CERAMICS PROCESSING

Introduction
The term ‘ceramics’ is derived from the Greek ‘keramos’ meaning ‘burned earth’ and is used
to describe materials of the pottery industry. Ceramics are defined as a class of inorganic, non-
metallic solids that are subjected to high temperature in manufacture and/or use. The most
common ceramics are composed of oxides, carbides, and nitrides. Silicides, borides,
phosphides, tellurides, and selenides also are used to produce ceramics. Ceramic processing
generally involves high temperatures, and the resulting materials are heat resistant or
refractory. Firing of ceramic bodies induces time-temperature transformation of the constituent
minerals, usually into a mixture of new minerals and glassy phases.
General characteristics of ceramics:
• High strength
• Wear resistant
• Chemically inert
• Brittle
• Refractory
• Thermal resistant
• Electrical resistant
• Non-magnetic

Categories in terms of application:

• Clays
• Glasses
• Abrasives
• Refractories
• Cements
• Advanced ceramics

1. Raw materials
A wide range of materials is employed by the ceramic industry to match the diversity of its
product range. Both natural and synthetic materials are used, many produced within Europe
but a few are imported. Sectoral needs are different and details of raw materials are listed in
the chapters regarding the different sectors.
Formulas (or bodies) of clay-based ceramics may consist of one single clay or more clays,
mixed with mineral modifiers, so-called ‘non-plastics’, such as powdered quartz and feldspar.
Common clay minerals (‘plastic clays’) are hydrated aluminium silicates that have resulted
from the weathering of rocks and there are two structural units involved in most clay mineral
lattices. One is the ‘silica sheet’ formed of tetrahedra consisting of a Si4+ surrounded by four
oxygen ions. The other structural unit is the ‘aluminium hydroxide or gibbsite sheet’, consisting
of octahedra in which an Al3+ ion is surrounded by six hydroxyl groups. These octahedral
sheets condense with the silica sheets to form the clay minerals.
There are a number of mineral species called clay minerals, but the most important are
‘kaolinite’, Al2O3·2SiO2·2H2O, ‘montmorillonite’, Al2O3·4SiO2·H2O and ‘halloysite’,
Al2O3·2SiO2·3H2O. Advanced ceramic products, which contain only a small fraction of clay
or none at all, are based on the following materials: oxides, carbides, nitrides and borides of
Al, Mg, Mn, Ni, Si, Ti, W, Zr and other metal ions. Typical examples are Al2O3 (alumina),
MgO (periclase or dead burned magnesia), SiC (silicon carbide), TiN (titanium nitride) and
WB2 (tungsten boride). Clays or argilliferous materials (sedimentary clays, schistous clay,
loamy clay, marl) are mostly used for the manufacture of bricks, roof tiles and clay pipes.
Organic additives (sawdust, paper binding substances, formed polystyrene) or inorganic
auxiliary agents such as kieselguhr or perlite can be added in order to obtain a greater pore
volume. In the facing brick and roof tile industry, metallic oxides such as MnO2, TiO2, Fe2O3,
chromites, and minerals such as CaCO3, CaMgCO3 can be added to obtain the desired colour
and/or to enhance porosity of the finished product. BaCO3 can be added to reduce
efflorescence. Such additives are added just before the shaping process, or in the raw material
preparation, either in solid or liquid form. Refractory products consist of clay, chamotte
(calcined and crushed raw plastic clay) and certain natural rocks such as quartzite, dolomite,
bauxite and magnesite, but also of the abovementioned synthetic materials, as for example
sintered corundum, silicon carbide or spinels. In order to produce compressible masses, binders
and aggregates are added to the milled raw materials. The expanded clay industry uses clays
with a specific expandability. Additives (e.g. flux, expansion aids, and release agents) are used
for promoting expansion.
Products manufactured by the wall and floor tiles, household ceramics and sanitaryware
industry predominantly consist of aluminium silicates and the clay minerals serve as plastic
raw materials. However, technical ceramics and inorganic bonded abrasives often contain only
a small amount of clay or in the case of technical ceramics none at all and are, therefore, based
on the metal borides, carbides, oxides and nitrides as mentioned above.
Quartz, feldspar, in some cases chalk, dolomite, wollastonite and steatite are used as fillers and
fluxing materials. Various ceramic products are glazed or engobed on the visible or whole
surface with glaze frits or engobing slips. In addition to the above-mentioned raw materials and
auxiliary agents, additional auxiliary agents, firing auxiliaries, fuels and sorption agents are
necessary for the manufacture of ceramics. Organic slip additives and binding agents are
employed as auxiliary agents in the shaping process. The firing auxiliaries consist of re-usable
fire-proofed capsules, plates and stanchions. Sorption agents such as calcium carbonate,
calcium hydroxide and fine chalk are employed in flue-gas treatment.

2. Preparation of raw materials

The mining of clay, kaolin, clayey materials, feldspar, quartz and most of the other raw
materials used, usually takes place in mines or quarries and in some cases the clay is also
obtained from riversides.
Depending on their characteristics and the stage of processing, the raw materials are stored in
open stockpiles, warehouses which are subdivided into boxes, large volume feeders, tempering
silos, ageing silos, souring silos or dry silos. The silos are equipped with level indicators,
overload valves and filters or gas displacement units, where displaced dusty air is blown off.
Some materials are also delivered in liquid or slurry form and therefore are stored in tanks or
other vessels.
The equipment for transportation within the plant is chosen according to the characteristics of
the material conveyed, such as granularity, resistance to attrition and flowability, temperature,
flowrate and the given space. The materials are moved with mine hoists such as bucket
elevators, chain conveyors, screw conveyors, pneumatic conveyors and slides. The casting slip
is partly pumped though pipelines.
First size reduction and preliminary homogenisation of raw materials is usually achieved in the
quarrying operation, but in order to meet the stringent technical requirements of modern
ceramic products, further preparation is necessary. One or more of the following processes may
be employed:
2.1 Pre-drying
Sometimes certain raw materials need to be pre-dried, for instance sand may be dried using
fluidised bed technology and also rotary dryers may be used. Many refined ceramic raw
materials are purchased from specialist suppliers – usually in a dry state.
2.2 Pre-blending
Blending of clays can begin in the quarry, e.g. by selective digging or by stacking the material
in superimposed horizontal layers, and then scraping this stockpile vertically to supply feed to
the factory.
2.3 Weathering
Large quantities of clay and mineral raw materials need to be stored at works producing clay
bricks and roof tiles, and initial storage is often in the open air. In certain cases – especially in
soft-mud processes – storage for a number of months improves the workability of the clay. The
process is known as ‘souring’ or weathering.
2.4 Primary and secondary crushing, grinding and screening
Coarse primary crushing of relatively dry/brittle clays may be effected by large toothed kibbler
rollers, usually located in the quarry, or by large jaw-crushers. Very hard raw materials (often
used to manufacture refractory products) are also reduced in size using jaw or cone-crushers,
both of which compress the lumps of mineral between a stationary and a moving hard surface.
Hammer mills achieve size reduction by impact forces – pieces of raw material fed into the
mill are shattered when struck by the rapidly rotating hammers. Edge runner mills (e.g. dry or
wet pan grinders) are suitable for reducing the particle size of more plastic raw materials. Pans
with perforated base plates ensure a defined maximum particle size, and wet pans have the
added function of allowing the tempering of clays with added water.
Crushing rollers are widely employed in the heavy clay industry to disintegrate, flatten and
homogenise clay particles. Pairs of parallel, smooth hard-steel rollers are driven in opposing
directions so that the raw material, fed between the rollers, undergoes nipping, shearing and
flattening. Size control is achieved by setting the gap between the rolls.
Clay shredders (and also roller mills) are useful in the case of plastic raw materials, and consist
of a rotating slotted drum fitted with cutter knives. The clay lumps are forced through the slots
in the form of shavings. Impact rotor crushers have two rotors carrying bolted-on impactors or
‘shoes’. They rotate towards each other and achieve continuous turning, mixing and
disintegration of the feed material.
2.5 Dry or wet milling
The comminution process described above typically achieves particle sizes of 2 mm or more.
Further size reduction is necessary for many ceramic applications, such as wall and floor tiles,
refractory products and tableware. Dry or wet roller mills are used to obtain particles of around
1 mm diameter. They consist of rotating vertically orientated rolls operating within an outer
ring, and pressure is developed between the roller and ring, e.g. by centrifugal force. Raw
material from the primary crushing stage is introduced to the mill with or without water, and
ground until the required size grading is achieved. Even finer grinding can be obtained using
continuous or batch ball mills (in which hard ceramic spheres are tumbled within horizontally
mounted drums). Ball mills are the normal choice for the ceramic floor and wall tile industry,
and when used wet they can produce powders graded below two hundred microns.
2.6 Dry screening/ Air classification
In order to optimise certain properties of ceramics (e.g. density), it is sometimes necessary to
blend defined size-gradings of material. Dry screening usually involves vibrating screens,
heated electrically to prevent the build-up of material and clogging. Air classifiers based on
separating cyclones may also be used for dry powder sizing. In either case, oversize material
is usually fed back to the grinder.
2.7 Spray drying
This process is widely employed in the wall and floor tile industry and also carried out for the
manufacture of tableware, technical ceramics and refractory products. The aqueous suspension
of raw material resulting from wet ball milling (solids content ~ 60 to 70 %) is sprayed under
pressure to produce fine droplets which contact a stream of hot air. Drying of the droplets
produces highly uniform, more or less spherical hollow granules (with a moisture content of
typically 5.5 to 7 %). This form of powder has high flowability, facilitating accurate filling of
the press dies and the subsequent pressing of quite large single tiles. Today, certain companies
are specialised in the preparation of spray dried powder. They deliver the prefabricated material
directly to the plants of the ceramic industry where further processing then takes place.
2.8 Calcining
Some ceramic raw materials are pre-fired, usually in rotary kilns, tunnel kilns or shaft kilns, to
improve their properties. For example, certain oxides (e. g. dolomite, magnesite) need to be
‘dead-burned’ at high temperatures, sometimes in excess of 1800 ºC, in order to make them
suitable for refractory manufacture. Calcining of clays (e.g. kaolin) reduces the plastic
shrinkage of bodies to which they are added, aiding size control of products and speeding firing
cycles. Today, certain companies are specialised in the preparation of calcined raw materials.
They deliver the prefabricated material directly to the plants of the ceramic industry where
further processing then takes place.

3. Component mixing
Mixing time, intensity and sequence have a significant impact on the properties of the mix and
consequently on the ultimate product. The prepared raw materials, in controlled proportions,
must be mixed and homogenised to achieve the required physico-chemical uniformity.
Depending on the ceramic sector concerned, mixing may range from large scale continuous
operations to carefully controlled small scale batch mixing. Proportioning may be on a volume
basis (e.g. via box feeders placed on conveyor belts), or by mass (e.g. via screw feeders linked
to weigh-belts). Most ceramic forming operations require raw materials with a defined water
or bonder content, and minor additives such as pigments, anti-scum agents and binders must
be accurately dosed and then uniformly distributed in the mix. In refractory manufacture, the
properties of some products are optimised by the careful blending of several grain size fractions
of raw material. Proportioning of the mix components is now often automated, with computer
control of the feeder mechanisms allowing rapid alteration of the ‘composition’ for the blend.
In some cases, mainly in the manufacture of bricks, the clay is also mixed with solid fuel
additives (such as fine coke) to reduce firing times.

4. Shaping/Forming
Traditional ceramic products were always shaped from raw materials in the plastic state
manually. At the present time, the demand is for stringent technical specifications covering
such properties as dimensional tolerance, density, strength, durability and refractoriness. In
many cases, aesthetic qualities are also of prime importance. The method of forming the ware
can have a profound effect on their ultimate properties, and a wide range of shaping techniques
has evolved in the various sectors of the ceramic industry.
a. Pressing
i. Mechanical pressing
Die boxes are charged with a pre-set volume of clay granules, and pressure is
usually applied from above and below, with pistons being driven by cam action
and aided by heavy flywheels.

ii. Hydraulic pressing

Use of a hydraulic press with high compaction force. Moist powder is pressed
in shallow dies.
iii. Impact pressing
This involves a high energy rate forming via pneumatic-mechanical impact
between a high velocity ram striking powder in a die. The technique is employed
in the manufacture of special refractory products
iv. Friction pressing
Mechanically driven friction (screw) presses are, in general, used for producing
refractory shapes, although they are gradually being replaced by hydraulic
presses
v. Isostatic pressing
 Some high-quality products require uniform densification, which can be
achieved by applying pressure equally on all surfaces. In the isostatic press,
rubber or polyurethane moulds are filled with ceramic powder and placed in a
liquid filled vessel. A high hydrostatic pressure is then applied, followed by a
demoulding of the objects. This technique is used in the refractory and technical
ceramics sectors as well as for the manufacture of tiles and tableware

ii. Extrusion
Extrusion is widely employed for the manufacture of clay bricks and blocks, vitrified
clay pipes and ceramic floor and wall tiles. The process is also used to make semi
finished ‘bats’ for subsequent pressing into roof tiles, refractory shapes, etc. The
extrusion process demands a plastic raw material, which usually implies substantial
clay content. The plastic body is tempered to the required consistency with water, and
then forced through the die of the extruder– usually by a powerful auger. A vacuum de-
airing stage is usually included prior to the auger, leading to improved consolidation of
the clay column. The latter is finally cut into units of the required length by forcing
sections of the column through a number of tightly stretched vertical wires.
iii. Moulding
Moulding of clayware demands far less power and energy than pressing or extrusion,
but requires a much softer (wetter) mix, leading to higher drying shrinkage and more
heat energy input for drying. Moulded bricks made by the so-called ‘soft-mud’ process
have special textural and aesthetic qualities, which are in great demand – partly to
maintain the rich architectural heritage of many cities and regions of Europe. Hand-
thrown bricks are still made and command high prices, but many moulded bricks are
now produced mechanically on sophisticated machines in Western Europe. The
machines still ‘throw’ individual clots of clay into pre-sanded moulds. Moulding of
ware is also performed in the refractory sector, in order to form large products
(sometimes weighing more than one tonne). The mix, which must have a precise
viscosity, is cast into the mould. In this case, vibration (applied to the mould or directly
to the mix using vibrating pokers) is used to consolidate the mix and ensure complete
filling of the mould. This process is known as ‘vibro-casting forming’.
iv. Slip casting
This process is extensively used in the manufacture of sanitaryware and table- and
Ornamental ware, and for manufacturing special and complicated refractory products
and technical ceramics. The finely ground mineral material is mixed with water to
produce a clay slip (a stable aqueous slurry) which is poured into a porous mould,
traditionally made of set gypsum plaster. The capillary suction of the mould draws the
liquid from the slurry to form a high solid cast on the inner surface of the mould. Wall
thickness increases progressively, and with time a completely solid body can be
achieved (if required) before removal from the mould. Sanitaryware products are
relatively large, and are formed by conventional slip casting or (more directly) in
pressure casting machines
 v. Fusion casting
This technique is expensive in terms of both cost and energy, so its use is confined to
specialist ceramic applications. Refractory bricks are subject to severe chemical and
physical attacks from molten slag, clinker, etc. Fusion casting involves pre-melting the
selected raw materials and pouring into moulds. The resulting units have high density,
low porosity and very strong intercrystalline coherence with a regular microstructure.
These properties confer improved resistance to corrosion and erosion, and excellent
mechanical strength at high temperatures. Controlled slow cooling is necessary to avoid
fracture of the cast pieces and to control the crystallisation process.

5. Drying of ceramic products

Traditionally, most clay articles were dried ‘naturally’ by standing in the air at an ambient
temperature. In the modern ceramic industry, it is necessary to optimise drying in terms of
speed, thermal efficiency and low wastage. With the exception of slow, gentle drying
processes, it is necessary to maintain close control of heating rates, air circulation, temperature
and humidity. Heat for drying air is now mainly supplied by gas burners and by hot air
recovered from the cooling zone of kilns. The heat for drying air can also be supplied with a
cogeneration or another fuel such as coal, biomass, biogas or petroleum coke. Ceramic raw
materials vary in their sensitivity to drying, but most benefit from an initial warming-up period
in conditions of high humidity (and little or no moisture removal) followed by the main drying
stage where the units meet hotter and drier air. The last few per cent of water is harder to
remove, requiring the hottest and driest air. Various forms of dryers have evolved to meet the
needs of the different sectors of the industry, examples are Hot floor dryers, Chamber dryers
(intermittent), Tunnel dryers (continuous), Infrared and microwave dryers etc
 6. Surface treatment and decoration of ceramic products
i. Texturing of clay products
The surface of clay products may be textured for functional reasons, e.g. to provide a non-slip
finish to floor tiles. A wide range of textures is also applied to clay products for aesthetic
reasons. An alternative technique is to extrude slightly oversize, then to trim to the correct
height and width using cutting wires.
ii. Applied facings
Soft mud bricks receive a surface coating of sand from the inside of the moulds, which are pre-
coated with the sand to act as a release agent. A variety of textures and fired colours can be
achieved by selecting the sand to suit the aesthetic requirements. In the case of pressed or
extruded bricks, blocks or roof tiles, sand or other granular minerals can be applied to header
and stretcher surfaces via compressed air blasting guns. In many cases, pigments are added to
the sand in order to vary the aesthetic finish.
iii. Glazing, engobing and other decorating techniques
Glazing is most common in the manufacture of ceramic wall and floor tiles, sanitaryware and
tableware and currently there is a growing market share for roof tiles as well. Engobing is
mainly employed in the manufacture of clay roof tiles and ceramic wall and floor tiles. Finely
ground glaze components – mainly frits in the case of ceramic tiles – are prepared as aqueous
suspensions. The viscosity and suspension characteristics are adjusted to suit the method of
application, which may be spraying, waterfall glazing, dry glazing or decorating. During the
glazing process, the dried green ceramic ware is in most of the sectors mentioned above –
except sanitaryware – hardened by biscuit firing and then, depending on the applied glaze
components, covered with a glassily melting, smooth, closed transparent or dusky layer. An
engobe is usually applied after the drying process, in some cases the products are engobed even
as green or fired ware.
During the engobing process, a fine grained, non-transparent light or coloured layer of a
ceramic mass is spread to the visible or whole surface by dipping or pouring. Screen printing
is one of the decorating techniques for tiles, due to the ease of application in the glazing lines.
The technique consists of printing a given design by means of one or more printing screens
(tensioned fabric with a set mesh aperture). The screen surface is masked, and the printing ink
only penetrates the openings of the designs to be reproduced. A squeegee forces the ink through
these openings, thus printing the design on the tile. Other decorating techniques are the gravure
technique and flexo space printing. In these techniques, the pattern is transferred directly on
one or more rolls. The ink is applied to the tile from these rolls and this technique enables
printing on the edges of the tiles or relief tiles. Also, the inkjet printing technique is emerging
nowadays. In the case of tableware, often hand painting or sliding ornaments are also applied.
iv. Firing
Firing is a key process in the manufacture of ceramic products, as it controls many important
properties of the finished ware. These include mechanical strength, abrasion resistance,
dimensional stability, resistance to water and chemicals, and fire resistance. When clay-based
ceramic products are fired in a kiln, any residual moisture is driven off at temperatures of
between 100 and 200 ºC. If organic matter and iron pyrites are present, oxidation takes place
at temperatures of between about 300 and 500 ºC. Water combined within the structure of clay
minerals (‘crystal water’) is usually released at temperatures of between 500 and 650 ºC, whilst
carbonates such as calcite and dolomite dissociate with the release of carbon dioxide in the
temperature range 750 to 950 ºC.
The most important changes relating to the development of ceramic properties involve the
breakdown of the lattice structure of the original clay minerals, followed by the formation of
new crystalline compounds and glassy phases. The temperature at which vitrification (glass
formation) takes place, varies according to the mineralogy of the clay. Vitrification usually
commences at about 900 ºC and is completed by about 1050 ºC (for many brick clays) or about
1100 ºC in the case of more refractory fireclays.
During the vitrification stage of ceramic firing, many non-clay minerals such as quartz, oxides
or iron, lime compounds and alkalis (oxides of sodium and potassium) become incorporated in
the fired body. Some sintering and solid solution occurs, and eutectic reactions take place at
the interface of mineral grains and melt phases. Non-clay products such as some refractory
products also depend on sintering, vitrification or recrystallisation stages, but in most cases
much higher temperatures are required to achieve the desired properties.
v. Product finishing
i. Machining (grinding, drilling, sawing)
ii. Polishing
iii. Carbon enrichment
Refractory products are required to work in extremely hostile working
environments, and for certain applications it is necessary to impregnate fired ware
with petroleum-based pitch. The presence of carbon in the final product offers
several advantages:
• it acts as a lubricant, beneficial for the working surfaces of sliding-gate plates
• the relatively high thermal conductivity of carbon increases the thermal shock
resistance of the product
• the carbon acts as a pore filter reducing the permeability of the product, which
in turn offers increased resistance to penetration by slag and metal.
iv. Addition of auxiliary materials e.g. water repellents, jointing materials,
insulation materials, adhesives, and also final assembly.

Assignment 2
Describe the manufacture of ceramic products for application in the following
areas:
1. Refractories
2. Automobile engine
3. Ceramic sensors
4. Carbide tools