Cement

Cement
The term cement is commonly used to refer

to powdered materials which develop
strong adhesive qualities when combined
with water
These materials are more properly known as
hydraulic cements
Gypsum plaster, common lime, hydraulic
limes, natural pozzolana, and Portland
cements are the more common hydraulic
cements, with Portland cement being the
most important in construction.
Dr.V.S.Gayathri & Dr.K.Yamuna
Definition
Cement is an inorganic
binding material
possessing adhesive and
cohesive properties and
capable of bonding
materials like stones ,
bricks , building blocks
etc.,
Port land cement is a

hydraulic cement produced
by pulverizing clinker
consisting essentially of
hydraulic calcium silicates,
usually containing one or
more of the forms of calcium
sulfate (gypsum)
Cement was first invented by the Egyptians.

Cement was later reinvented by the Greeks and
the Babylonians who made their mortar out of
lime
Later, the Romans produced cement from
pozzolana, an ash found in all of the volcanic
areas of Italy, by mixing the ash with lime
Portland cement
Portland cement is composed of four major
oxides
CaO
SiO2
Al2O3
Fe2O3 &
some minor oxides.
(Minor refers to the quantity not importance)
CaO (C), SiO2 (S), Al2O3

(A) & Fe2O3 (F) interact
in the kiln & form the
major compounds that
constitute cement
The proportions of these
oxides determine the
proportions of the
compounds which
affect the performance
of the cement
Abbrevia
tions
compounds
Chemical Formula
Tri Calcium
Silicate
3CaO.SiO2
C3S
Di Calcium
Silicate
2CaO.SiO2
C2S
Tri Calcium
Aluminate
3CaO.Al2O3
C3A
Tetra Calcium
Alumino
4CaO.Al2O3.Fe2O3
Ferrite
C4AF
Types of Portland cement

Average Compound
Composition
ASTM Type & Name

of P.C.
Type I - O.P.C.
Type II - Modified
C3S
C2S
C3A
C4AF
49
25
12
General Purpose
12
For Moderate Heat of

Hydration
46
29
Type III - High Early

Strength
56
15
12
C3S&C3A increased, C2S

decreased
Type IV - Low Heat

P.C.
30
46
13
C2S increased
12
Limit on C3A5%,
2C3A+C4AF25%
Type V - Sulfate
Resistant P.C.
43
36
Chemical Composition of PC
Cement Compound
Weight %
Chemical Formula (symbol)
Tricalcium silicate
45%
3CaO.SiO2 or Ca3SiO5 (C3S)
Dicalcium silicate
25 %
2CaO.SiO2 or Ca2SiO4 (C2S)
Tricalcium aluminate
10 %
3CaO .Al2O3 or Ca3Al2O6 (C3A)
9%
4CaO.Al2O3.Fe2O3 or Ca4Al2Fe2O10
(C4AF)
Gypsum
5%
CaSO4.2H2O
Calcium Oxide
2%
CaO
Magnesium Oxide
4%
MgO
Tetracalcium
aluminoferrite
Production / Manufacture
of
Port land Cement (PC)
RAW MATERIALS
1) Calcareous Rocks (CaCO3 > 75%)
Limestone
Marl
Chalk
Marine shell deposits
2) Argillocalcareous Rocks (40%<CaCO3<75%)
Cement rock
Clayey limestone
Clayey marl
Clayey chalk
Argillaceous Rocks (CaCO3 < 40%)
Clays
Shales
Slates
Steps
Raw materials are crushed, scree
screen
ned &
stored
Raw materials are mixed in definite
proportions to obtain raw mix
They are mixed either dry (dry mixing) or
made as slurry with water (wet mixing).
Dry Mixture or Slurry mix is fed into the
rotary kiln
As the materials pass through the kiln their

temperature is rised upto 1300-1600 C. The process
of heating is named as burning
The output is known as clinker which is 0.15-5 cm

in diameter
Clinker is cooled & stored
Clinker is ground with gypsum (3-6%) to adjust

setting time
Packed & marketted
Burning in Rotary Kiln

The raw mix enters at the
upper end of the kiln and
slowly works its way
downward to the hottest
area at the bottom over a
period of 60-90 minutes,
undergoing several
different reactions as the
temperature increases.
Dehydration zone (up to ~
450C): This is simply the
evaporation and removal
of the free water. Even in
the dry process there is
some adsorbed moisture in
the raw mix.
Calcination zone (450C 900C): The term

calcination refers to the process of decomposing a solid
material so that one of its constituents is driven off as a
gas. At about 600C the bound water is driven out of the
clays, and by 900C the calcium carbonate is
decomposed, releasing carbon dioxide. By the end of the
calcination zone, the mix consists of oxides of the four
main elements which are ready to undergo further
reaction into cement minerals
Solid-state reaction zone (900 - 1300C): CaO and
reactive silica combine to form small crystals of C2S
(dicalcium silicate), one of the four main cement
minerals. In addition, intermediate calcium aluminates
and calcium ferrite compounds form.
Clinkering zone (1300C 1550C): This is the hottest

zone where the formation of the most important cement
mineral, C3S (alite), occurs. C3S forms by reaction between
C2S crystals and CaO.
The clinkering process is complete when all of silica is in the
C3S and C2S crystals and the amount of free lime (CaO) is
reduced to <1%.
Cooling zone: As the clinker moves past the bottom of the
kiln the temperature drops rapidly and the liquid phase
solidifies, forming the other two cement minerals C3A
(aluminate) and C4AF (ferrite) . The nodules formed in the
clinkering zone are now hard, and the resulting product is
called cement clinker.
Chemical Changes occurring in Kiln
65-125C Free water evaporates
400-650C Clays decompose

Si2Al2O5(OH)2 (kaolinite) 2 SiO2 + Al2O3 + 2 H2O (g)
KAlSi3O8 (orthoclase) + SO2 + O2 3SiO2 + Al2O3 + K2SO4
500-650C Dolomite decomposes

CaMg(CO3)2 CaCO3 + MgO + CO2
650-900C Calcium carbonate reacts with silica to

form "incipient belite"
2 CaCO3 + SiO2 Ca2SiO4 + 2 CO2

2 MgO + SiO2 Mg2SiO4
Ca5(PO4)3OH + SiO2 1Ca3(PO4)2 + Ca2SiO4 + H2O(g)
700-900C Calcium carbonate reacts endothermically with

alumina and iron oxide to form incipient aluminate and
ferrite.
12 CaCO3 + 7 Al2O3 Ca12Al14O33 + 12 CO2
4 CaCO3 + Al2O3 + Fe2O3 Ca4Al2Fe2O10 + 4 CO2
4 CaCO3 + Al2O3 + Mn2O3 Ca4Al2Mn2O10 + 4 CO2
900-1050C When all available silica, alumina and iron

oxide have reacted, the remaining calcium carbonate
decomposes endothermically to calcium oxide.
CaCO3 CaO + CO2
1300-1425C Aluminate, ferrite and part of the

belite melt endothermically, and belite reacts with
calcium oxide to form alite.
Ca2SiO4 + CaO Ca3SiO5
Ca12Al14O33 4 Ca3Al2O6 +3 Al2O3
Reactions in nut shell
(12 to 4)
1. Belite is formed by the reaction between lime

and silica (700-900oC)
2CaO + SiO2 Ca2SiO4 (2C+S C2S)
2.Belite (Ca2SiO4) reacts with calcium oxide to

form Alite (Ca3OSiO4) (1300-1450oC)
Ca2SiO4 + CaO Ca3SiO5 (C2S + C C3S )
[Belite] + CaO [Alite]
3. Calcium oxide reacts with alumina to form

Calcium aluminate (1300-1450oC)
3CaO + Al2O3 Ca3Al2O6 (3C+A C3A)
4. Calcium oxide reacts with alumina and iron

oxide to form Calcium alumino ferrite
(700-900oC)
4CaO + Al2O3 + Fe2O3 Ca4 Al2 Fe 2O10 (4C+A + F C4AF)
Portland cement is made by mixing clinker with 2-6 % gypsum
Clinker
Gypsum
If too much gypsum is added it leads to distruptive

expansions of the hardened paste or concrete
Properties of cement
Cement forms paste like mass with water resulting in hydration
of compounds of cement. This mass then becomes stiff and
hard. The process of solidification comprises three stages
Hydration: Interaction between cement and water
Setting: formation of tobermorite gel
Hardening: formation of hard crystalline mass
Hydration & heat of hydration

As water comes into contact with cement
particles, hydration reactions starts immediately
at the surface of the particles
It is an exothermic process
The process of hydration is complex and results
in reorganization of the constituents of original
compounds to form new hydrated compounds
As the hydration proceeds the

deposits of hydrated
products on the original
cement grains makes the
diffusion of water to
unhydrated nucleus more
& more difficult
Hence the rate of hydration
decreases with time & as a
result hydration may take
several years.
The heat of hydration of

PC is on the order of 85100 cal/g
About 50% of this heat is
liberatedwithin 1-3 days
& 75% within 7 days
By limiting the
percentage of C3S &C3A
heat of hydration can be
reduced as too much heat
may lead to expansion
and crack in concrete
Chemistry of setting and Hardening

Setting is stiffening of the plastic mass
Hardening is crystalisation
In practice, the terms initial set & final set are used
Initial set ( with 24 hours) indicates the beginning of a noticeable

stiffening . It is mainly due to the hydration of C3A , C4AF.
Final set ( 7 28 days) is mainly due to the formation of

Tobermorite gel and crystallization of Calcium hydroxide (CH) .
CH does not contribute very much to the strength of portland
cement.
on hydration both calcium-aluminate and calcium alumino ferrite C3A

and C4AF forms the same product - Calcium-Alumino hydrate
C3A + 6H C3A .6H
C4AF + 7H C3A .6H + CFH
on hydration both calcium-silicates , C2S and C3S forms the same
product - Calcium-Silicate-Hydrate (C-S-H gel)
It is similar to a mineral Tobermorte. Hence it is named as
TOBERMORITE GEL
2C3S+6H C3S2H3 + 3CH (7 days)
2C2S+4H C3S2H3 + CH (28 days)
Chemical reactions during setting

3CaO.Al2O3
6H2O
3CaO.Al2O3.6H2O
4CaO.Al2O3.Fe2O3+7H2O 3CaO.Al2O3.6H2O+CaO.Fe2O3.H2O
Tobermorte Gel formation
2[Ca2SiO4] + 4H2O
3[Ca3SiO4] + 6H2O
3CaO.2SiO2.3H2O + Ca(OH)2
3CaO.2SiO2.3H2O + 3Ca(OH)2
70-80% of Portland cement is C2S & C3S

Therefore the strength of cement is mainly depend on hydrates of
these compounds ie Tobermorite gel
C3A and is characteristically fast reacting with water & may lead to
a rapid stiffening of the paste (with few hours) with a large amount
of the heat generation (Flash-Set)-(Quick-Set)
In order to prevent this rapid reaction ,gypsum is added to the

clinker
Gypsum, C3A & water react to form relatively insoluble CalciumSulfo-Aluminates

Calcium-Sulfo Aluminates are prone (less resistant) to sulfate attack
& does not contribute much for strength
C4AF: The hydration of ferrite phase is not well understand. Ferrite

phase has lesser role in development of strength
C3S hydrates at a moderate rate with greater heat generation.It is
also responsible for early strength ( compared to C2S)
C2S hydrates & hardens slowly and heat of hydration is also less &
and contributes to ultimate strength
Higher C3Shigher early strength-higher heat generation (roads,

cold environments)
Higher C2Slower early strength-lower heat generation (dams)
P.C.+waterthe compounds in the cement undergo chemical

reactions with the water independently, and different products
(hydrates) are formed
C3S
C2S
C3A
C4AF
Rate of Reaction
Moderate
Slow
Fast
Moderate
Heat Liberation
( heat of hydration)
High
Low
Very High
Moderate
Good
Poor
Good
Poor
Good
Good
Poor
Poor
Early Cementitious Value

Ultimate Cementitious Value
During hardening the solid cement material begins to gain strength

It depends on the chemical combination of cement and water
Hardening starts with great speed and the rate decreases with time
Hardening stops if the cement becomes dry
Abnormal setting reactions : Flash setting and False setting
Flash setting
Immediate stiffening of cement paste in a few minutes after mixing
with water. It is accompanied by large amount of heat generation
upon reaction of C3A with water
Gypsum is placed in cement to prevent flash-set
However too much gypsum will cause undesirable expansion after
hardening and lead to cracks
False setting
It is a rapid development of rigidity of cement paste without generation of

much heat
This rigidity can be overcome & plasticity can be regained by further mixing
without addition of water
Thus cement paste restores its plasticity & sets in a normal manner without
any loss of strength
Probable Causes of False-Set: When gypsum is ground with hot

clinker, gypsum may be dehydrated into hemihydrate
(CaSO4.1/2H2O) or anhydrate (CaSO4).
The hemi hydrate and anhydrate calcium sulphate on reacting with
water forms gypsum , which results in stiffening of the paste
Factors Affecting Setting Time

Temperature & Humidity
Amount of Water
Chemical Composition of Cement
Fineness of Cement (finer cement, faster setting)
Special cements
White Cement
Water resistant Cement / Water
Proof cement
White Cement
It is colorless due to the absence of iron and manganese
compounds (Fe2O3 + MnO 0.8%)
It is expensive and is used in marble work
If required , coloring agent can be added and the cement can be
made as colored cement
Uses
It acts as seal for pores and prevents the seepage of water
It is used to make water resistant concrete
It is also used to join ceramic tiles and mosaic tiles
Stone masonry
Fixing tiles on walls and floors
Construction of domes
White washing of walls ( replacement of lime)
Plastering monumental walls
Manufacture of cement paint
Manufacture of toys and house hold articles
Construction of garden furniture like benches and tables
Water resistant cement
It is hydrophobic in nature
They are impermeable to water and other fluids
Fatty acids are used to block pores within the concrete, preventing water
passage
It is prepared by mixing ordinary or rapid hardening cement and some

percentage of metal stearate ( Ca, Al etc)
It is resistant to water and oil penetration.
It is also resistant to acids, alkaline and salt discharged by industrial water
It is used for water retaining structure like tanks, reservoir, retaining walls,
pool, dam etc

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Cement

The term cement is commonly used to refer

Dr.V.S.Gayathri & Dr.K.Yamuna

Dr.V.S.Gayathri & Dr.K.Yamuna

Port land cement is a

Cement was first invented by the Egyptians.

Dr.V.S.Gayathri & Dr.K.Yamuna

Dr.V.S.Gayathri & Dr.K.Yamuna

CaO (C), SiO2 (S), Al2O3

Dr.V.S.Gayathri & Dr.K.Yamuna

Types of Portland cement

ASTM Type & Name

For Moderate Heat of

Type III - High Early

C3S&C3A increased, C2S

Type IV - Low Heat

Dr.V.S.Gayathri & Dr.K.Yamuna

Chemical Formula (symbol)

3CaO.SiO2 or Ca3SiO5 (C3S)

2CaO.SiO2 or Ca2SiO4 (C2S)

3CaO .Al2O3 or Ca3Al2O6 (C3A)

Dr.V.S.Gayathri & Dr.K.Yamuna

Dr.V.S.Gayathri & Dr.K.Yamuna

Dr.V.S.Gayathri & Dr.K.Yamuna

2) Argillocalcareous Rocks (40%<CaCO3<75%)

Dr.V.S.Gayathri & Dr.K.Yamuna

Argillaceous Rocks (CaCO3 < 40%)

Dr.V.S.Gayathri & Dr.K.Yamuna

Dr.V.S.Gayathri & Dr.K.Yamuna

As the materials pass through the kiln their

The output is known as clinker which is 0.15-5 cm

Clinker is cooled & stored

Clinker is ground with gypsum (3-6%) to adjust

Packed & marketted

Dr.V.S.Gayathri & Dr.K.Yamuna

Dr.V.S.Gayathri & Dr.K.Yamuna

Burning in Rotary Kiln

Dr.V.S.Gayathri & Dr.K.Yamuna

Calcination zone (450C 900C): The term

Dr.V.S.Gayathri & Dr.K.Yamuna

Clinkering zone (1300C 1550C): This is the hottest

Dr.V.S.Gayathri & Dr.K.Yamuna

Chemical Changes occurring in Kiln

65-125C Free water evaporates

400-650C Clays decompose

500-650C Dolomite decomposes

650-900C Calcium carbonate reacts with silica to

2 CaCO3 + SiO2 Ca2SiO4 + 2 CO2

Dr.V.S.Gayathri & Dr.K.Yamuna

700-900C Calcium carbonate reacts endothermically with

900-1050C When all available silica, alumina and iron

1300-1425C Aluminate, ferrite and part of the

Dr.V.S.Gayathri & Dr.K.Yamuna

Reactions in nut shell

1. Belite is formed by the reaction between lime

2.Belite (Ca2SiO4) reacts with calcium oxide to

Dr.V.S.Gayathri & Dr.K.Yamuna

3. Calcium oxide reacts with alumina to form

4. Calcium oxide reacts with alumina and iron