Cement Structure & Hydration Lecture

13-05-2014
NPTEL PROJECT
IIT DELHI
Concrete Technology
Module 1 ( Lecture 2)
Cement: Structure & Hydration
B. Bhattacharjee
CIVIL ENGINEERING DEPARTMENT

IIT DELHI
DEPARTMENT OF CIVIL ENGINEERING, IIT DELHI

1
General Outline
Structure of cement compound.

U Structure of compounds and
hydration.
U Main Chemical reactions.
U Hydration process
U Bonding Action
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Schematic representation
Schematic representation of the formation
and hydration of Portland cement
Component elements O2 Si Ca Al Fe
Component oxides CaO Si O2 Al2O3

Fe2O3
Cement compounds C3S C2 S C3A C4AF
Portland cements Various types
Hydration products C-S-H gel Ca(OH)2
B. Bhattacharjee
DEPARTMENT OF CIVIL ENGINEERING, IIT
DELHI
Heat of Hydration
Heat of hydration of pure

compounds
Compound Heat of hydration
J/g Cal/g
502 120
C3S
C2S 260 62
C3A 867 207
C4AF 419 100
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DELHI
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STRUCTURE OF CEMENT
COMPOUNDS
Silica has tetrahedral structure (SiO44-) with Si
Covalently bonded with 4 Oxygen is basic
repeating unit in structure of silica and silicates.
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SILICA
In Silica 3-D network of tetrahedra is formed
with each Oxygen bonded to 2 Si.
In crystalline Quartz the tetrahedra are
arranged in a three dimensional periodic pattern.
¾ In non-crystalline silica the tetrahedra are
randomly bonded.
In a three dimensional network of Silica other
oxides can be dissolved to yield a number of both
crystalline and non-crystalline silicates.
Cement is an example of above.
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STRUCTURE OF COMPOUNDS OF
CEMENT
The structure of C3S is built from Ca2+, SiO44-
(tetrahedron) and O2- ions ,last being bonded to
six Ca2+ ions.
The SiO44- tetrahedra are connected by
Ca2+ ions.)
¾ Alite is a solid solution and contains minor
amount of oxides besides CaO and SiO2.
It is polymorphic and differs structurally by
minor deformation from basic hexagonal
structure
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ALITE STRUCTURE
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SIMPLIFIED BELITE STRUCTURE

¾ Structure of C2S i.e., Belite involves Ca2+ ,
SiO44- and exhibit polymorphisms, like Alite.
Belite is also solid solution containing minor
quantities of other oxides
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STRUCTURE OF ALUMINATE
C3A does not exhibit polymorphism.
It is cubic and the structure is built from
Ca2+ ions and ring of six AlO4 tetrahedra of
formula Al6O18-18 .
Oxygen
Aluminum
Al6O18-18
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STRUCTURE OF ALUMINATE
The unit cell composed of 64 sub-cells, out of
which 8 are occupied by Al6O18 rings, Ca2+ ions
occur at the body centres of some of the
remaining sub-cells and corners of others.
It is polymorphic and differs structurally by

minor deformation from basic hexagonal
structure
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STRUCTURE OF FERRITE
The structure of Ferrite has Ca2+ , (Al,Fe)O4
tetrahedra and (Fe,Al)O6 octahedra.
Calcium
(Al,Fe)O4
(Fe,Al)O6
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STRUCTURE OF CEMENT
MINERALS
Common feature in all cement minerals is
Large anions bonded with Small sized
Ca cations .
It is difficult to identify individual minerals

In the cement through conventional techniques
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HYDRATION & WATER OF

CRYSTALLIZATION
Hydration is the process of formation of
Hydrates.
Hydrates are salts or compounds associated
with water of crystallization.
¾ Some anions are too large compared to the
size available cations such that the packing
efficiency of the compound will not come
within the range required for stability (0.64-0.74).
Compounds in Cement belongs to above
category.
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CRYSTALLIZATION
To achieve the required efficiency, these
unstable compounds incorporate water of
crystallization within their structure in order to
fill the space left around the cation.
The cation is then artificially enlarged so that
stability is achieved crystallization.
¾ Hydrated Water is chemically bound in the

structure and therefore not available for process
such as fungal growth.
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CRYSTALLIZATION
Relatively high temperatures are required to
remove chemically bound (hydrated)water of
crystallization from the structure.
This water is not physically detectable by a
moisture meter.
¾ Ions are usually formed from covalently
or ionically bonded structure.
Compounds of cement have large anions
With small cations, thus high affinity for
hydration.
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Main chemical Reactions

H2O is H ; Ca(OH) is CH
C3S(ALITE) REACTION:
2C3S + 6H C3S2H3 + 3CH

[ 100 ] [ 24 ] [ 75 ] [ 49 ]
C2S (BELITE) Reaction:
2C2S + 4H C3S2H3 + CH
[ 100 ] [ 24 ] [ 99 ] [ 22 ]
C-S-H is gel like & responsible for bonding
B. Bhattacharjee
DELHI
Main chemical Reactions

SO3 is ̅S; Ca(OH) is CH
C3A + 6H C3AH6
[ 100 ] [ 40 ] [ 140 ]
Ettringite C3A + 3C ̅SH2 +26H C6A ̅S3H32

Monosulphoaluminate
2C3A +4H + C6A ̅S3H32 3 C4A ̅SH12
Gypsum controls setting properties (Flash set)
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DELHI
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C3A & SETTING

C3AH6 Cubic crystalline & the reaction is rapid
leads to FLASH set of cement as a whole
GYPSUM delays the reaction by forming

ettringite layer on surface, setting takes place
by formation C-S-H
Too much GYPSUM results in false set like

setting of plaster of Paris and can be taken care
by remixing
B. Bhattacharjee
DELHI
STRUCTURE OF C-S-H
Exact chemical structure of C-S-H is
complicated & exhibit variable composition,
Hence , C-S-H.
The nano structure of CSH gel show no long
range order hence largely amorphous .
¾ Several different morphological types of

CSH have been identified based on evaluation
technique.
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DELHI
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HYDRATION REACTION
Reaction of cement with water results in
precipitation of colloidal gelatinous mass that
forms a network
Cement comes in contact with water,
hydration reaction takes place at the surface
and reaction product is formed there .
¾ The product is gelatinous, forms a coating
on the surface and acts as semi-permeable
Membrane.
Concentration of solute is high on the grain
side of the gel compared to solution out side
resulting in osmotic pressure.
B. Bhattacharjee
DELHI
HYDRATION REACTION
After induction time the osmotic pressure
ruptures the membrane and water comes in
contact with the un-hydrated portion of the
grain causing hydration product to progress
both inwards and outwards in to the voids
between grains
When product between each grain merge

setting (solidification) occurs due to lack of
water and as the system becomes closely
packed the hardening occurs.
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DELHI
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13-05-2014
HYDRATION
By addition of water to cement a plastic paste
is prepared.
Due to chemical reaction water is consumed
and paste tends to solidify, the process is
setting.
¾ Solid then hardens and gains strength.
First phase coincides with a chemically
dormant stage.
Complete solidification i.e., formation of
definite shape and volume referrs to final set
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DELHI
Hydration: Physical changes
Peak Temperature
6-7 hours
Final set 10 hours
maximum
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DELHI
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Hydration: Physical changes
Inner Product
(C-S-H etc)
Outer Product
(C-S-H etc)
Un-hydrated
Cement
Ca (OH)2
Capillary
Pores
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DELHI
Hydration: Structural Changes
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DELHI
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13-05-2014
HARDENED PASTE STRUCTURE

10µm
UH
Phase
Pores
H
phase
A typical BSE Image Binary Image of Pore Phase
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HARDENED PASTE STRUCTURE
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BONDING ACTION
C-S-H is gel and has large specific surface of
the order of 2-3×106 cm2/gm (sp. surface of
cement= 2250-4000cm2/gm).
The surface forces which are intermolecular
in nature amounting to nearly 7.03×105 kg/m2
(7.0MPa) are responsible for the cementing
action of gel to gel.
¾ Intermolecular forces are forces that act
between stable molecules or between functional
groups of macromolecules.
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SUMMARY
Structure of compounds .
Structure of compounds and Hydration.
Hydration Product and Process
Bonding Action
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13-05-2014
THANK YOU
FOR
HEARING

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13-05-2014

CIVIL ENGINEERING DEPARTMENT

DEPARTMENT OF CIVIL ENGINEERING, IIT DELHI

 Structure of cement compound.

Component oxides CaO Si O2 Al2O3

Cement compounds C3S C2 S C3A C4AF

Portland cements Various types

Hydration products C-S-H gel Ca(OH)2

Heat of hydration of pure

SIMPLIFIED BELITE STRUCTURE

It is polymorphic and differs structurally by

It is difficult to identify individual minerals

HYDRATION & WATER OF

HYDRATION & WATER OF

¾ Hydrated Water is chemically bound in the

HYDRATION & WATER OF

Main chemical Reactions

2C3S + 6H C3S2H3 + 3CH

C-S-H is gel like & responsible for bonding

Main chemical Reactions

Ettringite C3A + 3C ̅SH2 +26H C6A ̅S3H32

Gypsum controls setting properties (Flash set)

C3A & SETTING

GYPSUM delays the reaction by forming

Too much GYPSUM results in false set like

¾ Several different morphological types of

 When product between each grain merge

Hydration: Physical changes

Hydration: Physical changes

Hydration: Structural Changes

HARDENED PASTE STRUCTURE

A typical BSE Image Binary Image of Pore Phase

HARDENED PASTE STRUCTURE

DEPARTMENT OF CIVIL ENGINEERING, IIT DELHI

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Structure of cement compound.

It is polymorphic and differs structurally by

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