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

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 Hammurabis 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.

(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

quantities of ceramic tiles and other products per day here. Per day turnover in Rs. 500 crore, so its 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 clay (7) Bikaner clay (8) opaque glass (4) Al2O3 (5) STPP (6) China (10) grog.

(9) Transparent glass

(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 majors 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. Thats 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)

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.

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:

(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 earths crust. Atomic Number 8 11 12 13 14 19 20 26 Name Oxygen Sodium Magnesium Aluminum Silicon Potassium Calcium Iron Volume % 91.97 1.60 0.56 0.77 0.80 2.14 1.48 0.68

Average Composition of Crust Rocks (as Oxide) Name Silica Alumina Lime Soda Ferrous Oxide Magnesia Ferric Oxide Potash Water Titania Phos. Pentoxide Chemical Formula SiO2 Al2O3 CaO Na2O FeO MgO Fe2O3 K2O H2O TiO2 P2O5 % 59.26 15.35 5.08 3.81 3.74 3.46 3.14 3.12 1.26 0.76 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: - Quartz (8700C)

- tridymite(
163
0

1470 C)

-cristobelite(
200
0

1726 C)

melt

573
0

-Quartz

- tridymite

- cristobelite

117
0

-tridymite The inversions indicated by the horizontal arrows are reconstructive transformations (relatively slow), during which the bonds in the secondary coordination 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 -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 Quartz Nizamabad, A.P. Hyderabad, A.P. Gujarat Tura, Meghalaya Jaipur, Rajasthan Hyderabad (Sanatnagar) SiO2 99.75 99.96 99.40 99.12 98.11 99.13 Al2O3 0.15 0.06 0.21 0.41 0.12 Fe2O3 0.02 0.02 0.04 0.36 0.22 0.13

Constituents (%) TiO2 0.01 tr 0.07 CaO 0.09 0.68 0.09 MgO tr. tr. tr. K2O 0.07 0.10 Na2O 0.15 0.06 LOI .22 .19 .19

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 Feldspar Mihijam, Jharkhand Kodarma, Jharkhand Alwar Rajasthan Alwar Rajasthan Jhansi, M.P. Nellore, A.P. Sitampudi, Tamilnadu Raghudih, W.B. Chandla, M.P. Ajmer, Rajasthan 65.17 21.07 0.13 12.80 0.78
0.05

Constituents (%) SiO2 65.90 Al2O3 19.34 Fe2O3 0.29 TiO2 0.04 CaO MgO 0.35 tr. K2O 9.27
Na2O LOI

8.07

0.04

64.00

18.83

0.39

0.55

12.02

3.11

0.21

(1)

65.56

20.93

0.12

2.05

tr.

7.12

3.49

0.42

(2)

64.96

19.62

0.11

1.02

0.02

12.38

1.98

0.64

63.69 64.80

21.88 19.09

0.24 0.20

0.34 0.18

tr. 0.01

11.25 13.00

2.72 2.40

0.86 0.5

44.84

34.07

0.05

20.0 5

0.50

64.70

19.54

0.36

11.42

2.46

66.25

10.21

0.29

0.40

13.81

0.50

13

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 (0.1-0.3), 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 1. It has a three-layered structure consisting of two layers of silica tetrahedral and one central di-octahedral or trioctahedral 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) (b) K2Al2Si6O16 + 2H2O H2 Al2Si6O16 + 2KOH (removed by water flow) 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, wellcrystallized kaolinite particles. (ii) (iii) Plastic clay-soft and plastic Refractory shales soft and highly plastic. Fire clays occur in two modes namely: (a) (b) Well defined beds associated with coal seams. 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 SiO2 Al2O3 Fe2O3 Constituents (%) TiO2 CaO Mg O West Zone Gujarat Kutch Mineral Premier Minerals Ashapura Amrapali I II III Eklera Nadapar IRL Nadapar ISWL Umiya AMI China clay Himmar Nagar China clay East Zone Bihar Rajmahal (Pink) Rajmahal (White) Chaibasa (Gr. I) Chaibasa 46.68 48.90 47.90 46.59 35.29 34.51 36.00 35.95 1.90 1.71 1.25 1.12 0.89 0.50 tr. tr. 0.28 0.67 1.24 1.40 0.50 0.20 0.40 0.40 0.28 0.41 0.61 0.33 0.60 0.52 0.75 0.91 13.12 12.60 12.25 13.22 45.90 37.74 0.57 0.69 0.76 0.18 0.12 14.13 47.75 44.17 49.63 43.08 46.21 44.64 48.92 43.86 44.04 47.20 52.45 34.25 36.55 34.05 36.59 35.08 34.94 22.59 38.24 39.25 36.15 29.83 0.90 0.70 0.60 1.16 0.87 1.34 1.30 0.50 0.40 0.60 0.94 1.30 2.82 1.37 2.31 1.29 1.14 1.12 1.74 0.96 1.50 1.48 1.23 1.12 0.54 1.79 0.88 1.67 0.65 0.67 0.45 0.82 1.14 0.24 0.12 0.58 0.85 0.86 0.91 0.28 0.24 0.16 0.04 0.59 0.35 0.10 0.22 1.07 0.20 0.16 1.00 0.05 0.05 0.05 0.35 0.45 0.42 0.61 0.22 0.48 0.10 0.31 0.55 0.52 0.33 0.86 12.46 13.92 12.28 13.00 13.88 14.84 12.83 14.05 14.09 13.59 11.89 K2O Na2 O LOI

16

Source (Superfine) Simultala Ulatu Bagru West Benal Mukhdum Nagar I II Mhatomara Mahammad Bazar Kharidumri Dhatara Orrisa Mayurbhanj North Zone Kusumpur Delhi I II Rajasthan Modi Clay (P-90) Modi Clay(TT-75) South Zone Kerala Thiruvanantapurm 45.60 37.40 0.745 44.46 46.82 37.03 36.72 0.80 1.00 46.80 46.92 47.66 36.83 36.04 35.75 1.65 1.86 1.00 48.55 33.69 1.45 44.10 43.64 46.05 44.31 46.98 47.45 37.39 35.58 35.49 36.97 36.87 33.62 2.6 2.39 1.36 2.11 0.54 1.13 47.27 44.35 45.09 38.20 38.51 37.45 0.47 0.55 1.12

Constituents (%)

0.07 1.23 2.40

0.35 0.23 tr.

0.10 0.05 tr.

1.55 0.05 0.10

0.14 0.11 0.13

11.80 14.77 13.57

1.37 2.64 2.11 0.80 0.40 tr.

0.10 1.80 0.28 0.31 0.78 1.87

tr. tr. 0.20 0.26 0.11 1.25

0.20 0.13 0.27 0.60 0.42 0.52

0.79 0.36 0.03 0.29 0.13 1.08

13.48 13.50 13.86 14.34 12.98 13.17

0.53

tr.

1.27

0.17

11.16

tr. tr. tr.

0.03 0.92 1.01

0.07 0.26 0.20

0.57 1.06 0.99

0.11 0.39 0.53

13.63 12.76 12.86

tr. 0.21

2.00 0.70

0.41 0.25

0.07 0.15

1.02 0.18

14.64 13.87

0.89 9

tr.

0.414

0.02 0

0.02 2 0.43 9 0.03 4 0.13

14.86

Sasthavattom

44.11

38.17

1.30

1.55

tr.

0.042

0.02 4

14.26

Kannanalloor, Quilon Nyleswar (Jyothi),Cannanore Nyleswar (Neelex)

43.99

39.64

0.40

0.48

tr.

0.336

0.00 9

15.26

45.85

36.74

1.82

1.17

0.08

0.12

0.08

14.29

45.88

36.12

1.43

0.55

0.11

0.21

0.09

0.06

14.94

17

Source Nyleswar(Kerala) Nyleswar, Cannanore Payyangadi, Cannanore Kannapuram Mulavana, Quilon Kalluvathukkal Thiruvanantapurm Thonnakkal, Thonnakkal Grey Thonnakkal Red Pallipuram White Ramapuram, Cannanore Payyangadi, 41.75 33.37 5.02 42.72 47.85 47.91 46.47 46.44 45.91 45.86 46.48 42.97 38.95 36.70 35.26 38.13 37.85 37.21 34.53 33.21 36.19 3.89 0.71 1.64 0.28 0.33 0.90 3.05 2.49 3.73 44.87 36.94 1.28 47.32 47.94 35.97 36.43 1.30 1.30

Constituents (%) 1.07 0.93 0.26 tr. 0.22 0.12 0.04 0.20 0.07 14.09 13.35

0.94

tr.

0.31

0.23

0.09

15.43

0.48 0.33 0.40 0.79 0.69 0.67 0.95 0.99 1.90

0.05 tr. 0.23 tr. tr. tr. 0.11 0.23 tr.

0.27 0.44 0.35 0.59 tr. 0.27 0.36 0.65 0.74

0.19 0.13 0.23 0.02 0.08 0.46 0.56 0.80 0.29

0.13 0.11 0.23 0.08 0.12 0.19 0.27 0.15 0.58

13.19 14.04 13.67 14.20 13.88 14.37 13.82 15.02 13.73

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 fullers 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 sandsize. 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

Indias 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) (b) (c) (d) Refractory for Steel and Glass Industry Ceramics Foundry Others 35% 25% 21% 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, nonferrous 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, Jammu & Kashmir. The chemical composition of some important Bauxites: Tamilnadu and

Source

Constituents (%) SiO2 Al2O3 Fe2 O3 4.32 2.79 6.19 TiO2 1.94 1.93 3.00 CaO MgO K2O 0.24 0.08 ND Na2O 0.08 0.34 ND P2O LOI

Gujarat-I Gujarat-II Gujarat-III

1.53 4.00 2.50

55.61 59.27 55.23

3.42 0.45 2.90

1.23 tr ND

28.1 3.74 30.00

Saurashtra, Gujarat Ratnagiri, Maharashtra Belgaun, Karnataka Katni, M.P. Kolaba

1.40

60.75

1.85

0.30

0.01 32.30

3.00

49.2

14.2

4.0

28.10

3.00

59.00

3.55

8.02

28.10

6.70 1.28

55.10 59.20

4.52 4.90

7.78 4.15

0.25

0.18

26.81

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 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. biomaterials and additives to micro wave

24

Composition of Some Special Frits for Wall Tiles:

Borosilica Borosilicate te First Frit (Opaque) (Opaque) Lead Boro silicate Frit (Opaque) 52.91 6.81 0.18 Tr 5.59 0.46 5.05 0.88 9.80 1.70 8.87 7.20 Lead Lead Boro Borosilicate Frit silicate Frit (Transparent) (Semi Opaque) 35.76 8.75 0.13 Tr 4.95 0.20 3.08 2.25 26.23 3.25 7.24 2.50 15.30 0.45 58.43 7.09 0.33 Tr 4.55 0.10 6.30 1.45 12.03 1.83 7.26 0.36 Lead Boro silicate Frit (Transparent)

SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O PbO BaO Zno ZrO2 B2O3 LOl

62.00 8.60 0.30 Tr 3.83 0.69 4.50 2.00 9.14 8.71 0.30

55.40 8.30 0.26 0.05 4.55 2.90 5.00 0.63 6.15 8.53 8.20 0.24

42.23 4.86 0.02 Tr 4.40 0.10 4.58 0.66 27.51 0.58 6.13 8.67 0.26

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

glazes which mature at temperatures below 1150C. 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 then

such

frits

by milling ZnO this mixture

and to

H3BO3 with zirconium beads,

heating

1100C, 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, animal mainly as a builder, but also in, a

human foodstuffs

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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