Materials for Civil Engineering

Spring Semester
2008-2009
Ch 3- Cements
Definition and types of Cements
Portland Cements
History & Production
Raw Materials
Manufacture
Composition
Properties of the main
compound
Types of Portland Cement
Properties of Portland Cement

Prof.Mufid Samarai
 HISTORICAL BACKGROUND OF CEMENT
The use of cementing materials dates back to several hundred years.
Babylonians, Egyptians, Romans and Greeks have used at that time
cementing materials in one form or another. Egyptians have used calcined
impure gypsum to grout the space between the huge blocks of stone in
pyramids. Romans and Greeks have used certain volcanic deposits mixed
with lime and sand for construction.

The earliest cementing material is hydraulic lime. This when slaked and mixed
with sand yields lime mortar which is a cementing material. Mortars of high
quality have been widely used in famous forts, monumental structures, and
famous temples In 18th Century ,

Natural cement were produced from indigenous (local) materials in England ,

and later on in France and America.

It is in the 18 th centuries, that a British Engineer john Smeaton showed that a

hydraulic lime can be prepared not from pure hard limestone but from
limestone which contained a considerable amount of clayey matter.

The invention of modern Portland cement may be attributed to Joseph

Aspadin, an English brick-layer, in 1824. He was the first to realize the
importance of using high temperatures in the manufacture of cement.
Prof.Mufid Samarai
• Portland cement world consumption is
reaching 1.6 billion tones and each ton of
Portland cement clinker is accompanied by
the release of 1 ton of carbon dioxide.

• This is why it is estimated that about 7% of

the world carbon dioxide emission is
attributed to the Portland cement industry .
16
14
Cement in million Tons

14
12
12 10
10 9
8
6 6
6 5
3.8 4
4
2
0
1992 1993 1994 1995 1996 1998 2000 2003 2005
Year
Prof.Mufid Samarai
United Arab Emirates: Production of Portland Cement.
 Types of Cements
Cements: A material which possesses very good adhesive and cohesive
properties which make it possible to bond with other materials to form a
compact mass. That is cement is a material which possesses
cementitious properties. They are divided into two groups:

Hydraulic Cement: Sets and Hardened under water. Ex: Hydraulic Lime,
Portland Cements, Pozzolan, Slag, Natural……..

Nonhydraulic Cements: Does not set and Hardened under Water. It

requires air to hardened. Ex:Lime

Portland Cements: Is one of the most widely used materials in

conjunction with other materials to form
1- Concrete: Cement, Water, sand, gravel
2- Mortar: Cement, water, sand, and Lime
3-Plaster: Cement, water, Sand
4- Grout: Cement, Water, Silica Sand

Prof.Mufid Samarai
 Manufacture of Portland Cements
Raw Materials of Cements consist of:
1-Calcareous (CaCO3 > 75 %) ex: Limestone, Chalk, Shell
2- Argillocalcareous ( CaCO3 = 40- 75 %) ex: Clayey Limestone, Chalk, and
3- Argillaceous (CaCO3 < 40 %) ex: Slate, Shale, Clay
Impurities in limestone: are magnesia, silica, iron and alakalies

These ingredients are mixed in the

proportion of two parts calcareous and one
part argillaceous.

DRY PROCESS :They are crushed in a ball

mill in a dry state
WET PROCESS : mixed with water

Prof.Mufid Samarai
Manufacture of Portland Cement

Prof.Mufid Samarai
 Constituents of Portland Cements
Main Constituents of Cements : Lime (CaO) 60-67%, Silica
(SiO2)17-25%, and Alumina (Al2O3) 3-8%, Iron oxide 0.5-6%,
Alkalies (K2O+Na2O) 0.2-1.3%, Magnesia 0.1-1%,SO3
Chemical Changes Occurring in Rotary Kiln
1) Free water evaporates gradually up to a temperature of 120 °C
2)Clay loses its chemically combined water (i.e. kaolin =
Al 2O3 2SiO2 2H2O) At 500°C
3) Magnesium carbonates decompose at 600 °C
MgCo3 Mg O + CO2
4) Calcium carbonate decomposes at 900 °C
CaCO3 Ca O + CO2
5)Around 1250 °C the liquid phase is developed.
6) At 1280 ° C the formation of the major constituents of cement
starts.
Prof.Mufid Samarai
 TYPES OF PORTLAND CEMENTS
By changing slightly the chemical composition it is possible to obtain cements exhibiting
different properties. Hence, cement can be manufactured to suit the desired properties. The
following are the types of Portland cements.

•Type I Normal or Ordinary (OPC), Used for general purposes at no Sever exposure Ex:
Building, pavement….
•Type II Moderate Portland Cement, used for general purposes where moderate Sulfate &
Heat Resistance is required Ex: massive structures, abutments, piers, retaining walls….
•Type III High – early Strength PC:used for general purposes when high early strength is
desired (< 7 days). Generates a lot of heat and advised not to be used in hot climate.
•Type IV Low- heat-of-hydration PC: used when low heat of hydration is required ( hot
Climate) and in casting of huge structures (Dams, Mat foundations..)
•Type V Sulfate resistance PC (SRC): used high sulfate from sea water and soil
•Types IA, IIA, IIIA Air entraining cement: same as type I, II and III respectively but used
in concrete to improve resistance for freezing and Thawing by forming air bubbles in the
paste.
•Other Types:White Portland cement,Colored cement,Natural cements,Super sulfate cement,Masonry
cement,Trief cement,Expansive cement,Oil well cement,Hydrophobic
Prof.Mufid Samarai cement, and Water proof
cement,High alumina cement,Sleeper cement
 Compound Composition of Portland Cement
1- Tricalcium Silicate ( Alite) 3CaO.SiO2 C3S

2- Dicalcium Silicate (Belite) 2CaO.SiO2 C2S

3- Tricalcium Aluminate 3CaO.Al2O3 C3A

4- Tetracalcium Alumino Ferrite 4CaO.Al2O3.Fe2O3 C4AF

Tricalcium Dicalcium Tricalcium Tetracalcium

Silicate Silicate Alumino Ferrite Aluminate
3CaO.SiO2 2CaO.SiO2 3CaO.Al2O3 4CaO.Al2O3.Fe2O3
Value C3S C2S C3A C4AF
Cementing Good good Poor Poor
Rate of Reaction Medium slow Fast Slow
Amount of
Heat Liberated Medium Prof.Mufid Samarai
Small large Small
 TYPICAL COMPOUND COMPOSITION FOR VARIOUS
PORTLAND CEMENTS
Compound Composition %
Types of
Portland Cement C3S C2S C3A C4AF

I. Normal 50 24 11 8
II. Moderate 42 33 5 13
III. High early strength 60 13 9 8
IV. Low heat 26 50 5 12
V. Sulfate resisting 40 40 4 9

Prof.Mufid Samarai
 BOGUE’S EQUATIONS
Based on the word R.H. Bogue it is possible to calculate the potential
composition of Portland cement.
BOGUE’S EQUATIONS for the percentages of main compounds in cement are
given as below. The symbols in brackets represent the percentage of the given oxide in
the total weight of cement.
C3S = 4.07 (CaO) – 7.60 (SiO2) – 6.72 (Al2O3) – 1.43 (Fe2O3) – 2.85 (SO3)
C2S = 2.87 (SiO2) – 0.754 (C3S)
C3A = 2.65 (Al2O3) – 1.69 (Fe2O3)
C4AF = 3.04 (Fe2O3)
As an example for the use of these equations, the following typical cement oxide
composition is given:
CaO 63%; SiO2 20%;Al2O3 6% Fe2O3 3% ; MgO 1.5%; SO3
2%; Alkalies 1%; L.O.I 2%; I.R. 0.5%
C2S = 16.6%; C3S = 54.1%; C3A = 10.8%; C4AF = 9.1%
The L.O.I (Loss on Ignition) term refers to the extent of carbonation and
hydration of free lime and free magnesia due to the exposure (or long age) of cement to
the atmosphere.
The I.R. (Insoluble Residue) term is a measure of adulteration (aging) of cement, largely
arising from impurities in gypsum. Prof.Mufid Samarai
 PROPERTIES OF PORTLAND CEMENT

1-Fineness: is a measure of the cement particle sizes. Finer cement

has more surface area than coarse one.thus the chemical reaction
of finer cement are faster and generate more heat which leads to
early strength cement. To measure fineness is measured by
Wagner turbidimeter or Blaine air permeability apparatus.

Prof.Mufid Samarai
 PROPERTIES OF PORTLAND CEMENT

HEAT OF HYDRATION

2- Heat of Hydration:is a measure of the amount of heat

generated when water and cement react.

Prof.Mufid Samarai
 Properties of Portland Cement
3-Seting of Cement:
When Portland cement is mixed with water to make a soft paste, it
becomes gradually less plastic, and finally rigid to withstand a definite
amount of pressure.
•The time at which the cement paste loses its plasticity after the
addition of water is known as initial setting time.
•
•The time corresponding to the paste becoming a hard mass is known
as final setting time.
•At the time of the initial set the temperature rises rapidly and at final
setting the temperature reaches a peak value. For ordinary Portland
cement the initial setting time should not be less than 1 hour, and the
final setting time should not be less than 10 hrs.
•. Vicat and Gillmore needles are used for testing the setting time.

Prof.Mufid Samarai
 3-Seting of Cement
• Flash Set
• If the gypsum content is not enough to react with C3A, then the excess C3A
would react with water too rapidly forming calcium aluminates which cause the
flash setting of cement paste within few minutes. A high rise in temperature is
accompanying it, without any possibility to regain the plastic nature of set
paste upon remixing.

• False Set
• It is an unusual set that takes place within few minutes after the addition of
water. It differs than the flash set by the very low evolved heat. This set is
controllable and the plastic nature of the set paste can be retained by its
remixing without any necessity for water addition, where it will reset normally
with no adverse effect on the compressive strength.
• Possible Causes:

• 1)The drying out of gypsum water, so that it is absorbed from mixing water.
• 2) Poor storage conditions cause the alkalies to react CO2 forming carbonates
which react with water and Ca(OH)2 to form CaCO3.
• 3)During long time storage the surfaces of cement particles become in touch
with atmospheric moisture.
•
Prof.Mufid Samarai
 Properties of Portland Cement
4-Soundness: is the measure of expansion of hardened cement paste.
• Unsoundness is caused by undue expansion of some of the constituents and expansion
will result in disintegration and cracks.

• Unsoundness is caused by the presence of Lime, and/or MgO, and/or excess gypsum in
the cement. After the paste has set, moisture penetrates into free lime and hydration
starts and the slaked lime occupies larger volume. Hence expansion takes place.

• Unsoundness due to the presence of MgO is similar to that of lime, while that due to the
presence of excess non-reacting gypsum is manifested by the formation of ettringite.

• Soundness is determined by the Le Chatelier apparatus

or by high pressure steam boiler (autoclave method)

Unsoundness may be reduced by:

1. thorough mixing,
2. fine grinding,
3. allowing the cement to aerate for several days,
4. limiting the MgO content to less than 0.5%, and
5. limiting the lime saturation folder Prof.Mufid
(L.S.F) toSamarai
0.66% <= L.S.F <= 1.0%
 PROPERTIES OF PORTLAND CEMENT
COMPRESSIVE STRENGTH OF PORTLAND CEMENT

5-Compressive Strength: is a measure of the compressive strength of

cement mixed with uniform silica sand.

Prof.Mufid Samarai
 GYPSUM ADDED TO CEMENT
GYPSUM is added, in a specified percentage, so that it may react with the aluminates (C3A)
upon early hydration to form calcium sulfoaluminates which are of low solubility and help in
retarding the rapid reaction of C3A. C3A . 3CaSO4 . 31H2O, C3A . CaSO4 . 12H2O

ADVANTAGES
Causes an expansion of fresh concrete, and that is preferable.
The reaction is over when the gypsum is depleted, that is an aid in controlling the reaction
It helps in reducing the voids in concrete, and thus the strength is increased.
It is considered as a grinding aid,

OPTIMUM GYPSUM CONTENT

According to Lerch, the potimum gypsum content is that content that provides higher
compressive strength, less drying shrinkage, and low expansion in water.

Factors Affecting Optimum Gypsum Content

C3A content, Cement Fineness, Alkalies (Na2O, K2O) content, Curing Temperature, Curing
time

Prof.Mufid Samarai
 TYPES OF PORTLAND CEMENT
HIGH ALUMINA CEMENT:
•Also known as aluminous cement or aluminate cement. This cement is used to resist the attack of
gypsum bearing water and chemical attack. This cement is different from OPC right from
manufacturer and has high Alumina content.
•Its raw materials are limestone or chalk and bauxite (aluminate bearing mineral). The chemical
composition of this cement is Al2O3 39%, CaO 38%, SiO2 6%, Fe2O3 10%, FeO 4% and little magnesia
and titania (TiO2).
•Very high strength but losses strength in the presence of heat and humidity.

PORTLAND BLAST-FURNACE CEMENT:

• This type of cement is made by intergrinding postland cement clinker and granulated blast-furnace
slag (a waste product in the manufacture of pig iron and is a mixture of lime, silica, and alumina) the
proportion of slag being limited to 65% of the weight of mixture.
•Fineness of it tends to be higher but even then the rate of hardening is somewhat slower during the
first 28 days, and adequate curing is essential.

WHITE PORTLAND CEMENT:

•The greyish color of OPC is due to the presence of iron oxide.
•The process of manufacturing white cement is the same but the amount of iron oxide is limited to less
than 1%. This is achieved by choosing suitable materials such as chalk and limestone having low iron
contents, and white clays. Such cement are Prof.Mufid Samarai
more costly. This cement forms the base for colored
cements. Colored cements are made by intergrinding 3-10 % pigments
EXPANSIVE CEMENT :

Concrete shrinks during hardening process. Constituents blended with normal

cements may be used to form a concrete which neither shrinks, nor expand.
A particularly useful application of expansive cements is in repairing works
The most common expanding agent is calcium sulfoaluminate, with optimum 5% .
More of agent reduces the strength.
Expansive cements are classified as:
i) Non-shrinking cements, in which the expansion just neutralizes the
shrinkage, expansion= 2 – 5 mm/m
ii) Slightly expansive cements, with expansion = 5 – 6 mm/m
iii) Medium expansive cements, with expansion = 8 – 10 mm/m
iv) High expansive cements, with expansion = 12-15 mm/m

Prof.Mufid Samarai
 TYPES OF PORTLAND CEMENT
WATERPROOF CEMENT:
Waterproof substances are added to OPC during grinding, the substances being calcium stearate,
aluminum stearate and gypsum treated with tannic acid.
OIL WELL CEMENT:
In drilling of oil wells, cement is used to fill the space between the steel lining tube and wall of the well
and to grout the porous strata to prevent water or gas from gaining access to the oil bearing data. Oil
wells are taken up to a depth of 6000 meters.
Cements which are normally used and must be capable of being pumped for up to about 3 hours when
subjected to pressure of up to 1400 kg/cm2 and temperatures of about 150 C.

Prof.Mufid Samarai
Prof.Mufid Samarai
 Summary and Keywords
Cements: Hydraulic & ex, Argillaceous (% CaCo3) ex
Nonhydraulic Cements Impurities in Limestone, PC
Portland Cements PC composition and properties of
Usage: Concrete, Mortar, C3S, C2S, C3A, C4AF
Plaster, Grout Types of Portland Cement: I,
Main Constituents of PC : II, III, IV, V, IA, IIA, IIIA
Lime, Silica, Alumina, Iron Properties of Portland Cement
Oxide, Alkalies, Magnesia Fineness, Soundness,Time of
History of PC: who and Setting, Compressive strength,
when was discovered Heat of Hydration, los of
ignition, Specific Gravity
World Production of PC
Raw Materials of PC: Next Chapter 3b
calcareous ( % CaCo3) ex, Fresh concrete
Argillocalacreous
(%CaCo3) Prof.Mufid Samarai
Prof.Mufid Samarai