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INTRODUCTION TO CEMENT
Classification – Manufacture – Properties and Hydration of Cement
- PRAKASH KUMAR SEKAR
Contents
• Introduction
• Classification of cements
• Portland Cement
• Raw materials of Portland cement
• Cement Manufacturing Process
• Flow chart of Portland Cement manufacturing process
• Cement Manufacturing Video
• Mixing and Crushing
• Dry Process
• Wet Process
• Burning Process
• View of complete setup
• Rotary Klin zones
• Chemical Reactions
• Grinding and Packaging
• Setting and hardening
• Flow chart
• Sequence
• Chemical Reactions
• Special Cement
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)”
The cements have property of setting
and hardening under water, by virtue
of certain chemical reaction with it
and are called ‘hydraulic cements’
Chemical Composition of Cement
Lime 63%
Silica 22%
Alumina 06%
Iron oxide 03%
Gypsum 01 to 04%
Classification of Cements
Cements
Natural Cement
Puzzolana Cement
Slag Cement
Portland Cement
It is the variety of
artificial cement. It is
called Portland cement
because on hardening
(setting) its color
resembles to rocks near
Portland in England.
Portland Cement
“An extremely finely ground product by calcinising together , at above 1500o
C , an
intimate and properly proportioned mixture of argillaceous (clay) and calcareous
(lime) raw materials, without the addition of anything subsequent to calcination ,
excepting the retarder gypsum”
Clinker CCN Mass %
Tricalcium silicate (CaO)3 · SiO2 C3S 45–75%
Dicalcium silicate (CaO)2 · SiO2 C2S 7–32%
Tricalcium aluminate (CaO)3 ·
Al2O3
C3A 0–13%
Tetracalcium aluminoferrite
(CaO)4 · Al2O3 · Fe2O3
C4AF 0–18%
Gypsum CaSO4 · 2 H2O 2–10%
Calcium Oxide - CaO
2%
Magnesium Oxide - MgO 4%
Pile of Portland cement
Chemical Composition of Portland Cement
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
Powdered Coal or fuel oil
•For burning
Gypsum (CaSO4 2H2O)
•Retards and enhances quick setting
.
Manufacturing Cement
1. Mixing and Crushing of raw materials
a) Dry process
a) Wet process
2. Burning
3. Grinding
4. Storage and Packing
Manufacturing of Portland cement
Agillaceous
materials
Callareous
materials
Is Wet
process
Crushing &
Grinding
NO
Washing
Basin
Silos
Grinding
Slurry
Correcting Basin A
Rotary Klin
Hot Clinkers
Water
Powdered
coal + air
Cooler
Grinding in Ball
Mill
Storage Silos
Packing
2 -4 %
Gypsum
A
Flow Chart of Portland cement manufacturing process
YES
Mixing and Crushing: a) Dry Process
1. Mixing
2. Burning
3. Grinding 4. Storage &
Packing
• Raw materials are crushed , powdered
and mixed in right proportion ( Dry
Raw mix )
• Stored in silos
• 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
Mixing and Crushing: b) Wet Process
Figure showing manufacturing of cement using 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
stored in correcting basin
Burning Process : View of complete setup
Cold
Clinker
Hot Air
5 to 6o
inclined
refractory-lined rotary
kin
Air
Rollers
Powdered
Coal
Ball
mill
Gypsum
Cement to strong and
packing bags
Slurry
Slurry Tank
Hot clinker
Fig. Rotary Cement Klin
Air
Blast
Burning Process : Zones of Rotary Klin
Clinkering Zone
90 -120 m1250 – 1500o C
700 – 1000o C
400
o C
5 to 6 o
inclined
Slurry
Calcination Zone Drying ZoneRotary Klin
• Upper part of the kiln
• About 400 0
C
• Most of the water in the slurry
gets evaporated
• Center part of the kiln
• About 700o
C – 1000o
C
• Lime gets decomposed into CaO
and CO2
• Lower part of the kiln
• About 1250o
C - 1500o
C
• Reacts with clay to form various
bouge compounds
Burning Process : Chemical Reactions in Rotary Klin Zones
• Calcination Zone :
CaCO3 CaO + CO2
• Clinkering Zone :
2CaO + SiO2 Ca2SiO4 ( Dicalcium silicate – C2S )
3CaO + SiO2 Ca3SiO5 ( Tricalcium silicate – C3S )
3CaO + Al2O3 Ca3Al2O6 ( Tricalcium aluminate – C3A )
4CaO + Al2O3 + Fe2O3 Ca4Al2Fe2O10
(Tricalcium aluminoferrite – C4AF)
Grinding and Packaging
• 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)
Grinding
Packaging
• Ground cement is stored in silos
• From silos they are automatically packaged into bag which are about 50 Kg
• 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)
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”
Setting and hardening
Unhydrated Cement
Hydration
Metastable Gel
Crystalline hydration
products
Stable Gel Crystalline products
Figure showing setting and hardening of cement
Sequence of changes during setting and hardening
Cement
+
Water Paste
Hydration of
C3A and C4F
Gelation of
C3S
Gelation of
C2S and C3S
1st
day 7th
day 28th
day
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
•To avoid early setting of C3A , gypsum is added which acts as retarding agent
3CaO . Al2O3 + 6H2O 3CaO . Al2O3 . 6H2O + 880 kJ/Kg
C3A + 6H2O C3A . 6H2O + 880 kJ/Kg
[OR]
Tricalciumaluminate Hyderated tricalcium aluminate (Crystalline)
C3A + 3CaSO4 . 2H2O C3A . 3CaSO4 . 2H2O
Caclium sulpho aluminate
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
2C3S + 6H2O C3S2 . 3H2O + 3Ca(OH)2 + 500 kJ/Kg
[OR]
Tobermonite gel possesses a very high surface area and very high adhesive property
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
•Increase of strength is due to formation of tobermonite gel and crystalling
Ca(OH)2 of both C2S and C3S
2[2CaO . SiO2 ] + 4H2O 3CaO .2SiO2 . 3H2O + Ca(OH)2 + 250 kJ/Kg
2C2S + 4H2O C3S2 . 3H2O + Ca(OH)2 + 250 kJ/Kg
Dicalcium silicate Tobermonite gel Crystalline
[OR]
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
C4AF + 7H2O C3A . 6H2O
[OR]
Graphical representation of development of compressive strength
“Hydration and Hydrolysis of Bogue
compounds causes cement to develop
compressive strength”(Shown in the
figure )
Function of Gypsum (CaSO4·2H2O ) in cement
• Tricalcium aluminate (C3A) combines with water very rapidly with the evolution
of large amount of heat
• After the initial set, the paste becomes stiff.
• Adding gypsum retards the dissolution of C3A by forming insoluble calcium
sulpho-aluminate
• The above reaction shows how gypsum retards the early initial set of cement
C3A + 6H2O C3A . 6H2O + Heat
3CaO . Al2O3 . xCaSO4 . 7H2O
Heat of Hydration of Cement
• When cement is mixed with water, hydration , hydrolysis an gelation reaction
starts and some heat is liberated
• On an average of 500 kJ/Kg of heat is evolved during complete hydration of
cement
Bogue Compounds Heat of hydration (kJ/kg)
C3A 880
C3S 500
C4AF 420
C2S 250
Heat of hydration of Bogue compounds
Special Cement : White Portland Cement (or) White cement
• Is white in color due to absence of iron
compounds
• Obtained by calcining the raw materials of
Portland cement which are free from iron
oxide
Properties
• More expensive than ordinary Portland
cement
• Acts as pore – blocking and water – repelling
agent
 Repairing and joining marble pillars and blocks
 Manufacture of tiles and mosaic walls
Special Cement : Water proof Cement (or) Hydrophobic cement
• Is a cement obtained by adding water proofing
substances like calcium stearate, aluminium stearate
and gypsum with tannic acid to ordinary Portland
cement
Properties
• More expensive than ordinary Portland cement
• Acts as pore – blocking and water – repelling agent
 Used to make concrete which is impervious to water under pressure
 Used in construction, where absorption of water need to be avoided
 Used in construction of bridges and under water constructions

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Manufacture of cement - Classification and hydration

  • 1. INTRODUCTION TO CEMENT Classification – Manufacture – Properties and Hydration of Cement - PRAKASH KUMAR SEKAR
  • 2. Contents • Introduction • Classification of cements • Portland Cement • Raw materials of Portland cement • Cement Manufacturing Process • Flow chart of Portland Cement manufacturing process • Cement Manufacturing Video • Mixing and Crushing • Dry Process • Wet Process • Burning Process • View of complete setup • Rotary Klin zones • Chemical Reactions • Grinding and Packaging • Setting and hardening • Flow chart • Sequence • Chemical Reactions • Special Cement
  • 3. 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)” The cements have property of setting and hardening under water, by virtue of certain chemical reaction with it and are called ‘hydraulic cements’ Chemical Composition of Cement Lime 63% Silica 22% Alumina 06% Iron oxide 03% Gypsum 01 to 04%
  • 4. Classification of Cements Cements Natural Cement Puzzolana Cement Slag Cement Portland Cement It is the variety of artificial cement. It is called Portland cement because on hardening (setting) its color resembles to rocks near Portland in England.
  • 5. Portland Cement “An extremely finely ground product by calcinising together , at above 1500o C , an intimate and properly proportioned mixture of argillaceous (clay) and calcareous (lime) raw materials, without the addition of anything subsequent to calcination , excepting the retarder gypsum” Clinker CCN Mass % Tricalcium silicate (CaO)3 · SiO2 C3S 45–75% Dicalcium silicate (CaO)2 · SiO2 C2S 7–32% Tricalcium aluminate (CaO)3 · Al2O3 C3A 0–13% Tetracalcium aluminoferrite (CaO)4 · Al2O3 · Fe2O3 C4AF 0–18% Gypsum CaSO4 · 2 H2O 2–10% Calcium Oxide - CaO 2% Magnesium Oxide - MgO 4% Pile of Portland cement Chemical Composition of Portland Cement
  • 6. 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 Powdered Coal or fuel oil •For burning Gypsum (CaSO4 2H2O) •Retards and enhances quick setting .
  • 7. Manufacturing Cement 1. Mixing and Crushing of raw materials a) Dry process a) Wet process 2. Burning 3. Grinding 4. Storage and Packing
  • 8. Manufacturing of Portland cement Agillaceous materials Callareous materials Is Wet process Crushing & Grinding NO Washing Basin Silos Grinding Slurry Correcting Basin A Rotary Klin Hot Clinkers Water Powdered coal + air Cooler Grinding in Ball Mill Storage Silos Packing 2 -4 % Gypsum A Flow Chart of Portland cement manufacturing process YES
  • 9. Mixing and Crushing: a) Dry Process 1. Mixing 2. Burning 3. Grinding 4. Storage & Packing • Raw materials are crushed , powdered and mixed in right proportion ( Dry Raw mix ) • Stored in silos • 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
  • 10. Mixing and Crushing: b) Wet Process Figure showing manufacturing of cement using 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 stored in correcting basin
  • 11. Burning Process : View of complete setup Cold Clinker Hot Air 5 to 6o inclined refractory-lined rotary kin Air Rollers Powdered Coal Ball mill Gypsum Cement to strong and packing bags Slurry Slurry Tank Hot clinker Fig. Rotary Cement Klin Air Blast
  • 12. Burning Process : Zones of Rotary Klin Clinkering Zone 90 -120 m1250 – 1500o C 700 – 1000o C 400 o C 5 to 6 o inclined Slurry Calcination Zone Drying ZoneRotary Klin • Upper part of the kiln • About 400 0 C • Most of the water in the slurry gets evaporated • Center part of the kiln • About 700o C – 1000o C • Lime gets decomposed into CaO and CO2 • Lower part of the kiln • About 1250o C - 1500o C • Reacts with clay to form various bouge compounds
  • 13. Burning Process : Chemical Reactions in Rotary Klin Zones • Calcination Zone : CaCO3 CaO + CO2 • Clinkering Zone : 2CaO + SiO2 Ca2SiO4 ( Dicalcium silicate – C2S ) 3CaO + SiO2 Ca3SiO5 ( Tricalcium silicate – C3S ) 3CaO + Al2O3 Ca3Al2O6 ( Tricalcium aluminate – C3A ) 4CaO + Al2O3 + Fe2O3 Ca4Al2Fe2O10 (Tricalcium aluminoferrite – C4AF)
  • 14. Grinding and Packaging • 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) Grinding Packaging • Ground cement is stored in silos • From silos they are automatically packaged into bag which are about 50 Kg • 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)
  • 15. 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”
  • 16. Setting and hardening Unhydrated Cement Hydration Metastable Gel Crystalline hydration products Stable Gel Crystalline products Figure showing setting and hardening of cement
  • 17. Sequence of changes during setting and hardening Cement + Water Paste Hydration of C3A and C4F Gelation of C3S Gelation of C2S and C3S 1st day 7th day 28th day
  • 18. 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 •To avoid early setting of C3A , gypsum is added which acts as retarding agent 3CaO . Al2O3 + 6H2O 3CaO . Al2O3 . 6H2O + 880 kJ/Kg C3A + 6H2O C3A . 6H2O + 880 kJ/Kg [OR] Tricalciumaluminate Hyderated tricalcium aluminate (Crystalline) C3A + 3CaSO4 . 2H2O C3A . 3CaSO4 . 2H2O Caclium sulpho aluminate
  • 19. 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 2C3S + 6H2O C3S2 . 3H2O + 3Ca(OH)2 + 500 kJ/Kg [OR] Tobermonite gel possesses a very high surface area and very high adhesive property
  • 20. 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 •Increase of strength is due to formation of tobermonite gel and crystalling Ca(OH)2 of both C2S and C3S 2[2CaO . SiO2 ] + 4H2O 3CaO .2SiO2 . 3H2O + Ca(OH)2 + 250 kJ/Kg 2C2S + 4H2O C3S2 . 3H2O + Ca(OH)2 + 250 kJ/Kg Dicalcium silicate Tobermonite gel Crystalline [OR]
  • 21. 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 C4AF + 7H2O C3A . 6H2O [OR] Graphical representation of development of compressive strength “Hydration and Hydrolysis of Bogue compounds causes cement to develop compressive strength”(Shown in the figure )
  • 22. Function of Gypsum (CaSO4·2H2O ) in cement • Tricalcium aluminate (C3A) combines with water very rapidly with the evolution of large amount of heat • After the initial set, the paste becomes stiff. • Adding gypsum retards the dissolution of C3A by forming insoluble calcium sulpho-aluminate • The above reaction shows how gypsum retards the early initial set of cement C3A + 6H2O C3A . 6H2O + Heat 3CaO . Al2O3 . xCaSO4 . 7H2O
  • 23. Heat of Hydration of Cement • When cement is mixed with water, hydration , hydrolysis an gelation reaction starts and some heat is liberated • On an average of 500 kJ/Kg of heat is evolved during complete hydration of cement Bogue Compounds Heat of hydration (kJ/kg) C3A 880 C3S 500 C4AF 420 C2S 250 Heat of hydration of Bogue compounds
  • 24. Special Cement : White Portland Cement (or) White cement • Is white in color due to absence of iron compounds • Obtained by calcining the raw materials of Portland cement which are free from iron oxide Properties • More expensive than ordinary Portland cement • Acts as pore – blocking and water – repelling agent  Repairing and joining marble pillars and blocks  Manufacture of tiles and mosaic walls
  • 25. Special Cement : Water proof Cement (or) Hydrophobic cement • Is a cement obtained by adding water proofing substances like calcium stearate, aluminium stearate and gypsum with tannic acid to ordinary Portland cement Properties • More expensive than ordinary Portland cement • Acts as pore – blocking and water – repelling agent  Used to make concrete which is impervious to water under pressure  Used in construction, where absorption of water need to be avoided  Used in construction of bridges and under water constructions