Module: 6

Dr.R .N. Patel

Lecture: 26 Ceramic industries

Unit : 3

CERAMIC INDUSTRIES

INTRODUCTION
Ceramic is an inorganic, nonmetallic solid prepared by the action of heat
and subsequent cooling. Ceramic materials may have a crystalline or partly
crystalline structure, or may be amorphous (e.g. glass). Because most common
ceramics are crystalline, the definition of ceramic is often restricted to inorganic
crystalline materials, as opposed to the non-crystalline glasses.

The earliest ceramics were pottery objects made from clay, either by itself or
mixed with other materials, hardened in fire. Later ceramics were glazed and fired to
create a coloured, smooth surface. Ceramics now include domestic, industrial and
building products and art objects. In the 20th century, new ceramic materials were
developed for use in advanced ceramic engineering; e.g., in semiconductors.

The word "ceramic" comes from the Greek word Keramos means burnt stuff.
Earlier the term ceramic was applied to products made from natural earth material
that was not exposed to heat. But nowadays the silicate mainly used in the
construction industries and prepared by burning the clay products are called as
ceramics.

CLASSIFICATION
A broad sense classification divides the ceramic products in to two classes

1. Heavy clay products e.g. bricks, roofing tiles, drain tiles, hollow tiles, stoneware
and refractories
2. Pottery products e.g. chinaware, wall tiles, electric insulation

Ceramic may also be classified as porous and non-porous. The porosity is

depends on particle size, moulding pressure and temperature of vitrification.

Further, ceramic may be classified based on the method of production and

its uses into following classes.

1. Whiteware
2. Structural clay products
3. Refractory material
Module: 6
Dr.R .N. Patel
Lecture: 26 Ceramic industries

4. Special ceramic products

5. Vitreous enamel

RAW MATERIAL
The raw materials for ceramics are divided into following groups.

a) Plastics material such as clay

b) Fluxes such as feldspar
c) Non-plastics materials such as silica

a) Clay
Clay gives the main body to the ceramics. The advantage of using clay are it
is plastic when mixed with water becomes hard after drying and finally it becomes
irreversibly solid after firing. Clay is chosen according to the requirements of
particular products and is often blended.

Impurities in common clay incorporate specific qualities as follows.

 Iron oxide in common clay gives red colour to the burnt material
 Lime, magnesia, iron oxide and alkali oxides act as flux which lowers the
fusion point of clay
 Silica increases its porosity and refractory nature, while decreases shrinkage
 Clay containing very little and good deals of silica known as fire clays

b) Feldspar
Feldspar is general name given to the group of minerals. Flux materials like
feldspar (Na2OAl2O3.6SiO2) which is easily melting material decreases the melting
point of sand or quartz present in the ceramic body. So, that after firing glass like
material is obtained called as vitrified material, which is highly impervious and stable
to the environment. Fluxes are used for adding vitrifications, reducing porosity, to
increase the strength of cold articles and for bonding. Feldspar is used as fluxing
constituent in ceramic formulations along with clay. The common fluxing agents
which lower the temperature are borax, boric acid, soda ash, sodium nitrate,
potassium carbonate, calcined bones, lead oxides, lithium & barium minerals.

Type of feldspar
 Potash feldspar K2O.Al2O3.6SiO2
 Soda feldspar Na2O.Al2O3.6SiO2
 Lime feldspar CaO.Al2O3.6SiO2
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Dr.R .N. Patel
Lecture: 26 Ceramic industries

c) Silica or quartz
The non-plastic or leading admixture like sand or quartz gives strength to the
body. It is incorporated in ceramic formulation to reduce shrinkage and cracking
which is occurs during drying and firing.

PROPERTIES
The physical and chemical properties of ceramic depend upon component
present in it.

 The strength is mainly controlled by the factors like temperature, size and
shape, composition, surface condition and microstructure
 Mechanically they are brittle and highly resistant to compression
 Oxides and carbides which give high chemical and physical stability
 Electrical and magnetic properties are due to composition itself. E.g. oxides
are generally bad conductors where the non-oxides are semiconductors and
ceramics with transition metal ions shows the magnetic properties.
 Transparency depends upon the crystal lattice of ceramic which in turn is
dependent of composition, crystal structure, extent of polarization etc.

USES
Ceramic is one of the oldest materials used in construction with the time
quality and decoration has been added to its property and therefore they are at
present used in following

 Construction and decoration as bricks and tiles

 Metallurgy as construction material of furnace
 Chemical products as stoneware and porcelain
 In drainage of water
 In sanitation

The small uses includes pottery work, specialty ceramic like peuzo electric
and insulation material in electrical connections

Therefore, we conclude that ceramics deals with manufacture and technical

characteristics and raw material for article building.

Ceramics: What are ceramics, Subdivision of ceramics, General properties of ceramics, Permeable and
impermeable wares, Distinction between permeable and impermeable wares, Classification based on
reduction in porosity, Basic raw materials, Other ingredients, Manufacturing process, Grinding of raw
material, Mixing or preparation of bodies, Body preparation using clay in plastic form, Body
preparation using dry clay, Body preparation using clay slip, Filtering, Kneding, Jjollying, Slit casting,
Pressing, Extrusion, turning, Drying, Types of driers, Firing, Glazing, Frits, Decoration, Application of
colors to the pottery, Porcelain and china, Raw materials, Manufacture, Earthenware and stone wares,
Important points.
Module: 6
Dr.R .N. Patel
Lecture: 27 Whitewares

Module: 6
Lecture: 27

WHITEWARES

Whiteware are made by mixing china clay, feldspar and flint (SiO2) with or
without Whiteware having good strength, translucency and very low porosity can be
obtained by firing the products at 1450-15000C. Whitewares contain refractory body
and glassy coating known as the glaze. There is a corresponding variation in the
degree vitrification due to different amount of fluxes.

1. WHITEWARES
They are available in number of special types such as floor tiles, resistant to
abrasion, glazed or unglazed, impervious to stain penetration and wall tiles.

CLASSIFICATION

a) Earthenware
It is also known as semi-vitreous dinnerware which is porous, non-translucent
and soft glaze.

b) Chinaware
It is a vitrified translucentware with a medium glaze which resists abrasion and
used for non-technical application.

c) Porcelain
It is vitrified translucentware with a hard glaze which resists abrasion to a
maximum degree and may include chemical, insulating and dental porcelain.

d) Sanitaryware
It was made from clay which is porous but nowadays vitreous composition is
used. Prefired and sized vitreous grog is include with triaxial composition

e) Stonewares
They are the oldest ceramicwares which is used before porcelain. It is known
as crude porcelain but its raw materials are of poor grade and not well fabricated.
Module: 6
Dr.R .N. Patel
Lecture: 27 Whitewares

MANUFACTURE

Kaolin Water Water

Filter Press
Felspar
Slurry White
Casting Grinder Decoration
Wares
Gaze
Article
Furnace
Reactor Water Dilution Tank

Figure: Manufacturing of White Wares

It involves three steps

 Body of ware
 Glaze
 Decoration

Body of ware
Kaolin and feldspar are reduced to fine powder then suspended in the form
of cream. Then excess water is removed by filter press. By use of resulting the paste,
article can be obtained after moulding, are dried slowly and fired to get
porousware which is known as bisque.

Glaze
Porous article is covered with glaze to get water tight article which is done by
melting it over the surface of the body. Quartz, feldspar, boric oxide are the
constituent of the glaze which are finely ground and mixed with water which forms
slip then it is fired to higher temperature to produce smooth and glossy surface. The
glaze must be chose in such a way that resist the reagents and must have same co-
efficient of expansion as the body; otherwise the vessel which is exposed to change
of temperature will crack.

Decoration
Design may be painted on the body before glazing using metal oxide or
painted upon the glaze using coloured glass and article is fired so, the pigment melts
into glaze. It painted upon glaze then known as over glazed.
Module: 6
Dr.R .N. Patel
Lecture: 27 Whitewares

Applications
 Dishes
 Crucibles
 Spark plug
 Electrical insulator
 Laboratory equipment

Glazing
It is mixture of glass forming materials which is in form of fine powder e.g. lead
silicates, borosilicate etc. If mixture free from iron and colouring pigments then forms
colourless glaze.

Metal oxides
The following metal oxides are used for producing the colour to glaze.
 Iron oxide: Brown colour
 Iron oxide and lime: Cream colour and yellowish tint
 Copper oxide: Green colour
 Cobalt blue: Blue colour

Requisite of glazing
 To provide smooth, glossy surface to treated materials
 To protect the surfaces from the environmental or atmospheric actions
 To produce decorative effect
 To make the surface impervious to liquid, water etc.
 To improve appearance and durability of the article

Method of glazing
a) Salt glazing
b) Liquid glazing

a) Salt glazing
Sodium chloride is used to get glossy film over the earthenwares. Sodium
chloride is throwing to furnace where articles are in red hot condition. Due to heat
salt volatilize and react with silica which makes glossy film of sodium chloride.

b) Liquid glazing
Liquid glazing is much superior then salt method in which fine powder of glaze
mixture, colouring pigments are mixed with water to form a colloidal solution known
as slip glaze. The article is then burnt in kiln at low temperature. Then it is dipped into
glaze slip so the glaze materials fill up the pores of articles. To fuses and forming thin
glossy film, articles are fired into the kiln. Care should be taken that firing articles
Module: 6
Dr.R .N. Patel
Lecture: 27 Whitewares

does not comes in contact with direct fire, otherwise soot & dust should discoloured
the article. Delicated articles should be burnt in muffle furnace which is heated
externally while articles are kept inside.

PROPERTIES
 A traditional ceramic used to make pottery and porcelain. While, whiteware
ceramics often have a glassy structure.
 Any of a broad class of ceramic products that are white to off-white in
appearance and frequently contain a significant vitreous, or glassy,
component.
 Imperviousness to fluids, low conductivity of electricity, chemical inertness,
and an ability to be formed into complex shapes. These properties are
determined by the mixture of raw materials chosen for the products, as well
as by the forming and firing processes employed in their manufacture

USES
Whitewares find application in spark plugs, electrical insulators, laboratory
equipment, crucibles, dishes, and high-class potteries. Including products as diverse
as fine china dinnerware, lavatory sinks and toilets, dental implants, and spark-plug
insulators
Module: 6
Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

Module: 6
Lecture: 28

CLAY PRODUCTS AND REFRACTORIES

2. STRUCTURAL CLAY PRODUCTS

Water

Firing Clay
Soaking
Raw

Maturation
Grinding Moulding Product
Clay Mixing
Screening

Dryer

Figure: Manufacturing of Clay Products

Unglazed pipes, tiles, terracotta and building bricks are manufactured from
locally clays without glaze, which contain the fluxes needed for binding. For building
and face bricks, red burning clay is used, which is cheap and durable.
Bricks can be manufactured from

 Soft mud process

 Stiff mud process
 Dry press process

Soft mud process

The clay mixture contain 30% water is moulded in moulds. This mould bricks
are dried in tunnel drier. While common bricks are burnt in scove kiln, in which coal is
used as fuel. The kiln is built from the green bricks with the outside walls daubed or
scoved with clay. It is a variation of undraft type of kiln. After burning the kiln is
completely dismantled.
Module: 6
Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

Stiff and mud process

Clay mixture contains 12-15% water, which is just enough to stick together. The
clay is forced out through a die in a screw or auger machine. The extruded clay bar
passes long or short belt conveyor on to a cutting table on which a frame with
number of wires which automatically cuts the bar into appropriate lengths. These
bricks may be repressed to make face bricks.

Dry process
The water content of the clay is reduced to 4-7% which make the clay non-
plastic. The brick unit is moulded at high temperature.

PROPERTIES
 Depending on the content of the soil, clay can appear in various colours,
from a dull gray to a deep orange-red.
 Clays exhibit plasticity when mixed with water in certain proportions, when
dry, it becomes firm and when fired in a kiln, permanent physical and
chemical changes occur which converted clay into a ceramic material.
Because of these properties, clay is used for making pottery items, both
utilitarian and decorative.
 Different types of clay, when used with different minerals and firing conditions,
producing earthenware, stoneware, and porcelain.

USES
 Clay is the starting raw material for manufacturing bricks, tiles, terracotta,
pottery, earthenwares, sewer, drain pipes, and covers for electrical cables
 Clay is one of the oldest building materials on Earth, among other ancient,
naturally-occurring geologic materials such as stone and organic materials
like wood.
 Between one-half and two-thirds of the world's population, in traditional
societies as well as developed countries, still live or work in a building made
with clay as an essential part of its load-bearing structure. Also a primary
ingredient in many natural building techniques
 Used to create adobe, cob, cordwood, and rammed earth structures and
building elements such as wattle and daub, clay plaster, clay render case,
clay floors and clay paints
 A traditional use of clay as medicine goes back to prehistoric times. Kaolin
clay and attapulgite have been used as anti-diarrheal medicines
 Used where natural seals are needed, such as in the cores of dams, or as a
barrier in landfills against toxic seepage
 Clay tablets were used as the first known writing medium, inscribed
with cuneiform script through the use of a blunt reed called a stylus.
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Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

 Clays sintered in fire were the first form of ceramic, Bricks, cooking pots, art
objects, dishware, and even musical instruments such as the ocarina can all
be shaped from clay before being fired.
 Used in many industrial processes, such as paper making, cement production,
and chemical filtering.
 Used in the manufacture of pipes for smoking tobacco.

3. REFRACTORY MATERIALS
Refractories are ceramic materials that can withstand unusually high heat as
well as abrasion and the corrosive effects of acids and alkalis. They are used in
furnaces, stills for the cracking of petroleum, ceramic kilns, boilers, incinerators,
electrolytic cells for aluminum production etc. Refractories are an important
constituent of nuclear reactors. Jet engines would not last very long without
refractory parts.

Fire clay is an important raw material for refractories. In recent years non-clay
refractories of alumina, zirconia, silicon carbide, chromia, magnesite, graphite and
other less common materials are developed. The cost of these refractories is much
higher than that of fireclay. However, their use in critical parts of a furnace will keep
it in operating condition for longer periods, with less time taken out for repairs.

CLASSIFICATION

 Acid refractories
 Basic refractories
 Neutral refractories or special refractories

Acid refractories
The prime ingredient for acid refractory is silica. Acid refractory have high
temperature loadbearing capacity and are used in the arched roofs of steel and
glass making furnaces at temperatures as high as 16500C. At this temperature small
portion of the brick will actually exist as a liquid. Alumina should be kept at 0.2 to
1.0% by weight because it adversely effect on the performance of these refractories.
These refractory materials are resistant to acid slags that are rich in silica. But they
are readily attacked by basic slags composed of CaO and / or MgO, there so
contact with these oxides should be avoided.
Module: 6
Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

Sr. Acid refractories Fusion

No. temperature
1. Silica(SiO2) 17000C
2. Aluminium silica 17800C
(46% Al2O3 + 54% SiO2)
3. Alumina (Al2O3) 20500C
4. Silmanite 19000C
(63%Al2O3 + 37%SiO2)

Basic refractories
The main constituent of basic refractories is magnesia (MgO), along with
calcium, chromium and iron compounds. The presence of silica is harmful for use in
high temperature performance; Basic refractories are especially resistant to attack
by slags containing high concentrations of MgO and CaO, and find extensive use in
some steel making open hearth furnaces.

Sr. No. Basic refractories Fusion temperature

1. Magnesia 22000C
2. Bauxite 18000C
3. Dolomite 15000C

Special refractories or neutral refractories

The special refractories are relatively expensive due to use of high-purity oxide
materials and very little porosity. Alumina, silica, magnesia, beryllia (BeO), zirconia
(ZrO2) and mullite (3AI2O3.2SiO2), as well as carbide compounds, in addition to
carbon and graphite are used for manufacture of special refractories. Silicon
carbide (SiC2) has been used for electrical resistance elements, as a crucible
material, and in internal furnace components. As carbon and graphite are
susceptible to oxidation at temperatures in excess of about 8000C, they find limited
application in spite of refractory characteristics.

Sr. No. Neutral refractories Fusion temperature

1. Chromite 21800C
2. Graphite 30000C
3. Silicon carbide 27000C
4. Zirconia 22000C

Silica and high alumina refractories

Refractories are obtained from ores of silica or those of silica and alumina.
After mining or chemical production and calcining, refractory materials are crushed,
ground and prepared to size. They are then mixed with other materials and shaped
as bricks. Bricks are used for lining-melting and other applications. Bricks of acid,
Module: 6
Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

basic and neutral refractories having different shapes are available for furnace
construction. Bricks during construction work are boned and cushioned with the help
of a mortar consisting of chrome, silicon carbide, silica and alumina. Brick work may
be coated with thin mortar for further protecting the same during furnace operation.

MANUFACTURE
Composition of silica and basic refractory bricks

Sr. Type of Brick Silica Alumina Lime Magnesia Iron Chromic Other
No. (SiO2) (Al2O3) (CaO) (MgO) oxide oxide Oxides
(Fe2O3) (Cr2O3)
1. Silica 95-97 0.2-1.2 1.8-3.5 ---- 0.3-0.9 ---- 0.05-0.3
2. Basic
Chrome 3-6 15.33 ---- 14-19 11-17 30-45 1-2
Magnesite 3-6 0.4-2.0 1-5 85-95 0.5-4.0 ---- 0.5-1.0
Forsterite 33-39 ---- ---- 47-55 9-11 ---- 3-4

Composition of fireclays and high alumina bricks

Sr. Type of Brick Silica Alumina Titania Other

No. (SiO2) (Al2O3) TiO2 oxides
1. Fireclay
Super duty 49-53 40-44 2.0-2.5 3-4
Semi-Silica 72-80 18-24 1.0-1.5 1.5-2.5
Medium duty 57-70 25-36 1.3-2.1 4-7
Low duty 60-70 21-32 1.0-2.0 5-8
2. High Alumina
60% Alumina 31-37 57.5-62.5 2-3.3 3-4
80% Alumina 11-15 77.5-82.5 3-4 3-4
90% Alumina 8-9 89-91 0.4-0.8 1-2
99% Alumina 0.5-1.0 98-99 Trace 0.6

Water

Clay Hot air out

Rotary kiln
Dry Refractory
Grinding Press Bricks

Screening
Mixing Hot air in
Dryer

Figure: Manufacturing of Refractory

Module: 6
Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

It involves the following steps

Crushing
The clay is crushed to 25 mm in size.

Grinding
The crushed materials are ground in suitable grinding machine down to 200
mesh size.

Screening
Screening is carried out to separate fine and coarse materials. The desired
size material is used for brick making and oversize is recycled to grinding machine.

Mineral-dressing
Mineral dressing is used to purify the raw materials and producing better
refractories. Purification is carried out by settling, magnetic separation and by
chemical methods.

Storage
Pure materials are stored in storage bins using bucket elevators,.

Mixing
Proper distribution of plastic material throughout the mass is necessary for
easy moulding.

Moulding
It can be accomplished either manually or mechanically at high pressure.
Refractories of low density and low strength can be produce by hand-moulding.
While mechanical-moulding produces refractories of high density and strength.
Deairing is essential in order to increase the density and strength of refractory by
mechanical moulding.

Deairing
It is carried out by

 Allowing air inside the void space in the refractory to go out by decreasing
the rate of pressure application and release
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Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

 Double-pressing the material viz. first pressed and allowed to crack. Then it is
repressed again so as to close the voids.
 Applying vacuum through vents in the moulds

Drying
Drying is carried out to remove the moisture from refractories. Drying is carried
out in tunnel dryer usually very slowly and under well-set conditions of humidity and
temperature, depending upon the type of refractory. Rack cars are placed in a
long tunnel and heat is supplied by steam, which passes through the tunnel.

Firing
To stabilize and strengthen the structures of refractories firing is carried out in
tunnel kilns or shaft kilns or rotary kilns. The bricks are generally fired at a temperature
as high as or higher than their arc temperature.

The firing temperature of different bricks is as follows

 High-fired super duty bricks : 14800C

 Kaolin bricks : 17000C
 Some basic bricks : 18700C

PROPERTIES
The following properties need to be considered while selecting a refractory
material.

Refractoriness
Refractoriness is indicated in terms of pyrometric cone equivalent (PCE) value
which indicates the temperature of softening the refractory. PCE should be well
above the operating temperature. As inner end of the refractory wall is at higher
temperature compare to the outer end, therefore, unless the brick melts away
completely, it can often be used to withstand a temperature higher than its
softening temperature. The outer end will be at a lower temperature and still in a
solid state, thus giving strength.

Strength
Strength under the combined effect of temperature and load is an important
factor, particularly in taller furnaces, the refractory has to support a heavy load.
Refractory must be strong enough to resist physical wetting away and to take load.
Refractoriness under load is an important consideration because usually a refractory
fails at a lower temperature when subjected to load because some crystals which
have become fluidic act as a lubricant and deformation becomes easier when
subjected to load.
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Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

Specific gravity
Specific gravity reflects true porosity of refractory. Porosity increases with
increase in bulk density. It is also a criterion while buying the raw material because
raw materials of higher specific gravity will give fewer bricks or article per unit weight.
Eventually increases the production cost. Refractory material in powdered form is
used for making furnace lining or for repairs. Lesser weight of a material with lower
specific gravity will be required for this purpose. Materials of lower specific gravity
are also preferable because bricks in the lower part of a tall structure will not be
subjected to a heavy load

Porosity and slag permeability

If the refractory has open pores the gases and slags will enter the material
more easily and to a greater depth and may react and reduce the life of the
refractory.

Thermal expansion
In furnace design, allowance has to be made for thermal expansion. This
becomes a very important factor if the refractory is subjected to rapid changes in
temperature as a furnace door which is, on opening, is suddenly exposed to air at
room temperature. Within a single brick in the wall there may be a temperature drop
of a few hundred degrees from the hot face to the cold face. This causes
differences in thermal expansion in different sections of the brick. There may be
changes in the internal structures of the material with the result that there is
expansion in volume. All these result in the development of high internal stresses.

Thermal conductivity
It is important factor if the refractory is subjected to rapid changes in
temperature. Thermal conductivity should be low so that the heat of the furnace
may not be lost. Exceptions to this rule are coke over walls, mulle furnaces and
retorts which is heated form outside. They should be made of refractories of high
thermal conductivity. To prevent heat loss sometimes a refractory is backed by an
insulate material like asbestos. The life of refractories is shorter which are constantly
maintained at high temperature.

Electrical conductivity
It should be low for electrical furnaces. Except graphite, all other refractories
are bad conductors of electricity. The electrical resistivity of the refractories should
drop rapidly with increase in temperature.

Chemical composition
The chemical composition of the refractory should be such that the
surrounding do not chemically attack the refractory and corrode it.
Module: 6
Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

Characteristics of refractories
 Can withstand high temperatures without being fused
 Crucibles and furnace sides and bottoms containing molten metal are made
up of refractories
 Use as ladles for pouring metal into the mould
 Constitute furnace walls and roof and thus minimize heat losses

Properties of various refractory bricks

Sr. Type Class Properties
No.
1. High Alumina 50% Alumina to  High refractoriness which is increasing with
90% Alumina alumina content
 High mechanical strength at high temperatures
 Excellent to fair resistance to spilling
 Greater resistance to corrosion
2. Fireclay Low, medium  Good spilling resistance and thermal insulation
and high duty value
 Fair resistance to fluxes and acid slags
 Lower resistance to basic slags and fluxes
3. Fireclay Semi-Silica  Rigidity under load at high temperatures
 Resistance to structural spilling
 Volume stability
 Resistance to volatile alkalis or fumes
4. Silica Super duty  High refractoriness and resistance to abrasion
Conventional  High mechanical strength at high temperatures
 Greater thermal conductivity as compared to
high duty fireclay brick, at high temperatures
 High resistance to corrosion by acid slags
 Fair resistance to attack by oxides of lime,
magnesia and iron
 Readily attacked by basic slags and fluorine
 Poor resistance to spilling at low temperatures
5. Chrome fired  Better resistance to spilling
magnesite  High resistance to corrosion by basic slags
Chemically  Mechanical strength and stability of volume at
bonded high temperatures
6. Chrome fired  High-resistance to corrosion by basic and
moderately acid slags and fluxes
 Basic slags do not adhere to chrome bricks
 Absorbed iron oxide may damage expansion
 Possess thermal conductivity lower than that of
magnesite brick but higher than fireclay brick
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Lecture: 28 Clay products and Refractories

7. Magnesite fired -Magnesia  Extremely high refractoriness and high thermal

88-90% conductivity
-above 90%  Poor resistance to slags containing high % silica
-Chemically  Great resistance to corrosion by basic slags
bonded  Chemically boned and metal encased bricks
metal encased have marked resistance to spilling
8. Forsterite-Fired  Excellent strength at high temperature
 High refractoriness
 Attacked by acid slags
 Fair resistance to most basic slags
 Good corrosion resistance to alkali compounds

USES
Application and selection of different refractories

Sr. Type of refractory Name of the furnace used for melting ferrous metals
No. /alloys
1. Fire bricks  Bottom of induction furnace
 Sub-hearth of open hearth furnace
 Doors of open hearth furnace
 Spout of open hearth furnace
 Spout of direct arc furnace (acidic)
2. Silica brick  Side walls and roof of direct arc furnace
 Roof of open hearth furnace
3. Magnesite-chrome brick  Melting zone of basic cupola
 Direct arc furnace roof (for Ni and Cu melting)
4. Dolomite  Backing of open hearth furnace
 Side walls of direct arc furnace(basic)
5. Chrome magnesite brick  Side walls of direct arc furnace (basic)
 Side walls of open hearth furnace
 Blocks and ends of open hearth furnace
6. High Alumina fireclay  Ladle refractories - as lining nozzle, stopper etc.
7. Magnesite  Hearth and side walls of direct arc furnaces for
melting nickel and copper
 Sub - hearth of direct arc furnace for melting steel
(basic)
Module: 6
Dr.R .N. Patel
Lecture: 28 Clay products and Refractories

Refractories used in various furnaces

Sr. Furnace Refractory material

No.
1. Iron blast furnace Entire lining consists of fireclay but of different
qualities
Hearth and Bosh Coarsely ground fireclay
Shaft or stock Medium ground fireclay
Top Finely ground fireclay
Hot blast stoves Porous fireclay bricks
Hot blast main Fireclay
Bustle pipe Fireclay
2. Acid open-hearth Furnace
Portions above the working floor Silica bricks
Regenerative walls Fireclay bricks
3. Basic Open-hearth Furnace
Roof Silica bricks
Side walls Silica bricks
Hearth Dolomite or magnesite
4. Acid Bessemer Converter
Body Ganister
Tyres Fireclay
5. Basic Bessemer Converter Calcined dolomite or magnesite
6. Basic Electric Furnace
Roof Silica bricks
Bottom and sides A layer of fireclay bricks next to shell and upon
this a layer of magnesite
7. Cupola Fireclay lining
8. Reheating Furnace
Roof Silica bricks
Hearth Chromite or magnesite bricks
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Dr.R .N. Patel
Lecture: 29 Specialized ceramic products

Module: 6
Lecture: 29

SPECIALIZED CERAMIC PRODUCTS AND VITREOUS ENAMEL

4. SPECIALIZED CERAMIC PRODUCTS

Based on the specific requirements/application ceramic material having
special properties are developed and they are as follow

a) Ceramic composites
Materials with different combinations of properties are required in specific
applications like underwater, transportation and aerospace. E.g. in construction of
aircrafts, structural materials should have low densities. At the same time, they should
be strong, stiff, and resistant to abrasion, impact and corrosion. Ceramic composite
like cermet should fulfill such demands. Cermet is intimate mixture of ceramic and
metallic components in the form of powder, which are compacted and sintered.
Cemented carbide is probably the most common cermet which is composed of
extremely hard particles of a refractory carbide ceramic like tungsten carbide or
titanium carbide embedded in a matrix of a metal like cobalt or nickel which
increases toughness of the carbide particles. These carbides are widely used as
cutting tools for hardened steels. Cermet is also used in linings for brakes and
clutches and it is also used as heat shields, rocket nozzles and ram jet chambers in
aerospace application.

Ceramic metal composites can be produce by bonding of the two materials

which are heated below the melting point of individual components. Ceramic
catalyzes the conversion of metal into its oxide. As the metal oxide is formed, crystals
of the oxide grow into the crystal structure of the ceramic materials. Thus the bond
becomes strong between the two phases of the resultant cermet. Metals like Pt, Au,
and Ag exhibit the best bonding with the ceramic phase like Alumina, Magnesia,
Silica, Zirconia, or Beryllia. Their applications are gold coated ceramic wafers for
semiconductor chips, zirconia-lined steel for corrosion resistant uses, and ceramic
capped gold dental crowns. The process is also used for gem setting in gold.

b) Ferroelectric ceramics
Dielectric materials like insulators are known as ferroelectrics, which show
spontaneous polarization in the absence of an electric field e.g. Barium titanate
(BaTiO3) which have very high dielectric constants at relatively low applied field
frequencies and permanent electric dipoles. Another example of ferroelectrics is
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Dr.R .N. Patel
Lecture: 29 Specialized ceramic products

potassium dihydrogen phosphate (KH2PO4), Rochelle salt (sodium potassium

tartarate- NaK.C4H4O4.4H2O), KH2AsO4, NaTaO3, KTaO3, LiTiO3 etc.

BaTiO3 have piezoelectricity. For piezoelectric application poly crystalline

BaTiO3 is used which is cooled through the curie temperature in the presence of
strong electric field. This imparts permanent orientation to the dipoles in the resulting
ceramic materials.

Piezoelectric materials convert electrical energy into mechanical strains or

vies versa when employed in transducer. They are also employed in phonograph,
pick-ups, microphones and sonar detectors. They are employed in ultrasonic
generators which are used for mixing of powders and paints, homogenisation of
milk, aging of clays and the emulsifying of liquids etc.

High amount of voltage is generated because pressure is applied on

piezoelectric material. The spark that can be drawn from such a high voltage in
used for ignition in gas lighter, cooking stoves and cigarette lighters.

c) Ferromagnetic ceramic
Ferrites are an important class of compounds which having magnetic
properties. It formed by mixing of oxides of Iron with other metals. But they are poor
electrical conductors. Soft ferrites can be easily magnetized and demagnetized.
They are used in transformers, in capacitors, as microwave devices in
communicating radio signals, as memory devices in computers and tape recorders.
While hard ferrites are permanent magnets made from oxides of iron, barium and
strontium. Hard ferrites are used in motors and loudspeakers.

d) Ceramic biomaterials
Ceramics have many advantages as biomaterials. They are light weight,
more wear resistant and not attacked by enzymes and biochemical in the human
body. Ceramics are used in making artificial teeth, bone joints. It is also used in filling
the gaps in damaged bones which is facilitated by the similarity between natural
bone and calcium phosphate ceramics.

e) High alumina ceramic

They are mechanically strong dense and special ceramic material. They
possess good wear resistance, corrosion resistance and dimensional stability. So they
are used in insulators for electrostatic precipitators. It is also used in linings for mining
chutes and slides and in making of precision machine parts.

f) Sensors
When ceramic material is exposed to water vapour and certain gases it
transforms non-electrical signals into electrical ones. Humidity sensors are made from
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Lecture: 29 Specialized ceramic products

mixture of titanium oxide and magnesium chromates while gas sensors usually
ceramic semiconductors made from oxides of titanium, iron, tin, silver and zinc.

g) Ceramic superconductors
Ceramics which had been used as insulating materials could be better than
conductors. They are high temperature superconductors and show zero electrical
resistance. It can be prepared by fusing an oxide of barium and copper. Thus if
cables are made of superconducting material, one-fifth of the loss of electricity
during its transmission through aluminium or copper wires is avoided.

Super conductors can repel magnet and also applied in super-fast

magnetically levitated trains. It is also used in magnetic resonance imaging (MRI),
which is a modern diagnostic tool.

h) Ionic conduction
Ceramics materials are made into sodium-sulfur batteries which are used in
electric cars. Ions become mobile at high temperatures and able to carry electrical
charge across them is known as ionic conductivity.

5. VITREOUS ENAMEL

Besides flux and refractories, oxidizing agents such as pyrolusite, red lead and
nitre are included for the formation of enamel. In the formation of enamel colouring
agents, floating agents and free electrolytes are required. Lead oxide, boric acid,
potassium and sodium oxide are easily fusible compounds at lower temperature so
considered as fluxes. Refractories include feldspar; quartz and clay contribute to the
acidic part of the melt and give body to the glass. The basic part is supplied by the
flux.

MANUFACTURE

Raw materials
The raw materials used for the manufacture of enamel are feldspar quartz,
kaolin quartz and feldspar contribute to the hardness and resistance to the action of
acid of the enamel.

 Kaolin lends plasticity

 Fluxes: boric acid, borax
 Flux as well as oxidation agents: Red lead and lead carbonate
 Opacifiers: TiO2 SnO2, ZrO2, fluorspar, cryolite
 Floating agent: Clay and gums
 Colouring agents: Oxides, elements or frits
 Electrolytes: borax, Na2CO3, MgSO4 and MgCO3
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Dr.R .N. Patel
Lecture: 29 Specialized ceramic products

Manufacture
The manufacture of enamel glass (frit) is similar to the first stage of
manufacture of ordinary glass. The finely powdered raw materials are mixed in
proper proportioned and charged into a melting furnace. After the batch has been
uniformly melted, the melt is poured into a quenching tank to granulate it. The cold
water shatters the melt to innumerable pieces, which are called frit. The frit is then
ground into ball mill with porcelain balls where plastic clay is added to prevent the
separation of water from the powdered material. Than colouring agents and
opacifiers are used for milling. After milling the product is discharged and in the form
of thick enamel slip.

Articles of high carbon steels and of cast iron can be enameled. But before
the application surface of these objects should be cleaned thoroughly of all foreign
matters so that the coating of enamel may adhere well.

Enamel may be applied to the metal by slushing, brushing or spraying. e.g.

Iron sheet, or iron pieces are coated by dipping or slushing. In slushing enamel slips is
poured over the metal surface to allow the excess run off.

PROPERTIES
Vitreous enamel is opaque seldom transparent, coloured or colourless flux. It is
easily fusible material

USES
It is used as protective or decorative agent to coat the surface of glass,
porcelain and metals particularly iron sheets.