Raw materials for ceramic industries

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Raw materials for ceramic Industries

2.1 Introduction
Generally speaking, traditional ceramic industries use three main types of raw materials:
- Clays which give the main body of the product and ensure enough plasticity for the body to be
shaped.
- Feldspars which represent fluxing components since they melt at relatively low temperatures.
- Silica which is the main glass forming raw material.
In addition, other raw materials are often used, including limestone, magnesite (MgCO3),
soda ash (Na2CO3), bauxite (Al2O3.𝑥H2O), borax (Na2B4O7.10H2O) etc. …
A recurrent problem when dealing with ceramic raw materials in general is that their
composition is rarely kept constant over long periods of time even if they are quarried from the
same location. That is why it is important to have the following properties monitored so as to ensure
that the final product abides by the standard requirements in a continuous way:
Chemical and mineralogical composition – Particle size distribution – Plasticity for clays and
kaolin – Drying shrinkage for clays and kaolin – water absorption - color, etc.
2.2 Plastic raw materials
These may constitute more than 50% of the composition of ceramic bodies and are
necessary for the formation of the main body of the product. Besides, they impart workability to
the plastic mix formed by adding other materials such as feldspars and quartz. They are usually
related to the mineral kaolinite of chemical composition Al2O3.2SiO2.2H2O and to a lesser extent
to the mineral pyrophyllite of chemical composition Al2O3.4SiO2.H2O.
2.2.1 Structure of clay minerals
Both aforementioned minerals possess a sheet structure where Si – O tetrahedral and Al –
O – OH octahedral are the main building units. Actually, both are characterized by the presence of
a Si2O5 unit characteristic of sheet structures; the formulas of kaolinite and pyrophyllite minerals
can be written as Al2Si2O5(OH)4 and Al2Si4O10(OH)2 respectively.
Kaolinite mineral possesses a sheet structure in which the unit cell consists of one Si – O
and one Al – O – OH layers (Figure 2.1). That is why it is sometimes called a two layered type of
clay. Adjacent groups of Si – O and Al – O – OH in adjacent sheets are bonded by moderately
strong hydrogen bonds. That is why; water molecules insert themselves between the sheets with
relative difficulty, which accounts for the limited plasticity of kaolinite based clays. Figure (2.2)
details kaolinite structure.

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Si – O
Al – O – OH

Si – O
Al – O – OH

Si – O
Al – O – OH

Fig 2.1 Three Unit cells of kaolinite Fig 2.2 Two unit cells of kaolinite

On the other hand, pyrophyllite possesses a three layered structure where Al – O – OH

octahedra are sandwiched between two layers of Si – O tetrahedra. This results in the absence of
hydrogen bonds between adjacent unit cells. The only bonds between these unit cells will be of the
weak Van Der Waal type. This allows for much more water molecules to insert themselves between
the sheets causing swelling of the clay – water mix. Clay ores constituted out of that mineral are
highly expandable and are added in small amounts in conventional ceramic mixes to enhance
plasticity, a typical example being bentonite. Figures (2.3) and (2.4) illustrate the structure of this
three layered mineral.

Si – O
Al – O – OH
Si – O

Si – O
Al – O – OH
Si – O

Fig 2.3 Two Unit cells of pyrophyllite Fig 2.4 One unit cell of pyrophyllite

2.2.2 Effect of heat on clays

As clay is heated a series of physico – chemical changes take place. In case of kaolinite
based clays, adsorbed moisture is eliminated round 100 oC (Physical water). Organic impurities
usually oxidize in the temperature range 300 – 500oC. Next, chemical water is eliminated from
kaolinite molecules in the temperature range 500 – 700oC:

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Al2O3.2SiO2.2H2O = Al2O3.2SiO2 (meta-kaolinite) + 2 H2O

This reaction is associated with a theoretical weight loss of about 13.95%. In practice, this
loss ranges from 7 to 13% depending on the type of clay mineral involved. At about 900oC, meta-
kaolinite decomposes to mullite (3Al2O3.2SiO2) and cristobalite (SiO2) according to the reaction:
3 (Al2O3.2SiO2) = 3Al2O3.2SiO2 + 4 SiO2
Actually, there is much controversy regarding this reaction since γ – Al2O3 is formed at that
temperature which suggests first a decomposition of meta-kaolinite to alumina and silica followed
by a solid state reaction between part of the silica formed with alumina to form mullite. In theory,
on further heating a liquid will be formed around 1600oC. Final melting will take place at about
1900oC. In practice owing to the presence of fluxing impurities like sodium, potassium, calcium
and iron compounds, melting takes place at much lower temperatures.

Fig 2.5: The silica – alumina system

2.2.3 Clay ores

In traditional ceramic industries, two main types of clays are used, namely, kaolin clay and
ball clay. Occasionally, bentonite clay is added in minute amounts to promote plasticity.
(i) Kaolin clays
This type of clays is of metamorphic origin. It originated from the weathering of igneous
rocks over hundreds of millions of years. Consequently, it does not contain much organic impurity
and is usually white colored. However, owing to the absence of organic impurities, it suffers from
a relatively low plasticity. One factor that adds to that problem is the possible presence of non –
plastic sand in levels that may reach 40%. Also, the percent alumina in kaolin clay determines its
refractoriness ranging from 25 to 35% according to the level of sand impurities present. Kaolin
clays are usually quarried in open pits quarries.

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(ii) Ball clays

This is a sedimentary type of kaolinitic clays that has been transported over very long
distances, usually by water, to form deposits of often impure clays. The main impurities are of
organic origin owing to vegetable and animal debris that have been collected by the material. This
imparts high plasticity to the sedimentary mass that makes it often necessary to blend it with other
types to promote workability. Also, the long distance travelled by that clay type causes a gradual
reduction in the size of its particles due to their crumbling. Increased plasticity as well as reduced
particle size confers a high drying shrinkage of the wet products from the forming step. This, in
turns, produces dried articles with elevated dry strength although often of deformed shape. Most
ball clays are quarried from open pits although being sometimes obtained from tunneled mines.
The latter types are generally of higher purity than the former.
(iii) Bentonite clays
This type is a pyrophyllitic type clay that is related to the mineral montmorillonite of
chemical structure (Na,Ca)0.33.(Al,Mg)2.Si4O10. Bentonites are usually named after the dominant
cations present. Common types are sodium bentonite, potassium bentonite and calcium bentonite.
It is added in small amounts (< 1%), to ceramic mixes to promote plasticity. The main uses of
bentonite are in drilling mud and as a powerful adsorbent owing to the fineness of its particles.
Bentonite clay is known to swell in spectacular way in presence of water. This property is made
use by adding it in minute amounts to concrete mixes exposed to running water to decrease their
porosity as it swells in contact with water. The same property finds application in foundry sand
castings where small amount of bentonite are blended with the sand molds.
(iv) Shale clays
This is a type of low purity sedimentary clay in which the percent of clay minerals can be
as low as 60%. The main impurities present are quartz (about 30%), feldspars (about 5%) and iron
oxides (about 1%) besides organic matter with variable levels. Its mineralogical constitution is
usually of the kaolinite type although some sediment can also contain montmorillonite type
minerals. Its use is restricted to low cost articles in which whiteness is not a prime prerequisite like
pots and building bricks.
(v) Flint clays
This is a type of sedimentary clay of kaolinitic nature that is usually found in conjunction
with coal layers, often in coastal areas. It does not slake in water and is often associated with high
levels of silica. This type of clay has a low content of fluxing oxides making it a suitable raw
material for refractory brick making. Deposits of high purity constitute a category known as
refractory clays that possess elevated melting points.

2.2.4 Impurities present in clay ores

Clays are more often than not of low purity, particularly the sedimentary types. These
impurities strongly affect their properties in positive or negative ways. The main impurities usually
associated with clay ores are discussed in what follows:
(i) Silica
Silica is by far the most common impurity associated with clay ores where it normally exists
in the form of quartz. Its presence imparts less plasticity to clay making it less workable besides
causing severe abrasion to metallic parts in the shaping equipment. It also reduces the drying
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shrinkage thus producing dry articles with low mechanical strength. The percent silica in clays
depends also on the clay origin. Desert clays tend to contain high levels of quartz sometimes
exceeding 40%. The percentage silica present in a clay ore can be evaluated by a test known as
determination of free silica and described by Trobstl et al (2006).
(ii) Iron impurities
Iron is present in some clay deposits, particularly of the sedimentary type in the form of
goethite (FeO.OH) or hematite (Fe2O3). The percent iron oxides can constitute up to 7% of the clay
composition. Its presence has a fluxing effect on the clay, decreasing the temperature for melt
formation. It also imparts a yellowish to reddish color to the fired products shifting even to brown
if the level of iron oxides is very high. In fired articles that require a high level of whiteness, Fe
(III) reddish compounds are reduced to the almost colorless Fe (II) state by lowering the partial
pressure of oxygen in the firing kiln.
(iii) Alkali compounds
Residual clays were formed, as stated before, by the weathering action of igneous rocks.
These rocks are constituted of granite, feldspars and mica. Incomplete weathering can result in a
clay ore containing sodium or potassium ions due to the presence of feldspathic compounds. The
effect of alkalis is to exert a strong fluxing action that reduces the melting point of clay by values
that depend on the extent to which they are present.
(iv) Limestone
Limestone, mainly consisting of calcium carbonate, is sometimes present in clay deposits
as large veins. Its level does not usually exceed a few percent. Its presence is beneficial in case the
clay is to be used in wall tiles making as its presence is essential to prevent remote crazing of tile
glazed face. Otherwise, it lowers the plasticity and slightly decreases the melting point owing to
its moderate fluxing effect.
(v) Titania
Titania (TiO2) is essentially present as impurity in sedimentary clays where its content can
reach values as high as 4% while it does not usually exceed 1% in residual clays. It confers a
greyish color to the raw material and produces a slight fluxing action. Clays containing large
amounts of such impurity cannot be used whenever whiteness of the end product is a prime
prerequisite.
(vi) Organic matter
The organic matter present in clays, particularly those of the sedimentary type, usually
consists of a number of substances such as humic acid and fulvic acid. Both are not a single acid,
but rather a complex mixture of several acids produced by the biodegradation of dead organisms.
They both contain carboxyl and phenolic groups to different extents. They have been known to
increase clay plasticity since several millennia.
2. 3 Non – plastic raw materials
2.3.1 Silica
(i) Allotropic forms of crystalline silica
Silica occurs in three main allotropic forms. The form that is abundant in nature is α-quartz,
simply known as quartz. It consists of trigonal crystals that transform to hexagonal (β-quartz) when
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heated above 573oC. This type of transition is very rapid and reversible. It does not however
involve much change in the crystals dimensions: For α-quartz, a = 49.13 nm and c = 54.05 nm
while for β-quartz, a = 50.1 nm and c = 54.7 nm. That type of allotropic change is known as a
displacive transition. When slowly heated in presence of some oxide impurities β-quartz converts
to another polymorph: High tridymite. This transformation is sluggish and irreversible. It involves
a complete breakdown of the structure and is therefore termed reconstructive. High tridymite
forms as hexagonal crystals that convert to orthorhombic on cooling down below 160oC (Medium
tridymite). On further cooling below 105oC, a third monoclinic polymorph is formed: Low
tridymite.. These transitions are of the displacive type and hence occur rapidly and reversibly.
When slowly heated above 1470oC, tridymite converts irreversibly to a cubic form, known as β-
cristobalite. This form can directly be obtained from pure β-quartz when heated above 1490oC. β-
cristobalite when cooled below about 200oC transforms reversibly to a low temperature tetragonal
form: α-cristobalite. These polymorphic transformations are illustrated in Figure (2.5).
The different forms of silica undergo volume changes upon occurrence of the
aforementioned transformations. These are illustrated in Figure (2.6). This figure shows that the
displacive transitions are accompanied by relatively large expansion values. Quartz transition is
accompanied by about 1.4% increase in length while the corresponding values for tridymite and
cristobalite are 0.95% and 1.75% respectively. Such dimensional changes have a direct impact on
the operating conditions of firing kilns in the manufacture of ceramic articles.
(ii) The role of silica in the manufacture of ceramic products
Silica plays a dual role in the manufacture of ceramic products and tiles in particular. First,
being of non – plastic nature, it decreases the drying shrinkage of unfired articles. Too much silica,
however, decreases the dry strength besides causing severe abrasion to metallic parts of the forming
equipment. Besides, during firing and in presence of fluxing oxides, silica assists the formation of
a highly viscous liquid that slowly diffuses into the pores of the body. On cooling, this liquid
transforms into a glassy phase that pulls the particles together causing a firing shrinkage that
imparts high strength to the fired body. This bond formed between the particles is called the
ceramic bond.

Fig 2.5 Polymorphic forms of silica

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Fig 2.6 Volumetric changes accompanying allotropic transitions of silica

(iii) Silica ores

 Quartz crystals: The purest type of silica can be found in the form of well-shaped crystals. This
is used in the manufacture of quartz type watches and in piezoelectric applications. Smaller
bonded pure grains, called quartzite, are used in the manufacture production of refractory
bricks. If these bricks made of pure silica, they are used in the roofs of glass melting furnaces,
their commercial name being Dinas bricks.
 Quartz sand: This consists of lightly bonded quartz grains, usually of high purity and relatively
low particle size. It is essentially used in glass manufacture.
 Flint: This is a microcrystalline variety of silica, usually found in the neighborhood of sea
shores. It is used in the manufacture of whiteware products.
 Diatomite: Also called diatomic earth or kiezelguhr, this variety has evolved over millions of
years through the decarbonization of primitive living organisms constituted of two cells. Over
the millenia, there occurred a slow replacement of carbon atoms by silicon atoms finally yielding
an extremely porous type of silica. That is why it is mainly used as an adsorbing material, as
filter aid, in packaging and in a lot of other applications.
 Common sand: This is usually contaminated with iron oxides, giving it its yellowish color. It
is used in the manufacture of concrete and foundries.
 Silica fume (flour): This is an amorphous form of silica obtained as by-product of the ferrro-
silicon industry. It is composed of very fine particles of few microns size and usually possesses
a narrow particle size distribution. It is mainly used as an addition to concrete since it reacts
with calcium hydroxide present in its pores forming hydrates of calcium silicates that impart
elevated strength. Its addition to ceramic tiles has proved to be deleterious as it crystallizes to
cristobalite followed by rapid grain growth.
2.3.2 Feldspars
Feldspars are alkali or alkaline earth aluminum silicates. They are used as fluxing agents in
the ceramic industry. They are non-plastic and their addition decreases the drying shrinkage of the

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body. They are of moderate grindability, being easier to grind than quartz but more difficult than
clays. There are three main types of feldspars:
Albite or soda feldspar: Na2O. Al2O3.6SiO2,
Orthoclase or potash feldspar: K2O. Al2O3.6SiO2
Anorthite: CaO. Al2O3.2SiO2
Their fluxing power decreases in the order: K > Na > Ca, that is why; anorthite is seldom
used as flux in ceramic industries.
Their presence in a ceramic body allows lowering the firing temperatures and in presence
of silica, a viscous melt can be partly formed at a relatively low temperature. This will form the
ceramic bond upon cooling the fired body.
More often than not, the quarried feldspars are not purely sodic or potassic; rather they are
formed of a solid solution of both. Sometimes, feldspars are present in solid solution with nepheline
(K, Na) Al SiO4, in which case it is considered to be a feldspar – like material (feldspathoid) known
as nepheline syenite.
2.3.3 Carbonates
The carbonate that is mostly used in ceramic industries is calcium carbonate present in high
proportions in limestone, where its percentage can reach 99%. This is a major ingredient used in
wall tiles recipes where it is added in levels reaching 20%. Since it decomposes at temperatures in
the range 800 – 900oC, the evolution of carbon dioxide may cause troubles in the production line,
which requires careful monitoring of operating conditions in firing kilns. Dolomite, a solid solution
of calcium and magnesium carbonate is rarely used instead of limestone only if this latter is not
readily available.
Calcium carbonate is also the main raw material in cement manufacture while sodium
carbonate is used in the production of glass.
2.3.4 Alumina
Aluminum oxide occurs naturally as corundum, a very pure oxide ore, gibbsite, essentially
Al(OH)3, but more commonly as bauxite, a hydrated oxide often contaminated with iron oxides.
Alumina is extracted from bauxite through a process known as the Bayer process. It is used as a
refractory material for making crucibles, bricks, blocks, spark plugs etc…It has not been possible
to detect any bauxite on the Egyptian territory.
2.3.5 Zircon and zirconia
The chief source of zirconia (ZrO2), is zircon (ZrSiO4). It is locally found in black sand, in
the Rashid region, in north Egypt. The pure ore is used as an electrical insulator. The oxide, on the
other hand, is extremely refractory (M.P. = 2700oC) and is used alone or in association with other
oxides (like alumina and silica) to manufacture the refractory lining of glass melting tanks. It
suffers, however, from a main drawback, as it undergoes an allotropic inversion at about 1170 oC,
accompanied with a large volume change. Stabilized zirconia is obtained by adding CaO, in levels
from 10 – 20%, which forms a solid solution of reasonable volume stability. Zirconia is also used
in the manufacture of piezoelectric ceramics.

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2.3.6 Grog
Grog is a synthetic raw material obtained by calcining kaolin above 800oC. This way, the
non-plastic meta-kaolinite is formed. This is used as an addition to conventional mixes to reduce
shrinkage. Its merit over sand is that, being soft, it does not cause any abrasion of metallic
machinery used in the manufacturing processes. On the other hand, it is an essential ingredient in
the manufacture of aluminum silicate refractory materials. More often than not grog is obtained by
fine crushing of defective unglazed fired products.

Suggested additional reading

1. F.H. Norton, Elements of Ceramics, Mc Graw-Hill ed., 1968
2. W.E. Worrall, Ceramic Raw Materials, 2nd ed., Pergamon Press, 1982
3. B.V.S. Subba Rao, High Performance Ceramics, Proceedings of the seminar on high
performance ceramics, Hyderabad, 1987
4. C.B. Carter and M.G. Norton, Ceramic Materials, 1st ed., Springer science, 2007

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