Faculty of Architecture and Engineering

Civil Engineering Department

Lecture Notes

CEN2004-Materials of Construction
Chapter-3

Assoc. Prof. Dr. Pınar Akpınar

 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

Chapter-3 Portland Cement

Introduction:

Ancient Romans are known to be the first ones to use Concrete, which is one of the most popular
construction material all around the world. Concrete is made by mixing cement, water and aggregates
(fine and coarse). Binding property in concrete is due to Portland cement. Coliseum in Rome- in which
masonry was bonded by mortar, and Pantheon- also in Rome, having the world’s largest unreinforced
concrete dome, are two famous examples which have survived to this day with the cementitious
material still hard and firm.

Picture 3.1. Coliseum, Rome. Picture 3.2. Pantheon, Rome.

Romans also found that a cement made by adding crushed volcanic ash to pure lime could set under
water and this was used for the construction of harbors. Romans were able to produce different
cementitious materials for using in specific applications and in different situations

In 1759, Smeaton built the third Eddystone lighthouse in Southwestern England. He used a mix of
lime, clay and crushed slag from iron-making; this mortar was able to harden under water .

Later, Joseph Aspdin, who was a bricklayer in England, took out a patent in 1824 for "Portland
Cement". He produced a cement by firing finely-ground clay and limestone until the limestone was

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

calcined. The name “Portland Cement” was given originally due to the resemblance of the color and
the quality of the hardened cement to Portland stone- a clayey-limestone seen found in Portland Island
near England.

Manufacture of Modern Portland Cement

Portland cement (PC) used today is made primarily from calcareous materials such as limestone
(CaCO3) or chalk and from alumina and silica found as clay or shale. A raw mix is prepared from
these raw materials mainly including lime, alumina, silica, iron oxide and some other relatively minor
oxides, which later is burnt at clinkering temperature in “Rotary Kilns”. Raw materials of cement are
found nearly in all countries and cement plants operate all over the world.

The rotary kiln is a rotating cylindrical kiln which is slightly inclined with respect to horizontal. It has
a length up to 200m and a diameter of approx. 6m, with a long flame at one end. The raw mix is fed
into the kiln at the cool end and gradually passes down to the hot end called “clinker”, in which the
temperature rises up to 1500°C, then falls out of the kiln and cools down.

Picture 3.3. Rotary kiln used in cement manufacture

The product that comes out of the clinkering zone of the rotary kiln is called “clinker”. The clinker is
cooled and ground with the help of a cement mill, to a fine powder with some gypsum added. Addition
of gypsum adjusts setting time of PC. The resulting product is the commercial PC, so widely used
throughout the world.

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

Picture 3.4.

Chemical Composition of PC:

The raw materials used in the manufacture of PC consist of lime, silica alumina, iron oxide and some
other minorities.

Table 3.1. Approximate oxide composition for normal Portland Cement

Common Name Oxide Abbreviation Approximate

(in cement chemistry) %

Lime CaO C 60-67

Silica SiO2 S 17-25

Alumina Al2O3 A 3-8

Iron Oxide Fe2O3 F 1-5

Magnesia Mg O M 0.1-4

Alkalies Na2O N

K2O K 0.2-1.3

Sulfur Trioxide SO3 S 1-3

 Free Lime (Free CaO): Free Lime is undesirable since it hydrates much later than the other
compounds of cement. Besides, it causes a large volume expansion after its hydration, resulting in
disintegration of hardened concrete.

 MgO: Like free lime, MgO also causes detrimental expansion due to its late hydration

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

 SO3: It largely comes from gypsum, which is added to cement after its production. Gypsum is
added to prevent the immediate stiffening (flash set) of the cement paste.

 Alkali oxides (Na2O, K2O): A limit for alkali oxides is often specified for cement which are used
with reactive aggregates to prevent “alkali-aggregate” reactions, which results in disruptive
expansion.

-Loss on Ignition (LOI): Loss on ignition shows the extent of carbonation and hydration of free lime
and free magnesia due to exposure of cement to the atmosphere. LOI is determined by the loss of the
weight of a cement sample when heated at 1000 ºC.
ASTM & BS 12: LOI≤ 3%

- Insoluble Residue (IR): IR is a measure of adulteration of cement, largely arising from impurities in
gypsum. It is the fraction of cement that remains insoluble in HCl acid. It is a measure of
completeness of the reactions in the kiln.

ASTM: IR≤ 0.75%

BS 12-1951: IR ≤ 1.5%

All these compounds listed in the oxide composition table, interact at high temperatures in the kiln to
form a series of more complex products

Four compounds given below are usually regarded as the major constituents of cement:

Table 3.2. List of cement clinker compounds and their abbreviations in cement chemistry.
Name of the compound Oxide composition Abbreviation
Tricalcium Silcate 3CaO·SiO2 C3S

Dicalcium Silcate 2CaO·SiO2 C2S

Tricalcium Aluminate 3CaO·Al2O3 C3A

Tetracalcium Aluminoferrite 4CaO·Al2O3 ·Fe2O3 C4AF

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

Basic Information on the Clinker Compounds of PC

C3S: When it is mixed with water, it hardens very rapidly and it is largely responsible for initial set
and early strength. The early strength of PC concretes will be higher with increased percentages.

C2S: Hardens slowly and its effects on strength occurs at ages beyond 1 week.

C3A: Contributes to strength development in the first few days, because it is the first compound to
hydrate. However, it is the least desired component of PC because of its high heat generation and its
reactiveness with soils and waters containing “sulfates”. Cements, which are made with low C 3A
contents usually generate less heat and show greater resistance to expansion related problems caused
by sulfate attack.

C4AF: It presents in cement in small quantities. Compared to the other three compounds, it does not
affect the behavior significantly, however its presence may accelerate hydration of silicates.

Properties of Portland Cement

 Setting:
The term setting means stiffening of cement paste; it refers to a change from fluid to a rigid state.
“Initial set” occurs when noticeable stiffening starts (with a rapid rise in temperature) and “final
set” is the start of hardening (total loss of plasticity with a peak temperature). Setting time of
cement can be obtained by Vicat apparatus or with a Gillmore apparatus.

Picture 3.5. Vicat apparatus used to measure setting time of cement pastes

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

ASTM:

Initial setting time>45minutes & Final setting time >375 minutes

Factors affecting setting time of PC:

 Fineness of cement

 Composition of cement

 Water content of the paste

 Temperature and humidity

Very quick (in an undesired way) setting of cement may take place as either “flash set” or “false
set”.

Flash Set: is the rapid development of rigidity in a freshly mixed cement paste, usually
with evolution of considerable heat. It occurs when there is insufficient amount or no gypsum in
the cement. In this case C3A reacts with water very fast causing a high amount of heat liberation.
The paste becomes rigid in a very short time without gaining much strength.

 False Set: is the rapid development of rigidity in a cement paste without much
heat generation. If the paste is remixed (without the need of adding extra water), it
usually regain its plasticity, until it sets in a normally, without a loss of strength. The
causes of the false set are as the follows: 1-) dehydration of gypsum when interground
with too hot clinker. In such a case hemi hydrate or anhydrate are formed and when the
cement is mixed with water these hydrates form crystals of gypsum, resulting in stiffening
of the paste. 2-) Another reason can be the carbonation of the alkalies (if they are more
than the limits!) in the cement. During the storage these alkalies can be carbonated. Later
these alkali carbonates can react with portlandite in the cement paste, resulting in the
formation of CaCO3, which induces a rigidity of the paste.

 Heat of Hydration:
The hydration of cement is an exothermic reaction. The heat liberated by the reaction of water with
cement compounds is called heat of hydration. The heat of hydration of pastes of pure clinker
coumpounds are as the following:

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

Compound Heat of Hydration (cal/g)

C3S 120

C2S 62

C3A 207

C4AF 100

The amount of heat liberated in a cement paste is affected by the fractions of the compounds in the
cement. An ordinary Portland cement liberates a heat of hydration in the order of 85-100cal/g.

For common types of PC 50% of he total heat is liberated between 1-3 days and 75% in 7 days.

In large masses (e.g. dams) the heat generated during setting and hardening of the concrete is not
easily dissipated. Therefore, a rise in the temperature may result in expansion of the concrete mass.
The cooling and the contraction of the hardened concrete that will happen later may result in severe
cracking of the concrete mass.

The rate of heat liberation can be decreased by restricting the quantities of C 3A and C3S in the cement.

On the other hand, a high rate of heat liberation can be advantageous in certain cases such as in
concrete works during cold weather.

 Fineness:
“Fineness of cement” can be defined as the average size of the cement particles. A higher fineness
means a more finely ground cement where the particles are smaller.

Since the hydration starts at the surface of cement particles, it is the total surface area of cement that
represents the materials available for hydration. Hence, the rate of hydration depends significantly on
cement’s hydration. Increase in the fineness leads to an increase in the rate of hydration and therefore,
an increase in the rate of strength gain and heat evolution as well.
Finely grinded cement has both its advantages and disadvantages:

Advantages:

 Faster hydration
 Rapid hardening
 Higher early strength
 Less bleeding problems.

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

Disadvantages:
 More expensive
 Stronger alkali-aggregate reaction
 More shrinkage
 More gypsum should be added during the manufacture of PC.
NOTE: High fineness of cement also results in higher rate of heat evolution during hydration. This
can be a disadvantage or advantage depending on the conditions.

Fineness of cement is generally determined by Blaine Air Permeability Method. It is expressed in

terms of specific surface area of cement (cm 2/g). ASTM C150 states that the minimum fineness value
for an ordinaryPC should be 2800 cm2/g.

 Soundness:
Cement soundness is related to its volumetric stability after setting. The unsoundness of cement is
caused by undesirable expansion of some constituents after setting. The volume change
accompanied by expansion results in severe cracking and disintegration. The unsoundness is due
to the presence of free lime (CaO) and magnesia (MgO) in cement. Hydration products of these
compounds, Ca(OH)2 and Mg(OH)2, occupy a larger volume (i.e. yield expansion).

The soundness can be measured by Le Chatelier test or Autoclave test. Both of them measure the
length change before and after the test. The unsoundness can be reduced by limiting the free lime
and magnesia, fine grinding of the cement and thorough mixing of the paste.

TYPES OF CEMENTS:

According to ASTM: I)Portland Cements, II) Other Cements

According to EN: Different numbering for cement types (Please see page:

I. Portland Cements

 Type I- Ordinary Portland Cement (OPC):

Ordinary Portland cement (OPC) is used in general concrete construction work, when special
properties of the other cements are not needed (no sulfates sulfate attack risk, not very cold or not very
hot environments). It can be used for reinforced concrete buildings, for bridges, pavements, sidewalks,
concrete masonry units etc., if the mentioned risks do not present in the construction environment.
OPC is the most widely used cement.

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

 Type II-Modified Portland Cement:

This cement is used where moderately low heat generation is desirable or where sulfate attack of
moderate severity may occur. This cement has a rate of heat development which is lower than that of
Type I and higher than that of Type IV cement. So, it can be used where fresh concrete works should
be done in hot weather and also for some mass concrete works.
 Type III-High Early Strength (Rapid hardening) PC:
This cement gains strength rapidly because of a higher C 3S content and a higher fineness. This cement
may be useful when the formworks should be removed earlier for being used at another location, or
when the structure should gain enough strength for its completion at earlier ages Rapid–hardening
cement should not be used in mass concrete construction. However, it is useful when fresh concrete
works are needed to be carried out at low temperatures.

 Type IV- Low Heat Portland Cement:

This cement has lower C3S and C3A contents; so it has a low rate of heat of hydration and a slower rate
of strength development than that of OPC. It is beneficial for mass concrete works and when concrete
works are done in hot weather.

 Type V- Sulfate-resisting Cement:

This type of cement is used in structures where there is a high risk of sulfate attack. Sulfates may come
from soil, ground water, sea water, waste water and industrial effluents etc. Sulfate resistance is
achieved by limiting the C3A content.

II. Other Cement Types:

 Portland Blast-Furnace Slag Cement:

This type of cement is made by blending OPC with granulated blast-furnace slag. Blast–furnace slag is
a waste product in the manufacture of iron. Slag contains lime, silica and alumina. Slag hydrates
slowlier. The early strength of this cement is lower than that in OPC, where the later strengths of both
cements are similar. This cement is used in mass concrete due to its lower heat of hydration and in

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

sea-water constructions because of a better sulfate resistance. It is not suitable for cold weather
applications.

 Portland Pozzolan Cement:

Historically, pozzolans are the volcanic ashes found in Pozzuoli, Italy. This material is used since the
Roman times. Today, artificial pozzolans such as fly ash and silica fume are commonly used.

Pozzolans provide a lower cost, and a low rate of heat development. This kind of cement is especially
used in mass concrete constructions. Portland Pozzolan cement also provides sulfate resistance, so it
can be used in the sea sides.

 High- alumina Cement:

High-alumina cement (HAC) was developed at the beginning of this century initially to resist sulfate
attack. Limestone or chalk with bauxite are used as the raw materials of HAC.

HAC has a significantly higher rate of strength development: About 80% of its ultimate strength is
reached in 24 hours, and sufficient strength for removal of formworks is achieved at 6-8 hours. Due to
its rapid hydration, it has a very high rate of heat development. However, the strength and the
durability of HAC is observed to decrease drastically in the last decades. So, HAC is no longer used
for structural concrete, but it is still a valuable material for repair work of limited life and in temporary
works.

 Expansive Cement:
Expansive cements have the advantage of not yielding volumetric change due to the drying shrinkage,
so shrinkage cracks can be avoided in concrete. The use of expansive cement does not produce
shrinkless concrete. In the concretes made with expansive cement the expansion and the expected
shrinkage are compensating each other. Expansive cements are used in special applications such as
prevention of water leakage.

 White Portland Cement:

It is mainly used for architectural purposes. White cement is made from china clay, which contains
little iron oxide and manganese oxide, together with chalk or limestone free from impurities. Special
precautions should be taken while grinding the clinker to prevent contamination. The cost of white
cement is very high (twice of the cost of OPC). Hence, white concrete is often used as facings over
normal concrete surface.

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

Cement Types According to EN:

EN197-1:2000 Cement -Part 1: Composition, specifications and conformity criteria for common
cements

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 Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

References used for Chapter-3

 Concrete Technology, Neville A. M., & Brooks J. J., Prentice Hall, 2008.
 Properties of Concrete, Neville A. M., Prentice Hall, 2005.
 Concrete- Microstructure, Properties and Materials, Mehta P. K., Monteiro P. J. M., McGraw-
Hill, 2006.
 [Link]
 [Link]
 [Link]

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Dept. of Civil Engineering- CEN2004-Lecture Notes- Assoc. Prof. Dr. Pınar Akpınar

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