1 | Chapter 2 - CEMENT P a g e

Portland Cement
The basic ingredient of concrete, is a closely controlled chemical combination of calcium,
silicon, aluminum, iron and small amounts of other ingredients to which gypsum is added in the
final grinding process. Lime and silica make up about 85% of the mass.
Joseph Aspdin, a British bricklayer, in 1824 was granted a patent for a process of making
cement which he called Portland cement; its name is derived from a type of building stone that
was quarried on the Isle of Portland in Dorset, England.
Many people have claimed to have made the first Portland cement, but it is generally
accepted that it was first manufactured by William Aspdin.

Properties of Cement
1. Fineness
Fineness tests indirectly measures the surface area of the cement particles per unit mass :
Wagner turbidimeter test (ASTM C 115)
Blaine air-permeability test (ASTM C 204)
Sieving using No. 325 (45 m) sieve (ASTM C 430)
Fineness is expressed in terms of specific surface of the cement (cm
2
/gr). For OPC specific
surface is 2600-3000 cm
2
/gr.
As hydration takes place at the surface of the cement particles, it is the surface area of
cement particles which provide the material available for hydration. The rate of hydration is
controlled by fineness of cement. For a rapid rate of hydration a higher fineness is necessary.
However,
Higher fineness requires higher grinding cost
Finer cements deteriorate faster upon exposure to atmosphere.


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Finer cements are very sensitive to alkali-aggregate reaction.
Finer cements require more gypsum for proper hydration.
Finer cements require more water.

2. Soundness
Soundness is the ability of a hardened paste to retain its volume after setting.
Soundness is also defined as the volume stability of cement paste.
A cement is said to be unsound (i.e. having lack of soundness) if it is subjected to delayed
destructive expansion.
Unsoundness of cement is determined by the following tests:
Le-Chatelier accelerated test (BS 4550: Part 3)
Autoclave-expansion test (ASTM C 151)

3. Consistency
Consistency refers to the relative mobility of a freshly mixed cement paste or mortar or its
ability to flow.
Normal or Standard consistency of cement is determined using the Vicats Apparatus. It is
defined as that percentage of water added to form the paste which allows a penetration of 10
1 mm of the Vicat plunger.
Normal consistency of O.P.C. Ranges from 20-30% by weight of cement.
Consistency can be determined by:
Vicat Plunger Consistency Test
Consistency Test for mortar using the flow table

4. Setting Time
Setting refers to a change from liquid state to solid state. Although, during setting cement
paste acquires some strength, setting is different from hardening.
The water content has a marked effect on the time of setting. In acceptance tests for
cement, the water content is regulated by bringing the paste to a standard condition of
wetness. This is called normal consistency.
This is the term used to describe the stiffening of the cement paste.


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Setting time is used to determine if cement sets according to the time limits specified in
ASTM C 150.
Setting time is determined using either
the Vicat apparatus (ASTM C 191)
Gillmore needle (ASTM C 266)

The factors affecting the setting time are:
Temperature & Humidity
Amount of Water
Chemical Composition of Cement
Fineness of Cement (finer cement, faster setting)
Initial setting time is the time from the instant at which water is added to the cement until
the paste ceases to be fluid and plastic which corresponds to the time at which the Vicats
initial set needle penetrate to a point 5 mm from the bottom of a special mold.
Final setting time the time required for the paste to acquire certain degree of hardness.
This corresponds to the time at which the Vicats final set needle makes an impression on the
paste surface but the cutting edge fails to do so.
In practice, the terms initial set&final set are used to describe arbitrary chosen time of
setting. Initial set indicates the beginning of a noticeable stiffening & final set may be regarded
as the start of hardening (or complete loss of plasticity).
ASTM C 150 prescribes a minimum initial setting time of 60 minutes and a maximum final
setting time of 10 hours for Portland cements.
Gypsum in the cement regulates setting time. Setting time is also affected by
cement fineness
w/c ratio
admixtures

5. Early Stiffening (False Set and Flash Set)
Early stiffening is the early development of stiffening in the working plasticity of cement
paste, mortar or concrete. This includes both false set and flash set.



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False Set
False-Set is a rapid development of rigidity of cement paste without generation of much
heat. This rigidity can be overcome & plasticity can be regained by further mixing without
addition of water. In this way cement paste restores its plasticity & sets in a normal manner
without any loss of strength.
False set is evidenced by a significant loss of plasticity, i.e. stiffening, without the evolution
of much heat shortly after mixing.
False set is a kind of stiffening caused by rapid crystallization of interlocking needle-like
secondary gypsum.

Flash Set (quick set)
Flash-Set is the immediate stiffening of cement paste in a few minutes after mixing with
water. It is accompanied by large amount of heat generation upon reaction of C3A with water.
Evidence by a quick and early loss of workability and it is usually accompanied by evolution of
considerable heat from the hydration of aluminates.

6. Compressive Strength
Compressive strength of cement is the most important property.
It is determined by ducting compression tests on standard 50 mm mortar cubes in
accordance with ASTM C 109.
In general, cement strength (based on mortar-cube tests) cannot be used to predict
concrete compressive strength with great degree of accuracy because of many variables in
aggregate characteristics, concrete mixtures, construction procedures, and environmental
conditions in the field.

7. Heat of Hydration
It is the quantity of heat (in joules) per gram of un-hydrated cement evolved upon complete
hydration at a given temperature.
The heat of hydration can be determined by ASTM C 186 or by a conduction calorimeter.
Fineness of cement also affects the rate of heat development but not the total amount of
heat liberated.


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The approximate amount of heat generated using ASTM C 186, during the first 7 days
(based on limited data) are as follows:
Type Name Heat of hydration (kj/kg)
I Normal 349
II Moderate 263
III High early strength 370
IV Low heat of hydration 233
V Sulfate resistant 310

8. Loss on Ignition (LOI)
Loss on Ignition (L.O.I.) is the loss in weight of cement after being heated to 1000C. It
indicates the prehydration or carbonation due to prolonged or improper storage of cement &
clinker.
If cement is exposed to air, water & CO
2
are absorbed & by heating the cement upto
1000C loose these two substances.
The test for loss on ignition is performed in accordance with ASTM C 114.
A high weight loss on ignition of a cement sample (between 900 to 1000C) is an indication
of pre-hydration and carbonation, which may be caused by:
Improper and prolonged storage
Adulteration during transport and transfer
Loss on ignition values range between 0 to 3%.

9. Density and Specific Gravity
Density is the mass of a unit volume of the solids or particles, excluding air between
particles. The particle density of Portland cement ranges from 3.10 to 3.25 Mg/m
3
, averaging
3.15 Mg/ m
3
.
For mixture proportioning, it may be more useful to express the density as relative density
(specific gravity). On an average the specific gravity of cement is 3.15.


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Storage of Cement
Cement is moisture-sensitive material; if kept dry it will retain its quality indefinitely.
When exposed to moisture, cement will set more slowly and will have less strength
compared to cement that kept dray.
At the time of use cement should be free-flowing and free of lumps.

Raw Materials of Portland Cement
1) Calcareous Rocks (CaCO
3
> 75%)
Limestone
Marl
Chalk
Marine shell deposits
2) Argillocalcareous Rocks (40%<CaCO
3
<75%)
Cement rock
Clayey limestone
Clayey marl
Clayey chalk
3) Argillaceous Rocks (CaCO
3
< 40%)
Clays
Shales
Slates
Portland cement is made by mixing substances containing CaCO
3
with substances containing
SiO
2
, Al
2
O
3
, Fe
2
O
3
and heating them to a clinker which is subsequently ground to powder and
mixed with 2-6 % gypsum.

Cement Manufacture
Quarrying The extraction of essential rocks or minerals from an open pit on the earths
crust.
Proportioning, Blending and Grinding
Formation of Clinker
Finish Grinding


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Kiln Pyro-processing device used to raise materials to a high temperature in a continuous
process.
Clinker the solid material produced by the cement kiln stage that has sintered into lumps or
nodules, typically of diameter 3-25 mm.

Portland Cement Production Steps
1) Raw materials are crushed, screened & stockpiled.
2) Raw materials are mixed with definite proportions to obtain raw mix. They are mixed
either dry (dry mixing) or by water (wet mixing).
3) Prepared raw mix is fed into the rotary kiln.
4) As the materials pass through the kiln their temperature is rised upto 1300-1600 C.
The process of heating is named as burning. The output is known as clinker which is
0.15-5 cm in diameter.
5) Clinker is cooled & stored.
6) Clinker is ground with gypsum (3-6%) to adjust setting time.
7) Packing & marketting.

Reactions in the Kiln
100C free water evaporates.
150-350C loosely bound water is lost from clay.
350-650Cdecomposition of claySiO
2
&Al
2
O
3

600Cdecomposition of MgCO
3
MgO&CO
2
(evaporates)
900Cdecomposition of CaCO
3
CaO&CO
2
(evaporates)
1250-1280Cliquid formation & start of compound formation.
1280Cclinkering begins.
1400-1500Cclinkering
100Cclinker leaves the kiln & falls into a cooler.
Sometimes the burning process of raw materials is performed in two stages: preheating
upto 900C & rotary kiln.




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Chemical Composition of Portland Cement
Portland cement is composed of four major oxides (CaO, SiO
2
, Al
2
O
3
, Fe
2
O
3
90%) & some
minor oxides. Minor refers to the quantity not important.
Oxide Common Name Abbreviation Approx. Amount (%)
CaO Lime C 60-67
SiO
2
Silica S 17-25
Al
2
O
3
Alumina A 3-8
Fe
2
O
3
Iron-oxide F 0.5-6
MgO Magnesia M 0.1-4
Na
2
O Soda N
0.2-1.3
K
2
O Potassa K
SO
3
Sulfuric Anhydride 1-3

CaOlimestone
SiO
2
-Al
2
O
3
Clay
Fe
2
O
3
Impurity in Clays
SO
3
from gypsumnot from the clinker
The amount of oxides in a P.C. Depend on the proportioning of the raw materials and how
well the burning is done in the kiln. The chemical composition is found by chemical analysis.
CaO (C), SiO
2
(S), Al
2
O
3
(A) & Fe
2
O
3
are the major oxides that interact in the kiln & form the
major compounds.
Portland Cement alone sets quickly so some gypsum is ground with clinker to retard the
setting time. However, if too much gypsum is included it leads to distruptive expansions of the
hardened paste or concrete.
Alkalies (Na
2
O & K
2
O) may cause some dificulties if the cement is used with certain types of
reactive aggregates in making concrete. The alkalies in the form of alkaline hydroxides can react


9 | Chapter 2 - CEMENT P a g e
with the reactive silica of the aggregate & resulting in volume expansion after hardening. This
process may take years.
Insoluble Residue is that fraction of cement which is insoluble in HCl. It comes mainly from
the silica which has not reacted to form compounds during the burning process in the kiln. All
compounds of P.C. is soluble in HCl except the silica.
The amount of I.R., determined by chemical analysis, serves to indicate the completeness of
the reactions in the kiln.
ASTM C 150 I.R. 0.75%

Compound Composition of Portland Cement (Clinker)
Oxides interact with eachother in the kiln to form more complex products (compounds).
Basically, the major compounds of P.C. can be listed as:
Name Abbreviations
Tri CalciumSilicate
C
3
S
Di Calcium Silicate
C
2
S
Tri Calcium Aluminate
C
3
A
Tetra Calcium Alumino Ferrite
C
4
AF

Tricalcium Silicate: 3CaO SiO
2
= C
3
S
Hardens rapidly and is largely responsible for the initial set and strength.
Dicalcium Silicate: 2CaO SiO
2
= C
2
S
Hardens rapidly and is largely responsible for the initial set and strength.
Tetracalcium Aluminoferrite: 4CaO Al
2
O
3
FeO
3
= C
4
AlF
Contributes to strength development because it is the first compound to hydrate.

The degree to which the potential reactions can proceed to equilibrium depends on:
1) Fineness of raw materials & their intermixing.
2) The temperature & time that mix is held in the critical zone of the kiln.


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3) The grade of cooling of clinker may also be effective on the internal structure of major
compounds.
There are also some minor compounds which constitute few %, so they are usually
negligible. Moreover, portland cement compounds are rarely pure.
For example in C
3
S, MgO & Al
2
O
3
replaces CaO randomly.
C
3
SALITE & C
2
SBELITE
Ferrite Phase: C
4
AF is not a true compound. The ferrite phase ranges from C
2
AF to C
6
AF. *C
4
AF
represents an average.

Methods of Determining Compound Composition
Each grain of cement consists of an intimate mixture of these compounds. They can be
determined by:
1) Microscopy
2) X-Ray Diffraction

However, due to the variabilities involved the compound composition is usually calculated
using the oxide proportions.
3) Calculations (Bouges Equations)

Assumptions in Bouges Equations
1) The chemical reactions in the kiln proceeded to equilibrium.
2) Compounds are in pure form such as C
3
S & C
2
S
3) Presence of minor compounds are ignored.
4) Ferrite phase can be calculated as C
4
AF
5) All oxides in the kiln have taken part in forming the compounds.






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Influence of Compound Composition on P.C.
P.C.+waterthe compounds in the cement undergo chemical reactions with the water
independently, and different products result from these reactions.

C
3
S C
2
S C
3
A C
4
AF
Rate of Reaction Moderate Slow Fast Moderate
Heat Liberation High Low Very High Moderate
Early Cementitious Value Good Poor Good Poor
Ultimate Cementitious Value Good Good Poor Poor

Hydration of Portland Cement
Hydration is the chemical reactions with water.
As water comes into contact with cement particles, hydration reactions immediately starts
at the surface of the particles. Although simple hydrates such as C-H are formed, process of
hydration is a complex one and results in reorganization of the constituents of original
compounds to form new hydrated compounds.
At any stage of hydration the hardened cement paste (hcp) consists of:
Hydrates of various compounds referred to collectively as GEL.
Crystals of calcium hydroxide (CH).
Some minor compound hydrates.
Unhydrated cement
The residual of water filled spaces pores.
As the hydration proceeds the deposits of hydrated products on the original cement grains
makes the diffusion of water to unhydrated nucleus more & more difficult. Thus, the rate of
hydration decreases with time & as a result hydration may take several years.
At the beginning of mixing, the paste has a structure which consists of cement particles with
water-filled space between them. As hydration proceeds, the gels are formed & they occupy
some of this space.
1cc of cement 2.1cc of gel
Gel Pores: 28% of the total gel volume have diameter of 0.015-0.020 m. (very small-loss or
gain of water is difficult)


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Capillary Pores: 12.5 m diameter, with varying sizes, shapes & randomly distributed in the
paste.
Volume of capillary pores decreases as hydration takes place. Water in capillary pores is
mobile, can not be lost by evaporation or water can get into the pores. They are mainly
responsible for permeability.
C
2
S & C
3
S: 70-80% of cement is composed of these two compounds & most of the strength
giving properties of cement is controlled by these compounds.
Calcium-Silicate-Hydrate (C-S-H gel) is similar to a mineral called TOBERMORITE. As a
result it is named as TOBERMORITE GEL
Upon hydration C
3
S & C
2
S, CH also forms which becomes an integral part of hydration
products. CH does not contribute very much to the strength of portland cement.
C
3
S having a faster rate of reaction accompanied by greater heat generation developes
early strength of the paste. On the other hand, C
2
S hydrates & hardens slowly so results in less
heat generation & developes most of the ultimate strength.
Higher C
3
Shigher early strength-higher heat generation (roads, cold environments)
Higher C
2
Slower early strength-lower heat generation (dams)
C
3
A: is characteristically fast reacting with water & may lead to a rapid stiffening of the paste
with a large amount of the heat generation (Flash-Set)-(Quick-Set). In order to prevent this rapid
reaction gypsum is added to the clinker. Gypsum, C
3
A&water react to form relatively insoluble
Calcium-Sulfo-Aluminates.
When there is enough gypsum ettringite forms with great expansion
If there is no gypsumflash-set
more gypsumettringite formation increases which will cause cracking
Also Calcium-Sulfo Aluminates are prone (less resistant) to sulfate attack & does not
contribute much for strength. The cement to be used in making concretes that are going to be
exposed to soils or waters that contain sulfates should not contain more than 5% C
3
A.
C
4
AF: The hydration of ferrite phase is not well understand. Ferrite phase has lesser role in
development of strength. The hydration products are similar to C
3
A. Alumina & iron oxide occur
interchangebly in the hydration products.






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Heat of Hydration
Hydration process of cement is accompanied by heat generation (exothermic).
As concrete is a fair insulator, the generated heat in mass concrete may result in expansion
& cracking. This could be overcome by using suitable cement type.
The heat of hydration of OPC is on the order of 85-100 cal/gr.
About 50% of this heat is liberated within 1-3 days & 75% within 7 days.
By limiting C
3
S & C
3
A content,heat of hydration can be reduced.

Heat of Hydration of Pure Compounds



Heat of Hydration (cal/gr)
C
3
S
120
C
2
S
62
C
3
A
207
C
4
AF
100

Strength of Cement
1. Direct Tension (Tensile Strength)
2. Flexural Strength (Tensile Strength in Bending)
3. Compressive Strength

Types of Portland Cement
Cements of different chemical composition & physical characteristics may exhibit different
properties when hydrated. It should thus be possible to select mixtures of raw materials for the
production of cements with various properties.
In fact several cement types are available and most of them have been developed to ensure
durability and strength properties to concrete.


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It should also be mentioned that obtaining some special properties of cement may lead to
undesirable properties in another respect. For this reason a balance of requirements may be
necessary and economic aspects should be considered.
Standard Types: these cements comply with the definition of P.C., and are produced by
adjusting the proportions of four major compounds.
Special Types: these do not necessarily couply with the definiton of P.C. & are
produced by using additional raw materials.

Standard Cements (ASTM)
Type I: Ordinary Portland Cement
This is the general concrete construction cement when the special properties of the other
types are not required. It is commonly used where concrete will not be exposed to severe
weathering conditions. Its uses include pavements and sidewalks, reinforced concrete buildings,
water pipes, culverts and masonry units.
Suitable to be used in general concrete construction when special properties are not
required.

Type II: Modified Portland Cement
This is used where resistance to moderate sulfate attack is important. This produces less
heat of hydration than Type I. Their use is commonly on piers, abutments and retaining walls.
They are used in warm weather concreting because of their lower rise in temperature.
Suitable to be used in general concrete construction. Main difference between Type I&II is
the moderate sulfate resistance of Type II cement due to relatively low C3A content (%8).
Since C
3
A is limited rate of reactions is slower and as a result heat of hydration at early ages is
less. It is suitable to be used in small scale mass concrete like retaining walls.

Type III: High Early Strength P.C.
This cement is used where an early strength gain is important and heat generation is not a
critical factor. This cement supplies the strength required in a shorter period of time.
Strength development is rapid.
It is useful for repair works, cold weather & for early demolding.
Its early strength is due to higher C
3
S & C
3
A content.


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Type IV: Low Heat P.C.
Strength development of this type is slower than of type I. It is primarily used in large mass
placements such as gravity dams.
Generates less heat during hydration & therefore gain of strengthis slower.
In standards a maximum value of C
3
S&C
3
A& a minimum value for C
2
S are placed.
It is used in mass-concrete and hot-weather concreting.

Type V: Sulfate Resistant P.C.
This type is primarily used where the soil or groundwater contains high sulfate concentration
and the structure would be exposed to severe sulfate attack.
Used in construction where concrete will be subjected to external sulfate attack chemical
plants, marine & harbor structures. C
3
A is limited to 5%.

Type IA, IIA, IIIA: Air Entrained Portland Cement
Only difference is adding an air-entraining agent to the cement during manufacturing to
increase freeze-thaw resistance by providing small sized air bubbles in concrete.

Special Cements
Portland Pozzolan Cement (P.P.C.)
P.P.C. Produces less heat of hydration & offers higher sulfate resistance so it can be used
in marine structures & mass concrete. However, most pozzolans do not contribute to strength
at early ages.
The early strength of PPC is less.

Portland Blast Furnace Slag Cement (P.B.F.S.C.)
This cement is less reactive (rate of gain of strength & early strength is less but ultimate
strength is same)
High sulfate resistance, suitable to use in mass concrete construction and unsuitable for
cold weather concreting.


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Note: Both P.P.C. & P.B.F.S.C. Are called blended cements. Their heat of hydration &
strength development are low in early days. Because upon adding water C
3
S compounds start
to produce C-S-Hgels & CH. The Ch & the pozzolanic material react together to produce new C-
S-H gels. Thats why the early strength is low but the ultimate strength is the same when
compared to O.P.C.

White Portland Cement
The selected raw materials of this type have negligible amounts of iron and manganese
oxides, and process of manufacture is controlled to produced white color. Its primary used is
for architectural concrete products, cement paints, tile grouts and decorative concrete
W.P.C. s made from materials containing a little iron oxide & manganese oxide.
To avoid contamination by coal ash, oil is used as fuel.
To avoid contamination by iron during grinding, instead of steel balls nickel-molybdenum
alloys are used.

High Alumina Cement
The raw materials for H.A.C. s limestone and Bauxite (Al
2
O
3
& Fe
2
O
3
)
These raw materials are interground & introduced in the kiln clinkered at 1600C. Then the
obtained material is ground to a fineness of 2500-3000 cm2/gr.
It is basically different from O.P.C. & the concrete made from this cement has very different
properties.
It has high sulfate resistance.
Very high early strength (emergency repairs)
About 80% of ultimate strength is obtained within 24 hours. But the strength is adversely
affected by temperature. The setting time is not as rapid as gain of strength.
Initial setting time is 4 hrs & final setting time is 5 hrs.

Air-Entraining Portland Cement
This cement contains air entraining materials integrated with the clinker during manufacture.
This provides the resulting concrete an improved resistance to scaling and freeze-thaw action.
Also concrete produced from this cement contains microscopic air bubbles evenly spaced.



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Masonry Cement
This cement contain Portland cements, air-entraining additives and materials selected for
their ability to impart workability, plasticity and water retention properties.

Standard Turkish Cements
TS 19 groups them into 3:
P.. 32.5 min. Comp. strength is 32.5 MPa in 28 days.
P.. 42.5 min. Comp. strength is 42.5 MPa in 28 days.
P.. 52.5 min. Comp. strength is 52.5 MPa in 28 days.
Special Cements are:
TS 20 Blast Furnace Slag Cement
C 32.5 Cruflu imento
TS 21 White Portland Cement BP 32.5-42.5
TS22 Masonry Cement, H 16 (Har imentosu)
TS 26 Trass Cement, T 32.5 (Trasl imento)
TS 640 Fly Ash Cement, UK 32.5 (Uucu Kll imento)

TS EN 197-1
CEM cements :
Binding property is mainly due to hydration of calcium-silicates.
CEM I Portland Cement
CEM II Portland Composite Cement
CEM III Portland Blast Furnace Slag Cement
CEM IV Pozzolanic Cement
CEM V Composite Cement
Mineral Admixtures :
K : Clinker
D : Silica Fume
P : Natural Pozzolan
Q : Calcined Natural Pozzolan
T : Calcined Shale
W : Class C Fly Ash


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V : Class F Fly Ash
L : Limestone (Organic compound < 0.5%)
LL : Limestone (Organic compound < 0.2%)
S : Granulated Blast Furnace Slag