Ceramics

Ceramics may be defined as those products, which are made from clay or clay like plastic
materials and after having been shaped and dried, are subjected to burn at high temperature
in order to make them hard and give them desired mechanical strength.
Classification of ceramics
Classification of ceramics
Primarily ceramics are classified into two class
(i) Heavy ceramic wares : There are products, which consist of mainly clay with a very small
amount of other raw materials. For examples bricks, roof tiles, sewer pipes etc.
(ii) Pottery wares: Pottery wares are sub divided as
(a) Terra cotta: It includes all pottery wares
made from common clays and fired relatively
at low temperature. These are normally
porous and are not covered with glaze. The
colour of terra cotta varies from light yellow
to red. It is not hard like porcelain or
stone-wares. A hard nail can scratch it. The
common examples of terra cotta are the
potteries made by potter popularly known as
kumahr in Bangladesh.
 (b) Earthen wares: All potteries ( that are porous and
permeable to liquid) prepared from red burning clays and white
clays and coated with a glaze are included in this class. These
are made by firing at temperature higher than terra cotta as a
result these are harder than terra cotta.

(c) Stoneware: Potteries, which become impermeable to liquid Earthen wares:

because of firing at higher temperature, are called stonewares.
Stone-wares are dense and have slightly grayish or brownish
body. Sanitary wares such as Jars, wash-basins, drain water
pipes, carboys for keeping liquids specially acids are examples
of stone wares.

(d) Porcelain: Porcelains are the best type of all pottery wares. Stoneware
These are white, translucent and impermeable to liquid. The
composition of the body is adjusted in such a way that on
burning at high temperature it becomes completely translucent
to light.

Porcelain
 Classification of ceramics based on degree of vitrification
Depending on the basis of porosity and degree of vitrification ceramic products may be
classified as
(a) White wares: The ceramic wares having white colour and fine structure are generally
called white wares. These are vitrified products fired at moderately high temperature using
varying amount of fluxes. Because of varying amount and different kinds of fluxes used, there
is a wide variation in the degree of vitrification.
(b) Heavy clay products: In this class of products high percentage of fluxes is used. These are
fired at relatively low temperature and thus these products are less vitrified.
(c) Refractory materials: In this class of products very little, some times no fluxes is used.
Although these products are fired at high temperature but the vitrification is very less because
of the presence of very little amount of fluxes.
(d) Enamels: In these products high percentage of fluxes are used. These are fired at
moderate temperature but complete vitrification takes place because of the presence of high
percentage of fluxes.
(e) Glass: In this class of products moderate percentages of fluxes are used. These are heated
at high temperature and complete bitrification is done.
(f) Porcelain ware: Similar as described earlier.
(g) Stone ware: Similar as described earlier.
(h) Sanitary ware: The stonewares, which are used extensively for sanitary fixtures are known
as sanitary wares. Primarily made from clay, sanitary wares were porous and not vitrified.
However, white ware tiles are vitrified to a small extent. Sanitary wares are fragile and
become totally useless once they are broken.
 Classification of ceramics based on field of use
Depending on the main field of use ceramic products may be classified as
(a) Structural ceramics: These are the ceramic wares mainly used in constructing buildings
and various other structures related to this. Examples of this class of ceramics are building
bricks, common bricks, bricks block, hollow tiles, roof tiles etc.
(b) Fancy materials: These include the articles used for internal and external fancy of buildings
and structures. Examples of fancy ceramic materials are bricks and slabs etc.
(c) Refractory materials: Refractories are the materials, which retain their mechanical
properties at high temperature particularly at or above 1000 oC. In this class of products very
little, some times no fluxes is used. Although these products are fired at high temperature but
the vitrification is very less because of the presence of very little amount of fluxes.
(d)Special ceramics: In addition to the above classes, there are another group of burned clay
articles with specific properties. These are mainly used in radio industry, aviation instruments
etc. Now some structural ceramics are prepared in such a manner that meet the requirements
of using in radio electronics, aviation semiconductor, nuclear and rocket technology etc.
Silica ceramics and pyroceramics are the new materials, which have high resistance to
corrosion and high refractory’s properties. Pyroceramics are stronger than glass and high
carbon steel. These have high chemical and thermal stability, excellent dielectric properties.
Pyrocerams are made of uniformly crystallized glass and lie between glass and ceramics.
Quartz ceramics are made from quartz or rock crystal by press forming or casting and firing to
the sintering temperature. Quartz ceramics have high chemical and thermal stability, low
temperature expansion, low heat conductivity etc.
 Raw materials
Ceramics are in general made up of three basic raw materials. These are (a) clay, (b) sand, and
(c) feldspar.

(a) Clay: clay may be defined as a finely crushed and pulverized rock, which becomes plastic
when wet, leather hard when dried and rock like permanent mass when fired. It is the
principal raw material used for the manufacture of ceramics articles. Clays are essentially
consisted of aluminia and silicates. These result from the weathering action of igneous rocks in
which feldspar was a note worthy original mineral. During the conversion of rock to clay the
following chemical changes take place

K2O, Al2O3. 6SiO2 + CO2 + 2H2O → K2CO3 + Al2O3.2SiO2.2H2O + 4SiO2

(b) Sand or silica: Sand or silica occurs most abundantly in the crust of the earth as pure
mineral (SiO2). Quartz is the most common form of silica. The other forms of silica are vitreous
silica, crystobalite, tridymite, diatomite etc. Different form of silica are found in nature. Silica
is most abundantly obtained in the form β-quartz. The β-quartz converted into α-quartz at
573oC and vice versa, which accompanied by a rapid change of volume and results in cracking
of the ware particularly when it is rapidly cooled at this temperature. The other forms of silica
like tridymite, crystobalite are stable over a fixed range of temperature as shown below
 (c) Feldspar: Feldspar is abundantly available in the earth’s crust. It is the main constituent of
igneous rocks. Feldspar is not occure in pure state in nature. It is always associated with
quartz, clays, mica etc. The main sources of feldspar are granite and gneiss. Three fourth of
the known earth surface is made up of granite and gneiss which contains 60-90% feldspar.
Feldspar are insoluble in water but are attacked by the atmospheric carbonic acid (CO 2 + H2O))
and undergo decompositon with the formation of alkali carbonate, aluminium silicate and
sand. The aluminium silicate thus formed in a hydrated state is known as kaolinite, which is
the main constituent of white china clay. The most commonly used three types of feldspar in
ceramic industry are
(i) potash feldspar: K2O, Al2O3. 6SiO2
(ii) Sodium feldspar: Na2O, Al2O3. 6SiO2
(iii) Lime feldspar: CaO, Al2O3. 2SiO2
(d) Additives: In addition to these three basic raw materials some additives are also used in
small amounts such as fluxing agent, plastic materials, special refractory ingredients, colouring
materials etc.
Fluxes agents are substances, usually oxides, used in glasses, glazes and ceramic bodies to
lower the high melting point of the main glass forming constituents, usually silica and alumina.
A few examples of commonly used fluxing agents are
Borax (Na2B4O7), Cryolite (Na3AlF4), Pearl ash (K2CO3), Boric acid (H3BO3), Soda ash (Na2CO3),
and Fluorspar (CaF2) etc.
A refractory material is a material that retains its strength at high temperatures. A few
examples of commonly used refractory ingredients are
Dolomite (Ca/MgCO3), alumina (Al2O3), mulite (3Al2O3. 2SiO2), olivine ((FeO3/MgO).2SiO2),
Zirconia (ZrO2), Titania (TiO2) magnesite (MgCO3), Chromite (Cr2O3) etc.
 Classification of Clay:
On the basis of the composition and place of deposition clays are classified into two classes
(a) Primary clay: These clays are obtained at the place of their origin. The example of such
clay is china clay.
(b) Secondary Clay: These are transported clays. From the place of their origin they are
transported by wind, or water and are deposited in another place. These are also known
as sedimentary clays.
The chemical composition of clays are
(i) Kaolinite: Al2O3. 2SiO2.2H2O
(ii)Montomorillinite : (Mg/Ca)O. Al2O3. 5SiO2 nH2O
(iii) illite: K2O .MgO, Al2O3. SiO2 . H2O
Manufacturing process of ceramics
Depending on the types of ceramic products to be prepared there are three different methods
for manufacturing of ceramics.
(a) Wet process
(b) Dry process and
(c) Casting process
In all the process the basic raw materials are same. The difference between them are occur
largely in drying and shaping steps and also in the types of finished products. The overall
manufacturing process consists of several steps. Among these several steps of manufacturing
process of ceramic wares the main steps are as follows
(i) Grinding of raw materials, (2) mixing of ground raw materials, (3) Filtering and preparation
of dough like plastic clay, (4) shaping articles, (5) drying of articles and (6) firing of dried
articles.
The different steps of manufacturing ceramic white wares are presented in the flow diagram.
(a) Grinding of raw materials: To mix the raw materials uniformly, the raw materials are finely
ground first. There are various methods of grinding the raw materials. Calcianation is used
as a pre-crushing step. It makes the flint more brittle and easily crushable. Mechanical
crushing machines such as stone crusher, jaw crusher are used for breaking up large pices
of hard materials. These are subsequently reduced to smaller size by using pan mills, dust
mill. Edge runner mills are frequently used to crush calcined flint, sand, glass and frits. Ball
and pebble mills are used for grinding non-plastic materials into thorogh and uniform size.
Harding conical mills produce very regular grain sizes and therefore, very useful for the
manufacture of chinaware, earthenware, porcelain ware etc.
(b) Mixing of raw materials or preparation of bodies: In this step the ground raw materials are
mixed in a definite proportion so as to make the clay mixture of right consistency for a
particular shaping process and also to bring the desired properties on to the fired body. For
this purpose the ground raw materials along with water in a definite proportion are taken
in a mixing tank called blunger. After allowing sufficient time to mix thoroughly, the cream
colourd mixture is passed through a strainer in order to separate the coarse particle if there
is any. It is then passed through an electomagnetic separator in order to remove the iron
bearing particles form the mass. The mixing of clay with water and other ingredient is done
by several methods (1) mixing in semisolid state ,(2) mixing in dry state, and (3) mixing in
liquid state.
(c) Filtering of liquid mixture: in this step the liquid part of the mixture is filtered out by using
filter press. Filter press consists of a number of iron plates and frames, groved from inside
so that when they are tightened they form a number of chambers. The two ends of each
chamber are covered by filter cloths. The cloths are being pressed between the plates and
frames. The mass(slip) containing water is pumped inside each chamber and the pressure is
(d) Filtering of liquid mixture: Filtering liquid mixture is usually carried out in filter press. The
liquid part of slip is filtered out. Filter press consists of a number of iron plates and frames,
grooved from inside so that when they are tightened they form a number of chambers. The
two ends of each chamber are covered by filter cloths. The cloths are being pressed between
the plates and frames. The mass(slip) containing water is pumped inside each chamber and
then pressure is gradually increased. When pressure in each chamber becomes sufficiently
high the water of the slip is forced to com out through the cloth in the form of spray. The solid
part of the slip is retained wed condition and fills the individual chamber of filter press. The
resulting dough like material is called filter cake. Before giving shapes of the ceramic articles
the filter cake is put in pug mills in order to mix them well thereby to get an intimate mixture.

(e) Shaping Processes

Slip casting process
Jollying process
Stiff mud process
Hot process
Dry pressing
Extrusion process
 Slip Casting: The slip is poured into a porous plaster of paris mold so that water from the mix
is absorbed into the plaster to form a firm layer of clay at the mold surface
Drain casting - the mold is inverted to drain excess slip after a semi-solid layer has been
formed, thus producing a hollow product
Solid casting - to produce solid products, adequate time is allowed for entire body to become
firm
Hand Modeling:
Creation of the ceramic product by manipulating the mass of plastic clay into the desired
geometry. Potter's wheel is a round table that rotates on a vertical spindle, powered either by
motor or foot operated treadle. Products of circular cross-section can be formed by throwing
and shaping the clay, sometimes using a mold to provide the internal shape.
Jiggering: In this process in which a plastic clay slug is pressed between upper and lower
molds contained in metal rings, moisture is removed from the clay. The mold sections are
then opened, using positive air pressure to prevent sticking of the part in the mold.
(f) Drying of shaped wares: The shaped articles are carefully and properly dried before firing. If
the articles are not dried properly the cracks on article's surface invariably occur during firing.
Controlled drying of ceramic articles can be achieved by various methods. Drying on floor under
shed or in open sky is done for the manufacturing of bricks, tiles and other refractory articles. In
such cases the rate of drying process dependents upon the flow of air, temperature, sun shine
as well as upon the humidity of air. Hot floor drying rooms are usually used for larger shapes and
also for refractory articles those require moderately slow drying rate. Infrared drying is used for
thin ceramic wares, which require rapid drying. The rate of drying depends on the following
factors
(i) Surface area of the article: If the surface area of the article is large then the contact with
drying air will be more as a result the speed of drying will be increased.
(ii) Temperature: Higher is the temperature of the air used for drying larger is the evaporation
rate of water from the surface of articles.
(iii) Rate if air circulation: Higher is the rate of air circulation faster will be the rate of drying.
(g) Firing of ceramic ware: The dried ceramic ware is fired three times at different
temperatures ranging from 700-2000oC to impart hardness, durability and strength. Unglazed
ceramic wares are usually fired only once whereas glazed wares fired twice and glazed
decorative wares fired three times. For glazed wares after firing at 800-900 oC it is dipped into
slip usually prepared by mixing finely powdered quartz, feldspar, borax and lead oxide with
water to form slurry. The final firing is done when decorative ceramic ware is to be
manufactured. In this case after getting white ware by the second firing coloured design is put
in the form of sticker or by painting. It is then fired relatively at low temperature 500-600 oC to
get final decorative product.

Chemical conversion during firing of ceramic wares

The total manufacturing process starting from crushing to final product involves some
chemical conversion at different level of the process particularly in the heating steps. These
can be summarized as follows
1) Dehydration of absorbed or chemically combined water at 150-650 oC. The rate of
maximum dehydration occurs at 500-650oC.
2) Decomposition or calcination of CaCO3, MgCO3 etc. at 600-900oC.
3) Oxidation of ferrous iron, organic and other oxidizable matters at 350-900 oC.
4) Vitrification or silicate formation at 900oC and above.
The common ingredient of all ceramic products is clay (Kaolinite) and therefore, the chemical
reactions, which occurs on heating clay, are quite important. The first effect of the heat is to
drive off the water of hydration. This occurs at about 600-650oC and absorbs much heat
leaving an amorphous mixture of alumina and silica as shown below.
Al2O3. 2SiO2.2H2O Al2O3 + 2SiO2 + 2H2O
As the heating is continued, the amorphous form of alumina changes quite sharply at 940 oC
to a crystalline form of alumiana (ϒ-alumina) with the evolution of considerable amount of
heat. At a slightly higher temperature (above 1000oC), the alumina and silica combine to
form mullite (3Al2O3. 2SiO2). At a further higher temperature the remaining silica is
converted into crystalline crysobalite. Therefore, the over all fundamental reaction in the
heating of clay is

3Al2O3. 2SiO2.2H2O 3Al2O3 . 2SiO2 + 4SiO2 + 6H2O

Kaolinite mullite Crystobalite

The actual ceramic body contains many ingredients other than clay. Hence chemical
reactions involved as more complex and there will be some other chemical species besides
mulite and crystobalite present in the final product.
Vitrification produces some glassy materials, which cover up the the unmelted mass. During
vitrification volume shrinkage takes place. The degree of shrinkage mainly depends upon the
temperature and time of firing.
 Glazing of fired wares
The porous white wares are usually glazed to render it water or liquid proof. Glaze is
nothing but a thin exterior coating of low melting glass that melts onto the surface of the
first fired article. Glaze is applied on the surface of ceramic article to cover the pores, which
are invariably present in all classes of ceramic wares except hard porcelain. In fact the
numcer of pores in ceramic wares is dependent upon the firing temperature. Higher is the
firing temperature lower it’s the number of pores. For glazing a slurry is prepared by mixing
finely ground materials with required amount of water and some other materials such as
pigment, opacifier etc. Frit is prepared by fusing a mixture of acid refractories such as silica,
china clay, borax, feldspar etc. with basic refluxes such as soda, potash, fluorspar, cryolite
etc. The slip is applied by immersing article into the slip or by spraying or by brushing slip on
the surface of article. The main function of glazing is to block the pores, the other function
of glazing are
i) To produce an aesthetic appeal,
ii) to improve the appearance,
iii) to increase the durability of the article,
iv) to provide a fine, smooth and glossy surface,
v) to protect ceramic article from environmental action and finally,
vi) to make the surface impervious to liquid.
 Decoration
Decoration is the last step of ceramic ware manufacturing process. After decoration the
wares are checked, packed and sent to the store-house. The ceramic articles may be
decorated by applying colour dye either before or after glazing. Accordingly they are called
(a) under-glaze decoration and
(b) Over-glaze decoration
Under-glaze decoration: When decoration is done before the application of glaze and both
the glaze and colour dye are fused together directly by firing then it is called under-glazed
decoration. For under glazed decoration the colour dye is prpared by calcining colouring
metal oxide with china clay, feldspar, alumina etc. The calcined mixture is pulverized to a
fine powder, which is then mixed with gums and oil and then applied on aritcle by either
brash or spraying. In case of chinaware or porcelain ware the under glazed decoration is first
dried at room temperature. The ceramic ware after drying is covered with glaze as usual and
then fired. In this case, the glaze must react with colour but not dissolve the colour.
Over-glaze decoration: The decoration process is called over-glaze when the ceramic article
is first glazed then decorated and fired again. In other words over-glaze colours are applied
on the top of the glaze. The over-glaze colours are prepared by mixing colouring oxides with
frits of low melting temperature. The metal oxides that are used for producing different
colour are listed below
Oxide colour Oxide colour
Ferric oxide Yellow, red, brown and black. Manganese oxide violet, earth brown, black.
Cobalt oxide various shades of blue. Nickel oxide brown violet.
Copper oxide green, blue green, red-green. Uranium oxide yellow.
Tin oxide white.