LECTURE NOTES - CEMENT TECHNOLOGY – I

INTRODUCTION (1)

Introduction - Cement and its Manufacture

The dictionary meaning of ‘cement’ is ‘to join’. Cement may be defined as adhesive substances
capable of uniting fragments or masses of solid matter to a compact whole. Constructions are the
backbone of civilization and development of society. From the time immemorial, constructions
have evolved around some type of building blocks, joined together with some binder. Mud blocks,
pieces of stone cut and dressed to size, or bricks are examples of ‘building blocks’, which are
joined with, may be mud mortar (specially in climates with little or no rain), lime or cement mortar,
or even bitumen, and laid one over the other to erect the structure. Seen in this perspective,
cement is the essential binder of the present day constructions, and concrete, again made with
cement, is the leading building material the world over.

The use of cementing materials is very old. The ancient Egyptians used calcined impure gypsum.
The Greeks and Romans used calcined limestone and later learned to make lime mortar by
adding other substances like sand, crushed stone or brick, and broken tiles, to lime and water.
From the chemistry viewpoint, present-day cements bear similarity with lime, which was known as
the classical building material for many centuries. The process of lime manufacture and use in
lime mortar involves the following steps;

1. Burning of lime – CaCO3 → CaO + CO2

2. Slaking of lime – CaO + H2O → Ca(OH)2, and
3. Carbonation, hardening – Ca(OH)2 + CO2 → CaCO3 + H2O.

Burning of limestone to make quicklime means release of CO 2 occupying 44 percent by weight.

Such loss of mass makes quicklime porous. In contact with water, it absorbs water quickly, with
considerable evolution of heat (280 cal/gm). This is hydration of lime. The resultant volume is 20
percent greater than that of the reactants. It gives rise to expansive forces. Depending upon the
amount of water added slacked lime will have powdery appearance or highly dispersed paste,
also known as ‘milk of lime’. The particles of hydrated lime are extremely fine and develop
cohesive forces. Upon drying, it will harden and develop strength; which is not very high – may be
of the order of 30 – 40 kg/cm2. The actual hardening of lime mortar is completed on carbonation
with atmospheric CO2.

Silica (SiO2), as obtained in natural rocks and stones, occurs mostly in crystalline form – as in
quartz. In crystalline form, Silica is very stable and non-reactive. When heated to high
temperature, even the ordinary quartz variety of silicon becomes chemically reactive. In a silica-
containing aqueous solution mixed with lime, a precipitate forms rapidly, giving rise to a ‘gel’-like
mass of colloidal dimensions having cohesive forces. Around 1756, it was discovered that lime
made from limestone containing a considerable proportion of clayey matter gave better results.
This was the beginning of most important advances in the knowledge of cements. It was soon
recognized that if a mixture of lime and silica, in finely ground form and in required proportions, is
heated to sufficiently high temperatures, calcium silicates having hydraulic properties (i.e. capable
of hydrating and hardening in contact with water) are formed. This is the basis of cement
manufacture.

Various Unit Operations in Cement Manufacture

Normal Portland cement is defined as a synthetic mixture of calcium silicates formed from a
molten matrix from a suitably proportioned and homogeneously prepared mixture of
calcareous and argillaceous components. Accordingly, Portland cement is made primarily
from a calcareous material, such as limestone or chalk, and from alumina and silica found as clay
or shale. The manufacturing process involves the following principal stages;
 Mining of raw materials, size reduction and grinding,

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  Mixing them intimately in the desired proportions,
 Burning in a large rotary kiln at a temperature up to about 1450 oC, when the materials
sinter and partially fuse to form balls, known as ‘clinkers’,
 Cooling of the clinker and storage,
 Grinding of the clinker along with gypsum to a fine powdery form. This is ‘cement’.
Cement is stored in suitable containers like 50 kg bags, one-tonne ‘jumbo’ bags, or
tankers, for dispatch by road, rail or sea route to the point of use.

The above description is rather simplistic, and in actual practice, considerable innovations take
place. Take for example the raw materials. Clay may not be separately added and SiO 2 obtained
from the coal ash and what is contained in limestone may be sufficient. Alumina and iron oxides
are needed to act as flux in the clinker formation process, and additives like Bauxite and/or iron
ore may have to be separately incorporated in the raw mix. Finish grinding of clinker may not be
with only mineral gypsum but other forms of calcium sulphate may be used. Supplementary
cementitious materials like fly ash, burnt clay or granulated blast furnace slag can be added at the
stage of cement grinding to produce ‘blended’ or ‘composite‘ cements. Depending upon the raw
materials being mixed and fed to the kiln in dry form or as slurry with water, different ‘processes’
of cement manufacture are adopted. Finally, considerable engineering judgment and input of
material science in all stages of various unit operations are required to optimize the energy
requirement, meet demands of environmental restrictions and quality of the final product. All
these aspects will be covered in the lectures to follow.

Size of the Cement Industry in India.

India is the second largest cement producer in the world. The installed production capacity at
present is nearly 165 million tonnes (MT) annually. This comprises about 155 MT from ‘large’
plants (93 percent of the total) and another 11 MT from small-scale ‘mini’ cement plants. With 85
percent capacity utilization, it is capable of producing nearly 136 MT per year, nearly 95.5 percent
of production being contributed by the large plants.

Nearly 60 percent of the production is consumed by the housing sector, another 20 percent in
infrastructure, and balance 20 percent in ‘industry and others. About 10 MT of cement and
clinkers produced in India are exported.

The growth of the Indian cement industry, in terms of total capacity and production, number of
units of large plants (128) and kilns (164), average kiln capacity ( > 2000 tpd), proportion of
efficient and modern dry process kilns (96 percent), have been gradual over the years. The
figures given in brackets are for the year 2004/05.The rate of growth (CAGR) has been in excess
of 8 percent per year, which is projected to be sustained in the decades to come. The trend is
depicted in Figure I below.

The global scenario

The total production of cement world-wide is of the order of 2000 MT. The data on production by
seven leading cement manufacturing countries (2003 data) is given in Table I below.

Table I indicates that production in China is at the top position and India occupies the second
position, as already mentioned. One measure of economic development in any country is the ‘per
capita cement consumption’. Starting with a value of 57 kg / head in 1994/5 in India, the current
value of per capita cement consumption of about 130 kg will appear impressive, but it is much
lower than 723 kg in case of China, or even about 300 kg as the world average. This provides
impetus to the continuous growth of Indian Cement Industry, to make available the large
quantities of cement needed for the infrastructure sector – housing, roads, railways and ports,
power generation and other industrial activities.

TABLE I

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 Cement Production in MT – 2003 Data

Country Production % of Total

China 862 44.1
India 121.4 6.2
USA 92.8 4.7
Japan 73.8 3.8
Korea 59.1 3.0
Spain 44.8 2.3
Italy 43.5 2.2
Others 656.6 33.6
Total 1954

Reference Books

1. A. M. Neville, Properties of Concrete, Longmans,

2. Robert G. Blezard, The History of Calcareous Cements, in Lea’s Chemistry of Cement
and Concrete, 4th ed., Butterworth.
3. W. Czernin, Cement Chemistry and Physics for Civil Engineers, Chemical Publishing
Co., New York.
4. Cement Industry Data book, Cement Manufacturers Assn., New Delhi,
5. World Cement Directory, CEMBUREAU,

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VARIOUS PROCESSES OF CEMENT MANUFACTURE (1)

Classification of the process of cement manufacture is made on the basis of the state of the raw
materials as they are fed to the kiln for Pyroprocessing. The raw materials of calcareous and
argillaceous compositions are to be obtained from the nature, crushed, ground and blended
together with any other additives or correcting materials (to be described later) before they are
fed to the kiln.

The Wet Process – The earlier practice of cement manufacture was based on ‘wet’ process, in
which the kiln feed entered the kiln in the form of slurry, with moisture content varying from 30 to
50 percent by mass. Such practice was necessitated if the raw materials had high moisture
content. The materials in the slurry form could be blended more uniformly and dust losses were
lower. Energy required for grinding was relatively lesser, but more thermal energy was required
because of extra heat required to evaporate the water. For each 1% moisture content in the raw
mix, additional 33 kcal/kg of fuel is required. With the advent of more efficient ‘dry’ process plants
(described later), not many wet process cement plants are in operation at present. Many wet
process plants of old vintage in different countries have either been ‘converted’ to dry process or
simply shut down.

Since most of the discussion in this course will center on dry process, some description of wet
process of cement manufacture is given here. The process flow sheet shown in Figure I may
please be seen. Limestone, after necessary size reduction, is fed in a ball mill with the clay
dispersed in water. Limestone is ground to the fineness of flour and the resultant slurry is pumped
to storage tanks. When softer raw materials like chalk and clay are used, they are broken up and
dispersed in water in wash mills. The two mixtures are pumped to mix in desired proportions,
blended and stored in storage tanks. The resultant slurry would have solid particles of > 90µm
(micron) size not exceeding 2 percent, and moisture content between 35 to 50 percent. The
sedimentation of suspended solids in the slurry storage tanks is prevented by mechanical stirrers
or by compressed air, before it enters the kiln. The wet process kilns were of greater length than
the dry process, to accommodate the additional dehydration zone.

The Dry Process - As the name implies, in this process the kiln feed enters the kiln in dry powder
form. The raw materials are crushed and fed in correct proportions into a grinding mill, where they
are dried and reduced in size to a fine powder. The raw meal is blended in a blending silo, before
entering the kiln. This is called a long dry process kiln. In most modern plants, the raw meal is
passed through a suspension preheater, with or without a precalciner having a secondary firing
system (see Figure I). Since drying, decarbonation and calcinations of the raw meal take place
outside the kiln, the length of the kiln is considerably reduced, and capacity of production
increased. Kilns with preheaters and prcalcinators will be described in greater details later on.

The Semi-dry Process - This process is adopted sometimes, when the moisture content of the
raw meal is so high that it can not be economically dried by the waste heat from the kiln system.
The pulverized kiln feed prepared as in the dry process is first pelletised into small nodules in a
granulator, by means of addition of about 10 -15 percent water.

The nodules are then fed onto a traveling grate and heated by the exit gases from the rotary kiln.
The material gets partially calcined and fed to the rotary kiln down a chute. This is called grate
process or Lepol kiln (see Figure 2 above). Instead of granulating the kiln feed, some plants use
filter press cakes to feed the kiln. The wet-kiln feed slurry is first pressed through large presses
for removal of free water before the filter cakes are fed to the rotary kiln.

The fuel consumption in Lepol kilns is of the same order as in preheater and precalciner kilns.
The dust content in kiln exit gases is reduced as it passes through the feed bed. The clinkers
formed are of uniform size. However, the output rates are lower than preheater/precalciner kilns.
The changing profile of different types of cement plants over the years in India is indicated in
Table I below.

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 MANUFACTURING OF CEMENT Clay
Limestone boulder from mines
– FLOW CHART
LST Bauxite
Iron Ore
Clinkerization Section

Weigh Feeder

Crusher Crushed Limestone

Heap
Conveyor Belt

1
4 stage
Preheater 2 Raw Mill
Raw Meal Silo

3
4 Burner

Clinker Silo
Rotary Kiln

Calcining Zone
Burning zone Cooler Cement Mill

Classification as per Type of Kilns

The discussions so far have been in terms of rotary kilns for cement manufacture, which are more
common. For example, nearly 96 percent of total cement production in India is through dry
process rotary kilns. However, in areas where only a small production of cement is envisaged -
may be due to limitations of limestone availability, or the market and local demand for cement
being limited, or difficult terrain conditions making movement of heavy plant and machineries
difficult - small ‘mini’ cement plants employing vertical shaft kilns (VSK) are adopted. Nodules of
raw meal along with fine coal powder are prepared and fed from the top of the vertical kiln. The
heating takes place on a grate at the bottom. Because of the colour of the feed, it is called black
meal process. Of course, rotary kilns of smaller capacities can also be adopted.

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The first cement kilns were static vertical kilns. VSK’s were use in the Victorian era. Rotary kilns
came later, at the turn of the 20th century, when a kiln with a revolving cylinder lined with firebricks
for manufacture of cement was patented in 1877. In India, there are about 365 mini cement
plants, most being of vertical shaft kiln type. The capacity is required to be less than 600 tpd,
although in practice, they are of much smaller capacity. The total installed production capacity is
nearly 11 MT, producing about 6 MT annually. In China, the number is in thousands, although
many of these are being abandoned now.

TABLE I

Types of Cement Plants in India

↓ Items / Year → 1950 1960 1970 1983 1995 2001 2004

No. of wet kilns 32 70 93 95 61 32 30
Installed capacity 9151 25001 38441 39641 25746 13910 12780
(t/d)
% of total kilns 97.3 94.4 69.5 41.1 12 5 3
No. of Semi-dry 1 3 8 9 8 8 8
kilns
Installed capacity 250 1200 5000 5500 5244 5260 4135
(t/d)
% of total kilns 2.7 4.5 9 5.7 2 2 1
No. of Dry kilns - 1 18 50 97 117 126
Installed capacity 300 11865 51265 188435 282486 359727
(t/d)
% of total kilns 1.1 21.5 53.2 86 93 96
Total kilns 33 74 119 154 166 157 164

Reference Books

1. Neville, A. M., Properties of Concrete, Longmans,

2. Lea’s Chemistry of Cement and Concrete, 4th ed., Butterworth,

CHEMISTRY OF CEMENTS (3)

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Chemical Composition and Phases in Portland cement

Portland cement, being made from calcareous and argillaceous raw materials, is, as to be
expected, composed of compounds of oxides of calcium (CaO), silicon (SiO 2), aluminum (Al2O3)
and iron (Fe2O3). It is customary to express the chemical formulae of the compounds in cement
as the sum of the oxides e.g. Ca3SiO5 is expressed as 3CaO.SiO2. It does not mean that the
constituent oxides exist separately within the structure of the phases. One exception is MgO,
originating from impurities in the main raw materials.

Among the main oxides, CaO occurs as Calcite (CaCO3) in limestone. It decarbonates at about
temperature of 680OC and above.

CaCO3 → CaO + CO2

We had taken note of this reaction in connection with lime manufacture. It is an important reaction
in cement manufacture, both in terms of thermal energy consumed, reduction in solid volume and
the amount of CO2 emitted to the environment.

SiO2 occurs as aluminosilicates in clay or shale, rather than the oxides. Silica, SiO 2 exists
naturally in the pure state as different crystalline polymorphs (e.g. α–quartz, Crystobalite and
Tridymite). Poorly crystalline or amorphous forms are also found as in Opal and Flint etc.

Al2O3 and Fe2O3 are not essential for the hydraulic properties, but their presence is essential as
flux in the hottest zone of the kiln in cement manufacture, to keep the thermal energy required to
manageable economical levels. Minor components are those, whose presence even in small
amounts (<1.0 percent) can make profound difference in the manufacturing process, in the
environmental issues, or the properties of the cement. Primary among them are ‘alkalis’ - Sodium
(Na2O) and Potassium (K2O) oxides, which are really present as sulphates, and MgO. Others
include Chlorides (Cl -) Manganese (MnO2), Boron (B2O3), Phosphorous (P2O5), Titanium,
Chromium etc. These will be discussed later in this Course.

Cement Chemistry Notations

It is customary to abbreviate common oxides to single letters, e.g. C for CaO, and the compound,
for example Ca3SiO5 is first written as 3CaO.SiO2 and then expressed as C3S. The total list is
given below;

Cement Chemistry Notations

Item Oxide Notation
Cement / Clinker CaO C
SiO2 S
Al2O3 A
Fe2O3 F
MgO M
K2O K
Na2O N
TiO2 T
P2O5 P
Others CO2 Ć
SO3 S
H2O H
Gypsum, Calcium Sulphate CS
Hydration Products Calcium Silicate Hydrates C-S-H
Calcium Hydroxide CH
Typical Chemical Composition – The cement clinker has typically a composition of;

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CaO - 60 to 65 %,
SiO2 – 19 to 22 %,
Al2O3 – 5 to 8 %, and
Fe2O3 – 3 to 5 %.

After addition of gypsum (or other form of calcium sulphate) ≈ 5 %, the range of typical chemical
composition of ordinary Portland cement (taken from a UK source) is as given in the Table below.

Chemical Composition of Cement (Typical)

Item Amount, %
CaO 63.2 – 66.4
SiO2 19.5 – 22.2
Al2O3 4.1 – 6.2
Fe2O3 2.1 – 3.3
K2O 0.43 – 0.80
Na2O 0.14 – 0.24
SO3 2.5 – 3.0
MgO 0.8 – 1.4
Free Lime 0.9 – 2.1
Loss on Ignition (LOI) 0.7 – 1.7
Insoluble residue (IR) 0.5 – 1.7

Two terms in the above composition need explanation. Loss on ignition is the loss of mass when
heated to 1000OC, which could be due to any moisture or CO2 attracted during storage, CO2 in
the limestone filler when permitted to be added, any water content in gypsum not driven out
during manufacture, or any adulteration. Insoluble residue is what is insoluble in hydrochloric
acid; indicate free quartz, impurities from rock gypsum, or insoluble in adulterants. When
industrial wastes like fly ash, which are mostly acid-insoluble, are permitted to be added in
composite cements, the values of IR are higher.

In Indian cements, the values for CaO content could be somewhat lower, depending upon the
quality of limestone. Proportion of MgO in some cases can be higher, the upper limit being 5%.

The Phases in Portland cement

Before the phases present in cements are identified, let us consider how the oxides interact at
different compositions and different temperature, as binary, ternary and quaternary systems.
These are best studied in terms of phase diagrams. What is described here is a simple
explanation.

The System CaO – SiO2

The equilibrium phase diagram for the system CaO – SiO 2 is shown below. It contains four binary
compounds – CS, C3S2, C2S and C3S. The melting point of pure CaO is about 2750OC, and that of
SiO2 is about 1698OC. However, presence of each other lowers the liquidus temperature. Out of
the four phases, CS and C3S2 are not hydraulic, nor are they formed during cement manufacture.

C2S has a number of polymorphs. On cooling from higher temperatures, α - C 2S ultimately

transforms to β – form at 630OC. At still lower temperature transformation to γ - C2S, which is not
hydraulic, takes place. Fortunately, β – C2S can be stabilized to low temperatures by quenching,
or by forming solid solutions with a large number of oxide impurities like boric oxide (B 2O3) or
Phosphorous pentaoxide (P2O5) and MgO.

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C3S is the most abundant phase. Although a lower limit of solubility exists for C 3S at about
1250OC, its decomposition to C2S and CaO does not occur on cooling; C3S exhibits a range of
metastable modifications between room temperature and 1100 OC, which are;
Rhombohedra ( R ) → Monoclinic ( M ) → Triclinic ( T ) forms.

CaO – Al2O3 System

The relevant phase diagram is reproduced below. Presence of Al 2O3 (and Fe2O3) lowers the
liquidus temperature of CaO and helps in reducing the burning temperature for cement
manufacture. This system contains stable phases C3A, CA, C12A7, CA2 and CA6. Except CA6, all
other phases are hydraulic.

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For compositions common in ordinary Portland cement manufacture, C 3A is formed, which is
responsible for early hydration and setting. Gypsum is used to control the rapid hydration of C 3A –
phase and initial set. CA and C12A7 are predominant phases in aluminous cements. CA2 and CA6 –
phases may be present in those with high alumina content.

Ternary System CaO – SiO2 – Al2O3

Lime – rich binary phases comprise nearly 90 % of cement composition. The equilibrium phase
assemblage at the burning temperature for the cement manufacture consists of C3S, C2S and a
liquid phase of composition Lc shown in the figure below. This liquid phase is containing the
aluminous components. The final phase assemblage obtained on cooling is more complex. It will
consist of C3S, C2S, C3A and a melt. The melt, on cooling would crystallize to give C2S, C3A and
C12A7. In practice, all the four phases - C3S, C2S, C3A and C12A7 are obtained.

The System CaO – Al2O3 – Fe2O3

The most significant phase in this system has a composition Ca 2 (Alx Fe1-x)2O5, where x is
between 0.48 and 0.7.If CaO is also present x is fixed at 0.48, giving a composition close to C 4AF
– called the ‘Ferrite’ phase. This phase contains a number of other ions in solid solution. Fe 3+ also
dissolves in C3A, C12A7 and CA, up to about 4.5% at 1325oC.

The Quaternary System CaO – SiO2 - Al2O3 – Fe2O3

We can now take a look at the phases present in Portland cement, which is a quaternary system
in the four oxides, besides minor components. More than 95% of the composition of Portland
(and aluminous) cements comprise compounds containing CaO, SiO 2, Al2O3 and iron oxides.
There are no quaternary phases and at equilibrium, any mix composition will crystallize the
following four phases;

Alite – It is tricalcium silicate - Ca3SiO5, which is written as 3CaO.SiO2 or expressed as C3S. Pure
C3S consists of 73.7% CaO and 26.3% SiO2. In industrial clinkers, the composition is modified by
incorporation of Mg2+, Al3+ and Fe3+ ions in solid solutions, the total of impurity oxides is of the
order of 3 to 4 percent. The crystal structure of cement minerals have been studied in details,
which is not discussed here. In Indian cements, C3S content typically varies from 30 to 48
percent.

Belite – It is dicalcium silicate – Ca2SiO4, which is written as 2 CaO.SiO2 or expressed as C2S.

Pure C2S consists of 65.1% CaO and 34.9 % SiO2. In industrial clinkers, the composition of Belite
is modified by incorporation of foreign ions, usually Al2O3 and Fe2O3, the total impurity oxides

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being 4 to 6 percent. Limit of K2O substitution is ≈ 1.2 percent. In Indian cements, C2S content
typically varies from 27 to 45 percent.

It is to be noted that in Portland cements, the total of C 3S + C2S content is between 70 to 80

percent, perhaps closer to 75 percent.

Aluminate phase – It is tricalcium aluminate – Ca3Al2O6, which is written as 3 CaO.Al2O3 or

expressed as C3A. Pure C3A contains 62.3% CaO and 37.7% Al2O3. The composition is modified
by incorporation of foreign ions like Si4+, Fe3+, Na+ and K+. The substitution is substantial – it could
be 13 percent for cubic and 20 percent for orthorhombic modification of the crystal structure. In
Indian cements, C3A content typically varies from 4 to 10 percent.

Ferrite phase – It is tetra calcium alumino ferrite – Ca2AlFeO5, also written as 4 CaO.Al2O3.Fe2O3,
or abbreviated as C4AF. Ferrite phase can be prepared with any composition in the solid solution
series Ca2 (Alx Fe1-x)2O5, where x is between 0 and 0.7. C4AF is a particular form for x = 0.5. Pure
C4AF contains 46.1 percent CaO, 21 percent Al2O3 and 32.9 percent Fe2O3.The composition is
substantially modified by variation in A/F ratio and incorporation of foreign ions like Mg 2+, Si4+ and
Ti4+. Mn3+ can replace all the Fe3+ ions or up to 60 percent of Al3+ ions. The ferrite phase makes up
about 5 to 15 percent of ordinary Portland cement clinkers.

Calculation of Amount of Different Phases

Chemical analysis of cement or clinker is obtained in terms of oxides, as shown in the example
given above. Estimation of the relative proportions of the phases is accomplished by the
procedure known as ‘Bogue calculation’. It is based on the following steps;

 Assume that the compositions of the four major phases are C3S, C2S, C3A and C4AF.
 Assume that Fe2O3 occurs in C4AF.
 Assume balance of Al2O3 occurs in C3A.
 Deduct from the CaO content, the amounts attributable to C 3A and C4AF and solve two
simultaneous equations to calculate the amounts of C3S and C2S.

The formulae for clinkers are;

 C3S = 4.0710 CaO – 7.6024 SiO2 – 6.7187 Al2O3 – 1.4297 Fe2O3.

 C2S = - 3.0710 CaO + 8.6024 SiO2 + 5.0683 Al2O3 + 1.0785 Fe2O3.
= 2.8675 SiO2 – 0.7544 C3S.
 C3A = 2.6504 Al2O3 – 1.6920 Fe2O3.
 C4AF = 3.0432 Fe2O3.

For cements, put (CaO – 0.7 SO3) in place of CaO.

The above gives the potential phase composition and differs from the true phase composition
because;

 Equilibrium may not be maintained during cooling, and

 Composition of clinker phases differ from the pure compounds, as explained before.

The total of four phases calculated plus free lime will not add up to 100 percent, because minor
oxide components are ignored. It is implied that all the MgO occurs as periclase.

Reference Books

1. Lea’s Chemistry of Cement and Concrete, 4th ed., Butterworth.

2. R. H. Bogue, Chemistry of Portland Cement, Reinhold, New York.
3. H. F. W. Taylor, Cement Chemistry, Academic Press, London.
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CLINKER FORMATION (1)

For satisfactory clinker formation, the states of both heating (to a high temperature) and
subsequent cooling should be accomplished in a satisfactory manner, The chemical composition
of the raw materials and their proportions, the physical state i.e. fineness and homogeneity, and
the features of the kiln – cooler system are important. It is essential to approach phase
equilibrium at clinkering temperatures. The mineralogical state of the clinker obtained at the peak
firing temperature becomes thermodynamically unstable during the cooling stage. Rate of cooling
and quenching are important.

The reactions occurring during the burning of the raw meal and clinker formation are summarized
in the Table and the Figure below indicates the respective temperatures. Both are taken from
Lea’s ‘Chemistry of Cement and Concrete’.

Summary of Reactions Occurring during Clinker Formation

Reaction type Examples and comment

Decomposition
Diffusion
Melting
Liquid phase sintering
Polymorphic transformation
Evaporation / condensation
CaCO3 → CaO + CO2; one or more volatile
substances form in the course of reaction
2 CaO +SiO2 → Ca2SiO4; solid-state reaction
between components
Formation of C-A-F-S eutectic at 1338OC between
C3S, C2S, C3A and C4AF.
3 CaO + SiO2 → Ca3SiO5; precipitation of alite from
melt, in which the reactants are dissolved.
α -C2S → β and/or γ - C2S; polymorphic changes
occurring during cooling.
(Liquid)–K2SO4 → (vapour)-K2SO4; evaporation and
condensation of alkali sulphates.

In summary, we may note;

I. Below 1300OC – The reactions that take place are;

a. Decomposition of calcite at 680OC and above,

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 b. Activation of silicates through removal of water and changes in the crystal
structure at up to 700OC,
c. Decomposition of clay minerals ≈ 900OC,
d. Initial combination of calcite or lime from it with activated quartz and Al 2O3 and
Fe2O3 ≈ 700 - 900OC,
e. Belite forms at 900 – 1200 OC.

II. Between 1300 – 1450OC – Clinkering.

A melt is formed mainly from aluminate and ferrite phases. By 1450 OC, some 20 to
30 percent of the mix is liquid.
Much of belite and nearly all the lime react in the presence of the melt to form alite.
The material nodulises to form clinker.

III. During cooling – The liquid crystallizes giving mainly aluminate and ferrite. Polymorphic
transformations of the alite and belite occur.

Moduli Values –
In the manufacture of Portland cement, it is desirable that C 3S content is optimized and the free
(uncombined) lime content is minimized. For such a situation, the CaO content is given by;

CaO = 2.8SiO2 + 1.18Al2O3 + 0.65Fe2O3.

CaO
The ratio -------------------------------------------- is called ‘lime saturation factor’ (LSF).
2.8SiO2 + 1.18Al2O3 + 0.65Fe2O3

LSF largely shows the proportion of alite and belite in the clinker. In Portland cements, it is
typically in the range of 0.92 to 0.98, although specifications allow a range of 0.66 to 1.02. For
LSF> 1.0, free lime will be present. Please note that the above formula is for clinkers; for cement,
use (CaO – 0.7SO3) in place of CaO.

Some other useful limits are;

Silica ratio (SR) = SiO2 / (Al2O3 + Fe2O3). SR is typically in the range of 2.0 to 3.0. Increase in SR
means proportion of liquid is lower and the clinker becomes difficult to burn.

Alumina ratio (AR) = Al2O3 / Fe2O3. The value of AR can vary between 1.0 to 4.0. AR determines
the quantity of liquid formed at low temperature. At 1338 oC, the quantity of liquid is theoretically
maximum at AR of 1.38.

Role of Mineralisers and Flux –

It has been discussed how the presence of Al2O3 and Fe2O3 in the raw mix, although not essential
to the constitution of Portland cement, constitute a cheap source of fluxes lowering the thermal
energy required in cement manufacture. Al2O3 and Fe2O3 form a liquid melt, in which much of the
belite (C2S) and nearly all the CaO react, to form alite (C3S). Other volatiles like MgO, Na2O and
K2O also act as flux. When the ratio of A/F is > 1.38 and the amount of MgO present is < 2
percent, the amount of flux present at different temperatures is given by the formulae;
 Flux at 1338OC = 6.1 x% Fe2O3 + % MgO + % Na2O + % K2O.
 Flux at 1400OC = 2.95 x % Al2O3+ 2.2 x% Fe2O3 + % MgO + % Na2O + % K2O.
 Flux at 1450OC = 3.0 x % Al2O3+ 2.25 x% Fe2O3 + % MgO + % Na2O + % K2O.

Where the ratio A/F is < 1.38,

 Flux at 1338OC = 8.5 x % Al2O3 – 5.22 x% Fe2O3 + % MgO + % Na2O + % K2O.

13
If the level of flux is less than 19 percent, the coating formation is inadequate and refractories are
likely to be damaged. Excessive high flux levels at 1338OC will lead to ring formation at the point
where the kiln feed enters the burning zone. It is, therefore, necessary to ensure the optimum
level of flux by careful design of the raw mix. The desirable range could be about 19 to 26
percent. Somewhat higher level may be required in case of difficult raw materials, but not
exceeding 28 – 29 percent.

Mineralisers –

These are minor components or additives in the raw mix in small amounts, which increase the
activity of the clinker phases, facilitate formation of clinker having adequate properties with lower
grade limestone or at lower temperatures. From material science, it is known that the activity of a
single crystal may be enhanced by introducing ‘defects’ in the crystal structure. Extrinsic defects
can be induced in the clinker phases by crystallochemical substitution forming solid solution,
which contribute to the reactivity of the phases. Such levels of impurity-induced defects can take
place in the C3S and C2S phases in industrial clinkers

The role of mineralisers can be summarized under the following headings;

Fluxing action – Temperature of first formation of liquid are reduced; the viscosity and surface
tension of the liquid are modified; and crystal morphology is modified.

Phase relations – The relative thermodynamic stabilities of the clinker minerals are changed due
to solid solution effects;

Hydraulic activity – The reactivity of clinker minerals (alite, and more particularly, belite) are
modified by solid solution and/or crystal symmetry effects (defects).

In cement manufacture, liquid formation is assisted by traces of halides like Cl - and F-. Presence
of chlorine (Cl-) in the cement invites opposition from the users, because of risk of corrosion of
reinforcing steel. Fluoride addition has the unique combination of acting as a flux, lowering the
temperature of melt formation, reducing the viscosity and surface tension of the liquid and
enhancing the thermodynamic stability of C3S, enabling its formation at temperature < 1250 OC.
Formation of liquid may take place at lower temperatures also due to presence of sulphates and
carbonates, which have low melting point eutectics (≈ 800 - 900OC).

Among transition metal oxides, the effectiveness to aid C3S formation at 1350OC, at 0.5%addition
was found to be as follows;

CuO > ZnO > MnO2 > SnO2 > PbO.

Fluorspar, Fluorogypsum, Basalt and Barite are among the mineralisers used in the Indian
cement industry. Use of fluorspar has been reported to reduce the amount of free lime, increase
in C3S content or lower the clinkering temperature. Barium increases the reactivity of C 2S phase
by substitution in the crystal structure. Chromium and Titanium Oxide can increase the sizes of
alite and belite crystals. However, in all such cases, the amount has to be controlled very
carefully, to prevent other adverse effects.

Reference Books

1. Lea’s Chemistry of Cement and Concrete, 4th ed., Butterworth.

2. R. H. Bogue, Chemistry of Portland Cement, Reinhold, New York.
3. H. F. W. Taylor, Cement Chemistry, Academic Press, London.

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14
TYPES AND PERFORMANCE CHARACTERISTICS OF CEMENTS (4)
Cement is defined as ‘a hydraulic binder, which, when mixed with water, forms a paste which
sets and hardens by means of hydration reactions and processes and which, after hardening,
retains its strength and stability even under water’. Much of performance of cement is in terms of
setting, hardening and strength development as well as durability under the service condition.
The various types of cement are either in terms of levels of performance, or based on its chemical
composition.

Hydration Reactions –

Hydraulic hardening of Portland cements is primarily due to the hydration of calcium silicates but
other phases like aluminates also participate in the process. The products of hydration of cement
gradually fill the space between aggregate particles to give a continuous matrix. Relatively
impermeable composite results, which is strong in compression. The solubility of hydration
products in water being rather limited, the composite becomes stable and durable.

The cement paste sets and hardens as the hydration proceeds after contact with water. The term
setting denotes a rather sudden loss of plasticity of the paste and conversion to a solid material.
The strength at this stage may not be much. The term hardening denotes the development of
hardness and strength following the setting of cement paste.

The products of hydration of cement are chemically the same as the products of hydration of the
individual phases. The physical behavior of hydrating cement is similar to those of the two
calcium silicates. The rates of hydration of the phases are, however, different, as is apparent from
the figure below. C3A and C4AF phases have the highest rates of reaction, followed by C3S, and
C2S is the slowest to react.

The hydration product of calcium silicate phases, C3S and C2S, are calcium silicate hydrate with a
probable composition of C3S2H3 (abbreviated as C–S–H), and calcium hydroxide Ca(OH)2. The
reactions are of the types;

For C3S – C3S + 6H → C3S2H3 + 3 Ca(OH)2,

The corresponding masses involved are:

100 + 24 → 75 + 49.

For C2S – C2S + 4H → C3S2H3 + Ca(OH)2,

15
The corresponding masses involved are:

100 + 21 → 99 + 22.

The above equations indicate that both C3S and C2S require about the same amount of water for
reaction, but C3S produces more than double the amount of Ca(OH)2. C-S-H has the strength
giving properties, whereas Ca(OH)2 has no significant contribution towards strength, except
through pozzolanic reaction (see later).

The composition of C-S-H indicated as C3S2H3 is, at best, approximate. It indicates the molar ratio
of C/S to be 3, whereas, in hardened cement paste, it is much lower – between 1.4 to 2, 1.7 being
more probable. From the structural viewpoint, C-S-H is known to exist in variety of forms and
composition, and a more general description (CaO)x.SiO2. y.(H2O), with x and y having a range of
possible values, is more apt.

For C3A - C3A + 6H → C3AH6.

The corresponding masses involved are:

100 + 40 → 140.

For C4AF – Under comparable conditions the products of hydration of the ferrite phase are, more
or less, similar to those of C3A, although the rates differ.

The relative rates of gain of strength for hydrates of different phases are shown in the figure
below.

The rate of strength development of cement depends upon the relative proportion of different
phases present. For example, higher C3S content results in greater strength at early ages than
when the C2S content is more. Other factors like fineness of grinding are also important.

Role of calcium sulphate addition in cement

The final form of calcium aluminate hydrate existing in hydrated cement is probably the cubic
crystal C3AH6, but it is possible that a hexagonal C4AH12 crystallises out first and later changes to
the cubic form. The reaction of C3A with water proceeds very fast and leads to immediate
stiffening, which is called flash set. In order to prevent this, gypsum, or some other form of
calcium sulphate is added during grinding of cement clinker. In the presence of calcium sulphate,
the amount of C3A directly hydrating to C3AH6 is considerably arrested, and calcium sulpho-
aluminate hydrate (ettringite) – C6A.S3.H32 is formed first. Ettringite is also called trisulphate.

16
 C3A + 3CSH2 + 26H → C6A.S3.H32.
As hydration proceeds and the available calcium sulphate gets consumed, trisulphate ettringite
formed initially reacts with the excess of C3A to form calcium -aluminate monosulphate hydrate
(monosulphate) - C4ASH12 as the product of reaction;

C6A.S3.H32 + 2C3A + 4H → 3 C4ASH12.

A hexagonal calcium aluminate hydrate, C4AH19 also forms, which may be present as separate
crystals or in solid solution with monosulphate.

The calcium sulphate added is usually in the form of mineral gypsum, (calcium sulphate
dihydrate, CaSO4. 2H2O). Other forms are calcium sulphate hemihydrate, CaSO 4. ½ H2O or
calcium sulphate anhydrite, CaSO4.. In India, mineral gypsum is mostly obtained from the mines
in Rajasthan. Its purity (in terms of SO3 content) is limited. The quantity mined is not enough for
the entire cement production in the country and the distances involved are large in many cases.
Chemical gypsum, like phospho-gypsum and fluoro-gypsum obtained as waste products from
chemical industries is used. These may require washing to remove impurities. Marine gypsum
from sea bed has high purity, but the chloride content may exceed the value permitted in cement
specifications.

Rate of heat evolution during hydration

Hydration of cement is an exothermic reaction. The rate of heat generated helps in monitoring
different stages of hydration of cement and the setting process. This is shown in the figure below,
which indicates three peaks in the rate of hydration within first three days or so.

Immediately after contact with water, formation of hydrate phases gets underway. Alkali sulphate
– mainly K2SO4 dissolves in water within seconds, giving rise to the initial endothermic peak. The
hydration of C3A before SO3 comes into reaction is accompanied by evolution of much heat,
which is responsible for the first peak. As sulphates control the hydration of C 3A, a dormant
(induction) period follows, during which the rate of reaction is slow. This is because of initial rapid
release of Ca(OH)2 formed due to hydration of silicates leaves an outer layer of C-S-H, which
impedes further hydration. This stage lasts for about one to two hours, during which the cement
paste is workable. The surface layer is broken down and the rate of hydration increase slowly till it
reaches a second peak after some time – anything between four to ten hours, depending upon
the cement characteristics. During this period, the products of hydration of individual cement
grains come in contact with each other forming a network and setting takes place. Following this
peak, the rate of hydration again slows down, till the third peak is reached, due to reaction of C 3A
with ettringite, once SO3 is depleted.

Use of industrial wastes -

Various industrial wastes are used in cement, primarily as additions, which are blended or inter-
ground with cement clinker and calcium sulphate, to result in ‘blended’ or ‘composite’ cements.

17
Others can be used as raw materials in the manufacture of cement clinker. Use of chemical
gypsum for set control was mentioned above. Some of the industrial wastes used in cement are
discussed below.

Fly ash -

Fly ash is a pozzolana, which in itself, is not hydraulic, but can combine with lime in the presence
of water, to give cementitious products. Fly ash is obtained as fine particles in the exhaust flue
gases in coal-fired thermal power stations. These are collected in the electrostatic precipitators
and disposed of, either in dry or wet state. Typical chemical composition of Indian fly ashes is
given in Table I;

TABLE I

TYPICAL COMPOSITION OF INDIAN FLY ASH

SiO2 – 52 – 60 percent,
Al2O3 - 20 – 33 percent,
Fe2O3 – 2 – 7 percent,
CaO – 2 – 10 percent,
Loss on Ignition – 1.5 – 14 percent,
And small amounts of MgO. SO3, Na2O and K2O.

The quality requirements are specified in IS: 3812 – Part I – 2003, and are comparable to other
international specifications (Table 2). The main requirements, which govern the performance of
fly ash in cement and concrete, obtained from one source, can be summed up in terms of five key
parameters. These are;
 Specific surface area, Blaine’s,
 Residue on 45 sieve (325 mesh),
 Unburnt carbon, commonly measured as Loss on Ignition (LOI),
 Moisture content, unless collected dry, and
 Glass content.

Siliceous pozzolanicity of fly ashes require that the SiO 2 phase be in glassy form. The glass
content of Indian Fly ashes (20 – 35 percent) are lower than in other countries (70 – 90 percent)
and, to that extent, the reactivity are power. Reactivity goes up with fineness and can be
improved by further grinding.

Portland Pozzolana cement (Fly ash based) is specified in IS:1489 – Part I. It permits addition of
15 to 35 percent fly ash. Addition of 20 – 25 percent is common practice.

Hydration reaction of fly ash in cement- The pozzolanic reaction involves the active SiO2
component in fly ash combining, in presence of water, with the Ca(OH) 2 liberated during hydration
of silicate phases of Portland cement, to form calcium silicate hydrates (C-S-H).

CaO + SiO2 + H2O → C-S-H.

Such C-S-H differs in composition from that resulting due to hydration of the silicate phases in
Portland cements. In addition, ettringite is formed rapidly and is observed from 5 hours up to 28
days. Formation of C-S-H due to pozzolanic reaction manifest after the initial hydration of
Portland cement - may be 3 to 14 days after mixing with water, although C-S-H following
hydration of C3S phase is visible after 24 hours.. Nearly equal masses of silica and lime combine;
in other words, a pozzolana rich in content of active silica (for example, silica fume containing 85
to 90 percent silica in glassy form) can combine with equal mass of lime liberated by cement
hydration. With Indian fly ashes, much of the Ca(OH)2 remains unreacted in pozzolanic reaction.

18
Granulated Blast Furnace Slag -

Blast furnace slag is obtained from blast furnace used in manufacture of pig iron as a molten
stream at a temperature of 1400 – 1500OC. It consists essentially of silicates and aluminates of
calcium. Molten slag when allowed to cool in air, loses its glassy form. It should, therefore, be
water quenched to retain the glassy form and its reactivity. This is called granulation and what is
used in cement and concrete. Subsequent reference to slag will mean granulated blast furnace
slag, suitable for use in cement. The requirements of composition are covered in IS: 12089, which
lay down minimum glass content of 85 percent, for use in cement and concrete. The chemical
composition varies over a wide range (Table 3).

TABLE 2
SPECIFICATIONS FOR FLY ASH IN CEMENT AND CONCRETE
(Values are %, unless other units are indicated)

Item ASTM European Specifications India, IS: 3812 –Pt. 1

C-618 En-450 En-197-1 BS 3892-I Earlier -1981 Current – 2003
SiO2, min. 35 35
Reactive / soluble SiO2, min. 25 25 20
S + A + F, min. 70 70 70
MgO, max. 5 5
LOI (1 hour) max. 6 5–7 5-7 7 12 5
Total Alkalis, max. 1.5 1.5 1.5
SO3, max 5 3 2 2.75 3.0
Free CaO, max 1 1
Total/ reactive CaO, max. 10 10 10
Fineness, 45 micron, max 34# 40 *** 12 34
2
Blaine’s m /kg min. 320 320
Cement activity, 28 days 75* 75* 80** 80@ 80@
2
Lime reactivity, N/mm 4 4.5
Soundness, Lechatelier, mm 10 10 10 10
Autoclave, % 0.8 0.8 0.8

Notes
I. *** Permitted variation + 10% of average
ii. #Permitted variation +/- 5% of average
iii. * 25% fly ash
** 30% fly ash
@ 20% fly ash
iv. Water content - 95% in BS 3892, 105 % max in ASTM
v. Drying Shrinkage in IS 3892, < 0.15%
vi. Requirement of colour consistency in BS 3892

For use in the manufacture of Portland slag cement, the chemical composition of slag should
satisfy the following ratios;

19
CaO + MgO + 1/3 Al2O3
----------------------------------- ≥ 1.0,
SiO2 + 2/3 Al2O3

CaO + MgO + Al2O3

----------------------------------- ≥ 1.0,
SiO2

CaO + CaS + ½ MgO + Al2O3

----------------------------------- ≥ 1.5,
SiO2 + MnO

TABLE 3

TYPICAL CHEMICAL COMPOSITION OF SLAGS

Characteristics Range, percent

SiO2 29 – 36
Fe2O3 0–2
Al2O3 16 – 30
CaO 31 – 34
MgO 7 – 12
IR 0.4 – 5.5
S (Sulphide sulphur) 0.5 – 1.5
Glass content 80 - 95

IS: 455 permits addition of granulated slag in the range of 25 to 70 percent in the manufacture of
Portland Slag cement, by inter-grinding or separate grinding and blending. Because of relative
hardness of slag, the common level is 40 to 50 percent. Ground granulated slag can also be
added to OPC and other ingredients of concrete in a concrete mixer.

Hydration of slag in cement -

The difference between fly ash and slag is that the latter is hydraulic; slag, on its own can hydrate
in contact with water. However, the reaction is very slow. No hydration products can be observed
when slag is placed in water; however, there is evidence that the surface of the slag is modified
as soon as it comes in contact with water. The hydration of slag can be activated. Known
activators are sodium hydroxide, sodium carbonate, sodium silicate, calcium sulphate,
phosphogypsum, and of course, lime. Ca(OH)2 liberated by hydration of Portland cement
activates the hydration of the slag component in Portland slag cement. The slag surface is first
covered by Portland cement hydrates, then reacts with Ca 2+ ions from the supersaturated solution
forming C-S-H. Dissolution of Ca2+ and Al3+ ions from slag also leads to formation of the hydrate.
C-S-H formed by slag hydration has a lower C/S ratio, of the order of 0.5 to 1.4. Other products of
hydration of slag in cement are Ettringite, monosulphate aluminate and calcium aluminum
hydrates. The pH value is not reduced to any appreciable extent.

Silica Fume –

Silica fume is a by-product resulting from the reduction of high purity quartz with coal in electric
arc furnaces at temperature of 2000oC in the production of Ferro-silicon alloys or Silicon metal. In
the process, SiO-vapours are produced, which oxidise and condense in the form of very tiny
spheres of non-crystalline silica. Apart from IS: 15388 - 2003, ASTM C1240 or ACI Committee
Report 226 also offer ample guidance. The essential features of silica fume, which are of
importance to concrete making, are the very fine particles and high content of amorphous silica.
Silica fume should contain 85 - 90 percent SiO2, most of which should be in glassy form. It is
common practice to add silica fume as a replacement of OPC in concrete mixer.

20
Industrial wastes as raw mix component –

Fly ash and slag can be used in limited amounts in the raw mix composition. Much wider scope
exists for use of sludges, which are wastes from various chemical industries disposed off in liquid
form. A summary of typical chemical composition of various lime sludges is shown in Table 4.
These are obtained from fertilizer, paper, acetylene, sugar, chromium and soda ash industries
and have the potential to form part substitute of limestone. The major difficulty is that the sludges
are in wet form. In absence of wet process cement plants, these sludges must be dried before
use in dry process cement plants. Another aspect is the presence of impurities like P 2O5, F-, Cl-,
alkalis and Cr2O3 etc. in various amounts, which may limit the amount of sludges to be added.

In addition, the following industrial wastes have mineralizing properties;

 Phosphorous slag and phospho-gypsum,

 Fluoro phosphorous slag,
 Barium-bearing waste obtained in the manufacture of white mineral pigments, and
 Zinc-containing wastes.

Types of Cement –

Classification of cements in different types are done either on the basis of performance
characteristics like strength, setting and hardening, colour and heat evolution, or on the basis of
chemical composition and resistance to chemical attack. The various types of cements covered in
Indian (IS) specifications are listed in Table 5 below.

TABLE 5
Types of Cement Covered in IS Specifications

S. No. Generic Type Description IS

1 Ordinary Portland 33 Grade. 269

2 cement 43 Grade 8112
3 53 Grade 12269
4 Rapid Hardening 8041
5 Sulphate Resisting 12330
6 Low Heat 12600
7 Hydrophobic Cement 8043
8 White Cement 8042

9 Blended and Portland Slag Cement 455

Composite cements Portland Pozzolana Cement
10 - Fly ash based 1489-I
11 - Calcined Clay based 1489-II
12 Masonry Cement 3466
13 Supersulphated Cement 6909

14 Special Cements Oil Well Cement 8229

15 High Alumina Cement 6452
for Structural Use

ASTM C150 classifies Portland cement into five ‘types’;

21
  Type I – ordinary Portland
 Type II – moderate sulphate resisting / moderate low heat Portland
 Type III – rapid-hardening Portland
 Type IV – low heat Portland
 Type V – sulphate-resisting Portland.

In addition, ASTM C595 and ASTM C150 classify blended hydraulic cements as;

 Type I (SM), Type IS – Portland blast furnace

 Type I (PM), Type IP – Portland-pozzolana
 Type S – Slag cement.

European specification EN 197-1 has adopted an elaborate scheme of specifying different types
of cements. The features and comparison of the specification requirements in all the three are
given in a publication listed below.

Reference Books

1. Lea’s Chemistry of Cement and Concrete, 4th ed., Butterworth.

2. Neville, A. M., Properties of Concrete, Longmans
3. Mullick, A. K., Comparison of BIS, ASTM and EN Cement Standards, Publication no. 5,
Grasim Industries Ltd. (Cement Business), Mumbai.
4. Mullick, A. K., and Ahluwalia, S. C., Utilisation of Wastes in Indian Cement Industry,
International Symposium on Cement Industry Solutions to Waste Management, Calgary,
Canada, Oct. 1992.

--------

22
RAW MATERIALS AND MINING (4)

The raw materials for cement manufacture which are subject of geological exploration are mainly
limestone and clay. Both occur in the nature as rocks (mostly sedimentary rocks). In addition,
certain materials are incorporated in the raw mix in smaller quantities, in order to correct its
chemical composition in terms of moduli values discussed earlier. These are called ‘additives’
and comprise materials providing iron and alumina in the required proportions.

There are a number of parameters which determine the suitability of the raw materials for use in
cement manufacture. This is particularly important for limestone deposits, which, in India,
comprise more than 90 percent of the mass of the raw mix.

Parameters of Quality of Limestone Deposit –

Suitability of limestone is mainly judged on the basis of its chemical composition. Limestones
consist predominantly of CaCO3, as Calcite. In addition, they often contain Mg, Al and Fe
combined as carbonates and silicates; as well as silica as quartz. The reactions in the cement
burning process takes place between the individual phases present in the kiln feed. In few
instances, it has been possible to have a limestone of composition with LSF = 1, and silica ratio
and alumina ratio within desirable range for raw mix composition. Such a limestone is more
favourable, because the components are naturally present in a well blended form and can be
used singly in cement manufacture. However, most of the time, the composition deviates from
such ‘ideal’. It should be noted that mixture of ‘pure’ limestone and ‘pure’ clay will react less
favourably. Limestone containing some admixture of clay minerals is to be preferred. The
following classification in terms of CaCO3 content is applicable;

Pure limestone > 95% CaCO3

Marly limestone 85 – 95% CaCO3
Lime marl 70 – 85% CaCO3
Marl 30 – 70% CaCO3
Clay Marl 15 – 30% CaCO3
Marly Clay 5 – 15% CaCO3
Clay < 5% CaCO3

For cement manufacture, ‘Cement grade’ limestone should, conventionally have 46 – 47 % CaO,
or > 82 % CaCO3. If MgO is present (as MgCO3), the ‘Total Carbonates’ (TC) should be about
90%, with the proviso that MgO content does not exceed 6% as per IS requirements.

High Silica, low lime limestone with SiO2 > 14% and CaO < 44% is classified as ‘low grade’. For
intermediate compositions i.e. CaO > 44 % but < 46 %, it is called ‘marginal’ grade limestone. On
the other hand, limestone with CaO >48 % can be called ‘high’ grade and used as a ‘sweetener’
with limestone of lower CaO content, to yield a satisfactory raw mix.

The mode of origin of limestone e.g. whether sedimentary, igneous or metamorphic, influence the
mineral form, degree of crystallinity, grain size, cementing medium, intensity of compaction etc.
Each of these parameters influences the thermo-chemical reactivity. i.e. dissociation
characteristics and chemical combinability. For cement manufacture, fine-grained sedimentary
limestone deposits are preferred.

Clay Component –

The clay mineral component is generally a soft and loose-textured sedimentary rock deposit of
clays, slate, shale and crystalline slates. Depending upon the particle size, these are classified as

23
Clay (<0.002 mm),
Silt (0.002 – 0.063 mm),
Sand (0.063 – 2 mm) or
Gravel (> 2mm).

Suitability is judged by chemical composition in terms of silica ratio (SR) and alumina ratio (AR).
Mineralogical form of silica is important. Large amount of free quartz is not desirable.

Assimilation of coal ash in the clinker provides a source of silica in raw mix composition. With
high ash coal used in India, often no clay is required to be added separately.

Corrective materials –

Small amounts of materials other than limestone and clay are needed, containing high proportion
of oxides which may be deficient in the main raw materials. Laterite or quartz sand is used for
increasing SiO2; roasted pyrites or iron ore for Fe2O3; and bauxite for Al2O3. Mineralisers are
added with marginal or low grade raw materials or when the raw mix has low burnability.

Exploration and Reserve Estimation -

For the manufacture of 1 tonne of cement, on an average, 1.5 tonnes of limestone are required.
For setting up a one MT cement plant, limestone deposit of the order of at least 60 MT are
required for a life span of 40 years, and much more for longer life and/or larger plant size and
future expansion. Hence, the deposit of limestone has to be properly explored, assessed and
evaluated. The main purposes of exploration are;

1. Verifying the quality of raw materials;

2. Establishing the range of variation in the quality of raw materials throughout the working
life of the deposit; and
3. Estimating and verifying the workable reserves of raw materials.

Availability of limestone in any country is, prima facie, known through geological exploration
carried out by the nodal governmental agencies (GSI and State Geological Surveys in India).
With this information as the starting point, more focused and dedicated investigation is required to
establish availability of ‘cement grade’ limestone. The exploration is carried out in three stages;

Stage I – Field inspection of a number of deposits, surface tests, large area mapping and a
limited number of exploratory borings. The main aim is to find out the quality of the deposit.

Stage II – One or more deposits are selected for detailed investigation. Comprehensive drilling
programme enables the deposits to be broadly studied. Chemical characteristics, bedding
conditions, ground water and possibilities of working the deposit are established over extensive
areas. Suitability of the site for quarrying or open-cast mining are known.

Stage III – Detailed exploration is carried out with the help of grid of closely spaced bore-holes to
determine the chemical composition of limestone and the variation over short distances.

The amount of exploration and the number of bore-holes depend upon the variation in the
chemical characteristics; more intense exploration being necessary when the variation is large
and vice-versa. The variance of the geochemical data of the deposit enables it to be classified as
under;

Simple – when the co-efficient of variation is ≤ 4 percent,

Complex - ≤ 10 percent, and
Intricate - > 10, ≤ 20 percent.

24
Classification on the basis of extent of exploration – The deposits are classified as
under;

Measured – Reserves which have been subjected to detailed exploration and have
been fully investigated with regard to chemical features and range of variation,
bedding, tectonics, hydrological conditions and legal aspects.

Indicated – Reserves which have been investigated on the basis of widely spaced
bore-holes; the types of rock, chemical composition, structure and bedding
conditions are broadly known.

Inferred – Reserves which are tentatively determined on the basis of limited

investigation with few isolated bore-holes, such that the features are known only in a
general way.

On this basis, the reserves of cement grade limestone in India are estimated as
follows (NCB, 1991 data);

Measured – 16,610 million tonnes (MT),

Indicated – 11,889 MT, and
Inferred – 61,334 MT.

Total – 89,833 million tonnes.

There is regional imbalance in the availability with deposits being located in the states in
southern, western, northern and eastern zones, in that order. States like Andhra Pradesh,
Karnataka, Gujarat, Madhya Pradesh and Rajasthan account for nearly 75 percent of cement
grade limestone deposits and large plants are set up in these states in large numbers. Next
comes states like Himachal Pradesh, Meghalaya and J&K etc.; while states like West Bengal
have no deposits and no large plants. Similar is the situation in Bangladesh. Now a large cement
plant is being set up in Bangladesh for which limestone from Meghalaya will be transported by a
belt conveyor.

Mining and Quarrying of Limestone –

As indicated before, a million tonne cement plant producing 3000 T of cement per day (330
working days in a year) will need more than 5000 T of limestone to be quarried every day. Proper
planning and deployment of mining equipment is necessary.

The usual method is of large scale open-cast mining using benching technique, in which the
material in the deposit is quarried in several benches or steps, one above the other. The
operations are seldom confined to a single bench or single location at a time. In order to
compensate for variation in chemical characteristics of the rocks at different depths and different
locations in the deposit, several benches at several working points are worked upon
simultaneously.

Computer-aided mine planning programme developed for such purposes helps in selecting
locations and benches, as mining progresses. The software developed by NCB enables reliable
estimation of limestone reserves, its grade and quality variation and help in proper planning pit
design and cost effective mining. The software is used by Indian cement industry. Various quarry
floor or base levels should be connected to each other and the general ground level by ramps,
forming sufficiently wide roads with gentle slope (1 : 10) for haulage and movement of vehicles. If
ground water is likely to be encountered, provision for pumping out should be made.The mining of
limestone involves the following steps;

 Drilling,

25
  Blasting / ripping,
 Loading and haulage to the site of primary crusher.

Drilling – Large-hole blasting with blast holes in single row parallel to the slope of quarry face is
common. The holes are more than 12 m in depth – may be 20 to 30 m, and the holes are of 50 to
250 mm diameter. Another alternative is ‘surface blasting’ with holes distributed over an area
instead of single row. Rotary drilling or percussive rotary drills are used for forming the blast
holes. Depending upon the characteristics of the rock and the machine deployed, step bit, roller
bit or cross bits are used. The drilling machines are with fully hydraulic drive system and have
capacities of 30 m/hour or so. The entire assemblage comprising the power pack, hydraulic units,
drilling mast, rod magazine and other accessories are mounted on a traction unit, which can be
moved form one bench and location to other, as required.

The purpose of blasting is to loosen and fragment the rock mass. The blast holes are charged
with explosives and fired with the help of delay-type electric detonators (blasting caps). The
explosives can be powder type (ANC – ammonium nitrate–carbon) or gelatinous (gelatins,
gelignite). The specific explosive consumption can be of the order of 200 to 400 gm per m 3 of
solid rock to be blasted. Careful planning of blast hole location grid, its spacing, depth, diameter
and the amount of explosive charge is required to break the mass and to minimise the ground
vibration, noise and other hazards.

When the surface is inaccessible for blasting, ‘tunneling’ method can be adopted, but it is not very
common. In this method, tunnels are driven into the face of the deposit and fairly large amount of
charge is fired.

Secondary blasting – In normal course, the rock should be fragmented after blasting to a size,
which can be taken to the primary crusher for reducing to smaller size. In case oversize pieces or
boulders are obtained, they have to be broken up further, for ease of loading, haulage and
crushing. This is called ‘secondary blasting’. For this purpose, small diameter blast holes are
drilled into the boulder and explosive charge @ 60 to 90 kg / m 3 fired. Another method is to apply
gelatin type high explosive on the surface of the rock mass and fire; this is called ‘mud capping’. It
is rather noisy and not preferred.

Ripping – In case of heavily fissured rocks having thin bedding and coarsely crystalline structure,
ripping methods can be used. Ripping teeth are mounted at the rear end of a heavy crawler
tractor. As the tractor travels, the teeth penetrate into the rock. The teeth can be straight or
curved. Mechanical methods with pneumatic or hydraulic breaking hammers are also possible in
case of softer rocks and smaller deposits.

Loading and haulage –

The blasted rock is loaded in cable-operated excavators, hydraulic operators or wheel loaders.
Haulage to the primary crushing plant can be on rail-mounted vehicles or rubber-tired heavy
trucks or combination thereof. The trucks have payload of 15 to 20 T. Belt conveyors can be
used, when the primary crusher is located at the quarry site, so that the limestone after primary
crushing is transported for further size reduction. When the terrain condition is difficult, aerial
ropeways can be used. The range varies from 1 to 100 km and capacity is about 500 T/hour. The
speed of the ropeway is of the order of 4 m/sec.

Reference Books

1. Labahn and Kohlhaas, Cement Engineers’ Handbook, Bauverlag GMBH, Berlin

2. H. F. W. Taylor, Cement Chemistry, Academic Press, London.
3. Comprehensive Appraisal of Cement Grade Limestone Deposits in India, SP-15-
1985, National Council for Cement and Building Materials, New Delhi.
4. Norms for Exploration of Limestone Deposits, National Council for Cement and
Building Materials, New Delhi.

26
PYROPROCESSING AND CLINKER FORMATION (8)

During the process of cement manufacture, the following operations take place at the
temperatures indicated;

1. Slurry preheat and evaporation of free and chemically combined moisture– 100 - 550 OC,
2. Preheat and evolution of CO2 from the carbonates (calcinations) – 805 OC,
3. Formation of phases and clinkerisation– 800 to 1400 OC,
4. Clinker discharge and cooling.

These heat transfer functions in cement manufacture take place in the kiln ‘system’ – comprising
the preheater and precalcinator, the kiln, the cooler and the refractory. The heat for
pyroprocessing is supplied by the fuel, ignited by hot air and gases from the system. In this
section, the kiln, refractories, fuels and the flame characteristics will be described. The heat
transfer mechanisms and heat balance involved in cement manufacture will be discussed.

The Cement Kiln System –

Dry process plants with preheater and precalcinator will be mainly described, being more
common. The heat profile following the sequence of heat transfer operations are shown
schematically in the figures given below for a modern dry process kiln with preheater and
precalcinator, and also for a wet process kiln for comparison. There are significant differences in
the gas and material temperatures.

Material and Gas temperatures in a wet process (above) and dry process precalcinator kiln
(below)

27
From the figures given above, it is obvious that a dry process kiln with preheater/precalcinator will
be of smaller length than a wet process kiln. This is because; no part of the kiln is required for
driving the moisture off the kiln feed in a slurry form (as in wet process), evaporation of moisture
from the clay minerals and the preheating of the kiln feed. These operations are done outside the
kiln in a preheater tower (see figure below) i.e. before it enters the kiln. The heat exchange
between the gas and the material takes place in the cyclones while both are in suspension. What
is shown is a four-stage preheater, although five stages are more common and even six-stage
preheaters are used. The exit gas temperature leaving the top stage will be about 340 OC in a four
- stage preheater and lower in five- or six-stage. These exit gases are used to heat the material in
the grinding mills.

4-stage suspension preheater (top) and suspension flash furnace precalcinator (below).

28
In order to increase the production rates of preheater kilns, they are equipped with facilities of
auxiliary firing to pre-calcine the feed outside the kiln. Precalciners are suspension preheaters
equipped with a secondary firing system at the bottom-most stage, before the feed enters the kiln.
These are called ‘flash furnaces’. The degree of calcinations of the feed will be about 90 percent,
by burning 30 – 50 percent of the total thermal energy required. This operation can use fuel of
lower calorific value than required for clinkerisation. The air for firing the fuel comes from an
auxiliary duct parallel to the length of the kiln using the excess waste gas from the clinker cooler,
or it can come from the kiln itself. There are various designs of preheaters and different types of
precalcinator, which will be described later on.

The dimensions of the kiln i.e. the length and the diameter depend upon the capacity of the kiln. It
should be noted that the capacity is not the volume of the kiln, as the loading in a kiln with kiln
feed is only about 6 to 10 percent of the cross section. The length to diameter (l/d) ratio in a wet
or dry process kiln without precalcinator (called long dry kiln) is of the order of 30 to 35; in case of
a preheater and precalcinator the l/d ratio could be from 12 to 18 (short rotary kiln). It is supported
on two sets of rollers when l/d = 12 to 14 and three supports when l/d = 16 to 18.

The kiln is set in an inclination of 3 to 4.5 %, with the feed end being higher and discharge end
lower. The speed of rotation is about 1.5 to 2.5 rpm in case of long kilns and 2.5 rpm for shorter
precal kilns. Typical dimensions of kiln (length and diameter) adopted for different capacities in
India and abroad are given below. Unless otherwise mentioned, each has 5-stage preheater.

10,000 tpd – 6 X 96 m,
6,000 tpd – 5.25 X 70 m,
3,500 tpd – 4.6 X 70 m,
3,300 tpd – 4.4 X 52 m,
3,000 tpd - 4.2 X 50 m,
2,000 tpd - 4 X 54 m; to allow for future expansion,
1,000 tpd – 3 X 50 m (only SP),

Clinker Coolers - These are fitted at the discharge end of the kiln. It performs two functions;

 To cool the hot clinker discharged from the kiln, and

 To supply the kiln with necessary air for combustion of the fuel. Valuable heat from the
clinker is recuperated and enters the kiln as hot secondary air.

Clinker coolers are of different types (see figure below). What all types of coolers have in
common is that the cooling air flows directly through the clinker and some of the heated air is fed
as combustion air to the kiln. The exhaust air is also used for drying raw materials and fuel, or as
secondary air to fire in precalcinator.

Inclined reciprocating grate coolers –Clinker discharged from the kiln moves to- and fro- in a
traveling grate supplied with circulatory air (ambient) from a cold air fan forced upwards through
the grate and the bed of clinker. As the clinker is cooled, the air gets hot and is fed back by
means of a hot air fan as secondary air to the kiln system. The primary air for combustion is fed to
the kiln via a burner pipe, supplied by primary air fan. The temperature of cooled clinker is about
80 - 100 OC.

Continuous traveling grate coolers – These are similar to reciprocating grate coolers except that a
continuous moving grate belt is used. The clinker can be cooled to about 80 - 100 OC.

Planetary coolers – These are cooling cylinders attached to the circumference of the kiln. There
are no moving parts, no fans to control and all the air that passes through these tubes enter the
kiln and used for combustion. However, it is difficult to have planetary coolers in precalcinator
with tertiary ducts. The temperature of cooled clinker is about 150 OC.

29
Rotary coolers – These were used in earlier times and not in use with modern kilns. The
temperature of cooled clinker is about 150 OC.

Shaft coolers – The clinker is discharged into a vertical shaft with cooling air supplied from the
bottom. The temperature of cooled clinker is about 300 OC.

What are described above are ‘direct’ coolers. In addition, there are separate ‘after’ coolers to
lower the final temperature to acceptable value. These are particularly adopted in case of large
capacity kilns. These after coolers often receive clinkers at 300 to 350 OC and discharge at 80 to
100 OC. One particular type is called ‘G-coolers’.

Refractory –
In order to protect the steel shell of the kiln from the high temperature encountered during
manufacture of cement, a lining of refractory material is provided. The refractory materials are
usually ‘bricks’ of appropriate size and shape so that they can be laid on the round periphery of
the kiln. Alternatively, the material is cast in a plastic stage inside the kiln and allowed to harden,
much like laying concrete lining. These are called ‘castables’.

The requirement of refractoriness varies from zone to zone in the kiln, depending upon the
temperature. It is the greatest in the burning zone. What helps the matter is the formation of a
‘coating’ on to the refractory lining. Coating is a mass of clinker and the dust particles that
adheres to the lining, having changed from a liquid or semi-liquid to a solid state. A kiln feed with
a high liquid content at clinkering temperature is more effective in coating formation. This
happens in easy-burning raw mixes with adequate amount of flux i.e. iron, alumina, magnesia

30
and alkalis. Ash in coal also helps in coating formation. The flame characteristics (to be discussed
later) also have an influence in coating formation.

Requirements of refractory – From the above, it is clear that the refractory should possess the
following characteristics;

1. Resistance to temperature encountered in the zone,

2. Spalling resistance – ability to withstand high temperature changes inside the kiln,
caused by start up, shut down or upset operating conditions,
3. Coatability – ability to pick up a coating and maintain it,
4. Abrasion resistance,
5. Slag resistance, i.e. resistance against chemical attack from the materials inside the kiln.

Choice of refractory material depends upon test results and records of prior use. Tests are
routinely conducted for compressive and tensile strength, modulus of elasticity, chemical
analysis, thermal conductivity, density, porosity and gas permeability. Specific performance tests
are for melting point, deformations under hot load, linear shrinkage etc. One important test is
called ‘refractoriness under load’ (RUL) which gives value of deformation of the refractory brick
when subjected to a specified temperature under a specified load for a specified time. The results
of hot load are expressed as the temperature at which a definite deformation takes place.

Types of Refractories – In line with different temperature profiles, refractory materials of different
chemical composition and properties are used in different zones of the kiln system. The
requirements of the burning zone are most demanding. The following types are used in the
burning zone;
 Alumina – silica group – the main components being alumina and silica. Refractoriness
increases with alumina content and high-alumina (Al2O3 > 70 percent) refractory is used
in the burning zone. With increasing alumina content, strength, conductivity and spalling
resistance also increase. The bricks are manufactured by dry press or a stiff mud brick.
 Basic group – manufactured mainly from periclase (dense crystalline magnesia), dead
burned magnesite and chrome ore. For rotary kilns, majority of refractory used are of
magnesia-chromium classification (Mag-Chrome) with periclase forming the major
component (85 % +). In Chrome – Mag bricks, chrome ore forms the major component.
In these formulations, periclase is responsible for high refractoriness and volume stability
and chrome supplies hot strength and spalling resistance. Basic refractories take to
coating formation in a better manner than high-alumina bricks as the coating fuses with
the surface layer of the refractory and are thus preferred for the burning zone.
 Dolomite bricks - composed mainly of CaO and MgO and have close affinity to the
chemical composition of the kiln feed. Once the kiln attains the operating temperature,
they form a coating very rapidly.
 Spinnel – bonded bricks – these are newer development, having 10 – 15 % alumina and
80 – 85 % MgO. They offer much longer service life than mag-chrome liners. However,
these cost more than other bricks.

For other places, refractory materials of different compositions are used. Details are given in the
Table below.

Service life and reasons of failure – For a kiln operator, kiln shutdown due to refractory failure is
the main concern. This manifests as a ‘red spot’ in the kiln shell, where shell temperature
becomes excessive due to lack of protection by the refractory lining. This can lead to warping of
the kiln shell and replacement may be called for. The ideal refractory life should coincide with the
planned annual shutdown. Thus, service life of 11 or 23 months is ideal. While in the cooler
regions in the kiln system, refractory materials last for up to 5 years, in the burning zone, the life
could be as short as a few days or extend up to two years. The reasons of unsatisfactory service
life of refractory are as follows;
 Frequency of kiln shutdowns,
 Too rapid heating of the refractory,

31
  Overheating the kiln, improper kiln operation,
 Quality of the refractory material, improper installations,
 Chemical composition and uniformity of the kiln feed,
 Mechanical condition of the tire and the kiln shell, and
 Poor location and poorly directed flame pattern, as discussed later.

Types of refractory material for different locations

Location Type and composition RUL, OC

Cooling zone High alumina (>70%) bricks or mag- 1500
chrome bricks
Burning zone Dolomite bricks (MgO >96%) 1600 -
1700
Transition zone Alumina or high alumina bricks; mag- 1600
chrome bricks (MgO > 65%)
Preheating zone Fireclay brick with Al2O3 content 1350
decreasing towards feed end;
lightweight bricks
Clinker cooler Acid fireclay brick 1300

Fuels, Combustion and Flame Characteristics -

For cement manufacture in India, solid fuels in the form of coal are traditionally used; elsewhere
liquid (heavy oil) or gaseous fuels (natural gas, LPG) are also used. In addition, the recent trend
is to use waste materials having heat value as alternative fuels in cement manufacture.

The origin of coal is from decomposition of vegetation with anaerobic bacteria and subjected to
thermal and mechanical loads for centuries. The main constituents in coal as fuel are carbon,
hydrogen, oxygen and sulphur, besides moisture and ‘ash’. The combustible part of coal is
composed of complex organic molecules. The volatile matter, which is the matter released on
heating to 800 OC, should be of the order of 18 to 22 percent, and ash content low.

A classification system for coal is on the basis of combustion behavior. It includes four main coal
ranks, starting from most difficult to ignite to the easiest; anthracites, bituminous, sub-bituminous
and lignite – in that order. These are also according to their ages; anthracite being the oldest and
lignite the youngest. With age and residence time at high temperature and pressure, older coal
formations have less volatiles and more ‘fixed’ carbon, thereby the difficulty in ignition. Some
details of different types of coals and other fuels used in abroad are given below;

Details of coal types and other Fuels

Group Moisture Volatile Fixed Ash, % Calorific value,

,% matter, % Carbon, % kcal/kg
Anthracite 2 3 – 12 88 – 67 7 – 18 7525 – 6800
Bituminous, 3 – 12 18 – 40 74 – 39 4–9 8000 - 6380
Sub-bituminous 16 - 25 28 – 34 39 8 – 12 5400 – 4800
Lignite 35 28 – 50 30.8 6 4000
Heavy fuel oil 0.1 – 0.2 86 # - 9500
Natural gas - - 58 # - 7500

# - Total carbon content.

Indian coals are mostly sub-bituminous, while imported coals e.g. from Australia are bituminous.
The ash content in Indian coals is high and calorific value low. Although, 20 to 25 % ash content
is considered satisfactory, often ash content in excess of 30 – 35 percent and calorific value ≈
3,500 kcal/kg are encountered. The coal ash gets incorporated in the clinker structure during

32
sintering and should be taken into account in working out the raw mix proportions. Chemical
composition of ash is similar to that of fly ash discussed before, with SiO 2 content in excess of 55
percent. If the weight of coal used is about 20 percent of the weight of clinker, and the coal
contains 25 percent ash with 55% silica, about 2 - 3 percent SiO 2 of clinker weight is contributed
by coal alone.

Coal should be dried and pulverized to a fine powder before firing. The fineness of coal is
expressed as residue in 90 µ sieve (R90). For coal with ash content up to 20 – 25 percent, it
should be of the order of about 10 percent. The residue on 200 µ sieve should 1 to 2 percent and
nil on 500 µ sieve. A rule of thumb for such coal (ash ≤ 20%) is R90 = half of volatile matter.
Lignite coals have high volatile matter (> 50%) and may pose explosion and fire hazard during
grinding and storage. Often, it may have to be flooded with inert gases.

Depending on its chemical composition (percent C, H, S, O and water, W), the net calorific value
of coal can be calculated as;

Hu = 33,900 * C + 1, 21,400 *(H – 1/8 * O) + 10,500 * S – 2,500 * W, in KJ / kg units,

or

Hu = 8,096 * C + 28,994 *(H – 1/8 * O) + 2,508 * S –597 * W, in Kcal / kg units.

For proper combustion of fuel, supply of sufficient amount of oxygen (through air) and the
required temperature to ignite the fuel-oxygen mixture are necessary. As the fuel is injected in the
system, it remains in suspension in the kiln atmosphere. Sufficient time must be available to
accomplish complete combustion while the fuel is in suspension in the kiln. The requirement of
oxygen for combustion is worked out as follows;

(i) C + O2 = CO2; 12 units of C combine with 32 units of O, i.e. C kg of carbon requires

8/3 * C kg of oxygen.
(ii) 2 * H2 + O2 = 2 * H2O; 2 units of H combine with 16 units of O, i.e. H kg of hydrogen
requires 8 * H kg of oxygen.
(iii) S + O2 = SO2; 1 unit of S combines with 1 unit of O, i.e. S kg of hydrogen requires S
kg of oxygen.

Taking into account the amount of oxygen already present in the coal, combustion of 1 kg coal
requires (8/3 * C + 8 *H – O + S) kg of oxygen. I kg of air contains 0.23 kg of oxygen and 0.77 kg
of nitrogen. Hence air requirement for combustion of 1 kg coal is

(8/3 * C + 8 *H – O + S) / 0.23 kg; i.e.

(11.6 * C + 34.78 * H – 4.35 * O + 4.35 * S) kg of air.

In other countries having good quality fuel, on an average, 1 kg of fuel requires 10.5 kg of air. The
coal required for cement manufacture depends on the moisture content and heat value. It was
mentioned that in India, the weight of coal consumed in dry process precalcinator plants is about
20 % of the weight of clinker produced. This will give some idea about the volume of air to be
supplied for combustion of coal.

The ignition temperatures of different types of fuels are;

Coal – 250 OC,

Fuel oil – 200 OC,
Natural gas – 550 OC,
Petroleum coke – 595 – 620 OC.

Incomplete combustion of coal due to inadequate supply of oxygen results in formation of carbon
mono-oxide (CO) rather than CO2, and only 31 percent of potential heat following complete

33
conversion of C to CO2, is generated. For satisfactory operations, it is essential that incomplete
combustion must be avoided and there should be no trace of CO in the kiln exit gases. If, in order
to ensure complete combustion, the amount of air supplied is more than what is required,
presence of oxygen will be noticed in the exit gases. Such excess air means larger volume of air
than required has to be raised to the operating temperature in the kiln, less heat available for
actual burning process, lower flame temperature and greater heat loss.

Ideally, there should be neither any trace of CO nor of oxygen in the kiln exit gases. In practice,
this is difficult to achieve. The burning conditions in the kiln not being the ideal, often traces of CO
and free oxygen are found together in the exit gas. A practical solution is to work on a range of
free oxygen in the exit gas being not less than 0.7 percent, or more than 3.5 percent under stable
operating conditions, as shown in the figure below. The most desirable range of oxygen in the kiln
exit gas is between 1 to 1.5 percent.

Use of alternate and secondary fuels -

Driven by the concern for reducing fuel cost, as well as need for environmental improvement,
alternate fuels derived from waste materials, which have some heat value, are being increasingly
used in the cement industry. These include rubber, rubber tires, paper, paper waste, waste oils,
waste wood, paper sludge, even animal meals and animal remains have been tried. Some
cement plants in India have used rice husk as part fuel, in combination with coal. Homogeneity of
the waste materials should be ensured. In this sense, burning in the cement kiln is not
incineration, but ‘valorisation’. The process ensures high level of efficiency in energy recovery
from the waste. The thermal energy recovered is used in the kiln itself, and the non-combustible
portions become raw materials.

Attention has been focused on use of petroleum coke (Pet Coke), which is a solid by-product
from oil refineries. Global tendency is to use low or very low sulphur content in liquid fuel oils, and
the residue with high sulphur and less volatiles result. Pet Coke has 8 to 12 percent volatiles,
residual moisture about 1 percent and can be considered to be similar to imported low volatile
bituminous coals. What is distinct is high sulphur content of the order of 5 to 8 percent. Presence
of sulphur in the fuel causes operational difficulties. Burning of high sulphur fuel requires
appropriate burner design and higher primary air consumption, in order to ensure high flame

34
intensity. As mentioned before, the ignition temperature is 595 – 620 OC. It has to be pulverized to
R90 = 5 percent, corresponding to 8 to 12 percent volatiles. Life of refractory may be affected. The
SO3 content in the clinker is of the order of 1 to 1.5 percent, which does not contribute to control
of setting time in the way externally added gypsum does. Consequently, the total SO 3 content in
cement tends to become higher.

Flame characteristics – To an experienced kiln operator, the flame is characterized by many

parameters – length, shape, point of ignition, direction and colour. A typical flame is sketched
below, which shows that on leaving the nozzle of the burner pipe, the flame first has a plume,
followed by the point of ignition and then, finally the flame. The length could be the total flame
length from the tip of the nozzle to the end or the ignited flame length from the point of ignition.

The percentage of combustion air present and the velocity of fuel-air mixture at the tip of the
burner are the main factors influencing the length of the flame. It is always preferable to have as
short a flame as possible, with the fuel getting ignited soon after it leaves the burner. Ignition
takes place in the burning zone and the flame extends to the calcining zone. Lack of combustion
air makes the flame long, as it searches for oxygen further back in the kiln.

A high tip velocity of about 70 – 80 m/s gives exceptionally good flame pattern, as it happens in
indirect firing. If the velocity is about 45 – 66 m/s, as it happens in case of direct firing, a lazy
swirling flame results. In any case, the tip velocity should be more than 35 m/s to keep the coal
particles in suspension in the circular burner pipe and not allow them to settle down. The quantity
of total air – primary air, secondary air and any parasite air due to leakages, is controlled by the
speed of ID fan; the greater the speed, more is the air. The primary air velocity should be twice
that of flame propagation speed, so as to prevent a flashback of the flame. Generally, under
stable operating condition, there is no change in the flame length, as long as the air-fuel ratio is
maintained constant.

The initial ignition of the fuel is primarily dependant on sufficient heat to ignite the fuel and on
sufficient air to obtain combustion of the fuel. During the initial start of the kiln, when the kiln
temperature is too low to ignite the fuel, a pilot burner (auxiliary torch) is placed at the mouth of
the burner pipe to obtain good ignition. The temperature of the flame is given by the relation;
Hv
T = -------------------,
1.11 * A *s
Where,
T = Flame temperature, OC,
Hv = Heat value of the fuel, kcal/kg,
A = amount of air required for combustion, kg/kg of fuel,
s = specific heat of combustion gas, adopt 0.29.

The values obtained by this calculation are of the order of 2000 to 2650 OC. In practice, lower
values are obtained and the colour of the flame changes. The following is a guide;

35
 Temperature of flame and colour

Flame Temperature, OC Colour of the

flame
White to dazzling white >1540
Light yellow to white 1320 – 1540
Yellow to light yellow 1090 – 1320
Orange to yellow 900 – 1090
Bright cherry red to orange 825 – 900
Cherry red to bright cherry red 750 – 825
Dark red to cherry red 650 – 750
Lowest visible red to dark red 475 – 650
Lowest visible red 475 >

Heat Transfer and Heat Balance -

Total heat transfer in the entire kiln system involves all the three modes – conduction, convection
and radiation. Some examples are;

Radiation: Flame ----------------------- Feed bed

Hot kiln wall ---------------- Feed bed
Conduction: Heat from kiln interior --- Kiln shell
Kiln chains ----------------- Feed bed
Convection: Hot kiln exit gases ------- steam in boiler tubes.

Heating the feed bed inside the kiln is primarily by radiation. In the burning zone, the kiln feed in a
‘sticky’ condition is in a constant state of agitation. Aided by the rough and uneven surface of the
coating, it rises along the upward-moving side of the kiln and then tumbles back. The hot particles
coming in contact with colder parts, transfers heat by conduction. Meanwhile, new particles are
exposed to heat transfer by radiation. The coating receives heat from hot gases by radiation. Part
of the heat then radiates to the bed of the feed and part of the part is transferred by conduction as
the feed comes in contact with the wall tumbling back. As a result, the temperature of the wall is
lowest when it emerges from the bed and highest immediately before it comes into contact with
the feed bed (see figure below).

36
Heat exchangers in the form of chains were common in wet process plants and sometimes used
in dry process plants also. The chains get heated by the gases and transfer heat to the feed by
conduction, as they come in contact. A similar action takes place when heat is transferred from
the kiln wall to the feed. The flame radiates heat to the coating. Part of the heat is radiated to the
feed bed and part is transferred by conduction, when the feed comes in contact with the wall. The
heat transfer in preheater tower is more efficient, as the time taken is small. The difference
between the material and gas temperastures is small.

Heat Balance – In an ideal situation, the thermal energy expended during cement manufacture for
clinkering the raw mix should match with the thermal energy supplied by the ignition of the fuel. In
practice, this is not the case. The theoretical heat required for clinker formation is estimated to be
of the order of 400 – 440 kcal/kg, yet the thermal energy consumed varies from about 1396
kcal/kg in wet process plants (31% efficiency), 1194 kcal/kg in dry process (37% efficiency) to
about 750 – 850 kcal/kg in preheater-precalcinator kilns (about 57 % efficiency).A heat balance
consists of compiling all the heat that is given to the kiln and then comparing this total to the total
of thermal work done and losses taking place. Such an exercise helps in conservation of thermal
energy by better ‘house-keeping’ and operational practices. These will be discussed in greater
detail later, in lecture on ‘energy conservation’.

The theoretical heat required for clinker formation depends on the chemical composition of the
raw mix and kiln feed. This can be calculated by the empirical formula;

Q = 2.2*Al2O3 + 6.48*MgO + 7.646*CaO – 5.1165*SiO2 – 0.59*Fe2O3;

where the oxides are expressed as percentages in the kiln feed (loss free basis) and
Q is the heat required, in kcal/kg.

Typical Heat Balance Calculation #

Item SP- kiln Wet Process kiln

Heat Input
From fuel 858 1378
From raw materials 39 11
From cooling air -5 -7
Total Input 892 1382
Heat Expenditure
Theoretical heat required for 396 389
clinker burning
Evaporation of water 4 565
Exit gas losses 184 224
Dust losses 5 3
Radiation and convection losses 154 86
Losses at the cooler 109 84
Unaccounted for @ 40 31
Total Expenditure 892 1382

# - All heat values are in kcal/kg.

@ - Unaccounted losses are calculated by difference to balance input and output.

Take, for example, the following composition of kiln feed on loss free basis;

Al2O3 = 4.84,
CaO = 67.43,
SiO2 = 20.71,
Fe2O3 = 2.78,
MgO = 2.58, and
Loss on ignition = 0.00.

37
Then, using the above formula;

Q = 10.648 + 16.718 + 515.57 – 105.963 – 1.642

= 435.33 kcal/kg.

The Table above gives typical heat balance computation for a wet process kiln and a dry process
pre-heater kiln. The above are by way of example only. Many modern dry process preheater
plants in India have reported thermal energy requirements of the order of 670 to 700 kcal/kg, and
the average consumption figures for the industry are comparable to the best in the world. The
computations given above should generate possible ideas for reducing the requirement of heat in
cement manufacture. You are encouraged to think of possibilities.

Reference Books

1. Labahn and Kohlhaas, Cement Engineers’ Handbook, Bauverlag GMBH, Berlin.

2. K. Perey, The Rotary Cement Kiln, Edward Arnold.
3. W. H. Duda, Cement Data Book, All volumes, Verlag GmBH, Berlin.
4. Report of VDZ Congress, 2002.

------

38
OTHER UNIT OPERATIONS (7) -

Contents –

Size reduction – crushing, grinding; homogenization and blending; cement grinding; process
control and instrumentation; optimization of operations.

PLANT AND MACHINERIES (7) -

Contents -

Different types of preheaters and precalcinator; grinding mills; packing; lay out; plant
maintenance; safety in operations.

Reference Books –

1. Labahn and Kohlhaas, Cement Engineers’ Handbook, Bauverlag GMBH, Berlin.

2. K. Perey, The Rotary Cement Kiln, Edward Arnold.
3. W. H. Duda, Cement Data Book, All volumes, Verlag GmBH, Berlin.
4. Report of VDZ Congress, 2002.

39
CONCRETE TECHNOLOGY (6) -

Basic Concepts -
Concrete is the most widely used man-made construction material the world over. It finds wide
applications ranging from boundary walls and beams and slabs for simple housing units to exotic
applications like tall structures and sky-scrappers, long-span bridges, large dams, nuclear power
projects, thermal power plants, expressways, industrial structures etc.

There are many reasons for such versatility of concrete. It is made of constituents, which are
available from natural resources (e.g. aggregates and water), manufactured from naturally
occurring raw materials (e.g. cement), or industrial wastes and by-products (e.g. fly ash, slag,
silica fume). When the ingredients are mixed with water, concrete in its plastic stage can be
moulded to any desired shape, and upon hardening, attain the desired mechanical strength, load-
bearing capacity and durability for the service environment. Concrete technology is the
technology of the constituent materials; their proportioning; workmanship in mixing, placing,
compaction, finishing and curing; and its properties in the fresh and hardened states. An
important consideration of cement manufacturing is the properties of cement which are critical for
its end use in the concrete constructions.

Concrete making materials – The basic constituents of concrete are cement, aggregate, and
water. Cement and water comprise the binder matrix, within which particles of mineral filler - the
aggregate are embedded to form the composite. With the progress of knowledge, at least two
more components are recognized – various industrial wastes as part substitute of cement, and
chemical ‘admixtures’ to be dosed at the time of mixing the ingredients. Small discrete fibers of
steel or polypropylene are sometimes added to impart special properties to concrete. All these
are being used, in various degrees, in the concrete being made in the country at the present time.

Cement – Various types and grades of cement, which result from variations in chemical
composition and physical properties were discussed under the topic ‘Types and Performance
Characteristics of Cements’. Chemical composition and physical characteristics of cements
influence a number of properties of the concrete made with it, most notably the strength and
durability of concrete. The general trend of rate of strength development of different types of
cement (ASTM classification) is shown in the figure below. Although the initial strength
development is different, the long-term strength at say five years’ time tends to be similar in all
the cases. If at all, the cements with lower strengths at initial ages – types II and IV have the as
high strength as type III in the long term.

40
The strength of concrete depends upon a large number of factors, which is described later on.
One of the factors is the strength of cement, when tested in standard mortar cubes as per the
specification. As per IS specifications, strength of cement is tested in 1:3 cement mortar made
with ‘standard’ sand and at water-cement ratio of about 0.4, at temperature 27 OC and relative
humidity 95 %+. It has been shown that for identical mix proportion of concrete, its compressive
strength depends upon the strength of cement – the higher the cement strength, greater is the
strength of concrete (see figure below). In India, OPC is graded into three strength grades – 33
grade, 43 grade and 53 grade, the grade designation indicating the minimum strength at 28 days.
It is customary to use cement of higher strength characteristics for high strength concrete.

The influence of cement characteristics on the durability of concrete against chemical attack is
discussed later on.

Industrial by-products – use of fly ash, granulated blast furnace slag and silica fume has been
discussed under the topic ‘Types and Performance Characteristics of Cements’.

Aggregates – aggregates are important because they occupy nearly 75 percent volume of
concrete. They can be viewed as fillers in the matrix of cement paste (cement + water), or as
building blocks jointed together by the cement paste – just like stone masonry is jointed by
cement mortar. In any case, the aggregates can not be considered to be inert, as they influence
the properties of concrete through the rock type, size, shape and texture, and chemical and
micro-structural characteristics. The properties of concrete that are influenced by aggregates are;
workability, strength, abrasion and wear resistance and durability etc.

Aggregates are arbitrarily classified as ‘fine’ and ‘coarse’ on the basis of size. Fine aggregate,
also called ‘sand’, is of size 4.75 mm and below; while coarse aggregate, also called ‘stone chips’
or ‘gravel’, are of higher sizes. Coarse aggregate of 20 or 40mm sizes are used for structural
concrete and 80 mm or 150 mm for mass concrete as in dams. For thin sections with high

41
concentration of reinforcement steel, 10 mm MSA coarse aggregate are used. Aggregates
obtained from natural sources are commonly used, while artificial aggregates can also be used.
Other classifications are in terms of shape – rounded or angular; texture – smooth or granular; or
the way the size is reduced – natural weathering as in river sand, gravel or boulders, or crushed
rock. Classification in terms of unit weight can be ‘normal weight’, as is mostly used, ‘lightweight’
as are most artificial aggregates, or ‘heavy weight’ as are used for nuclear reactors and radiation
shielding.

Indian standard specification IS: 383 lays down the requirements of concrete aggregates from
natural sources. It is not proposed to consider all of them in this lecture; however, the
requirements of size distribution are described. The principle of densest possible packing of
materials, requires that the group should consist of particles of different sizes, each being smaller
than the previous one. This principle will be clear from the following example. If we try to fill a
container with spheres of the same diameter, there will be void left, occupying 36 percent of the
total volume. These voids can be filled up to some extent with spheres of size smaller than the
size of voids, and the residual void filled up with next smaller size, and so on. The same principle
applies to concrete aggregate, which should comprise of particles of successive smaller sizes.
The size distribution is determined by the proportion passing standard sieve sizes. The sizes as
per IS specification are; 150, 80, 40, 20, 10, 4.75, 2.36 and 1.18 mm, 600 micron, 300 micron and
150 micron sizes. The desirable ‘grading’ for each nominal maximum size (MSA) of say, 20 mm
or 40 mm, as well as the sand fractions are given in IS: 383. These lots are to be judiciously
combined to result in satisfactory grading of the combined aggregate.

The importance of grading of aggregate is in the way it facilitates densest possible packing. Ideal
grading as given in the specifications is not always available, so whatever materials are available
are to be judiciously combined to achieve the goal of dense packing. Another effect is the total
surface area, to be covered by cement paste. For the same total volume, the smaller the size of
particles, larger is the surface area. This determines the water requirement. In particular, fine
aggregate is graded as per the sieve analysis in different ‘zones’ in IS: 383. The details are as
under;

Grading of Fine Aggregate as per IS: 383

Sieve Size Percentage passing

Zone I Zone II Zone III Zone IV
10 mm 100 100 100 100
4.75 mm 90 – 100 90 – 100 90 – 100 95 – 100
2.36 mm 60 – 95 75 – 100 75 – 100 95 – 100
1.18 mm 30 – 70 55 – 90 75 – 100 90 – 100
600 micron 15 – 34 35 – 59 60 – 79 80 – 100
300 micron 5 – 20 8 – 30 12 – 40 15 – 50
150 micron 0 - 10 0 - 10 0 - 10 0 - 15

These limits are shown graphically in the Figure below. From the above, it is clear that sand
belonging to zone I is the coarsest and zone IV the finest. Sands falling in zone II or zone III are
very suitable for concrete. Zone IV sand will increase the water demand in concrete enormously;
it is used for plastering.

Water – The usual amount of mixing water in concrete varies from 140 litres to about 200 litres
per cubic meter of concrete. Thus, water occupies nearly 15 – 20 percent by volume and about 6
– 9 percent by weight of concrete. Compared to other ingredients of concrete, the quality of water
usually receives less attention. However, there are many instances of distress to concrete
because of mixing and curing water not being of appropriate quality. IS: 456 specifies that water
used for mixing and curing shall be clean and free from harmful amounts of substances that can
be deleterious to concrete or steel reinforcement. The permissible limits for solids in water, tested
as per IS: 3025, is given below. In addition, there are additional tests for alkalinity (as carbonates
and bicarbonates) and acidity in water prescribed in IS: 456.

42
Grading limits for sand in different zones, IS: 383

Permissible Limits for Solids in Water, IS: 456

43
 Item Limit, mg/l, max
Organic 200
Inorganic 3000
Sulphate (as SO3) 400
Chloride (as Cl -) 2000 for plain concrete, 500 for RCC
Suspended matter 2000

Chemical admixtures and superplasticisers – admixtures are materials, usually organic

chemicals, which are added to the concrete (usually in small amounts) before or during its mixing,
with a view to modifying one or more properties of concrete in the fresh or hardened state.
Although intended to modify one property of concrete, many admixtures are capable of modifying
more than one property. The classification in IS: 9103 is based on the intended use, as will be
clear from the nomenclature given below;

 Set-accelerating admixtures,
 Set-retarding admixtures,
 Water-reducing admixtures,
 Air-entraining admixtures, and
 Superplasticisers.

Among the list above, superplasticisers, both normal and set-retarding types are more prominent.
They can significantly reduce the amount of mixing water required in concrete. Use of
superplasticisers help in improving the workability of concrete, improve strength by lowering the
water-cement ratio, improve durability, or combination thereof. Commonly used superplasticisers
are based on Melamine Sulphonates (MSF) or Naphthalene Sulphonates (NSF), Modified
Lignosulphonates (MLS), Acrylic Polymer (AP) or Polycaboxylatethers (PCE) etc.

The performance of concrete admixtures depends upon both the admixture and the cement and
their compatibility, in addition to concrete mix proportions and the environmental conditions in the
field. Among the characteristics of the cement, which affect the performance of admixtures are
the C3A, SO3 and alkali contents, nature of sulphate, and the fineness of cement. It is necessary
to evaluate concrete admixtures for specific use with the concrete-making materials and mix
proportions to be used in the work, under the field conditions.

Properties of Concrete –
Concrete is required to have necessary characteristics both in the fresh and hardened states.
After mixing, fresh concrete should be amenable to placing in the formwork and consolidating it.
This is called workability. Strength and durability are important properties in the hardened states.

Workability - Workability of concrete is not a single measure, but have four distinct aspects;

 The mix should be stable, in that it should not segregate during transportation and placing.
The tendency of bleeding should be minimized.
 The mix should be cohesive and mobile enough to be placed in the form around the
reinforcement and should be able to be cast into the required shape.
 The mix should be compactable to achieve proper and through compaction in the situation of
placing and with the facilities of compaction, and
 It should have finishability to obtain a satisfactory surface finish.

The various factors influencing workability are;

• Materials and Mix Proportions – water content, maximum size of aggregate, shape of
aggregate – whether rounded or crushed, fineness of sand and coarse : fine aggregate ratio.
• Temperature and Humidity - high temperature causes evaporation and reduces slump,
dry weather reduces workability.

44
• Delay in placement- workability reduces with time elapsed after mixing.

There are a number of test methods for workability of concrete, each measuring a particular
aspect. These test methods are described in IS: 1199 and can be viewed in the laboratory. Slump
test, which essentially measures the ‘wetness’ of concrete, is more popular because it is easy to
carry out. Compaction factor (CF) test measures the compaction achieved by a given input of
compacting effort, is more suitable for ‘low’ workability. Vee-bee time test is suitable for ‘very low’
workability – also called ‘zero slump’ concrete. Flow table test, described in IS: 9103 is suitable
for ‘high’ workability to ‘flowing’ concrete, as in ‘self compacting’ concrete (SCC) to be described
later on. IS: 456 gives general guidance for the degree of workability, which is reproduced below.

Requirement of Workability (IS: 456-2000)

Placing conditions Degree of workability Slump, mm

Pavements with pavers; Very low CF 0.75 – 0.80 #
shallow sections
Mass concrete; lightly Low 25 – 75
reinforced sections in slabs,
beams, walls, columns; floors;
hand placed pavements; canal
lining.
Heavily reinforced sections in Medium 50 - 100
slabs, beams, walls, columns.
Slipform work; pumped Medium 75 – 100
concrete
Trench fill; In-situ piling High 100 – 150
Tremie Concrete Very high Flow > 600 mm #

# - slump test is not suitable and other tests indicated are more appropriate.
Strength of concrete – Concrete is relatively stronger in compression and weak in tension. Hence,
compressive strength of concrete is considered to be most important. Many other desirable
properties of concrete are held to be related to its compressive strength – albeit indirectly, so
much so that compressive strength is many times taken synonymous with the overall quality of
concrete. As per Indian practice, compressive strength is determined on 150 mm cube
specimens. The procedure is detailed in IS: 516. In USA and some other countries, the strength
is determined on 6" diameter and 12" high (150 mm x 300 mm) cylindrical specimens.

Compressive strength of concrete depends upon a very large number of intrinsic and external
parameters. The single most important factor is water cement ratio. As long as the concrete is
workable, greater is its strength, the lower the water-cement ratio (see figure below). Next is the
importance of cement strength, which has been described before. There is a saying ‘a chain is
not stronger than its weakest element’. Aggregates occupying nearly 75 percent of the total
volume are not, per se, the limiting factor. This is because the mechanical strength of commonly
used aggregates is far greater than that of concrete made with it. If the broken piece of a concrete
specimen after testing is examined, failure would be noticed to have taken place around the
aggregate particles, and sometimes through the mortar phase, but very seldom failure in the
aggregate pieces are found. The aggregate-mortar interface is thus the weakest link. The
aggregates influence strength of concrete by way of controlling the bond at the aggregate- mortar
interface. The shape and size of the test specimen are also important.

45
As a general rule, the following observations can be made, each having profound scientific
reasons;

 Strength increase with age of test and duration of moist curing,

 Crushed rock aggregates give higher strength than river shingles or pebbles,
 Aggregates with granular texture result in higher strength than with smooth texture.
 Smaller maximum size of aggregates (MSA) results in higher strength than larger MSA.
 Concrete tested in 100 mm cube specimen will give higher strength than 150 mm
specimens.
 The strength of a concrete measured in 150 x 300 mm cylinder specimen is about 80
percent of the strength determined on 150 mm cube specimen.
 Higher speed of loading during strength test gives higher strength value.

Tensile strength of concrete can be measured by ‘split cylinder’ test (IS: 5816) or flexural test on
beam specimens under ‘two-point’ loading (IS: 516). As a general rule tensile strength of brittle
materials like concrete are about one-tenth of its compressive strength (see Figure below).
Flexural strength is somewhat greater than tensile strength determined on split cylinders and is a
design parameter for concrete pavements.

Durability - Durability of concrete is ‘its resistance to various deteriorating agencies that may
reside inside the concrete itself, or be present in the service environment to which the concrete
structure is exposed’. For proper performance of a structure, it is important to ensure not only
adequate strength and load-carrying capacity but also durability. Concrete under conditions of
normal usage is quite durable. However, there are a number of deteriorating agencies which can
attack concrete. The causes could be physical, mechanical, thermal or chemical in nature. In this
lecture, the action of chemical agencies like chlorides, sulphate, carbon di-oxide, acids etc.
present in the service environment and in soils, sub-soil and ground water, which can attack the
cement + water (cement paste) system and reinforcement will be discussed. In each case, it is
necessary to understand the origin of the problem, so that solutions can be suggested. The basic
mechanisms are described below.

The main products of hydration of cement are C-S-H, C-A-H and C-H. The response of the
hydration products to the principal deteriorating agencies like sulphate (SO 3--), chlorides (Cl-) and

46
carbon dioxide (CO2) are documented in the text books. While calcium hydroxide (CH) and
calcium aluminate hydrates (CAH) are the fast reacting components of the cement paste; CSH is
also susceptible to attack by all the three aggressive ions. In many cases, the type and extent of
reaction depend upon the cations. The basic chemical reactions, which are widely reported in the
literature, are summarised below;

Sulphate Attack: The main reactions of sulphate attack on concrete are as under;

 Formation of sulphoaluminates (ettringite) by reaction of CS and C-A-H

C3A + 3 CS H2 + 26 H  C3A(CS)3H32,
Results in increase in volume of reaction products, causes expansion and spalling;

 Formation of calcium sulphate (gypsum) in reaction with CH

NS + CH + 2H  NH + CS H2

The acidic nature of sulphate attack causes surface deterioration by softening without expansion.
Magnesium sulphate reacts; in addition, with the C-S-H phase leading to its decalcification i.e.
substitution of Mg+ for Ca+ and formation of M-S-H and other expansive salt identified above.
Formation of brucite (MH) and gypsum takes place in reaction with CH, especially in seawaters;

 MS + CH + 2 H MH + CSH2
Both contributing to deterioration

When alkali sulphate concentration is high and conditions are favourable, formation of alkali
sulphate crystals take place; for example

 NS + 10 H  NS H10 (mirabilite)
Contributing to surface deterioration by spalling and splitting.

47
Carbonation: Carbon dioxide in air or dissolved in water reacts with hydrated cement systems.
CH-phase is most susceptible to carbonation. Other products of cement hydration can also be
affected by carbonation, being finally decomposed to form calcium carbonate and hydrated silica,
alumina and ferric oxide. For example, total carbonation of CSH gel can lead to decomposition
into calcite and amorphous silica;

 C3S2H3 + 3 C  3CC + 2S +3H

Formation of thaumasite has also been reported at lower temperatures. In all such reactions, OH -
is consumed, thus lowering down the pH of pore solution.

Chlorides: Besides being the principal cause of reinforcement corrosion as described later,
chloride salts react with hydrates phases also. Reaction of chlorides with hydrates of C 3A and
C4AF, forming Friedel’s Salt and its ferrite analogue is the primary mechanism of ‘chloride –
binding’. Magnesium chloride leads to ion exchange between Calcium and Magnesium. Calcium
chloride reacts with cement hydrates to form expansive compound calcium oxychloride (3CaO,
CaCl2, 15H20).

Alkali-Aggregate Reaction: Chemical reactions between aggregate containing certain reactive

constituents and alkalis (sodium and potassium salts) and hydroxyl ions released by the hydration
of cement can have deleterious effects on concrete. Alkali-silica reaction (ASR) involves rocks
and minerals containing reactive forms of silica. Amorphous, microcrystalline and poorly
crystalline silica, fractured or strained quartz and glassy silica are among the commonly known
alkali-reactive forms of silica. Granite, granite gneiss and schist, quartzite and sandstone,
containing strained quartz is among the reactive rocks found in India. Expansion and cracking
leading to loss of strength, elasticity and durability are among the physical manifestations of ASR.
Environmental conditions, notably presence of moisture and temperature are important
parameters.

Corrosion of Reinforcement: The basic mechanism of corrosion of steel, as an Electro-

chemical phenomenon, can be summarised in terms of an anode process and a cathode process;

 Anode: Fe → 2 e- + Fe2+
(Metallic iron)
 Cathode: ½ O2 + H2O + 2 e- → 2(OH)-
In addition, the corrosion undergone by steel is due to combination of iron and (OH -) ions;
 Fe + ½ O2 + H2O → Fe2+ + 2(OH) → iron hydroxide (rust).

The process is summarised in the Figure below.

For transformation of metallic iron to rust, the requirements are;

1. Iron must be available in a metallic (Fe) state at the surface of the reinforcing steel;
2. Oxygen and moisture must be available for the cathode process; and

48
3. The electrical resistivity of concrete must be low to facilitate the electron flow in the metal
from anodic to cathodic areas.

From engineering stand point; two types of situations are necessary to be considered. The steel
reinforcement, being well protected in the alkaline medium in concrete, would take a certain
amount of chloride ion to be present so that corrosion can take place. On the other hand, if the
passivity is destroyed because of one reason or the other, and the pH of concrete is below a
certain threshold value, only oxygen and water are needed for corrosion to take place. Presence
of chlorides is not necessary. Concrete constructions, in order to be durable, have to ensure that
the limiting amount of chloride ions is not exceeded in concrete and neither the pH value of
concrete is lowered below the threshold value. Practical limits of tolerable chloride ion
concentration and limiting pH value are best arrived at by in-service record of concrete.

From what is described above, it is seen that most of the deteriorating actions are expansion-
producing, which causes cracking. Such cracking allows more of the aggressive ions to permeate
inside the concrete, thereby producing more distress. Presence of moisture is necessary for the
chemical reactions to take place and proceed. In addition, there could be cracking caused by
thermal effects, which would also allow the ingress of the chemical agencies into concrete. A
logical approach to prevent deterioration comprises;

 Make concrete as dense and impermeable as possible, by adopting low water-cement ratio
and thorough compaction. Most specifications suggest water-cement ratio to be 0.45 or less,
depending upon the severity of the service environment, because low water-cement ratio
ensures low permeability of concrete (see Figure below).
 Use of right type of cement, including composite cements. Portland Pozzolana cement (PPC)
and Portland Slag cement (PSC) are recommended to combat sulphate attack, lower the heat
of hydration and reduce the risk of reinforcement corrosion.
 Adequate cement content to retain passivity of steel and allow proper workability of concrete;
use of chemical admixtures and superplasticisers. IS: 456 gives guidance on minimum
cement content and maximum water-cement ratio for concrete exposed to aggressive
environments of varying degrees.
 Steps to alleviate thermal cracking in massive sections.

49
Rational use of cement in concrete –
From the discussions above, it should be clear that cement plays a vital role in ensuring the
desired properties of concrete for a particular application. Rational use of cement means use of
cement of the right quality in right quantity to ensure satisfactory concrete mix. The proportions of
ingredients of concrete, e.g. cement, coarse and fine aggregate, and water is chosen on a
scientific basis, aided by trials. This is called concrete mix design. Although there are a number of
‘methods’ of mix design, they are all approximate and only lead to trial mixes. Since there is
nothing as an exact method of concrete mix design, there are some cardinal principles that lead
to the trials. These are;

 The workability of concrete depends upon the water content in the mix, for a given set of
aggregates (maximum size, grading, coarse to fine ratio),
 The compressive strength of concrete depends primarily on the water-cement ratio; when
cement quality is variable, it also depends on the strength of cement, and
 The durability of concrete depends upon the water-cement ratio, cement content and the
'type' i.e. chemical composition of cement. Potential for alkali-silica reaction depends upon
the potential reactivity of the aggregates and the cement characteristics. At present, there are
no reliable, short-term tests for long-term durability of concrete. Hence , design for durability
is adherence to guidance given in the specifications, for example, IS: 456.

High Performance Concrete -

Definitions - Many attempts have been made to define high performance concrete. A quantitative
definition is that ‘It should have a maximum water-cement ratio of 0.35, a minimum durability
factor of 80 percent in freeze-thaw resistance test as per ASTM C666, a minimum compressive
strength of 21 MPa at 4 hours, 34 MPa at 1 day or 69 MPa at 28 days.’

However, such quantitative definitions may not be satisfactory in all situations. Among more
general, qualitative definitions are;

 Concrete, which meets special performance requirements that cannot be always

achieved routinely by using only conventional materials and normal mixing, placing and
curing practices. The requirements may involve enhancement of characteristics such as
strength, toughness, volume stability or service life in severe environments; or

 The essential feature of this concrete is that its ingredients and proportions are
specifically chosen so as to have particularly appropriate properties for the expected use
of the structure; these properties are usually a high strength or a low permeability.

Since the specification of high performance concrete is derived from its intended use, qualitative
definitions are more appropriate. Apart from high compressive strength, such applications may
focus on other properties of concrete, like elastic modulus, abrasion - erosion - cavitations
resistance, high workability, self-leveling and self-compacting properties etc. Durability of
concrete is a common thread and high strength may not be always emphasized. A good example
is the tunnel lining concrete for the Channel Tunnel in Europe. Requirements of durability dictated
that the co-efficient of permeability should be of the order of 10 13 m/s. The compressive strength
of concrete was required to be 45 MPa. By adopting water-cement ratio of 0.35, the requirement
of permeability was met. The compressive strength achieved was about 63 MPa, far in excess of
the design requirement.

High performance concrete is made with the same cements, aggregates, admixtures, additives,
and water, as in normal usage, but with proper curing and adequate quality control. One
important consideration is that it should be possible to produce high performance concrete in the
field with uniform characteristics between batches and placed in the structure with conventional
methods. Development of high performance concrete follows certain logical steps, as discussed
below.

50
The Logical Development - The development of high performance concrete is based on the
following well-known relationships of concrete technology;

For high strength, water-cement ratio should be low. The strength - w/c ratio rule holds good for
concrete strength of about 100 MPa or more.

Low water-cement ratio is also required for low permeability of concrete, which is vital for high
durability. Impermeability is also aided by pore filling effects of fine pozzolanic additions. The
relationship between coefficient of permeability of cement paste and water-cement ratio is such
that the permeability increases asymptotically for water-cement ratio above 0.45 or so. That is
why, most concrete specifications limit the water - cement ratio to about 0.45 or so for concrete
exposed to severe service environments. Thus, low water-cement ratio ensures both high
strength and low permeability, or high durability.

Low water-cement ratio will require high cement content to ensure that the amounts of water and
cement paste are adequate for the workability of concrete. However, too high a cement content
will cause high heat of hydration and increase cracking tendency. Hence, part of the cement is to
be replaced by other cementitious materials like silica fume, fly ash or ground granulated slag, or
combinations thereof. Such fine powders also help in pore filling and reduce permeability.

Use of low water-cement ratio and other cementitious materials as silica fume etc. makes use of
superplasticisers mandatory.

Thus, the composition of high performance concrete is automatically chosen - cement,

aggregates, water, superplasticisers, silica fume and fly ash or slag.

Mechanisms of high performance - High strength and low permeability are logical developments
of presence of silica fume and superplasticiser in concrete. The dual requirements of high
strength and low permeability are linked to each other through the need to reduce the volume of
relatively larger capillary pores. As pointed out earlier, this is achieved through reduction in water-
cement ratio as well as dense packing of fine particles.

The role of superplasticisers, long chain molecule organic compounds, is to get adsorbed onto
cement grains, impart a negative charge to them, which repel each other and get deflocculated
and dispersed. The resulting improvement in workability of concrete could be either to produce
flowing concrete for the same cement and water contents as in the control mix. Alternately, it
enables water content to be reduced by about 20 percent or more and results in high strength,
because of low water-cement ratio.

The role of silica fume is many-fold. Because of enormous surface area as well as relatively large
content of glassy silica, it is a very reactive Pozzolana. When contribution of silica fume to the
compressive strength of concrete is compared based on water-cement ratio in the mix, mixes
containing silica fume has higher compressive strength at 28 days. It also helps in augmenting
early strength of concrete. Since the heat of hydration of both are of the same order, use of silica
fume enables the heat rise in concrete to be lowered - a critical advantage for mass concrete.
However, incorporation of silica fume in concrete increases the water demand. Hence,
superplasticisers are required.

Dense packing is another basis of superior performance of concrete containing silica fume and
superplasticiser. The cement grains, which in normal circumstances tend to flock together, are
dispersed by superplasticiser. The extremely fine silica fume particles are then packed in the
space between dispersed cement grains and normally packed fine and coarse aggregate. The
overall result is a denser microstructure. A concrete exhibit less porosity with no evidence of
capillary pores and only very narrow - less than 0.5m gel pores is visible under high
magnification in electron microscope. C-S-H gel particles in concrete containing silica fume
appear not as individual particles, but rather as a massive, dense structure. By residing in the

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pores in hydrated cement paste, silica fume particles, on hydration, block the pores. Such pore-
refining action reduces the size of pores.

Another important mechanism is improving the transition zone around aggregate particles. In
normal strength concrete with only cement, the transition zone around aggregate is 20m to 100
m wide and richer in calcium hydroxide and ettringite, as against C-S-H phase in the bulk matrix.
The porosity is also higher. Thus, the transition zone forms a weak link. In presence of silica
fume, dense C-S-H occupies all the space around aggregate and direct bond with aggregate is
established. The porosity of the transition zone is eliminated. Result of strengthened transition
zone is reduction in micro cracking at the interface between cement paste and aggregate. The
stress-strain curve remains linear up to about 85 percent of failure stress or higher.

Improvement in Durability –

Corrosion Resistance - From durability considerations, reduction in air and water permeability is
important. Improved corrosion resistance of high performance concrete in terms of impermeability
to chloride and oxygen diffusion, improved electrical resistance and chloride-binding capacity are
reported.

Alkali-Silica Reaction (ASR) - Through the presence of silica fume and low water-cement ratio,
high performance concrete helps in alleviating alkali-silica reaction in concrete. The C-S-H formed
due to pozzolanic reactions between silica fume (and / or fly ash) and calcium hydroxide has
lower C/S ratio and arrests alkali ions in solid solution. The alkalinity in the pore solution is
reduced. Consequent to the depletion of calcium hydroxide in pozzolanic reactions, which is the
main source of calcium in the system and can exchange with some alkali (Na or K) in the ASR
gel, the ‘alkali cycle’ is broken. Presence of moisture is required for ASR expansion to take place
and continue. Reduced permeability of concrete makes ingress of water from the outside difficult
and alleviates ASR.

Mix design and field practices - Choice of materials, concrete mix design and field practices are
quite critical for high performance concrete. There is not much experience to go by and practices
with normal grades of concrete are of little help.

Mix Design - Some points to remember are;

 Mixes are cohesive, free from segregation, but 'sticky'. May require about 25 mm more
slump for comparable level of workability than in normal grades.
 Quality control will, perforce, be stringent, so standard deviation (SD) is not likely to
exceed 5 MPa or Coefficient of variation (COV) not more than 3 to 4 percent. Hence,
margin over characteristic strength need not be high. This will save on cement content.
 MSA of coarse aggregate should be 20 mm. Proportion of coarse aggregate to sand
content may be 1.0 - 1.5. Presence of fine powders increases water content.
 Project specifications in many cases stipulate the maximum water-cement ratio and
percent of silica fume to cement by weight.

Steps of mix design are suggested below;

1. Check compatibility of superplasticiser to cement and establish its water reducing

efficiency. With viable superplasticisers, reduction in water content of 25 - 30 percent is
possible. Establish optimum dosage by trials on cement + water mixes.

2. Make preliminary estimate of water-binder ratio (w/b) for target strength by establishing
such relationship. For target 28-days compressive strength in 80 -100 MPa range, start
trial mixes with cement + silica fume at steps of 400 - 450 kg/m3 and w/b at 0.25, 0.30
and 0.35. Effort should be made to keep the cement content minimum possible.
3. For each trial, gradually increase the amount of superplasticiser until the desired
workability is attained.

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 4. Adjust the sand and coarse aggregate contents, until optimum result is obtained.

Field Practices, Curing - The mix design arrived after laboratory trials should be tested for
physical properties. Next, the mix design should be checked under field conditions and necessary
adjustments made to allow for placing and transportation methods and required slump retention.
A further mock-up or prototype testing should preferably be made to see the effect of
reinforcement congestion. Detailing of rebar may have to be altered in critical areas.

The optimum sequence of mixing of ingredients should be established by trials and no prior
guidance is possible. Mixing time will be longer than in normal mixes.

Temperature of fresh concrete at the mixing stage should be kept lower than what is stipulated at
the time of placement, to allow for temperature rise during transportation. Cooling of aggregates
may be necessary. In addition, ice flakes may replace part of the mix water. Insulation of drums of
transit mixers and concrete pipelines is preferable.

High performance concrete containing silica fume is cohesive, so there is little bleed water to rise
to the top and offset water lost due to evaporation. Plastic shrinkage cracking is likely, if curing is
not proper. Initial curing should commence after initial setting of concrete and removal of side
forms, with moist covers, opaque colour plastic sheets or curing compound. Final moist curing
should commence after final setting and continue for at least 7 to 10 days.

Reference Books –

1.      A.M. Neville, Properties of Concrete, 4th Ed., Longman, (Indian Edition),
2.      P. K. Mehta and P. J. M. Monteiro: Concrete: Microstructure, Properties and Materials,
Indian Edition, Indian Concrete Institute, Chennai.
3.      Handbook of Concrete Mixes, SP – 23 (ST), Bureau of Indian Standards, New Delhi.

. Indian Standards Specifications -

1.      IS: 456 -2000, Code of Practice for Plain and Reinforced Concrete,
2.      IS: 383 – Specifications for Aggregates from Natural Sources,
3.      IS: 9103 – Specification for Chemical Admixtures,
4.      IS: 516 and IS: 1199 – Methods of testing concrete,
5.      IS: 3812 – Methods of testing of Aggregates.

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