Structure of ceramics

Amjad Hanif
Learning objectives

At the end of this lecture the students will be to

• Describe the composition and structure of ceramics.

• Explain the properties of the ceramics.

Ceramics
• The word ceramic is derived from the Greek word keramos which literally
means ‘burnt stuff’ but which has come to mean more specifically a material
produced by burning or firing.

• The first ceramics fabricated by man were earthenware pots used for
domestic purposes. This material is opaque, relatively weak and porous and
would be unsuitable for dental applications.

• It consisted mainly of kaolin.

Structure of Ceramics

• Ceramics are compounds of metallic elements and non metallic

substances such as oxides, nitrides and silicates. (Dental ceramics are
non metallic inorganic structures primarily containing compounds of
oxygen with one or more metallic or semi metallic elements).

• Ceramics can appear as either crystalline or amorphous solids, the

latter group being called glasses.
• Zinc oxide is a type of ceramic widely used in dentistry.

• There are many other applications of ceramics in dentistry; they are

used as

1. Fillers for composite resins

2. In glass ionomer cements

3. In investments and porcelains.

Ceramic raw materials

• Silica (SiO2) forms the basis of many ceramics and can exist in many
different forms.

• Silica occurs as a crystalline material in the form of quartz,

crystoballite and tridymite or as glass as in the example of fused silica

• This ability of a compound such as silica to exist in different forms

with distinctly different characteristics is known as polymorphism.
• Silica is used as the basis for the formation of many complex ceramic
formulations particularly in combination with aluminium oxide with which
it forms alumino silicate glasses as used in glass ionomer cements.

• Similarly, feldspathic glasses are used in ceramic restorations and are

compounds containing oxides of aluminium and silicon in combination
with potassium, sodium or calcium.
Crystalline and amorphous ceramics
Crystal transitions

When a solid is heated, it can undergo a number of transformations, the

most easily recognizable of which is when the solid melts. This change
of crystal from solid to liquid is known as crystal melting transition and
is accompanied by a change in the volume of a material.
Crystal transition

A simple means of representing this change is to plot the specific volume of a

material against the temperature. There is a sharp rise in volume of the
material at the melting point of the crystal. Figure 1

This is not surprising when one thinks that this transition is one from an
ordered crystalline structure to that of disordered liquid; the packing density of
the atoms in the liquid will be considerably less than that in the crystalline
solid.
Figure 1

Figure 1
Crystal transition
• The specific volume temperature curve for crystalline silica is as
shown in Figure 2. In this diagram there are number of solid-solid
transitions as well as the usual transition from solid to liquid. Silica is
in the form of quartz at room temperature which changes to tridymite
at 870C.
• A further transformation takes place at 1471C, where tridymite
changes to crystobalite.
• Crystobalite finally melts at 1713C.
Figure 2
Glass transition
• When an amorphous solid such as a glass is heated, it does not show a
discrete solid-liquid transition as the material is not crystalline. Instead
what happens is that, at some point, there is an increase in the rate of
change of the specific volume as shown in Figure 3. The temperature
at which this change in the slope of the specific volume occurs is
known as the glass transition temperature, Tg
• Solids which are formed by moving through a glass transition rather
than a crystal melting transition will be amorphous and are referred to
as glasses.
Figure 3
Formation of a glass
• Due to regular shapes atoms tend to form ordered structures. Small
molecule such as methane are able to form crystalline structure and
even linear alkanes form crystalline structure but large irregular
molecules have a high probability of forming glass on solidification
• For crystals to grow nuclei of crystallization must be present. These
are usually in the form of impurities such as dust particles that are
virtually impossible to exclude. Thus if there is any chance that the
material can take up an ordered crystalline structure, it will usually do
so.
Formation of glasses
• Silica can form either glasses or crystalline solids and their specific
volume temperature curves are shown in figure 4. When crystallization
occurs on cooling there is a sharp (curve a) discrete reduction in
specific volume. This contraction is due to configurational contraction
as there is large increase in the packing fraction when changing from a
disordered liquid to an ordered crystalline solid. Once this sharp
contraction is completed the material continues to contract by normal
thermal contraction.
Figure 4
• If crystallization did not occur, the material would follow curve b; the
liquid continues to contract, partly by normal thermal contraction and
partly by configurational contraction.
• This contraction continues as the temperature drops, until Tg, the glass
transition temperature is reached, where upon the rate of contraction
slows down markedly. At this point the configurational contraction has
stopped and only normal thermal contraction is taking place.
The formation of a glass
• What happens at the glass transition temperature is that the super
cooled liquid has become so viscous that configurational changes can
no longer take place and the liquid structure has been frozen in. The
temperature at which this occurs is not a sharply defined point but is a
range of temperature of some 50 C represented by bend in the curve.
Once the super cooled liquid has cooled to below its glass transition
temperature, it is now described as glass.
The Formation of a Glass
The question is “What happens at Tm that determines whether the crystal or glass
forming” route is followed?”
Vitrification
• When silica melts, it produces an extremely viscous liquid, which
means that the molecules can only move past one another very slowly.
This is not conducive to the formation of crystalline solid, since
crystallization requires rapid rearrangement of the molecules.
• Any crystal nuclei will therefore tend to grow very slowly especially
given the complex structure of crystalline silica, which is similar to
that of diamond.
• Thus if a liquid is cooled quickly, the solid formed is likely to be glass.
The process of forming of glass is called vitrification.
Glass Formers

• The essential component that allows the formation of glass is silica,

which can itself become either a glass or a crystalline solid on cooling.

• The formation of glass can be understood more simply by considering

two dimensional representation, in which one bond is missing from
each of the atoms in the silica
Figure 5: Two dimensional representation of
crystalline silica (a) position of atoms (b) oxygen
triangles
Glass formers
• When molten silica is cooled rapidly, the crystalline structure does not
have time to form, so the silica solidifies as a glass which is called
fused glass (Figure 6). The high melting point of this material 1713C
makes it too expensive for general use. If certain metal oxides are
mixed with silica, the melting temperature is greatly reduced.
• As an example a composition of three quarters silica and one quarter
sodium oxide will melt at only 1339C. Such oxides are called mixed
oxide glasses (Figure7)
Glass Formers
• The metal atoms form positive ions that disrupt the oxygen tetrahedra
such that not all of the oxygen atoms are shared(Figure 7). The silica
plays the role of a glass former and the metal oxide acts a glass modifier.
• Oxides of titanium, zinc, lead and aluminium can all take part in the
formation of glassy network and produce stiff network structures.
• Soda(Na2O) and lime (CaO) considerably lowers the viscosity and thus
the Tg, by causing extensive disruption of the network. This eases the
production of glass.
• Boric oxide (B2O3) is also capable of acting as a glass former, producing
boron glasses
Glass Former
• Although it is possible to make glasses from mixture of crystalline
silica and metal oxides, this is an expensive approach. It is much
cheaper to use naturally occurring minerals with the required glassy
structure, because the nature has already carried out the vitrification
process.
• At one time only naturally occurring feldspars were used by the
manufacturer and these were modified with other metallic oxides to
produce fillers and dental porcelains with the required properties.
Nowadays many glasses are produced synthetically, as this allows
greater control over the composition and properties.
Devitrification
• It is possible that a small amount of crystallization will occur in the
production of a glass, although the rate of crystal growth is very low.
• When a glass begins to crystallize, the process is called devitrification.
It may happen when the glass is kept at an elevated temperature for a
long time, allowing some reorganization of the molecules. The glass
will tend to take on a translucent appearance due to the scattering of
light from the surface of small crystals. This is the basis of formation
of glass ceramics.
Figure 6
Figure 7
Two dimensional representation of pure silica
Two dimensional representation of
glass (a) position of atoms (b) oxygen
mixed oxide(a) position of atoms
trinagles
(b) oxygen triangle