Lecture Notes on Cement Chemistry & Types

Hydration of cement
The reaction of cement hydration is exothermic. Measurements using a conduction
calorimeter can give the rates of heat evolution at various stages.
A typical heat evolution pattern from cement hydration is presented in Figure 1. There are
three characteristic peaks for ordinary Portland cement. The initial heat burst corresponds to
the instantaneous high rate of heat evolved when cement is brought into contact with water.
This is due to the heat of wetting (Heat of wetting = Surface energy – Energy required for
interface creation). Hydration of C3S and C3A also contribute to this peak.

The initial burst is followed by a slowdown of the heat evolution rate. The rate does not
become negative or zero at any stage, implying that although slowly, the reactions do
continue. This is termed as the ‘dormant’ or the ‘induction’ period. This period is followed by
the main peak of cement hydration, which is associated with the rapid dissolution of C3S to
form CSH and CH, and formation of ettringite (AFt) from C3A.
A slowdown of the hydration process beyond the main peak leads to lower rates of heat
evolution. A broader peak is associated with the conversion of ettringite to monosulphate
(AFm). The latest calorimeters can also detect an extra endothermic peak in the beginning
that corresponds with the dissolution of potassium sulphate (when it is present in the cement).
It is difficult to obtain the correct relationship between heat evolution and temperature unless
the system is perfectly insulated. Another problem is the dependence on the water to cement
ratio. Water has a much higher specific heat than cement, thus when more water is present, a
higher degree of heat will be required to increase the temperature of the system. Cement
contains highly soluble alkali oxides (Na2O and K2O). The dissolution of these compounds
is responsible for the high alkalinity (pH 12 – 13) of the pore solution. Thus, the hydration of
cement actually takes place in the pore solution, and not in water.
Reactions during hydration
Reactions involving the silicates
2 C3S + 6 H —›C3S2H3 + 3 CH (1)
2 C2S + 4 H —›C3S2H3 + CH (2)
The above reactions are perfectly stoichiometrically balanced. However, C-S-H does not
have a well defined stoichiometry. The C/S of C-S-H can vary from 1.5 to 2, and commonly

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is around 1.8. The main difference in the hydration of the two silicates lies in the amount of
CH formed in the reaction. It is evident from the above equations that 3 times as much CH is
formed from C3S hydration as in C2S hydration.
C-S-H does not have a definite structure is thus termed as a gel. CH deposits as hexagonal
crystals, generally oriented tangentially to pore spaces and aggregates along the longitudinal
axis.
Reactions involving the aluminates
In the absence of gypsum, calcium aluminate hydrates form from C3A, resulting in a flash set
of the cement paste.
2 C3A + 21 H —›C4AH13 + C2AH8 (3)
C2AH8 is a metastable phase that deposits as hexagonal platelets (similar to CH). Above 30
oC, it is converted to cubic hydragarnet (C3AH6). In the presence of gypsum, ettringite
formation occurs.
C3A + 3 C S H2 + 26 H —›C6A S 3H32 (4)
Ettringite (or the AFt phase) gets deposited as acicular, columnar, hexagonal crystals. The
presence of tubular channels in between the columns can lead to high water absorption and
swelling by ettringite. This is one of the theories explaining the expansion caused by
ettringite formation.
Nearly all the SO42- gets combined to form ettringite in an ordinary Portland cement. If there
is still C3A left after this reaction, it can combine with ettringite to form monosulphate (or
AFm phase) which has a stoichiometry of C4AS H12-18. If there is sufficient excess C3A,
then C4AH13 can also form as a hydration product, and can exist in a solid solution with
AFm.
C4AF produces similar hydration products as C3A, with the Al3+ being partly replaced by
Fe3+. The final hydration product depends on the availability of lime in the system. In the
presence of gypsum, C4AF produces an ironsubstituted ettringite. Higher the ratio
C4AF/C3A, lower is the conversion of ettringite to monosulphate.

Stages in Cement Hydration

1. Pre-induction period (first minutes):
Rapid dissolution of ionic species (alkali sulphates contribute K+, Na+, and SO42-; CaSO4
dissolves until saturation, contributing Ca2+ and SO42-)
C-S-H forms on the surface of dissolving C3S. C/S of C-S-H is lesser than of C3S, thus an
increase of the Ca2+ concentration in the liquid phase occurs. Formation of electrical double
layer, and the precipitation of CH leads to the dormant period. C3A dissolves, and reacts with
SO4 2- to form AFt, which forms a surface barrier. C4AF also reacts to form AFt. Only very
small % of C2S reacts at this stage.
2. Induction (dormant) period (first few hours):
CH concentration in the liquid phase reaches a maximum and then starts to decline. The
concentration of SO42- remains constant as the amount consumed due to AFt formation is
balances by the amount dissolved from gypsum.
3. Acceleration stage (3 – 12 hours after mixing):
Nucleation and growth of C-S-H (often termed as the ‘second-stage CSH’) and CH occurs.
C2S also starts hydrating substantially. Ca2+ concentration in the liquid phase declines as
Ca(OH)2 starts precipitating. SO42- concentration starts to decline with increasing AFt
formation, and adsorption of SO42- on C-S-H.
4. Post-acceleration period:
Slow down due to decline in non-reacted material, and because the process becomes diffusion
controlled. The contribution of C2S increases steadily, leading to a decline in the rate of
formation of CH. Consumption of SO42- leads to a conversion of AFt to AFm.

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The progress of hydration, both in terms of the unhydrated compounds consumed, as well the
hydration products formed, has been presented in Figure 2. In the first few minutes, about 2 –
10 % of C3S hydrates, and a significant fraction is consumed within 28 days. The rate of
hydration depends upon the reactivity of alite (i.e. the amount of foreign ions present within
the alite structure). With an increase in the amount of SO3, the C3S reaction becomes faster.
However, beyond a limit, SO3 can start causing retardation.
The hydration of C2S is a slow process, and does not pick up for many hours. On the other
hand, 5 – 25% of C3A reacts in the first few minutes of hydration. The initial reactivity
depends on the quantity and quality of alkalis present (K+ increases reactivity, while Na+
decreases it).The reactivity of C4AF is dependent on the A/F of the cement.
The method of grinding cement may also influence the hydration kinetics. Cements ground in
high pressure roller mills set faster than in ball mills, because of higher reactivity of C3A and
C3S phases, and a lowered rate of decomposition of CaSO4.

Hydrated cement paste is composed of capillary pores and the hydration product. The pores
within the structure of the hydration product are termed ‘gel’ pores. This hydration product
includes C-S-H, CH, AFt, AFm, etc. Gel pores are included within the structure of hydrated
cement. According to Powers, 1/3 of the pore space is comprised of gel pores, and the rest are
capillary pores. The pores inside cement paste contain water (or pore solution), which can be
classified into:
1. Capillary water: Present in voids larger than 50 Ao. Further classified into: (a) free water,
the removal of which does not cause any shrinkage strains, and (b) water held by capillary
tension in small pores, which causes shrinkage strains on drying.

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2. Adsorbed water: Water adsorbed on the surface of hydration products, primarily C-S-H.
Water can be physically adsorbed in many layers, but the drying of farther surfaces can occur
at about 30 % relative humidity. Drying of this water is responsible for a lot of shrinkage.
3. Interlayer water: Water held in between layers of C-S-H. The drying of this water leads
to a lot of shrinkage due to the collapse of the C-S-H structure.
4. Bound water: This is chemically bound to the hydration product, and can only be
removed on ignition. Also called ‘non-evaporable’ water.
2 and 3 are together called ‘gel’ water.

Note: Theoretically, 0.23 g of bound water is required to completely hydrate 1 g of cement.

The remaining water fills up the pores within the structure of the hydrated cement paste
(hcp), called the gel pores.
Types of cements
Cements are classified based on:
 Chemical Composition
 Physical properties
 Additives to the cement powder
 Special purpose or use
The general classification is similar for standards around the world. Two primary
classification schemes are
presented here – ASTM and BIS.
ASTM Classification
ASTM C150 classifies cement into 5 primary types:
 Type I: General purpose (Type IA for air entrained cement)
 Type II: Moderately sulphate resistant, and moderate heat of hydration (Type IIA for
air entrained cement)
 Type III: High early strength
 Type IV: Low heat of hydration
 Type V: Sulphate resistant
The typical compound composition for these cements is given in Table 1.

Table 1. Compound composition (%) for ASTM cements

ASTM Type C3S C2S C3A C4AF
I 45-55 20-30 8-12 6-10
II 40-50 25-35 5-7 10-15
III 50-65 15-25 8-14 6-10
IV 25-35 40-50 5-7 10-15
V 40-50 25-35 0-4 10-20
ASTM C595 also classifies two blended cements – Portland Slag Cement (Type IS) and
Portland Pozzolana Cement (Type IP). While Type IS consists of 25 – 70% slag by mass,
Type IP consists of 15 – 40% of a normally pozzolanic material by mass (fly ash, volcanic
ash etc.).
BIS Classification
Although the general pattern of classification is similar in BIS as in ASTM, the names for the
cements are different. BIS classifies cements into the following major categories:
 Ordinary Portland Cement – IS:269-1989 (further classified into 33, 43, and 53 grade;
the grade implies the
 strength achieved by the cement mortar at 28 days)
 Portland Cement, Low Heat – IS:12600-1989

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 Rapid Hardening Portland Cement – IS:8041-1978

 Portland-Pozzolana Cement (PPC) – IS:1489-1976
 Portland-Slag Cement (PSC) – IS 455-1976
Compared to OPC, the low heat cement has higher proportion of C2S, while the rapid
hardening cement has higher C3S and fineness. BIS classifies OPC into three different
strength grades, which are primarily achieved by differences in C3S contents and fineness.
However, the long term strength of concrete does not really depend on the grade of cement.
Only the strength gain rate of concrete is faster for the higher grade cements.
Nowadays, OPC is not readily available in most areas of India, and the construction industry
has slowly but surely made a shift towards PPC. This is a positive development, as PPC
results in a more durable concrete in the long run. In India, PPC consists primarily of low
calcium fly ash, at a replacement level of 20 – 30%. While a slower rate of strength gain is
inevitable, the ultimate strength and durability of concrete with PPC are better that for OPC.

Types of Cement:
A number of different types of cement are manufactured, by varying the ratio of the raw
material and/or by adding some additional materials.
Some of the most common cement classifications are:

1. Ordinary Portland Cement.

2. Rapid hardening cement,
3. Ultra-rapid hardening cement.
4. Low heat cement,
5. Quick setting cement,
6. High alumina cement,
7. Blast furnace slag cement,
8. Pozzolana cement,
9. White cement,
10. Hydrophobic cement,
11. Super sulfate cement,
12. Low alkali cement,
13. Water proof cement,
14. Air entraining cement,
15. Expansive cement,
16. Colored cement.
We will discuss the above types of cement in detail below.

Every type of cement has their own properties, advantages, and disadvantages. In
this article, you are going to learn the most important properties of different types
of cement in details.

Following are the cement types.

1. Ordinary Portland Cement.

Definition.
Portland cement is a product obtained by the calcination at a very high
temperature, an intimate mixture of correctly proportioned calcareous and
argillaceous materials.

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The calcined product which is called clinker.

Clinker is then finally pulverized by grinding into a very fine powder and is finally
mixed with calcium sulfatae or gypsum to obtain cement.

Raw Materials of Portland Cement.

The commonly raw material included in cement is as follow.

(a) Calcareous materials and (b) argillaceous materials.

The Calcareous materials include compounds of calcium and magnesium, such as
Limestone.
And Argillaceous ones include mainly silica, alumina, and oxide of iron such as
clay and shale.
Cement is manufactured in several varieties, but the most common one used is the
normal setting or ordinary cement, usually called Portland cement.
These are manufactured with two or more raw materials. They have to be correctly
proportioned and thoroughly mixed.

Lime, silica, and alumina are the important ingredients.

Composition of Portland Cement.

To understand the technique of proportioning of raw materials, it is necessary to
know the following.

(i.)  Composition of Portland cement

(ii.) The Constituents that go to form it.
(iii.) The function played by the Constituents.
The Chemistry of cement is very complicated. An engineer should understand the
functions played by each constituent in imparting the properties of  setting and
hardening of cement.
( a. ) Mineral Constituents.
The important constituents of Portland cement could be represented as shown in
the following table.

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( b. ) Acidic Alkaline Constituents:

The acidic constituents are SiO2, Al2O3, Fe2O3 and the alkaline ones are CaO and
MgO. Omitting the rest, The Percentage of acidic Constituents is round about 32,
and that of the alkaline ones is 63.5.

                        Acidic and Alkaline Constituents.

Thus, from the above composition for a normal setting Portland Cement, the values
are :

(2.8 X 0.37 + 1.1 X 0.07 + 0.7 X 0.02) / (1.0 X 1.1 + 1.4 X0.04)

=  (1.3 + 0.08 + 0.02) / (1.1 + 0.05) = (1.13/1.15) = 1 (approximately)

These ratios are termed as “Cement Modulii”.

( c. ) Necessity of proportioning
It will, therefore, be seen that in order to have constituents of definite composition
as mentioned above,

it is necessary that the calcareous and the argillaceous materials should be carefully
selected and proportioned.

It is possible theoretically to make a mixture of raw materials and to calcine or to

heat the same to a very high temperature to obtain Clinker.

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But it is necessary that a thorough and intimate mixing of the raw materials is
essential to ensure a thorough and a complete chemical reaction between the
ingredients while clinkering.

Functions of Ingredients.
( i. ) Lime (CaO).
Lime forms nearly two-third of cement and therefore, its proportion has an
important effect on its qualities.

A sufficient quantity of lime must be present in the raw materials to form the
required silicates and aluminates of calcium.

A deficiency in lime reduces the strength and causes it to set quickly; an excess
will make cement unsound and causes it to expand and disintegrate.
Usually, lime is kept below the required value.

( ii. ) Silica (SiO2).

The quantity of silica should be enough to form dicalcium silicate and tricalcium
silicate. Silicate imparts strength to cement and is present usually to the extant of
about one-fifth of the cement.
( iii. ) Alumina (Al2O3).
Alumina has the property of imparting quick setting quality. It lowers the
clinkering temperature.

Since a specific high temperature is necessary to form clinker of the required

composition, an excess of alumina weakens the cement.

Compounds of alumina react readily with water. Alumina forms about one-
fifteenth.

( iv. ) Magnesia ( MgO ).

This is usually kept at a very percent. The permissible percentage is 1.5 to 3.
Within these values, it has no bad effects, but when present in large percentages,
magnesia is harmful.

( v. ) Calcium Sulphate ( CaSO4 ).

This is in the form of gypsum and has an effect of slowing down the setting action.
Gypsum is added after the clinker is formed and during the process of grinding
clinker.

( vi. ) Oxide of Iron ( Fe2O3 ).

Oxide of iron requires a very high temperature to enter into chemical reaction with
calcium and aluminum to form tricalcium alumino-ferrite, which imparts hardness
and strength.

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The color of cement is due to iron compounds.

( vii. ) Sulfur.
As calculated on the basis of sulphuric and hydride. SO 2 is limited to 2 percent. An
excess quantity of sulfur causes the cement to become unsound.
( viii. ) The Alkalies.
Alkalies present in the raw materials are carried away ordinarily in the flue gases
during clinkering, so that cement contain very small quantities of the same, often
less than 1 percent.

An excess of alkaline matter causes efflorescence.

2. Rapid Hardening Cement:

Definition:
It is also known as High-Early-Strength cement. It is manufactured with such
adjustments in the proportion of raw materials.

So that the cement produced attains maximum strength with-in 24-72 hours.

Properties:
Two essential properties of Rapid Hardening Cement are following.

(i) It contains relatively more tri-calcium silicate. This is done by adding a greater
proportion of limestone in the raw materials compared to that required for ordinary
cement.
(ii) It is more fine-grained ( Air permeability 3250 cm 2/gm ) than the ordinary
cement.
This factors helps in quicker and complete hydration of cement particles during
setting and helps in gaining early strength.

However, the setting time and ultimate strength of Rapid Hardening Cement are

same as of Ordinary Cement.
Uses:
It is a special purpose cement. It is used in that types of projects, where quick
hardening is required.

3. Ultra-High Strength Cement.

In advanced countries, an Ultra-high early strength cement is produced by
separating the finest fraction ( above 700 m 2/kg ) from the rapid hardening cement
at the manufacturing stage itself.
This is achieved by using special devices called cyclone air elutriator. Such cement
is used for very high early strength concrete.
4. Low Heat Cement:
Definition:

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It is that type in which a very low amount of heat or hydration is liberated during
setting and hardening. Mostly it is used in massive concrete structures
like Dams etc.
Properties:
(i) The proportion of di-calcium silicate (C2S) is almost double than ordinary
cement.
(ii) The proportion of tetra calcium alumino-ferrite (C4AlFe) is also increased to
one and one-half time.
(iii) The proportion of tricalcium silicate (C3S) and tri-calcium aluminate (C3Al) is
reduced by about 50 percent. This is because these compounds are known to
liberate a very high amount of heat during hydration.
Most important qualities of low heat cement are summarized as follows:

Fineness: The residue in the Sieve Test shall not exceed than 10 percent.

Setting Time: The initial setting time shall not be less than 60 minutes. And the
final setting time shall not be less than ten hours.
Strength: It should develop a compressive strength not less than:
(a) 70 kg/sq.cm in 3 days.
(b) 115 kg/sq.cm in 7 days.
(c) 265 kg/sq.cm in 28 days.
Uses:
It is mostly used in mega projects construction like DAMS. If we use ordinary
Portland cement instead of low heat cement in such structures,

Cracks will develop in such structures due to the great amount of heat liberated
during setting and hardening.

And a DAM with cracks is a useless structure. But when low heat cement is used,
this danger (development of cracks) can be eliminated.

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5. Quick Setting Cement:

These Types of Cement are quite different than rapid hardening cement.
Its quality is that it set into a stone-like mass within a period of fewer than 30
minutes.

This property, of setting as quickly as possible is achieved by following controls in

the manufacturing process:

(i) The quantity of retarding agents like gypsum is reduced to a bare minimum.

(ii) The quantity of alumina-rich compound is reduced.
(iii) The clinker is ground to extreme fineness.
Quick setting cement is used only in very specific situations such as while
constructing piers for bridges and other structures in running or standing water.
6. High Alumina Cement:
Definition:
These Types of Cement contains alumina in considerably larger proportions
(average 40 percent) than normal cement.

High Alumina cement is manufactured by calcining a well-proportioned mixture

of Limestone and Bauxite (Al2O3, n H2O).
No other raw material is added, not even gypsum is mixed with the clinker during
grinding.

The total Alumina content is generally above 32 percent.

Properties:
The most important properties of high alumina cement are summarized below:

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(i) It is resistant to the corrosive action of acids and salts of seawater.

(ii) The ratio of alumina to lime is kept between 0.85 and 1.30.
(iii) It gains compressive strength of 400 kg/sq.cm within 24 hours and 500
kg/sq.cm after 72 hours.
(iv) It evolves great heat during setting. Due to this, it is not suitable for use in
mega projects like Dams.
But at the same time, it gives an advantage to high alumina cement for use in frost
forming areas.

(v) They react quickly with lime. Therefore, it must not come in contact with lime.
Uses:
Unfortunately, it is more costly. Therefore it is used only in those situations where
resistant against corrosion is required.

It is commonly used in construction work near and along sea-shore.

7. Blast Furnace Slag Cement:

Definition:
It is a modified type of Portland cement which contains 25-65 percent (by weight)
of blast furnace slag.

It is manufactured by grinding clinker and specific amounts of blast furnace slag

together. A small percent of gypsum is also added for controlling its setting time.

The slag, as we know, is a waste product from the blast furnace which is used in
the manufacture of iron (Ferrous Metal).
Properties:
The slag cement offers a number of advantages, which are the following.

(i) They possess better workability, cohesiveness, and plasticity. These qualities are

explained to be due to lesser specific gravity and greater specific surface area of
slag cement.
(ii) They have better resistance to sulfates of alkali metals, alumina, and iron.
(iii) It produces low heat. This property makes it useful for use in mega projects
like Dams.
(iv) It is economical as compared to ordinary cement.
Uses:
It is better suited for use in marine structures as in docks, harbors, and jetties. It is
also used in road construction in marshy and alkaline soils.

8. Pozzolana Cement:
In this cement type, clinker and pozzolanic material such as (volcanic ash, fly ash,
etc.) are mixed in a definite proportion with Portland cement.

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The pozzolanic materials do not have any cementing qualities when used alone, but
when mixed with Portland cement, they react with cement components and form
compounds with cementing properties.

The pozzolana cement has many properties similar to ordinary Portland cement.
But it also offers some additional properties, which are given below.

(i) It produces less heat. Due to this property, it can be used in mega projects.
(ii) It offers greater resistance to sulfates and corrosive actions of sea water.
These qualities make it more useful for construction near or along the coast and
also in sulfate soil. It can also be used in sewage works and for underwater
construction.

9. Colored Cement:
In this type of cement, pigment (color) is mixed with the Portland cement in a
definite proportion.

The Pigment is mixed in a finest powdered state. The amount of pigment used
depends upon the shade of the desired color.

It is, however, generally less than 10 percent (by weight). The following pigments
are used to obtain colored cement.

(i) Chromium oxide is used for green color.

(ii) Cobalt is used for blue color.
(iii) Iron oxide is used for various shades of red, brown and yellow color.
(iv) Manganese dioxide is used to obtain black and deep brown color.

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This type of cement is extensively used for top coat in flooring and decorative
purposes in various places in a building.

10. White Cement:

It may also be defined as a special type of Portland cement when used it gives a
milky or snow-white appearance.

White cement is manufactured from pure limestone (chalk) and clay that are totally
free from iron oxides and any other pigments like manganese and chromium.

The kiln is fired by oil rather than by coal to avoid any contamination.

There strength and setting time is similar to ordinary Portland cement.

White cement is the most favored material for use in making highways curbs and
for a variety of ornamental work.

They are also used widely for making cast stones of appealing appearance.

White cement is comparatively a costly cement type and is, therefore, used only
selectively.

11. Hydrophobic Cement:

It is a special type of cement containing admixtures which reduce the affinity of
cement grains for water.

Such cement types are used especially in cold, frost-forming conditions.

Admixtures of naphtha a soap and acidol are generally added to achieve this
property.

12. Super Sulfate Cement:

These types of cement are manufactured by adding additional quantities of calcium
sulfate and blast furnace slag in the Portland cement.

It is especially useful for mass concrete work especially in sulfate-rich

environment and marine conditions. Besides, it is comparatively economical than
other types of cement.

13. Low Alkali Cement:

Such types of cement are specially made Portland cement in which alkali content is
kept below in minimum amount, by exercising very strict control over the
composition of the raw material used.
They are used in those circumstances where aggregates -for making concrete- are
suspected to contain reactive silica.
14. Water Proof Cement.

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Water proof cement is prepared by using some of the waterproofing material like
Ca, Al with the ordinary cement during the process of cement manufacturing.
They are mostly used in the structures where water proofing is required, like in the
Dams, Water Tanks, etc.

15. Air Entraining Cement.

This cement type is manufactured by adding some indigenous air entraining agents
such as glues, resins, sulfates, etc., during the grinding stage of clinker.

They are used to improve the workability of concrete with smaller water-cement

ratio and they also improve the frost resistance of concrete.
16. Expansive Cement.
These types of cement have the quality to expand slightly with time. But they do
not shrink during and after the time of hardening.

They are mostly used for grouting purposes in anchor bolt and prestressed concrete
ducts.

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