CEMENT CHEMISTRY & TYPES OF CEMENT

Cement is a hydraulic binder, i.e., an inorganic, non-metallic, finely ground substance which, after
mixing with water, sets and hardens independently as a result of chemical reactions with the mixing
water and, after hardening, it remains its strength and stability even under water. The most
important area of application is therefore the production of mortar and concrete, i.e., the bonding
of natural or artificial aggregates to form a strong building material which is durable in the face of
normal environmental effects.

Portland cement is the name given to a cement obtained by intimately mixing together calcareous
and argillaceous, or other silica, alumina, and iron oxide bearing materials, burning them at a
clinkering temperature, and grinding the resulting clinker. Nevertheless, cement can be considered
as being in frozen equilibrium, i.e., the cooled products are assumed to reproduce the equilibrium
existing at the clinkering temperature.

Major Compounds in Cement: In all the Portland Cements, there are four major compounds. The
variation in percentage composition of compounds influences the properties of cement. These
compounds are given in table 1.1 below:

Table 1.1
Composition of cement

Name of Oxide Abbreviati Approx

SN Function
compound composition on Percentage
1 Tricalcium Mainly responsible for
3CaO.SiO2 C3 S 45-55%
Silicate early & later strength
Dicalcium Mainly responsible for later
2 2CaO.SiO2 C2 S 20-30%
Silicate strength (7 days and beyond)
C3A increases rate of
Tricalcium hydration of C3S. C3A gives
3 3CaO.AI2O3 C3 A 6-10%
Aluminate flash set in absence of
gypsum
It hydrates rapidly but its
Tetracalcium 4CaO.AI2O3 contribution to strength is
4 C4AF 15-20%
Aluminoferrite Fe2O3 uncertain and generally very
low.

These main phases are present in the clinker and in the non-hydrated Portland cement.
They are formed at high temperature (1450 °C) in the cement kiln. Compounds referred as C3S, C2S,
C3A and C4AF are known as the main crystalline phases of Portland cement. The phase composition
of a particular cement can be quantified through a complex set of calculation known as the Bogue
Formula.

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Main phases in Portland cement before and after hydration:

These oxides are used to build more complex compounds. The main crystalline phases described
hereafter are related respectively to the composition of:

 Clinker and non-hydrated Portland cement, and;

 Hardened cement pastes obtained after hydration and cement setting.
 Hydrated cement paste
 Hydration products formed in hardened cement pastes (HCP) are more complicated,
because many of these products have nearly the same formula and some are solid-
solutions with overlapping formula. Some examples are given below:

CCN Actual Formula Name or Mineral Phase

CH Ca(OH)2 or CaO • H2O Calcium hydroxide
2(CaO) • SiO2 • 0.9-1.25(H2O), and/or;
C-S-H CaO • SiO2 • 1.1(H2O), and/or; Calcium Silicate Hydrate
0.8-1.5(CaO) • SiO2 • 1.0-2.5(H2O)
C-A-H This is even more complex than C-S-H Calcium Aluminate Hydrate
AFt C3AS3H30-32 Aluminum trisulfate, or ettringite
AFm C2ASH12 Aluminum monosulfate
C3AH6 3CaO • Al2O3 • 6 H2O Hydrogarnet

 The hyphens in C-S-H indicate a calcium silicate hydrate phase of variable

composition, whilst CSH indicates a calcium silicate phase CaH 2SiO4.

Different types of cement produced in India:

 Ordinary Portland Cement (OPC): This is by far the most common cement used in general
concrete construction when there is no exposure to sulphates in the soil or in ground water.
In consequence, modern cements have higher 28 days strength than the past, but the later
gain in strength is smaller. A practical consequence of this is that we can no longer expect
‘improvement with age’. Ordinary Portland cement is the cement most widely used.
Moreover, using highly early strength cement for a given specified 28 days strength of
concrete, it is possible to use a leaner mix, with higher water/ cement ratio. Some of these
mixes have an inadequate durability.

 Portland Pozzolana Cement (PPC) contains up to 35% fly ash. The fly ash is pozzolanic, so
that ultimate strength is maintained. Because fly ash addition allows a lower concrete water
content, early strength can also be maintained. Where good quality cheap fly ash is
available, this can be an economic alternative to ordinary Portland cement.

As a rule, Portland Pozolana Cements gain strength slowly and therefore require curing over
a comparatively long period, but the long term strength is high shows that similar behaviour
occurs where the pozzolana replaces part of cement, but the long-term strength depends on
the level of replacement.

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  Portland Slag Cement (PSC) contains up to 70% ground granulated blast furnace slag, with
the rest Portland clinker and a little gypsum. All compositions produce high ultimate
strength, but as slag content is increased, early strength is reduced, while sulfate resistance
increases and heat evolution diminishes. Used as an economic alternative to Portland
sulfate-resisting and low-heat cements.

The hydration of slag is initiated when lime liberated in the hydration of Portland Cement
provides the correct alkalinity; subsequent hydration does not depend on lime. Typical uses
are in mass concrete because of lower heat of hydration and in sea-water construction
because of a better sulphate resistance (due to a lower C3A content)than with ordinary
Portland cement. Slag with a low alkali content can also be used with an aggregate
suspected of alkali reactivity.

 It is necessary to use cement of appropriate grade and type for specific applications
and environment conditions. Various type of cement produced in India are shown in
table 1.1.

Table 1.1
Various type of cement under IS codes.

Sl.No.
Cement Variety As per code

Gd-33 IS : 269-1989
1 OPC (Ordinary Portland Cement) Gd-43 IS : 8112-1989
Gd-53 IS : 12269-1987
PPC(Portland Pozzolana
2 IS : 1489-1991
Cement)
PBFSC (Portland Blast Furnace
3 IS : 455-1989
Slag Cement)
Others Rapid Hardening Cement
IS : 8041-1990
Low Heat Cement
4 IS :12600-1989
Sulphate Resisting Cement
IS :12330-1988
Super sulphated Cement
IS : 6909-1990

1.2 The physical and chemical characteristics of various cements are given in Table 1.3 & 1.4

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 Table 1.3

Physical characteristics of various types of cement

Sr. Type of Finene Soundness Setting Time Compressive Strength (MPa)

No. Cement ss (minutes)
(m2 / Le- Chat Autoclave Initial Final 1D 3D 7D 28 D
Kg) (max) (max) (%) (min) (max) (min) (min) (min) (min)
Min (mm)
33 grade OPC
1 225 10 0.8 30 600 NS 16 22 33
(IS 269–1989)
43 grade OPC
Min-43
2 (IS 8112– 225 10 0.8 30 600 NS 23 33
Max-58
1989)
53 grade OPC
3 (IS 12269– 225 10 0.8 30 600 NS 27 37 53
1987)
Sulphate
Resisting
4 Cement. SRC 225 10 0.8 30 600 NS 10 16 33
(IS 12330–
1988)
Portland
Pozzolana
5 Cement. PPC 300 10 0.8 30 600 NS 16 22 33
(IS 1489–
1991) Part-I
Rapid
Hardening
6 Cement. PPC 325 10 0.8 30 600 16 27 NS NS
(IS 8041–
1990)
Portland Slag
7 Cement. PSC 225 10 0.8 30 600 NS 16 22 33
(IS 455–1989)
Super
Sulphated
8 400 5 NS 30 600 NS 15 22 30
Cement. (IS
6909–1990)
Low Heat
9 Cement. (IS 320 10 0.8 60 600 NS 10 16 35
12600–1989)
Masonry
10 Cement. (IS * 10 1.0 90 1440 NS NS 2.5 5.0
3466–1988)
43-S grade
11 OPC (IS 8112– 370 10 0.8 60 600 NS NS 37.5 NS
1989)
53-S grade
12 OPC (IS 370 10 0.8 60 600 NS NS 37.5 NS
12269–1987)
NS-Not specified.

*residue on 45 Micron IS sieve, Max, Percent (by wet sieving) is 15.

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 Table 1.4

Chemical characteristics of various types of cement

Sr. Type of Lime Alumina Iron Insoluble Magnesia Sulphuric Loss on Ignition
No. Cement Saturation Ratio (%) Residue (%) Max. Anhydride (%) Max.
Factor (%) Min. (%) Max. (%) Max.
33 grade OPC 0.66 Min.
1 0.66 4.0 6.0 3.5 5.0
(IS 269–1989) 1.02 Max.
43 grade OPC
0.66 Min.
2 (IS 8112– 0.66 4.0 6.0 3.5 5.0
1.02 Max.
1989)
53 grade OPC
0.80 Min.
3 (IS 12269– 0.66 4.0 6.0 3.5 4.0
1.02 Max.
1987)
Sulphate
Resisting
0.66 Min.
4 Cement. SRC NS 4.0 6.0 2.5 5.0
1.02 Max.
(IS 12330–
1988)
Portland
Pozzolana
X+4 (100-
5 Cement. PPC NS NS 6.0 3.0 5.0
X)/100
(IS 1489–
1991) Part-I
Rapid 2.5 % Max.
Hardening When C3A is
Cement. PPC 5.0 or less.
0.66 Min.
6 (IS 8041– 0.66 4.0 6.0 3.0% Max. 5.0
1.02 Max.
1990) When C3A is
greater than
5.0
Portland Slag
7 Cement. PSC NS NS 4.0 8.0 3.0% Max. 5.0
(IS 455–1989)
Super
Sulphated
8 NS NS 4.0 10.0 6.0% Min. NS
Cement. (IS
6909–1990)
Low Heat 2.5 % Max.
Cement. (IS When C3A is
12600–1989) 5.0 or less.
9 NS 0.66 4.0 6.0 3.0% Max. NS
When C3A is
greater than
5.0
43-S grade LOI 5.0% Max.
0.66 Min.
10 OPC (IS 8112– 0.66 4.0 5.0 3.5 C3A 10.0 % Max.
1.02 Max.
1989) C3S 45.0% Min.
53-S grade LOI 4.0% Max.
0.80 Min.
11 OPC (IS 0.66 4.0 5.0 3.5 C3A 10.0 % Max.
1.02 Max.
12269–1987) C3S 45.0% Min.

X - Declared percentage of fly ash. NS - Not specified.

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1.5 Factors affecting choice of cement: Following factors govern choice of cement.

 Durability Characteristics

 Functional requirement - Deflection, crack width etc.

 Design parameters- Strength, fineness, setting time requirement etc.

 Speed of construction- Time for construction etc.

 Environmental Conditions- Ground conditions, soluble salts, sulphates, Chemical plants etc.

1.6 Suitability of various types of cement:

A. 33 grade OPC:

 It is used for normal grade of concrete upto M-20, plastering, flooring, grouting of
cable ducts in PSC works etc. The fineness should be between 225 and 280.

B. 43 grade OPC:

 It is the most widely used general purpose cement.

 For concrete grades upto M-30, precast elements.
 For marine structures but C3A should be between 5 - 8%.

C. 53 grade OPC:

 For concrete grade higher than M-30, PSC works, bridge, roads, multistoried
buildings etc.
 For use in cold weather concreting.
 For marine structures but C3A should be between 5 - 8%.

D. Portland Slag Cement (PSC) i.e. OPC + granulated slag: It gives low heat of hydration. The
slag should be more than 50% and upto 70%. It is used for ;

 Marine and off shore structures- very high chloride and sulphate resistant.
 Sewage disposal treatments works
 Water treatment plants
 Constructions which are expected to be attacked by dissolved chlorides and sulphate
ions.
 Should be mainly used for all future structures.

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 E. Portland Pozzolana Cement: IS: 1489(part-I) - 1991 (using flyash):

 It gives low heat of hydration and reduces the leaching of calcium hydroxide. This
cement should be used only after proper evaluation. This should be tested as per IS:
1489 (Pt I) – 1991. It is used for :
 hydraulic structures- dams, retaining walls
 Marine structures
 Mass concrete works- like bridge footings
 under aggressive conditions
 Masonry mortar and plastering.

F. SRC- Sulphate Resisting Cement: (C3A < 5%)

 Sulphate Resisting Portland Cement is a type of Portland Cement in which the

amount of tricalcium aluminate (C3A) is restricted to lower than 5% and 2C3A + C4AF
lower than 25%. The SRC can be used for structural concrete wherever OPC or PPC or
Slag Cement are usable under normal conditions.

 The use of SRC is particularly beneficial in such conditions where the concrete is
exposed to the risk of deterioration due to sulphate attack, for example, in contact
with soils and ground waters containing excessive amounts of sulphates as well as
for concrete in sea water or exposed directly to sea coast . The IS 456 (revised draft
code) has made elaborate provisions for use of particular type of cement against
different percentages of soluble sulphate salts. These provisions are given in table
1.6 below:

Table 1.6
Recommendations of different cements (for application) based on SO3 in soil.

Concentration of Sulphates
In soil Total SO3 expressed as SO3
Class Type of cement
% SO3 in 2:1 water : In ground water
soil extract (g/L) (g/L)
1 > 0.2 <1.0 <0.3 OPC, PSC or PPC
OPC, PSC or PPC
2 0.2 – 0.5 1.0-1.9 0.3-1.2
SSC or SRC
SSC or SRC
3 0.5 – 1.0 1.9-3.1 1.2 – 2.5
PSC or PPC
4 1.0 – 2.0 3.1-5.0 2.5 – 5.0 SSC or SRC
SRC or SSC with protective
5 >2.0 >5.0 >5.0
coating

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The use of SRC is recommended for following applications:

 Foundations, piles
 Basement and underground structures
 Sewage and water treatment plants
 Chemical factories
 Suitable for underground works where Sulphate is present in the Soil and water.

Attention:

i) Sulphate resisting cement is not suitable where there is danger of chloride attack.
This will cause corrosion of rebar.
ii) If both Chlorides and Sulphates are present, Ordinary Portland Cement with C3A
between 5& 8 should be used.

Sulphate resistance of cements : Chemical resistance of various types of cement in different

environmental conditions is given in table 6.7 .

Table 1.7

Type of Chemicals resistance to sulphates

Cement Moderate High Very High
Ordinary Portland C3A <8% C3A <5% C3A =0%
2C3A+C4AF<25% C4AF< 20%
or or
C4AF +C2F<25% C4AF +C2F<20%
Pozzolana No special C3A <6% C3A < 3.5%
prescription
Slag Slag > 36% Slag > 70% C3A < 2%

G. Low heat portland cement : Low Heat Portland Cement is particularly suited for making
concrete for dams and many other types of water retaining structures, bridge abutments,
massive retaining walls, piers and slabs etc. In mass concreting, there is often considerable
rise in temperature because of the heat produced as the cement sets and hardens. The
shrinkage which occurs on subsequent cooling sets up tensile stresses in the concrete, may
result in cracking. The use of low heat cement is advantageous since it evolves less heat
than OPC. This cement is not available in the market on regular basis and has to be obtained
on specific orders.

H. Rapid hardening cement : The Rapid Hardening Cement is used for repair and rehabilitation
works and where speed of construction and early completion is required due to limitations
of time, space or other reasons. The cement is to be used in cold weather concreting i.e.

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 temp < 5 0C. Rapid hardening cement is basically OPC but its fineness is 3250 cm2/gm
against 2250cm2/gm in case of OPC. The compressive strength after 1 day is 16 N/mm2 and
that of 3 days 27N/mm2. These days higher grade OPC are available in the country to meet
these requirements and therefore, this cement is not being manufactured and marketed on
regular basis. The characteristics of this cement can be effectively met by only good quality
53 grade OPC.

I. Special grade cement (43-S and 53-S): Special Grade Cement is manufactured as per
specification laid down by BIS IS 8112 & 12269. It is a very finely ground cement with high
C3S content designed to develop high early strength required for manufacture of concrete
sleeper for Indian Railways. This cement can also be used with advantage for other
applications where high strength concrete is required. This cement can be used for
prestressed concrete elements, high rise buildings, high strength concrete etc.

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