Government College University Faisalabad,

Layyah Campus

M UMAR ALI
Roll No. 1307

Submitted To: Sir Saif- Ur- Rehman

Department: Chemistry 4th Semester

Session: 2022-2026

INDUSTRIAL
2024

CHEMISTRY
ASSIGNMENT

Topics:
• Cement Industry
• Portland Cement
 CEMENT INDUSTRY

Historical Background
Ancient History
• The first archaeological discovery of consolidated whitewashed floor made from burned limestone and
clay was found in modern-day Turkey and dates back 12,000 years ago.
• The first fired clay bricks were developed in the so-called Fertile Crescent.
• Around 800BC, the Phoenicians used the knowledge that a mixture of burnt lime and volcanic ash, today
called 'pozzolana', could be used to produce hydraulic lime, that was not only stronger than anything
previously used, but also hardened under water.

Roman Empire
• The Romans developed new masonry techniques, with which they could erect grand buildings with heavy
foundations.
• One such development was "opus caementitium", a type of concrete made of lime with aggregates of
sand and crushed rock.
• This was mostly used between masonry stones or bricks, serving as formwork.
• Other cements used crushed brick, tiles and ceramic pottery as aggregates.

Age of Enlightenment
• In 1756, the British engineer John Smeaton made the first modern concrete (hydraulic cement) by adding
pebbles as a coarse aggregate and mixing powered brick into the cement.
• Smeaton developed his new formula for concrete in order to build the third Eddystone Lighthouse, but his
innovation drove a huge surge in the use of concrete in modern structures.
• In 1824, the English inventor Joseph Aspdin invented Portland Cement, which has remained the dominant
form of cement used in concrete production.
Industrial Revolution
• The Industrial Revolution led to the development of cement manufacture.
• During the 20th century, cement manufacture spread worldwide.
• By 2019 China and India had become the world leaders in cement production, followed by Vietnam, the
United States, and Egypt.

Invention of Cement
The invention of cement is attributed to Joseph Aspdin of Leeds, Yorkshire, England, who in 1824 took out a patent
for a material that was produced from a synthetic mixture of limestone and clay. He called the product “portland
cement” because of a fancied resemblance of the material, when set, to portland stone, a limestone used for
building in England. Here are some key points about the history of cement:
• Ancient Greece and Rome used hydraulic cements made from lime and volcanic ash.
• The Nabatea people used a precursor of modern-day concrete around 6500 BCE.
• The Assyrians and Babylonians used clay as a bonding substance, while the Egyptians used lime and
gypsum cement.
• The Romans developed concrete using lime, water, and volcanic ash.
• John Smeaton developed modern concrete in 1756 using hydraulic cement.
• Joseph Aspdin invented Portland Cement in 1824.
 • Joseph Monier invented reinforced concrete in 1849.

Fig 1.1

Definition
Cement is defined as:
“The material or product obtained by pulverizing the clinkers obtained by the fusion of calcareous and argillaceous
Components, with 2 to 4 percent of gypsum is called cement.”
OR
“Material obtained by burning an intimate mixture of calcareous (lime bearing) and argillaceous (clay material) at a
sufficiently high temperature to produce clinker by incipient fusion and subsequently grinding and resulting
clinkers to a fine powder.”
Calcareous Material
Calcareous material involves limestone, marble, chalks and marine shells these produces CaO.

Fig 1.2
Argillaceous Material
Argillaceous materials consist of clay, shale, slate, and blast furnaces slag. These provides components as
Aluminates and Silicates.
Average Composition of Cement
Cement is actually a mixture of so many components, each one of these has its own individual properties. Hence
variation in composition, the rate of heating and the maximum temperature to which it is heated along with the
finances of the product, should have effect on final properties of cement.
Portland Cement consist of essentially a mixture of various aluminates and silicates of calcium, Ca3.SiO4
(Tricalcium silicates) & Ca2Al2O4 (Dicalcium aluminates)
Types of Cement on the basis of Composition
Following are the types of Cement on the base of composition
• Ordinary Portland cement: This is usually composition cement used for general construction work. This
cement is used where elasticity is required.
• High Alumina cement: Calcium aluminate cements are cements consisting predominantly of hydraulic
calcium aluminates. Alternative names are “aluminous cement”, “high-alumina cement”. This type of
cement is used in those places which are near the seaside, because this cement can stand with various
changes of weather.
• White Cement: White Portland cement or white ordinary Portland cement is similar to ordinary, gray
Portland cement in all aspects except for its high degree of whiteness.

Fig 1.3
• Sulphate Resisting Cement: Sulphate Resisting Cement is a type of Portland Cement in which the amount
of tricalcium aluminate (C3A) is restricted to lower than 5% and (2C 3A+C4AF) lower than 25%, which
reduces the formation of Sulphate salts. The reduction of Sulphate salts lowers the possibility of Sulphate
attack on the concrete.
• Rapid hardening cement: Rapid Hardening Cement (RHC) is a certain type of Portland cement typically
used in concrete construction to develop high strength earlier than Ordinary Portland Cement (OPC).
Quick setting Cement: Quick Setting Cement (QSC) is a special cement formulation which rapidly develops
compressive strength and significantly reduces waiting on cement (WOC) time compared to conventional
cement systems.
• Low heat Cement: Low Heat Cement is specially blended to provide a lower heat of hydration in concrete.
This unique attribute makes it ideal for mass concrete pours where the rate of temperature rise and the
maximum temperature achieved must be controlled in order to reduce the risk of thermal cracking.
 • Blast Furnace Slag cement: Slag cement is a hydraulic cement formed when granulated blast furnace slag
(GGBFS) is ground to suitable fineness and is used to replace a portion of Portland cement. It is a
recovered industrial by-product of an iron blast furnace.
• Colored Cement: Colored cements are made by grinding 5 to 10 percent of suitable pigments with white
or ordinary gray Portland cement.
• Hydrographic Cement: Hydrophobic cement is obtained by grinding Portland cement clinker with a film-
forming substance such as oleic acid in order to reduce the rate of deterioration when the cement is
stored under unfavorable conditions. It is also known as Hydrographic cement.
Types of Cement on the basis of Hydraulic power
Following are the types of Cement on the ability of the cement to set in the presence of water
a) Hydraulic Cement: (e.g., Portland Cement) set the chemical relation results in mineral hydrates that are not
very soluble in water and so are quite double in water and safe from chemical attack.
b) Non-Hydraulic Cement: It does not set in wet conditions or under water rather, it sets as it dries and reacts
with carbon dioxide in the air. It is resistant to attack by chemical after setting.

Fig 1.4

Properties of Good Cement

The properties of cement can be categorized into two types namely physical properties and chemical properties.
Physical Properties of Cement
• Fineness: It is the biggest factor for the undeterrable strength of cement. Fineness in cement is achieved
by grinding the clinker during the process of production.
• Soundness: The capacity of not changing of properties of the material like change in volume; when water
is added upon it is soundness. Material with high soundness has a higher strength. So, cement should also
have high soundness. Cement should be the cause of high soundness in mortar and concrete.
• Consistency: Uniformity in the nature of the material leads to higher consistency. So, cement should have
high consistency. Consistency is the cause of the uniform nature of the material. In other words, the
flowing ability of cement paste is called consistency.
• Compressibility: Cement has high compressive strength. Thus, it provides the stability and durability to
the structure. Cement is the best binding building material to be mixed with concrete in terms of
compressibility. So, cement should have compressive strength.
• Strength of Cement: Compressive, tensile, and flexural strength play a vital role in the durability and
quality of cement.
Factors affecting the strength of cement
• Water-Cement ratio of a mix.
• Cement-Fine aggregate ratio
• Curing Conditions
• Size and shape of a specimen
• The manner of molding and mixing
• Loading conditions
• Age of cement
a) Heat of hydration: The chemical reaction between cement and water is called the heat of hydration. When
water is added to cement, heat is generated. This can affect the quality of cement because excessive
hydration leads to undesired strength. Hydration depends upon the water-cement ratio, uniformness,
temperature of curing, etc.
b) Setting Time: When water is added to cement; it hardens and sets. Setting time may depend upon uniformity
of cement, water-cement ratio, presence of admixtures, etc. The initial setting time of the cement should not
be less and the final setting time should not be high.
The best initial and final setting time for cement is given as:
• Initial Setting Time: 30-45 Minutes
• Final Setting Time: Below 10 Hours

Chemical Properties of Cement

• Lime: If the lime is used more than 65 %; it may result in the problem of expansion.
• Alumina: Excess use of alumina quickens the setting time but weakens the cement.
• Iron oxide: It is also called Ferric Oxide. It is responsible for the color of the cement.
• Alkaline: The high amount of alkali use leads to difficulty in the regulation of setting time and the low
amount leads to discoloration of cement.
• Sulfur Trioxide: If the amount of Sulfur Trioxide used is more than the cement becomes unsound in
nature.
• Silica: Silica provides high compressive strength, abrasion resistance, and bond strength to cement.
• Magnesia: If the magnesia is used in high amounts, then it results in unsoundness and uneconomical.

Manufacturing of the Cement

Raw Material
A normal batch of cement consists of about
• 75% lime stone
• 20-25% clay
• 3-4% gypsum.
The raw material used for the manufacture of cement are
Lime stone (CaCO3): It provides lime, CaO, chalk, marble and alkali water can also be used since these also supply
Cao
Clay: The composition of clay is Al2O3, SiO2, Fe2O3 and water. Clay supplies silica (SiO2) and Alumina (Al2O3) to
the cement. Some of clay do not contain Fe2O3 and the cement obtained in this care is white and hard to burn
Gypsum (CaSO4.2H2O): Gypsum is used in the manufacturing of cement. The addition of gypsum decreases the
setting time of cement.
Sui gas: Sui gas is used as a fuel in most of cement kilns in Pakistan

MANUFACTURING PROCESS OF CEMENT

Manufacturing process of cement consists of following steps;
• Grinding and mixing of raw material
 • Burning of mixture at specific temperature for a correct duration
• Grinding the burnt product called clinker along with gypsum

Unit Process and Unit Operations for Manufacturing of Cement

These are two methods available for the manufacturing of cement
• Wet Process
In the wet process, the clay is mixed with water in wash mills to remove foreign materials like Flint. The powdered
limestone is then mixes with clay paste in the proper proportions and the mixture is finely ground and
homogenized the resulting paste. The slurry contains 40 % water
• Dry Process
In the dry process, the raw material is first dried and mixed in proper proportions and Pulverized to such a fineness
that 90-95% passes a 100-mesh sieve.
• Choice of Process
Choice of process depends on following conditions.
• Local climate conditions of factory
• Price of the fuel and fuel consumption
• Physical state of raw material
If the raw material is wet, cost of fuel is low and climate is humid then wet process is used. On the other hand,
If the raw material is dry, cost of fuel is high and climate is dry then dry process is used
Comparison between Wet and Dry Process
Wet Process Dry Process

Soft and crystalline materials are used. Hard and crystalline raw materials are used.

High temperature is required for burning the raw Cooperatively low temperature is required for
material. burning the raw material.
Crushed raw material is mixed in the presence of Crushed raw material is material the absence of
water. water.

No dust problem is present. Dust problem is present.

No loss of material takes place. Loss of material takes place.
In this process, raw materials are pulverized by In this process calcareous material such as lime
using a Ball mill, which is a rotary steel cylinder stone (calcium carbonate) and argillaceous material
with hardened steel balls. When the mill rotates, such as clay are ground separately to fine powder in
steel balls pulverize the raw materials which form the absence of water and then are mixed together in
slurry (liquid mixture). The slurry is then passed the desired proportions.
into storage tanks, where correct proportioning is Water is then added to it for getting thick paste and
done. Proper composition of raw materials can be then its cakes are formed, dried and burnt in kilns.
ensured by using wet process than dry process.
Corrected slurry is then fed into rotary
kiln for burning.
It is free from severe damages owing to high It is associated with several problems arise due to
cutting temperature. high cutting temperature, such as accelerated tool
wear, reduced tool life, oxidized surface, residual
stress, poor machinability, etc.
The Dry PROCESS produces dustier and stormier atmosphere which cause health hazard

Wet Process
• Specificity
The specific feature of wet process is that the raw materials are prepared in water whereas in dry process, the
materials are ground and mixed in dry state
• Raw Material
In wet process soft and plan raw material are used the material after being crushed is fed into the grinding mill and
then into the classifier from where it is pumped to the correcting tank to make it homogenous and its composition
is therefore adjusted.
“The ground limestone, clay and H2O are mixed thoroughly to form semi viscous mass called Slurry”
• Grinding Mill
The clay is washed with H2O to remove the first stone then the raw material along with clay are fed into the
grinding mill where the size of particles is reduced in the presence of H2O.
• Classifier
The ground material is then sent to classifier where the oversized particles are retained and sent back to the
grinding mill where the size of particles are reduced in the presence of water the uniform material easily passes
through the classifier
• Correcting Tank
The uniform material is then sent to the correcting tank where Slurry is also introduced. The mixture is constantly
stirred to make it homogenous.
• Paddle Mixture
After correcting tanks, the mixture is finally homogenized in the paddle mixture after through mixing it is subjected
to filtration, so as to remove excess of H2O. The residual product is then fed into the rotary kiln where it is
subjected to combustion with coal gas or fuel oil.
• Description of Rotary Kiln
It is a rectangular steel tube having length of 50 to 150 meters and a diameter of about 3 to 4 meters.
It is provided with screw conveyer rearrangement for introducing the raw material. the rotary kiln is provided with
an inner living of fire bricks.
It is also provided with gears by means of which rotary kiln rotates. The temperature at the top of the kiln is
minimum whereas at the lower and it reaches to as maximum of 1400oC.

Zones of Rotary Kiln

• Dehydration Zone: In this zone evaporation of free water from the fuel and evolution of combined water from
the clay takes place. Temperature in this zone is 100-500oC
• Calcination Zone: In this zone decomposition of lime stone takes place with evolution of CO2 Temperature in
this zone is kept 500- 1000℃
CaCO3 → CaO + CO2
• Burning Zone: In this zone mixture of lime, silica, alumina and Fe2O3 along with other oxides is heated.
At 1000-1450 ℃ the main reaction of cement formation takes place;
3CaO + SiO2 → Ca3SiO5

Clinker Formation
The Product is in the form of granular mass pebbles known as “Clinker” which varies in size 1/8 to 3/4 in diameter.

Composition Chemical Formula Abbreviation Molecular Weight Content %

Tricalcium Silicate 3CaO. SiO2 C3S Tricalcium Silicate 3CaO. SiO2

Dicalcium Silicate 2CaO. SiO2 C2S Dicalcium Silicate 2CaO. SiO2

Tricalcium 3CaO. Al2O3 C3A 270 5.13

Aluminate
Tetra Calcium Ferro 4CaO. Al O. Fe O C AF 486 12.15

• Cooling Zone: Now, these clinkers are passed to cooler where they get cooled. At this zone, the temperature is
kept at 150-200 ℃, ground very fine in ball mil so that 92% of its passes through 100 mesh sieves.
At this stage 2% Gypsum is added in the form of fine powder and mixed well with cement. Gypsum is added
just to control the setting time”.
Storage of Cement
Cement should be stored in a dry, well-ventilated area, protected from moisture and humidity. The storage space
should be clean, free from contaminants, and away from direct sunlight.Cement bags should be stacked on pallets
or shelves, not directly on the floor, to prevent moisture absorption.
Proper storage helps maintain cement's quality and prevents degradation, ensuring optimal performance in
construction applications.

Fig 1.6

Dry Process
• Specificity
The specific feature of dry process is that the materials are ground and mixed in dry state whereas in wet process
the raw materials are prepared in water
• Raw Material
In this process crystalline and hard raw material is used when crystalline and hard raw material is available. In dry
or semi dry process for manufacturing of cement, the raw material is crushed and fed in the correct proportion
into a grinding mill. The process is quite economical.
Significance of Dry Process
The equipment used in dry process kiln are comparatively smaller.
The process is quite economical.
• D Grinding Mill
The raw materials are crushed and fed in the correct proportion into a grinding mill. The raw materials are dried
and reduced in size to a fine produce into grinding mills. "The dry powder is called raw meal."
• Blending Silo
The raw meal is pumped into a blending silo. Adjustment in the proportion of the materials required for the
manufacture of cement in Silo.
• The raw meal blended by passing compressed air
• To obtain a uniform and intimate mixture
Compressed air
• Induces upward movement of powder.
• Decreases apparent density.
Formation of Uniform Mixture
The air is passed over aerated quadrants. Therefore, the aerated powder tends to behave like a liquid and by
assailing all quadrants in true for a total pained of about one hour a uniform mixture is obtained. In some cement
manufacturing processing plants continuous blending is used.
Formation of Pellets
The blended meal is further passed into sieve and then fed into a rotating dise called granulator. A quantity of
water about 12% by eight is added to make the blended meal into pellets. In this manner hard pellet about 15mm
in diameter use formed.
Introduction into Rotary Kiln
Following are the different zones of rotary kiln
• Pre-Heating Zone
• Burning Zone
• Calcination Zone
• Cooling Zone
i) Pre-Heating Zone
The pellets are baked hard in pre-heating zone on grate by means of hot gases from Kiln.
ii) Burning Zone
The pellets then entre the pin where temperature is about 1450 °C.
• The total concomitance of coal in this method is only about 100 K
• When compared to the requirement of about 220 Kg for producing a ton of cement in wet process.
Chemical Reactions
The dry material under goes a series of chemical reactions in lime, silica and alumina recombines.
• The fused mass turns fuses into balls of diameter 3 to 25 nm known as clinker.
Composition of slinks from previous Melton
3CaO+ SiO2 Ca2SiO5
(Tricalcium silicate)
Al2O3 + Cao Ca (AlO2)2
(Calcium aluminate)
iii) Calcination Zone
In this zone, decomposition of line stone takes place with evolution of CO.
CaCO3 CaO + CO2
In this zone temperature is 500-1000 °C.
iv) Cooling Zone
The clinker drops cooled the temperature in this zone is 150-200 °C.
Clinker is cooled under control.
Addition of Gypsum
Cooled clinker and 3 to 5% of gypsum are growth in ball mill to required fineness. "Gypsum is added in the cement
to increase setting time."

Storage and Transportation of Cement

Cement should be stored in a dry, protected area to prevent moisture damage. Transportation should be done in
dry, covered vehicles to prevent exposure to rain or humidity. Cement bags should be handled carefully to avoid
punctures and tears, which can lead to moisture entry. Proper storage and transportation help maintain cement's
quality and strength, ensuring optimal performance in construction projects.
 Fig 1.7

Setting of Cement
Definition:
When cement is mixed with water and resulting mass becomes hard and very resistant to pressure this process is
known as setting of cement.
• The setting of cement is mainly due to the hydration of calcium silicates.
• These calcium silicates compounds of cement get hydrated and form a complex hydro silicate.
Reactions during Setting of Cement
a) Reactions takes place in first 24 hours:
After mixing with water the calcium aluminates absorb water and form a colloidal Gel (collide is more solid form
then sol)
3CaO.Al2O3+ 6H₂O 3CaO.Al2O3.6H20
(Hydrated colloidal gel of tricalcium aluminate)
2CaO. SiO2 + xH₂O 2CaO. SiO2. xH₂O
3Ca0. Al2O3 also react with Gypsum to form calcium sulpho-aluminate.
Gypsum
Gypsum is a mineral and is a hydrated calcium sulphate in chemical form.
• Gypsum plays a very important role in controlling the rate of hardening of the cement.
So, it is generally termed as retarding agent of cement.
• It is mainly used for regulating the setting time of cement and as indispensable component.
The main purpose of adding gypsum in the cement is
• To slow down the hydration process of cement once it is mixed with water.
The gel formed starts losing water partially be evaporation and by forming hydrates with un hydrated constituents
thus cement sets to hard mass.
b) Reaction between 1 to 7 days:
Tricalcium silicate and tricalcium aluminates hydrolyze to produce crystals of Ca (OH)2 and Al (OH)
3CaO.SiO2 + H20 Ca (OH)2 + 2CaO. SiO₂
Needle like crystals Ca studied in colloidal gel an impart strength to it.
3CaO.Al2O3 + 6H20 3Ca (OH)2 + 2AI(OH)3
Al (OH), Inters ticks resulting in hardening the mass. The gel starts losing water Partially by evaporation and sets
hard mass.

Cement Industry in Pakistan

At the time of pollution in 1947, there was four cement plants in west Pakistan which produced about 330,000
tons of cement every year.
• However, in 1954 the production of cement went up to 660,000 tons.
• In 1956 two more cement factories were set up at Daud Khel and Hyderabad
But even then, the production of cement was not enough to meet the increasing demand of the construction
industry in the country.
For a developing country like Pakistan rate of developing projects. Efforts were thus made to build more factories.
• The total production of these 22 cement plants in 9,578,802 metric tons annum. In Pakistan,
infrastructure projects and the housing sector are the key drivers for consumption of cement. Going
forward, consumption of cement from these two sectors is projected to increase.
• The cement industry in Pakistan contributes in the Gross Domestic Product (GDP)
• It creates employment opportunities for thousands of people and it creates huge revenue for the
Government in the form of taxes.
• It directly or indirectly contributes in the economic development of Pakistan

Applications of Cement Industry

Uses of cement are given below:
✓ It is used in mortar for plastering, masonry work and pointing.
✓ It is used for making joints during drains and pipes.
✓ It is used in concrete for lying floors, roofs and constructing lintels, beams and pillars.
✓ It is used for water tightness of structure.
✓ It is employed for the construction of wells, water tanks, roads and tennis courts etc.
✓ It is used to build fie proof and thermal proof structures. It is used to build hydrographic and frost
 resistant structures.
✓ It is used to build chemical proof structures. It is used as a grout material.
✓ It is used to manufacture precast members.
✓ Cement slurry is used for filling small crack in concrete structures.

Portland Cement
Portland cement is the product obtained by pulverizing clinker, consisting of hydraulic calcium silicates to which
some calcium sulfate has usually been provided as an interground addition. When first made and used in the early
19th century in England, it was termed Portland cement because its hydration product resembled a building stone
from the Isle of Portland off the British coast. The first patent for Portland cement was obtained in 1824 by Joseph
Aspdin, an English mason. The specific gravity of Portland cement particles is about 3.15. There are four primary
phases in Portland cement: tricalcium silicate (C3S), dicalcium silicate (C2S), tricalcium aluminate (C3A), and tetra
calcium aluminoferrite (C4AF). The strength and other properties of concrete are mainly derived from the
hydration of tricalcium and dicalcium silicates. The composition of any of these phases in a particular clinker will
not be precisely in the composition indicated.

Fig 2.1
Types of Portland cement
The properties of cement during hydration vary according to:
• Chemical composition
• Degree of fineness
It is possible to manufacture different types of cement by changing the percentages of their raw materials.
i) Ordinary Portland cement
This type of cement use in constructions when there is no exposure to sulfates in the soil or groundwater.
The chemical composition requirements are listed in Iraqi specification NO. 5., as shown below:
Lime saturation factor = 𝐶𝑎𝑂−8.8(𝑆𝑂8 )

8.8 (𝑆88888 )+ 8.8 (88888 888 )+ 8.88 (𝐹888 𝑂8)

L.S.F. is limited between 0.66-1.02
This factor is limited – to assure that the lime in the raw materials, used in the cement manufacturing is not so
high, so as it causes the presence of free lime after the occurrence of chemical equilibrium which cause
unsoundness of cement. While too low a L.S.F. would make the burning in the kiln difficult and the proportion of
C3S in the clinker would be too low.
• Percentage of SO3 limited by 2.5% when ≤7%, and not more than 3% when C3A>7%
• Loss of ignition L.O.I 4% (max.)
• Percentage of MaO 5% (max.)
• Fineness not less than 2250 cm2/g
• C3S limits (42 – 67) %
• C2S limits (8 – 31) %
• C3A limits (5 – 14) %
• C4AF limits (6 – 12) %

Fig 2.2
ii) Rapid Hardening Portland Cement
This type develops strength more rapidly than ordinary Portland cement. The initial strength is higher, but they
equalize at 2-3 months. Setting time for this type is similar for that of ordinary Portland cement. The rate of
strength gain occurs due to increase of C3S compound, and due to finer grinding of the cement clinker (the min.
fineness is 3250 cm2/g (according to IQS 5). Rate of heat evolution is higher than in ordinary Portland cement due
to the increase in C3S and C3A, and due to its higher fineness. Chemical composition and soundness requirements
are similar to that of ordinary Portland cement.
Uses
a) The uses of this cement are indicated where a rapid strength development is desired (to develop high early
strength, i.e. (its 3 days strength equal that of 7 days ordinary Portland cement), for example:
• When formwork is to be removed for re-use
• Where sufficient strength for further construction is wanted as quickly as practicable, such as concrete
blocks manufacturing, sidewalks and the places that cannot be closed for a long time, and repair works
needed to construct quickly.
b) For construction at low temperatures, to prevent the frost damage of the capillary water.
c) This type of cement does not use at mass concrete constructions.
Special Types of Rapid Hardening Portland Cement
a) Ultra-High Early Strength Cement
The rapid strength development of this type of cement is achieved by grinding the cement to a very high fineness:
7000 to 9000 cm2/g. Because of this, the gypsum content has to be higher (4 percent expressed as SO3). Because
of its high fineness, it has a low bulk density. High fineness leads to rapid hydration, and therefore to a high rate of
heat generation at early ages and to a rapid strength development (7 days strength of rapid hardening Portland
cement can be reached at 24 hours when using this type of cement). There is little gain in strength beyond 28 days.
It is used in structures where early prestressing or putting in service is of importance. This type of cement contains
no integral admixtures.
b) Extra Rapid Hardening Portland Cement
This type prepares by grinding CaCl2 with rapid hardening Portland cement. The percentage of CaCl2 should not be
more than 2% by weight of the rapid hardening Portland cement.
By using CaCl2:
• The rate of setting and hardening increase (the mixture is preferred to be casted within 20 minutes).
• The rate of heat evolution increases in comparison with rapid hardening Portland cement, so it is more
convenient to be use at cold weather.
• The early strength is higher than for rapid hardening Portland cement, but their strength is equal at 90
days.
• Because CaCl2 is a material that takes the moisture from the atmosphere, care should be taken to store
this cement at dry place and for a storage period not more than one month so as it does not deteriorate.

Fig 2.3

iii) Low Heat Portland Cement

Its composition contains less C3S and C3A percentage, and higher percentage of C2S in comparison with ordinary
Portland cement.
Properties
• Reduce and delay the heat of hydration.
• It has lower early strength compared with ordinary Portland cement.
• Its fineness is not less than 3200 cm2/g
Uses
It is used in mass concrete constructions: the rise of temperature in mass concrete due to progression in heat of
hydration cause serious cracks. So, it is important to limit the rate of heat evolution in this type of construction, by
using the low heat cement.
iv) Sulfate- resisting Cement
This type is similar to ordinary Portland cement but it contains Lower percentage of C3A and C4AF which considers
as the most affected compounds by sulfates and higher percentage of silicates in comparison with ordinary
Portland cement. For this type of cement C2S represents a high proportion of the silicates.
C4AF is more resistance to sulfate than C3A because a layer will form which surround the free C3A leading to
reduce its affect by sulfates, and since it is not easy to reduce Al2O3 in raw material so Fe2O3 (iron powder) may
be add to mix to increase C4AF and decrease C3A.
Fe2O3 + C3A → C4AF
Iraqi specification no. (6) limits - max. C3A content by 3.5%
- min. fineness by 2500 cm2/g
American standard (ASTM) - Max C3A content by 5%
- 2C3A + C4AF ≤ 20%
Properties
• Low early strength.
• Its resulted heat of hydration is little higher than that resulted from low heat cement.
• Its cost is higher than ordinary Portland cement – because of the special requirements of material
composition, including addition of iron powder to the raw materials.
For the hardened cement, the effects of sulfates are on two types:
• Hydrated calcium aluminates in their semi-stable hexagonal form (before its transformation to the stable
state – C3AH6 as cubical crystal form – which have high sulfate resistance) react with sulfates (present in
fine aggregate, or soil and ground water), producing hydrated calcium sulfoaluminate, leading to increase
in the volume of the reacted materials by about 227% causing gradual cracking.
• Exchange between Ca (OH)2 and sulfates resulting gypsum, and leading to increase in the volume of the
reacted materials by about 124%.
v) Portland Blast furnace Cement
This type of cement consists of an intimate mixture of Portland cement and ground granulated blast furnace slag.
Slag – is a waste product in the manufacture of pig iron.
Chemically, slag is a mixture of 42% lime, 30% silica, 19% alumina, 5% magnesia, and 1% alkalis, that is, the same
oxides that make up Portland cement but not in the same proportions. The maximum percentage of slag use in this
type of cement is limited by British standard.
B.S. to be 65%, and by American standard ASTM C595 to be between 25-65%.
Properties
• Its early strength is lower than that of ordinary cement, but their strength is equal at late ages (about 2
months).
• The requirements for fineness and setting time and soundness are similar for those of ordinary Cement.
• The workability is higher than that of ordinary cement.
• Heat of hydration is lower that of ordinary cement.
• Its sulfate resistance is high.
Uses
• Mass concrete
• It is possible to be use in constructions subjected to sea water (marine constructions).
• May not be use in cold weather concreting.
vi) Pozzolanic Cement
This type of cement consists of an intimate mixture of Portland cement and pozzolana. American standard limit the
pozzolana content by 15-40% of Pozzolanic cement. Pozzolana, according to American standard ASTM C618, can
be defined as – a siliceous or siliceous and aluminous material which in itself possesses little or no cementitious
value but will, in finely divided form and in the presence of moisture, chemically react with calcium hydroxide at
ordinary temperatures to form compounds possessing cementitious properties. It is essential that pozzolana be in
finely divided state as it is only then that silica can combine with calcium hydroxide (produced by the hydrating
Portland cement) in the presence of water to form stable calcium silicates which have cementitious properties.
Types of Pozzolana are Natural Pozzolanic materials, such as – volcanic ash and Industrial Pozzolanic materials,
such as – fired clay, rice husks ash
vii) White Cement
White Portland cement is made from raw materials containing very little iron oxide (less than 0.3% by mass of
clinker) and magnesium oxide (which give the grey color in ordinary Portland cement). white clay is generally used,
together with chalk or limestone, free from specified impurities. Its manufacture needs higher firing temperature
because of the absence of iron element that works as a catalyst in the formation process of the clinker. In some
cases, kreolite (sodium- aluminum fluoride) might be added as a catalyst. The compounds in this cement are
similar for those in ordinary Portland cement, but C4AF percentage is very low. Contamination of the cement with
iron during grinding of clinker has also to be avoided. For this reason, instead of the usual ball mill, the expensive
nickel and molybdenum alloy balls are used in a stone or ceramic-lined mill. The cost of grinding is thus higher, and
this, coupled with the more expensive raw materials, makes white cement rather expensive.
Properties
• It has a slightly lower specific gravity (3.05-3.1), than ordinary Portland cement.
• The strength is usually somewhat lower than that of ordinary Portland cement.
• Its fineness is higher (4000-4500 cm2/g) than ordinary Portland cement
• It used in architectural purposes.
viii) Modified Portland cement
In some application, a very low early strength may be a disadvantage, and for this reason a modified cement was
developed (60% low heat Portland cement and 40% ordinary Portland cement) this cement has a higher rate of
heat development than that of low heat Portland cement, and a rate of gain of strength similar to that of ordinary
Portland cement. This cement is recommended for structures where a moderately low heat generation is desirable
or where moderate sulfate attack may occur.
ix) Colored Portland Cement
It is prepared by adding special types of pigments to the Portland cement. The pigments added to the white
cement (2-10% by weight of the cement) when needed to obtain light colors, while it added to ordinary Portland
cement when needed to obtain dark colors.
Pigment properties
• It is required that pigments are insoluble and not affected by ambience.
• They should be chemically inert
• Don’t contain gypsum that is harmful to the concrete.
• Don’t affect on strength development of concrete.

x) Other types of Portland Cements

a) Anti-bacterial Portland Cement
It is a Portland cement grounded with an anti-bacterial agent which prevents microbiological fermentation. This
bacterial action is encountered in concrete floors of food processing plants where the leaching out of cement by
acids is followed by fermentation caused by bacteria in the presence of moisture.
b) Hydrophobic Cement
It is prepared by mixing certain materials (stearic acid, oleic acid, … etc. by 0.1-0.4%) with ordinary Portland
cement clinker before grinding, to form water repellent layer around the cement particles, so as the cement can be
store safely for a long period. This layer removes during mixing process with water.
c) Water proof Portland cement
It is prepared by mixing waterproofing substance (calcium stearate, Aluminum stearate, gypsum treated with
tannic acid, and non-saponifiable oils) with ordinary Portland cement clinker while grinding. These materials make
cement impermeable to liquids.

Manufacture Process of Cement

The manufacture procedures of Portland cement are described below.
• Mixing of raw material
• Burning
• Grinding
• Storage and packaging
i) Mixing of raw material
The major raw materials used in the manufacture of cement are Calcium, Silicon, Iron and Aluminum. These
minerals are used in different form as per the availability of the minerals.
The mixing procedure of the manufacture of cement is done in 2 methods,
• Dry process
• Wet process
Table shows the raw materials for Portland cement manufacture

Fig 2.4
a) Dry Process
The both calcareous and argillaceous raw materials are firstly crushed in the gyratory crushers to get 2-5cm size
pieces separately. The crushed materials are again grinded to get fine particles into ball or tube mill. Each finely
grinded material is stored in hopper after screening. Now these powdered minerals are mixed in required
proportion to get dry raw mix which is then stored in silos and kept ready to be sent into rotary kiln. Now the raw
materials are mixed in specific proportions so that the average composition of the final product is
maintained properly.
b) Wet Process
The raw materials are firstly crushed and made into powdered form and stored in silos. The clay is then washed in
washing mills to remove adhering organic matters found in clay. The powdered limestone and water washed clay
are sent to flow in the channels and transfer to grinding mills where they are completely mixed and the paste is
formed, i.e., known as slurry. The grinding process can be done in ball or tube mill or even both. Then the slurry is
led into collecting basin where composition can be adjusted. The slurry contains around 38- 40% water that is
stored in storage tanks and kept ready for the rotary kiln.
ii) Burning of Raw Materials
The burning process is carried out in the rotary kiln while the raw materials are rotated at 1-2rpm at its
longitudinal axis. The rotary kiln is made up of steel tubes having the diameter of 2.5-3.0 meter and the length
differs from 90-120meter. The inner side of the kiln is lined with refractory bricks. The kiln is supported on the
columns of masonry or concrete and rested on roller bearing in slightly inclined position at the gradient of 1 in 25
to 1 in 30. The raw mix of dry process of corrected slurry of wet process is injected into the kiln from the upper
end. The kiln is heated with the help of powdered coal or oil or hot gases from the lower end of the kiln so that the
long hot flames is produced.
As the kiln position is inclined and it rotates slowly, the material charged from upper end moves towards lower end
at the speed of 15m/hr. In the upper part, water or moisture in the material is evaporated at 400oC temp, so this
process is known as Drying Zone. The central part i.e. calcination zone, the temperature is around 10000C, where
decomposition of lime stone takes place. The remaining material is in the form of small lumps known as nodules
after the CO2 is released.
CaCO3 CaO + CO2
The lower part (clinkering zone) has temperature in between 1500-17000C where lime and clay are reacts to
yielding calcium aluminates and calcium silicates. These aluminates and silicates of calcium fuse to gather to form
small and hard stones are known as clinkers. The size of the clinker is varying from 5-10mm.
The lower part i.e. clinkering zone has the temperature around 1500-1700C. In the region lime and clay reacts to
yield calcium aluminates and calcium silicates. This products of aluminates and silicates of calcium fuses together
to form hard and small stones known as clinkers. The size of the small and hard clinkers varies from 5 to 10mm.
2CaO + SiO2 Ca2SiO4
(declaim silicate (C₂S))
3CaO + SiO2 Ca3SiO5
(tricalcium silicate (C3S))
3CaO + Al2O3 Ca3Al2O6
(dicalcium aluminate (C2A))
4CaO + Al2O3 + Fe2O3 Ca4Al2Fe2010
(tetra calcium aluminoferrite(C4AF))
The clinker coming from the burning zone are very hot. To bring down the temperature of clinkers, air is admitted
in counter current direction at the base of the rotary kiln. The cooled clinkers are collected in small trolleys.
iii) Grinding of Clinkers
The cooled clinkers are received from the cooling pans and sent into mills. The clinkers are grinded finely into
powder in ball mill or tube mill. Powdered gypsum is added around 2-3% as retarding agent during final grinding.
The final obtained product is cement that does not settle quickly when comes in contact with water. After the
initial setting time of the cement, the cement becomes stiff and the gypsum retards the dissolution of tri-calcium
aluminates by forming tricalcium sulfoaluminate which is insoluble and prevents too early further reactions of
setting and hardening.
3CaO.Al2O3 + xCaSO4.7H2O 3CaO.Al2O3.xCaSO4.7H2O
iv) Storage and packaging
The grinded cement is stored in silos, from which it is marketed either in container load or 50kg bag.