LECTURE 1

CEMENT
Sep. 2015

Presented by: Mr. Milton McIntyre

Introduction
Brief History
Manufacture of Portland cement
Chemical Composition of Portland cement
Hydration of cement
Physical properties of Portland cement
Types of Portland cement
Test on properties of cement
Questions

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

Cement is a fine, powdery substance

that has adhesive and cohesive
properties when mixed with water and
is capable of bonding mineral
particles together.
The term cement is used to describe
the bonding material used with stones,
sand, bricks, building blocks, etc.

Cement is classified into two categories: hydraulic and non-hydraulic,

based on the way in which they set and harden.

Hydraulic cement - have the property of setting and hardening

under water by virtue of a chemical reaction.

Non-hydraulic cement do not have the property of setting and

hardening under water but require air to harden
(Lime CaCO3
CaO + CO2).

Cement used in the making of

concrete are considered to be
Hydraulic cements.

Pantheon in Rome
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Hydraulic lime: made from calcination of siliceous or

argillaceous (clay-rich) limestone. (used as stucco and plaster)
Natural cements (Roman cement): made from calcination of
naturally occurring argillaceous limestone and clay or shale
below sintering temp.
Type N used with Portland cement in general concrete
construction
Type NA air-entrained cement used like type N.
Inferior to Portland cement (not recommended for use where
strength is important.

Portland cement: most used cement and most important

hydraulic cement. Made by the mixing clinker with gypsum.
(2900F).
Blended cements: Mix of Portland cement with one or more
Supplementary Cementitious Material (SCM) like pozzolan or
slag additives.

Expansive cements: Contains a constituent that during

hydration, setting, or hardening, undergoes expansion but
remains sound and eventually develops strength. Used where
shrinkage cannot be tolerated.
Aluminous cements (high-alumina): Limestone and bauxite
are the main raw materials. Used for refractory applications
(such as cementing furnace bricks) and certain applications
where rapid hardening is required (high-early strength - sets
and harden within 48hrs). (2900F). Sensitive to high temp.
(reduced strength when moist)

Special Portland cements

White Portland cement
Colored cements decorative purposes
Oil-well cements slow setting used to seal deep wells
Regulated cements rapid setting or hardening used in the
manufacture of blocks, pipes, pre-stressed and precast
concrete also patch works.
Waterproofed cement made with water repellant to
reduce permeability.
Hydrophobic cements made with water-repellant materials
used to prolong the life of cement during storage (shipment)

Ancient Egyptians used calcined impure gypsum to make cement

materials.
Greeks and Romans used calcined limestone and later added
lime and water, sand, crushed stone and brick or broken tiles
(lime mortar).

For underwater construction they mixed lime and volcanic ash or

finely grounded burnt clay tiles (known as Pozzolanic cement).
Named after the village of Pozzuoli, Mt. Vesuvius, where the
volcanic ash was found.
The term Pozzolanic cement is still used today to describe
cements obtained by the grinding of natural materials at
normal temperature.
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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It was not until the eighteen century that John Smeaton, the first
to understand the chemistry of hydraulic lime (obtained by
burning a mixture of lime and clay), discovered that the best
mortar was produced when pozzolana was mixed with limestone
containing considerable proportions of clayey matter.

James Parker developed what was referred to as the Roman

cement. This was another type of hydraulic cement obtained by
calcining argillaceous limestone, patented as Portland cement by
Joseph Aspdin in 1824.
This cement was prepared by heating a mixture of finely-divided
clay and hard limestone in a furnace until CO2 was driven off.
(no clinkering)
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

Brief History of Portland Cement

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Modern cement prototype was first made in 1845 Isaac Johnson.

He burnt a mixture of clay and chalk at higher temperatures until
clinkering, allowing the reactions necessary for the formation of
strongly cementitious compounds to take place.
The name Portland cement was so called due to the
resemblance of the colour and quality of the hardened cement to
Portland stone - a limestone quarried in Dorset, England.
The term Portland cement is still used world wide today to
describe cement obtained by intimately mixing together
calcareous and argillaceous , or other silica, alumina and iron
bearing materials and burning them at clinkering temp and
grinding the resulting
clinker.
Prepared by: Mrs. Barbara A. Cooke Aug.13, 2010

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Modern Portland cement is made Essential ingredients are:

Lime (CaO)
from a mixture of natural
Silicon Dioxide (SiO2)
argillaceous and calcareous
Aluminum Oxide (Al2O3)
materials.
Iron (Fe2O3)
Magnesium (MgO)
Gypsum (Ca(SO4)2(H2O))
Found in nearly every country

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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The manufacture of cement consists essentially of grinding the raw

materials, mixing them intimately in certain proportions and burning
in a large rotary kiln at temperatures between 1400 and 1600 C,
where the raw material sinters and partially fuses into balls known
as clinker.
The clinker is cooled and ground to fine powder, with some gypsum
added, and the resulting product is the commercial Portland cement
so widely used throughout the world.

The mixing and grinding of the raw materials are done mainly by
one of two processes, wet or dry. The method of manufacture
depends largely on the hardness of the raw materials used and on
their moisture content.
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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http://www.youtube.com/watch?v=n-Pr1KTVSXo&feature=player_detailpage

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Abbreviation notation: C = CaO, S = SiO2, A = Al2O3, F = Fe2O3.

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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Minor compounds are :

Magnesium Dioxide (MgO)

Titanium Dioxide (TiO2)
Manganese (III) Oxide (Mn2O3)
Potassium Oxide (K2O)
Sodium Oxide (Na2O)
Sulphur Oxide (SO3)

K2O and Na2O are the main ones of concern and are called
alkalis, which cause disintegration and affect rate of strength
development in concrete.
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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The presence of alkalis in Portland cement has these main effects;

It increases the early strength development and reduces the
long-term strength development of a cement paste.
It also increases the alkalinity (pH level) of a fresh cement
paste, which may cause dermatitis or burns in the human skin.
It also reacts with some alkalis reactive aggregate, which can
cause concrete to deteriorate.

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C3S and C2S are mainly responsible for the strength and
durability properties of the cement and the C3A and C4AF
contents need to be strictly controlled as the C3A content
particularly affects the ability of the cement to resist sulphate
attack.
C3S hardens rapidly and is responsible for the initial set and
early strength, while C2S hardens slowly and contributes
largely to strength increase at ages beyond one week.
The ratio of C3S to C2S helps to determine how fast the cement
will set, with faster setting occurring with higher C3S contents.
Prepared by: Mrs. Barbara A. Cooke

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C3A releases large amounts of heat during the first few days
of hardening. Cements with a lower C3A content promote
resistance to sulphates.
C4AF acts as a flux in the burning of clinker by reducing the
clinkering temperature. It hydrates rapidly but contributes very
little to strength.
The ferrite phase causes the brownish gray colour in cements
and is often used for aesthetic purposes.

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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C3S = 4.07(CaO) 7.60(SiO2) 6.72(Al2O3) 1.43(Fe2O3)

2.85(SO3)
C2S = 2.87(SiO2) 0.75(3CaO.SiO2)
C3A = 2.65(Al2O3) 1.69(Fe2O3)
C4AF = 3.04(Fe2O3)

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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Varying the proportions of the main compounds in cement can

result in different chemical properties suitable for various
applications.

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

 Type I - no special characteristic requirements and is used in

general construction applications.
Type II - has moderate sulphate resistance and heat of
hydration. This type of cement is used mainly for structures built
in hot environments, or in soil or water high in sulphate, such as
drainage systems, floor slabs and foundations.
Type III - cement has applications requiring strength at an early
stage, as it develops strength soon after pouring.
Type IV - is useful in limiting heat caused by hydration and is
therefore used in massive concrete structures, such as dams.
Type V - has a high sulphate resistance, which is best used to
resist that chemical radical in soil or water.
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Blended hydraulic cement consists of a mixture of either OPC and

Pozzolan or OPC and ggbs, combined during or after the grinding
process of manufacture.
The use of blended cements in concrete:

reduces mixing water requirements

Improve strength performance in some cases
reduce bleeding
reduce energy cost
improves finishability and workability
enhances sulphate resistance
inhibits alkali-aggregate reaction
reduces heat evolution during hydration, thus moderating the
occurrences for Prepared
thermal
cracking.
by: Mrs. Barbara A. Cooke Aug.13, 2010

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Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

There are two main types of blended cements; they are as follows:
Type 1S Portland-Blast Furnace Slag cement
Type 1P Portland Pozzolan cement
Type 1S cement is an intimate blend of Portland cement and
finely ggbs.
Slag is obtained as a waste product from the manufacture of pig
iron.
It varies greatly in composition and physical structure depending
on the steel making processes used and the method of cooling of
the slag.

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Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

The slag cement can be produced in three ways:

a) it may be used directly as a raw material with limestone (the
conventional method use in the dry process)
b) it may be used on its own with the presence of an activator or
starter as a cementitious material (ggbs)
c) it may be used by mixing Portland cement with dry ggbs
(either by inter-grinding with clinker and gypsum or by dry
blending of the powders).
Each method of production produces a different class of blastfurnace cement as each will contain a different range of
proportions of slag expressed as a percentage by mass

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Type 1
OPC

Type 1S
Slag

Type 1P

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Hydration is the term given to the chemical reaction that take

place when cement comes in contact with H2O. Either by true
hydration or hydrolysis.
In the presence of water the silicates and aluminates in cement
form products of hydration which in time produce a firm hard
mass.

The products of hydration of cement have a very low solubility

in water. The hydrated cement bonds firmly to the un-hydrated
cement.
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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Hydration of cement is a continuous process and can take years

to complete.
The main products of hydration are classified as calcium
silicate hydrate (C3S2H3) and tricalcium aluminate hydrate
(C3AH6)

The C3S (alite) and C2S (belite), hydrates to form C3S2H3

described as C-S-H
2C3S + 6H C3S2H3 + 3Ca(OH)2
2C2S + 4H C3S2H3 + Ca(OH)2
The C3A compound hydrates to form C3AH6 described as
C-A-H
C3A + 6H C3AH6
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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The progress of hydration of cement can be determined by

different means, such as the measurement of:
1.
2.
3.
4.
5.

The amount Ca(OH) 2

The heat evolved by hydration
The specific gravity of the paste
The amount of chemically combined water
The amount of un-hydrated cement present (using X-ray
quantitative analysis)
6. The strength of the hydrated paste

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

Physical Properties of Cement

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Setting time
Consistency
Fineness
Soundness
Compressive strength
Density
Heat of hydration
Loss on ignition
Insoluble residue

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Setting is the term used to describe the stiffening of cement

paste after it has been mixed with water. This is often confused
with 'hardening' but setting and hardening are two different
things.
Hardening is the process of strength growth and may continue
for weeks, months, or even years after the concrete has been
mixed and placed.
Hardening is due largely to the formation of calcium silicate
hydrates as the cement paste hydrates over time.
Setting is due to early-stage calcium silicate hydrate (C3S2H3)
formation .
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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The terms 'initial set' and 'final set' are arbitrary definitions of
stages of setting (early and later set) of cement. The initial
setting of cement is as a result of the rapid hydration of C3S and
the final set results from the slow rate of hydration of the C2S
compound.
Even though C3A reacts readily with H2O to form calcium
aluminate hydrate crystals, the addition of gypsum retards this
formation allowing C3S to set first.
If C3A was allowed to set first, the calcium aluminate hydrate
crystals formed would be very porous and that would adversely
affect the strength characteristics of the cement paste.
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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The setting of cement paste is also affected by temperature.

At low temperatures setting is retarded (set slower).
In temperatures higher than 30C (85F), the rate of the setting
of cement may increase with time; therefore care must be
taken to control the temperature of concrete for maximum
strength development.

Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

False Set
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False set is the term used to describe the abnormal premature

(early) stiffening of cement within a few minutes of mixing with
water.
During this occurrence no considerable heat is evolved.
The plasticity of cement paste that experience false setting can
be easily restored without affecting the strength, by remixing
without the addition of water until normal setting has occurred.
False setting maybe as a result of dehydrated gypsum being
mixed with clinker that is too hot. It could also be caused by
the association with the alkalis present in cement.

Flash set
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Flash set is the term used to describe the violent reaction of

pure Tricalcium Aluminate (C3A) with water, which occurs when
insufficient gypsum is added to Portland cement.
This reaction causes a rapid (immediate) hardening of the
cement paste usually with the production of considerable
amount of heat.
Unlike false setting, the plasticity of flash set cement paste
cannot be restored by further mixing, without the addition of
water.

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Standard consistency
This determines the water content for any
given cement required to produce a neat
paste of a standard consistency (specified
resistance to penetration by a standard
plunger) [61mm).
Setting time
This test determines the initial & final setting
times of a cement paste, by observing the
penetration of a needle (Vicat) into a cement
paste of standard consistence until it reaches
a specified value (51mm).
Prepared by: Mrs. Barbara A. Cooke Aug.13, 2010

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Fineness is the term use to describe the size of the cement grains.
A change in the fineness can cause variations on the strength of
cement and by extension in concrete.
The fineness affects the heat release and the rate of hydration.
The rate of hydration of cement starts at the surface of the
cement particles and it is this surface area that represents the
cement availability for hydration.

Greater cement fineness or surface area, increases the rate at

which cement hydrates and accelerates strength development
over time.
Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010

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Finer cements also leads to a stronger reaction with alkalireactive aggregates (higher shrinkage and cracking).
The quantity of gypsum required to be added in cement
increases for cements having finer particles to ensure adequate
retardation of C3A hydration.
An increase in the fineness of cement particles also has an effect
on the water requirement for a cement paste to reach standard
consistency. The water required for consistency decreases as the
fineness of cement increases up to approximately 4000 cm2/g.
The reverse occurs for particle sizes finer than approx.
4750cm2/g (ASTM, 1970).
The minimum surface area for a typical Portland cement grain
when measured using the Blaine method is given as 280 m2/kg
(2800 cm2/g).

Fineness (gran size)

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Blaine apparatus

Wagner turbidmeter

Soundness of cement
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Soundness is the ability of hardened cement paste to retain its

volume after setting. This test determines the extent of
expansion of any given hardened cement paste. The term
expansion refers to a change in volume of paste after it has
set.
Such expansion may take place due to the delayed or slow
hydration, or other reaction of free lime, magnesia (excess
periclase dead-burnt crystalline MgO) and calcium sulfate
(excess gypsum) present in hardened cement.
Cement which undergoes expansion is considered as unsound.
Le Chatelier or Autoclave apparatus is used to conduct this test.

Autoclave Expansion

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Le Chatelier mould set

Strength of cement
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This test determines the

mechanical strength of
hardened cement-sand mortar
or concrete of specific
proportions at a given age
(usually 3, 7 and 28 days)
under strictly controlled
conditions.

There are different forms of

strength tests: tension, direct
compression and flexure.

Density of cement
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The relative density (specific gravity)

of cement is a measure of the weight
of a unit volume of the solids, to that of
the weight of an equal volume of
water.
It is particularly useful in connection
with the design and control of concrete
mixtures.

A Le Chatelier flask is used to observe

the displacement of Kerosene when a
known mass is introduced.

Heat of Hydration (HOH)

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This refers to the amount of heat generated when cement

reacts with water. The heat of hydration is the result of an
exothermic chemical reaction between cement and water.
HOH is measured as the quantity of heats of solution of unhydrated and hydrated cement, J/kg, in a mixture of nitric and
hydrofluoric acids at a given temperature: the difference
represents the heat of hydration.
HOH is influenced by the chemical composition of the cement
(C3S &C3A), cement content, water/cement ratio, fineness,
admixtures and curing temperature. Any variation in one of
these factors may cause an increase in the heat of hydration.

Loss on Ignition (HOH)

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The loss on ignition of PC is a test used

to show the extent of carbonization
and hydration of free lime and free
magnesium due to the exposure of
cement to the atmosphere.
It is determined by heating a cement
sample of known mass to
approximately 1000C until a constant
mass is obtained and the loss of mass
calculated.
A high loss on ignition may be cause by
improper and prolonged storage
during transport and transfer.

Insoluble Residue
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IRs are non-cementing materials that are present in Portland

cement.
It is measured to show the extent of adulteration of cement
which is largely as a result of impurities in gypsum.
It is determined by treating a sample of cement with
hydrochloric acid.
The presence of insoluble residues in the excess of 7% by mass
can reduce the compressive strength of cement mortar by as
much as 11.5% during the early ages.

Reading Assignment
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Read-up on Concrete Aggregates for

next week.

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Prepared by: Mrs. Barbara A. Cooke

Aug.13, 2010