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Chapter 2.

Raw Materials Selection

by A. K. Chatterjee*

Dispersed and homogenized raw mixes for the manufacture of portland cement clinker consist
basically of two generically different natural raw materials calcium carbonate (or limestone) and
aluminosilicates (or argillaceous substances) that are complementary in nature in meeting the
stoichiometric needs of forming the clinker phase assemblage. At times, when such stoichiometric
needs cannot be met by the above two primary components, certain corrective materials such as
bauxite, laterite, iron ore or blue dust, sand or sandstone, etc. are used to compensate the specific
chemical shortfalls in the raw mix composition. For certain processing advantages a few chemical
reagents are used as slurry thinners in the wet process and raw grinding operation, as granulation
activators in the process of nodulization in semi-dry plants, as mineralizers in clinker formation,
and as grinding aids in the cement milling process. These are essentially surface-active materials and
are used in very small quantities, when required. Further, in the context of environmental amelioration and resource conservation, a large number of industrial wastes or byproducts are used as basic
or corrective raw materials in the cement industry.

Fig. 2.1.1. Limestone quarry for use in cement operation.

*Former Director, The Associated Cement Companies Ltd., India.



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A fairly comprehensive review of chemico-mineralogical characteristics of cement raw materials

was published by Chatterjee (1983). This chapter is an attempt to focus on the issues relating to the
selection of natural raw materials. The blending materials like ground granulated blast furnace
slag, volcanic ash, calcined clay or metakaolin, pulverized fuel ash, and condensed silica fume on
one hand, and the set retarders like gypsum on the other, have not been dealt with in this chapter.


It has been broadly estimated by Oates (1998) that about 4500 million tons of limestone are used per
annum worldwide. The major uses are in two areas: as aggregate in construction and as the primary
raw material for cement making. The quantity of limestone used in the manufacture of cement is
estimated at about 1500 million tonnes or one-third of what is generally mined every year. A limestone quarry for use in cement manufacturing is shown in Figure 2.1.1.
It is claimed that limestone has been in use for construction purposes since the Stone Age, and
apparently the early records mention that Giza Pyramids used limestone for construction some
5800 years ago. There is evidence that by about 1000 B.C. there was widespread use of lime for
buildings by many civilizations across the globe. There are also indications in the literature about
extensive use of limestone as aggregate in lime-concrete since the Roman times. Obviously, the
development of portland cement in the 19th century caused the major expansion in demand for

Genesis of Limestone Rock

Limestone is classified as a sedimentary rock and its genesis in the geological time frame has
depended on the following pre-requisites:
1. Availability of calcium ion and carbon dioxide gas in the terrestrial system for their chemical
2. A basin with conducive physico-chemical conditions for deposition
3. An appropriate mechanism of deposition
4. Suitable conditions for diagenesis
5. Geotectonic movements leading to global distribution of limestone deposits
Although each deposit of limestone has a unique history in terms of the above conditions, certain
common facts and features are presented below.

Basic mechanism. It is widely believed that in order of abundance in the earths crust, calcium
holds the fifth position after oxygen, silicon, aluminum, and iron. On the other hand, carbon dioxide, according to Oates (1998) makes up about 0.03% by volume of the earths atmosphere. The
combination of dissolved calcium ions and carbon dioxide results in the sedimentary deposition of
calcium carbonate, which is subsequently converted into limestone rock.

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The deposition takes place primarily in two different environments: marine and inland waters, the
descriptions of which have been given by Scoffin (1987) as well as by Tucker and Wright (1990).
The primary marine environment, of course, has its own variety that includes beaches, tidal, subtidal flats, lagoons, reefs, shelves, slopes, and deep basins. Whenever the physico-chemical conditions in the basins had been favorable in terms of concentration, temperature, salinity, water levels,
turbidity, etc. for deposition, thick carbonate deposits formed in shallow seas within a 30 band on
either side of the equator.
So far as the mechanism of deposition is concerned, two main types are recognized inorganic
and organic. The inorganic route involves the direct precipitation or crystallization of carbonate.
This mechanism had occurred in the environments of both marine and inland waters, and had
resulted in some commercially significant deposits.
But it has generally been observed that most of the commercially viable deposits of carbonate
rocks were formed by the organic route. This happened because of the fact that carbonate-secreting organisms such as bivalves, gastropods, brachiopods, corals, echinoderms, foraminifera, various algae, etc. had existed in seawaters quite extensively. A few illustrative scanning electron
micrographs of some fossils associated with limestones are given in Figures 2.1.2 to 2.1.7. Many
such organisms, such as algae, are known to remove carbon dioxide from water, causing precipitation of fine chemical carbonate. Certain other organisms directly remove calcium carbonate from
marine water to form their shells, the accumulation of which gives rise to carbonate deposits. The
carbonate sedimentation by the organic route also had taken place in inland waters but the resultant deposits are generally not as extensive nor commercially as important as those produced in
marine environments.

Diagenesis. Conversion of carbonate sediments into rocks is geologically known as diagenesis

and involves the steps briefly outlined here. After the carbonates form from chemical and mechanical breakdown of preexisting rocks and are, thereafter, transported as detrital particles or in chemical solution for deposition or precipitation in standing bodies of water in a layered sequence, the
process of lithification starts under low-temperature low-pressure conditions.

Figure 2.1.2. Gastropod.

Figure 2.1.3. Cephalopod of cretaceous period.


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Figure 2.1.4. Asilina of ecocene period.

Figure 2.1.6. Diatoms in a miocene limestone.

Figure 2.1.5. Foraminifera of oligocene


Figure 2.1.7. Surface striations on the


Simple compaction, cementation, neomorphism, microbial micritization, etc., are the specific variants of the diagenetic processes, some details of which have been furnished by Tucker (1991). For
example, compaction occurs during the burial process when the pebbles are crushed, the particles
are closely packed, and pressure-induced dissolution and recrystallization take place. In the cementation process, water supersaturated with calcite passes through porous carbonate layers resulting
in the growth of calcite crystals in pores. The most common cement in medium-to-coarse grained
limestone is sparite or calcite spar. Silica as quartz crystals also acts as a cement in some limestones. In microbial micritization many organisms bore into carbonate deposits and the holes
become filled with calcium carbonate, called micrite, that typically forms an envelope around the
skeletal grains. Neomorphism refers to the progressive transformation of aragonite to calcite or
recrystallization of calcite into coarser crystals.

Distribution of Limestone in Space and Time

According to Wiersma (1990), limestone deposits cover about 10% of earths land surface and are
found in many countries. This has happened, despite the genetic history of limestones that the
deposits were essentially formed in shallow seas in the band 30S to 30N due to the effective
growth of carbonate-producing organisms in clear water with less inflow of terrigenous material

Raw Materials Selection


washed from the land. It is evident, therefore, that those parts of the continental plate, which have
remained south of 30S generally, have little limestone. Conversely, those continents that drifted
into, and in some cases across the band 30S to 30N, are relatively rich in limestone deposits.
So far as the distribution of limestone deposits in time is concerned, despite very precise physicochemical and climatic prerequisites for the carbonate deposition as mentioned earlier, the limestone deposits are encountered almost in all the geological eras and periods that span over 600
million years as indicated below:
Quaternary era

up to 1 million years
(Recent times to Pleistocene period)

Tertiary era

up to 75 million years
(Pliocene, Miocene and Eocene periods)

Mesozoic era

up to 225 million years

(Cretaceous, Jurassic and Triassic periods)

Palaeozoic era

up to 600 million years

(Cambrian, Ordovician, Silurian, Devonian, Carboniferous, and
Permian periods)

Precambrian era

unconfirmed up to 5 billion years

(Keewatin, Huronian, Keeweenawan, and Laurentian periods)

Limestones are not common in the Precambrian shields, although where shallow seas had formed
some carbonate deposition took place. It is believed that such Precambrian limestones were deposited either as inorganic precipitates or as a result of the biochemical activity of very simple
organisms such as bacteria. It may also be mentioned here that most of the Precambrian carbonates have been subjected to metamorphism and dolomitization during the long post-deposition
period. The Palaeozoic to Quaternary Eras are all fossiliferous and have favored the deposition and
formation of carbonate rocks although, according to Strakhov and others (1954), rocks of certain
geological periods (Ordovician or Cretaceous) show predominance of carbonates, while those of
certain other periods (viz. Upper Carboniferous or Triassic) are relatively poor in carbonates.
Further, the limestone deposits in different geographical regions and geological ages had different
environments of deposition. For example, the Carboniferous limestone deposits in England were
formed in equatorial and subtropical conditions, while the later Jurassic limestones and the Cretaceous chalk deposits were formed in the warm temperate zone, apparently at progressively higher
latitudes. From geotectonic evidence it has been seen that where there was progressive subsidence
of the sea bed over prolonged periods, very thick deposits accumulated, an illustration of which
are the Triassic deposits in the Western Dolomites which have a thickness of more than 2000 m.


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It is the general view of geologists that the sea levels were higher in the past than at present and the
area of shallow seas capable of sustaining carbonate-producing organisms was considerably greater
then. As a result, the environmental condusiveness for carbonate deposition apparently was more
extensive in the Mesozoic and Tertiary periods.

Calcium Carbonate Minerals and Their Solubility Effects

Crystallo-chemically there are three broad groups of calcium-bearing carbonates: calcite, aragonite, and dolomite. Based on the data furnished by Boynton (1980) and Chilingar and others
(1967), the relevant thermo-chemical characteristics of these carbonates are given in Table 2.1.1. In
the formation of carbonate deposits there could be different mechanisms by which the surface
layers of the sea become super-saturated with respect to aragonite, calcite and dolomite. The rate
of formation of dolomite is much slower than that of calcite and aragonite. The aragonite structure is generally very low in magnesium (typically less than 0.5% MgCO3). Calcite structure could
either be low in magnesium with less than 4% MgCO3 or high with typically 11% to 19% MgCO3.
Table 2.1.1. Thermo-Chemical Characteristics of Calcium Carbonate Minerals







Mn, Fe, Mg





Dissociation temperature at
760 mm pressure and 100%
CO2 atmosphere




Sr, Pb, Zn


(aragonite to calcite)


Fe, Mn, Co, Zn


725C (MgCO3)


Aragonite is pseudo-stable with respect to calcite under ambient conditions and has a higher
solubility in water by about 7% at all temperatures. It has been reported that aragonite slowly
re-crystallizes into calcite in the presence of water. However, in the absence of water this transformation takes places at 400C to 500C. Calcite is metastable with respect to dolomite in seawater
that contains dissolved magnesium. The process of dolomitization is a slow geological process, and
it is slowly reversed in the presence of fresh water.
According to Ghosh (1983), rise in temperature of seawater in the proximity of shelf or equator
decreases the solubility of CO2 in water and favors precipitation of CaCO3. Agitation of water by
breakers releases CO2 and favors carbonate precipitation. The solubility of CO2 decreases with
decrease in atmospheric pressure. Evaporation in restricted basins results in a decrease in CO2 and
an increase of salinity, facilitating carbonate deposition.

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Notwithstanding what has been stated above regarding the solubility of calcium carbonate minerals, it may be mentioned here that the high calcium and dolomitic limestones are among the most
chemically stable substances. Decomposition never occurs at ordinary temperatures and these
minerals are also unaffected by CO2 -free water, except for very negligible dissolution as mentioned
by Boynton (1980).

Classification of Limestones
Limestone is treated as an omnibus term and is often imprecisely used to represent any calcium
carbonate-bearing rock. However, it can be classified on the basis of various criteria, depending on
the purpose for which a given classification is deemed necessary. A fairly detailed treatise on the
classification of limestones has been furnished by Ghosh (1983). Most classifications obviously are
for geological needs. For the purposes of industrial applications like cement making, one may
derive ones own version from such classifications and distinguish one limestone from the other in
terms of their genesis, lithology, mineralogy, texture, and microstructure.
The major platform of distinction is the presence or absence of fossils related to the organic or
inorganic genesis. Having recognized this differentiation, one may further classify the types based
on broad lithology. This mode of distinction can be developed as follows:
1. Inorganic sedimentary limestones typical examples include travertine deposited from
natural hot springs; tufa, a soft porous rock also associated with natural springs; stalactites
or stalagmites, columnar calcitic deposits inside the caves; micrites originating from
calcitic mud or silt, etc.
2. Fossiliferous sedimentary limestones rocks of widely differing textural and microstructural
characteristics and fossil content broadly differentiated as biosparites or biomicrites. While
the former represent the more extensively occurring massive well-bedded limestones consisting of fossil skeletons or small shells in a recrystallised calcitic matrix, the latter refer to the
limestones having organic debris in a micrite matrix. Within this broad frame one may
further distinguish the following types:
i. Algal limestone resulting from the action of algae
ii. Oolitic or pisolitic limestone showing round calcitic grains
iii. Reef or coral limestone characterized by nonbedded large fossiliferous deposits
iv. Chalk representing a white soft rock with very little land-derived silty material, generally
thick (50 m to 400 m) in deposition
v. Marl designating an impure soft rock of marine origin in which varying amounts of clay
and sand are present in a loosely knit crystalline structure
vi. Sea sand, essentially of quaternary age, representing calcareous sand carried on to sea
beaches, occasionally with a mixed mineralogy of aragonite and calcite



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3. Metamorphic carbonate rock marble which is highly crystalline and often highly
dolomitic, although marbles derived from pure limestones through metamorphism without
dolomitization, consist simply of coarse white calcite grains
4. Igneous carbonate rock Carbonatite, which is effusive in nature and rare in occurrence
All of the above limestones can be further classified on the basis of certain textural and compositional yardsticks, some illustrations of which are given in Table 2.1.2 and 2.1.3.
The micro-structural variations encountered in different limestones are illustrated in Figures 2.1.8
to 2.1.16.

Table 2.1.2. Impurity Based Classification of Limestones

CaCO3, wt. %
> 97

Type of major impurity

Nomenclature of rock

MgCO3 and other minor and

trace elements

Ultrahigh calcium limestone/calcite

95 97

Same as above

Calcite limestone

80 95

MgCO3 + others

Magnesian limestone

SiO2 & Al2O3 + others

/cherty limestone


40 80%

+ others

Ferruginous limestone

C + others

Carbonaceous limestone

P + others

Phosphatic limestone

MgCO3 + others

Dolomitic limestone

Table 2.1.3. Classification Based on Crystal Size

Crystal size range as
proposed by Volkonskii
(1972), mm


< 0.01

Micro crystalline

0.10 0.01

Very fine grained

0.25 0.10

Fine grained

0.06 0.004

0.50 0.25

Medium grained

0.20 0.06

1.00 0.50

Coarse grained

1.0 0.20

> 1.00

Very coarse grained

Crystal size range given

by Oates (1998), mm
< 0.004 (micrograined)

Raw Materials Selection


It may be relevant to recapitulate here a few of the classical approaches made in the past to differentiate the limestones. A classification often referred to by the geologists is by Pettijohm (1957)
which distinguishes calcirudite, calcarenite, and calcilulite based on gravel, sand, and silt-sized
carbonate particles respectively.The classifications based on calcite and dolomite content as
proposed by Carozzi (1960), based on Ca/Mg ratio as proposed by Chilingar (1957), or based on
calcite, dolomite, and clay content as reported by Bissell and Chilingar (1967) are often useful for
specific purposes. Fitting a given limestone resource to one or more classifications ultimately helps
in understanding its behavioral pattern by comparison with parallels.

Geological Characteristics of Limestone Deposits from

Exploitation Perspective
While the classification of limestones as explained in the previous section is important for a broad
understanding of this important natural resource, the selection of a limestone deposit for exploration and use demands looking at each limestone deposit from different perspectives as the user is
ultimately concerned with specific features of its suitability for an end use.
Based on the geological complexities, age, basin configuration, amenability to prospecting, and
proving operations as well as minability and post-mining treatment, the limestone deposits can be
sub-divided into different types as reported earlier by Ghosh and Chatterjee (1979). All limestone
deposits in India, for instance, have been brought under three categories: simple, complex, and
The simple deposits are large, continuous, bedded, horizontal-to-low dipping deposits that are
geologically undisturbed with abundant outcrops and are uniform in quality. These kinds of
deposits require the least intensity of prospecting for proving of reserves. The complex deposits
include the ones that are moderately or steeply dipping, gently folded, consistent, medium to large
deposits; deposits with frequent intercalations or variable thickness, coral limestone deposits,
limeshell layers or sea sand deposits that are highly variable in shape and thickness;

Figure 2.1.8. Very coarse grained (>1.5 mm)

calcite with euhedral quartz at calcite

Figure 2.1.9. Microcrystalline limestone with

subhedral to euhedral calcite (10 to 40


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Figure 2.1.10. Microcrystalline limestone

with subhedral calcite (<10 microns) showing inter-crystalline porosity. Finer quartz
grains embedded at the calcite boundary.

Figure 2.1.13. Microcrystalline limestone

with subhedral to anhedral calcites, (10 to 30
microns) showing inter-crystalline porosity.

Figure 2.1.11. Microcrystalline limestone

with calcites (40 to 80 microns) embedded in
the fine anhedral matrix.

Figure 2.1.14. Calcite grains ( <10 microns)

with calcareous cementing materials, high

Figure 2.1.12. Matrix at places shows flaky


Figure 2.1.15. Rhombic calcites in calcareous

cementing materials. Overgrowth (authigenic) on the rhombic calcites, with porous
cementing material.

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Figure 2.1.16. Coarse euhedral calcite

embedded in fine grained matrix.

lenticular, folded, or structurally disturbed deposits; or deposits in hilly terrains with a little structural disturbance. The intricate deposits include highly complicated, highly folded, faulted and
dislocated, and highly lenticular deposits or those deposits that are interbedded with clay or shale,
or show extreme variations in form, thickness, and assay values. Many Precambrian limestone
deposits belong to this category. A high degree of intensity of prospecting is required in assessing
deposits of this kind, particularly for mechanized mining.
It should be borne in mind that the adequacy of exploration and proving of a limestone deposit
for setting up a cement plant ultimately has to be judged by the optimum expenditure incurred in
the exploration program in order to avoid risky ventures of developing inadequately explored
deposits or unprofitable propositions of setting up a cement plant on over explored deposits.
The most judicious course to assess the adequacy of an exploration program of a limestone deposit
is to adopt the minimum risk factor method which is based on the reliability of reserves estimated
in terms of quality and quantity.
The tentative target of an exploration program for a given deposit is to ensure the estimate of its
reserves of appropriate reliability as indicated in Table 2.1.4. Arriving at the delineation of reserves
of the reliability level of the proved category is considered a prerequisite for the preparation of a
detailed project report and final investment decisions.


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Table 2.1.4. Illustrative Targets of Limestone Reserves for Cement Plants at the
Resource Proving Stage
of reserve


stage of proving


Vg  1%
Vr  10%


Quantity, million tons

3000 tpd

5000 tpd

7500 tpd





Vg  3%
Vr  30%





Vg  4%
Vr  50%





* Vg is the anticipated deviation of CaO content from the actual value as mined.
* Vr is the anticipated difference between the estimated and mined reser ves.

Advances in exploration and exploitation software. The developments in planning of

exploration as well as in methods of compilation, processing, and interpretation of data are
phenomenal due to massive advances in computing power and software design. These developments have influenced the process of raw materials exploration and planning for cement manufacture. McCaffrey (1999) postulates that a relational geological database allows storage and query of
all geo-chemical quality parameters in addition to physical attributes such as mining thickness.
Complex 3D geological and quality models can be developed to assist in deposit visualization.
Statistical and multiple element compositing tools can be used to investigate the quality distribution. It is possible to take advantage of available software for 3D visualization of the different
stages of exploration, raw mix proportioning models, etc. Austroplans Geo-byte, Mapteks Vulcan
3D, and Surpac 2000 of Surpac Software International are examples of a few popular software
programs used around the world.


Broad Specification of Cement-Grade Run-of-Mine Limestone
It has already been mentioned that the chemical composition of limestone for cement manufacture should be such that it gives in combination with an argillaceous component and, under
unavoidable circumstance with corrective materials, a raw mix of appropriate composition. Hence,
no rigorous specification can be drawn up for the cement-grade limestone. Notwithstanding this,
according to Ghosh and Chatterjee (1979), an attempt was made several years back to specify the
cement-grade limestone in a way that does not exceed the limiting oxide values given in Table
2.1.5. However, this is not a substitute for the comprehensive test to which every limestone under
consideration for industrial use should be subjected in combination with supplementary and
corrective materials.

Raw Materials Selection


Table 2.1.5. Broad Chemical Specification of Cement-Grade Run-of-Mine Limestone

MgO (max)
SiO2 + Al2O3 + Fe2O3

Acceptable range for

manufacture of ordinary
portland cement, wt. %

Limiting values taking

into consideration other
types of cement, scope of
beneficiation or blending, wt. %

44 52

Minimum 40


To satisfy the LSF* and MS* of raw mix


< 0.5

< 3.0

R2O(K2O + Na2O)

< 0.6

< 1.0

Total S and SO3

< 0.6

< 0.8


< 0.6

< 1.0

< 0.015

< 0.05

< 8.0

< 10.0

Free SiO2

* LSF = Lime saturation factor, MS = Silica modulus.

Additional Desirable Technological Characteristics

For use in cement making the most important technological requirement from limestone is its
proper dissociation to release reactive lime in the kiln system. The salient aspects of the decarbonation reaction of the carbonate minerals had been dealt with by Chatterjee (1983). It may suffice to
mention here that in the process of raw materials selection, one may have to be cognizant of the
effects of two major factors of limestone on its calcination behavior viz. 1) the associated minerals
and impurities and 2) textural features including grain size of calcite.

Associated Minerals and Impurities

The effect of the associated minerals and impurities is basically to lower the decomposition
temperature as the dissociation pressure of calcite is increased by oxides like SiO2, Al2O3, and
Fe2O3. It has also been observed that the lime crystals obtained from the dissociation of dolomite
are 1.5 to 2.0 times smaller than those obtained from calcite. As a result, the reaction surface is
larger when lime crystals are available from dolomites, resulting in faster reactions.
It is known that MgO in limestone can be present in various forms: magnesium silicates, dolomites, magnesite, ankerite, brucite, etc. The growth of the periclase crystals in a clinker is obviously
related to the temperature at which different magnesium minerals release magnesia on decomposition (Table 2.1.6). The lower this temperature, the greater the chances of crystal growth, particularly in situations where magnesia does not react with other oxides to form any transitional phase.


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Table 2.1.6. Decomposition Temperature of Magnesian Minerals (Volkinskii, 1972)


Chemical composition

Decomposition temperature, C



700 750









375 490

Magnesian Siderite

The presence of coarse grains of quartz or siliceous veins is undesirable as it may affect the grindability and reactivity of the limestone as explained later in this chapter. The presence of sulfur as
sulfate is undesirable as it is difficult to decompose.

Physico-Textural Features
The physical properties of limestones show wide variation, apparently related to the prior history
of rock formation and the resultant minerographic and textural features.
The color of limestones reflects the level and nature of associated minerals and impurities. High
purity calcite limestones are white in color and other shades in the less pure varieties are essentially
caused by carbonaceous and ferruginous materials.
Depending on the mineralogy and texture, the porosity of the limestones, according to
Schwarzkopf (1994), varies from almost zero to 30%, while the upper value for chalks and marls
often goes up to 40% and 50% respectively. For predominantly occurring compact limestones, it is
in the range of 2% to 5%. Similarly, dolomites normally show relatively low porosity level
(1% to 10%).
The water absorption in limestones follows the pattern of pores and level of porosity. While it may
be negligible in dense varieties, it may go up to 20% in porous chalky varieties.
The Mohs hardness of most limestones lie in the range of 2 to 4. The apparent density of limestones on drying at 110C ranges from 1.5 to 2.6 g/cm3.
In addition to the above basic physical properties, a few characteristics like crushability and grindability as well as the physical behavior of crushed and screened limestones are important for the
process of cement manufacture.

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Crushability is a generalized parameter expressing the energy consumed in crushing a rock under a
dynamic load. The property takes into account the elastic, plastic, and strength behavior of a given
sample and is measured as a work index. Similarly, grindability is determined with the help of a
specially designed ball mill according to standard practice and is expressed as Bonds index. For
details, one may refer to the article by Bond. The Bond grindability index for commonly occurring
compact limestones lies in the range of 4 to 13 kWh/short ton.
Sometimes, for crusher selection purposes, the compressive strength of limestones, determined on
sized cylindrical samples, is used. The compressive strength of limestones, like other properties,
also shows wide variation from 10 to 200 MPa.
The bulk density largely depends on the apparent density of limestones, their particle size distribution, and particle shape. In general, the reported range of variation of bulk density of limestones is
1400 to 2700 kg/m3, although typical values fall in the range of 1400 to 1600 kg/m3.
The external angle of repose for screened limestone is generally 35 45 but is affected by size
distribution, fines level, and moisture content.
The abrasion resistance characteristic of crushed stone is often called for in the process of technological assessment.
A broad framework of sequential steps and scope of technological assessment of limestones has
been given by Ghosh and Chatterjee (1979). Some of the desirable characteristics are 1) the average
size of calcite crystals (not particle size) should preferably be less than 0.25 mm, 2) presence of
coarse grains of quartz and siliceous veins is undesirable, 3) limestone should have low moisture
content (<5%), and 4) limestone should have low compressive strength (below 100 MPa).
For a general appreciation of the extent of variability of physical properties encountered in limestones and difficulties of correlating the physical properties with their chemical characteristics, a
set of data for some limestone samples of different ages is furnished in Table 2.1.7.
The limestones shown here are all high in silica content. Reasons for the major differences in
grindability probably include differences in the mineralogy of the siliceous contaminant.



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Table 2.1.7. Physical and Chemical Characteristics of Some Limestones of

Different Ages

CaO (total), %












SiO2 (total), %











L.O.I., %











Calcite, %











Quartz, %













Dolomite, %





Sp. gravity











Bulk density,











Porosity, %











Abrasion, %






strength, MPa




Bonds index,
kWh/short ton





30.64 30.65
140.0 157.6
6.82 11.36





Dependence of Decarbonation Behavior on Limestone

It has already been indicated that the reactivity of a limestone is dependent on the crystal size of
calcite and other associated minerals, and more particularly of quartz. This is evident from Table
2.1.8 in which the characteristics of two different limestones and their decarbonation behavior in
air at 800C have been shown. Limestones A and B are comparable in their chemical composition,
while they significantly differ in their calcite crystal size. This difference is reflected in the slower
decarbonation of limestone B, when both limestones were ground to the same level of 15% residue
on 90 m to eliminate the effect of differential particle size on the decarbonation reaction.
On the whole, it has been observed that the finer the crystal size or the finer the particle size and
the more impure a limestone, the lower the activation energy of dissociation, which may vary in a
wide range from 30 to 60 kcal/mole.
There is also a tentative inverse correlation between the activation energy and the peak temperature of decomposition, as well as the activation energy and the rate of decomposition of a given
limestone. It has also been experimentally established that the lower activation energy of limestone
dissociation has a strong positive effect on the activation energy of clinker phase formation with
higher lime combinability, as reported by Sinha and others (1980).

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Table 2.1.8. Effect of Calcite Crystal Size on the Decarbonation Rate of Limestones
Limestone A

Limestone B

Composition, wt. %
Free SiO2



Calcite, size m



Weight loss at 800C in air as a function of residence time, %

30 min.
60 min.
90 min.
120 min.



The expression argillaceous materials
refers to all fine-grained natural earthy
substances that are alternatively known as
clay. It includes shales and argillites.
Chemically, these materials are essentially
hydrous aluminum silicates, with magnesium or iron substitution wholly or in part
for the aluminum in certain minerals, and
with alkalies or alkaline earths also present
as essential constituents in a few others. A
shale deposit as a source of argillaceous
materials in cement manufacturing is
shown in Figure 2.1.17.

Figure 2.1.17. Shale pit as a source of argillaceous

additives for raw mix in cement manufacturing.

Some argillaceous materials are composed of a single clay mineral but in many there is a mixture of
them. In addition to the clay minerals, many argillaceous materials contain non-clay minerals like
quartz, calcite, feldspar, sulphidic species, etc. Many others may contain organic substances as well as
water-soluble salts. Some clay materials may contain phases that are amorphous.


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Structurally, these clay minerals are part of the larger family of phyllosilicates and are characterized
by interlinked tetrahedral and octahedral sheets. The structural configuration of clay minerals has
been dealt with in fair detail by Grim (1962), Brindley and Brown (1989), and Velde (1992), a
summary of which is presented below.
The structural variations among the clay minerals can be understood by considering various physical combinations of tetrahedral and octahedral sheets and the electrostatic effect chemical substitution has on the structural units. The tetrahedral sheets are composed primarily of Si4+ and
oxygen, but minor amounts of Al3+ or Fe3+ may substitute for Si4+. The substitution of Mg2+ for
Si4+ leaves the tetrahedral sheet negatively charged. The cations of the octahedral sheet are
composed primarily of Al3+, Fe3+, Mg2+, and Fe2+, but all other transition elements, except Sc, may
be included. The anions of the octahedral sheet are O2-, OH1- and F 1-. The smallest unit of the
octahedral sheet contains three octahedra having an ideal net charge of negative six, i.e. three O2-.
If the negative charge is balanced by two trivalent cations, the layer is referred to as dioctahedral
layer; if balanced by three bivalent cations, the layer is referred to as a trioctahedral layer.
Substitution of bivalent cations for trivalent cations, and univalent cations (Li1+) for bivalent
cations or unfilled octahedral sites, leaves the octahedral layer a net negative charge. The tetrahedral apical oxygen is shared with the octahedral layer to join the two types of layers.
The least complicated clay minerals are the 1:1 clay minerals composed of one tetrahedral (T) layer
and one octahedral (O) layer. These 1:1 clay minerals are also referred to as TO minerals. The TO
package has a basal spacing (nominal thickness) of 0.7 nm (7), and the minerals are commonly
referred to as 7 minerals. Clay minerals that are composed of two tetrahedral layers and one octahedral layer are referred to as 2:1 clay minerals or TOT minerals. The apical oxygens of the two
tetrahedral sheets project into the octahedral sheet. The 2:1 structure has a basal spacing (nominal
thickness) of 1.0 nm (10). The multitude of variation in clay minerals is caused by substitution in
the octahedral and tetrahedral layers, resulting in charge deficits. The manner in which the charge
deficit is balanced leads to many of the useful and unique properties of clay minerals.
As a result of such diversity of constitution of argillaceous materials, their technical assessment for
specific applications is rather complex. Broadly speaking, the property controlling factors in
argillaceous materials are the following:
1. Clay minerals
2. Non-clay minerals
3. Organic substances
4. Exchangeable ions and soluble salts
5. Particle characteristics including shape, size, and orientation
6. Structural assembling formed by 1:1 or 2:1 linkage of tetrahedral and octahedral sheets as well
as neutralization of excess layer charge by various interlayer materials

Raw Materials Selection


Some relevant data regarding the structure and properties of clay minerals are furnished in
Table 2.1.9.

Table 2.1.9. Structure and Properties of Commonly Encountered Clay Minerals


Broad composition



1. Allophane

mAl2O3 nSiO2 pH2O Often associated

with sulfates and phosphates.

X-ray amorphous

2. Kaolinite


1:1 layer type

(001) = 7.21
b = 8.99
Flaky habit.

3 15

3. Halloysite

Two forms:
(OH)8Si4Al4O10 or
Halloysite minerals are made up of
successive layers with the same structural composition as those of kaolinite.
A little substitution seen.

The basal spacing of

the dehydrated form
is the same as of
Kaolinite but of the
hydrated form is 10.1
. Tubular habit.

5 40

4. Montmorillonite (OH2)4Si8Al4O20nH2O Composition

without the interlayer material:
Frequent substitution of Si in tetrahedral layer and/or Mg, Fe, Zn, Ni, Li,
etc. for Al in octahedral layer. Lattice
always unbalanced.

2:1 layer type Equidimensional extremely

thin flakes.

80 150

5. Illite

Muscovite-like dioctahedral:
(OH) 4 K 2 (Si 6 Al 2 )Al 4 O 20 Biotitic type
is trioctahedral with incorporation of
Mg and Fe. Illites differ from mica in
having less replacement of Al for Si,
less K and less randomness of silicate

Structural character
istics same as the
micas, 2:1 layer type.
Small poorly defined
flake commonly
grouped in irregular

10 40

6. Chlorite

Alternate mica-like
(OH2)4(SiAl)8(MgFe)6O20 and brucitelike structure (MgAl)6(OH)12 Various
members of the chlorite group differ
from each other in the kind and amount
of substitutions within the brucite layer
and the tetrahedral and octahedral
positions of the mica layer.

(2:1) + 1 layer type.

Thickness of layer consisting of mica and
brucite sheet is 14
(twice that of Kaolinite)
and hence difficult to
distinguish with Kaolinite in XRD.

10 40

7. Attapulgite

Composition of the balanced

ideal cell of Attapulgite
(OH2)4(OH)2Mg5Si8O4H2O, Sepiolite
and polygorskite show variations in
the composition of Al, Mg and Si.

2:1 inverted ribbons.

Generally seen as
bundles of lath-shape

20 30


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Genesis and Occurrence of Clays

According to Worrall (1968), there are mainly two types of clays by genesis residual and sedimentary. Residual clays are those which have not been transported by natural agencies and are
found side by side with the weathered igneous rocks from which they are formed. Sedimentary
clays, in contrast, are those which have been removed from their place of origin by natural agencies.
Residual clays can be obtained in a comparatively pure state, while sedimentary clays are rarely
obtained pure as these materials get contaminated during transportation. The transportation
factor also makes the particle of residual clays smaller and irregular.
Grim (1962) had explained that argillaceous alteration products are often found around metalliferous deposits due to hydrothermal action. In such residual clays there is zonal arrangement of the
clay minerals around the source of alteration with mica and kaolinite being close to the sources
and chlorite and montmorillonite being more distant.
All types of clay minerals, with the possible exception of attapulguite, have been identified in various types of soils. The character of the clay mineral found in a given soil depends on the nature of
the parent material and also on the climate, topology, vegetation, duration of the alteration
process, course of transportation, etc.
Illite and chlorite appear to be the dominant clay mineral constituents in sediments preferably
accumulating in seas. Montmorillonite is much less abundant in sediments older than the
Mesozoic as compared to the younger sediments. It is also seen that kaolinite is less abundant in
very ancient sediments than in those deposited after about the Devonian period. Attapulgite and
sepiolite have not been reported in sediments older than the Tertiary age.

Rock Association of Clay Minerals

Argillaceous rocks generally show the presence of multiple clay minerals. Shales generally contain
illite and chlorite. Montmorillonite is a common constituent of many shales of Mesozoic and
younger age. Kaolinite is a common mineral of some shales but usually in minor proportions.
Slates are also composed of illite and chlorites but with higher degree of crystallinity.
The carbonate rocks show the association of a wide range of clay minerals, with illite and chlorites
more predominant than kaolinite and montmorillorite.

Physical Properties of Clays

Properties like plasticity, specific surface, water requirement, suspension stability, coagulation of
clay particles, swelling, etc. are of considerable importance in raw meal preparation, particularly in

Raw Materials Selection


the wet and semi-dry processes. Clays with at least 7 to 15 plasticity index and having 10% particles of +0.2 mm size and cumulative 20% particles of 0.08 mm size with cation exchange capacity
of 11 to 12 meq/100g are reportedly considered suitable as cement-making variety in situations
where clay has a process role other than providing the stoichiometric requirements.

Thermochemical Reactivity
Experience has established that aluminosilicate, when present in raw mixes from the argillaceous
component, turns out to be significantly more reactive than fine-ground silica. It has been generally observed that the water vapor and hydroxyl group released from the argillaceous materials
shows some catalytic effect on the dissociation of calcium carbonate and the subsequent solid-state
oxidic reactions.
The trends of decomposition of a few clay minerals are shown in Table 2.1.10. It is evident that the
temperature ranges over which different clay minerals release water and hydroxyl ions as well as
transform into an amorphous state before stable phase formation are different. It is obvious, therefore, that their reactivity with lime and other oxides would not be identical in different situations.
However, still there is no unanimity in the views of different investigators regarding the order of
reactivity of different clay minerals. As reported by Volkonskii and others (1973), in accordance
with one investigation, the decreasing order of reactivity was as follows:




Another investigation reports the following decreasing order of reactivity:




Notwithstanding such differences, it is evident that micaceous minerals have a tendency to show
relatively low reactivity.
It may also be borne in mind that the argillaceous materials have a high probability of containing
titania, alkalies, sulphides, sulfates, and phosphates. The reactivity may be strongly influenced by
the presence of the above constituents.


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Table 2.1.10. Decomposition Behavior of Some Clay Minerals (Volkonskii and

Others, 1973)
Approximate temperature
of completion, C


Temperature of
initiation of
recrystallization, C





















When the primary components of a raw mix do not jointly permit achieving the desired range of
modulii values, a third or even a fourth component is added, known as corrective materials. It has
been a practice to recognize that a material with more than 70% silica, 40% iron oxide, or 30%
alumina can be termed as siliceous, ferruginous, or aluminous corrective materials.
Sand, sandstone, or quartzite acts as the source of siliceous corrective material. Other conditions
being equal, the grain size and specific surface of silica in free form (and particularly of the least
reactive forms like quartz and chalcedony), determine the rate of reaction in a kiln feed. According
to Makashev (1976), the reactivity of different types of silica, free or combined, increases in the
following order:
Quartz < chalcedony < opal < -cristobalite and -tridymite < silica from
feldspars < silica from mica and amphibole < silica from clay minerals < silica
from glassy slags.
On the whole, silica in amorphous state or derived from silicates or hydrosilicates is preferable to
silica in other forms.
The correction of iron oxide in a raw mix is generally done with iron ore, which may either be
magnetitic or haematitic. A haematite with colloidal texture or martitized magnetite is quite reactive with lime and alumina. Limonite (FeOOHH2O), often associated with laterite, is more reactive than the ferric oxide hydrate phases like goethite and lepidocrocite. It has been observed by
Makashev (1976) that the reactivity of raw material is often favorably influenced by the presence of
iron oxide in the ferrous state, the appearance of which is obviously dependent on the parent
mineral. For example, chlorite and glauconite may release FeO below 500C, while geothite and
lepidocrocite yields Fe2O3 at about 300C. The iron-bearing minerals thus play an important role

Raw Materials Selection

in shaping the reactivity of the kiln feed, although for alite formation the mineralogy is of little
import since most of the iron has entered the clinker melt by this point.
The correction of alumina is done with the help of bauxite or aluminous laterite. Mineralogically
these rocks contain such aluminous minerals as gibbsite (Al2O3 H2O), boehmite (Al2O3 H2O),
and diaspore (Al2O3 H2O). Generally these phases show low crystallinity and high energy in the
green state, dehydrate at 300C 500C, and give rise to different forms of alumina that ultimately
define their reactivity at higher temperatures.


In the cement production process, since there are quite a few unit operations employing different
hardware systems, it is important to examine the role of raw materials in this perspective.
For example, a full understanding of the characteristics of the limestone to be used in a given situation will help in selecting the right type of crusher. Some key requirements include:
Crushing strength (kg/cm2) or crushability index
Hardness value
Abrasion value
Identity of impurities
Moisture content (minimum and maximum)
While the first three parameters are important for selection of type and materials of construction,
the last two factors may strongly influence the process. It is understood that the handling of wet
sticky materials may affect the throughput and increase the maintenance cost. Similarly, most
materials to be crushed contain inclusions, which have totally different behavioral patterns from
one another when introduced into a crusher or a screening system. The characteristics of these
inclusions play an important part in the selection of the right equipment.
It may be relevant to mention here that the jaw crushers and gyratory crushers are designed to
handle hard or abrasive materials. A gyratory crusher is generally chosen for the large feed size and
capacity required in modern quarries, whereas jaw crushers are used in relatively small primary
applications. Of all the types of crushers available for the primary and secondary crushing of limestone and clay, the double roll crusher is certainly the most versatile. It can handle dry dusty material to extremely wet and sticky material. According to McCater (1996), this type of crusher can
handle limestones with a compressive strength of up to 140 MPa. The impact crushers are often
preferred for their high reduction ratio. However, there are, limitations with its ability to handle
sticky and abrasive materials.



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The above examples show that the crusher selection strongly depends on full characterization of
raw materials. Similarly, the selection of a grinding system also involves proper understanding of
raw material characteristics, and particularly its
Grindability index
Moisture content as fed to the system
Abrasiveness, often inferred from free silica content.
The ultimate objective is to achieve the targeted particle size distribution, average particle size, and
specific surface with least consumption of energy and other operating costs. It has been reiterated
by Schnatz (1999) that ball mills are cost-effective only when a high degree of wear is expected due
to, say, high quartz content. High pressure grinding rolls can be profitably used for relatively dry
raw materials. Roller mills are generally preferred for raw grinding due to their low energy
consumption and the option of simultaneous drying.
Coming to the pyroprocessing, it may be mentioned that different raw mixes with more or less the
same chemical composition and equal fineness may have greatly differing burnabilities. The reason
for the differences lies in the variation off the mineral composition of the raw mix constituents,
their crystal size, and particle size. According to the F. L. Smidth training modules (1997), worldwide experience has shown that poor burnability is primarily caused by the presence of coarse
grains of calcite (+125 m) and quartz (+45 m). Deleterious effects of the presence of coarse
grains of dolomite (+125 m), feldspar (+63 m), and shale (+50 m) have also been reported.
The volatile matters, and more particularly alkalies and chlorides, present in the raw materials have
a very strong bearing on the process of clinkerization in the present-day preheater-precalciner
rotary kilns. The circulation of these volatiles in the system without any bypass imposes certain
upper input limits for these constituents in raw mixes. On a loss-free basis, these limits are
normally considered as follows:
K2O + 0.65 Na2O
Chlorine as Cl
Sulphur as SO3


The study of alkalies, and sulfur- and chloride-bearing minerals in the raw materials becomes
essential in this context.

Cement production is dependent on a wide spectrum of sedimentary and metamorphic rocks,
limestones being the most critical in terms of quality and quantity.

Raw Materials Selection

A limestone resource required for setting up a cement plant first needs to be examined from the
point of view of its prospectivity. The geological history defines the complexity of a deposit and an
appropriate exploration program is necessary for proving the deposit and arriving at a reliable estimate of the reserve in terms of quality and quantity. A rational approach is to classify the deposits
in terms of their geological complexity and the reserves in terms of their reliability so that the
quantum of exploration could be decided for a given deposit to arrive at proved, probable, and
possible reserves required for setting up a cement plant.
After proving a limestone resource, it is essential to undertake its thorough compositional assessment. A limestone with a minimum of 44% to 45% CaO and maximum 3.0% to 3.5% MgO, 0.6%
R2O, 0.6% to 0.8% SO3 , and 0.015% to 0.05% Cl is regarded as a cement grade limestone,
provided its SiO2 , Al2O3 , and Fe2O3 contents satisfy the ultimate modulii values of raw mixes. The
compositional ranges of aluminosilicate materials cannot be defined as rigidly as they have to
match the principal carbonate component. In general, an argillaceous component with more than
3% R2O and/or 1% SO3 may be considered, prima facie, unsuitable. For most of the minor
constituents, 0.5% is regarded as a safe limit. A special examination is called for if some of the
constituents exceed this limit.
The comminution and thermal behaviors of raw materials primarily depend on their mineral
phases and microstructural features. The crystal size of calcite and the associated mineral assemblage define the dissociation characteristics of limestone in a very effective manner. The mineralogy of argillaceous materials is quite complex due to their layered structure, frequent ionic
substitutions in the layers, unbalanced charges, and inclusion of interlayer materials. Because of
these complications, the choice of clay can be guided more by Si: (A,F) ratio, volatile contents,
fusibility, granulometry, cation exchange capacity (CEC), etc. In the ultimate evaluation it is
important to note that the concurrence of carbonate dissociation and thermal decomposition of
aluminosilicate components is considered a basic necessity for high reactivity and proper burning.
The above concepts are equally applicable for all other siliceous, ferruginous, or aluminous corrective materials, when their use becomes unavoidable due to stoichiometric needs. Different forms of
silica, aluminum hydrates, ferri/ferous minerals, etc., present in the above corrective materials
influence the burning process quite significantly and hence demand careful evaluation in terms of
overall impact on the raw mix burnability.
In cement production, size reduction is an important material preparation step. The amenability
of limestones to size reduction processes is apparently controlled, inter alia, by the free and fixed
silica content and the crystal size variations of calcite and quartz phases. The hardware selection
for comminution is also dependent on the above mineralogical and microstructural features.
Since the ultimate burning process is involved with the prior size-reduction steps, there has been a
progressive evolution of the limiting particle size for different mineral forms, supported by experi-



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mental findings. In raw materials selection the attainability of such particle size distribution
patterns requires specific attention.
All in all, it should be realized that the production of cement is to a large extent dependent on
natural raw materials, and more specifically on limestones.
Since the scale of cement operation is large, the location of a plant for its life is decided by the
occurrence of a limestone deposit. The technological suitability and consistent supply of raw materials are, therefore, of paramount significance. All efforts for proper selection of raw materials are
absolutely essential.

The author is thankful to his colleagues at the Companys Research and Consultancy Directorate
and more particularly to Mr. S. A. Khadilkar and Mr. P. G. Lele for providing test data on raw
materials from the Directorates database and also, to Dr. S. K. Jatty for helping with the scanning
electron micrographs of limestone samples.

Bissell, H. J., and Chilingar, G. V., Developments in Sedimentology, 9A, Elvesier Publishing
Company, Amsterdam 1967, page 37.
Bond, F. C., Crushing and Grinding Calculations, Parts I & II, Bulletin 07R9235C, Allis-Chalmers,
Milwaukee, USA, pages 1-14.
Boynton, R. S., Chemistry and Technology of Lime and Limestone, John Wiley and Sons, New York,
1980, 578 pages.
Brindley, G. W., and Brown, G., Crystal Structures of Clay Minerals and Their X-ray Identification,
Mineralogical Society, London, 1980, 495 pages.
Chatterjee, A. K., Chemico-mineralogical Characteristics of Raw Materials, Advances in Cement
Technology, Ed. Ghosh, S. N., Pergamon Press, Oxford, 1983, pages 39-68.
Chilingar, G. V., Jour. Sedimentary Petrology, Vol., 27, 1957, page 187, as referred to in by S. P.,
Ghosh, 1983.
Chilingar, G. V.; Bissell, H. J.; and Fairbridge, R. W., (Editors), Carbonate Rocks: Physical and
Chemical Aspects (Developments in Sedimentology 9B), Elsevier Publishing Co., Amsterdam 1967,
413 pages.
F. L. Smidth & Co., Kiln Operation and Optimization Training Module, International Cement
Review, May 1997, pages 60-64.
Ghosh, S. P., Raw materials Geological Characteristics, Advances in Cement Technology, Ed.
Ghosh, S. N., Pergamon Press, Oxford, 1983, pages 1-38.
Ghosh, S. P., and Chatterjee, A. K., Norms for Exploration, Opening-up and Quarrying of
Cement-grade Limestone Deposits, Process Technology of Cement Manufacturing, VDZ Congress
77, Bauverlag GmbH, Wiesbaden and Berlin, 1979, pages 91-98.

Raw Materials Selection

Grim, R. E., Applied Clay Mineralogy, McGraw-Hill Book Co., New York, 1962, 422 pages.
Makashev, S. D., Effect of Raw Materials Physico-Chemical Properties on Reactivity of Raw Mix
and Clinker Minerogenesis Processes, 6th ICCC, Moscow, September 1976, Section I-4,
pages 1-17.
McCaffrey, L., Quarry Optimisation, Middle Eastern Cement and Construction Materials,
February 1999, pages 25-29.
McCarter, J., Crushing It Right, International Cement Review, February 1996, pages 51-57.
Oates, J. A. H., Lime and Limestone, Wiley-VCH Verlag GmbH, Weinheim, 1998, pages 1-25.
Pettijohn, F. J., Sedimentary Rocks, Harper & Row, New York, 1957, 660 pages.
Schnatz, R., Selecting Grinding Systems, World Cement, January 1999, pages 61-69.
Schwarzkopf, F., Lime Burning Technology A Manual for Lime Plant Operations, 3rd Ed., Svedala
Industries, Kennedy Van Saun, 1994.
Scoffin, T. P., An Introduction to Carbonate Sediments and Rocks, Blackie, 1987.
Sinha, S. K.; Handoo, S. K.; and Chatterjee, A. K., Communition and Dissociation Characteristics
of Indian Limestones, 7th ICCC, Paris, II, 1980, pages I-108 I-113.
Strakhov, N. M., and others, Formation of Sediments in Recent Basins, (in Russian), Izt-vo Akad.
Nauk, USSR, Moscow, 1954.
Tucker, M. E., and Wright, V., Carbonate Sedimentology, Blackwell Scientific Publications, London,
Tucker, M. E., Sedimentary Petrology, An Introduction to the Origin of Sedimentary Rocks, Blackwell
Scientific Publications, London, 1991.
Velde, B., Introduction to Clay Minerals Chemistry, Origins, Uses and Environmental Significance,
Chapman & Hall, London, 1992, 198 pages.
Volkonskii, V. V.; Makashev, S. D.; and Shteirt, N. P., Technological, Physico-mechanical and
Physico-chemical Studies of Cement Raw Materials (in Russian), Izd-vo Literatury Po Stroitelstvu,
Leningrad 1972.
Wiersma, D. J., The Geology of Carbonate Rocks, Proc. International Lime Congress, September
1990, pages 13-14.
Worral, W. E., Clays, Their Nature, Origin and General Properties, Maclaren and Sons, London,
1968, 124 pages.



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