prepared by the co-precipitation method. The
general setup of this synthesis is shown in Figure 29. First, aqueous Ca(NO3)2 and Na2SiO3
solutions were prepared in a water bath at 75 ° C to achieve fast and complete dissolution and
were then cooled to ambient. After that, both solutions were continuously added at a constant
dosing rate to the PCE solution while stirring at 20 ° C under N2 atmosphere. Moreover, the
pH of the reaction solution was continuously monitored using a pH electrode submerged in
- 53 -
the solution and was adjusted to 10.4 or 11.7 by the addition of 1M HNO3, or to 12.4 and
13.8 by adding 30 wt. % NaOH as needed. When the addition of Ca(NO3)2 and Na2SiO3 was
finished, the white suspensions were stirred for another 24 hours at room temperature.
Detailed process parameters used in the synthesis of the C-S-H – PCE nanocomposites are
listed in Table 5.
The C-S-H – PCE nanocomposites were then characterized by several techniques

29
including XRD, FT-IR, Si MAS NMR spectroscopy, TEM, particle size analysis, TOC
measurement, etc. Moreover, their effectiveness in cement was tested in mortar and concrete.
The working mechanism of these nanocomposites in cement was investigated via isothermal
heat flow calorimetry, in-situ XRD and 29Si MAS NMR spectroscopy.
Figure 28: Sequence of steps performed in the preparation and characterization of the
C-S-H – PCE nanocomposites
- 54 -
Figure 29: Experimental setup for the synthesis of the C-S-H – PCE nanocomposites
- 55 -
Table 5
Process parameters used in the synthesis of the C-S-H – PCE nanocomposites
Experiment *
Parameters
A1 A2 A3 A4 ** A5
Mode of addition Drop wise Drop wise Drop wise Drop wise Drop wise
Ca/Si ratio 1.5 1.5 1.0 1.0 1.0
Type of PCE MPEG MPEG IPEG IPEG IPEG

- 8PC6 - 45PC2
- 17PC6 - 45PC6
- 25PC6 - 45PC8
- 45PC6
- 114PC6
Concentration (wt. %)
- Ca(NO3)2 42.4 42.4 42.6 42.6 42.6
- Na2SiO3 15.1 15.1 20.0 20.0 20.0
- PCE 3.85 mM 9.1 % 6.7 % 6.7 % 6.7 %
Dosing rate (mL/min)

- Ca(NO3)2 0.52 0.52 0.61 6.8 0.61
- Na2SiO3 1.16 1.16 1.16 13.0 1.16
- HNO3 - - 0.51 6.3 0.51
pH 11.3 11.3 10.4 - 13.8 11.7 11.7
Temperature (°C) 20 20 20 20 20
Mixing speed (rpm) 300 300 300 300 300
Atmosphere N2 N2 N2 N2 N2
Reaction time
- Addition time (min) 8 8 8 18 8
- Ageing time (hrs) 24 24 24 24 0 - 24
* Experiment: A1 in paper #1, A2 in paper #2, A3 in paper #3 - #5, A4 in paper #6 and

A5 in paper #7
** This was a 1 L batch; all other batches 20 mL only.
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4.2.2 Principal techniques
Specific charge amount
The anionic charge amount of the PCE polymers was measured by polyelectrolyte titration
using a particle charge detector PCD 03 pH (BTG Mütek GmbH, Herrsching, Germany).
The principle of this method is based on the measurement of a streaming current generated
by charged polymer molecules which adsorb via van der Waals forces on a moving surface.
Charge neutralization is achieved by addition of an oppositely charged polyelectrolyte which
can form a polyelectrolyte complex and leads to a zero streaming current (isoelectric point).
First, the aqueous anionic polymer is filled into the plastic measuring cell with a fitted
piston. Dissolved polymer molecules adsorb on the surface of the piston and on the wall of
the cell. The piston is vertically oscillated in the cell by a motor leading to separation of the
free counter-ions from the adsorbed polymer. At the Platinum electrodes, the counter-ions
induce a current which is amplified and finally shown on the display. During the
polyelectrolyte titration, a standard solution of 0.001 N cationic poly-DADMAC (polydiallyl
dimethyl ammonium chloride) was dropped continuously to the PCE solution until the
isoelectric point was reached [156]. The titration of each sample was done three times and the
average of the specific charge amount was calculated as follows Equation 17.
𝑉∗𝑐
q = Equation 17
𝑚
where V: consumption of poly-DADMAC (L)
c: concentration of poly-DADMAC (eq/L)
m: mass of PCE in the aqueous solution (g)
q: specific anionic charge density (eq/g)
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Particle size analysis
The particle size of the C-S-H or C-S-H – PCE nanocomposites was determined via
dynamic light scattering (DLS) which is a technique for measuring the random changes in the
intensity of light scattered from a suspension or colloidal solution. Generally, particles
suspended in solution undergo a random motion known as Brownian motion. A
monochromatic light source, typically a laser, is shot into a sample and then the molecules
scatter the light in all directions. The Brownian motion of particles or molecules in
suspension leads to different intensities of the scattered light. Analysis of these intensity
fluctuations is detected at a known scattering angle θ by a fast photon detector and from this
the particle size is calculated by using the Stokes-Einstein equation (Equation 18).
𝑘𝐵 𝑇
Dh = Equation 18
3𝜋𝜂𝐷𝑡
where Dh is the hydrodynamic diameter
Dt is the translational diffusion coefficient
kB is Boltzmann’s constant
T is thermodynamic temperature
η is dynamic viscosity
X-ray diffraction
X-ray diffraction (XRD) is a powerful technique for characterizing crystalline materials. It
provides information on the crystal structure, crystal orientation and other structural
parameters such as grain size, crystallinity, strain and crystal defects.
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X-ray diffraction peaks are produced by constructive interference of a monochromatic
beam of X-rays diffracted at specific angles from each set of lattice planes in a sample which
is described by Bragg’s law (Equation 19). The peak intensities are determined by the
distribution of atoms within the lattice. Consequently, the X-ray diffraction pattern is the
fingerprint of the periodic atomic arrangements in a given material. Comparison with spectra
from the ICDD (International Centre for Diffraction Data) database of X-ray diffraction
patterns enables the phase identification of a large variety of crystalline samples. The XRD
patterns of C-S-H and C-S-H – PCE nanocomposites obtained from a BRUKER AXS D8
diffractometer are shown in chapter 5.
n = 2d sin Equation 19
where d refers to the spacing between the atomic planes in the crystalline phase and λ is the
X-ray wavelength.
Fourier-transform infrared spectroscopy
Fourier-transform infrared (FT-IR) spectroscopy is an analytical technique used to identify
organic, polymeric, and in some cases inorganic materials (e.g. silica polymorphs).
Moreover, IR is most useful in providing information about the presence or absence of
specific functional groups. This technique measures the infrared radiation absorbed by a
material at resonant frequencies which is a characteristic of its molecular component and
structure.
Generally, a beam of the middle infrared light (400 - 4,000 cm-1) is generated by an IR
source and passed through the sample. The IR radiation induces stronger molecular vibrations
in covalent bond of the material including stretching, bending, scissoring, rocking and
twisting. The absorption occurs when the frequency of the IR is the same as the vibrational
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frequency of a bond or collection of bonds in a molecule. The signal of the transmitted light
obtained from the detector is an interferogram which can be Fourier transformed to get the
actual spectrum. The FT-IR spectrum is basically presented as a plot of intensity of the
transmission versus transmitted frequency or wavenumber.
Nuclear magnetic resonance spectroscopy
Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a
magnetic field (B0) absorb and re-emit electromagnetic radiation. This energy is at a specific
resonance frequency which depends on the strength of the magnetic field and the magnetic
properties of the isotope of the atoms.

29
Solid-state Si NMR spectroscopy is a nondestructive technique and powerful tool for
investigating the structure and dynamics of crystalline and amorphous silicate materials. In
silicates, the 29Si chemical shifts reflect the degree of polymerization of the SiO4 tetrahedra.
In cement-based systems, this technique has played an important role in the characterization
of the silicate chain structure in calcium silicate hydrate (C-S-H) which is the main hydration
product of Portland cement.
The binding motif of silicate present in the synthesized C-S-H and C-S-H – PCE
nanocomposites was identified by 29Si MAS NMR spectroscopy using a Bruker Avance 300
MHz instrument operating at a resonance frequency of 59.595 MHz. The powder samples
were sifted into a 7 mm zirconia rotor and spun at 5 kHz. All spectra were recorded with a
relaxation delay of 45 seconds, and tetrakis(trimethylsilyl)silane was used as external
standard. The 29Si NMR spectra were analysed by deconvolution of the different signals for
the Qn species using Origin93 software. The linewidth and lineshape of the spectra were fit
according to the Voigt model.
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Total organic carbon content
The total organic carbon (TOC) content of the C-S-H – PCE nanocomposites was
determined using a High TOC II instrument (Elementar, Hanau, Germany). First, the total
organic carbon present in the PCE polymer and the non-adsorbed part of PCE remaining in
the aqueous phase after 24 hours of stirring were measured. From this, the amount of PCE
adsorbed on C-S-H surfaces was calculated from the difference between the amount of PCE
added and the amount remaining in the filtrate (depletion method).
In the High TOC II apparatus, the sample containing organic carbon is oxidized in a
combustion tube packed with a platinum catalyst at 900 °C in synthetic air. The concentration
of the carbon dioxide generated from the oxidation process is measured via a non-dispersive
infrared (NDIR) detector. The amount of organic carbon present in the sample is calculated
based on the values obtained for mono potassium phthalate which is used as calibration
standard.
Transmission electron microscopy
Transmission electron microscopy (TEM) is a microscopic technique used to observe
features such as structure, crystallization, morphology and stress of very small specimens.
This technique uses an accelerated beam of electrons which is transmitted through an ultra-
thin specimen (less than 100 nm thick) or a suspension on a grid to form an image. The
lighter areas of the image represent the places where a greater number of electrons are able to
pass through the sample and the darker areas reflect the denser areas of the object.
A transmission electron microscope is composed of several components such as an
electron gun, electromagnetic lenses, vacuum chamber, condensers, specimen stage and
phosphorescent screen. An electron gun creates electrons which are accelerated to extremely
high speeds using electromagnetic coils. The electrons are focused into a small beam by a
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condenser lens and passes through the specimen. Then, the objective lens focuses the portion
of the beam that is emitted from the sample into an image. The image produced by TEM is
called a micrograph which is observed onto a phosphorescent screen.
In this thesis, morphology of the C-S-H – PCE samples was captured by TEM performed
on a JEOL JEM 2011 instrument (JEOL, Japan) equipped with a LaB6 cathode. The C-S-H –
PCE suspensions were diluted with water or isopropanol and dispersed in an ultrasonic bath
for 5 minutes. After plasma surface treatment, the dispersed samples were dropped on a 300
Cu mesh with carbon support films (Quantifoil Micro Tools GmbH, Germany).
Isothermal heat flow calorimetry
Isothermal heat flow calorimetry is a powerful technique used for measurement of heat
production during the hydration of cement which is exothermic and for monitoring the
hydration kinetics of cement at a constant temperature. The heat production in a sample is
detected by a heat flow sensor as heat is conducted to a heat sink (surrounding) that is in
contact with the air thermostat. For each sample, it is necessary to have a reference sample
that is on a parallel heat flow sensor. This arrangement reduces the noise in the measurements
from temperature fluctuations entering the instrument. The output from the calorimeter is the
difference between the sample signal and the reference signal which is recorded continuously
and in real time.
The determination of heat flow relies on the so-called Seebeck effect which is the direct
conversion of temperature differences to electric voltage. Then, the thermal power is
calculated by the following Equation 20.
P = (U – U0) Equation 20
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where P is the thermal power (in watts),  is the calibration coefficient (in watts/volt), U is
the voltage (in volts) and U0 is the baseline voltage (in volts).
Hydration kinetics of cement paste in this study was tracked by isothermal heat flow
calorimeter (TAM AIR, Thermometric, Järfälla, Sweden) at 20  C. A cement paste was
prepared from 4 g of (blended) cement and 1.8 g of DI water (w/c = 0.45), mixed in a glass
ampule for 2 minutes and placed into the calorimeter. Dosages of the C-S-H and C-S-H–PCE
nanocomposites were 0.35 - 2.0 % (as solid) by weight of cement (bwoc).
Mortar testing
The method for determination of the compressive and flexural strengths of mortar was
according to DIN EN 196-1.
The mortar consisted of 450 g of cement, 1,350 g of standard CEN sand and 225 g of
water (w/c = 0.5 for CEM I 42.5R) or 198 g of water (w/c = 0.44 for API Class G cement).
Moreover, the C-S-H – PCE suspensions were used in a standard mortar at the dosage of 0.35
– 2.0 % (as solid) by weight of cement (bwoc). The mixing operation was carried out
automatically as follows:
Amounts of DI water and cement were placed into the mixing bowl and then the mixer
was immediately started at low speed. After 30 sec of mixing, the sand was added and
steadily stirred for 30 sec. Then, the mixer was switched to high speed and mixing continued
for additional 30 sec. After that, the mixer was stopped for 90 sec and a plastic scraper was
used to homogenize the mortar adhering to the wall and bottom part of the bowl. Then
mixing was continued again at high speed for 60 sec.
The spread flow of fresh mortar was measured via flow table test. After that, the mortar
was cast into 40 x 40 x 160 mm prism steel molds and compacted on a vibrating table for 2
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minutes. The specimens were then covered with a plate of glass and cured for 6, 8, 12, 16 and
24 hours in a climate chamber at a temperature of 20 ± 1 ° C and 90 % relative humidity. To
obtain the strength values after 28 days, the specimens were demolded after 1 day and then
cured in water at 20 ± 1 ° C. After curing, the compressive and flexural strengths were
measured using an instrument from Toni Technik, Berlin, Germany (Figure 30). The
compressive and flexural strengths were calculated by following Equations 21 and 22,
respectively.
Rc = Equation 21
6
where Rc is the compressive strength (MPa), Fc is the maximum load at fracture (N), and
1600 is the area of the auxiliary plates; 40 mm x 40 mm (mm2).
5∗ ∗
Rf = 3
Equation 22
where Rf is the flexural strength (MPa), b is the side of the square section of the prism (mm),
Ff is the load applied to the middle of the prism at fracture (N), and l is the distance between
the supports (mm2).
Figure 30: Test apparatus used to determine the compressive and flexural strengths of mortar
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Concrete testing
Concrete was prepared in a 30 L pan-type mixer according to ASTM C192 at 23 ± 2 ° C.
The mix proportion of concrete is listed in the paper in section 5.3. The fly ash blended
cement was used at 400 kg/m3, the ratio of aggregates-to-cement was 4.5 and the w/c ratio
was fixed at 0.41. IPEG-PCE superplasticizer was used to adjust the workability of the fresh
concrete to a slump value of 16 ± 0.5 cm. The dosages of the C-S-H – PCE composite tested
were 0.8 % and 2.0 % bwoc. Additionally, a defoamer (DOWFAX DF141 from Dow
Chemical, USA) was used to achieve a constant fresh concrete density of 2,420 ± 10 kg/m3.
First, dried aggregates including gravel and sand were put to the pan-type mixer and
soaked with half the amount of water for 5 min. After that, cement was added to the mixer
and the rest of water and other admixtures were continuously added into the concrete mixture
during the mixing process. The total mixing time was 5 min. From the fresh concrete, the
temperature was measured and tested for slump, density and air content. Moreover, concrete
samples were cast into 100 x 100 x 100 mm molds and cured for 6, 8, 10, 12, 16 and 24 hours
in a climate room at 23 ± 2 ° C and a relative humidity > 95 %. To obtain the 7 and 28 day
values, the specimens were removed from the molds after 1 day and then cured in a saturated
lime solution. The compressive strength data were collected from an UH-2000kNI instrument
from Shimadzu Corporation, Kyoto, Japan (Figure 31).
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Figure 31: Compressive strength test apparatus for concrete
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CHAPTER 5. RESULTS AND DISCUSSION
5 Results and discussion
This chapter presents the main results which are presented in the publications organized
in four main topics:
5.1 Influence of different PCE structures on the properties of C-S-H particles and their
effectiveness as strength accelerators in ordinary Portland cement
5.2 Effect of synthesis parameters on the accelerating effectiveness of C-S-H – PCE
nanocomposites in Portland cement
5.3 Application of the C-S-H – PCE nanocomposite as an accelerator in blended cements
5.4 Mechanism of the nucleation and growth of C-S-H – PCE nanocomposites
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5.1 Influence of different PCE structures on the strength

enhancing effect of C-S-H particles
This section describes the role of the molecular architecture of PCE superplasticizers on
the size of the C-S-H particles and their strength enhancing effect. Moreover, the structures of
the C-S-H – PCE nanocomposites were studied. A special focus was placed on MPEG PCE
superplasticizers possessing different side chain lengths and grafting density (molar ratio of
methacrylic acid to methoxy polyethylene glycol methacrylate ester).
5.1.1 Effect of the side chain length of PCE
C-S-H – PCE nanocomposites were synthesized by the co-precipitation method from
Na2SiO3 and Ca(NO3)2 in the presence of the MPEG PCE copolymers. The molar ratio of
CaO/SiO2 present in the starting materials was 1.5. Here, five MPEG PCEs possessing the
same grafting density (MAA : MPEG-MA molar ratios of 6:1), but different side chain
lengths (8, 17, 25, 45 and 114 ethylene oxide (EO) units) were employed in the precipitation.
For the structure of the synthesized products, a semi-crystalline composition like in C-S-H
(I) was determined via XRD. Moreover, evidence from FT-IR and TOC measurements
suggested that the PCE polymers were adsorbed onto the surface of the C-S-H particles.
More bulky PCEs such as those exhibiting long side chains occupied the surfaces of the
initial C-S-H foils more densely which better prevented the further growth of C-S-H. This led
to smaller sizes of the C-S-H particles as detected by dynamic light scattering (DLS). The
PCE polymer with the longest pendant groups (114 EO units) produced the smallest particle
sizes of the C-S-H – PCE composite and exhibited the strongest seeding effect for the
hydration of the silicate phases in cement, as was observed via isothermal heat flow
calorimetry. Accordingly, this nanocomposite achieved the largest gain in early compressive
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and flexural strengths of mortar, with an ~ 80 % increase over that of the neat OPC sample
(Figure 32).
Figure 32: Compressive strength of mortars cured for 16 hours and admixed with 0.35 % wt.
of the C-S-H – PCE nanocomposites synthesized by using different PCE
polymers
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Paper #1
C-S-H - PCE nanocomposites for enhancement of early strength
of Portland cement
(Effect of the side chain length of PCE)
V. Kanchanason, J. Plank
Proceedings of the 14th ICCC International Congress on the Chemistry of Cement,
Abstract book p. 326, Proceedings CD, Section 4: Admixtures, Beijing, China 2015.
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5.1.2 Effect of the grafting density of PCE
As mentioned before, anionic PCE copolymers can adsorb on the C-S-H surfaces and the
length of side chains of the PCE polymers presents the key to restrict the C-S-H particles to
their original nanosize, as is desirable for a strong seeding effect in cement.
In this part, three PCE superplasticizers possessing different grafting densities (the molar
ratio of methacrylic acid (MAA) to methoxy polyethylene glycol (MPEG) methacrylate ester
was varied between 2:1, 6:1 and 8:1), yet exhibiting the same side chain lengths of 45 EO
units were employed in the precipitation of C-S-H. The C-S-H – PCE nanocomposites were
successfully synthesized as confirmed by XRD and FT-IR measurements.
It was found that, the amount of the PCEs adsorbed on C-S-H increased with increasing
anionic character of the PCE resulting from a higher MAA content in the PCE. Here, higher
molar ratios of MAA : MPEG-MA (> 6:1) led to a higher adsorbed amount of PCE on C-S-H
and produced a larger portion of small size C-S-H particles (d50 ~ 100 nm).
These particularly small C-S-H – PCE nanocomposites are most advantageous to boost the
early compressive strength of mortar after 12 and 16 hours which increased about 60 % over
the neat cement (Figure 33).
The mechanism behind is that the C-S-H – PCE nanocomposites accelerate the
29
polymerization of the mono silicates to polysilicates in cement, as was found by Si MAS
NMR spectroscopy.
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Figure 33: Compressive strength development of mortars cured for 16 hours and admixed
with 0.35 % wt. of the C-S-H – PCE nanocomposites synthesized from PCEs
exhibiting different grafting density (anionicity)
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Paper #2
C-S-H – PCE nanocomposites for enhancement of early strength
of cement
(Effect of the grafting density of PCE)
19. ibausil, Bauhaus-Universität Weimar, Tagungsband 1, Weimar, Germany (2015)

759 – 766.
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5.2 Effect of synthesis conditions on the effectiveness of C-S-H –

PCE nanocomposites as accelerators in Portland cement
This section describes the influence of process parameters during the synthesis of the C-S-
H – PCE nanocomposites on their characteristics and performance. A commercial isoprenyl
oxy poly(ethylene glycol) based superplasticizer (IPEG PCE) possessing very long side chain
lengths (93 EO units) was employed in the synthesis of C-S-H. Moreover, various factors
such as pH value, Ca/Si ratio and temperature were adjusted during the preparation of the C-
S-H – PCE nanocomposites to achieve a 100 % increase over the neat OPC sample for the 16
hour compressive strength of mortar.
5.2.1 Effectiveness of C-S-H – PCE nanocomposites in Portland cement
First, the experiments were designed via a tool called Box-Behnken Design (BBD) by
using the MINITAB software. C-S-H – PCE nanocomposites synthesized under 16 different
conditions were admixed at 0.35 wt. % to mortar which was then tested for compressive
strength after 16 hours of curing. Thereafter, the relation between the synthetic variables and
the resultant mortar strengths was analyzed via the regression equation.
The strength results are presented in Figure 34. It was found that addition of the C-S-H –
PCE compounds synthesized under different conditions clearly promoted the early strength
development of mortars. The highest compressive strength value was obtained from a C-S-H
– PCE nanocomposite synthesized at a Ca/Si ratio of 1.0, at pH = 11.7 and a temperature of
50 ° C. The increase was ~ 10 N/mm2 which represents a 100 % increase over that of the
control sample. In comparison, the C-S-H – PCE compound prepared at the low pH value of
10.9 and high temperature (75 ° C) did not show an accelerating effect in cement. It produced
a compressive strength value which was comparable to that of the neat cement.
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Figure 34: Compressive strengths of mortars cured for 16 hours and admixed with 0.35 %
bwoc of C-S-H – PCE nanocomposites synthesized under various conditions
To quantify the dominant control factor, the response surface regression was analyzed and
the results are shown in Table 6. According to the theory, the p-values of factors less than
0.05 are most effective and should be considered. It was observed that only the pH value
played a dominant role during the synthesis of the nanacomposite and significantly impacted
the early strength of mortar, while the Ca/Si ratio and temperature were less important
factors. According to this, the optimum condition to achieve the largest gain in compressive
strength as obtained from the regression equation (Equation 23) was: pH = 12.3, Ca/Si = 1.0
and 20 ° C, as is shown in Figure 35.
To verify this result, the effect of pH values (pH = 10.4 - 13.8) during the synthesis on
structure, composition and morphology of C-S-H – PCE compounds and their effectiveness
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on early strength of mortar was studied in another series of experiments. This is presented in
the following section 5.2.2.
Strength = -283.244 + 46.6676a - 0.0146972b + 14.7106c - 1.84971(a*a) - 1.28125(a*c)

Equation 23
Table 6
Variance analysis according to the BBD model relating to the compressive strengths of
mortars admixed with differently synthesized C-S-H – PCE nanocomposites
Parameter Compressive strengths of mortar samples

P T Coefficient
Constant 0.000 29.123 8.4412
pH (a) 0.000 5.217 1.1700
Temp (b) 0.101 -1.804 -0.4042
Ca/Si (c) 0.546 -0.624 -0.1400
pH*pH (a*a) 0.009 -3.231 -1.1838
pH*Ca/Si (a*c) 0.068 -2.044 -0.5125
Figure 35: Finding the optimal condition for the synthesis of the C-S-H – PCE
nanocomposite
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5.2.2 Effect of pH on the composition, structure and morphology of

C-S-H – PCE nanocomposites
As was shown in section 5.2.1, the pH value during the synthesis had the strongest effect
on the performance of the synthesized C-S-H – PCE nanocomposite used as a strength
enhancer in cement. For this reason, studies on the influence of the pH conditions on the
characteristic properties of the C-S-H – PCE nanocomposite were performed. The results are
presented in three papers that follow this section.
First of all, C-S-H – PCE was precipitated from Na2SiO3 and Ca(NO3)2 solutions in an
isoprenolether (IPEG) - based PCE solution at pH values of 10.4, 11.7, 12.4 and 13.8. It was
confirmed that the pH value plays a critical role for the nanostructure, composition (Ca/Si
ratio) and morphology of the C-S-H – PCE products obtained. Furthermore, it influences the
PCE adsorption on C-S-H.
An increase of pH value from 10.4 to  11.7 changed the C-S-H structure from amorphous
to semi-crystalline, as was evidenced by XRD measurement. A decrease in the basal spacing
in the semi-crystalline structure was also found when the pH increased. However, no
evidence from XRD supported the intercalation of the IPEG-PCE into the C-S-H lamellar
structure.
Furthermore, the silicate chains present in the C-S-H – PCE nanocomposites were
investigated via 29Si MAS NMR spectroscopy. According to this, branched silicate chains in
C-S-H – PCE developed only at the low pH of 10.4. At higher pH values, no more bridging
sites occurred and the degree of polymerization of the silicate chains decreased, leading to
shorter chain lengths in C-S-H.
The composition of C-S-H is typically described by the Ca/Si ratio. The Ca/Si ratio of the
nanocomposites increased with a rise in pH and reached a value close to the initial ratio of
1.0.
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The morphology of the C-S-H – PCE nanocomposites was also affected by the pH. It was
found that at pH = 10.4, globular, agglomerated C-S-H particles were precipitated which at
pH  11.7 transformed to a foil-like morphology.
Additionally, the pH value influenced PCE adsorption on C-S-H which controls the
particle size of the product. The results revealed a reduction in the amount of PCE adsorbed
on the C-S-H foils at pH above 11.7, resulting from the decreased anionic charge of PCE
owed to counter-ion condensation. The highest PCE adsorption was observed at pH = 11.7,
leading to the highest amount of ultra-small nanofoils.
In summary, it became apparent that the pH value during the synthesis of C-S-H – PCE
nanocomposites besides the PCE composition presents the most important factor to control
the nanostructure, morphology and particle size of the nanocomposites. The C-S-H – PCE
nanocomposite obtained at pH = 11.7 consisted of the smallest foil-like particles, performed
the strongest seeding effect on cement hydration, and produced the largest gain in the early
strength of mortar. In comparison, globular C-S-H – PCE particles prepared at pH = 10.4
exhibited only a minor accelerating effect on cement hydration.
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Paper #3
Role of pH on the structure, composition and morphology of
C-S-H – PCE nanocomposites and their effect on early
strength development of Portland cement
Cement and Concrete Research, 102 (2017) 90 – 98.
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Paper #4
Relationship between the structure and morphology of C-S-H –
PCE nanocomposites and their accelerating effect in cement
Tagung Bauchemie, Bauhaus-Universität Weimar, Tagungsband 1, Weimar, Germany,
GDCh-Monograph, 52 (2017) 36 – 40.
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Paper #5
Effectiveness of C-S-H – PCE nanocomposites possessing globular
and foil-like morphology on early strength development of
Portland cement
2nd ICCCM International Conference on the Chemistry of Construction Materials, Technische
Universität München, Munich, Germany, GDCh-Monograph, 50 (2016) 85 – 88.
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5.3 Application of the C-S-H – PCE nanocomposite as an

accelerator in blended cements
The previous studies have demonstrated that the C-S-H – PCE nanocomposite can act as
an excellent seeding material for Portland cement and enhances the early strength of e.g.
mortar. Here, the effectiveness of a C-S-H – PCE nanocomposite on the early strength
development of blended cements made from fly ash, slag and calcined clay was investigated.
5.3.1 Fly ash blended cement
In this publication, the effectiveness of a C-S-H – PCE nanocomposite on the early
strength development of mortar and concrete produced from a fly ash blended cement was
addressed. Additionally, the mechanism of using the C-S-H – PCE seeding admixture in the
blended cement was studied via in-situ XRD and calorimetric measurements.
It was found that the C-S-H – PCE nanocomposite drastically enhanced the early strength
of mortar and concrete, particularly at 6 - 24 hours of hydration, without any adverse effect
on final strength at 28 days. Furthermore, this admixture improved the workability of fresh
mortar and concrete, leading to a significant reduction in the dosage of superplasticizer in the
mix design.
The hydration of the silicate phases (C3S/C2S) present in the clinker was extremely
accelerated by the C-S-H – PCE nanocomposite, as monitored by isothermal heat flow
calorimetry. Moreover, a continuous consumption of Portlandite starting at ~ 9 hours of
curing was observed via in-situ XRD measurement. This indicated that the C-S-H – PCE
nanocomposite can even stimulate the pozzolanic reaction of the fly ash in the blended
cement, an extremely important result, as it makes the use of such low CO2 cements more
practical.
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Based on these results it can be concluded that the C-S-H – PCE nanocomposite can
accelerate both the hydration of cement and the pozzolanic reaction of the fly ash, leading to
exceptionally high early strength values.
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Paper #6
Effectiveness of a calcium silicate hydrate – polycarboxylate ether
(C-S-H–PCE) nanocomposite on early strength development of
fly ash cement
Construction and Building Materials, 169 (2018) 20 – 27.
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5.3.2 Slag blended cement

In this part, the performance of a C-S-H – PCE nanocomposite on the strength
development of mortar made from slag blended cement (35 wt. % slag) was studied.
Moreover, the working mechanism of the C-S-H – PCE composite which nanocomposite was
used in the slag blended cement was elucidated via in-situ XRD and calorimetric
measurements.
It was found that the C-S-H – PCE nanocomposite considerably improved the strength
development of mortar, particularly within the first 24 hours, without a decrease in the final
strength at 28 days of hydration (Figure 36).
Interestingly, the nanocomposite also improved the strength development of the mortar
during all stages of hydration (6 hrs - 28 days). While, the compressive strength of the mortar
prepared from slag cement without nanocomposite showed lower strength values than the
OPC.
Figure 36: Compressive strength of mortar samples prepared from slag cement (w/b = 0.45)
after 6, 10, 16, 24 hours, 7, 14 and 28 days of curing at 20 ° C and > 95 % relative
humidity
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Hydration of the slag blended cement was tracked by isothermal heat flow calorimetry
(Figure 37). The results revealed that addition of the C-S-H – PCE nanocomposite to the slag
cement significantly accelerated cement hydration and increased the total heat released
during the accelerating period which can be assigned to the nucleation and growth of the C-S-
H and Portlandite phases from the silicate phases (C3S, C2S) in cement.
Figure 37: Heat evolution of the slag-blended cement (w/b = 0.45) admixed with 2.0 % bwoc
of the C-S-H – PCE nanocomposite
The hydration products such as hemi carboaluminate (Hc) and Portlandite were monitored
via in-situ XRD measurement. The relative intensities of the Hc and Portlandite reflections
appearing at 10.8 and 18 ° 2 were plotted over time (Figure 38). A continuous consumption
of Portlandite starting at ~ 12 hours of curing was found. Additionally, an increase in the
amount of Hc generated in the slag cement admixed with the C-S-H – PCE nanocomposite
was observed after ~ 12 hours of curing, while the formation of Hc in the neat slag blended
cement was detected only after 24 hours. These evidences suggest that Portlandite is
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consumed over time through two reactions; presumably the pozzolanic reaction of slag which
also produces C-S-H, and the formation of Hc.
Figure 38: Intensity of hemi carboaluminate (top) and Portlandite (bottom) reflections at 10.8
and 18 ° 2 respectively from in-situ XRD measurements of the slag cement,
hydrated with and without C-S-H – PCE nanocomposite
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5.3.3 Calcined clay blended cement
In this section, the effectiveness of a C-S-H – PCE nanocomposite on the strength
development of mortar produced from a calcined clay-blended cement (35 wt. % calcined
clay) is reported. Furthermore, the impact of the nanocomposite on the pozzolanic reaction in
the blended cement was studied via in-situ XRD and calorimetric measurements. As C-S-H –
PCE, the product described in paper #6 was selected (Ca/Si = 1.0, pH = 11.7 and 20 ° C).
It was observed that the C-S-H – PCE nanocomposite significantly improved the strength
development of a mortar without a reduction in the final strength after 28 days of curing
(Figure 39). Most impressively, after the first 24 hours the increase was ~ 100 % over that of
the control sample. Thereafter, the difference between the control sample and the admixed
samples decreased, but still were ~ 10 - 20 % higher than that of the control sample.
Figure 39: Compressive strength of mortar samples made from a calcined clay-blended
cement (w/b = 0.5) after 6, 10, 16, 24 hours, 7, 14 and 28 days of curing at 20 ° C
and > 95 % relative humidity
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Hydration of the calcined clay blended cement was monitored by isothermal heat flow
calorimetry (Figure 40). It was found that addition of the C-S-H – PCE nanocomposite to the
clacined clay-blended cement considerably accelerated the hydration of the silicate phases
present in the clinker and also increased the total heat released during the accelerating period.
This behavior was nearly the same as observed in the hydration of the slag blended cement.
Figure 40: Heat evolution of the calcined clay-blended cement (w/b = 0.5) admixed with
2.0 % bwoc of the C-S-H – PCE nanocomposite
Furthermore, the impact of the nanocomposite on the pozzolanic reaction was studied via
XRD measurements. These experiments were conducted to find an explanation for the
superior early strength development observed for the calcined clay-blended cement as shown
in Figure 39.
Figure 41 shows the XRD plot of the relative intensities of the hemi carboaluminate (Hc)
and Portlandite reflections appearing at 10.8 and 18 ° 2 over time, respectively, as
monitored via in-situ XRD measurement. An extremely early and strong formation of Hc in
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the clacined clay cement admixed with the C-S-H – PCE nanocomposite was observed after ~
8 hours of curing, while the amount of Hc generated in the neat calcined clay cement
increased only after ~ 24 hours. Moreover, a very early consumption of Portlandite starting at
~ 18 hours was detected in the calcined clay cement with the nanocomposite (Figure 41).
This indicates that the C-S-H – PCE nanocomposite can also accelerate the pozzloanic
reaction of calcined clay and stimulate the formation of Hc in the calcined clay cement.
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Figure 41: Intensity of hemi carboaluminate (top) and Portlandite (bottom) reflections at 10.8
and 18 ° 2 respectively from in-situ XRD measurements of the calcined clay
cement, hydrated with and without C-S-H – PCE nanocomposite
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5.4 Nucleation and growth of the C-S-H – PCE nanocomposites
This part describes the effect of an isoprenyl oxy poly(ethylene glycol) (IPEG) based PCE
on the nucleation and crystallization of C-S-H nanofoils.
First, the early nucleation and crystallization of C-S-H between 12 seconds and 24 hours
precipitated from Ca(NO3)2 and Na2SiO3 solutions at a Ca/Si ratio of 1.0 in the presence of an
IPEG-PCE superplasticizer was investigated by capturing the initial precursors of C-S-H via
transmission electron microscopy (TEM). Moreover, the effectiveness of the C-S-H – PCE
nanocomposites prepared at different ageing times on the early strength development of
mortar was measured.
It was observed that in this precipitation reaction, at first a metastable precursor of C-S-H
formed at the beginning exhibits a globular morphology and later converts to C-S-H
nanofoils following a non-classical nucleation mechanism. The presence of the IPEG-PCE
strongly delays the transformation from globular to nanofoil-like C-S-H for several hours
because of a layer surrounding the globules. Because of this slow conversion, particularly
small C-S-H nanofoils are produced with excellent seeding effect. Furthermore, the C-S-H
nanofoils prepared after 24 hours of ageing exhibit a stronger seeding effect for the hydration
and early strength development of cement than those taken from shorter ageing times.
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Paper #7
Early nucleation and crystal growth of C-S-H – PCE
nanocomposites used as strength enhancers in cement
The 12th International Conference on Superplasticizers and Other Chemical Admixtures
in Concrete, Beijing, China, October 28 - October 31, 2018.
(Submitted on 15th December 2017)
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CHAPTER 6. SUMMARY AND OUTLOOK
6 Summary and outlook
This thesis focused on the synthesis of C-S-H – PCE nanocomposites that are used as
seeding materials to accelerate the hydration of cement, resulting in enhanced early strength
of Portland cement and blended cements. The mode of action of these nanocomposites in
cement was also highlighted.
C-S-H – PCE nanocomposites were successfully synthesized by the co-precipitation
method from Na2SiO3 and Ca(NO3)2 solutions in the presence of PCE copolymers. It was
observed that the particle size and the characteristics of the synthetic C-S-H – PCE
compounds are the key to obtain a strong seeding effect in cement.
In the first part of this thesis, the size of C-S-H particles was controlled using PCE
copolymers of specific molecular structure. A PCE polymer possessing very long pendant
groups (114 EO units) and low grafting density (molar ratio of MAA : MPEG-MA = 6 : 1)
can produce the smallest particle sizes for the C-S-H  PCE composite, which exhibit the
strongest seeding effect for the hydration of cement. Consequently, this nanocomposite
achieves the largest gain in the early strength of mortar.
In the second part of this thesis, among the various conditions used for the synthesis of C-
S-H  PCE nanocomposites, the pH value was found to play the most important role in
obtaining a superior seeding material. The reason is that the pH value strongly affects the
nanostructure, composition and morphology of the C-S-H – PCE products, and also impacts
the PCE adsorption on C-S-H which generally controls the particle size of the C-S-H – PCE
product. Furthermore, the structure of C-S-H – PCE nanocomposite precipitated at the
optimal pH value (of 11.7) is semi-crystalline and consists of shorter, non-branched silicate
chains. Moreover, this nanocomposite contains the highest amount of ultra-small nanofoils,
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which shows an optimal seeding effect in cement and the highest early strength development
of mortar.
In the third part of this thesis, effectiveness of the C-S-H – PCE admixture on early
strength development of fly ash and slag blended cements was investigated. It was found that
addition of the C-S-H – PCE nanocomposite drastically increases the early strength
development of mortar and concrete, particularly during the first 24 hours of hydration,
without a decrease in final strength (28 days). A mechanistic study revealed that the C-S-H –
PCE nanocomposite greatly accelerates the reaction of the silicate phases present in the
clinker. Moreover, it can also stimulate the pozzolanic reaction of fly ash, slag and calcined
clay, consequently leading to higher early strength values there as well.
In the last part of this thesis, the effect of an IPEG PCE on the time-dependent nucleation
and crystallization of C-S-H was studied via TEM. The results reveal that the initial
precipitation product consists of a metastable C-S-H precursor which exhibits a globular
morphology and then converts to C-S-H nanofoils, following a non-classical nucleation
mechanism. In the presence of the IPEG-PCE, the conversion from C-S-H globules to the
nanofoils is delayed for several hours because a layer, presumably of PCE polymer, coats the
globules. Moreover, it was found that the C-S-H – PCE nanofoils aged for 24 hours show the
strongest seeding effect for the hydration and early strength development of cement.
The work documented in this thesis includes a study on the effect of various parameters
during synthesis of C-S-H – PCE nanocomposites and their effectiveness in cements. Further
studies are suggested to improve the performance of this nanocomposite and to investigate
other beneficial points, as follow:
- Use of other PCEs (e.g. amphoteric PCEs, star-shaped PCE) to stabilize the C-S-H
particles
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- Study of the interaction of C-S-H with polymers other than PCEs such as
phosphated comb polymers, polyethylene imines, polyamidoamines,
polyvinylalcohol, etc.
- Further control of the size of the C-S-H particles by adjusting process parameters
such as the droplet size of the raw material solutions, by using a high speed mixer
(e.g. homogenizer) or micro reactor.
- Application of the C-S-H – PCE nanocomposites in other blended cements such as
limestone blended cements, etc.
- Clarification of the composition of the layer surrounding the metastable C-S-H
globules found at very early nucleation when PCE is present.
- Study of the very early nucleation and crystallization of C-S-H in actual cement:
does it also involve an amorphous, metastable, globular precursor?
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CHAPTER 7. ZUSAMMENFASSUNG UND AUSBLICK
7 Zusammenfassung und Ausblick
Der Fokus dieser Arbeit liegt in der Synthese von C-S-H – PCE Nanokomposit-
Materialen, die Kristallisationskeime bilden und somit eine beschleunigende Wirkung auf die
Zementhydratation haben, wodurch die Frühfestigkeit von Portland- und Kompositzementen
deutlich erhöht werden kann. Darüber hinaus war ein weiteres Ziel dieser Dissertation, den
Wirkmechanismus dieser Nanokomposite im Zement näher zu untersuchen.
Die Synthese der C-S-H – PCE Nanokomposite erfolgte mittels Co-Präzipitation aus
Na2SiO3- und Ca(NO3)2 - Lösungen in Anwesenheit von PCE-Fließmitteln. Hierbei wurde
beobachtet, dass die Kristallkeimbildung im Zement von der Partikelgröße und den
Materialeigenschaften der synthetisierten C-S-H – PCE-Verbindungen abhängt.
Im ersten Teil der Arbeit wurde die Größe der C-S-H Partikel durch die molekularen
Eigenschaften der PCEs gesteuert. Ein PCE-Polymer mit einer sehr langen Seitenkette (114
EO-Einheiten) und einer niedrigen Seitenkettendichte (molares Verhältnis MAA : MPEG-
MA = 6:1) ergab die geringste Partikelgröße für die C-S-H – PCE-Nanokomposite. Sie waren
am besten als Kristallisationskeime für die Hydratation der Silikatphasen (C3S und C2S)
geeignet. Folglich ergaben diese Nanokomposite die höchste Zunahme an Frühfestigkeit bei
den Mörtelproben.
Im zweiten Teil der Arbeit stellte sich von allen getesteten Reaktionsbedingungen der pH-
Wert als entscheidendes Kriterium heraus, um möglichst wirkungsvolle Kristallisationskeime
zu erhalten. Die Gründe hierfür sind, dass der pH Wert stark die Nanostruktur, die
Zusammensetzung und die Morphologie der C-S-H – PCE-Nanokomposite beeinflusst und
auch die PCE-Adsorption beeinflusst, wodurch prinzipiell die Partikelgröße der C-S-H
Produkte reguliert wird. Die Nanokomposite, die bei einem pH-Wert von 11.7 hergestellt
werden, sind semi-kristallin und bestehen aus kürzeren, unverzweigten Silikatketten.
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Außerdem enthält dieses Nanokomposit die höchste Menge an ultra-kleinen Nanofolien,
welche optimale Keimbildner im Zement sind und somit die beste Frühfestigkeitsentwicklung
ergeben.
Im dritten Teil der Arbeit wurde die Effektivität der C-S-H – PCE-Nanokomposite auf die
Frühfestigkeitsentwicklung von Zementen mit Flugasche und Schlacke untersucht. Es stellte
sich heraus, dass die Zugabe von C-S-H – PCE-Nanokomposit die Frühfestigkeit von Mörtel
und Betonproben – insbesondere in den ersten 24 Stunden der Zementhydratation – sehr stark
erhöht, ohne jedoch die Endfestigkeit nachteilig zu beeinflussen (28 Tage). Eine
mechanistische Studie ergab, dass die C-S-H – PCE-Nanokomposite die Hydratation der
silikatischen Phasen, die im Klinker erhalten sind, stark beschleunigen. Außerdem kann es
die puzzolanische Reaktion von Flugasche, Schlacke anregen und calcinierten Tonen, womit
die sehr hohen Frühfestigkeitswerte dieser Zemente erklärt werden können.
Im letzten Teil der Arbeit wurde der Effekt eines IPEG-PCE auf die Keimbildung und
Kristallisation von C-S-H mittels TEM untersucht. Die Ergebnisse Zeigten, dass zuerst
metastabile C-S-H-Vorstufen, die eine tröpfchenförmige Morphologie aufweisen, gebildet
werden und sich nach einem nicht-klassischen Nukleationsmechanismus in C-S-H-
Nanofolien umwandeln. In Gegenwart des IPEG-PCEs findet die Transformation der C-S-H-
Tröpfchen zu Nanofolien einige Stunden später statt, da eine Schicht, die vermutlich aus PCE
besteht, die Tröpfchen umhüllt. Außerdem zeigte sich, dass C-S-H-Nanofolien, die 24
Stunden gealtert wurden, die besten Kristallisationskeime für die Hydratation und die
Frühfestigkeitsentwicklung von Zement darstellen.
Die Dissertation beschäftigte sich außerdem mit dem Einfluss verschiedener
Reaktionsparamater auf die Eigenschaften von C-S-H – PCE-Nanokomposite und deren
Effektivität in Zement. Weitere Studien sollten sich mit der Verbesserung der Wirksamkeit
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dieser Nanokomposite beschäftigen. Dazu sollten folgende Punkte eingehend untersucht
werden:
- Einsatz anderer PCEs zur Stabilisierung der C-S-H Partikel, wie z.B. von
amphoteren PCEs, sternförmigen PCEs, etc.
- Untersuchung der Wechselwirkung von C-S-H mit andern Polymeren wie z.B.
Phosphat-Polymeren, Polyethyleniminen, Polyamidoamine, Polyvinylalkoholen,
etc.
- Kontrolle der C-S-H Partikelgröße durch Anpassen der Prozessparamater wie z.B.
der Tröpfchengröße bei der Zugabe der Ausgangslösugen (Ca(NO3)2, Na2SiO3)
durch Einsatz eines Hochgeschwindigkeitsmixers oder eines Mikroreaktors
- Einsatz von C-S-H – PCE-Nanokompositen in anderen Kompositzementen.
- Chemische Identifizierung der Schicht um die metastabilen C-S-H-Tröpfchen
Kügelchen, die zu Beginn der C-S-H-Bildung gefunden wurde
- Untersuchungen zur frühen Nukleation und Kristallisation von C-S-H im
eigentlichen Zement: verläuft die Nukleation von C-S-H dort ebenfalls über eine
amorphe, metastabile, tröpfchenförmige Vorstufe wie bei der hier angewandten
Copräzipitationsmethode?
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New Advanced Admixtures

Vietnam Concrete Association (VCA)

Hanoi, 13 March 2019

Prof. Dr. Johann Plank

PCEs can introduce significant amounts of air into concrete

C3S responsible for early strength of concrete:

© Prof. Plank 2019

Ca3(SiO4)O (triclinic) Ca2(SiO4)

C3S is tricalcium oxy silicate

© Prof. Plank 2019

Disadvantage: they all reduce final strength !

C-S-H foils C-S-H needles

2. E.T. Rodriguez, I.G. Richardson, L. Black, E. Boehm-Courjault, A. Nonat, J. Skibsted,

• C-S-H seed crystals accelerate C-S-H formation

© Prof. Plank 2019

TEM image of C-S-H – PCE Mortar testing according to DIN EN 196-1

© Prof. Plank 2019

Nanofoils form inside the metastable C-S-H droplets

© Prof. Plank 2019

OPC Clinker + 35 % fly ash + 2,0 % C-S-H – PCE:

Earlier consumption of Portlandite (Ca(OH)2) signifies

OPC Clinker + 35 % Slag + 2,0 % C-S-H – PCE:

© Prof. Plank 2019

© Prof. Plank 2019

C-S-H - PCE initiates C-S-H crystallization also in the pore solution

normally, C-S-H crystallizes only on the surface of cement particles

decreased porosity and permeability increase durability

© Prof. Plank 2019

A Comprehensive Study on Calcium Silicate Hydrate –

Vollständiger Abdruck der von der Fakultät für Chemie der

Doktors der Naturwissenschaften (Dr. rer. nat.)

Vorsitzender: Univ.‐Prof. Dr. Michael Schuster

Die Dissertation wurde am 23.01.2018 bei der Technischen Universität München

one must climb a long ladder to reach them”

The Royal Guidance of His Majesty the King Bhumipol Adulyadej

valuable guidance, encouragement, motivation, and immense knowledge throughout my Ph.D

Liu Jingnu for all their administrative work.

This thesis includes the following publications:

Peer reviewed SCI(E) journal:

Role of pH on the structure, composition and morphology of C-S-H – PCE

nanocomposites and their effect on early strength development of Portland cement

Cement and Concrete Research, 102, 2017, 90-98.

Effectiveness of a calcium silicate hydrate – polycarboxylate ether (C-S-H–PCE)

nanocomposite on early strength development of fly ash cement

Construction and Building Materials, 169, 2018, 20-27.

Non-review conference papers:

The 12th International Conference on Superplasticizers and Other Chemical Admixtures

in Concrete, Beijing, China, October 28 - October 31, 2018, accepted

their accelerating effect in cement

Tagung Bauchemie, Bauhaus-Universität Weimar, Tagungsband 1, Weimar, Germany,

GDCh-Monographie, 52, 2017, 36-40.

Effectiveness of C-S-H – PCE Nanocomposites Possessing Globular and Foil-Like

Morphology on Early Strength Development of Portland Cement

2nd ICCCM International Conference on the Chemistry of Construction Materials,

Technische Universität München, Munich, Germany, GDCh-Monographie, 50, 2016, 85-

C-S-H – PCE nanocomposites for enhancement of early strength of cement

19. ibausil, Bauhaus-Universität Weimar, Tagungsband 1, Weimar, Germany, 2015, 759-