MATE1000 Lecture 24 Ceramics

(Callister, Chap. 2, p. 20-24; Chap. 13, p. 381-389 & 406-415; Chap. 20, p. 664-670)

What is a Ceramic?
Ceramics are inorganic, non-metallic materials that are usually compounds of two (or more)
elements. The interatomic bonding between the atoms in a ceramic varies from completely
ionic (if the elements comprising the ceramic come from opposite sides of the periodic table)
to mainly covalent (if the elements come from the middle of the periodic table). Traditional
examples of ceramics are china, porcelain, bricks and tiles. More modern examples include
zirconia (ZrO2) and silicon carbide (SiC).

Crystal Structures of Ceramics

The crystal structures of ceramics are often more complex than simple metals, which are
elements or solid solutions of one element in another. In ceramics with predominantly ionic
bonding the crystal structures are made up of electrically charged ions rather than atoms. The
metallic ions (from the left of the periodic table are positively charged cations), because
they have given up their valence electrons to the non-metallic ions the anions, which are
negatively charged and come from the right hand side of the periodic table.
To ensure that the solid ceramic is electrically neutral the sum of the positive charges on the
cations must balance the negative charges on the anions. Hence, Na+ and Cl- will form NaCl,
Ca2+ and F- will form CaF2 and Al3+ and O2- will form Al2O3.
The other factor that governs the crystal structure of the ceramic is the ionic radii of the
cations (rc) and anions (ra). The cations, which have lost electrons, are usually smaller than
the anions, which have gained electrons - ie rc/ra < 1. Each cation wants to have as many
anions around it as possible, and each anion also requires the maximum number of cation
nearest neighbours. Stable ceramic structures form when the anions surrounding a cation are
all in contact with that cation. The resulting coordination number the number of anion
nearest neighbours per cation depends on the ratio rc/ra. To form a solid the ions must
adopt a three-dimensional arrangement. This means the coordination number must be
either 4 (cation at the centre of a tetrahedron of 4 anions), 6 (cation at the centre of an
octahedron of 6 anions), 8 (cation at the centre of a cube of 8 anions) or 12 (cation surrounded
by 12 anions with rc 1).

rc/ra = 0.225 - 0.414 rc/ra = 0.414 - 0.732 rc/ra = 0.732 - 1.0

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When the elements making up the ceramic come from the centre of the periodic table, the
ionic character of the bonding reduces and it becomes more covalent in nature. Extreme
examples are diamond or SiC, where the bonding is almost entirely covalent see Table at
right. With the reduction in the ionic character of the
bonding the radius ratio (rc/ra) rules governing the Material %ge Ionic
different crystal structures become much less important. Character
Instead the structures formed depend on the number of CaF2 89
valence electrons (N). With N valence electrons the MgO 73
maximum number of bonds that can be formed is 8 - N. NaCl 67
For N 6, molecules or chains are formed (eg. Cl2 & O2 Al2O3 63
or Se). N = 5 leads to molecules or sheets of atoms (eg. SiO2 51
As, Sb, Bi). Only when N = 4, and the maximum number Si3N4 30
of bonds is 4 can the covalently bonded atoms form a ZnS 18
three dimensional crystal structure the ZnS structure SiC 12
(eg. diamond or SiC) with coordination number 4.
Note that covalent bonds are strong, directional bonds that link specific atoms.

Carbon
Carbon is a unique material usually classified as a ceramic because of its strongly covalent
bonding. It is usually used as fuel (coal, coke), but it can exist in several polymorphic forms,
which may be hard (diamond) or soft (graphite).
Graphite is the stable form of carbon at normal temperatures and pressures. It has a layer
structure with carbon atoms in a hexagonal arrangement each carbon atom in the layer is
bonded to three other carbon atoms. The remaining electron in each atom participates in a
weaker, delocalised bond between the layers. Sliding of one layer over another is therefore
particularly easy the reason why graphite is such
a good solid lubricant. Other desirable properties
of graphite are reasonable electrical conductivity
parallel to the hexagonal sheets (see later), high
strength and chemical stability at elevated
temperatures in non-oxidising atmospheres, low
coefficient of thermal expansion, high thermal
conductivity and resistance to thermal shock (see
later) and good machinability.
Diamonds crystal structure is a variant of the zinc blende (ZnS) structure with carbon atoms
occupying all positions Zn and S. Each carbon atom is covalently bonded to 4 other carbon
atoms to form an extremely strong three-dimensional network. Diamond is one of the hardest
substances known, is optically transparent with a high refractive index, and has low electrical
conductivity, but reasonably high thermal conductivity. It is an extremely valuable material
even for industrial applications (abrasives, grinding materials, drill tips, etc.). Hence, the
considerable effort devoted to making artificial diamonds - at high temperatures (1800K) and
pressures (200kb) or diamond films/coatings by chemical vapour-phase deposition.
Fullerenes are the most recently discovered (1985) form of carbon and consist of hollow
spherical clusters of say 60 carbon atoms buckyballs named after Buckminster Fuller who
invented the geodesic dome. Other forms, including nanoscale tubes, have been produced.

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The Properties of Ceramics
Typical properties of ceramics are:-
high melting point (applications in furnaces and engines),
low electrical and thermal conductivity (applications as insulators),
high elastic modulus combined with low density (applications where weight reduction is
important),
high compressive strength, but very low tensile strength and fracture toughness
(applications in construction where stresses are compressive),
chemically inert (applications in corrosive or oxidising atmospheres),
In many cases inexpensive and easy to fabricate.
A comparison of some typical properties of metals and ceramics is shown below.
Typical Values
Property
Metals Ceramics
Electrical Conductivity (-1m-1) 7
110 to 610 7
110-12 to 110-1
Thermal Conductivity (Wm-1K-1) 30 to 300 2 to 40
Thermal Expansion (K-1) -6
1210 to 2410 -6
210 to 1010-6
-6

Density (Kgm-3) 2000 to 8000 2000 to 4000

Elastic Modulus (GPa) 50 to 200 100 to 500+
Tensile Strength (MPa) 100 to 1500 50 to 700
Fracture Toughness (MPam-) 20 to 80+ 2 to 12
Elongation 2 to 40% NIL
Many of these properties can be explained in terms of the interatomic bonds in ceramics.

Mechanical Properties
With very few exceptions, ceramics have high elastic moduli because of the strong ionic
or covalent interatomic bonds. Examples of the high Youngs modulus of ceramics include
diamond (1000 GPa), SiC (440 GPa), Al2O3 (390 GPa) and ZrO2 (200 GPa). Graphite (27
GPa) is one exception because of the weak bonding between the hexagonal sheets of carbon
atoms.
Unlike metals, ceramics are not ductile and are
extremely difficult to deform. Metals deform by slip
the sliding of one layer of atoms over another. This
is easy because the bonds between metal atoms are not
directed and, because the atoms are all identical, it
does not matter if atoms in one layer move from one
stable position to the next.
In ionic crystals slip is very difficult because the
process of sliding atoms over each other disturbs the
arrangement of the electrically charged ions, and
forces similarly charged ions to be next to one another.
In covalent crystals the bonds are directed and form a
framework that resists deformation.
Hence, dislocations move easily in metals, but are very
difficult to move in ceramics, except at high temperatures.

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When ceramics are loaded in tension, they reach stresses at which pre-existing cracks can
propagate and cause failure, well before they can deform. Ceramics are therefore very brittle
in tension, have essentially zero ductility and low fracture toughness. Ceramics can only
resist compressive stresses, which do not cause cracks to grow.

Conductivity
Electrical conductivity of ceramics is usually low because there are no mobile charge
carriers, such as the free electrons in metals. In covalently bonded ceramics the electrons
are tied up in the interatomic bonds and are not free to move. An exception is graphite,
where the three of the four valence electrons are associated with the bonding in the sheets
while the fourth valence electron is not localised and can contribute to electrical conductivity.
In ionic crystals the ions have stable outer electron shells, as a result of the give and take
of valence electrons. This means that the electrons can not contribute to electrical
conductivity. However, if an ionic crystal is melted, the ions themselves can conduct
electricity.
Thermal conductivity in solid materials is the result of heat being transported by thermal
vibration of the atoms and by the movement of free electrons. The electronic component
of heat transfer in ceramics is very small, because of the absence of free electrons. However,
some heat conduction can occur via thermal vibration of the atoms or ions.

Thermal Stresses and Thermal Shock Resistance

Most solid materials expand on heating (and
contract on cooling). On heating the atoms
vibrate and their potential energy increases.
This thermal expansion is the result of an
increase in potential energy caused by the
thermal vibration. Provided the curve of
potential energy as a function of interatomic
distance is asymmetric (as it is in most
materials), then increasing the potential
energy results in an increase in the average
interatomic spacing, as shown in the diagram.
The greater the interatomic bonding forces
the deeper and narrower the potential energy
trough becomes. Hence, materials with very
strong interatomic bonds (eg. ceramics) will
have lower thermal expansion coefficients
than materials with weaker interatomic bonds
(eg. metals and, to an even greater extent,
polymers).
Thermal stresses result from restrained thermal expansion or contraction. For example, if a
material of length L is rigidly clamped at either end and is then heated up by an amount T,
the change in length is TL, where is the coefficient of thermal expansion (units K-1).
The strain () in the rigidly clamped bar is = T, and this generates a stress = ET,
where E is the elastic modulus of the material. These thermal stresses can be very large
for example, in alumina a temperature change of only 300K will generate a stress of 960MPa!

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The buckling of railway lines (without adequate provision for expansion via expansion joints)
is a classic example of restrained thermal expansion. However, thermal stresses can be
generated in apparently unrestrained solid bodies, provided the temperature distribution inside
the body is not uniform.
When a solid body is heated or cooled the internal temperature distribution will depend on the
size and shape of the body, the thermal conductivity of the material and the rate of
temperature change. Rapid heating (or cooling) of large bodies of a material with a low
thermal conductivity will result in the establishment of significant temperature gradients.
For example a thick plate rapidly heated from the outside may still have relatively low
temperatures in the centre of the plate, while its exterior is quite hot. This temperature
gradient will generate compressive stresses in the surface, where the material tries to expand
and is prevented from doing so by the cooler material at the centre of the plate. The surface
compressive stresses will be balanced by tensile stresses in the interior of the plate. If an
originally hot plate is cooled rapidly, the temperature gradients and the resulting stresses are
reversed tensile stresses in the surface balanced by internal compressive stresses
Ductile materials, such as metals (and polymers), can accommodate the thermally induced
stresses via plastic deformation. Brittle materials like ceramics cannot do this, and any
significant thermally induced tensile stresses (thermal shock) can result in brittle fracture.
Surface damage can produce flaws and microcracks, so brittle ceramics are more susceptible
to thermal shock on cooling (tensile surface stresses) rather than on heating (compressive
surface stresses).
The ability of a material to withstand this form of failure is known as its thermal shock
resistance. This depends on both the thermal and the mechanical properties of the material.
For a given temperature change T, increasing the thermal conductivity (k) of the material
will reduce the thermal gradients and hence the resulting thermal stresses. The thermal stress
is proportional to the elastic modulus (E) and the coefficient of expansion (), so that
reducing these two material properties will improve the thermal shock resistance. Finally, the
possibility of brittle failure depends on the fracture strength (f) of the material. The
resistance of a material to thermal shock can therefore be related to a thermal shock
resistance parameter (TSR) given by:

fk
TSR
E
If altering the heating/cooling rates or minimising temperature gradients by changing the
shape of a component can not prevent thermal shock, a material with more appropriate values
of the properties in the equation above should be selected. The easiest parameter to control is
probably the thermal expansion coefficient. For example, reducing the CaO and Na2O
contents of glass and adding sufficient B2O5 to form borosilicate glass (Pyrex), reduces the
thermal expansion coefficient by a factor of 3. This is sufficient for cooking utensils.
Polycrystalline aggregates of lithium aluminium silicate, which is anisotropic with thermal
expansion coefficients that vary from 6.510-6 K-1 to minus 210-6 K-1, have an average
thermal expansion coefficient close to zero and are suitable for domestic ceramic cooking
hobs. Introducing porosity or ductile phases, which serve to impede propagation of
thermally induced cracks, is another approach to increasing thermal shock resistance by
raising f.