INTERNAL STRUCTURE of

HARDENED CEMENT
PASTE
 Kinetics and Reactivities of PC
Components
• The rate of hydration during the first few days is in the order
of C3A > C3S > C4AF > C2S.

C3A
Aluminate
C3S
C4AF
Rates of hydration
C2S
of the four main
chemical
components of PC.
 Kinetics and Reactivities of PC
Components

• C3A hydrates rapidly

but its strength is low

• C3S contributes to
strength at early ages

• C2S contributes to
strength at later ages

Strength development over time of the four

main chemical components in PC.
 Hydration Products of Cement
Hydrations of pure cement compounds:
• The mechanism of hydration of the cement as whole is very
complex and has not been fully understood yet.
• So far, the only approach to studying the hydration of Portland
cement is to investigate the reaction mechanism of individual
compounds separately.
• This assumes that the hydration of each compound takes
place independently and no interaction occurs. Although this
assumption is not valid completely, it helps to understand the
chemistry of hydration.

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Silicates
• 2C3S + 11H→C3S2H8 + 3CH
• 2C2S + 9H→ C3S2H8 + CH

The principal hydration product is Another product is CH, calcium

C3S2H8, calcium silicate hydrate, or hydroxide (lime).
C–S–H

• Although C3S and C2S produce the same hydration products, their reaction rates
are very different;
• C3S reacts very fast at the early stage, releases more hydration heat, and
contributes most to early age strength of concrete.
• C2S reacts very slowly, releases less heat, and contributes minimally to early age
strength of concrete. C2S contributes the most to the long-term strength of
concrete.
Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Silicate Hydrate
(C-S-H)
 C-S-H is an amorphous, colloidal (with very small
particles) material with variable chemical and
physical structure.
 It is the major phase,
 Occupies 2/3 of the paste volume,
 Microporosity associated with this phase is about
25%,
 Huge surface area
 Forms a continuous matrix,
 Small crystals of calcium hydroxide (CH), embedded
 Smaller crystals of calcium sulfoaluminate hydrates, within the C-S-H
 Some unhydrated residues of the original cement grains matrix
CSH provides the strength of hardened cement paste,
therefore, strength of concrete.
 Calcium Silicate Hydrate
(C-S-H)
 Its average composition has a CaO/SiO2 (C/S) ratio of 1.5-
1.7,
 However, the C/S ratios of individual particles may vary
over 1-3,
 C-S-H has considerable quantities of impurity oxides,
alumina and sulfur,
 Its water content is variable,
 Water associated with C-S-H ranges from:
 chemically bound water
 weakly bound water to the surface through van der Waals
 Calcium Silicate Hydrate
(C-S-H)
 Chemically bound water is represented by the formula
3CaO.2SiO2.H2O and obtained after very strong drying in
vacuum (D-drying),
 When water is removed from C-S-H, its physical structure
changes considerably,
 C-S-H is a metastable, particularly saturated “xerogel”
similar to silica gel formed by precipitation from solution,
 The way of removing water influences the microstructural
changes [if more gentle drying is used, then structural
rearrangements are much less, and the material more
closely approximates to the original xerogel structure].
Models of Calcium Silicate Hydrate
(C-S-H)
Munich Model

According to this model:

 Coupling between colloidal particles of C-S-H is
dominated by the interfacial energies of the particles,
 Water adsorption reduces this energy and disjoining
pressures between particles are created.
Powers-Brunauer Model

 Based on layer structure,

 Individual particles made up from 2 or 3 elementary
sheets,
 Water loss from between the sheets occurs only at low
relative humidities and is irreversible,
Feldman-Sereda Model

 Based on much more irregular layer structure,

 Properties are influenced much more by interlayer
water between the irregular sheets which can move
apart reversibly,
 All micropores are considered to be interlayer
regions and are created as the C-S-H stabilizes.
 Models of Calcium Silicate Hydrate
(C-S-H)
• Kondo et al. tried to reconcile Powers-Brunauer
and Feldman-Sereda models;
• Taylor proposed a combination of subcrystalline
particles based CaO sheets with condensed
Si2O7 units with intervening amorphous regions
containing polysilicate anions and water
molecules.
 Calcium Hydroxide (C-H)

• Another hydration product is CH, calcium hydroxide.

• CH is formed in solution by crystallization and occupies
about 20-25% in the hardened cement paste (hcp).
• This product is a good crystalline with a plate shape in
most cases.
• Size of the crystals depends on the amount of space
available.
• Much lower surface area than CSH
• Does not contribute much to strength
• Dissolves easily with water

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Hydroxide (C-H)
• Keeps the pore solution alkaline (pH > 12) and it is good
for corrosion protection of steel.
• From a durability of concrete point of view, CH may lead
to leaching due to its solubility, carbonation due its
reaction with carbon dioxide, alkali aggregate reaction
due to its high pH value, or sulfate attack due to its
reaction with sulfate. Hence, in contemporary concrete
technology, there has been a trend to reduce amount of
CH in concrete as much as possible.
• However, a minimum amount of CH is needed to keep
the high alkali environment in concrete.
Calcium Sulfoaluminate Hydrates

• Calcium Sulfoaluminates do not contribute

much for strength.

• If only C3A hydrates : C3A + 6H  C3AH6

• This reaction is very fast  Flash setting
• To prevent flash setting, gypsum is added during the
production of cement.
 Calcium Sulfoaluminate Hydrates
• 10-15% (by volume) of cement paste
• The primary initial reaction of C3A with water in the presence
of a plentiful supply of gypsum is;
Tricalcium
aluminate + gypsum + water → ettringite

• C3A + 3CSത H2+ 26H →C6ASത 3H32

The 6-calcium aluminate trisulfate-32-hydrate, is usually called

calcium sulfoaluminate hydrate and more commonly
ettringite, which is the name of a naturally occurring mineral of the
same composition. The nickname of ettingite is AFt.
Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Sulfoaluminate Hydrates

• The effect of ettringite on concrete strength can be evaluated

in two cases.
• In case 1, ettringite is formed before the paste has hardened
and gained strength due to hydration of C3S. It will contribute
to the early strength development of concrete since the
needle-shaped crystals can work as reinforcement for the
surrounding C–S–H, and the expansion is not so significant.
• In case 2, if ettringite is formed after the concrete has
hardened and free space has been occupied by other
DANGER

hydration products, it will make its space to grow by breaking

the hardened hydration products and hence create cracks and
volume instability.
Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Sulfoaluminate Hydrates
• The ettringite is stable as long as there is sufficient gypsum
available and at a temperature lower than 60℃. If all the
gypsum is consumed before the C3A has completely hydrated or
the temperature rises to above 60℃, it can be broken down
during the hydration of the conversion to monosulfoaluminate:

• 2C3A + C6A Sത 3H32 + 4H →3C4ASH

ത 12
Tricalcium
+ ettringite + water → monosulfoaluminate
aluminate

• Monosulfoaluminate is also called tetracalcium aluminate

monosulfate-12-hydrate. Its nickname is AFm.
• Monosulfoaluminate is the stable phase in mature concrete
 Calcium Sulfoaluminate Hydrates

• When monosulfoaluminate is brought into contact with a new

source of sulfate ions, ettringite can be formed again:
• C4ASത H12 + 2CSത H2 + 16H → C6ASത 3H32
Monosulfo
+gypsum+ water → ettringite
aluminate
• Sulfate attack is mainly the result of the reaction of
monosulfoaluminate with sulfate ions (from sea water or salty
soil). This reaction causes internal volume expansions, which
lead to internal microcracking and hence overall concrete
deterioration.
• Therefore, C3A is limited for concretes to be exposed to
sulfates.
• If C3A < 5%  Sulfate resisting cement
 Calcium Sulfoaluminate Hydrates

• The hydration products of C4AF are similar to those of C3A.

However, the reaction rate of C4AF is slower than that of C3A.
When reacting with gypsum, the following equation applies:

ത 2+ 21H → C6(A, F)Sത 3H32 + (F, A)H3

• C4AF + 3CSH

Tetracalcium Ferric-aluminum
aluminate hydrate hydroxide

• The expression C6(A, F)Sത 3H32 indicates that iron oxide and
alumina occur interchangeably in the compound.

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
Components of Hardened Cement Paste

Components Description Remarks

C-S-H Amorphous, metastable gel Includes micropores,

variable composition
CH (Calcium hydroxide) Relatively large crystals Does not lose moisture at
(10 µm-1mm) room temperature

Calcium aluminate hydrates Very small crystals Principally

(1-10µm) monosulfoaluminate (solid
solution), traces of
ettringite and hydrogarnet
Unhyrated cement - -

Capillary pores Remnants of water-filled Includes mesopores and

space macropores (wide range of
pore sizes)
Hardened Cement Paste
Components of Hardened Cement Paste

Portland cement after 24 hours hydration time

CSH
CH
Ettringite
Influence of Hardened Cement Paste Components
on Paste Properties
Component Strength Deformation Durability

C-S-H Provides major cohesive forces but Water loss from Very insoluble.
weak because of microporosity. micropores causes Water in micropores does not
Dry concrete is stronger then wet shrinkage (on drying) freeze and has low mobility (low
(stronger van der Waals bonds). and creep on loading. permeability).

CH Contributes by reducing porosity. Is dimensinally stable. Block capillary pores, hence

Cleavage may limit strength of Restrain C-S-H lower permeability. Slowly
high strength paste. deformations. leached by water, which causes
efflorescence and increases
permeability. Carbonates, and is
dissolved by acids
Calcium Not significant. Minor effect. Causes sulfate attack by
aluminate Reduces total porosity. reforming ettringite and causing
hydrate expansion.
Unhyrated Significant only in low porosity Restrain C-S-H Renewed hydration may cause
cement pastes. deformations. autogeneous healing of internal
cracks.
Capillary Total porosity is the major factor Fine pores contribute to Porosity influences permeability
pores influencing strength. shrinkage and creep. and diffusivity. Large
pores increase water flow
through concrete.
 Physical Aspect of Hydration
When water is added to cement, what happens?
•Dissolution of cement grains
•Growing ionic concentration in “water” (now a solution)
•Formation of compounds in solution
•After reaching a saturation concentration, compounds
precipitate out as solids (“hydration products”)
•In later stages, products form on or very near the surface of the
anhydrous cement
 Schematic
representation of
HYDRATION

a) anhydrous cement
b) the effect of hydration after 10 minutes
c) 10 hours
d) 18 hours
e) 1–3 days
f) 2 weeks.
 Hydration of Cement

1 cm3 cement 2.06 cm3 cement gel

HYDRATION
Time = 0

Time = t1
 HYDRATION
t2 > t1

t3 > t2
 HYDRATION
t4 > t5

t5 full hydration
Results of a realistic digital model of cement hydration

Phases are color coded: a) Cement particles dispersed in water just

Black=water (pores) after mixing.
Red = C3S b) 30% hydration, ~ 1 day
Blue = C2S c) 70% hydration, ~ 28 days
Yellow = C-S-H gel
 Cement Hydration

Schematic description of
the hydration process in a
cement paste
a. Setting and hardening
b. Structure formation
 Cement Hydration
The main characteristic features
observed are the reduction in
porosity accompanied by the
formation of continous matrix of
C-S-H, in which are embedded;
• unhydrated cement grains,
• microscopic crystals of
monosulfoaluminate, and
• relatively massive crystals of
calcium hydroxide.

Schematic description of the reaction

products and microstructure which
develop during the hydration of PC.
Cement Hydration
Cement Hydration
Cement Hydration
Cement Hydration
Cement Hydration
Porosity

Minutes Hours Days

Cement Hydration

Development of
cement hydration
products in a PC
paste over a 28-day
period
Another Representation of Hydration Degrees
 Cement Hydration

• A cement particle
coated with C-S-H
(bottom left) is
sorrounded by
ettringite needles
growing into the pore
space.
• A few platelets of
monosulfoaluminate
can be seen in the
upper left.
• A large crystal of
calcium hydroxide is
at the far right.

Scanning electron micrograph of hardened PC

paste after 7-days curing.
 Cement Hydration
• The bright areas (A)
represent the
remnants of
unreacted cement
particles surrounded
by a dense coating of
C-S-H.
• A pocket of
monosulfoaluminate
(M) lies adjacent to
one cement particle.
• The ground mass
consists of calcium
hydroxide (light
gray, labeled C), C-
S-H (dark gray) and
Backscattered SEM Picture of a cut and polished porosity (black).
hardened PC paste after 28 days curing.
 HYDRATION as a summary
• Is the chemical combination of cement and water to form
hydration products
• Takes time
• May not proceed to 100% completion

Formation of hydration products over time leads to:

• Stiffening (loss of workability)

• Setting (solidification)
• Hardening (strength gain)
 Composition of cement paste at
different stages of hydration
• 1 cm3 cement  2,06 cm3 cement gel
(if fully hydrated)

Water

Cement

Hydration degree: 0%
What is the water/cement ratio of this mixture?

If the specific gravity of cement is

3.1 g/cm3 ;
water/cement ratio of this paste is =
200 / (100x3.1) = 200/310 = 0.65
Hydration degree: 50%
Hydration degree: 75%
Hydration degree: 100%
 HEAT OF HYDRATION
Hydration process of cement is accompanied by
heat generation (exothermic).

About 50% of this heat is liberated within 1-3

days & 75% within 7 days.

By limiting C3S & C3A content heat of

hydration can be reduced.
 Heat of Hydration of Pure Compounds

Heat of Hydration
(cal/g)

C3S 120
C2S 62
C3A 207
C4AF 100

The heat of hydration of OPC is on the order of 85-100 cal/gr.

As concrete is a fair insulator, the generated
heat in mass concrete may result in expansion
& cracking. This could be overcome by using
suitable cement type.

It could also be advantages for cold wheather

concreting.
 Studying Cement Hydration with
Calorimetric Curve
• The cement hydration process was traditionally studied using
the calorimetric method.
• The hydration stages were identified by heat liberation
measurement and the hydration mechanism was explained
based on heat evolution.
• Some limitations (Gartner et al., 2002) were pointed out, such
as that the liberated heat content was simply proportional
neither to the degree of cement hydration nor to the
development of the physical properties.
• This method provides only an approximation of the
understanding of cement hydration and leaves space for
cement scientists and engineers to explore more accurate
ways.
A Typical Calorimetric Curve of
Portland Cement

Rate of heat evolution during the hydration of PC

 Stages of Calorimetric Curve

• Kinetics of reaction, chemical processes, and relevance to

concrete of the different reaction stages of cement
 Studying Cement Hydration with
Calorimetric Curve
• Isothermal
calorimetry can
be used to study
many factors
influencing
cement
hydration, such
as
– Temperature,
– Admixtures,
– Supplementary
Materials.
 New Understanding of The
Dynamics of Cement Hydration
• Setting of fresh cement paste:
– Cement hydration is a complex physical–chemical process.
– During the process, a cement–water mixture is changed from a fluid
state to a porous solid state.
– An adequate understanding of the mechanism of cement hydration is
necessary for a full appreciation of cement concrete properties.
 Studying Cement Hydration with
Electrical Resistivity
• Recently, the dynamics of the cement hydration process have
been studied with an advanced monitoring technique,
noncontact electrical resistivity measurement as shown in
following figure:

Electrical
resistivity
measurement
setup
• Electrical resistivity
development and the
rate in resistivity of the
cement paste during
the first 24 h.
 Studying Cement Hydration with
Microstructural Investigations
• To investigate the cement hydration process and understand
what happens at each characteristic point on the resistivity
and its differential curves, microstructural investigations can
be conducted such as;
– Scanning electron microscopy (SEM),
– X-ray diffraction (XRD),
– Differential thermal analysis (DTA),
– Fourier transform infrared spectroscopy (FTIR).
 RELATION BETWEEN THE CONCEPTS OF
CONCRETE DURABILITY AND PERFORMANCE
 Concrete
Concrete extremely complex system of:
• Solid phases
• Pores
• Water
with a high degree of heterogeneity.
 Structural Levels of Concrete

 This heterogeneity is considered on several

levels.
 For material modelling purposes, Wittmann
introduced the idea of these 3 levels :

• micro
• meso levels
• macro
 Structural Levels of Concrete

According to Wittmann:
Structural Level Characteristic Features Type of Models

Micro-level Structure of hardened Materials science models

cement paste,
xerogel
Meso-level Pores, Materials engineering
cracks, models,
inclusions, mechanical and numerical
interfaces models
Macro-level Geometry of structural Structural engineering
elements models,
materials laws
Structural Levels of Concrete
Structural Level Shape

Micro-level

Air voids
Meso-level
Paste
Aggregate
ITZ

Macro-level
concrete
 Structural Levels of Concrete
 Detailed structure of hardened cement paste is
extremely complex, being an intimate mixture of diverse
components with widely varying properties.
 References
• Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
• Young, J. F., and Mindess, S., Gray, R.J., Bentur, A., The Science and Technology of Civil
Engineering Materials, Prentice Hall, New Jersey, 1998.
• https://www.youtube.com/watch?v=4XMRUDJUFQw
• Sandberg, P., Zacharias, M., and Brown, D., Calorimetry for Cement, Calmetrix Inc, USA/UK,
2015.
• Dyer, T., Concrete Durability, CRC Press, Taylor & Francis Group, Florida, 2014.
• Folic, R., Durability Design of Concrete Structures - Part 1: Analysis Fundamentals, UDC
624.012-3(045), Facta Universitatis Series: Architecture and Civil Engineering, 7(1), 1 – 18,
10.2298/FUACE0901001F, 2009.
• Witmann, F. H., Deformation of concrete at variable moisture content, In book: Mechanics of
Geomaterials (pp.425-459) Publisher: John Wiley & Sons Ltd, Editors: Z. P. Bazant, January
1985.
• Pang, G. S., Chae, S. T., and Chang, S. P., Predicting Model for Pore Structure of Concrete
Including Interface Transition Zone between Aggregate and Cement Paste, International
Journal of Concrete Structures and Materials, 3(2), 81-90, DOI 10.4334/IJCSM.2009.3.2.081,
December, 2009.