Cement

Industries
 Introduction
• Cement
o Inorganic material
o Having Adhesive and Cohesive properties
o Sets and Hardens when mixed with water (Hydrolysis and Hydration)

• Uses
o Building, Roads, Bridges and Dams etc

• Types
Hydraulic (Portland Cement)
Hardens because of hydration, can hardens under water or when constantly exposed to
wet weather
Non-Hydraulic Cement (Lime and Gypsum plasters)
Slaked lime hardens because of its reaction with atmospheric carbon dioxide
History
 Portland Cement:
• “The product obtained by Pulverizing clinker, consisting essentially of
Hydraulic calcium silicates, usually containing one or more forms of
calcium sulfates as an inter-ground addition”.
• The reactions involved in the hardening of the Cement are Hydration
and Hydrolysis.
Types of Cement:
Natural Cement (Hydraulic lime):
Burning of 20-40 % clay, carbonate of lime and small amount
magnesium carbonate
Artificial Cement:
Calcination of calcareous (Ca) material followed by the clinkering
process with argillaceious (Al + Si) material at high temperature.
Based upon the applications,
appearance and constituents
Principle Constituents:
Origin of Basic Constituents
Basic Component’s Abbreviation
Basic Component Abbreviation
CaO C
SiO2 S
Al2O3 A
Fe2O3 F
MgO M
SO3 S*
Na2O N
CO2 C*
H2O H
K2O K
Chemical Composition of Grey Cement:
Compounds and Functionality
Chemical Composition of White Cement:

• Except for color, white cement has the same properties as the grey
cement.
Manufacturing Process
• Calcination:
The basic chemistry of cement manufacturing process begins with
decomposition of Calcium carbonate (CaCO3) at about 900 degree
Celsius to calcium oxide (CaO, lime) along with libration of gaseous
carbon dioxide (CO2).
• Clikering Process:
This is follow by Clinkering process in which calcium oxide reacts at high
temperature (typically 1400-1500 degree Celsius or above) with
silicates, aluminates and ferrites of calcium that comprises the clinker.
The clinker is then ground or milled together with gypsum and other
additives to produce cement.
 Manufacturing Process:
• The manufacturing process basically involves the following steps:

• Storage and Preparation of raw-materials

• Burning
• Grinding
• Storage and Packaging
Process Routes:

Wet processes are more energy consuming, therefore more expensive.

Raw Materials
•Clay
•Limestone
•Gypsum
•Water
Dry Process:
Wet Process:
 Wet Process VS Dry Process
Wet Process
 Moisture content of slurry is 35-
50%
 Size of Kiln needed to manufacture
the cement is bigger
 The amount of heat required is
higher, so the fuel consumption is
higher
 Less economical
 Raw materials can mix easily,
therefore better homogenous
mixture is obtained
 The machinery and equipment do
not require much maintenance
Dry Process
 Moisture content of Pellets is 12%
 Size of Kiln needed to manufacture
the cement is smaller
 The amount of heat required is
lower, so the fuel consumption is
lower
 More economical
 Difficult to control the mixing of
raw materials, so it is difficult to
obtain a homogenous mixture
 The machinery and equipment
need more maintenance
 Gyratory
Hammer Mills
Crusher
Tube / Ball Mills
 Grinding circuit types:
• Closed Circuit Grinding:
Fines particles are passed on while the coarse material is returned to
the grinding section.
• Open Circuit Grinding:
In this type of grinding circuit, raw material is ground continuously until
its mean fineness has reached a desired value.
Clinker Burning:
 Pre-heater/Pre-Calciner
• The heat transfer of hot kiln gasses to the raw meal take place in a
counter current manner. The raw-materials are heated up to 900
degree Celsius within less than a minute.
• The quantity of the fuel used in the rotary kiln can be reduced by
introducing a proportion of fuel into pre-heater.
• The fuel in pre-calciner is burnet at comparatively low temperature,
so that the heat transfer to the raw meal is very efficient.
• The material is burned for less than a minute and its exit temperature
is around 900 degree celcius, 90-95% of calcite is decomposed.
Advantages of Pre-calcination:
1. Decrease the size of kiln,
2. Decrease in capital cost,
3. Increase in the rate of material passing through the kiln,
4. Lengthen the life time of refractory lining used in rotary kiln (due to decreased
rate of heat to be provided with in kiln)(high alumina,high magnesia),
5. Less NOx are formed, because majority of fuel is burned at low temp.
 Clinker Burning:
• Next step is to heat the blended mixture of raw ingredients to convert it into
a granular material called Cement Clinker.
• This requires maximum temperatures that are high enough to partially melt
the raw mixture. Because the raw ingredients are not completely melted,
the mixture must be completely and thoroughly agitated to ensure that the
clinker forms with uniform composition and this is achieved by using a long
rotary kiln, that slopes downward and rotates slowly.
• When the mixture is ready to enter the Kiln, the dry raw mixture has 85% of
particles less than 90 micrometer in diameter.
 Kiln Heating:
• To heat the Kiln, a mixture of fuel and air is injected to the kiln and is
burnet at its bottom end.
• The hot gasses travel up the Kiln to the top through dust collector,
electrostatic precipitators and out a smokestack (Chimney).
• A variety of fuels can be used for this purpose including pulverized
coal or coke, natural gas, lignite and fuel oil.
• These fuels create varying types and amounts of ash, which tend to
have compositions similar to some of the aluminasilicate ingredients
in the raw mixture.
• Since this produced ash combines with the raw mixture inside the
kiln, this must be taken into account in order to correctly predict the
cement compassion.
• Old waste products such as waste tyres can also be used for heating
purposes, this saves money on fuel, helps in waste recycling, reduces
CO2 emissions and provides safe mode of disposal.
 Heating Zones in Rotary Kiln:
1. Dehydration Zone: (500 degree Celsius and above)
• This is simply removal and evaporation of water content.
• Evaporation of water at approximately 100 degree Celsius. (endo)
• Evolution of combined water from clay at 500 degree Celsius. (endo)
• Both Dry process and Wet process requires dehydration zone, for the
removal of entrained moisture. But in case of Wet processes,
dehydration zone requires up to half of the length of kiln.
2. Calcination Zone: (500-900 degree Celsius)
• At the temperature about 900 degree Celsius, calcination reaction
takes place with the production of Lime and evolution of Carbon
dioxide. (endo)
• By the end of Calcination zone, the mixture now contains oxides of
four main elements (Ca, Al, Si, Fe), that are ready to undergo further
reaction to yield cement minerals.
• Until this point no melting takes place, therefore mixture is still in
powdered form and free flowing.
 Heating Zones in Rotary Kiln:
3. Solid-State reaction zone: (900-1250 degree Celsius)
• As the temperature is increased beyond 900 degree Celsius, still there
is no melting but solid-state reactions began to occur.
• CaO and reactive Silica combine to form small crystal of C2S
(dicalcium silicate), (one of the four main cement minerals). (exo)
• In addition, intermediate calcium aluminates and calcium ferrite
compounds form. These agents play an important role in clinkering
process as fluxing agents, therefore mixture start to melt at relatively
low temperature of about 1300 degree Celsius.
• Without there fluxing agents, the formation of calcium silicate
cement minerals would be slow and difficult.
4. Liquid formation zone: (1250-1280 degree Celsius)
• Commencement of liquid formation. (endo)
• This semi-liquid mixture becomes sticky to the tendency for adjacent
particles to stick together.
• As a result of fusion small mineral lumps are formed that are called as
Nodules. That are agglomerated due to the presence of liquid layer.
Heating Zones in Rotary Kiln:
• Clinkering Zone: (1300-1700 degree Celsius)
• This is the hottest zone where the formation of most important
cement minerals, C3S (alite), occurs.
• The formation takes place as soon as the intermediate calcium
aluminate and ferrite phases melt.
• Inside this liquid layer the conversion of C2S to C3S take place due to
its further reaction with CaO.
• The process goes to completion when all the silica is in the C3S and
C2S crystals and the amount of free lime is also reduced to minimal
level (<1%).
• Also the formation of important cement minerals C3A and C4AF takes
place.
• The material coming out of the clinkering zone consist up of hard,
granular masses from 3 to 20 mm in size, called Clinker.
 Heating Zones in Rotary Kiln:

Note:
Dry kiln may be as short as 45m, but in wet processes 90-180m
kilns are common.
Internal diameter is between 2.5m to 6m.
The kiln are rotated at from ½ to 2 rpm depending upon size.
The kiln as downward slope of 4-5 percent. The materials are
fed in at the upper end and travel slowly to the lower firing end,
taking 1-3 hr.
High alumina and High magnesia brick lining are used to
withstand at high temperatures, and severe abrasions and
chemical attack.
Heating Zones in Rotary Kiln:
 Cooling Zone:
• The hot klinker coming out of the rotary kiln is discharged to the air-
quenching coolers, which quickly brings its temperature down to 100
– 200 degree Celsius.
• The rate of cooling from maximum temperature down to 1100 degree
Celsius is important. Because in this temperature range C3S may
decompose back to C2S and CaO (cement reactivity decreases).
• Therefore it is suggested that during this temperature range cooling
must be done in a rapid manner.
• Cooling zone recover the energy from hot mixture, and the resultant
hot air is then again send to the rotary kiln.

Klinker grinding:
• Then the resultant cooled klinker is ground to fine powder along with
the addition of settling retarders (Gypsum=calcium sulfate), air-
entraining, water proofing agents, plaster etc are added.
 Initial and Final Settling Time:
• Initial Settling time:
The time when the cement water paste attains a certain degree
of hardness is known as initial settling time.
• Final Settling time:
It is that stage at which cement water paste had attained
sufficient strength. Final settling time of cement should not be
more than 10hr.
Typical Compound composition in ordinary Portland Cement:

Compound Content, %
C3S 54
C2S 17
C3A 11
C4AF 9
 Basic Types of Portland Cement
Classification Characteristics Applications
Type 1 General Purpose Fairly High C3S content for good Buildings, bridges,
early strength development pavements etc

Type 2 Moderate sulfate Low C3A content (<8%) Structures exposed

resistance to soils or water
containing sulfate
ions
Type 3 High early Ground more finely, may have Rapid construction,
Strength even more C3S cold weather
concreting

Type4 Low heat of Low content of C3S and C3A, Massive structures
hydration (slow blended mixture such as dams
reacting)
Type 5 High sulfate Very low C3A content (<5%) Structures exposed
resistance to high quantity of
sulfate ions.
 Basic Types of Portland Cement
• The ASTM has designed five types of portland cements, designated
type 1-5.
• In terms of performance they differ primarily in the rate of early
hydration and in their ability to resist sulfate attack.
• Type 2 and 5 are designed to their resistance against sulfate attack.
• Sulfate attack is a severe phenomena that causes severe damage to
concrete structure.
• It is the chemical reaction between hydration products of C3A and sulfate
ions that enter the concrete from outside environment.
• The products generated by this reaction have the larger volume that the
reactants, and this creates stresses that forces the cement to expand and
crack.
• Although the hydration products of C4AF are similar to those of C3A,
they are less vulnerable to expansion, so the designation of Type 2 and
Type 5 focuses on keeping the C3A content low.
 Basic Types of Portland Cement
• Type 3 cement is designed to develop early strength more
quickly than type 1 cement,
• Therefore this is useful for maintaining the rapid pace of construction.
• The advantages are particularly important in cold weather, which
significantly reduces the rate of hydration.
• The downsides of rapid reacting cement are a shorter period of
workability, greater heat of hydration, and slightly lower ultimate
strength.
• Type 4 cement is designed to release heat more slowly than
type 1 cement, meaning of course that it gains strength more
slowly.
Setting and Hardening of Cement
• There are many components that contribute to the heat of hardening
after 28 days, that are as follows,
• C3A > C3S > C4AF > C2S
• Cement are made with less heat of hydration by controlling the
amount of C3A and C3S but high in C2S.
• This thing is accomplished by,
• Adding Fe2O3 that takes the Al2O3 out of circulation as C4AF, therefore
diminishing the amount of C3A.
• By decreasing the CaO/SiO2 ratio.
• (Controlling the heat of hydration , heat of settling of cement is used in
the construction of all large dams to avoid cracking the structure from
heat stresses during settling and cooling).
• Structures can be cooled during setting by circulating cold water through
pipes, placed in concrete mass.
Setting and Hardening of Cement

Heat of Hydration in Joules per gram

Strength contribution of various components in portland cement

Types of Cement depending upon
characteristics: (Self-study)
1. Pozzolans
2. High Alumina Cements
3. Silicates Cements
4. Sulphur Cements
5. Polymer Concrete
6. Magnesium Oxychloride Cement