Chapter -1

General Introduction
1.1 History of Ceramic and Ceramic Tiles:
The basic meaning of Greek word ceramic is given in Sanskrit language. In
Sanskrit ceramic means to fire or heat. In Greek language ceramic means
god Ceramos. The ceramic means the art of the potter. This technique is very
ancient but now it become modern. In common word the ceramic means the
combination of clay with other substance in different mixture ratio and then
fired it for hardness. Ceramic are made by following mainly four steps.
(1) Mixing (2) Shaping (3) Drying (4) Firing
At the present time, the term generally denotes all articles developed by heat
in which clays have been used. The German and French. equivalents of
this term are keramic and ceramiake respectively. In the U.S.A. the cement,
lime, glass and enameled iron industries are included in the term ceramic. But
in Europe this is considered undesirable. The art of pot making is the oldest of
all human arts. It is naturally very difficult to trace the development of this art
systematically. In the following paragraphs attempt has been made to give
only a brief history of the development of various types of ceramic industry in
Asia and Europe. Perhaps the first people that used clay articles for their use,
where the ancient Egyptian vessel of terracotta, which were intended to contain
provisions for the deceased have been found in the tombs of the Memphite
period (5000-3000 BC) and some, bricks found under the valley of the Nile are
supposed to have been made about ten thousand years ago. At latter period
these people also discovered the art of making glazed clay-wares, the
remnants of which are still to be seen in their pyramids and temples. The fine
pottery of latter period is most often covered with a thin glaze, colored with sky
blue or pale green sometimes the clay paste itself is colored but more often left
white.
In India, clay products in various forms have been used since very ancient
times’ recent excavations have shown that this art of potting thrived in a fairly
advanced state as early as four thousand years ago. There can be no doubt
that objects found in the excavations of Harappa and Mohenjodaro on the Indus

2
valley are closely connected and roughly contemporary with the Sumerian
antiquities dating from the third or fourth millennium before Christ. These
ceramic-wares have similarity with those of kish and a seal identical with those
found at Harappa and Mohenjodaro has been discovered in the debris beneath
the temple of Hammurabi’s time.
Mention of pottery is made in the Vedic Hymns (2000-3000 BC) but the law of
Manu Condi fined between 6th and 9th Centuries BC are more explicit. Earthen
vessels are universally used in India are potters constitutes one of the great
function castes of the Hindu social system. Much of the prehistoric potteries of
India are of red, brown, and a black tint has shining unglazed surface and is far
superior in design and workmanship to the common forms of today.
Specimens of glaze tiles after the Persian style were unearthed during the
excavations of Gour, a seat of Mahomedan Kings of Bengal during the 11th
century. historically, man has desired to create living spaces which were
beautiful, durable, and user friendly.with that in mind, ceramic tile has been
made by man for 4000 years.beautiful tiles surfaces have been found in the
oldest pyramids, the ruins of babylon, and ancient ruins of greek
cities.decorative tile work was invented in the near east, where it has enjoyed
a longer popularity and assumed a greater variety of design than any where in
the world. during the islamic period, all methods of tiles decoration were
brought to perfection in persia. in europe decorated tiles did not come into
general use outside moorish spain until the second half of the12th century.
the tiles mosaics of spain and portugal,the maiolica floor tiles of rennaisance
italy,the faiences of antwerp, the development of tiles iconography in England
and in the Netherlands, and the ceramic tiles of Germany are all prominent
landmarks in the history of ceramic tile.
In Punjab, the manufactures of glazed tiles or pottery dates from the period of
Chengiz-Khan (1206-1221). The charms of this pottery are the simplicity in
shapes, the directness and property of Ornamentation and the beauty of
coloring.
Porter defined global competitiveness as the National level, as the ability
to export many goods produced with high productivity, which allows the nation
to import many goods involving lower productivity.

3
 (Wall tile 518 B.C.Iran ) (Maiolica tile of 16th century Italy)

There are many things and articles are produced by ceramic material .Due to
very important property like hardness, strength, high melting point, electric
conductivity, brittleness, ceramic used to produces many extra ordinary useful
products.
There are so many products producing in ceramic industries the
products are classified as raw materials and manufacturing techniques.
1.2 Origin of the problem :
The basic requirement of human being is Roti, Kapada and Makan.
Now a day ceramic tiles and ceramic ware are become basic requirement of
people in the world. The people demand various types of high qualities ceramic
tiles and other ceramic products are ever increasing. Also high demand of
ceramic tiles and sanitary product in estate market in the world is increasing
day by day. Ceramic tiles and other ceramic material are useful in Industries,
scientific research, medical science, electronics components, space science,
space yaan technology etc. Now a days ceramics materials useful in advance
applications and demand of ceramics materials are increase in feature.
Morbi, Wankaner and Than are Western part of India situated in Rajkot
District Gujarat. More than 400 units are manufacturing ceramic tiles and
ceramic materials and other ceramic building materials of various qualities. Also
20 huge plants of ceramic tiles producing vitrify tiles. Now a day large demand
of vitrify tiles in building construction. The above units producing large

4
quantities of ceramic tiles and other products per day here. Per day turnover in
Rs. 500 crore, so it’s big output oriented industries. The raw materials used to
manufacturing ceramic tiles are mainly from Gujarat, Rajasthan and
Andhrapradesh mine and some material collect from other part of country and
imported from Russia the following raw materials are used to produce ceramic
tiles. (1) Quartz (2) Feldspar (3) Zircon (4) Al2O3 (5) STPP (6) China
clay (7) Bikaner clay (8) opaque glass (9) Transparent glass (10) grog.
(11) Talc (12) volsonite (13) Dolomite (14) Lime stone Etc..
There are many industries in Gujarat developed and manufacturing
glazed tiles, wall tiles, crockery, the development is due to availability of raw
material, availability of natural gas, entrepreneurship of people, well trained
workers and positive policy of State Government. Ceramic industries are in
region of Than, Morbi, Wankaner, Himatnagar, Mahesana and Ahmedabad in
Gujarat.
Now a day technology is developed well but most of ceramic industries
used old technology and producing low quality products and they not able to
provide variety in products many industries suffering from following technical
problems.
1. Standard raw materials can not easily available in ceramic zone.
2. Huge quantities of rejection product during firing process in ceramic
ware.
3. Difficult to stand in market against china products.
4. Fuel cost is very high.
5. High bank interest against bank loan for industries.
6. Old technique in quality control.
7. Old material analytical technique.
8. There is no particular R&D section in major’s plants.
9. Poor mentality to implement high education thought in improvement of
work in ceramic industries.
10. Majority workers are in ceramic industries from out state.
11. Due to impurity present in raw material during the firing huge quantities
of reject product to destroy this waste is a big question It is harmful for
environment.
12. Ignorance of technical knowledge.

5
 Due to this reason it is difficult to stand in international competition.
By studying above factor I have decided to study basic raw material of ceramic
tiles, for thermoluminescence. Because T.L.(Thermoluminescence) is very
sensitive to any imperfection in impurity. That’s why TL is very useful tools in
Quality Control in Ceramic tiles raw materials.

The present minerals under study were collected from Bhor ghats,
Sangamaner, Nashik also from various ceramic processing industries Morbi.
Rajkot district in Gujarat.

Over all eighteen verities of the minerals were collected among them the
following nine minerals are selected to TL study ,X RD and TGA. (1)Quartz (2)
Feldspar (3) Zircon (4) Al2O3 (5) Sodium Tri Poly Phosphate (STPP) (6)

6
China clay (7) Bikaner clay (8) opaque glass (Frit-O) (9) Transparent glass
(Frit-T). Two samples namely Grog and Mixture are the part of the pre final and
final product of ceramic tiles these two sample are also subjected to TL
measurement before and after irradiation, XRD study and Thermo Gravimetric
Analysis (TGA). Induction coupled plasma atomic emission spectroscopy
(ICPAES) of three sample namely China Clay, Bikaner Clay and Mixture has
been done.
In ceramic tiles and sanitary ware the manufacturing process is mixing of
various type of minerals in appropriate quantities are taken and ball milled for
six to eight hours in distilled water the obtained slurry is sieved to get
appropriate particle size around 15 micron are collected for further processes.
The present TL study of minerals is intended to suggest the quality of
the raw material at input stage of the ceramic tiles industry. TL dosimetry
studies are done in case any accident like nuclear fall out these ceramic tiles
fixed in the toilet, bathroom, and flooring, may be used to get total radiation
received from the accident day to sample analyzed day.
Ceramic products made from inorganic substance First body of the
ceramic made from clay, quartz and Feldspar as main component and talk,
volosonite, dolomite and also used for making body then give appropriate
shape to the body and fired by suitable temperature, there are so many
conventional ceramic product but mainly are given below :
(1) Virtues sanitary ware: It is high qualities ceramic product made
from clay, Quartz and Feldspar. It has very high hardness.
(2) Dust Press Ceramic Tiles: This tiles is water absorption tiles
mainly made from China clay, Bikaner clay, Volsonite ,Calsite,
Talc.
Stoneware crockery ware: The body of this type ceramic is very hard like stone.
Cup and saucers are made from this type ceramic. Main component made for
plastic clay, china clay, quartz and feldspar. This ceramic fired at temperature
12000C.70% of ceramic product in India provided by Morbi and other unit are in
Rajkot district.

7
 Map indicating Sangamner, Nashik ,Maharashtra State, India

1.3 Rocks and Minerals

The earth can be physically described as a ball of rock (the crust or
lithosphere), partly covered by water (the hydrosphere) and wrapped in an
envelop of air (the atmosphere). To these three physical zones one may add
the biological zone (the biosphere). The crust or lithosphere is made up of a
great variety of rocks containing only a handful of elements.
Rocks are the aggregate of minerals and are the individuals units
constituting the crust of the earth or the lithosphere. Some of them were
formed during consolidation of molten silicates (magma) and are describing
as the igneous rocks (granite, basalt etc.). During later periods, the primary
rocks suffered erosion by wind, water, ice, etc. and the products of such
decay were carried away by the natural forces and deposited as loose
sediments. Later on, they were subjected to compaction and the resulting
products are known as the sedimentary rocks (e.g. sandstones and shales).
The rocks occurring in any region may suffer physico-chemical change and
accordingly, develop remarkable changes in their mineral compositions or
texture or both. The processes which bring about such changes are known as
metamorphism and the resulting products are the metamorphic rocks. The
dominant rocks occurring in the crust fall in the two contrasted groups:

8
(a) Light rocks, including granite and related types and sediments such as
sandstones and shales They are rich in silica (65-70%), while alumina is the
most abundant of the remaining constituents.
(b) Dark and heavy rocks, mainly basalt and the related types They are
known as basic rocks (with about 60% silica). Certain heavier rocks called
ultra basic rocks (sp. gr. 3.4, 40-45% silica) are also present. In these rocks,
silica is still the most abundant single constituent but iron oxide and
magnesia, singly or together generally take the second place.
Some of the elements, e.g. gold, copper, sulphur, carbon (as diamond
or graphite) make minerals by themselves but most minerals are compounds
of two or more elements. More precisely, minerals are the natural inorganic
substances of fixed chemical composition and are very commonly
characterized by the presence of typical atomic structure with or without the
development of the corresponding external crystalline form e.g., Quartz. The
study of minerals involves knowledge of their crystalline form, internal
structure, the physical and chemical properties, the optical characteristics and
their mode of occurrence. A mineral from which one or more metals or
metallic compounds can be extracted economically, is known as an ore
mineral, e.g. the mineral bauxite which is an important ore of aluminum metal
as well as aluminum oxide which is an essentional ingredient of certain types
of refractories as well as technical ceramic items.
The Abundance of Elements on the earth’s crust.
Atomic Number Name Volume %
8 Oxygen 91.97
11 Sodium 1.60
12 Magnesium 0.56
13 Aluminum 0.77
14 Silicon 0.80
19 Potassium 2.14
20 Calcium 1.48
26 Iron 0.68

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 Average Composition of Crust Rocks (as Oxide)
Name Chemical Formula %
Silica SiO2 59.26
Alumina Al2O3 15.35
Lime CaO 5.08
Soda Na2O 3.81
Ferrous Oxide FeO 3.74
Magnesia MgO 3.46
Ferric Oxide Fe2O3 3.14
Potash K2O 3.12
Water H2O 1.26
Titania TiO2 0.76
Phos. Pentoxide P2O5 0.28

1.4 Quartz:
Quartz: The purest natural crystalline form of silica is quartz, containing more
than 99.95% SiO2. The other abundant sources of silica are the acid igneous
rocks, sands, sandstones and quartzite containing varying amounts of
impurities. In all these raw materials SiO2 exists in the form of ∝-quartz. Flint,
which is a mixture of chalcedony and quartz, is also used as a source of silica
in some countries.
Under optical microscope, quartz is identified by its colorless,
nonpleochroic habit in plane polarized light; shape is commonly anhedral,
often found as perfect euhedral crystal. It does not show any cleavage, but
some conchoidal fractures are observed within the grains. Anisotropic under
cross polarized light, quartz shows first order interference color which is highly
variable (grey, yellow etc.). It gives adulatory or patchy extinction which is one
of the most characteristic features of Quartz especially in metamorphic rocks.
Refractive index is low, slightly higher than Canada balsam (1.55), the outline
being feebly visible in plane polarized light. Quartz grains often show
numerous tiny vitreous inclusions of other minerals. Quartz is distinguished
from alkali Feldspar by its positive relief in balsam, lack of alteration and

10
cleavage. Quartz lacks the multiple twinning of most Feldspar and differs from
the untwined oligoclase by uniaxial figure and lack of cleavage.
Silica can exist in polymorphic forms. The sequence of polymorphic inversions
can be represented as follows:

α- Quartz (8700C) ↔ α- tridymite( 0

1470 C) ↔ α-cristobelite( 0
1726 C) ↔melt
↕ ↕ ↕
0 0 0
573 c 163 c 200 c
β-Quartz β- tridymite β- cristobelite

↕
0
117 c
γ -tridymite
The inversions indicated by the horizontal arrows are reconstructive
transformations (relatively slow), during which the bonds in the secondary co-
ordination sphere are broken and the SiO4 tetrahedral are completely
rearranged. The activation energy for the changes is high and as a result the
high temperature forms can be under cooled without transformation to the
stable state. The inversions indicated by the vertical arrows are known as the
displacive type of transformations which proceeds at a relatively fast rate.
In presence of impurities in the form of solid solutions, at about 8700C
∝-tridymite. which gradually transforms to α-cristobalite above 14700C.
Cristobalite ultimately melts at 17260C and on cooling forms vitreous silica.
The quartz-cristobalite transformation starts on the surface or the boundary
face of quartz grains leading at first to formation of a strongly disordered
quartz followed by the formation of a disordered cristobalite. Subsequently it
turns into a regular form. The most important consequence of the polymorphic
transformation of quartz is the changes in the specific gravity and volume
Uses : Quartz is widely used in the manufacture of soda-lime-silica glass
and white wares. Quartzite containing about 98% SiO2 are used for the
manufacture of silica bricks, used in steel making furnaces, specially at the
roof of an acid open-hearth, checkers, converter etc. They are also used in

11
 coke-ovens and the roof of glass tank furnace. For refractory use, the
combined Al2O3 and TiO2 should be < 2.5% and for superior qualities < 1%.
With Na2O and K2O < 0.1% CaO < 0.3% and MgO < 0.1%, quartzite are
considered to be of suitable quality.
The pure, untwined, clear and transparent quartz crystals possess
piezo-electric properties and are used in telecommunication. Quartz is also
the source of element silicon, used in the manufacture of non-oxide ceramics
(e.g. SiC, Si3N4) and ferro-silicon.
Chemical Composition of Quartz:

Source Constituents (%)

Quartz SiO2 Al2O3 Fe2O3 TiO2 CaO MgO K2O Na2O LOI
Nizamabad, A.P. 99.75 0.15 0.02 - - - - - -
Hyderabad, A.P. 99.96 - 0.02 - - - - - -
Gujarat 99.40 0.06 0.04 - 0.09 tr. - - .22
Tura, Meghalaya 99.12 0.21 0.36 0.01 - - - - -
Jaipur, Rajasthan 98.11 0.41 0.22 tr 0.68 tr. 0.07 0.15 .19
Hyderabad 99.13 0.12 0.13 0.07 0.09 tr. 0.10 0.06 .19
(Sanatnagar)

1.5 Feldspar :
Feldspar is the most important group of rocks forming silicate
(tectosilicate) minerals. The acid intrusive rocks (pegmatite) are the chief
source of Feldspars.
At high temperatures there is a continuous series of solid solution
between potash-Feldspar and soda-Feldspar. These types of Feldspar are
mainly found in alkali igneous rocks like granite, syenites etc. and also in
some metamorphic rocks. Large quantities of Feldspars suitable for ceramic
industry are found in Rajasthan and also in Tamilnadu, Gujarat, Orissa, Bihar,
M.P. and in West Bengal.
Uses : Feldspar is a common flux and is used in various types of ceramic
bodies, the fluxing action depending on the amount and type of alkalies
present. Unlike pegmatites and nepheline syenites, feldspar has a rather slow

12
fluxing action due to the high viscosity of the melt. Potash feldspar is generally
preferred in ceramic glazes. Potash spar fuses at cone 8 to 9 as compared to
cone 4 for some high soda spars. In a fired body it increases the strength,
hardness and coefficient of expansion and improves the transluscency and
vitrification.
Feldspars are also used in glazes, enamels and glass as a cheap
source of alkalies. For use in glass, the ferric oxide content should be less
than 0.2%, silica not more than 67% and alumina not less than 17%. Potash
spars are more commonly used in glass since pure varieties are more
abundantly available.
Occurrence and chemical composition of Feldspar
Source Constituents (%)
Feldspar SiO2 Al2O3 Fe2O3 TiO2 CaO MgO K2O Na2O LOI

Mihijam, 65.90 19.34 0.29 0.04 0.35 tr. 9.27 8.07 0.04

Jharkhand
Kodarma, 64.00 18.83 0.39 - 0.55 - 12.02 3.11 0.21

Jharkhand
Alwar (1) 65.56 20.93 0.12 - 2.05 tr. 7.12 3.49 0.42

Rajasthan
Alwar (2) 64.96 19.62 0.11 - 1.02 0.02 12.38 1.98 0.64

Rajasthan
Jhansi, M.P. 63.69 21.88 0.24 - 0.34 tr. 11.25 2.72 0.86

Nellore, 64.80 19.09 0.20 - 0.18 0.01 13.00 2.40 0.5

A.P.
Sitampudi, 44.84 34.07 0.05 - 20.0 0.50 - - -

Tamilnadu 5
Raghudih, 64.70 19.54 0.36 - - - 11.42 2.46 -

W.B.
Chandla, 66.25 10.21 0.29 - - 0.40 13.81 - 0.50

M.P.
Ajmer, 65.17 21.07 0.13 - - - 12.80 0.78 0.05

Rajasthan

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1.6 Clays and related minerals :
Clays are essentially hydrated aluminosilicate minerals having fine
particle sizes, usually below 2 microns. Clay minerals have layered structures
and occasionally aluminum is replaced by magnesium, iron, alkali or alkaline
earth elements partly or wholly.
The important physico-chemical properties of clays depend not only on
the composition and structure of the respective clay minerals, but also on the
particle size and shape. The principal clay minerals are as follows :
Kaolinite Group: Kaolinite (Al2O3, 2SiO2, 2H2O) is normally well crystallized as
hexagonal plates (0.1-0.3µ), has a medium plasticity and base exchange
capacity.
Halloysite (Al2O3, 2SiO2, 4H2O): It has a two layer structure containing
weakly bound molecules of water between the structural layers, which is given
out even at 400 C. The particles are of elongated shape (rods and tubes). The
mineral has a higher exchange capacity and plasticity due to finer particle size
in comparison to kaolinite. It is frequently associated with kaolin and kaolinitic
clay.
Montmorillonite Group : Montmorillonite Commonly exists as fine
particles having sizes less than 1µ. It has a three-layered structure consisting
of two layers of silica tetrahedral and one central di-octahedral or tri-
octahedral layer. The gaps between the layers are readily penetrated by water
which produces swelling. The mineral exhibits high degree of dispersion,
plasticity, swelling property and base exchange capacity. It shows high drying
and firing shrinkage.
Bentonite is a montmorillonitic clay, having properties similar to that of
montmorillonite.
Formation of Clays:
Clays are said to have originated from weathered igneous rocks
composed of Feldspar and Quartz. The reactions during weathering of
Feldspar leading to formation of clay a given below. The steps involved are
essentially (a) hydrolysis (b) decomposition and (c) hydration.

(a) K2Al2Si6O16 + 2H2O → H2 Al2Si6O16 + 2KOH (removed by water flow)

(b) H2Al2Si6O16 → H2 Al2Si2O8 + 4SiO2

14
(c) H2Al2Si2O8 + H2O →Al2 (Si2O5) (OH)4

When the environment provides carbonic acid.

(d) K2Al2Si6O16 + 2H2CO3 Al2 (Si2O5)(OH)4 + K2CO3 + 4SiO2
Here also K2CO3 is leached out by rain water. When the parent rock
contains impurities like lime, magnesia, iron etc. impure clays are obtained.
Simulated laboratory experiments reveal that kaolinite is the end product
under acidic conditions whereas the presence of alkalies (potassium in limited
concentration) favors formation of smectite or mica. Under similar conditions,
if magnesium is present, montmorillonite is formed. At or above 3500C and
under a moderate pressure, pyrophyllite is formed in presence of an excess
Al2O3, from boehmite. At higher temperatures other Al2O3 phases develop.
Types of Clays:
Kaolin primarily consists of kaolinite mineral. Two types of kaolin are
recognized namely, (a) Residual or primary kaolin and (b) Sedimentary or
secondary kaolin which are finer in size.
Bikaner Clay is a highly plastic kaolinitic clay, having very fine particle
size. It has a softening point (16750C) lower than that of pure kaolin and is
sometimes used as bonding clay in refractories. The main use is in white ware
compositions to improve the plasticity, workability and the green strength of
the finished products.
Fireclays have a disordered kaolinitic structure and unlike pure kaolin,
are not white burning, primarily due to the presence of iron oxide and titania
as impurity in the clays. Fireclays can be classified under the following
categories as follows:
(i) Flint clay-A dense, hard, non-slakable, massive, non-plastic clay
having flint like nature. These are composed of fine, well-
crystallized kaolinite particles.
(ii) Plastic clay-soft and plastic
(iii) Refractory shales – soft and highly plastic.
Fire clays occur in two modes namely:
(a) Well defined beds associated with coal seams.
(b) Lenticular beds associated with coarse sediments.

15
 The color and other characteristics of fireclay depend on the mode of
formation.
Clays generally contain appreciable amounts of Organic matter, such
as lignite or humic acid. The mineral impurities commonly present are quartz,
feldspars, micas, iron and titanium bearing minerals, limestone, magnesite,
gypsum, garnet and tourmaline. Excepting quartz, the other impurities act as
fluxes and reduce the Pyrometric Cone Equivalent (PCE).

Chemical Composition of Some Indian Clays:

Source Constituents (%)

SiO2 Al2O3 Fe2O3 TiO2 CaO Mg K2O Na2 LOI
O O
West Zone
Gujarat
Kutch Mineral 47.75 34.25 0.90 1.30 1.23 0.24 0.35 0.45 12.46
Premier Minerals 44.17 36.55 0.70 2.82 1.12 0.12 0.10 0.42 13.92
Ashapura 49.63 34.05 0.60 1.37 0.54 0.58 0.22 0.61 12.28
Amrapali I 43.08 36.59 1.16 2.31 1.79 0.85 1.07 0.22 13.00
II 46.21 35.08 0.87 1.29 0.88 0.86 0.20 0.48 13.88
III 44.64 34.94 1.34 1.14 1.67 0.91 0.16 0.10 14.84
Eklera 48.92 22.59 1.30 1.12 0.65 0.28 1.00 0.31 12.83
Nadapar IRL 43.86 38.24 0.50 1.74 0.67 0.24 0.05 0.55 14.05
Nadapar ISWL 44.04 39.25 0.40 0.96 0.45 0.16 0.05 0.52 14.09
Umiya 47.20 36.15 0.60 1.50 0.82 0.04 0.05 0.33 13.59
AMI China clay 52.45 29.83 0.94 1.48 1.14 0.59 0.35 0.86 11.89
Himmar Nagar
China clay 45.90 37.74 0.57 0.69 0.76 0.18 0.12 - 14.13
East Zone
Bihar
Rajmahal (Pink) 46.68 35.29 1.90 0.89 0.28 0.50 0.28 0.60 13.12
Rajmahal (White) 48.90 34.51 1.71 0.50 0.67 0.20 0.41 0.52 12.60
Chaibasa (Gr. I) 47.90 36.00 1.25 tr. 1.24 0.40 0.61 0.75 12.25
Chaibasa 46.59 35.95 1.12 tr. 1.40 0.40 0.33 0.91 13.22

16
Source Constituents (%)
(Superfine)
Simultala 47.27 38.20 0.47 0.07 0.35 0.10 1.55 0.14 11.80
Ulatu 44.35 38.51 0.55 1.23 0.23 0.05 0.05 0.11 14.77
Bagru 45.09 37.45 1.12 2.40 tr. tr. 0.10 0.13 13.57
West Benal
Mukhdum Nagar I 44.10 37.39 2.6 1.37 0.10 tr. 0.20 0.79 13.48
II 43.64 35.58 2.39 2.64 1.80 tr. 0.13 0.36 13.50
Mhatomara 46.05 35.49 1.36 2.11 0.28 0.20 0.27 0.03 13.86
Mahammad Bazar 44.31 36.97 2.11 0.80 0.31 0.26 0.60 0.29 14.34
Kharidumri 46.98 36.87 0.54 0.40 0.78 0.11 0.42 0.13 12.98
Dhatara 47.45 33.62 1.13 tr. 1.87 1.25 0.52 1.08 13.17
Orrisa
Mayurbhanj 48.55 33.69 1.45 0.53 tr. 1.27 - 0.17 11.16
North Zone
Kusumpur 46.80 36.83 1.65 tr. 0.03 0.07 0.57 0.11 13.63
Delhi I 46.92 36.04 1.86 tr. 0.92 0.26 1.06 0.39 12.76
II 47.66 35.75 1.00 tr. 1.01 0.20 0.99 0.53 12.86
Rajasthan
Modi Clay (P-90) 44.46 37.03 0.80 tr. 2.00 0.41 0.07 1.02 14.64
Modi Clay(TT-75) 46.82 36.72 1.00 0.21 0.70 0.25 0.15 0.18 13.87
South Zone
Kerala
Thiruvanantapurm 45.60 37.40 0.745 0.89 tr. 0.414 0.02 0.02 14.86
9 0 2
Sasthavattom 44.11 38.17 1.30 1.55 tr. 0.042 0.02 0.43 14.26
4 9
Kannanalloor, 43.99 39.64 0.40 0.48 tr. 0.336 0.00 0.03 15.26
Quilon 9 4
Nyleswar 45.85 36.74 1.82 1.17 0.08 0.12 0.08 0.13 14.29
(Jyothi),Cannanore
Nyleswar (Neelex)” 45.88 36.12 1.43 0.55 0.11 0.21 0.09 0.06 14.94

17
Source Constituents (%)
Nyleswar(Kerala) “ 47.32 35.97 1.30 1.07 0.26 0.22 0.04 0.07 14.09
Nyleswar, 47.94 36.43 1.30 0.93 tr. 0.12 0.20 - 13.35
Cannanore
Payyangadi, 44.87 36.94 1.28 0.94 tr. 0.31 0.23 0.09 15.43
Cannanore
Kannapuram “ 42.72 38.95 3.89 0.48 0.05 0.27 0.19 0.13 13.19
Mulavana, Quilon 47.85 36.70 0.71 0.33 tr. 0.44 0.13 0.11 14.04
Kalluvathukkal 47.91 35.26 1.64 0.40 0.23 0.35 0.23 0.23 13.67
Thiruvanantapurm 46.47 38.13 0.28 0.79 tr. 0.59 0.02 0.08 14.20
Thonnakkal, “ 46.44 37.85 0.33 0.69 tr. tr. 0.08 0.12 13.88
Thonnakkal Grey “ 45.91 37.21 0.90 0.67 tr. 0.27 0.46 0.19 14.37
Thonnakkal Red “ 45.86 34.53 3.05 0.95 0.11 0.36 0.56 0.27 13.82
Pallipuram White “ 46.48 33.21 2.49 0.99 0.23 0.65 0.80 0.15 15.02
Ramapuram, 42.97 36.19 3.73 1.90 tr. 0.74 0.29 0.58 13.73
Cannanore
Payyangadi, “ 41.75 33.37 5.02 2.16 tr. 0.89 0.30 0.48 15.99

China Clay:

The best quality china clays are found in Kundara, Quilon and also in
Cannanore, Ernakulam, and Trivandrum districts of Kerala. The estimated
total reserve of crude clay is 7.5 lakh tones. The spray dried Kaolin is
marketed under the trade name “Kundara Kaolex”. Processed clays from
Kannapuram, Payyangadi and Nylswar (Cannanore) do not conform to the
Grade-I due to high Fe2O3 and TiO2 which can be removed by High Intensity
Magnetic Separation (HIMS). Grade I china clays are available at
Marthandamkonam and Thonnakkai (Trivandrum). The total estimated
reserves in the area is nearly 222 lakh tones.

Good quality China clays occur near Gollahalli, (South Kanara), near
Karalgi in the Khanpur taluk, Belgaum.

The Bageshpura deposit in Hassan is being used in ceramic industry.

In Gujarat (West Zone), china clays available do not conform to Grade I

18
although some of them can be upgraded by HIMS. In the East Zone good
quality clays are available in Simultala (Bihar) and Kharidumri (West Bengal).
Impurities present in other clays limit their use in white ware manufacture. In
Rajasthan, some of the Nim-ka-Thana china clays conform to the
specifications for the Grade I but they are not suitable for casting slips due to
high CaO contents. Also in Rajasthan near Badana and Khanda Sirol (Kota)
good quality china clay is said to occur. A new deposit has been discovered
near Karabaria-ka-Ganta, about 7 kms to the southeast of Udaipur. The
estimated reserves are nearly 398 lakh tones, in addition to about 339 lakh
tones of brown and buff coloured clays. A number of deposits have also been
discovered in other states and explorations are in progress.

Ball/Plastic Clays:. Ball clays conforming to the Grade I plastic clays are
almost non-existent. However, many of them are widely used in whiteware.
These are from Bhimadole and Ellore in Andhra Pradesh. Than in Gujarat.
Kumbalam, Paddappakara, Ramapuram and Payangadi in Kerala, Chandia in
M.P. Bikaner in Rajasthan. Panruti and Neyveli in Tamilnadu and Rajhara in
Bihar. Of these, Bikaner and Than are considered to be best. For H.T.
insulators plastic clays are imported. However, Than and Neyveli clays are
used in small amounts after purification.

Clays are widely used in the manufacture of ceramics such as earthenware,

fine china, stonewares, bricks, tiles, pipes aggregates in castable, mortars etc.
The fine grained kaolinites mixed with montmorillonites find application in
foundry moulding sands. Purer forms of kaolin have extensitve applications in
paper, textile, rubber and cosmetic industries. As a decolouriser of oils it is
known as ‘fuller’s earth’. Mixtures of montmorillonites and kaolinites are also
used as cracking catalysts for heavy petroleum fractions. Other areas of
limited use are leather, paint, plastics, soaps, polishing compounds,
emulsifying agents, medicine etc.

Fire Clays: Fire clays are used in the manufacture of a wide range of
aluminosilicate refractories with varying Al2O3 contents ( 24 to 70%). A good
quality of fire clay has 24 to 26 percent water of plasticity and firing shrinkage
in the range 6 to 8 percent. The three processes generally employed for
beneficiation of clays are (a) Size separation through simple levigation

19
technique; (b) Hydrocycloning by a wet route; (c) Magnetic Separation by
High Intensity Magnetic Separator (HIMS); (d) Froth floation and (e) Chemical
treatments, such as, acid leaching and bleaching.

1.7 Zircon :

Zircon (ZrSiO4) is found in nature as an accessory mineral in igneous

rocks such as granite and pegmaties. More commonly, it is found as a
constitutent of beach sand along with ilmenite, monazite etc.

Zircon crystallizes in tetragonal system and the large crystals occur as

square prisms or in irregular forms. Finer crystals occur as grains of sand-
size. Its hardness is 7.5 and the sp.gr. Varies in the range 4.2 to 4.86 at
15400C and above zircon breaks down to zirconia (ZrO2) and silica which on
cooling recombine to form zircon. Optically, zircon sands are colourless,
subrounded to rounded in nature.

Baddeleyite is a relatively uncommon rock mainly composed of

zirconia. Artificial crystals of baddeleyite are prepared from zircon. It occurs as
tabular monoclinic crystals.

Occurrence

Andhra Pradesh: Crystals of zircon occur as a minor constiuent of

nephline syenites in Khammam; coastal areas of Vishakhapatnam and
Bhimunipatnam, as a constituent of monazite-ilmenite sands.

Kurnool: Chandrapalle, Marrikunta, Yaparlapadu and Gadidemdygu,

minor occurrences.

Bihar: Hazaribagh: Domchanch; pegmatite veins producing zircon

crystals. Gaya : Akbari Pahar.

Kerala: Palghat :Chowghat-Blangad, Veliyangad; beach sands

containing 2.7 to 8.7% zircon, Chavara in Quilon.

Tamilnadu: Manavalakurichi, Kanyakumari; beach sands constaining 5

to 6% zircon.

20
 India’s estimated reserve of zircon is about 3.6 million tones. The high
purity zircon is produced after several stages of electrical, magnetic and
gravity separations.

Uses: Zircon nozzles of different shapes are used for continuous casting of
steel. Zircon-alumina refractories in different shapes are widely used as
feeder refractories in the glass industry. In ceramics, zircon has manifold
applications, mostly for its very high refractoriness and chemical resistance. It
often forms an important constituent of chemical stoneware and porcelain
bodies. In glaze and enamels, it is used as an opacifier. Due to the high
hardness and abrasion resistance, it is used for making high density grinding
media. Premium grade zircon is used for production of high performance
electrofused refractories and ultra-white grade of tiles, sanitaryware and
tablewares. The major uses of zircon are as follows:

(a) Refractory for Steel and Glass Industry 35%

(b) Ceramics 25%

(c) Foundry 21%

(d) Others 19%

The world supply of zircon has grown from 0.68 m tones in 1979 to
about 1.09 m tones in 1990 and expected to grow further at the rate of about
4% per year. The demand for zircon in foundries and in refractories, non-
ferrous and ceramics industries is increasing at a rate of 2.6% to 3.0% and
5.0% respectively. A new area of demand has opened up for zircon in the field
of zirconia ceramics. It is estimated that the demand of zircon for zirconia
ceramics is around 0.185 m. tones in the world and is expected to grow at an
annual rate of 6.5%used for neutron absorption.

1.8 Bauxite :

The term ‘Bauxite’ does not refer to a specific mineral but to rocks
consisting chiefly of the hydrated aluminium oxides namely gibbsite, boehmite
and diaspore.

Bauxite can be difined as a rock composed of aluminium hydroxide,

besides impurities in the form of silica, clay, salt and iron hydroxide. The

21
mineral content of bauxite bears a close relationship with the residual
ferruginous rock (laterite) commonly found in tropical regions. Bauxite and
laterite show a tendency to occur together and it is not easy to distinguish
them from their chemical compositions. Bauxite usually contains certain
principal ore forming minerals, minor constituent minerals and mineral
impurities. The principal ore forming mineral of bauxite is Gibbsite, along with
Boehmite, Diaspore, and hydrated iron oxides in minor amounts.

Gibbsite is colourless to pale brown in thin section, feebly pleochroic

and commonly occurs as tiny tabular crystals, showing pseudohexagonal
outline. Perfect basal [001] cleavage may be present. The interference
colours are first order grey, white or yellow. Normal twinning is common on
[001] plane, oblique extinction is nearly 250. Coarse platy gibbsite occurs in
circular and lenticular patches and is generally surrounded by medium to fine
grained gibbsite. The occurrence of the scattered flower like growth of coarse
platy gibbsite in places are very common within fine gibbsite grains mixed with
iron oxide. Deep reddish brown iron and titanium oxides are generally
associated in patches with medium to fine grains of gibbsite. In places
gibbsite grains of different sizes are also seen in the red matrix showing
presence of an aluminous core in a ferruginous mantle.

Diaspore is observed under the microscope as blades, radiating from

center and cleavage is perfect to [001]. Elongated crystals give straight
extinction and are usually colourless in plane polarized light. They show first
order interference color of blue, green etc., refractive index is higher than that
of balsam.

Bauxite deposits were formed from all types of alumina bearing rocks.
Such rocks are rich in feldspar, amphiboles, pyroxene and clay minerals. The
rock type includes syenite, granite, basalt etc. It is a product of chemical
weathering of aluminous minerals such as feldspar, nepheline and corundum.
Intensive weathering effects are evident from the redistribution of the
insolubles.

Alumina can exist in various forms. On heating bauxite, it loses the

chemically combined water turning first to gamma alumina and finally to alpha

22
 alumina. Conversion to alpha alumina is complete at 1300-14500C. The
common impurities present in bauxite are kaolinitic clay, quartz, calcite,
(calcium carbonate) iron oxide (limonite) and various hydroxide bearing
minerals. The iron oxide content is generally above 2 to 3% and often more
than 5%. Bauxite rock is normally medium soft to hard in nature. It has a
cellular, porous or fine grained compact structure and shows a conchoidal or
uneven fracture pattern. The color ranges from light grey, cream, yellow or
pink to dark brown and dark red, depending on the amount of coloring
impurities, particularly iron oxide present in the mineral.The different grades of
bauxite mostly occur in the states of Andhra Pradesh, Madhya Pradesh,
Chattishgarh, Bihar, Jharkhand, Gujarat, Maharashtra, Tamilnadu and
Jammu & Kashmir.

The chemical composition of some important Bauxites:

Source Constituents (%)

SiO2 Al2O3 Fe2 TiO2 CaO MgO K2O Na2O P2O LOI
O3
Gujarat-I 1.53 55.61 4.32 1.94 3.42 1.23 0.24 0.08 - 28.1

Gujarat-II 4.00 59.27 2.79 1.93 0.45 tr 0.08 0.34 - 3.74

Gujarat-III 2.50 55.23 6.19 3.00 2.90 ND ND ND - 30.00

Saurashtra, 1.40 60.75 1.85 0.30 - - - - 0.01 32.30

Gujarat

Ratnagiri, 3.00 49.2 14.2 4.0 - - - - - 28.10

Maharashtra

Belgaun, 3.00 59.00 3.55 8.02 - - - - - 28.10

Karnataka

Katni, M.P. 6.70 55.10 4.52 7.78 - - - - - 26.81

Kolaba 1.28 59.20 4.90 4.15 0.25 0.18 - - 0.08 29.62

23
Uses: Bauxite is larely consumed by aluminium industry where ferruginous
bauxites with a low silica content and having an alumina to silica ratio>3 are
preferred. Bauxite is used in high alumina refractory compositions. It melts
between 1740-18200C. In refractory grade bauxites total magnesia, lime,
potash and soda content should not exceed 1%. Those containing higher
amounts of silica (sialites) can be used provided the iron content is low.
Bauxite and diaspore based refractories contain more alumina than those
containing sillimanite group of minerals but higher amounts of glassy phase,
lack of volume stability and porosity restrict the use of bauxite as refractory
raw material. It is also used for the manufacture of special ceramic items such
as abrasion resistant dies for wire drawing and chemically resistant ceramics.

1.9 Frit :

Frit is a ceramic composition that has been fused, quenched to form a glass,
and granulated. Frits form an important part of the batches used in
compounding enamels and ceramic glazes; the purpose of this pre-fusion is to
render any soluble and/or toxic components insoluble by causing them to
combine with silica and other added oxides.

In antiquity, frit could be crushed to make pigments or shaped to create

objects. It may also have served as an intermediate material in the
manufacture of raw glass. The definition of frit tends to be variable and has
proved a thorny issue for scholars. In recent centuries, frits have taken on a
number of roles, such as biomaterials and additives to micro wave
dielectric ceramics.

Archaeologists have found evidence of frit in Egypt, Mesopotamia,

Europe, and the Mediterranean. The definition of frit as a sintered, polycrystal
line, unglazed material can be applied to these archaeological contexts. It is
typically colored blue or green.

24
 Composition of Some Special Frits for Wall Tiles:

Borosilica Borosilicate Lead Lead Lead Boro – Lead Boro

te First Frit Boro Boro- silicate Frit silicate Frit
(Opaque) (Opaque) silicate silicate Frit (Transparent) (Transparent)
Frit (Semi
(Opaque) Opaque)

SiO2 62.00 55.40 52.91 35.76 58.43 42.23

Al2O3 8.60 8.30 6.81 8.75 7.09 4.86

Fe2O3 0.30 0.26 0.18 0.13 0.33 0.02

TiO2 Tr 0.05 Tr Tr Tr Tr

CaO 3.83 4.55 5.59 4.95 4.55 4.40

MgO 0.69 2.90 0.46 0.20 0.10 0.10

Na2O 4.50 5.00 5.05 3.08 6.30 4.58

K2O 2.00 0.63 0.88 2.25 1.45 0.66

PbO - - 9.80 26.23 12.03 27.51

BaO - 6.15 1.70 3.25 1.83 0.58

Zno - - - 7.24 - 6.13

ZrO2 9.14 8.53 8.87 2.50 - -

B2O3 8.71 8.20 7.20 15.30 7.26 8.67

LOl 0.30 0.24 - 0.45 0.36 0.26

Uses of Frit: Frits are indispensable constituents of most industrial ceramic

glazes which mature at temperatures below 1150°C. Frits are typically
intermediates in the production of raw glass, as opposed to pigments and
shaped objects.But they can be used as their own entities in a number of
high-tech contexts. Frits made predominantly of silica, diboron trioxide, and
soda are used as enamels on steel pipes.Another type of frit can be used as a
biomaterial. Molten soda-lime-silica glass can be “poured into water to obtain
a frit,” which is then ground to a powder. These powders can be used as
“scaffolds for bone substitutions.” Also, frits can be added to high-tech

25
ceramics. Scientists have made such frits by milling ZnO and
H3BO3 with zirconium beads, then heating this mixture to
1100°C, quenching it, and grinding it. This frit is then added to a
Li2TiO3 ceramic powder. This addition is beneficial: the ceramic can sinter at a
lower temperature while still keeping its “microwave dielectric properties."1.10
Sodium Tripolyphosphate :

(STPP, sometimes STP or sodium triphosphate or (STPP), with formula

Na5P3O10, is a polyphosphate of sodium. It is the sodium salt of triphosphoric
acid. sodium tripolyphosphate is prepared by heating a stoichiometric mixture
of disodium phosphate, Na2HPO4 and monosodium phosphate,
NaH2PO4 under carefully controlled conditions.

2Na2HPO4 + NaH2PO4 → Na5P3O10 + 2H2O

Uses: It is used in various applications such as a preservative for seafood,
meats, poultry and pet foods. It is also used in toothpaste and as a builder
in soaps and detergents, improving their cleansing ability. The United
States Food and Drug Administration lists STPP as "generally recognized as
safe", along with salt, vinegar, and baking powder.

STPP is a solid inorganic compound used in a large variety of

household cleaning products, mainly as a builder, but also in, a
human foodstuffs animal feeds, industrial cleaning processes
and ceramics manufacture. STPP is widely used in regular and compact
laundry detergentsand automatic dishwashing detergents (in powder, liquid,
gel and/or tablet form), toilet cleaners, surface cleaners, and coffee urn
cleaners .

Food Applications:

In foods, STPP is used to retain moisture. Many governments regulate

the quantities allowed in foods, as it can substantially increase the sale weight
of seafood in particular.

Many people find STPP to add an unpleasant taste to food, particularly

delicate seafood. The taste tends to be slightly sharp and soapy and is
particularly detectable in mild-tasting foods. The increased water holding
properties can also lead to a more diluted flavor in the food.

26
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