Engineering Chemistry

Engineering Materials – Cement

Dr. Jeetendra Bhawsar

Department of Chemistry – Medi-Caps University

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Dr. Jeetendra Bhawsar
Contents

• Introduction
• Classification of cements
• Portland Cement
• Raw materials of Portland cement
• Cement Manufacturing Process
• Flow chart of Portland Cement manufacturing process
• Cement Manufacturing
• Mixing and Crushing
• Dry Process
• Wet Process
• Burning Process
• View of complete setup
• Rotary Klin zones
• Chemical Reactions
• Grinding and Packaging
• Setting and hardening

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Introduction

“A cement is a binder, a substance that sets and hardens and can bind other materials
together. It principal constituents for constructional purpose are compounds of
Ca(calcareous) and Al + Si (argillaceous)”

Chemical Composition of Cement The cements have property of setting

Lime 63% and hardening under water, by virtue
Silica 22% of certain chemical reaction with it
Alumina 06% and are called „hydraulic cements’
Iron oxide 03%
Gypsum 01 to 04%

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Classification of Cements

Cements

Natural Cement

It is the variety of
Puzzolana Cement
artificial cement. It is
called Portland cement
because on hardening
Slag Cement (setting) its color
resembles to rocks near
Portland in England.
Portland Cement

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Composition of Cement
“Portland cement is the most common type of cement in general usage in many
parts of the world. It is a basic ingredient of concrete, mortar and most non-
specialty grout. It is a fine powder produced by grinding.

Composition Source
Lime Stone, Calcite,
Calcarious Material (CaO)
Sea Shell
Siliceous Material (SiO2) Clay, Sand, Flyash
Argelleceious Material (Al2O3) Al Ore, Bauxite, Clay, Flyash

Ferriferous Material (Fe2O3) Fe Ore, Hematite

Gypsum 1-6%

Chemical Composition of Portland Cement

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Raw materials of Portland Cement and it‟s use

Calcareous materials, CaO [eg.

Limestone ]
• Principal Constituent and its proportion can
be regulated
• Excess of lime reduces the strength and
makes the cement expand & disintegrate
• Lesser amount of lime also reduces the
strength by quick setting
Argillaceous materials, Al2O3 and SiO2
[eg. Clay ]
• Imparts strength
• Makes quick setting
• Excess of alumina weakens the cement

Gypsum (CaSO4 2H2O)

• Retards and enhances quick setting

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Manufacturing Cement

1. Mixing and Crushing of raw

materials
a) Dry process

a) Wet process

2. Burning

3. Grinding

4. Storage and Packing

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Manufacturing of Portland cement
Agillaceous Callareous Powdered
materials materials A Rotary Klin
coal + air

NO Crushing & Hot Clinkers

Is Wet Grinding
process

YES Cooler
Silos

Washing
Grinding in Ball 2 -4 %
Mill Gypsum

Basin

Storage Silos

Grinding Water

Packing

Slurry

Correcting Basin A
Flow Chart of Portland cement manufacturing process
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Mixing and Crushing: a) Dry Process

• Raw materials are crushed , powdered

and mixed in right proportion ( Dry
Raw mix ) 1. Mixing
• Stored in silos 2. Burning
• Burning of dry raw mix is
carried out in rotary kiln
• Klin rotates at speed of 1
RPM and is slightly inclined
in position of 5 – 6 o C

Hot clinkers are cooled with atmospheric air

and pulverized together with 2-3% of gypsum
in ball mills

3. Grinding 4. Storage &

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Mixing and Crushing: b) Wet Process

• Limestone is crushed,
powdered and stored in silos

• Clay is washed with water to

remove organic matter and
stored in basin

• Both these materials are mixed

in grinding mill to form slurry

• Slurry contains 38-40% water

Figure showing manufacturing of cement using wet process stored in correcting basin

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Burning Process : View of complete setup
Fig. Rotary Cement Klin

Slurry Tank
Powdered
Coal 5 to 6o inclined
refractory-lined rotary
kin Slurry
Hot Air

Air
Blast
Air
Rollers

Hot clinker

Cold
Clinker
Gypsum

Ball Cement to strong and

mill packing bags

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Burning Process : Zones of Rotary Klin

Rotary Klin Slurry

• Upper part of the kiln

• About 400 0C
• Most of the water in the slurry
gets evaporated

• Center part of the kiln

5 to 6 o inclined • About 700oC – 1000oC
• Lime gets decomposed into CaO
and CO2

• Lower part of the kiln

• About 1250oC - 1500oC
• Reacts with clay to form various
bouge compounds

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Burning Process : Chemical Reactions in Rotary Klin Zones

• Drying Zone : (4000C)

Slurry Dry Powder

• Calcination Zone : (7000C – 10000C)

CaCO3 CaO + CO2

• Clinkering Zone : (10000C- 12000C)

2CaO + SiO2 2CaO.SiO2 ( Dicalcium silicate – C2S )

3CaO + SiO2 3CaO.SiO2 ( Tricalcium silicate – C3S )

3CaO + Al2O3 3CaO.Al2O3 ( Tricalcium aluminate – C3A )

4CaO + Al2O3 + Fe2O3 4CaO.Al2O3. Fe2O3

(Tricalcium aluminoferrite – C4AF)

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 Grinding and Packaging
Grinding (12000C- 14000C)
• Cooled clinkers are ground to fine powder in
ball mills
• At final stages of grounding about 2-3% of
powdered gypsum is added.
(This is to avoid setting of cement quickly when it comes in
contact with water)

• Gypsum acts as a retarding agent for early setting of the cement

3CaO + Al2O3 + x CaSO4 . 7H2O 3CaO . Al2O3 . xCaSO4 . 7H2O

After initial set Gypsum Tricalcium sulphoaluminate (Insoluble)

Packaging

• Ground cement is stored in silos

• From silos they are automatically packaged into bag which are about 50 Kg
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Properties of cement : Setting and hardening

 When the cement is mixed with water, hydration and hydrolysis reactions of
Bogue compounds of cement begin, resulting in formation of gel and crystalline
products.

 These products have the ability to surround inert materials liks sand , bricks ,
crushed stones, etc.

“ Setting is the stiffening of original plastic mass due to the formation of

tobermonite gel”. It can be divided into 2 stages a) Initial Set b)Final Set

 Initial Set is when paste being to stiffen

 Final Set is when the paste beginning to harden and able to sustain some
loads

“ Hardening is the development of strength due to formation of crystals”

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Sequence of changes during setting and hardening

Cement 1st day 7th day 28th day

Hydration of Gelation of Gelation of
+
C3A and C4F C 3S C2S and C3S
Water Paste

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Setting and Hardening : Chemical Reactions

Day 1 :
• When cement is mixed with water, hydration of tricalcium aluminate (C3A)
takes place within a day
• The paste becomes rigid, which is known as Initial set or Flash set

3CaO . Al2O3 + 6H2O 3CaO . Al 2O3 . 6H2O + 880 kJ/Kg

Tricalciumaluminate Hyderated tricalcium aluminate (Crystalline)
[OR]
C3A + 6H2O C3A . 6H2O + 880 kJ/Kg

• To avoid early setting of C3A , gypsum is added which acts as retarding

agent

C3A + 3CaSO4 . 2H2O C 3A . 3CaSO4 . 2H2O

Caclium sulpho aluminate

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Setting and Hardening : Chemical Reactions contd…

Day – 2 to 7 :
• After hydration of C3A, C3S beings to hydrate to give tobermonite gel and
crystalline Ca(OH)2, which is responsible for initial strength of the cement
• The hydration of C3S gets completed within 7 days

2[3CaO .SiO2] + 6H2O 3CaO.2SiO2 . 3H2O + 3Ca(OH)2 + 500 kJ/Kg

Tricalcium silicate Tobermonite gel Crystalline
[OR]
2C3S + 6H2O C 3S2 . 3H2O + 3Ca(OH)2 + 500 kJ/Kg

Tobermonite gel possesses a very high surface area and very high adhesive property

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Setting and Hardening : Chemical Reactions contd…

Day – 7 to 28 :
• Dicalcium silicate (C2S) reacts with water very slowly and gets completed in 7
to 28 days

2[2CaO . SiO2 ] + 4H2O 3CaO .2SiO2 . 3H2O + Ca(OH)2 + 250 kJ/Kg

Dicalcium silicate Tobermonite gel Crystalline
[OR]
2C2S + 4H2O C3S2 . 3H2O + Ca(OH)2 + 250 kJ/Kg

• Increase of strength is due to formation of tobermonite gel and crystalling

Ca(OH)2 of both C2S and C3S

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Setting and Hardening : Chemical Reactions contd…

• After initial hyderation of tetracalcium alumino ferrite (C4AF) , hardening takes place
through crystallization , along with C2S

4CaO . Al2O3 . Fe2O3 + 7H2O 3CaO . Al2O3 . 6H2O + CaO . Fe2O3 . H2O + 420 kJ/Kg
Tetracalcium alumino ferrite Crystalline Gel
[OR]
C4AF + 7H2O C3A . 6H2O

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IS Specification of Portland Cement

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