Manufacture of Cement Chemical Composition Heat of Hydration Structure of Hydrated Cement Water Requirement Types of Cement

SCOPE
Manufacture Of Cement
Chemical Composition
Heat Of Hydration
Structure Of Hydrated Cement
Water Requirement
Types Of Cement
MANUFACTURE OF CEMENT
Limestone or chalk Clay or shale
Grinding
Blending
Heating to 1300C~ 1500C

To form clinker
Addition of 3~4% of Gypsum
Final grinding and packing

CHEMICAL COMPOSITION
•Composition of raw materials:

Oxide Content in %
CaO 60-67
SiO2 17-25
Al2O3 3-8
Fe2O3 0.1-4
MgO <6
SO3 <2.75
•There is a definite relationship between the constituents as per IS

CaO-0.7SO3/2.8SiO2+1.2Al2O3+0.65Fe2O3 = 1.02 to 0.66
Al2O3/Fe2O3 = Not < 0.66
•The raw materials combine at clinker temp to form complex compds.The four major
compds are-
Compd Formula Abbreviated formula %Content
Tricalcium Silicate 3 CaO.SiO2 C3S 45
Dicalcium Silicate 2 Cao.SiO2 C2S 25
Tricalcium aluminate 3CaO.Al2O3 C3A 6~12
Tetracalcium aluminoferrite 4CaO.Al2O3.Fe2O3 C4AF 6~8
HYDRATION OF CEMENT
•Anhydrous cement compds when mixed with water react to form hydrated
compds of very low solubility.The reactions are exothermic and heat liberated
is called heat of hydration.
•Different compds hydrate at different rates and liberate different qty of heat
Compd HOH (J/g)
C3S 502 50% total HOH evolves in 1-3 days;75% in
C2S 260 7 days and upto 91% in 6 months
C3A 867
C4AF 419
6
CAL/GM/HR 5
3 Heat liberated
0
0 4 8 12 16 20 24
TIME HRS
1.00
0.80
FRACTION
HYDRATED C2S
0.60
C3S
0.40 C3A
C4AF
0.20
0.00
10 TIME(LOG)-DAYS
800
COMPRESSIVE
700
STRENGTH
600
Kg/Cm2
500 C4AF
C3A
400
C2S
300
C3S
200
100
0
1 10 100 1000
AGE-DAYS
•Gypsum ( CaSO4.2H2O ) is added to clinker to prevent rapid hydration
of C3A which can lead to flash set of cement (which is setting of cement much
before permissible initial setting time). A protective layer of calcium
sulphoaluminate is formed on the surface of the C3A crystal and controls its
further reactions. However excessive amounts of dehydrated gypsum leads
to crystalisation of gypsum in solution called false set.
•Cement grains hydrate to a depth of approx 4 micron after 28 days.Generally
only particles less than 50 micron are fully hydrated However the hydrated
product adheres firmly to the unhydrated core and the unhydrated cement left in
the core does not reduce the strength of concrete as long as the products are fully
compacted.
Calcium Silicate Hydrates
•Reaction of C2S & C3S with water result in formation of calcium silicate hydrate
And calcium hydroxide.The approx equaton is-
2(3CaO.SiO2)+6H2O > 3Cao.2Sio2.3H2o+3Ca(OH)2
2(2CaO.SiO2)+4H2O > 3CaO.1 SiO2.3H2O + Ca(OH)2
•Ca(OH)2 is not a desirable product as it is soluble and gets leached out making
concrete porous.Hydrates with C2S are better than C3S
•Calcium Aluminium Hydrates
•The hydrate is comparatively unstable &C3AH6 is the only stable compd
upto 225C.
•The reaction of C3A with water is very fast and controlled by addition of gypsum
•The hydrate does not contribute much to the strength of the paste except to the
early strength .
•Harmful where concrete is likely to be attacked by sulphates.
•Hydrated calcium ferrite is more stable and comparatively more resistant to
attack by sulphates .It does not contribute much to the strength of the paste.
(why add alumina & ferric oxide? What happens if excess of CaO?)
Al2O3 & Fe2O3 influences the formation of C3S.Helps to fuse and form
clinker and adds to initial strength.
Excess CaO at the cost of Al2O3 & Fe2O3 makes it difficult to combine
with other compds and free lime will exist in the clinker causing unsoundness
of cement .
STRUCTURE OF HYDRATED CEMENT
•The product of hydration is called tobermorite gel as it resembles a natural

mineral called tobermorite.The gel has a specific area of 2 million sq cm per gm
•Initially the gel is formed to a depth of approx 4 micron of the cement crystal
in 28 days. Rate of hydration progressively decreases as availability of water to
the internal of the cement crystal (15~20 micron) reduces.
Composition of cement paste at different stages of
hydration
Fresh Paste
6
VOL OF PASTE
4
CW
3
URC
2
0
0.3 0.35 0.7
CW-Capillary water
W/C RATIO
URC-Unreacted cement
Composition AT 67% hydration
5
VOL OF PASTE
4
CW
3 HP
URC
2
0
0.3 0.35 0.6
CW- Capillary water

W/C
HP-Hydrated paste
URC-Unreacted cement
100% Hydration
5
Vol of paste
4
CW
3 HP
URC
2
0
0.3 0.35 0.7
CW- Capillary water

W/C
HP- Hydrated paste
URC- Unreacted cement
WATER REQUIREMENT FOR HYDRATION
•Hydration of C3S & C2S requires about 23% of water by wt of cement. This
water chemically combines with cement and is therefore called bound water
•Some water is imbibed in the gel pores which is estimated at about 15% by
wt of cement.
•Bound and gel water are complimentary to each other. Without gel water
no further hydration can take place
•Total water reqd is 38% by wt of cement. Excess of water causes capillaries
•With progress of hydration the vol of gel due to complete hydration could fill
up space earlier occupied by water upto w/c ratio of 0.6 or so. The gel
occupies about twice the vol of unhydrated cement.
FACTORS AFFECTING RATE OF HYDRATION

•Composition of cement
•Amount of gypsum
•Fineness of cement
•w/c ratio
•Curing conditions and temperature
•Admixtures
TYPES OF CEMENT
•33 Grade ordinary portland cement

43 Grade
53 Grade
Gde represents 28 day str in MPa. Sp area not>225m2/kg.
Low chem resistance. Medium rate of evolution of HOH.
•Portland Pozollana Cement. Fly ash or clay pozollanas do not have
cementitious prop by themselves but react with Ca(OH)2 and water
to form compds with cementitious prop.10~25% pozollana.Sp area
300m2/kgLow rate of setting but final str same as opc High chem
resistance. Low rate
HOH
•Hydrophobic cement -Clinker ground with water repellant film forming
substance like oleic acid or stearic acid. Water repellant film is formed around
each grain of cement and is broken when mixing with aggregates. Used in
remote and heavy rainfall areas like Assam , Arunachal etc where long
period of storage reqd .
•Portland Slag cement -Clinker , gypsum & last furnace slag ( Approx 25%)are
Crushed. Low HOH evolution . Resistant to sulphates , Initial str due to clinker
and later due to slag
•Low Heat Portland Cement -Decrease C3S & C3A and increase C2S . Used
in mass concreting where internal temp can be high leading to shrinkage and
Cracks . IST/FST 60/600.
•Sulphate Resistant Cement -Lower C3A ( not> 5%) and C4AF.Used in marine ,
sewage treatment wks and where soil has high qty of sulphate
•Oil Well Cement - Used to seal annular space between steel casing and rock and to
plug fissures in rock at great depths where temp can be 175C & press 1300kg/cm2
The cement slurry should flow so retarders such as starches . Cellulose etc are added

Manufacture of Cement Chemical Composition Heat of Hydration Structure of Hydrated Cement Water Requirement Types of Cement

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Manufacture of Cement Chemical Composition Heat of Hydration Structure of Hydrated Cement Water Requirement Types of Cement

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SCOPE

Limestone or chalk Clay or shale

Heating to 1300C~ 1500C

Addition of 3~4% of Gypsum

Final grinding and packing

•Composition of raw materials:

•There is a definite relationship between the constituents as per IS

•The product of hydration is called tobermorite gel as it resembles a natural

CW- Capillary water

CW- Capillary water

FACTORS AFFECTING RATE OF HYDRATION

•33 Grade ordinary portland cement

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