Conventional ceramics:

aluminosilicate, clay, and glaze

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Aluminum Silicate
Alumina, Al2O3, and silica, SiO2, are two most abundant
minerals of the earth crust. The class of minerals containing
aluminum oxide and silicon oxide is called aluminum silicates.
Many minerals contain aluminum and silicon oxides. For
example, three minerals andalusite, sillimanite, and kayanite all
have the same chemical composition of Al2O(SiO4). Topaz is
closely related in chemical composition, Al2O(SiO4)(OH,F)2.
Beryl, Be3Al2(Si6O18, contains rings of (SiO3)6 type. It is usually
found in cavities of granite. This mineral is also known as
aquamarine, a precious stone. This is the main source of Be
metal. A closely related mineral is cordierite, Al3(Mg,
Fe)2(Si5AlO18).
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Aluminum Silicate, cont
Layer aluminum silicates such as
kaolinite goup of minerals of
Al4(Si4O10)(OH)8 is resulted from
weathering of feldspar group of
minerals, (K, Na)(AlSi3O8, or
Ca(Al2Si2O8. The kaolinite group is an
important clay mineral.
The picture shown here is the structure
of kaolinite. Two layers are shown here,
the bottom octahedral layer represent
the oxygen atoms and the 6-coordinated
Al atoms or ions. Some of these oxygen
atoms are shared with 4-coordionated
silicon on the top layer, each
tetrahedron represent a SiO4 group.

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What are Aluminosilicates?
When some of the Si4+ ions in silicates are replaced by Al3+ ions, the group is called
aluminosilicate. For each Si4+ ion replaced by an Al3+, the charge must be balanced by
having other positive ions such as Na+, K+, and Ca2+ ions. Feldspar group and zeolites are
typical aluminosilicates by this definition.
For example, the following minerals belong to the feldspar group.
Sanidine, [(K,Na)AlSi3O8]4
Orthoclase, [(K, Na)AlSi3O8]4
Albite, [NaAlSi3O8]4
Anorthite, Ca[Al2Si2O8]
The alkali ions are held in place to balance the charges due to the presence of Al3+ ions
instead of Si4+ ions. The Al3+ ions seem replace Si4+ ions in the chains of corner shared
tetrahedra of SiO4 groups.
However, the bonding between Al and Si can be different. Silicon atoms or ions tend to
be bonded to 4 oxygen atoms in a tetrahedral fashion, but aluminum ions tend to be
bonded to 6 oxygen atoms in an octahedral fashion.

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Aluminosilicate
Aluminosilicate minerals are minerals composed of
aluminium, silicon, and oxygen. They are a major
component of kaolin and other clay minerals.
Andalusite, kyanite, and sillimanite are naturally
occurring aluminosilicate minerals that have the
composition Al2SiO5.
Hydrated aluminosilicate minerals are referred to as
zeolites and are porous structures that are natural
occurring materials.
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Aluminosilicate, cont
In general, aluminosilicate structures can be grouped
into: silimanite (Al2SiO5), andalusite (Al2SiO5),
kyanite (Al2SiO5), and topaz (Al2SiO4(F,OH)2).

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Aluminosilicate, cont
Zeolite is a class of hydrated aluminosilicates, consist of large cage-like
structures with open channelways.
Jaujasite is a representative zeolite. This link represented its structure using
large polyhedra. All lines in the structure shown are oxygen bridges -O-, the
oxygen atom is located not on the line but somewhere next to it. The angle -
O- of the two bonds is about 110. Points where lines meet are the locations
of Si4+ that are surrounded tetrahedrally by four oxygen atoms. They can be
substituted by Al3+. As a result, the frame work is negatively charged. Thus,
zeolites can trap positive ions: H+, Na+, K+, Ca2+, Cu2+ or Mg2+.
The name 'zeolite' is said to have its origin in the two Greek words zeo and
lithos which mean 'to boil' and 'a stone'. The phenomena of melting and
boiling at the same time is a novel property. The name 'zeolite' was first
used by the Swedish mineralogist Cronstedt to describe stilbite, the first
recognized mineral zeolite, which was discovered in 1756. Over 100 years
later, the reversible desorption/adsorption of water in this mineral was
recognized.
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Clay
The term clay is used in a number of ways. It can refer to:
A member of a large group of fine-grained platy minerals
related to micas.
It can refer to a mixture of minerals with clay-size particles,
i.e. <1/256 mm)--These are generally dominated by clay
minerals.
It can refer to a mass of minerals (primarily clay minerals)
that behave plastically when wet.
In this lecture, we will consider clay as a mass of minerals
dominated by clay minerals.

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Clay, cont
Clay is a natural earthy, fine-grained material
comprised largely of a group of crystalline minerals
known as the clay minerals.
These minerals are hydrous silicates composed mainly
of silica, alumina, and water.
Several of the clay minerals also contain appreciable
quantities of iron, alkalis, and alkaline earths.

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Structure of Clay
Clay minerals are hydrous (water) aluminum
phyllosilicates (sheet silicates)
Clay minerals are made of three basic building blocks:

Sheets of linked Sheets of linked

silica tetrahedra alumina octahedra

Plus assorted positive ions that bond these sheets together,

mostly hydrogen (protons), potassium, iron, and
magnesium.
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Structure of Clay Alumina
Silica

In both cases, silica sheets and Hydrogen ions

alumina sheets are covalently Alumina

bonded (oxygen atoms share Silica
electrons). Alumina
The result is a composite Silica
Potassium ions
aluminosilicate sheet. Silica
Alumina
These composite sheets are Silica
Potassium ions
ionically bonded together by Silica
Alumina
positive hydrogen or metallic ions.
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Properties of Clay
When slightly wet, clay is typically highly cohesive
(i.e. it sticks together very well).
This relates to the high surface area of the broad, flat
surfaces of the mineral grains.
Small amounts of water cling to the clay particles
and each other, producing a high degree of
intergranular cohesion.
This is similar to what happens when you take two
pieces of glass, put some water in between them and
then push them together (one on top of another).
If you have ever tried this you will note that it is
relatively difficult to pull the plates apart or to push
them in opposite directions.

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Occurring of Clay
There are many different kinds of clay minerals, but on a practical level,
we can loosely categorize clays into two main types:
Primary clays (also called china clays or kaolin)
Found close to their original site of formation (i.e. site of weathering
or alteration) due to little or no post-formation transport.
Consist mostly of the clay mineral kaolinite
Secondary clays (also called sedimentary clays)
Transported from original site of formation (i.e. site of weathering)
found far away from their original site of weathering
Can contain kaolinite, but also generally also contain other clay
minerals as well as quartz, iron oxides, and organic matter (more
heterogeneous).

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Clay used for traditional ceramics
Rarely do potters use a clay from a single source as a working
clay.
Most ceramic clays are blends of materials from different
sources.
Experience has taught us that the best results are obtained
when several different clays are blended together.
Such a blended clay is called a clay body.
By blending, potters can vary the texture and color of their
clays.
A material called grog (crushed quartz or pre-baked clay) is
also added to some clay bodies.

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Grog in ceramics
Grog is commonly either sand or fired clay which has been crushed
and sized (typically much coarser than the main potting material).
Grog particles are larger and more rigid than clay particles and lack
water content which allows them (in sufficiently high concentrations)
to effectively stiffen the soft clay matrix.
Grog reduces the shrinkage effects associated with firing due to its
inability to contain or retain water.
Therefore, its presence reduces the overall shrinkage of the clay
during the drying (dehydration) process; more grog = less overall
shrinkage, less grog = more shrinkage.
Less shrinkage means that less clay is required to produce a finished
piece of a given volume.

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Clay bodies
Clay bodies can be loosely categorized into
three basic types:
Earthenware
Stoneware
Porcelain

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Earthenware
Typically made from secondary clays.
Well suited for the manufacture of thick-
walled vessels such as mugs, plates, and
flower pots.
Cheapest to make (secondary clays more
common than primary clays).
Not fired to vitrification temperatures
(relatively low T; 900-1100 deg. C).
Colour can range from white to terra cotta
(if iron oxide present).
Texture ranges from fine to rough,
depending on grog content
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Stoneware
Made mostly from primary clays bodies.
Suited for the manufacture of vessels that are
stronger (thinner walled) than earthenware
Also used to make non-porous products such as
floor tiles and drainage pipes.
Typically not fired to vitrification temperatures
(intermediate T; 1200-1300 deg. C).
Often coarse in texture (contains grog).
Color: usually brown due to presence of iron
oxide.
Textured often with fine speckles
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Porcelain
Made from primary clays.
Suited for manufacture of very thin objects
that are very strong (e.g. dinnerware).
Smooth texture (no grog).
Homogeneous composition and lack of grog
requires vitrification (High T; 1200-1500 deg.
C).
Porcelain was produced as early as 10th
century in Asia (hence the term China for
high quality porcelain).
Bone is sometimes added to the clay for more
translucent appearance (hence bone china)
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From Clay Body to Ceramics
Air drying:
A ceramic piece is air-dried to a greenware state before it is fired.
Wet clay contains a large amount of water (25 % minimum). When clay dries, water evaporates
from it.
As this happens, clay particles are drawn closer together, resulting in shrinkage.
If drying (and therefore shrinkage) is uneven, stresses are produced in the clay, forming cracks
or warped areas. This is why it is important to ensure that the piece is of fairly uniform
thickness and that the clay is thoroughly mixed (if more than one type is being used).
Kiln drying:
Complete drying doesn't take place until the piece is placed in the kiln.
This happens when the boiling point of water has been reached.
Water molecules between the clay particles are then evaporated away.
Evaporation of the water content of the clay must be allowed to occur slowly, or the formation
of steam within the body of the clay may cause it to burst.

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The Big Transformation
After all the free water is driven off (above 500 deg. C), the major
transformations of the clay take place.
At this point, the clay is irreversibly changed as hydrogen and oxygen
of the clay minerals are driven off as water.
The remaining solid material of the clay produces the minerals
mullite and quartz.
3 Al2Si2O5(OH)4 Al6Si2O3 + 4 SiO2 + 6 H2O
Kaolinite (s) mullite(s) quartz(s) water(g)
Mullite is a mineral which occurs only rarely in nature

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Crystal structure change
The strength of fired clay is increased
by the formation of a meshwork of
needle-like mullite crystals.
Mullite is an aluminum silicate mineral
characterized by elongate crystals.
These lace the structure together,
giving it cohesion and strength.

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Vitrification
Finally, the mineral components of the
ceramic fuse together.
Glass fills in spaces between the
interlocking mullite crystals, binding them
together.
When cooled, the ceramic, now made of
fused mineral components, is hard and
durable.
Some shrinkage can occur at this point.
Thus, heating conditions must be carefully
controlled.
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Differences in Firing Temperatures
Clays vitrify at various temperatures depending upon the clay minerals
present, as well as the amount of impurities (e.g. iron oxides) present
in the clay body.
Primary clays (as used in porcelain) vitrify at very high temperatures
(1250 1400 oC). This is because the clay body (almost pure kaolinite)
has a very high melting point.
Secondary clays (as used in earthenware) vitrify at lower temperatures
(700- 1200 oC). Iron oxides in such clays can contribute to lowering the
average melting point of the clay body.
Porosity also differs between items made of primary and secondary
clays primary clays produce items with lower porosity than those
made of secondary clays.
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Glaze
After the ceramic has completed its firing process, it is
glazed.
Glaze is a layer or coating of a vitreous substance which has
been fired to fuse to a ceramic object to color, decorate,
strengthen or waterproof it.
Glaze is basically a form of glass, consisting basically of
Glass-forming minerals (e.g. silica, feldspar)
Stiffeners (such as clay)
Fluxes which lower the melting point of the other glaze
components (calcite and dolomite are common fluxes).
When fired, these ingredients melt (over 2000 oC). A glass
results from cooling of this molten stuff

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Glaze, cont
Just as impurities can alter the color of natural minerals,
small amounts of certain substances can be added to glaze
to produce different colors.
Common glaze additives and resulting colors are:
Copper oxide: greens and blues
Cobalt oxide: blues and violet
Iron oxide: yellow, orange and red
Manganese dioxide: deep purple
Additives are also used to increase the opacity of glazes.
Common ones are titanium oxide and tin oxide.
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