KWAME NKRUMAH

UNIVERSITY OF SCIENCE AND THECHNOLOGY

Department of Chemical Engineering

Silicate technology II
Ceramics and refractories
Prepared by
Zsuzsanna Momade
© 2023
TABLE OF CONTENT

1 INTRODUCTION .................................................................... 3

1.2 Ceramic products ....................................................................................... 5

2 CLAYS .................................................................................10

2.1 Silicate structure .......................................................................................10

2.2 Clay minerals ............................................................................................ 15
2.3 Clays .......................................................................................................... 18
2.4 Polymorph transformation ...................................................................... 20
2.5 Phase diagrams ……………………………................................................ 23

3 OPERATIONS IN THE SILICATE INDUSTRY ......................... 32

3.1 Selection of raw materials ....................................................................... 32

3.2 Crushing and milling ................................................................................ 33
3.3 The plasticity of raw materials ................................................................ 35
3.4 Forming ..................................................................................................... 36
3.5 Drying ........................................................................................................ 40
3.6 Firing .......................................................................................................... 44
3.7 Glazing ....................................................................................................... 56
3.8 Decoration ................................................................................................. 64

4 CERAMIC PRODUCTS ......................................................... 66

4.1 Bricks and tiles ......................................................................................... 66

4.2 Porcelain ................................................................................................... 72
4.3 Earthenware .............................................................................................. 78
4.4 Stoneware ................................................................................................. 80
4.5 Steatite ceramics ...................................................................................... 82
4.6 Abrasives .................................................................................................. 84

5 REFRACTORIES ................................................................. 86

5.1 Types of refractories ................................................................................ 87

5.2 Properties of refractories ......................................................................... 88
5.3 SiO2-base refractories (Silica) ................................................................. 93
5.4 Alumino-silicate refractories (Fireclay) ………………............................ 97
5.5 High-alumina refractories ...................................................................... 100
5.6 Basic refractories ....................................................................................103

REFERENCES .......................................................................... 112

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1 INTRODUCTION
The ceramic industry is one of the largest industries. It is basic to the successful
operation of many other industries. Almost every industrial production line, office, and
home is dependent on ceramic materials.

The word ceramic can be traced back to the Greek term keramos, meaning "a potter"
or "pottery." Keramos in turn is related to an older Sanskrit root meaning "to burn."
Thus, the early Greeks used the term to mean "burned stuff" or "burned earth" when
referring to products made of clays and hardened by fire. Nowadays the sense of the
term is wider and not quite explicit. In this course it is used (as in most European
languages) to cover products related by character of the material and by the way of
manufacture to the original sense of the term ceramics not including glass and
cements.

Until the 1950’s, ceramic manufacture was mainly based on empirical principles; it
was an empirical art. Manufacturers utilized only certain types of raw materials and
technologies developed on the basis of long-term experience.

A brief history of clay and glass ceramics

24,000 B.C. Animal and human figures made from clay and fired at 500-800C in
the Stone Age were found in the Czech Republic
14,000 B.C. Tiles were made in Mesopotamia and India
9-10,000 B.C. First pottery vessels made to store water and food
8,000 B.C. In Mesopotamia, clay tokens are first used
7,000 B.C. Mortar is used with sun-dried brick in Jericho
Human and animal figures were made from clay in Egypt (terra-cotta)
5-8,000 B.C. Glass was discovered in Egypt
4,000 B.C. Floor tile were used in the Near and Far East
3,000 B.C. In Mesopotamia, where there were no suitable stones for building,
brick buildings were made (Babylon/Babel in Babylonia)
Babylonians wrote their history on clay tablets (Gilgamesh epos)
Potter’s wheel is known in Egypt and Asia
2,500 B.C. Glass ornaments and beads appear in Egypt
1,500 B.C. First glass vessels are made in Egypt
1,400 B.C. White stoneware was made in China (Shang Dynasty)
1,200 B.C. In ancient Greece, amphorae were made
1,000 B.C. Glazed stoneware made in China
200 B.C. The Chinese invented white porcelain (during Han Dynasty)
100 B.C. In Syria the process of glassblowing is invented
600 Extensive porcelain export from China (during Tang Dynasty)
1100 Traders brought Chinese porcelain to Europe
1291 In Venice, glassmakers learn to produce clear glass
1550 Refractories were developed
1575 Porcelain dinnerware (soft-paste porcelain) is produced for the first
time in Florence, Italy (Medici porcelain)

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 1688 In France, large sheets of glass are being made for mirrors and
windows
1708 Johann Friedrich Böttger in Germany discovered the secret of making
hard-porcelain. In 1710 the Meissen porcelain factory was established.
Mid-1800’s Porcelain electrical insulators developed
1915 Heat- and shock-resistant borosilicate glass is developed and sold as
cooking implements under the trade name Pyrex
20th century Synthetic ceramics
1940’s Capacitors and magnetic ferrites
1960’s Alumina insulators for voltages over 220 kV
Carbides, nitrides
1970’s Cellular ceramics for catalytic converters
1980’s High temperature superconductors
21st century Nanotechnology

As it can be seen, the Europeans were not responsible for many of the early inventions
in pottery; they were mostly trying to copy Chinese and Near East ceramics. Europe’s
contribution was to industrialize the process.

Ceramics
The properties of a material are dictated by
 the type of atoms present,
 the type of bonding between the atoms, and
 the microstructure of the material.

The ceramic materials are held together by covalent and ionic bonds. Their
microstructure can be entirely crystalline, or a combination of crystalline and glassy,
the glassy phase surrounding small crystals, bonding them together. They consist of
arrays of interconnected atoms; there are no discrete molecules.

The atomic structure primarily affects the chemical, physical, thermal, electrical,
magnetic, and optical properties. The microstructure also can affect these properties
but has its major effect on mechanical properties and on the rate of chemical reaction.
Ceramics can be defined as inorganic, nonmetallic materials with a
heterogeneous structure composed of crystalline substances of various
composition and arrangements, which may be permeated by a glassy phase. They
usually contain pores. They are typically crystalline in nature and are compounds
formed between metallic and nonmetallic elements such as aluminum and oxygen
(alumina - Al2O3), calcium and oxygen (calcia - CaO), silicon and nitrogen (silicon
nitride - Si3N4)...

Due to the wide range of properties of the ceramic materials, they are used for a
multitude of applications. In general, most ceramics are:

 hard,  refractory,  nonmagnetic,

 rigid,  thermal insulators,  oxidation resistant,
 wear-resistant,  low thermal expansion,  prone to thermal shock,
 brittle  electrical insulators,  chemically stable.

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1.2 Ceramic products
Traditional ceramics
Traditional ceramics are those comprising the silicate industries—primarily clay
products, refractories, cement, and silicate glasses. They are produced in high volume.
The silicate industries compose by far the largest part of the whole ceramic industry.

The products of silicate industry:

 Glass products (sodium-calcium-silicate glasses)—it is the largest segment
 Lime and cement products—they are the next largest segment
 Whitewares
It is a very divers group. It includes pottery, porcelain, and similar, porcelain like
compositions.
 Porcelain enamels—mainly silicate glass like coatings on metals
 Structural clay products
It includes brick, roofing tile, sewer pipe and a variety of similar products.
 Refractories
40% are fire-clay products
40% are heavy nonclay refractories (magnesit, chromit, ...)
 Abrasives
mainly silicon carbide (SiC) and alumina (Al2O3) abrasives

The microstructure of the traditional ceramics is built up of usually mullite

(3Al2O3·2SiO2) crystals and different modifications of silica crystals (SiO2) embedded
in a glassy phase, depending on the Al2O3 and SiO2 content of the raw materials.

New ceramics
Literally, dozens of the new ceramic materials unknown 20 years ago are now being
manufactured and used. From this point of view, the ceramic industry is one of the
most rapidly changing industries, with new products having new and useful properties
constantly being developed. These ceramics are being developed because there is a
need for new materials to transform presently available designs into practical,
serviceable products. By far the major hindrance to the development of many new
technologically feasible structures and systems is the lack of satisfactory materials.
New ceramics are constantly filling this need. As the demand for new and better
properties has led to the development of new materials, the availability of new
materials had led to new uses based-on their unique properties.

They are often referred as advanced ceramics, “special”, “technical”, or “engineering”

ceramics. They exhibit superior mechanical properties, corrosion/oxidation resistance,
or electrical, optical and/or magnetic properties.

Examples:
– the telecommunication industry demanded insulators, which had lower dielectric
losses, higher dielectric constants and dielectric strength than porcelain
– the metallurgical and glass industry required lining materials, which can withstand
high temperature, chemical effect of melts and slags, and sudden heating and
cooling

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– the furnaces needed ceramic materials, which can withstand high temperatures and
corrosive hot gases
– the ignition plug for cars required ceramics with high thermal conductivity and
good electric insulation to be able to withstand high temperature differences
– the lathe, planning and milling machines needed hard, good thermal conductor
ceramic materials, which would keep sharp for machine-tools
– the rocket and spacecraft industry required several new materials to be able to
withstand extreme conditions e.g. the thermal barrier tiles to protect the shuttle Al
frame from the extreme temperature of 1660°C encountered upon re-entry into
earth’s atmosphere (carbides, borides, nitrides, silicides based materials)
– the operation of atomic power stations needed new materials many of which could
be only made by ceramic production technology (UO2 ceramic heating elements,
moderators, etc)
– in medicine ceramic materials are used as implant or even coatings to metal
replacements bones (hip, knee,...), to replace diseased heart valves, dentists use
ceramics for tooth replacement implants

The new ceramics are of particular interest because they have unique or outstanding
properties. They have been developed in order to fulfill a particular need in greater
temperature resistance, superior mechanical properties, special electrical properties,
and greater chemical resistivity.

These different requirements could not be met by using only one raw material — clay.
The ceramic industry now produces materials not only based on the Al2O3 - SiO2
system but SiO2, TiO2, ZrO2, Cr2O3, MgO, BaO, CaO, Na2O, Li2O, high melting point
pure metals, as well as carbides, nitrides, borides, and silicides of metalloids in the
periodic table 3rd, 4th, 5th, and 6th groups.

Today very often they call materials of different composition ceramics, if among the
raw materials there are some, which are not organic or not metals and are made by
processing steps common in the ceramics industry.

New ceramics include:

 Pure oxide ceramics—for use as special electrical and refractory components.
The oxides most often used are alumina (Al2O3), zirconia (ZrO2), thoria (ThO2),
beryllia (BeO), magnesia (MgO), spinell (MgAl2O4), and forsterite (Mg2SiO4).
 Nuclear fuels—based on uranium dioxide (UO2)
 Electrooptic ceramics
 Magnetic ceramics
A variety of compositions and uses has been developed. They form the basis of
magnetic memory units in large computers. They are used in high-frequency
microwave electronic applications as well.
 Single crystals
e.g. ruby laser crystals, sapphire tubes, large quartz crystals, ...
 Ceramic nitrides—as refractories for special applications
e.g. aluminium nitride is a laboratory refractory used for melting aluminium,
silicon nitrides, SiAlON, boron nitride,...

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 Metal-ceramic composites—for the machine-tool industry as refractories
e.g. various carbides bonded with metals and mixtures of chromium alloy with
aluminium oxide.
 Ceramic carbides
Silicon carbide (SiC) and boron carbide (BC) are important abrasives
 Ceramic borides—have unique high-temperature strength and oxidation resistance
 Ferroelectric ceramics
e.g. barium titanate has extremely high dielectric constant (100 times larger than
that of other insulators)
 Nonsilicate glasses
They are useful for infrared transmittion, special optical properties, and
semiconducting devices.
 Molecular sieves—similar to, but are more controlled than, natural zeolites.
They are used to separate different molecular sizes.
 Glass-ceramics
They are a whole new family of materials based on fabricating ceramics by
forming as a glass and then nucleating and crystallizing to form a highly crystalline
ceramic material.
 Pore free crystalline oxides
They are based on alumina, yttria, spinel, magnesia, ferrites, ...

The branches of ceramics industry

1. Structural ceramics: it deals with building materials like bricks, roofing tiles,
refractory bricks
2. Fine ceramics: porcelain, stoneware, earthenware (wall tiles, sanitary ware,
faience, drains and sewer pipes, floor tiles, chemical ware,
dinnerware, electrical porcelain, decorative ceramics)
3. Oxide ceramics: mainly the technical ceramics based on oxides used as
semiconductors, transistors, and magnetic materials
MgO-Al2O3-SiO2 system: cordierite, forsterite ceramics (Mg2SiO4)
corundum (Al2O3), thoria (ThO2), berylla (BeO), magnesia (MgO),
zirconia (ZrO2)
titania (TiO2) — used as capacitors
ferrite ceramics MeO·Fe2O3 — they are ferromagnetic
4. Metal ceramics called cermets

Classification of ceramics products

The classification of ceramic products is difficult; often there is no sharp borderline
between the groups.

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The manufacturing procedures are similar for all these different ceramic products. The
production steps are as follows:

(1) Selection of raw materials (depending on the expected properties of the

product)
(2) Comminution
(3) Forming
(4) Drying
(5) Firing to develop the desired properties of the product
(6) Processing after firing

Market
Ceramics is a multibillion-dollar industry. Worldwide sales will reach $500 billion by
2020. The general distribution of industry sales is as follows:

Glass 55%
Advanced ceramics 17%
Whiteware 10%
Porcelain enamel 9%
Refractories 7%
Structural clay 2%

More than half of the advanced ceramics are electrical and electronic ceramics
(capacitors, electrical porcelain, engineering ceramics like bearings, dies, nozzles,
optical fibers etc.)

Vitrified clay  pipes, 1%

Sanitary  ware, 6% Enamel,  1%

Table‐ and ornamental ware, 7%

Wall and floor tiles, 31%

Technical  ceramics,  8 %

Abrasives,  9%

Refractory products,  17% Bricks  and roof tiles, 20%

Ceramic market share in Europe in 2018

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2 CLAYS
Clay is recognized by certain properties. It is an earth, which when mixed with water,
forms a coherent, sticky mass, that is readily moldable; if dried, it becomes hard and
brittle and retains its shape, but can again be made soft by the addition of water;
finally, if baked to a red heat, it becomes still harder and then is no longer susceptible
to the action of water. Clays vary over wide limits of chemical, mineralogical, and
physical characteristics but a common characteristic is their crystalline structure,
consisting electrically neutral aluminosilicate layers, which lead to a fine particle size
and plate like morphology and allows the particles to move readily over one another.

Geologists define clay as any mineral in a rock with a grain size less than 4 μm, even
though the mineral may not be a clay mineral. Silt is defined as a rock with particle
size between 4-62 μm. Silt sized particles are usually non-clay minerals and clay sized
particles are usually clay minerals, although non-clay minerals may also fall into this
category.

2.1 Silicate structure

Silicates are compounds of silicon and oxygen combined Element (mass) %
with one or more metal ions. Since silicon and oxygen Oxygen 46.6
together make up almost 75% of the earth's crust, silicates Si 27.7
are by far the most commonly found minerals. Over 90% Al 8.1
of the minerals in the Earth’s crust are silicates. Fe 5.0
Ca 3.6
Atomic arrangements in hundreds of silicates having Na 2.8
complex chemical compositions have a beautifully simple K 2.6
structure. Mg 2.1
All others 1.7
In ionic crystals (halides, oxides, and silicates generally) each positive ion is
surrounded by several negative ions and each negative ion is surrounded by several
positive ions. The structure of ionic crystals can be best described by the connection of
coordination polyhedron of anions surrounding each cation. The coordination
number is the number of anions surrounding the cation.

The ion radius ratio of Si4+ and O2- corresponds to

a tetrahedral coordination, and 4 oxygen ions are
arranged around a central silicon ion. Oxygen
ions may be coordinated with only 2 silicon ions
in silica. This low coordination number makes Si4+
close-packed structures impossible for SiO2. The O2–
SiO44- tetrahedra can be linked in compounds
such that corners are shared in several ways.

The negative charge on the tetrahedron is 4-, which can be balanced in a number of
ways. For example, the oxygen ion can be shared by two adjacent tetrahedra, in which

9
case the net charge is zero. Then no further balancing is necessary. If, on the other
hand, the oxygen is not shared, the negative charge will be balanced by a metal ion
(e.g. Fe, Ca, Mg).

Al3+ ion is larger, than Si4+ ion, therefore it sits in

the middle of an octahedron.
0.29 nm

Silicate minerals are classified on the basis of the degree of polymerization of the
[SiO4]– 4 tetrahedra. The main types of silicates are based on the number of bridging
oxygens per [SiO4] – 4 tetrahedron.

In a stable structure the corners, rather than the edges or the faces of the coordination
polyhedra tend to be shared.

(a) (b) (c)

Tetrahedra and octahedra linked by sharing (a) corner, (b) edge, and (c) face

Diagrammatic representation
of

View from the top, looking down.

Top point of tetrahedron facing
you

Flat base of tetrahedron facing you.

Top point of tetrahedron pointing away from

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The general types of silicates are:

Orthosilicates [SiO4] 4- (or island silicates)

4- The SiO44- tetrahedra are independent of one another; other
[SiO4] cations hold them together. Their chemical formula has SiO44-
Examples: forsterite Mg2SiO4, fayalite Fe2SiO4, wilmenite
Zn2SiO4, olivin (MgFe)2SiO4, zircon ZrSiO4, etc.

Pyrosilicates [Si2O7] 6- (or group silicates)

The [Si2O7] 6- ions are composed of 2 tetrahedra joint with 1
[Si2O7] 6- corner. This kind of silicate is rare. Examples: rankinite
6- Ca3Si2O7, NaSi2O7, akermanite Ca2MgSi2O7
[Si3O9]
Metasilicates [SiO3] 2- (or ring silicates or cyclosilicates)
2 corners are shared to form a variety of ring and chain
structures. Example: benitoite BaTi(Si3O9)

[Si4O12]8–

12-
[Si6O18] Examples: beryl/emerald Be3Al2(Si6O18),
tourmaline NaMg3Al6(BO3)3(Si6O18)(OH)4
cordierite (Mg,Fe)2Al3(Si5AlO18)

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Minerals with chain structures comprise a large group. Those with compositions
corresponding to a single chain [SiO3]n2n- are the pyroxenes and those with double
chains [Si4O11]n6n-, the amphiboles. The asbestos minerals are amphiboles.

e.g. diopside CaMg(SiO3)2

enstatite MgSiO3
Single chains [SiO3]n2n- e.g. wollastonite CaSiO3

e.g. sillimanite Al2O3·SiO2

[Si2O5]n2n- mullite 3Al2O3·2SiO2

Double chains [Si4O11]n6n- e.g. tremolite Ca2Mg5(Si4O11)(OH)2

asbestos Mg3(Si2O5)(OH)4

[Si6O17]n10n- e.g. pellyte

Framework structures (tectosilicates) (SiO2)n

Many important silicate structures are based on an infinite 3-dimensional silica
framework. Every coordination tetrahedra join other tetrahedra at every corner.
Examples: every polymorphic forms of SiO2, where all 4 corners of [SiO4]4–
tetrahedron are shared allowing a small variety of 3-dimensional structures of pure
silica to be formed (quartz, tridymite, cristobalite — each exists in 2 or 3
modifications), feldspars and zeolites.

β-quartz Synthetic zeolite (ZSM-5)

Feldspars are one of the most widespread groups of minerals. They alone constitute
for more than half of the earth’s crust and are essential minerals in most igneous and
metamorphic rocks. The layer and chain silicates emerge by feldspar weathering.
Quartz is the 2nd moat abundant mineral in the Earth crust after feldspars.

Si4+ ion is often replaced by as much as 50% Al3+. Because the latter ions are larger
than Si4+ they open out the framework creating gaps amongst the tetrahedra. These
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gaps are often occupied by opportunistic metal ions such as K+, Na+ and Ca2+. Such
combinations give rise to particular chemical properties and hence to distinguish these
from "simple" framework silicates. These minerals are known as the feldspar
silicates. They are typically rather uniform in physical properties.

Examples: albite (soda feldspar) NaAlSi3O8 (or Na2O·Al2O3·6SiO2),

orthoclase (potash feldspar) KAlSi3O8 (or K2O·Al2O3·6SiO2),
anorthite CaAl2Si2O8,
celsian BaAl2Si2O8, etc.

In zeolites, the aluminium-silica framework is much more open than that for feldspars.
In these minerals, the framework is sufficiently open to form relatively large channels
in the structure. The alkali and alkali earth ions, which neutralize the charges, can be
exchanged in aqueous solutions, leading to their use as water softeners. In addition, the
channels can be used as molecular sieves for filtering mixtures on the basis of
molecular size. More than 200 synthetic zeolite types and 50 natural zeolites are
known.

Sheet silicates (phyllosilicates) [Si2O5] 2 –

Phyllosilicates (phyllo, Greek for "leaf"), formerly known as sheet or layered
silicates, are minerals in which all the [SiO4]4– tetrahedra share corners with 3 others,
thus forming infinitely extending layers or sheets. The 4th corner is unshared and all
these unshared O2- ions point in the same direction. In the middle of the hexagon
formed by the unshared corners, there is room for an OH- group. The Si to O ratio in
the silicate layer is 2:5, which together with the OH- groups gives a formula ending
with Si2O5(OH)-. The sheets are held together in stacks by metal ions and because
these can bridge the sheets in a number of alignments they gives rise to the huge
variety of minerals in this group.

The key families include the serpentines, the clay minerals, talcs, micas, and
chlorites.

[Si4O10]4 - SiO4 tetrahedron

Al(O,OH) octahedron
SiO4 silicon tetrahedra

13
 Muscovite
KAl2(AlSi3O10)(OH)2
from the mica group

Pyrosmalite – single net of tetrahedra Zeophylite – single net of tetrahedra

with 4, 6, and 12-membered rings with 12-membered rings

In spite of their differences, the layered structures common to all produce very similar
physical characteristics. For example, the minerals normally occur as tabular or platy
crystals and because of the relatively weak bonding between the layers, they are
typically very soft.

2.2 Clay minerals

The clay minerals consist of hydrated aluminium silicates that are fine-grained (<2µm)
and develop plasticity when mixed with water. They vary over wide limits in
chemical, mineralogical, and physical characteristics. The nature and properties of clay
minerals are determined in large extent by their structures.

Tetrahedra and octahedra like each other. They form layers, which lay on each other
like a stack of paper. Either a tetrahedral layer (T) and an octahedral layer (O) form a
unit (T – O) or 2 tetrahedral layers build a sandwich T – O – T with an octahedral
layer in the middle.

2-layered clay minerals

In the crystal structure of the common clay mineral a [Si4O10]4- layer of SiO44-
tetrahedra joins at the corners with an AlO(OH)2 layer of Al(O,OH)6 alumina

14
octahedra. The oxygen ions projecting down from the [Si4O10] 4- plane are built into
the AlO(OH) plane, the layers can be combined to give a composition of
(Si4O10)(OH)8Al4. The sheets are held together only by van der Waals bonds. This is
the most common clay mineral kaolinite, which is a 2-layered mineral. [Other
notations found in literature for kaolinite are: (Si2O5)(OH)4Al2; or with oxide
composition: Al2O3·2SiO2·2H2O ]

Halloysite is another 2-layered clay mineral. It contains structural water layers

between the double layers.

2-layered clay minerals

3-layered clay minerals

Isomorphous substitution
Isomorphous substitution of cations is common, with Al3+ and sometimes Fe3+
substituting for some of the Si4+ ions in the tetrahedral network and Al3+, Mg2+, Fe2+
and other substituting for one another in the octahedral network. These isomorphous
substitutions lead to a net negative charge on the structure. This negative charge can be
balanced by K+ or Na+ in the large open cavities in the (Si4O10)4- sheets. Example: in
mica, the negative charge is balanced by K+.

Occasional substitutions, which lead to a negative charge, are balanced in the clay
minerals by loosely held positive ions, which fit on the surface of the particles or
between the layers. These ions can easily be exchanged and are responsible for the
observed base exchange capacity.

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Serpentine is also a 2-layered clay mineral: (Si4O10)(OH)8Mg6, where the 2 Al3+ in the
octahedral coordination is substituted by 3 Mg2+.

3-layered clay minerals

When an Al(O,OH)6 octahedral plane is joined on both sides to a (Si4O10)4- tetrahedral
plane, then a 3-layered clay mineral is formed (see figure before). These can all be
derived from pyrofillite: (Si4O10)(OH)8Al2

Many clay minerals can be derived from this structure by different substitutions.

Talc: in place of the 2Al3+ in the octahedra there are 3Mg2+: (Si4O10)(OH)2Mg3 or
with oxide composition: 3MgO·4SiO2·H2O
Muscovite (Mica): some of the Si4+ is substituted by Al3+ in the tetrahedra and the
negative charge is balanced by K+ between the 3-layered sheets:
(AlSi3O10)(OH)2Al2K (or K2O·3Al2O3·6SiO2·2H2O)
Illite: it is a hydrated muscovite
Montmorillonite: in the pyrofillite, every sixth Al3+ in octahedra is substituted by
Mg2+ and 1 alkali ion enters the water layer to balance the charges:
(Si4O10)(OH)2Al1.67Mg0.33Na0.33·4H2O. The alkali ions can be
exchanged.

The 3-layered clay minerals take up water easily between the layers and swell
strongly. In alkali media, they form colloid dispersed systems.

Summary of clay minerals

2-sheet 3-sheet
Group kaolinite illite montmorillonite
Oxide
Al2O3·2SiO2·2H2O K2O·3Al2O3·6SiO2·3H2O Al2O3·4SiO2·H2O·nH2O
Composition
Other members dickite, nakrite hydromuscovite nontronite
of the group halloysite allevardite, vermiculite beidellite
fire-clay glaukonite bentonite

Kaolinite plates (SEM image)

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2.3 Clays
Origin of clays
Clays are a major components of soils. They are found all over the world in large
quantities. They are secondary minerals produced by weathering of alkali feldspars.
(Feldspars are major constituents of granite and basalt and are the most common rock-
forming minerals. They contain alumina, silica, and varying amounts of Na, K, or Ca.
They make up more than half of the Earth crust.) Weathering is nature’s way to break
down rocks into smaller particles. Weathering is a slow, continuous process that
affects all substances exposed to the atmosphere.

The weathering is a physical or chemical process depending on

– the nature of the parent material (rock hardness, grain size, mineral and
chemical composition, ...),
– climate (temperature, temperature variation, frost action, humidity,
rainfall),
– topography (direction of water flow),
– vegetation (pH of the down seeping water),
– chemical processes, and
– the time during these factors have been operated.

Most chemical weathering is caused by water, which can dissolve most minerals that
hold rocks together. CO2, SO2 and SO3 is soluble in water producing weak carbonic or
strong sulphuric acids.

Weathering yields clay minerals and silica when carbonic acid reacts with feldspar as
follows:

K2O·Al2O3·6SiO2 + 2H2O + CO2 Al2O3·2SiO2·2H2O + 4SiO2 + K2CO3

Potassium feldspar Kaolinite

In addition to kaolinite (or other clay minerals), clays also contain quartz and feldspar.
The quartz component is not affected by the weathering process. Typically, clays
contain ~50% clay minerals + 50% non-plastic materials.

Clays that remain at the original site of decomposition are known as primary clays.
They are relatively rare. These deposits supply the white china clay or kaolin.
Secondary clays are clays that have been washed away from the feldsparic rocks and
have been deposited in beds that may be far from their origin. Therefore, the mined
clay contains quartz, mica, limestone, gypsum, pyrite, etc. The grinding action of clay
particles in water and ice created very fine particles, making secondary clay extremely
plastic.

Properties of clays
Clays can be classified according to their technological application as refractory or
non-refractory clays.

17
 Classification of clays

Non-refractory clay Refractory clay Kaolin

Clay minerals kaolinite kaolinite kaolinite group
illite halloysite illite
montmorillonite
chlorite
glaukonite
Other calcium carbonate, small amount of small amount of
minerals iron oxide (pyrite), quartz and feldspar, quartz and feldspar,
quartz, feldspar, iron oxide iron oxide
mica, gypsum,
humic acid,
soluble salts
Color yellow, gray, brown, gray white,
reddish, blue grayish white
Color after red, pink, beige white,
firing yellowish red grayish white
Temperature around 1200°C above 1600°C above 1600°C
of softening
Usage bricks, tiles, pottery, fireclay refractory fine ceramics like
stoneware, sewer pipe porcelain, refractories,
paper industry, cosmetics,
pharmaceutical industry,
chemical industry
Note: chlorite and pyrofillite clay minerals are missing from the table because they do not fit the grouping

Types of clays
Fireclay: Firing at a high temperature, it is used in stoneware bodies to provide silica
and alumina, refractory materials, and to increase the heat resistant quality
of the clay. They have a fusion point higher than 1600°C. They are of
sedimentary origin. They are relatively plastic. Their typical oxide
composition is:
SiO2: 40-55%
Al2O3: 30-45%
LOI: 10-14%

“Earthenware”, “stoneware”, and “porcelain” are also used in conjunction with clay.

These categories are based on the fired density of the finished ware.

“Earthenware” can be applied to any type of clay, which has a 10-15% water
absorption (porosity) after it is fired to maturity. This clay has the lowest
firing temperature. It is the most commonly found clay in nature, and is the
raw material to make bricks, tiles, and most pottery products. It is fired
between 700-1150°C. In its raw state, the presence of iron oxide makes this
clay appear brown, red, gray, or greenish. When fired, it is anything from
red or tan to brown or black.

18
“Stoneware” clays have 2-5% porosity after firing to maturity, and are usually fired at
1150-1300°C. They are called stoneware clays because the fired wares
exhibit stone-like characteristics: a hard, dense surface with often
variegated color. Stoneware clay bonds well with its glaze and it is
completely leak-proof after firing to maturity. Fired stoneware has colors
from buff or light gray to brown or dark grey.

“Porcelain” clay is characterized by 0-1% porosity after firing to maturity. Its main
component is kaolinite. By itself, kaolin has a melting point ~1800°C and
is difficult to form because of low plasticity. To achieve the dense, white,
translucent clay body known as porcelain, kaolin is mixed with other clays
to achieve a high degree of workability and to lower the firing temperature.
Typically, porcelain is fired above 1260°C in the USA and above 1400-
1450°C in Europe.

Earthenware and stoneware clays can be found just about anywhere on the world.

Kaolin (or China clay): It is a white clay, primarily kaolinite. Originally, it was mined
in China at the base of Mount Kao-ling meaning “high hill”. Primary
kaolins are 95% pure. Kaolins have been exposed to less weathering so the
particle size is usually larger and therefore kaolins are less plastic than
other types of clays. Usually it is moderately plastic and fires white.

Since the main components of clays are clay minerals, these components determine the
properties of clays. Their most characteristic property is their plasticity.

Clay particles are tiny hexagonal plates, about 100 times longer than their thickness.
When water of plasticity is added to the dry clay, moisture between the flat plates
creates a surface tension attraction so that the particles do not easily pull apart, but
they slide over one another. The flat shape of the clay particle and the surface tension
when water is added gives the strength and plasticity to clay.

Every clay becomes plastic after addition of small amount of water. How plastic the
clay is determines how it could be shaped. The very plastic clays are thixotropic.
Plastic clays take up more water and during drying, shrink more.

2.4 Polymorph transformation

Polymorphs are crystalline modifications of the same chemical substance. Many
materials exist in more than one crystal form. The transformation occurs at a constant
temperature. The 2 polymorphs can exist together only at this temperature. At every
other temperature only 1 modification is stable, the one with lower free energy.
Polymorphism in elements is called allotropy.

[Allotropes of C: graphite, diamond, fullerenes, graphenes, diamane, nanotubes, glassy

carbon; allotropes of P: white, black, and red phosphorous; allotropes of O: O2 and
ozone O3; allotropes of S, Sn, As, Se, Sb etc]

19
There are 2 general types of polymorphic transformations depending on the kind of
changes occurring in the crystal: displacive and reconstructive transformations.

Displacive transformation (“high-low” transformation or “high-low” inversion)

During displacive transformation, the original bonds between the coordination
polyhedra remain, only the angle of attachment changes. This type of transformations
is rapid and occurs at a definite temperature.

Reconstructive transformation
During reconstructive transformation, the attachments of the polyhedra break away
and new bonds form. To break and reform bonds requires greater energy, and
consequently these transformations occur but slowly.

The polymorphic form that has the lowest free energy is the most stable over a
particular range of temperature, and others will tend to transform into it.

(a) Displacive
transformation
Reconstructive transformation

(b) (c)

(d)

Open form of structure (a) showing displacive transformation

into collapsed forms (b) and (c) and reconstructive transformation
into basically different form (d)

Many transformations are speeded up by the presence of a liquid in which the greater
solubility of the unstable form allows it to go into solution and then precipitate as the
more stable one.

20
There are a number of characteristics of the polymorphic forms related to displacive
transformations in silicates:
S The high-temperature form is always the open form.
S The high-temperature form has the larger specific volume, the larger heat capacity,
and the higher entropy.
S The high-temperature form has the higher symmetry—in fact, the low-temperature
form is a derivative structure of the high-temperature form.
S High-temperature forms can be cooled to room temperature in a metastable state
without the polymorphic transformation occurring at all.

Silica
The transformations observed for silica are of particular interest to silicate technology.

Polymorphic forms of silica

1025°C

867°C 1470°C 1713°

β-quartz γ-tridymite β-cristobalite melt

160°C

573°C β-tridymite 230°C

105°C

α-quartz α-tridymite α-cristobalite

The circled temperatures represent reconstructive, the rest displacive transformations.

α- and β-quartz
α-quartz, or simply 'quartz', has
a hexagonal structure of (SiO4)- 4
tetrahedra with a three-fold axis
of symmetry. β-quartz has a
six-fold symmetry.

21
 Hexagonal tridymite crystals Octahedral cristobalite crystal

2.5 Phase diagrams

A phase is a portion of a system that has uniform physical and chemical
characteristics. Two distinct phases in a system have distinct physical or chemical
characteristics and are separated from each other by definite phase boundaries. A
phase may contain one or more components (chemically recognizable species). A
single-phase system is called homogeneous, systems with two or more phases are
mixtures or heterogeneous systems. (Examples of common multi-phase systems: ice
cubes in water constitutes a two-phase system; a mixture of oil and water is also a two-
phase system) A phase diagram is any graphical representation of the state variables.

Ceramic products are heterogeneous, multi-phase systems and therefore their

properties depend on the properties and relative amounts of phases present.

At equilibrium, a system is in its lowest free energy state for composition, temperature,
pressure, and other imposed conditions. When a given set of system parameters is
fixed, there is only 1 mixture of phases that can be present, and the composition of
each of these phases is determined. Phase-equilibrium diagrams provide a clear and
concise method of graphically representing this equilibrium situation. One use of
phase diagrams is to represent which phase or phases we might expect to be present as
a function of temperature.

The time that it takes to reach equilibrium state depends on factors other than the final
composition, mainly the nature of processes taking place. Particularly for systems rich
in silica, the high viscosity of the liquid state slows down reactions and equilibrium is
not reached. Most silicate products are not in equilibrium, but in a “frozen”, metastable
state, in which the system is at lower but not at the lowest free energy state.

Lots of work was carried out in the 1950s and 1960s, but many systems have remained
almost completely unexplored; and it is not a well-funded research topic.

22
2.5.1 Gibb’s phase rule
Gibb’s phase rule relates the number of components and the number of degrees of
freedom in a system at equilibrium by the formula

F=C–P+2

where P = number of phases present

C = number of components (elements or compounds) in a system in
equilibrium
F = degree of freedom, that is the number of variables that can be changed
independently while still remaining in the same phase

2.5.2 One-component systems

In a single-component system, the phases that can occur are vapor, liquid, and various
polymorphic forms of the solid. According to Gibb’s phase rule to fully characterize a
phase in a one-component system at equilibrium 2 variables (usually the pressure and
temperature) are needed (F=1–1 +2 = 2).

The largest number of phases that can occur is 3 (0=1–P+2, P=3) — invariant point.
The lines on the phase diagram represent conditions for 2 phases to exist together at
equilibrium.

The most important one-component system in the silicate industries is that of the SiO2.
573C
Only the α-quartz β-quartz transformation is rapid and reversible, the others
are very slow. Therefore, the high-temperature forms do not transform into the
equilibrium quartz form, they rather stay in metastable form on cooling. Even the
metastable forms can undergo transformation.

Equilibrium diagram for SiO2 (after Fenner, 1913)

23
 melt

Pressure
Silicate glass β-cristobalite

β-cristobalite
α-cristobalite γ-tridymite
γ-tridymite
β-tridymite
α-tridymite
β-quartz

α-quartz

867
163
117

230

573

1025
1470

1670
1713
Temperature, °C
Stability of metastable phases in the SiO2

Example: Once formed, the transformation between cristobalite and quartz is so

sluggish that β-cristobalite commonly transforms on cooling into α-cristobalite.
Similarly, γ-tridymite commonly transforms into α- and β-tridymite rather than into
the equilibrium quartz form. Even silica glass can cool to room temperature and
remain indefinitely in this state.

At any constant temperature, there is a tendency to transform into another phase of

lower free energy and the reverse transition is thermodynamically impossible. It is not
necessary, however to transform into the lowest energy form. Example: At 1100°C
silica glass could transform into β-cristobalite, β-quartz, or γ-tridymite. In practice,
when silica glass is kept for a long time at this temperature, it crystallizes, or
devitrifies, to form metastable β-cristobalite, not the stable γ-tridymite, because the β-
cristobalite is structurally the most similar to silica glass. On cooling β-cristobalite
transforms into α-cristobalite.

The polymorphic transformation of SiO2 is a real technological challenge for the

industry. The densities of various forms are quite different which can cause significant
volume change during transition.

Densities of various phases of SiO2, kg/m3

Quartz Tridymite Cristobalite Glass

α β α β γ α β
2630 2650 2270 2270 2250 2330 2215 2200

24
 Volume changes accompanying polymorphic transitions of SiO2

Transformation Volume change, %

α-quartz → β-quartz 2.4
α-quartz → γ-tridymite 15.1
α-quartz → β-crystobalite 19.8
α-quartz → melt 19.9

2.5.3 Two-component systems

If one phase is present: F=C–P+2, F=2–1+2, F=3 (pressure, temperature,
composition). However, the effect of pressure is small for many condensed-phase
systems, and we are concerned with systems at or near atmospheric pressure.
Therefore, phase diagrams at constant pressure can be drawn with temperature and
composition as variables.

If 1 phase is present, both temperature and composition can be arbitrarily varied.

If 2 phases are present, F=C–P+2, F=2–2+2, F=2. If pressure is fixed, only 1 variable
can be arbitrarily changed (either temperature or composition).

The maximum number of phases that can be present at fixed pressure (F=1) is
F=C–P+2, 1=2–P+2, P=3.

Number of Number of Representation

phases variables on the phase diagram
1 3 3-dimensional surface
2 2 plane
3 1 line
4 0 point

Solid solutions
A solution is a homogeneous mixture in which the atoms or molecules of one
substance are dispersed at random into another substance. Solutions can form in
liquids and solids. The amount of one substance that can be dissolved into another is
its solubility. In a solid solution the "solute" is distributed homogeneously throughout
the "solvent" as atoms or molecules (not as microcrystals). The properties and
composition of a solid solution are uniform as long as it is not examined at the atomic
or molecular level.

There are 3 different categories of solubility:

 Limited solubility (e.g. sugar in water; Cu in Zn; C in Fe)
Only a certain amount of one substance may completely dissolve into the other
substance. If this solubility is surpassed then one of the original components will
remain—now 2 phases exist. Many materials behave this way.
 No solubility (e.g. oil/water; Pb/Cu)
When 2 substances are insoluble, almost none of either substance will dissolve in
the other.

25
 Unlimited solubility (e.g. alcohol/water; Cu/Ni)
The 2 substances are able to dissolve completely into any amount of the other
substance. After the solution is thoroughly mixed only 1 phase is produced.

Interpretation of phase diagrams

For a given temperature and composition we can use the phase diagrams to determine
 the phases that are present
 the compositions of the phases, and
 the relative fractions of the phases (lever rule).

Complete solid solution — Figure 1(a)

A and B are completely soluble in each other in the liquid state and in the solid state as
well. At relatively low temperatures there is a single, solid-solution phase field
labelled .

The upper boundary of the 2-phase region is called the liquidus, that is the line above
which a single liquid phase will be present. During cooling, the first solids begin to
form at the liquidus temperature. The lower boundary of the 2-phase region is called
the solidus and is the line below which the system has completely solidified. When the
solid is heated, the first bit of liquid will form at the solidus temperature.

Eutectic diagrams
The Greek word eutectos means “easily melted”. When a second component is added
to a pure material, the freezing point is often lowered. A complete binary system
consists of lowered liquidus curves for both end members. The eutectic temperature
is the temperature at which the liquidus curves intersect and is the lowest temperature
at which liquid occurs. The eutectic composition is the composition of liquid at this
temperature, the liquid coexisting with 2 solid phases. At the eutectic temperature, 3
phases are present, so the variance is 1. Since pressure is fixed, the temperature cannot
be changed unless 1 phase disappears.

Eutectic diagram with no solid solution — Figure 1(b)

Eutectic diagram with limited solid solution — Figure 1(c)

The 2 components are partially soluble in each other. The components do not exist in a
single solid solution near the middle of the composition range. As a result, 2 solid
solution phases, α and β, are distinguishable. They frequently have different crystal
structures. The crystal structure of α will be that of A, and the crystal structure of β
will be that of B. This is because each component serves as a solvent for the other, the
“impurity” component. For example α consists of B atoms in solid solution in the
crystal lattice of A.

26
T

Liquid
At the eutectic temperature, there are 3 phases in equilibrium:
α+L L+β the melt with the eutectic composition E, one of the solid
αE βE phases with composition αE, and the other solid phase with a
E
composition of βE.
α α+β β

A B

Compound formation— Figure 1(d)

2 components may form an intermediate compound C between A and B that has
precise chemical composition. The compound is shown by the vertical line. The
compound has a different crystalline structure from that of the parent substances and
consequently forms another solid phase in the system.

Peritectic diagram — Figure 1(e)

In all of the binary diagrams so far, the pure components have had distinct melting
points. In some systems, however, the components will form stable compounds (C)
that may not have such distinct melting point. C is a stable compound formed from A
and B. It does not melt at a single temperature. C becomes unstable before its melting
point is reached and dissociates into a liquid (L) and one of the components as a solid
phase. The compound C will undergo incongruent melting, that is the liquid formed
upon melting has a composition other than C. As C melts it decomposes at the same
time. The term peritectic is used to describe this incongruent melting phenomenon.
Peritectic comes from the Greek phrase meaning “melting nearby”. The peritectic
reaction can be written as
heating
C  
 L  A

The liquid formed has a composition at point 1 on figure 1(e).

Congruent melting: the liquid formed upon melting has the same composition as the
solid from which it was formed.

Summary of the main types of phase diagrams:

1. Solid Melt phase changes

(a) The 2 components are completely soluble.

(b) The 2 components are NOT soluble in each other, and they form a eutectic
system.
(c) The 2 components are partially soluble forming solid solutions of α and β, and
they form a eutectic system.
(d) The 2 components form a compound (AmBn) which has congruent melting.
(e) The 2 components form a compound (AmBn) which has incongruent melting.

27
 T T T

Liquid Liquid Liquid

Liquidus
L +
α+L L+β
B+L
A+L Solidus α β
Eutectic
 temp. α+β
A+B
A B A B A B
1(a) 1(b) 1(c)

T T

Liquid Liquid

C+L 1
B+L A+L
B+L C is a compound of
C+L
A+L A and B with a
A+C C+B composition of AmBn
A+C C+B
A C B A C B
1(d) 1(e)

Interpretation of phase diagrams

For a given temperature and composition we can use the phase diagrams to determine
 the phases that are present
 the compositions of the phases, and
 the relative fractions of the phases (lever rule).

To find the composition in a 2-phase region:

(1) Locate composition and temperature in diagram
(2) In the two phase region draw the tie line or isotherm
(3) Note intersection with phase boundaries. Read compositions at the
intersections. The liquid and solid phases have these compositions.

To find the amounts of phases in a 2-phase region we use the Lever Rule:
(1) Locate composition and temperature in diagram.
(2) In 2-phase region draw the tie line.
(3) Fraction of a phase is determined by taking the length of the tie line to the
phase boundary for the other phase, and dividing by the total length of the tie
line.
 + 

R S m= S/(R+S)

28
 (MgO is periclase)

Phase diagram of SiO2 – Al2O3 system

This system is the basis for fireclay productions and is very important in porcelain and
other glazed fine ceramic product.

29
SiO2 and Al2O3 form a compound called mullite having a wide variation of chemical
composition between the limits of 3Al2O3·2SiO2 and 2Al2O3·SiO2. Mullite with the
first composition can take up a lot of Al2O3 into its lattice as a solid solution.

Mullite is one of the most important and most widely studied oxide materials for both
traditional and advanced ceramics.

Legend

Crystal structure of mullite

The crystals structure is made up of edge-sharing Al(O,OH)6 octahedra interconnected

by tetrahedral double chains of SiO4-4 tetrahedra.

Needle like mullite crystals (SEM image)

Mullite and silica (SiO2) forms a eutectic with a relatively low melting point of
1595°C. The eutectic composition corresponds to 7 mass % Al2O3. The closer we get
to the eutectic composition, the more the liquid phase (melt) is formed during heat
treatment, causing deformation of the products. This is the reason why fireclay
products have more than 20 mass % Al2O3.

30
3 OPERATIONS IN THE CERAMICS INDUSTRY
3.1 Selection of raw materials
The selection of raw materials is crucial for the properties of the final products. The
quality of raw materials (purity), its physical and chemical characteristics determine
the phase composition of the products.

The ceramics industry uses a huge number of different raw materials. These can be
grouped according to the role they play in the manufacturing process as follows:

(a) Plastic raw materials

The so-called traditional ceramics products are made of plastic raw materials, which
make up 50-100% of the raw material mix. These materials are the clays with varying
purity and refractoriness, and kaolins. The plasticity is given by the colloidal-size
crystalline clay minerals.

(b) Non-plastic raw materials

They reduce drying and firing shrinkage, whilst simultaneously reducing plasticity.
They are coarse-grained, usually non-porous, or at least so stable that they do not
shrink on firing. Typical examples are quartz, corundum, calcined clay, ...

The new non-clay based ceramics do not use plastic raw materials. Their non-plastic
raw material content is at least 85%. These materials are often not even natural
minerals but the products of the chemical industry. The ones of natural origin are talc
[Mg3(Si2O5)2(OH)2 Mg-hydrosilicate], zircon (Zr-silicate), wollastonite [CaSiO3 Ca-
silicate]. The synthetic ones are pure oxides and double oxides like Al2O3, BeO, MgO,
ThO2, ZrO2, SiC, BC, Ti3N4, MoSi2, BaTiO3, PbTiO3, PbZrO3, ...

(c) Leaning additives

These are added to raw material mixes to reduce plasticity. They are usually rich in
SiO2 or CaCO3, like sand, marl, and limestone. (Marl is a CaCO3 rich mudstone,
which contains variable amount of clay and silt: 35-65% clay + 65-35% carbonate)

(d) Fluxes
They are not plastic. Their main purpose is to reduce firing temperature, that is to
produce a melt on firing at a lower temperature. They promote or accelerate sintering
and in many cases stabilize polymorph crystal modifications.

For traditional ceramics feldspars [K(AlSi3)O8, Na(AlSi3)O8, Ca(Al2Si2)O8], Na2CO3,

borax (Na2B4O7·10H2O), fluorspar (CaF2) are used.

For the new ceramics, they rather use alkali earth oxides, mainly BaO, CaO, and SrO.

31
(e) Plasticity improving additives (plasticizers)
They are used where the raw materials are not plastic. The simplest way would be to
use plastic clays, but it is not possible for the new, synthetic ceramics, because the Al-
silicates would adversely affect the properties of the products. Clays can be used up to
5% in steatite.

In synthetic ceramics organic materials are used such as dextrin, paraffin oil, humic
acid, methyl cellulose, polyvinyl alcohol solution, waxes, starch, ... These increase the
strength of the unfired products as well. However, during firing, oxidizing atmosphere
is required to burn the carbon out completely.

(f) Doping impurities

These are impurities added intentionally to create lattice defects. There are a huge
number of additives used for this purpose, although in very small quantities.
Therefore, the main difficulty is to achieve homogeneous distribution of these
additives. (e.g. CaO, MgO, ZrO2 ...)

3.2 Crushing and milling

Detailed treatment of theory and equipment has been discussed in the course of
Mechanical Separation Processes.

Every ceramics product will only have the designed properties, if the raw material mix
is homogeneous. To ensure homogenous distribution, the first step in production is
comminution.

Comminution is very important in chemical technology. The chemical and physical

changes (e.g. dissolving of solids in liquids, leaching, interaction of solid materials at
high temperature, ...) occur mainly on the surface of particles.

The particle size distribution is also important in ceramics mixture preparation, since it
allows the porosity of dried, green ware to be controlled. The pores become closed by
firing and the ware shrinks as a whole.

In technical practice, the shrinkage should be kept as low as possible, thus ensuring
– more accurate maintenance of dimensions,
– more rapid firing (temperature gradients in the ware bring about stresses, which are
proportional to shrinkage within the sintering interval and may result in cracking),
and
– the possibility of manufacturing large products.

The most effective way of attaining low porosity of green ware is to ensure its suitable
particle size distribution. The minimum porosity is attained where the voids between
the coarse particles are completely filled by fine particles. (e.g. For single-size
spherical particles, a porosity of about 40% could be obtained. A maximum particle-
packing density is achieved at a ratio of ~ 70% coarse and 30% fine material when 2
particle sizes are used.)

32
The common comminution equipment used in ceramics industry are:
 jaw crusher,
 roll mills,
 edge-runner mills, and
 ball mills.

For large particle-sized raw materials jaw crushers are used to reduce the particle size
to min. 20 mm linear size. The material then can be further ground in roll mills, where
the final particle size is 1/5 - 1/6 of the feed. 1-2 mm particle size can be achieved by
edge-runner mills (also called pan mill), which can operate dry or wet.
Shaft

Drive

Rollers

Steel
frame
Pan

Edge-runner mill

The wet edge-runner mills consist of 2 main parts: 2 rollers and a pan. The rollers
rotate about a horizontal axis and move around the shaft in the pan. The 2 rollers move
at different radii. The material to be ground falls onto the outer path in the pan where
the roller on the larger radius compresses it. A plate moving behind the roller directs
the material to in front of the inner roller. The pan under the inner roller is perforated
with holes 6-12 mm wide and 30-40 mm long. The wet edge-runner mill is used for
clays containing 15% moisture or more. Water is even sprayed into the mill during
operation, so it is not only grinding, but also mixing, wetting and homogenizing the
clay.

The dry edge-runner mill is used for materials containing less than 10-11% moisture.
Here the pan rotates and the rollers only rotate about the horizontal axis but not move
around the shaft.

The particle size is further reduced in ball mills. To achieve the desired 2 µm average
particle size, the energy requirement is high. The large portion of this energy is lost to
friction as heat. The milling time determines the particle size achieved. The particle
size decreases exponentially with milling time, so after a certain time reduces very
little. The efficiency of milling depends on the rotational speed of the mill and the
mass ratio of materials to be ground and the balls.

33
The silicate based ceramics raw materials are milled in mills made of or lined with
silicates. The balls are of the same material ( 50-100 mm flint, porcelain, or steatite).
This way impurities are not introduced into the silicate material. Pure oxides cannot be
ground in silicate mills. They are usually milled in steel lined ball mills with steel
grinding medium. The iron impurity introduced during milling is removed by dilute
HCl-washing. (Flint is a hard, sedimentary quartz. It was used in the stone-age to
make tools.)

3.3 The plasticity of raw materials

The first main problem in the production of ceramics is the workability of the raw
material mix. It means, whether the raw material is plastic enough. A material is said
to be plastic, if on addition of not much of water it forms a plastic mass.

In ceramics the term plastic mass denotes an easily workable mixture, which keeps its
shape after forming even after drying. Up to certain stress, such a mixture behaves as a
solid and exhibits approximately elastic behavior. It is irreversibly deformed only
beyond a critical stress called yield stress. Its rheological behavior is essentially of
Bingham plastic type.

The most characteristic property of the oldest ceramics raw material, clay, is its
plasticity. The very plastic clays are called “fat”, the less plastic ones are “lean”. Oxide
raw materials are not plastic.

The plastic behavior results from the adsorption of water on the surface of the fine
particles. Almost every particle is surrounded by a thin layer of water, making it
possible for the particles to move relative to each other without the breaking or
cracking the mass. The water film between the particles leads to capillary forces,
which is the key to plasticity. Capillary forces are weak, but the stronger the force of
adhesion of water on the particles surface, the stronger the ability of the article to keep
its shape after forming.

To achieve plastic behavior, it is necessary that the material be very fine grained. The
necessary fineness is achieved by milling. Therefore, one of the main aims of milling
is to achieve plasticity.

In case of metal and oxide ceramics, fine milling and the addition of water is not
enough to make the raw material plastic. The addition of plasticizers in a few tenth of
% improves plasticity. However, the properties of pure oxide ceramics can be spoiled
by even a small amount of impurities; therefore, their plasticity cannot be improved
this way.

In the processing of basic oxides, washing of the oxide with HCl improves plasticity.
HCl peptizes the mass, resulting in increased surface area by making the surface
rough, and the chemical products of the reaction are useful.

If the particle size of the raw material mix is between 0.1-0.2 µm, then it can be
molded by adding water to it and pouring it into plaster moulds (casting), regardless of
their chemical composition.

34
3.4 Forming
The method of forming depends on the plasticity of the raw material. This and the
required dimensional accuracy determine the amount of water needed in forming.

Forming processes can be classified according to the amount of water used as wet and
dry (semidry) forming. There is no sharp separation between the classes.

The amount of water added

in the different molding techniques

Molding Water
technique added, %
Casting 25-40
Plastic molding 20-25
Wet pressing 8-16
Semi-dry pressing 4-8
Dry pressing 1-4

The classes of forming techniques are:

(1) Casting of fluid suspension
– casting of slips containing 25-40% water into porous plaster moulds
– casting of mixes containing a thermoplastic binder into metal moulds
 hot casting under pressure of 0.4-0.6 MPa (4-6 atm)
 injection moulding under pressure of 20-80 MPa (200-800 atm)
(2) Wet forming of plastic mass (8-25% water)
– extrusion of a stiff plastic mix using augers, max. pressure being 1.5-4 MPa
(15-40 atm)
– hand throwing, jiggering and jolleying, pressing into moulds (3-15 MPa)
(stamping), cutting, turning
[Jiggering is shaping hollow ware, jolleying is shaping flat ware]
(3) Dry forming (1-4% water)
die pressing, isostatic pressing

The traditional ceramics (bricks, porcelain, ...) are formed by wet processes, the oxide
and metal ceramics by dry pressing.

The plasticity of the raw material is particularly important in the wet processes. The
longer the clay “rests” after milling in the wet state, the more plastic it will be. (The
plastic mass of the Chinese porcelain was rested 2 generations before forming, and this
gave its excellent plasticity.) In today’s industrial processing long resting of the clay is
not feasible. The plasticity can however be improved by kneading and mixing.
Especially good plasticity can be obtained by using a vacuum auger (vacuum pug
extruder).

3.4.1 Slip casting

The casting of aqueous suspensions (slips) into plaster moulds is one of the traditional
ceramic forming techniques, which is used for asymmetrical and complicated thin-
walled shapes. Slip is a suspension of clay and/or other materials in water.

35
The porous mould adsorbs the water from the slip and a firm layer is formed at the
contact with the mould. The layer adheres to the wall and can be removed after partial
shrinkage. In other cases, the adsorption of water by the mould is allowed to proceed
until a massive shape is formed through the mould space.

Slip casting was originally used only with mixes containing a clay component, which
has to be deflocculated in order to achieve
 a suitable viscosity with minimum water content, and
 a stable suspension which does not settle in the mould.

Deflocculation is carried out by using salts containing monovalent cations (e.g.

NH4OH, Na2CO3, Na2SiO3 — waterglass, sodium hexametaphosphate (NaPO3)6 ...).

Slip casting can also be used in the forming of comparatively coarse-grained mixes as
well as in that of non-plastic substances (e.g. corundum). With non-plastic substances,
special care must be taken about perfect deflocculation by controlling the pH of the
slip using acid (HCl) or alkaline medium.

Plaster of Paris (POP or gypsum plaster) is still the most suitable for casting moulds,
being comparatively cheap and allowing easy manufacture of moulds. Its water
absorption ability, which depends on the size and amount of pores, can be readily
controlled by adjusting the water ratio and the setting temperature. Their disadvantage
is their limited life of 50-200 cycles. Between individual cycles, the moulds can be
dried at temperatures up to 100°C when at least 5% water remains in the mould,
otherwise the gypsum dehydrate would decompose.

3.4.2 Plastic forming

Plastic masses are formed by various methods ranging from simple manual ones to
automated processes.

Extrusion
The plastic mass is usually homogenized and degassed in pug extruders (augers). The
auger produces a continuous strip, which is cut for the appropriate length and
processed further. This forming technique is used in the manufacture of bricks, tubes,
rods, etc. from both clay-based and non-plastic mixes. The latter have to be plasticized
with organic plasticizers.

The mix is led into

chamber A (pug mill)
where it is homogenized
and then forced by auger C
through the openings in
plate B. The mass is
divided into small
cylinders, which are
degassed under vacuum in the vacuum chamber G where about 80-90% of the air
leaves. The bits are rejoined by auger E. The material is then extruded through the
steel die whose shape is adjusted to that of the required by the ware.

36
Some processes involve the use of pre-shaped extruded blanks. The further processing
of these blanks can be as follows:
 they can be pressed in a steel die to obtain straight and smooth edges (e.g.
refractory bricks) by hydraulic press (2-50 MPa = 20-500 atm)
 after partial drying they can be machined by turning (suitable for rotary shapes e.g.
porcelain insulators)
 they can be pressed into plaster mould (jiggering and jolleying: these are
mechanized versions of throwing on the potter’s wheel) (e.g. household ceramics)

(a) (b) (c) (d)

A piece of homogeneous degassed plastic mass (a) is placed on a revolving plaster

mould of suitable shape (b). The material is then pressed with a heated revolving tool,
which imparts to it a flat shape (c, d). The heating is required in order to form a steam
film at the surface, which prevents adhesion of the ware to the tool. On drying, the
object is released from the mould, which is returned to the production cycle.

3.4.3 Powder pressing

Ceramic materials used in the electrical and refractory industry are “dry” pressed using
raw material powders of 3-6% moisture content and high pressures between 5-100
MPa (50-1000 atm) to the required shape. Because of the high pressure, the pressed
pieces acquire enough strength for further processing. The shape of the bodies is
maintained by the same forces that keep solid objects together. A powder compact,
before it has been fired, is composed of individual grains separated by 25-60 vol.%
porosity.

Powder pressing has the advantages of

 providing dimensional accuracy by reducing drying and firing shrinkage,
 saving of heat in drying, and
 possibility of automation.

The pressure applied greatly depends on

 the physical characteristics of the powder,
 the size and shape of the particles,
 the quantity and quality of adsorbed gases,
 the shape and size of the die,
 the mode of pressing, and
 additives used.

37
Die pressing
This is by far the most common process for small components with very simple shapes
and where very high production rates are required.

The pressure in the powder is not uniform during the pressing: close to the compacting
plunger is substantially higher than in deeper layers due to wall friction. It is also
higher in the middle of the form than at the sides in the direction perpendicular to the
movement of the die. The pressure distribution can be improved by pressing from both
top and bottom. The higher pressure and therefore the thicker compaction results in a
higher density at both ends. Perpendicularly to the direction of pressing the density is
the highest in the middle of the object and decreases towards the sides. This results in
differential shrinkage in firing.

moving die

powder
compaction line

stationary die

The strength of the pressed article also depends on the particle size and particle size
distribution of the powdery material. (For homodispers, spherical particles the strength
is independent of the particle size, since putting the particles side-by-side the void
formed is larger for larger particles than for smaller particles, but the porosity is the
same. Only the size of the pores produced is different. If the voids are filled with
smaller spheres, the density could be increased.)

The smaller the average particle size, the smaller the pores produced and smaller the
firing shrinkage. However, as the average particle size decreases so does the strength
of the pressed ware. This limits the average particle size.

For non-plastic raw materials, powder metallurgical methods are used. Examples of
these methods are hot pressing and isostatic pressing.

Hot pressing
Hot pressing is done at high pressures of 20 - 400 MPa and high temperatures of 800-
2300°C where the particles start to melt, and/or recrystallize on the surfaces. This way
the particles fuse together and give a very dense article with a high strength. The press
molds are made of graphite. Those materials that would react with graphite are pressed
in cermets (most commonly Ni-bonded TiC based cermets). It is limited to simple
solid shapes like flat plates, discs, blocks, rings, nozzles, rods, and cylinders.
Examples of products: optical windows, ceramic armour, cutting tools, heat engine
components, ceramic bearings, resistors, microwave absorbers etc. made from Al2O3,
SiC, Si3N4 silicon nitride, BN boron nitride, TiC etc. (Cermet is a composite material
composed of ceramic and metallic materials. The metal is used as a binder for an
oxide, boride or carbide. The metals used are Ni, Mo, Co.)

38
Hot pressed Si3N4 Hot pressed BN

Isostatic pressing
Isostatic pressing is a method by which a liquid is used to produce uniform hydrostatic
pressure acting on all sides producing uniform density in the article. This method is
particularly suitable in forming of rotary or thin walled shapes, and in the forming of
large ware, which could not be pressed by classical methods. (e.g. floor tiles)

The powder mix (d) is put into a flexible rubber

mould (c and b) and then hydrostatically
compressed in a fluid (normally oil, glycerine) (a) to
give uniform compaction through the body. Shapes
of much greater complexity can be made than in die
pressing. The first application was in the
manufacture of spark plugs.

3.5 Drying
Articles made by plastic forming contain considerable amount of water, which must be
evaporated before firing, otherwise with rapid temperature increase the water would
produce steam resulting in cracking of the pieces. For economic reason, however, the
drying should be as fast as possible.

3.5.1 Theory of drying

In articles, having clay in their composition water can be present in the following
ways:
(1) Water added to make forming easier (10-40%)
This water forms continuous layers mutually separating the clay particles. (A)
(2) Water found in the pores (6-10%)
This is the water that fills the space between clay particles that are in mutual
contact. (B)

39
(3) Water adsorbed as a thin film on the surface of the particles (1%)
This film is 1-2 molecules thick. It is difficult to remove this film. It can only
be driven off in the final stage of drying.
(4) Water between the clay layers of swelling type clay minerals
(5) Structural water
The removal of structural water (OH)- disintegrates the crystal lattice of clay.

During drying the first 3 category of water is removed.

[Drying shrinkage: where does all that water go?

Water creates films between particles of about 0.05 µm. Particle size of 1 µm has
about 100,000 particles of clay, with 100,000 water films along a 10 cm length. If each
film is 0.05 µm thick, then this is about 5% linear shrinkage. About 30-50 vol.% of
empty space is left behind.]

The drying process can be followed in different ways:

 The moisture content may be determined as a function of time, which results in the
drying curve.
 By the drying rate curve (the 1st derivative of the drying curve).
 By measuring some physical property, such as bulk density, linear shrinkage, or
pore volume, during drying.
critical moisture
moisture content, %

removed moisture, %/h

A B

B C
C

drying time, h moisture content, %

Drying curve Drying rate curve

Property (1)
(2) (1) Linear shrinkage
(2) Pore volume
(3) Bulk density
(3)

Moisture content, %
40
During drying, first the water added for forming leaves. The linear shrinkage is
proportional to the water loss. The water evaporates from the surface of the body and
is replaced from within. Shrinkage occurs as a result of capillary forces, which act
similarly as if the object were exposed to external pressure. Shrinkage proceeds until
the particles come into direct contact. This is the period of constant drying rate (A on
the drying curve) where the unbound water is removed. If the water cannot be supplied
at the rate as it evaporates from the surface, the surface shrinks faster than the interior
and stresses arise (1st falling drying rate period; B on the drying curve). Cracks in the
body occur as soon as the stress exceeds the ultimate tensile strength. This is why the
process requires very careful control in this stage.

The 2nd falling drying rate period (C on the drying curve) is the period when
evaporation takes place inside and vapour diffuses to the surface, without moisture
shifting from the inside of the ware. When the water evaporates from the pores (2nd
type), the shrinkage is slower than the moisture content change. This is the period of
decreasing drying rate. Finally, when the adsorbed water leaves, no shrinkage
occurs. This is when the plasticity of the mass sizes. This is the most critical part of
drying.

Not every kaolin and clay behaves the same way during drying. If the maximum
allowable moisture gradient is high during drying, the clay is not sensitive to drying. If
it is low, the clay is said to be sensitive.

The strength of dry clays lies in the range of 0.5-10 MPa.

The final moisture content in dried ware is usually 1-2% depending on the temperature
and air humidity.

If the drying shrinkage is excessive, warping and cracking of the ware occurs. To
prevent this, larger grain-sized non-plastic materials are added up to 50% (temper).
This reduces the number of water films, and hence less drying shrinkage occurs. It
decreases the workability (plasticity) as well!

3.5.2 Driers
Drying can be accomplished naturally (like in some brick factories) or by warm air
with appropriate humidity. Since water can only leave the surface of the ware at a
given rate, the dryer should not remove moisture faster from the ware than as it
evaporates from the surface. In conventional air dryers, the amount and speed of water
removal are regulated by the air velocity and relative humidity within the dryer. The
air temperature also plays a role, since higher air temperature lowers the relative
humidity. In general, the temperature should be as low as possible (~20°C above the
room temperature).

41
The drying time for a given ware depends on:
 the moisture content of the piece
 the size and shape of the ware (thinner ware dries faster than thick ware,
and smooth shapes dry faster than complex shapes)
 the forming process used
 how difficult the mix is to dry

Types of driers:
 chamber drier (batch drier)
 channel drier
 tunnel drier (continuous driers)
 spray drier

Chamber driers
They consist of a large number of chambers in pairs. Each two chambers have a
common air supply and recirculation system. Every chamber has its own entrance.
Their disadvantage is that at the side and the corners the articles are still wet when in
the middle they are already dry. This wastes a lot of energy by heating the dry
products.

Channel driers
The green ware is packed onto cars, conveyor belts, or roller conveyors after forming.
The dry ware is repacked onto other cars for firing (→ high labor cost).

Tunnel driers
The green ware after forming is packed onto a car. The same car goes through the drier
and the furnace without repacking.

In the channel or tunnel, the ware moves ahead until complete drying. The air usually
moves in a countercurrent fashion.

1 Fresh air 4 Cars with the ware to dry

2 Air preheating 5 Exit lock chamber
3 Suction of wet air 6 Entrance lock chamber

Schematic of a tunnel drier

Spray drier
For dry or semi-dry forming, the slurry (40-50% water) from the ball mill is dried in
spray driers by hot flue gases at 400-500°C. This type is used for producing the
powders for floor tiles, electro-porcelains, oxide ceramics, and steatite products.

42
3.6 Firing
Firing is the most important step in the manufacturing of ceramics. The final properties
of ceramics products are attained during firing. During firing the crumbling, porous
weak green ware becomes a strong, dense ceramic.

The firing temperature depends on the composition of the ceramics; pottery is fired at
900°C, some oxide ceramics, or metal cermets at 2000°C.

This photograph shows an iron-containing

earthenware at 900°C.

At 800°C, reaction produced a mixture of

crystalline particles in a glassy matrix,
forming a harder, less permeable ware. By
900°C, the ware consists entirely of a
viscous liquid that will barely hold its
shape. Higher firing temperatures would
cause slumping or bloating.

During the firing process, changes occur initially in many ceramics: there may be
solid-state reactions forming new phases, polymorphic transformations, decomposition
of crystalline compounds to form new phases or gases, and a variety of other changes,
which are frequently of great importance in particular cases but are not essential to the
mainstream events.

43
Processes occurring during firing:

Temp.,°C Process
100 Water of plasticity evaporates (unbound water, evolution of steam)
~450 Chemically combined water is given off from kaolinite (evolution of
steam). Other types of clays loose chemically combined water between
450-600°C (minor shrinkage, increase in porosity).
~500 Organic matter begins to burn out, blackening the surface as they are
driven off.
573 Quartz changes structure (α-quartz → β-quartz) and expands by 2 vol.%
~600-800 Salts that have precipitated out in the interstices of the particles during
drying melt to form a liquid film between clay and temper particles.
Capillary pressure “glues” particles together.
Surface diffusion and vapor transport of clay constituents begin, results in
necking.
~870 Decomposition of limestone: CaCO3 → CaO + CO2
~800-900 Clays react with fluxes, such as K2CO3 to form a viscous silicate liquid in
the interstices of the particles and crystalline material.
~900 Volume diffusion occurs (further necking, shrinkage, densification).
Crystal structure of most clays is lost, resulting in high-temperature
alteration products (shrinkage).
1050-1200 Feldspars begin to melt and dissolve silica and some other materials
creating a glassy phase of the ceramic (pores close, rapid decrease in
porosity).
1250-1400 Vitrification yields ~100% dense ceramics. Glass forms from the liquid
on cooling. After firing, the ceramic consists of
60% glass 20% mullite (3Al2O32SiO2) 20% quartz

3.6.1 Solid-state sintering

The word sinter derives from the Greek sintar, meaning ash or slag.

The firing of ceramics is a sintering process. Sintering is the process through which
small particles fuse or join together to form a monolithic, dense body, in the absence
of large scale melting. Sintering frequently occurs at high temperatures but below the
melting point, where the atomic motion in the solid state is significant. Most high
melting point materials (nearly all ceramics) are sintered.

During sintering two major changes commonly occur:

 Grain growth (increase in grain size)
 Densification (change in pore size and number to give a decreased porosity
resulting in volume shrinkage and densification)

44
Sintering of 4 spherical particles Neck

Pore Grain
boundary

Before sintering After sintering

The photographs show the sintering process of finely powdered (< 20 µm) Al2O3. The
melting point of Al2O3 is 2054°C,
but sintering takes place at 1600-
1800°C according to the fineness.
After a neck is formed between the
particles, they enclose a spherical
pore, which tends to contract and
become eliminated by the effect of
the surface tension. In an ideal
case, the final sintering yields the
product on the 2nd photograph.

Driving force
Sintering is driven by the system’s attempt to reduce its surface area. The free energy
of the system decreases as a result of elimination of the solid-gas interface.
[Phenomenologically, the process is analogous with the joining of water drops on a
glass plate through the effect of surface tension. The connecting neck, which is formed
first gradually widens until the 2 drops become one. This process proceeds rapidly
because the low viscosity allows for rapid deformation of the drops. Solid particles
must first be heated to a temperature, which renders them capable of deformation and
even then, the joining is slow and incomplete.]

Sintering rate is affected by

 particle size,
 diffusion coefficient,
 temperature.

The sintering rate is roughly proportional to the inverse of the particle size. (In
changing from a 10-µm to a 1-µm particle, the rate of sintering is increased by a factor
of 10.) For larger particles even longer periods of heat treatment do not cause
extensive sintering; as the particle size decreased, the rate of sintering is raised.

Since diffusion coefficients are strongly temperature dependent, sintering rate is

strongly dependent on temperature. Sintering of pure solids takes place well below
their melting point, usually 0.8-0.9 of the melting point expressed in K.

45
3.6.2 Vitrification
To vitrify is to make glasslike.

Vitrification is the densification with the aid of a viscous liquid phase. It is the major
firing process for the great majority of silicate systems. [In some literature,
vitrification is defined as being identical to densification, or sintering during firing, but
the more specific usage is preferred!]

The rate of densification by vitrification depends on

 particle size (inversely proportional)
 viscosity (inversely proportional) — viscosity changes rapidly with
temperature and composition,
 temperature
 surface tension (directly proportional). For silicates, it does not change
much by composition, so it is not really a variable.

When large amounts of melt are formed (e.g. in the firing of porcelain), the melt is
uniformly distributed through the system and forms a continuous phase containing
dispersed solid particles and pores filled with air or other gases. The pores shrink due
to contracting effects of surface tension.

The melt may be present in small amounts (up to 10-20%) in some other systems but it
still can bind together solid particles. The melt in this case is pulled into the points of
contact between the solid particles.

46
 900-1000°C

Partial
sintering

BRICKS

1000-1100°C
Partial
vitrification

UNFIRED POTTERY
CLAY (Terra-Cotta)

1250-1400°C
Almost
complete
vitrification

PORCELAIN

Crystalline phase Glass Porosity

Sintering of a typical clay

3.6.3 Firing shrinkage

The porosity of greenware (25-50%) is removed during the firing process.
Greenware is a ceramics that has been shaped, but not yet fired; that is it can be wet,
damp, dry, or bone dry. The volume firing shrinkage is equal to the pore volume
eliminated. If firing is carried to complete densification, the fractional porosity
originally present is equal to the firing shrinkage. This commonly amounts to as much
as 30-40% volume shrinkage or 12-15% linear shrinkage. This causes difficulty in
maintaining close tolerances of the final product.

47
Depending on the forming process, the total linear shrinkage (drying + firing) is:
 slip casting 22-30%
 pressing 12-20%
 dry pressing 6-12%

Firing shrinkage can be substantially decreased by addition of non-shrinking material

to the mix (temper). E.g. grog (pre-fired and ground clay) is commonly added to fire-
clay bricks, flint is added to porcelain. Other tempers are charcoal, wood ash, sand,
crushed limestone, plant fiber, crushed rock, ...

For some special applications, complete freedom from all porosity and complete
density are required, but for other applications, residual porosity is desirable.

Warping
The major difficulties are warping or distortion caused by different amount of firing
shrinkage at different parts of the ware. Non-uniform shrinkage can even cause cracks
to open.

Causes of warping:
 Density variation in the green ware
The density after firing is nearly uniform, and there is higher shrinkage for the
parts that had a low density than for the part that had a high density in the
green ware. (e.g. in pressed ware, pressure variation in the ware during
pressing; in casting, settled or segregated suspension results in density
difference in the ware)
 Temperature gradient within the ware
 Vitreous ware can warp under gravity force
(especially large heavy pieces like sanitary ware)
 Frictional forces (drag) of the ware against the setter or sagger
This means that the bottom surface tends to shrink less than the upper surface.

The shapes of green ware must be designed so that the final shape, including shrinkage
and warp, comes out right.

Differential firing shrinkage of

(a) pressed crucible (due to
green density variation)
(b) tile (due to temp. gradient)
(c) sanitary ware (due to
gravity settling)
(d) sanitary ware (due to
friction force of setting)

48
Firing mishaps
Problem Cause of problem (and solution)
Rapid generation of steam (ware not dry enough, or T increased
Shattering/blowing
too fast)
Cracking, "lime popping" (due to CaO + H2O → Ca(OH)2,
Spalling
prevent fire under 700 °C or over 1000°C)
Uneven distribution of heat in kiln; uneven density distribution
Warping
in green ware; uneven contraction upon cooling
Sagging Firing to a T too high
Addition of temper reduces firing shrinkage as well as lower
Excessive firing
contraction on cooling. Quartz and lime increase cooling
shrinkage
contraction thus increasing alkaline glaze fit compatibility.
Particles too large → cracks form along temper particles during
Cracking
firing

Correct setting methods for firing are important in eliminating difficulties caused by
firing-shrinkage variations (large tiles and brick do not give much difficulty).

(h) (g) (f)

Setting methods for (a) cup and bowls, (b) large bowls, (c) earthenware, (d) hotel china plates,
(e) bone china plates, (f) frit porcelain plates, (g) hard porcelain plates, (h) tile, (i, j) brick
checkerwork

49
 Saggars are strong boxes made of
refractory to hold ware prepared with
a glaze.

Plate setter

Stilt

Kiln furnitures

3.6.4 Firing schedule

Firing temperatures vary between 900-1550°C, depending on the type of ceramics.
Special ceramics can be fired at much higher temperatures (e.g. corundum at
~1700°C). The total firing time is usually hours or even tens of hours, but most of the
time is spent in heating and gradually cooling the ware.

50
The optimum firing temperature is determined experimentally.

The firing process can be followed by the change of physical properties of the green
ware, like
 density,
 porosity,
 shrinkage, and
 mechanical strength.

Increasing the firing temperature initially

Measuring value of property

Porosity
has only small effect on the physical
properties. Then at certain temperature
range, characteristic of every material, the
change of properties are fast. Finally, further
Strength;
Density increase of temperature does not affect the
property any longer.
Shrinkage
The firing temperature is the temperature
Firing temperature, °C at which no further physical changes occur
in the ceramic body, and above which there
Change of properties of ceramics during
firing
is a deterioration of the properties of the
ware.

In practice, the apparent porosity is measured, which is the ratio of open pore volume
to the exterior specimen volume. It can also be characterized by the water absorption,
i.e.
mass of water absorbed
apparent porosity 
mass of dry specimen

Extending the firing time can be equivalent to a certain degree to increasing the firing
temperature. This is only valid for temperatures not far from the melting point of the
material (e.g. instead of firing at 1400°C, we can fire at 1350°C for a longer time, but
we cannot achieve the desired properties at 1100°C with even a very long firing time).

The variables to control during firing are:

 firing temperature
 firing time
 firing atmosphere (oxidizing or reducing)
E.g. in case of TiO2 based ceramic material the firing atmosphere
determines whether the product will be a capacitor (an insulator) or a
thermistor (semi-conductor)
 ratio of air/fuel
 gas turbulence (faster flow, better heat transfer)

51
The firing temperature can be measured by
 thermocouple
Fe-Co up to 700°C
Ni-CrNi up to 1100°C
Pt-PtRh up to 1600°C
 optical pyrometer (between 700-1600°C, quite subjective)
 Seger-cones

Seger cone
Seger cones are small trigonal pyramids
made of different silicate mixtures, which
“melt” (soften) at calibrated temperatures
between 600-2000°C. There are 60 Seger
cones available in 20-50°C intervals. A
series of them (e.g. 4), that have melting
points in the expected furnace temperature is
placed into the furnace. The cones will bend.
The melting point of the one touching the
base support with its peak at a heating rate of 3-5°C/min is the firing temperature.

They are not suitable to measure absolute temperatures, because their melting point
depends on the rate of heating. However, since the ceramic materials behave the same
way, they are excellent for relative measurements.

Firing temp.,°C Ceramic product Seger cone Pyroscope cone

900 “Biscuit” /Bisque SK 10a PK 90
1000 Brick SK 5a PK 100
1200 Faience SK 6a PK 120
1300 Stoneware SK 10 PK 130
1400 Technical porcelain SK 14 PK 140
1500 Chamotte (fire-clay) SK 18 PK 150
1580 Criterion for refractoriness SK 26 PK 158
1710 Al2O3-ceramics SK 32 PK 171

52
3.6.5 Furnaces
Main requirements for furnaces:
 to give uniform quality of products
 not to produce rejects
 low operating cost

Fuels used for firing:

 wood
 coal
 oil
 gas
 electricity

Operation can be:

 intermittent (batch), or
 continuous.

Firing of furnace can be:

 direct firing (the flame and flue gases are in contact with the products), or
 indirect firing (the heat transfer is through the wall: muffle kiln).

Several different types of kilns are used for firing, including

 muffle kilns,
 chamber kilns,
 continuous multi-chamber kilns,
 tunnel kilns.

The highest cost in operation is the cost of energy (fuel).

The heat energy consumption of the furnace depends on a number of factors:

 type of kiln
 kind of firing
Direct-fired kilns have lower energy consumption than muffle kilns.
 thermal insulation
Good thermal insulation is crucial in saving energy. Good thermal insulation
allows shorter residence time too.
 continuous or intermittent operation
Lower for continuous kilns
 type of fuel
Electric kilns are the most expensive.
 firing temperature
 kiln furniture
The type and number in the kiln
Kiln furniture consists of heat-resistant slabs, shelves, ports, saggars or setters,
cars, etc. that support the ware in the kiln during firing. Kiln shelves are
commonly made of SiC, high-alumina, or cordierite. Triangular ceramic stilts
keep the ware up off the shelves so the glazed bottom does not stick to the
shelf. They have only small marks in the glaze when they are removed.

53
 Because porcelain and even some high-fire stoneware soften at the firing
temperature, anything made from them will slump and warp if it is placed on
stilts. Therefore, objects made of these clays must be placed flat on the shelf;
for that reason they must have unglazed feet.
 heat recycle
Exit flue gas can heat combustion air in recuperative burners.

9
10 8
11
12
13 1 - 16 Chambers:
14
7 1-2 Filling
15 3 Empty
6
5 4-5 Emptying
4 6-8 Cooling
3 9 - 11 Firing
16 2 12 - 13 Preheating
14 - 16 Drying
1

Hoffmann-type continuous multichamber kiln

The Hoffmann kiln is mainly used in brick- and roofing tile manufacturing. It is a
continuous, moving fire kiln in which the fire is always burning and moving forward
from chamber to chamber. It is fired from the top by usually coal, rice husk, but oil can
also be used. There are feed holes in the kiln roof for feeding of fuels. Fuel is fed at an
interval of every 15-20 min. There are openings on the side to take the bricks in or out.
The section between 2 openings is called a chamber. After a chamber is filled, the side
is closed with paper and the opening is walled up. The fire advances ahead along the
channel. The combustion air is sucked through the chambers under emptying and
cooling. It cools the bricks meanwhile it heats up, before it reaches the firing zone. The
flue gas is sucked through the preheating zone before it leaves through the stack. In the
firing zone (chamber 9) the bricks are already hot and glowing because of the hot flu
gases, before they would start burning fuel. The fire advances 7-12 m a day. The
residence time for a chamber is between 140-250 h (6-10 days). It can produce 10-20
thousand bricks/day.

The tunnel furnace is the most widely used

furnace. It is continuous, the ware advances
along the length of the furnace. The ware is
packed on the refractory (fireclay) platform of
the cars. The platforms of the cars standing side
by side form the bottom of the furnace. The
cross section and the length of the kiln depend
on the type of ware to be fired (20-200 m). It
has 3 zones: preheating (25-30% of the length),
firing (30%), and cooling (40-45%) zones. The
Cross-section of tunnel kiln
54
combustion air is sucked from the end of the kiln through the cooling zone. The
preheating is done by the flue gases before they leave through the stack. The natural
draft is not sufficient, therefore high capacity (from 3 to 20,000-80,000 m3/h) flue gas
fans are used. The kiln is fired with oil or gas from the top (in case of bricks), or from
the sides (in case of porcelain).

Temp.,°C
1200
Preheating zone ~ 60 m
800 Firing zone ~ 25 m
Cooling zone ~ 35 m

400

20 40 60 80 100
Time, h
Schedule for firing bricks in a tunnel kiln

Some figures about heat requirements in modern furnaces:

 Bricks 300 kcal/kg (1260 kJ/kg)
 Fireclay 900 kcal/kg (3780 kJ/kg)
 Magnesite 1100 kcal/kg (4620 kJ/kg)
 Porcelain 3500 kcal/kg (14700 kJ/kg)

3.7 Glazing
Many ceramics article production does not end with firing. Further processing steps
may include:
 glazing
 decoration
 metal coating and connections
 grinding

A glaze is a glasslike coating on the surface of the ceramic ware, which is formed
during firing from the raw materials of the glaze.

Function of glaze:
 to make porous ware watertight,
 to increase the mechanical strength,
 to increase the chemical resistance,
 to protect the surface from moisture, dust and other dirt, which may
permanently adhere to the surface,
 to make the ware easily cleanable,
 to increase the aesthetic value of the ware, and
 to increase the commercial value of the ware.

55
 Glaze (glassy) The ceramic glaze is closely related to glasses and
Transitional
enamels. A glaze, however, cannot be considered
layer in its entire thickness as glass, because it is not
completely isotropic, but gives a phase transition
Ceramic
body
towards the ceramic body.

3.7.1 Classification of glazes

Glazes have different composition and properties. They can be grouped according to
many criteria. Many prepared glazes are available commercially.
 According to their production:
– raw glazes
(The ingredients are ground in suspension and applied on the ware.)
– frit glazes
(Frit is a glaze component made by melting raw powdered
minerals to fuse and then quenching into water to cool and grinding
into fine powder. (So frit is a glass of special composition.) Fritting
is done to make raw, soluble and/or toxic components insoluble by
combining them with silica or other added oxides. and to lower the
fusion point of the individual materials by combining them. Frits
are available commercially. Many raw glaze materials (Rb, Ba,
Cd,...) soluble in water and could be released from the glaze during
the use of the ware.)
– salt glazes
 According to their composition:
– alkaline glazes
(Alkaline glazes have Na or K fluxes. Although they produce
brilliant colors when coloring oxides are added to them, are rather
soft, and can easily be scratched. They are difficult to fit to the clay
body and tend to craze.)
– lead glazes
(They melt at a low temperature, fit the clay body well, and take
color well.)
– lead-free glazes
– tin glazes
(Opaque white glazes to cover the color of the clay body)
– boron glazes
– boron-free glazes
– feldspar glazes
(Feldspars are natural frits that could form a glaze if fired at high
enough temperature. Feldspar when pulverized and spread onto the
surface gives a milky white glaze. Its fusion point can be lowered
by adding a little ground limestone.)
 According to their melting point:
– low melting point glazes (800-1150°C)
– high melting point glazes (1250-1350°C)

56
  According to their color:
– colored
– colorless (transparent overglaze)

 According to their surface:

– shiny and glossy
– matt
(the matt effect is produced by large number of tiny crystals in the
glaze, which break up the light)
– smooth
– crystalline
– opaque
– transparent
– crazed (intentionally)
– metallic (gold)

3.7.2 Glaze composition

The glaze recipes up to the end of the19th century were empirical and as family secrets
were inherited by the eldest son of the family. The firs and only rule about glaze
compositions were formulated by Seger.

Seger grouped the oxides forming the glazes into 3 groups:

1) Basic oxides (Fluxes)
They are the alkali and alkali earth oxides: R2O + RO, and PbO
These are the network modifier oxides in the glass.
2) Amphoteric or transitional oxides (Refractories)
They are mainly Al and Fe(III) oxides: R2O3
They are the intermediate oxides in glass.
3) Acid anhydrides (Glass formers)
Mainly SiO2 and B2O3
They are the network formers in glass.

A glaze could be made of SiO2 alone, but since its melting point is so high (1713°C),
that would be impractical since few clay bodies could withstand such high
temperature. Generally, as much silica as possible is used in a glaze, because silica
adds durability and chemical resistance. Fluxes are used to reduce the melting point by
forming eutectics.

A common source of alumina in glazes is kaolin or china clay. Alumina increases

viscosity, helping to keep the glaze materials suspended as well as helping the glaze
adhere to the ware. Alumina, even if used in very small amounts, also adds strength
and durability to the glaze and helps prevent the glaze from running. Without alumina,
glazes tend to crystallize during the cooling process.

Comparison of chemical composition of glazes is made possible with the Seger

formula of glazes.

57
The oxide composition of the glaze is expressed with mole ratios with the following
rules:

 The sum of the mole ratios of basic oxides is always 1:

RO + R2O = 1
They are always written on the left hand side under each other. The transitional
oxides are written in the middle column and the network formers on the right.
 The ratio of the sum of the basic oxides to the network formers
[(RO+R2O+3R2O3):SiO2] varies between 1:1 to 1:10. If it is greater, the oxides
crystallize out from the glaze and the glaze loses its glassy state.

Example 1:

Acid anhydrides
Basic oxides Transitional oxides
(network formers)
0.3 K2O
0.5 Al2O3 4 SiO2
0.7 CaO

Example 2:

Acid anhydrides
Basic oxides Transitional oxides
(network formers)
0.3 PbO
0.3 CaO
0.35 Al2O3 3.2 SiO2
0.2 Na2O
0.2 K2O

The best grouping of glazes is done according to the type of product they are used for.

58
Glaze type Seger composition Firing temp.,°C
Pottery glaze 1.0 PbO 1.4-1.6 SiO2 900-1000
Lead oxide faience 0.25 Na2O
glaze (contains 0.35 CaO 0.2 Al2O3 2.5 SiO2 1200
large amount of 0.40 PbO 0.5 B2O3
PbO and B2O3)
Lead free 0.25 K2O
faience glaze 0.25 Na2O 0.2 Al2O3 2.4 SiO2 1200
0.5 BaO 0.6 B2O3
0.11 K2O
Porcelain glaze 0.67 CaO 1.0 Al2O3 10 SiO2 1400
0.22 MgO
At the beginning of sintering (~1200°C) NaCl and water is
introduced into the firing zone of the kiln. The NaCl evaporates,
Salt glaze
dissociates thermally, and reacts with the steam then with the
for stoneware
ceramic body. It penetrates the pores of the ware and forms a
feldspar-like very resistant coating.
0.3 K2O 0.3 Al2O3
Clay glaze 4.0 SiO2 1200-1300
0.7 CaO 0.2 Fe2O3

3.7.3 Glaze raw materials

PbO
It was an indispensable component for low melting point glazes. PbO melts at 880°C.
It is the only oxide which forms a water-insoluble glaze with SiO2 (e.g. 1:1 PbO:SiO2
glaze melts at 900°C). PbO makes the glaze softer, increases its elasticity, and gives it
a medium thermal expansion. The lead glaze dissolves the coloring oxides well
producing rich, brilliant, deep colors. It makes the glaze quite easy to fit to most clay
bodies. It is introduced into the glaze as PbO, PbCO3, or Pb3O4. Weak acids, like
acetic acid (vinegar) leach lead out from the glaze. Lead compounds are poisonous! It
is banned on kitchenware.

Alkali oxides (Na2O, K2O, Li2O)

They are fluxes, not toxic, and cheap. They increase the thermal expansion of the
glaze, reduce the melting point and viscosity, and promote the dissolving of other
oxides in the glass. Glazes containing a lot of alkali are soft and easily worn or
scratched, and soluble in acids. Most glazes contain them. (Their maximum proportion
is 28%.)

CaO
Improves the hardness, strength, gloss, and chemical resistance of glazes and reduces
thermal expansion and tendency to cracking. (Its max. proportion could be 16-18%.
Above this amount, the glaze will crystallize out.) It is introduced as limestone,
dolomite (CaMg(CO3)2), or chalk (CaCO3).

59
BaO
Its effect is similar to PbO. It substitutes PbO in lead free glazes.

MgO
It is a high temperature flux.

Al2O3
It is an indispensable component of high-melting glazes. It is introduced as feldspar,
kaolin, fire clay, or burned (calcined) clay. It increases viscosity, helping the glaze to
adhere to the ware. It helps prevent the glaze from running down off vertical surfaces.
It prevents glazes to recrystallize during the cooling process and thus may become
opaque. Without alumina, many glazes would have rough surfaces, opacity, or mottled
textures. It also adds to the hardness, durability, and tensile strength of glazes.

SiO2
It is the most important network former. It increases the melting point, hardness,
compressive strength, resistance to abrasion, chemical resistance of the glaze. It
reduces the thermal expansion of the glaze and for this reason it controls the fit of the
glaze to the body. It is introduced as sand or flint (a variety of quartz), kaolin, or
feldspar. For 1 mol of Al2O3 there should be 10 mol of SiO2.

B2O3
It mixes well with SiO2 and can partially substitute it. It is a low melting point
substance with strong fluxing power. It improves upon every quality of the glaze. It is
introduced as Ca(BO2)2, Zn(BO2)2 borate, H3BO3 boric acid, B2O3, and
Na2B4O7·10H2O borax.

SnO2
It is the most important component of opaque glasses. It does not dissolve in the melt
of the glaze. 9-12% SnO2 makes a transparent glaze white. 5% SnO2 + 5% TiO2 gives
a matt (not glossy) glaze.

TiO2
It is present as TiO2 crystals in the glaze; it is a very good opacifier. It increases acid
resistance of the glaze. It can be used up to 15%.

Coloring oxides
The glaze is colorless or transparent if it is made of the above-mentioned oxides. The
colorants are colored metal oxides added in a few percentages to the glazes. They are
often not shown in the Seger formula. Low-fired glazes have a much wider range of
colors than high-fired glazes. The color of glazes depends on:
 the type of coloring oxide used
 the glaze composition
The same oxide gives different colour in lead-, lead-free, alkali-, and
boron-containing glazes.
 the firing atmosphere.

60
The most important coloring oxides are: CoO (blue, turquoise, black), CuO (green,
yellow, red), NiO (gray, yellow, red), MnO2 (violet, brown), Fe2O3 (yellow, brown,
reddish-brown, red), gold (crimson, pink), U2O (yellow, orange, red), SnO2 (white),
As2O3 (white), etc.

3.7.4 Glaze flaws

– crazing
– shivering
– crawling
– pitting and pinholing
– blistering and blebbing
– under-firing and over-firing

Glaze fit
As mentioned above, the glaze composition influences the amount that the glaze
contracts upon cooling after firing. Hence, it is important that the composition of a
glaze be such that it has similar thermal contraction as the ceramic body. If not...

Crazing: the glaze contracts more than the ceramic body; as the body contracts, the
glaze is forced to “stretch out” and cracks (the glaze is under tension). These
cracks may be present when the ware is first taken from the kiln, or they may
develop days or months after the ware has been fired.

Correction of glaze composition in case of crazing to decrease the thermal expansion

of the glaze:
 increasing the SiO2 content,
 if RO:SiO2 ratio > 3, increasing Al2O3 content,
 substituting part of RO and R2O with R2O3 (increasing B2O3), or
 increasing the feldspar content of the glaze.

Shivering is the reverse of crazing. The glaze contracts less then the ceramic body. As
the body contracts, the glaze experiences compressive stresses, and rises off the
body while cracking and peeling.

Crazing

Crazing Shivering Shivering

61
Crawling: the glaze parts during melting and leaves spots of clays exposed. The crawl
may expose only a few tiny places; or the glaze may roll up into droplets or blobs,
or it may be found in a melted puddle on the kiln shelf below the piece. Crawling
may result from glazes being applied over unclean bisque ware and the glaze
cannot adhere properly.

Pitting/Pinholing: they are minute pits in the glaze, resembling miniature volcano
craters. It is difficult to cure.

Blistering Gases may be released from decomposing materials from the ceramic body
or the glaze itself until about 950°C (O2, CO2, CO, SO2, SO3, metal fumes, H2O
vapour) forming bubbles in the glaze (many glazes melt long before this
temperature). These bubbles burst during early stages of cooling.

Blebs are raised bumps appearing on the surface of glazed ware. They are caused by
air pockets, which will lie just below the surface of the clay. These air pockets at
the high temperature swell like balloons leaving a raised place or bump on the
finished ware.
Under-firing or over-firing gives colors quite different from the colors developed by
normal firing. Under-fired pieces have a rough, scratchy, and unpleasant harsh
surface. Over-fired ware is shiny and the glaze may run too thin on the upper parts
of the ware, gather around the foot.

62
3.7.5 Processing

(1) Grinding
The raw ingredients are ground together into a fine suspension in ball mills (35-40%
water).

(2) Fritting (optional)

The purpose of frit production is to make the glaze ingredients insoluble in water to
avoid efflorescence and poisoning. The coloring oxides are mixed and melted with
some small amount of glaze silicates at 1300-1400°C, then poured into cold water
where it solidifies forming a colored glass breaking up into small particles. This frit is
then easily ground with other glaze constituents together. Frits are available on sale.

(3) Application
Glazes are applied in suspensions onto the dried unfired body (green) or to the fired
unglazed body (biscuit/bisque) by dipping the article into the suspension if the body is
porous, or by spraying it onto the article if it is not porous. Brushing can also be used.
Poor application is a very frequent cause of glaze flaws. Glazes, which are too thick,
may run, blister, crawl, or cause the ware to stick to the kiln shelves.

(4) Drying

(5) Firing
Firing can be done in one or in several steps.
 If the glaze was applied on the unfired body, then the glaze firing is the firing of
the ceramic body as well in one step (e.g. electrical insulators, electroceramic
products, sanitary products, some floor tiles). The process can be fully automated.
This method is favored in the very large-scale cheap product manufacturing.
 In the traditional technologies, the ware is fired first without the glaze, and the 2nd
firing is done with the glaze.
– For porous ceramic articles, the 1st firing (without glaze) is at a higher
temperature (biscuit firing). The glaze is a low melting point frit glaze and
the 2nd firing is at 100-150°C lower, than the 1st one.
– For dense ceramic articles (porcelain), the 1st firing (without glaze) is at a
lower temperature. Its purpose is to make the body strong and porous
enough for the glazing. The 2nd firing is at a temperature 400-500°C higher,
than the 1st one.

The temperature has to be “just right”.

 If it is too high, the glaze will flow too much (low viscosity) and collect in
pools. (The viscosity of the glaze can be increased with increasing its Al2O3
content, or the firing temperature can be reduced.)
 If it is too low, the glaze will not completely melt and flow over the rough
surface of the ceramic body.

Pieces have to be prevented from sticking together, therefore saggers or setters are
used.

63
3.8 Decoration
3.8.1 Painting
Faience and porcelain glazed with transparent glazes and other glazed products can be
decorated by painting using bright colored metal-oxides or other compounds stable
under firing conditions (e.g. spinels).

The coloring body in the paint is made from the coloring oxide and some small
amount of glaze silicate melted at 1300-1400°C to produce a frit. The frit is then finely
ground. The fine powder of the coloring body is mixed with some liquid to form a
suspension for application.

The paints can be applied by brush (hand painting), by spraying, using templates,
stamping, printing, and using transfer pictures or decals. (Decals are images printed
with china paint—translucent overglaze— that is held in suspension on a special paper
between 2 layers of decalmania lacquer. To apply a decal to a glazed surface, it is cut
out, soaked in water for a few seconds and then the decal is slipped off to transfer the
image to the ceramic surface.)

Types of paints: 
 paints under the glaze
The coloring body of the paint is frit, which is mixed with small amount of
kaolin, alumina, or grog (to prevent the coloring body to dissolve in the glaze).
It is coated with transparent glaze and fired at 900-1000°C for a short period of
time. (Most of the coloring bodies decompose or change their color above
1000°C.)
 Majolica paints
They are paints under the glaze, but they are applied on the dried and glazed
surface and not on the glazed and fired surface. The paint sinks into the glaze
during firing.
 reactive paints
It is applied similarly to the majolica paints. The coloring body of the paint
however reacts with the components of the glaze during firing and diffusion
occurs both horizontally and vertically. As a result, the pattern spreads, the
contours will not be sharp. Because of the vertical diffusion the pattern can
“sink” into the glaze, therefore the surrounding surface will by higher than the
pattern.
 paints above the glaze
They are applied on the glazed and fired surface, then after painting a decor
firing fixes the paint. These paints are made up of the coloring body plus some
flux mixed with thick turpentine oil. The flux used is a low melting point glass.
Its role is to melt the paint at 600-900°C onto the surface of the high melting
point glaze. Gold is also applied this way. (The gold powder is mixed with oil
and some borax, HgCl and Bi(NO3)3. It is fired at 600-700°C. It sinks into
those glazes, which melt below 1100°C.)
 high-temperature paints

64
 They are applied on glazed porcelains and fired at high temperatures (1200-
1300°C). At this high temperature, the porcelain glaze softens and the pain
sinks into the glaze.
 luster paints
They are made of salts of resin acids and metal oxides diluted with oil. They
are applied as a thin film on the fired glazed surface and fired at low
temperatures. When the oil burns out in firing providing a local reducing agent,
the metal becomes fused to the surface of the glaze. A thin film of pearly luster
color will coat the glaze. Bi-luster gives white, Fe-luster gives yellowish luster
color.
Paint Glaze

Before firing
Ceramic body

After firing

Firing
temperature 1400°C 1230-1300°C 850°C

(a) (b) (c)

Application of ceramic paints (a) paint under glaze
(b) paint sinking into the glaze
(c) paint above the glaze

3.8.2 Grinding
Since the ceramic ware shrinks during drying and firing, it is difficult to keep the
dimensional accuracy of the ware. The tolerance depends on the forming method:
 slip casting ± 5%
 pressing ± 3%
 dry pressing ± 2%.
Often the tolerance required is smaller than above values. In this case, the ware is
ground with SiC grinding wheel. The local overheating of the ware is avoided by
water-cooling.

65