UNIT- 2: CEMENT & ADMIXTURES

Babylonians were perhaps the first to use clay as cementing material. In ancient
times stones have been invariably used as a construction material with lime as
the binder for construction of forts and defense structures. Egyptians have
used lime and gypsum as cementing materials in the famous Pyramids.

The calcareous rocks used by the Romans were either composed of

limestones burned in Kilns or mixtures of limestones and puzzolanic
materials ( volcanic ash, tuff ) combining into a hard concrete.

The natural cement is obtained by burning and crushing the stones containing
clay, carbonate of lime (CaCO3) and a little quantity of magnesia. The natural
cement is brown in color and is also known as Roman cement.

The artificial cement was invented by a mason Joseph Aspdin in England in

1824. He took out a patent for this cement and called it Portland cement
because it had resemblance in its color after setting, to a variety of sandstone
which is found in Portland in England.

The manufacture of Portland cement was started in England around 1825.

Belgium and Germany started the same in 1855. America started the same in
1872 and India was installed in Tamil Nadu in 1904.

PROPERTIES OF CEMENT:

It gives strength to the masonry works.

It is an excellent binding material.
It is easily workable
It offers good resistance to the moisture
It possesses a good plasticity.
It hardens early.
COMPOSITION OF ORDINARY CEMENT/ PORTLAND CEMENT: The ordinary
cement contains two basic ingredients namely, argillaceous (clay predominates )
and calcareous ( calcium carbonate predominates). A typical chemical analysis
of an ordinary cement is as follows:

Ingredient Oxide / % Range Function

composition
Lime CaO 62 60 65 Controls strength and soundness. Its
deficiency reduces strength & setting time
Silica SiO2 22 17 25 Imparts strength. Excess cause slow setting
Alumina Al2O3 5 38 Responsible for quick setting, if in excess,
it lowers the strength / weakness the cement
Calcium CaSO4 4 34
sulphate
Iron oxide Fe2O3 3 0.5 6 Gives colour, hardness & strength to the
cement
Magnesia MgO 2 0.5 4 Gives color, hardness. If in excess, it
causes cracks in mortar.
Sulphur SO3 1 12 A small amount of sulphur is useful in
making sound cement. If it is in excess ,
it causes cement to become unsound.
Alkalies (Na2O+K2O ) 1 0.1 0.4 These are residues and if in excess
cause efflorescence and cracking

Excess in quantity of ingredients cause unsound, prolonging of setting time.

However, the rate of setting of cement paste is controlled by regulating the
ratio SiO2 / (Al2O3 + Fe2O3).

USES OF CEMENT: Cement is widely used in construction of various

engineering structures. Following are various possible uses of cement:

Cement mortar for masonry works

Cement Concrete for laying floors, roofs, lintels, beams, stairs, pillars etc
Construction of important engineering structures such as Bridges,
Culverts, Dams, Tunnels, storage Reservoirs; Docks etc
Making Cement Pipes
Manufacture of precast pipes, dust bins, fencing posts etc..

ORDINARY PORTLAND CEMENT: The artificial cement is obtained by burning

at a very high temperature of a mixture of calcareous ( limestone ) and
argillaceous ( clay ) materials. The calcined product is known as the CLINKER.
A small quantity of gypsum is added to the clinker and it is then pulverized
into very fine powder which is known as the CEMENT. This cement is also
known as the normal setting cement or ordinary cement.
The Ordinary Portland Cement has been classified as 33 Grade ( IS269: 1989);
43 Grade ( IS 8112:1989) AND 53 Grade (IS 12669:1987). The physical
requirements of all these three types of cement are almost same except for
compressive strength and are as follows:

Grade
S.No Physical requirement 33 43 53
1 Fineness ( m2/Kg) 225 225 225
2 Soundness 10mm 10mm 10mm
3 Setting time ( minimum) 30 minitues 30 30
Setting time ( maximum ) 600 minitues 600 600
4 Compressive Strength
(MPa or Mega Pascals) not less than
72 hours ( 3 days ) 16 23 27
168 hours ( 7 days ) 22 33 37
672 hours ( 28 days ) 33 43 53

IS:10262 has classified the OPC grade-wise from A to F based on 28 day

compressive strength as follows:
Category Strength
A 32.5 37.5
B 37.5 42.5
C 42.5 47.5
D 47.5 52.5
E 52.5 57.5
F 57.5 62.5

MANUFACTURE OF CEMENT: Cement can be manufactured by using either

from natural cement stones ( in case of Roman cement, Puzzolana cement,
Medina cement etc ) or artificially ( Portland cement ) by using calcareous
and argillaceous materials.

Calcareous ( limestone, marl, chalk, marine shell ) and argillaceous ( clay, shale,
slate etc) materials are used in the manufacture of Ordinary or Portland
cement. From these materials, others like silica, iron-oxide, and small quantities
of other chemicals such as Na, K, S are obtained during the process of
manufacturing of cement. Cement can be manufactured either by dry process
or wet process.

DRY PROCESS ( Modern Technology ) : This process is adopted when the

raw materials are quite hard. The process is slow and the product is costly.

The raw materials of limestone and clay are first reduced in size of about 25 mm
in crushers. A dry air is then passed over these materials. These dried
materials are then pulverized into fine powder separately in the ball mills.
 Ball mill is a key equipment to grind the
crushed materials, and the ball mill is
widely used in powder-making production

All these materials are stored in hoppers / bins / silos and they are then mixed
in correct proportions.

Hoppers, bins and silos are used in the aggregate, cement,

chemical, mining and wastewater treatment industries for storing
many bulk materials.
Bins are used for storing smaller volumes of bulk materials.
Hoppers are similar to bins except with an open top. Silos are
typically designed for storing large volumes and are cylindrical in
shape with a cone.
Storage capacities up to 10,000 cubic feet can easily be
Bins handled with hoppers, bins and silos.
Fig: Hoppers / Silos

The product obtained after calcination at a temperature of about 1400 1500o C

in rotary kiln is called CLINKER.

The clinker is cooled rapidly to preserve the metastable compounds and their
solid solutions and then ground in Tube Mills where 2 3 % of gypsum is adding
added. The purpose of gypsum is to retard the setting of cement.
Generally, cement is stored in bags of 50 kg. A flow diagram is
shown in fig. of dry process

Rotary Kiln: The building material kiln is mainly used in cement industry, such as lime kiln, cement kiln.

The dry process has been modernized and it is widely used at present because
of competition in producttion; lesser consumption of power; automatic proper
temperature control ; advancement of instrumentation; computerization and quality.
Flow diagram of manufacturing of cement
WET PROCESS ( old technology ) : Wet process was used for the manufacture
of cement started from 1913 onwards and till early 1980. The operations
involved in the wet process of cement manufacture are mixing; burning and
grinding.

The crushed raw materials are fed into ball mill and a little water is added
to make a thick paste. This paste, usually contain about 14% of moisture is
dried and made ready for the feed of rotary kiln where it loses moisture and
forms into lumps or nodules.. These are finally burned at 1500 1600oC
where the nodules change to clinker at this temperature. Clinker is cooled
and then ground in tube mills. While grinding the clinker, about 3% of
gypsum is added. The cement is then stored in silos from where it is
supplied.

During the operation of ball mill; the steel balls in it pulverize the raw
materials which form a slurry with water. This slurry is passed to silos (storage
tanks), where the proportioning of the compounds is adjusted to ensure desired
chemical composition.

The chief advantages of the wet process are the low cost of grinding the
raw materials, the accurate control of composition and homogeneity of the
slurry, and the economical utilization of fuel.

Why gypsum is to be added during the manufacture of cement ???

The gypsum is the hydrated sulphate of calcium and its chemical composition
is CaSO4 2H2O. It contains 79.1% calcium sulphate and 20.9% water.

When gypsum is added to 205 degree centigrade, its specific gravity increases
from 2.3 to 2.95 due to loss of water. As a binding material, the gypsum
quickly sets and hardens. It is soluble in HCl but insoluble in H2SO4.

Gypsum has a number of valuable properties like bulk density,

incombustibility, good absorbing capacity, good fire resistance, rapid drying
etc.. Because of all these properties, gypsum is used in the manufacture of
cement to increase its setting time.

PLASTER OF PARIS : Plaster of Paris is a calcium sulfate hemi-hydrate (CaSO4,

H2O) derived from gypsum by firing this mineral at relatively low temperature of
160 170oC and then reducing it to powder. In ancient times, in Paris, all the
walls of wooden houses were covered with plaster as protection against fire. Since
then the plaster was named as Plaster of Paris.
POP powder is mixed with water to form a paste which releases heat and then
hardens once dried under normal temperature. Unlike mortar and cement, plaster
remains quite soft after drying, and can be easily rubbed or scratched with metal
tools or even sandpaper. On heating, further upto a temperature of about
20oC, the entire water is driven off and the resulting product is known as the
Gypsum Anhydrite.

FIELD TESTS & LAB TESTS FOR CEMENT: In engineering construction,

the main qualifications of a cement are permanency of structure; strength and
a rate of setting. To determine these qualifications, both physical and
chemical tests are made, the former on account of importance more often
than the other. However, following field tests are to be carried out to
ascertain the quality of cement:

The cement should feel smooth when touched in between fingers.

If it is felt rough, it indicates adulteration with sand.
If hand is inserted in a bag of cement, one should feel cool and not
warm.
If a small quantity of cement is thrown in a bucket of water, it should sink
and should not float on the surface.
The color of cement should be uniform and the typical cement color is
grey.
The cement should be free from any hard lumps. Such lumps are formed
by the absorption of moisture from the atmosphere.

As a result of long experience the physical tests which have come into
general use in determining the acceptability of cement are:

1. Soundness
2. Strength:
3. Consistency Test and
4. Fineness.

SOUNDNESS: It is an important test to assure the quality of cement since

an unsound cement produces cracks, disintegration and leading to failure
finally. The purpose of this test is to detect the presence of uncombined lime
in cement. This test is ensured by limiting the quantities of free lime and
magnesia ;which slake slowly causing change in volume of cement ( known
as unsound).

Some of the aggregates may be chemically unstable with certain chemical

constituents react with alkalies in cement which may cause abnormal
expansion and cracking of concrete.
Soundness of cement may be tested by Le-Chatelier method or by authoclave
method. For OPC (Ordinary Portland Cement ) ; RHC ( Rapid Hardening Cement
); LHC (Low Heat Cement); PPC (Portland Puzzolana Cement); soundness is
limited to 10 mm whereas HAC ( High Alumina Cement ); SSC (Super
Sulphate Cement ) it should not exceed 5 mm.

STRENGTH: Cement is tested for Compressive and Tensile strength

because the cement hydrates when water is added to it. So, the strength of
mortar and concrete depends upon the type and nature of cement.

Hydration of cement: T h e c h e m i c a l r e a c t i o n b e t w e e n c e m e n t
a n d w a t e r i s k n o w n a s hydration o f c e m e n t

Conditions affecting strength:

Cement is very strong at early stages if a high lime or high alumina
content is present.
Gypsum and Plaster of Paris in small percentages also tend to
increase the strength slightly but when present in quantities more than
3%, these substances provide variable effects.
The strength of cement is greatly also influenced by the degree of
burning, the fineness of grinding.
An under burnt cement is likely to be deficient in strength.

Compressive Strength.: Compressive Strength is the basic data required for

mix design. By this test, the quality and quantity of concrete can be
controlled and the degree of adulteration is checked.

The compressive strength at the end of 3 days, 7 days and 28 days are
given in table and the results are expressed in N/mm2

Type 3 days 7 days 28 days

OPC 16.0 22.0 33.0
PPC 16.0 22.0 33.0
LHC 10.0 16.0 35.0
RHC 27.5 - -
HAC 35.0 - -

Tensile Strength: Tensile Strength may be determined by Briquette Test

method or by Split Tensile Strength Test.

The Tensile strength of cement affords quicker indications of defects in the

cement. However, the test is also used for the determination of rapid
hardening cement. The tensile strength at the end of 3 days and 7 days for
OPC is 2.0 N / mm2 and 2.5 N/ mm2 respectively.

( 2.0 N / mm2 = 20 kg / cm2 ) ( 2.5 N/ mm2 = 25 Kg / cm2 )

Consistency Test: This is a test to estimate the quantity of mixing water to

form a paste of normal consistency.
Vicat apparatus is used to determine the consistency
test. 300 gms of cement is mixed with 25% water. The
paste is filled in the mould of Vicats apparatus and
the surface of the filled paste is smoothened and
leveled. A square needle 10 mm x 10 mm attached to
the plunger is then lowered gently over the cement
paste surface and is released quickly. The plunger
pierces the cement paste. The reading on the
attached scale is recorded. When the reading is 5
7 mm from the bottom of the mould, the amount
of water added is considered to be the correct
percentage of water for normal consistency.

FINENESS: This test is carried out to check proper grinding of cement. In

other words, the degree of fineness of cement is the measure of the mean
size of the grains in it.

There are 3 methods for testing fineness:

The Sieve method -- using 90 micron sieve

The air permeability method ( Lea Nurse and Blains method )
The sedimentation method ( Wagner Turbidimetre )

SIEVE METHOD: 100 gms of cement sample is taken and air set lumps if
any, in the sample are broken with fingers. The sample is placed on a 90
micron sieve and continuously sieved for 15 minitues. The residue should not
exceed the limits specified below:

OPC 10% of residue by weight

RHC 5% of residue by weight
PPC 5% of residue by weight

Air Permeability method: In this process, a cement sample of 20 mm height is

placed in the Lea and Nurse apparatus and air pressure is applied. A
manometer is connected to the top and bottom of the permeability apparatus
and the pressure is so adjusted.
The specific surface (Surface area is the measure of how much exposed area a
solid object has, expressed in square units ) for various cements should be as
specified in table:

Type of Specific
cement surface not
less than
cm2/gms
OPC 2250
RHC 3250
LHC 3250
PPC 3000
HAC 2250
SSC 4000

Fig: Permeability Apparatus

Wagner Turbidimetre method: This method is to be adopted to estimate the

surface area of one gram of cement. The cement is dispersed uniformly in a
rectangular glass tank filled with kerosene. Then, parallel light rays are
passed through the solution which strike the sensitivity plate of a
photoelectric cell. The turbidity of the solution at a given instant is measured
by taking readings of the current generated by the cell.

By recording the readings at regular intervals while the particles are falling in
the solution, it is possible to secure information regarding the grading in
surface area and in size of particle. Readings are expressed in sq cm per
gms.
ADMIXTURES: Admixture is defined as a material, other than water, aggregates,
cement, that is added to the concrete batch immediately before or during mixing.
Admixtures change properties of the concrete such as colour, curing, temperature
range and setting time.

Concrete is being used for wide varieties of purposes to make it suitable in

different varieties of purposes to make it suitable in different conditions.
Ordinary concrete may fail to exhibit the required quality performance or
durability under different conditions. In such cases, admixture is used to
modify the properties of ordinary concrete so as to make it more suitable for
any situation.

Classification of admixtures as given by MR Rixom is:

Plasticizers ( Water Reducers )

Superplasticizers ( High Range Water Reducers )
Retarders
Accelerators
Air entraining Admixtures
Mineral Admixtures
Chemical Admixtures
Waterproofing Admixtures
Gas forming Admixtures
Colouring Admixtures

Plasticizers and Superplasticizers specifically developed in Japan and Germany

around 1970 and later on they were made popular in USA and Europe, Middle
East. Unfortunately, the use of plasticizers and Superplasticizers have not
become popular in India till recently ( 1985).

Plasticizers ( Water Reducers ): Concrete in different situations require

different degree of workability. A high degree of workability is required in
situations like deep beams, columns and beam junctions, pumping of
concrete for considerable distances. One must remember that addition of
excess water, will only improve the fluidity or the consistency but not the
workability of concrete.

The easy method generally followed at the site in most of the conditions is
to use extra water to overcome different situations which is unengineering
practice. Today, the use of plasticizers help the difficult conditions for
obtaining higher workability without using excess of water.
Superplasticizers ( High Range Water Reducers ): Superplasticizers
constitute a relatively new category and improved version of plasticizer, the
use of which was developed in Japan and Germany during 1960 and 1970
respectively.

Use of Superplasticizers permit the reduction of water to the extent upto 30%
without reducing the workability. The use of superplasticizer is practiced for
production of flowing, self levelling, self compacting and for the production of
high strength and high performance concrete. Superplasticizers can produce:
Same w/c ( water cement ratio ); same workability ; increased strength,
homogeneous character etc..

Retarders: A retarder is an admixture that slows down the chemical process

of hydration so that concrete remains plastic and workable for a longer time.
The retarders are used in casting purposes. They are also used in grouting oil
wells. Oil wells are sometimes taken upto a depth of about 6000 meter deep where
the temperature may be about 200oC. The spacing between the steel tube and
the wall of the well and to prevent the entry of gas or oil into other rock
formations are to be sealed with cement grout. For all these works cement
grout is required to be in mobile condition for about 3 to 4 hours even at
that high temperature without getting set.

Accelerators: Accelerating admixtures are added to concrete to increase the rate

of strength development in concrete to reduce the required period of curing. In the
past one of the commonly used materials as an accelerator was calcium chloride.
The recent studies have shown that calcium chloride is harmful for reinforce
concrete.

Air entraining Admixtures: Air entrained concrete is made by mixing a

small quantity of air entraining agent or by using air entraining cement. These
air entraining agents modify the properties of plastic concrete regarding
workability, segregation, finishing quality of concrete. Entrained air is
intentionally incorporated, minute spherical bubbles of size ranging from 5
microns to 80 microns distributed evenly in the entire mass of concrete. Air
entraining admixture is used to prevent frost scaling in concrete .

The following types of air entraining agents are used for making air
entrained concrete:

Natural wood resins

Animal or vegetable fats and oils such as olive oil, stearic acid; oleic acid.
Various wetting agents such as alkali salts
Miscellaneous materials such as the sodium salts of petroleum
sulphonic acids, hydrogen peroxide and aluminium powder

The common air entraining agents are Vinsol resin, Darex, Airalon, Orvus,
Teepol, Petrosan, Cheecol etc..

Air entrained concrete has been used in the construction of Hirakud dam,
Koyna dam, Rihand dam etc.
Chemical admixtures: Chemical admixtures are added to concrete in very small
amounts mainly for the entrainment of air, reduction of water or cement content,
plasticization of fresh concrete mixtures, or control of setting time.

Mineral admixtures: Mineral admixtures (fly ash, silica fume [SF], and slags ) are
usually added to concrete in larger amounts to enhance the workability of fresh
concrete; to improve resistance of concrete to thermal cracking and sulfate attack;
and to enable a reduction in cement content.

USES:

A proper use of admixtures offers certain beneficial effects to concrete, including

improved quality, acceleration or retardation of setting time, enhanced frost and
sulfate resistance, control of strength development, improved workability, and
enhanced finishability.

Fly Ash

Fly ashes are finely divided residue resulting from the combustion of ground or
powdered coal. They are generally finer than cement and consist mainly of glassy-
spherical particles as well as residues of hematite and magnetite and some
crystalline phases formed during cooling.

Use of fly ash in concrete started in the United States in the early 1930's.

In addition to economic and ecological benefits, the use of fly ash in concrete
improves its workability, reduces segregation, bleeding, heat evolution and
permeability, and enhances sulfate resistance.

One of the most important fields of application for fly ash is PCC pavement, where a
large quantity of concrete is used and economy is an important factor in concrete
pavement construction.

Mix Design: The substitution rate of fly ash for portland cement will vary depending
upon the chemical composition of both the fly ash and the portland cement. The rate
of substitution typically specified is a minimum of 1 to 1 pounds of fly ash to 1
pound of cement. It should be noted that the amount of fine aggregate will have to be
reduced to accommodate the additional volume of fly ash. This is due to fly ash
being lighter than the cement.
The amount of substitution is also dependent on the chemical composition of the fly
ash and the portland cement. Currently, States allow a maximum substitution in the
range of 15 to 25 percent.

The two properties of fly ash that are of most concern are the carbon content and the
fineness. Both of these properties will affect the air content and water demand of the
concrete.

The finer the material the higher the water demand due to the increase in surface
area. The finer material requires more air-entraining agent to five the mix the desired
air content. The important thing to remember is uniformity.

If fly ash is uniform in size, the mix design can be adjusted to give a good uniform
mix.

The carbon content, which is indicated by the loss of ignition, also affects the air
entraining agents and reduces the entrained air for a given amount of air-entraining
agent.