Ceramics

1.0 Overview
Stone and granite are the oldest known ceramics. Their use in the construction industry has
been largely replaced by two other ceramics, cement and concrete. The last 10 years has seen
a significant development in the area of ceramics with the advent of an exciting range of high
performance engineering ceramics which have the potential to replace and possibly improve
on metals in many demanding applications. These ceramics are very wear resistant making
them suitable for tools, their inertness makes them ideal for biocompatible applications like
hip replacement joints. Their high melting temperature has resulted in a development
programme looking into applications in turbines and turbo chargers. Modern body armour is
made from a ceramic sewn into a fabric vest.
One way of classifying ceramics is into 5 groups:-

1. Glasses
2. Vitreous ceramics (clay products, brick etc.)
3. High performance ceramics (alumina, zirconia etc.)
4. Cement and concrete
5. Rock and minerals

Although the properties of ceramics do differ, they have one common and undesirable
feature. They are all brittle. Most ceramic materials are cheap as the main constituents of
many include silicon, aluminium, oxygen and nitrogen which occur abundantly. However, it
is the processing costs that make ceramics expensive.

Self-test activity – Write a list of the advantages and disadvantages of using ceramics
materials. Include processing, properties and in service use.

1.1 Crystal Structures

The bonding in a material determines many of its properties. The brittleness and electrical
conductivity of ceramics is due to the type of bonds present. Ceramics can either be purely
ionic or purely covalently bonded, but most are a mixture of the two types. The crystal
structures of ceramics can be complicated so only some simple examples are used here.
Glasses are considered in a separate section. Ceramics, like other materials, will contain
structural defects and impurities. We can exploit these defects to give electrical conductivity
via ionic diffusion. An example of this is the solid oxide fuel cell. Metals can be added to
glasses to get amber, blue and green glass.
Lead and silver in glass can give a range of reflected colours.

1.1a Ionic Ceramics

These typically occur between a metal and non-metal e.g. alumina Al2O3 and zirconia ZrO2.
Like the ionic bond between sodium and chlorine in sodium chloride the metal atoms have a
positive charge (electropositive) and the non-metal a negative charge (electronegative). The
strong attraction between these unlike charges results in an ionic bond. The simple ceramic
structure based on a general formula AB has what is called the 'rock salt' structure based on
sodium chloride. Here, to achieve the maximum electrostatic interaction each Na+ has 6 Cl-
neighbours and no Na+ and vice versa. This is the most efficient way of arranging single
charged species. The NaCl crystal is made up of a face centred cubic arrangement of sodium
ions interlocked with a face centred cubic chlorine crystal. Other ceramic structures of
general formula AB2, for example, have more complicated structures determined by the
requirement for overall electrical neutrality and ion size.

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1.1b Covalent Ceramics
These are compounds of two non-metals e.g. silica SiO2 or are just pure elements e.g.
diamond and graphite from carbon. The structure of covalent ceramics are that they are not
so densely packed and are often non-crystalline, e.g. commercial glasses are amorphous
networks based on silica. Perhaps the ultimate covalent ceramic is diamond which has a 4 co-
ordinated arrangement of carbon atoms within the cubic unit cell. It is not a close packed
structure (close packed structures have 12 neighbours = co-ordination number of 12) so its
density is low. Diamond is extremely hard with exceptional wear resistance and is very
strong. Very hard structural ceramics like silicon carbide SiC are used for load bearing
components, high temperature bearings and engine parts and has a structure close to that of
diamond and is one of the hardest known substances.

Self-test question – How does the interatomic bonding and crystal structure of a ceramic
relate to some of the advantages and disadvantages on your list from Section 1.0?

Self-test activity – Compare the atomic arrangement of carbon as diamond to that of carbon
as graphite and a buckyball.

1.2 Forming of Engineering Ceramics

1.2a Powder Pressing and Sintering

Because of their high melting points ceramics cannot be processed by techniques used in
polymers and metals. A different technique is used called 'sintering' where the ceramic in
powder form is compressed at a temperature usually around 2/3Tm. Under these conditions
the particles 'sinter', that is, they bond together reducing the surface area of the particles and
increasing in density. Full density is not achieved by this technique, as there is some residual
porosity in the form of small rounded holes, Fig 1. This porosity can be as high as 20% and
the pores tend to weaken the ceramic by inducing stress concentrations, although for rounded
pores this can be small. More serious is the presence of cracks, Fig. 2, which usually cannot
be seen but are nevertheless present in most ceramics as a result of the processing. Longer
sintering can reduce porosity but inevitably there will still be some residual porosity.
Sintering aids can be added to the raw ceramic powder to achieve maximum density, usually
by introducing a low melting point glassy phase.
Crystalline ceramics form polycrystalline microstructures similar to metals, each grain is
more or less a perfect crystal meeting its neighbours at grain boundaries. Higher densities
and smaller grains are obtained by a different technique, “hot pressing or hot isostatic
pressing”, the simultaneous application of temperature and high pressure to a ceramic
powder. The powder is squeezed in a die or pressure vessel while it is at its sintering
temperature. Full density can only be reached by pressure sintering. The shorter process time
compared to normal sintering gives no opportunity for grain growth and as a consequence the
mechanical properties are good. Die pressing allows precision products to be manufactured
without any subsequent finishing. The drawback is that the dies and process are expensive.

pore

a) particles after pressing b) pore formation as c) pores grow smaller as

sintering begins sintering proceeds

Figure 1. Particle coalescence during sintering

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Grain boundaries Microcracks caused by
where two thermal or mechanical
crystals meet stress

Pores left by
processing Grains (crystals)
of the ceramic

Fig. 2 A typical crystalline ceramic microstructure

1.2b Reaction Bonding

Some ceramics are produced by what is called 'reaction bonding' e.g. silicon carbide SiC.
This process is cheaper that sintering and gives good precision. If the silicon and carbon
powders are sintered together a simultaneous reaction takes place forming silicon carbide.

Si + C = SiC

Occasionally the silicon/carbon mixture is mixed with polymers to make it plastic allowing it
to be rolled, extruded or pressed as in normal polymer processing. In this way complicated
shapes can be achieved. The polymer is 'burnt out' at high temperature where the silicon and
carbon react. However, like all good ideas there is a penalty to be paid and that is the
porosity is high, formed from voids left by the polymer. On the plus side the dimensional
stability after sintering is usually of the order of 0.1% which makes finishing operations
unnecessary.

1.2c Slip Casting

Ceramic shapes can be cast by a technique called 'slip casting'. This technique has the
advantage of forming thin walled and complex shapes of uniform thickness. It is also used as
an economical means of producing development parts and on short production runs. This
process consists of a stable suspension or 'slip' of the ceramic, clay and water. This is then
poured into a porous mould, usually plaster of Paris, allowing the water to be absorbed near
the surface and leaving a semi hard layer. Pouring out the remainder of the 'slip' leaves this
semi-hard layer on the surface of the mould. The mould material is then dried and the
ceramic part is then removed from the mould and then 'fired' at the appropriate temperature
to give the final ceramic. Variations of this technique include pressure and vacuum casting
where the 'slip' is shaped under vacuum or pressure.

Note: There are many other specialised ceramics processes, especially in the electronics
industry, such as tape making and the production of films. One way to produce thin films that
has been extensively researched and developed at Brunel is ink jet printing. Another novel
route to form some ceramics is to start with a special polymer, called a pre-ceramic polymer,
and then convert it to a ceramic. Glasses and ceramics can also be produced in fibre form.

Self-test questions – Why are ceramics so difficult to process? What sort of problems can
occur in a ceramic material because of the processing route?

1.3 Ceramic Materials and Applications

Ceramic materials are most useful in high temperature applications because of their
mechanical and physical properties, corrosion resistance and inertness. Another way of
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classifying ceramics is into one of six groups: glasses; clay products; refractories; abrasives;
cements; advanced ceramics. The last group, detailed below, includes carbides, borides,
nitrides and oxides.

Alumina (Al2O3)
* Operates at high temperatures where good strength is required
* Used in electrical applications where high electrical and thermal resistance is required
* Classic example is the motor car spark plug insulator
* Used in replacement body parts like hip joints because of its inertness

Aluminium nitride (AlN)

* Good electrical insulator but has a higher thermal conductivity than alumina because of its
simpler atomic structure so it is a suitable replacement for alumina particularly where
electrical insulation and good thermal conductivity is required. Its thermal expansion
coefficient is close to that of silicon making it useful as an integrated circuit substrate.

Zirconia (ZrO2)
* Can be transformation toughened
* Used as a thermal barrier coating on superalloy aircraft turbine engine components

Silicon carbide (SiC)

* Hard refractory carbide
* Outstanding oxidation resistance at high temperatures
* Used as a protective coating on other ceramics and metals against extreme temperatures

Silicon nitride (S3N4)

* Most useful combination of engineering properties
* Oxidation and high temperature strength lower than silicon carbide
* Used in automotive and gas turbine engines providing higher operating temperatures for
less weight compared to metals.

Titanium diboride (TiB2)

* Good conductor of heat and electricity
* Excellent toughness
* Used for body armour

Sialon (Si3Al3O3N5)
* Good stiffness and fracture toughness
* Low thermal expansion
* Used in engine components
* Used for high temperature and wear environments

Urania (UO2)
* Nuclear reactor fuel
* Excellent dimensional stability
* Crystal structure can accommodate the products of the fission process

Self-test questions – What are the advantages of using ceramic components in internal
combustion engines? What factors are limiting the development of the ceramic engine?

1.4 Joining of Ceramics

Ceramics cannot be bolted or riveted as the contact stress would cause a brittle failure. For
this reason ceramics tend to be bonded to other ceramics or metals using techniques which
minimise these stress concentrations.
Diffusion bonding of ceramics is a result of the parts being heated and compressed until they
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fuse together, similar to 'sintering' the parts together. Even dissimilar materials can be
bonded in this way.
Glaze bonding is achieved by coating the parts in a low melting point glass (600 oC). The
parts are pressed together and the temperature raised to the melting point of the glass.
Ceramics can be joined to metals by using adhesives or by brazing. Brazing the two together
is achieved by first applying a thin metal coating e.g. molybdenum to the surface of the
ceramic to be joined. The metal part is then brazed to the treated ceramic surface. Epoxy
resins can also be used to join parts at low temperature.

1.5 Electrical Properties

Ceramics are used in many electrical and electronic applications such as electrical insulators
and capacitors. The ionic and covalent bonding in ceramics restricts their electron mobility
which gives them excellent insulating properties. The chemical composition and
microstructure of electrical grade ceramics must be closely controlled.
Some ceramic materials become superconducting at higher critical temperatures than metals
but still below room temperature. An example is yttrium barium copper oxide (YBa2Cu3O7).
It becomes superconducting at 92K which means it can be cooled with liquid nitrogen.
Liquid nitrogen is cheaper then liquid hydrogen and liquid helium. The inherent brittleness of
the materials is limiting its fabrication into some useful superconducting shapes, such as
wires.

1.6 Thermal Properties

In general ceramics are good thermal insulators. Because of their high heat resistance they
are used as refractories where hot liquid and gaseous environments are encountered,
particularly in the metal, chemical and glass industries. At higher temperatures, thermal
conductivity by radiant heat transfer can occur. This is more pronounced with optically clear
materials.
Ceramics used in insulation are usually porous. Heat transfer across pores is low as they
contain air. Room temperature thermal conductivity of ceramics is between 2 and 50 W.m-
1
.K-1 and air is 0.02 W.m-1.K-1.

1.7 Mechanical Properties

Ceramics are brittle and the strength of ceramics varies considerably. Many ceramics are
hard and have low impact resistance. Ceramics have a well defined Young’s modulus which
is generally higher than those of metals (elastic deformation of metallic bond compared to an
ionic or covalent bond) and this is one of the reasons why ceramics and glasses are used as
reinforcing agents in composite materials.
The inherent brittleness of ceramic materials is further exaggerated by the presence of cracks,
porosity, foreign inclusions, glassy phases and large grain sizes which may be introduced
during manufacturing. These flaws vary in size, shape and orientation within a single
component and from component to component. This limits the ceramic to withstand a tensile
stress as a crack or flaw will tend to concentrate the applied stress. The crack propagates and
leads to failure of the ceramic.
A simple relationship has been formulated by Griffith, Fig 3., which states that for a flaw or
crack the stress at the tip of the crack is given by;

σa ∀ 2 σ √a/r

Where σa actual tip stress

σ applied tensile stress
a length of the crack
r radius of the crack

The stress at the tip of the crack is therefore large when the radius of the crack is small or the
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length of the crack is large. If the actual tip stress exceeds the yield strength of the ceramic
then the crack will propagate and cause failure even if the applied stress may be small.

Radius, r

σ
Fig. 3 A Griffith flaw in a ceramic component

A typical stress/strain curves for ceramics is that of a brittle material, Fig.4. Because of their
rigid ionic and covalent structures ceramics do not undergo appreciable elastic deformation
and as a consequence the modulus of elasticity (Young’s modulus) is large. Failure of the
ceramic occurs with little, if any, plastic deformation and no localised reduction in area 'neck'
as seen on ductile materials. Little or no plastic deformation is typical of a brittle fracture.
The strength of ceramics as we have seen is determined by many factors, chemical
composition, microstructure, flaws and cracks, temperature and environment. Grain
boundaries are an important surface defect in ceramics where the smaller the grain size the
stronger the ceramic as the finer grains help to reduce stresses that develop at grain
boundaries. Smaller grain sizes are a result of using finer ceramic raw materials.

250

Aluminium Oxide

Stress (MPa)

Glass

0 6
0 0.0012
strain
Figure 4: A stress/strain curve for alumina and glass. Both fail in a brittle manner.

The slope of the curve represents Young’s Modulus, also called the elastic modulus. The
Young’s modulus for alumina is one of the highest at 393GPA. Fused silica glass 73GPa,
soda lime glass 69GPa. Steel has a value of 207 GPa. The higher the modulus, the stiffer the
material.
The modulus of a ceramic decreases as porosity increases.

Self-test question – Why are ceramics so weak when bond strength suggests they should be
strong?

1.8 Glasses
Glass is a ceramic material based on silica, silicon dioxide (SiO2). Unlike crystalline
ceramics, the constituents of glass are heated to fusion and cooled to a rigid state which is
amorphous in structure i.e. no long range order. Fused silica glass, the most important single
component glass, has a high spectral transmission and is not subject to radiation damage
which causes 'browning' in other glasses. This makes it an ideal glass for space vehicle
windows and optical systems in spectrophotometric devices. However, it is difficult to
process because of its high melting point and is expensive.
Glass used in bottle manufacture contains additives such as soda, NaO, to reduce the melting
temperature and make the glass much cheaper.

There are a number of different glasses. The common ones are listed here.
1. Fused silica
Difficult to melt and fabricate, usable to 1000oC, very low expansion and high thermal shock
resistance. Used in optical systems and specialist windows.
2. Soda lime
Easily fabricated, widely used in varying grades, used in windows, containers, electric bulbs.
Its chemical and heat resistance is poor.
3. Lead silicate
Readily melted and fabricated with good electrical properties. High lead absorbs X-rays.
Used in low melting solder sealing glasses, radiation windows, fluorescent lamp envelopes.
They have a high refractive index and are used in some optical glasses.
4. Borosilicate (trade name Pyrex in cookware)
Low expansion, good thermal shock resistance and chemical stability, widely used in the
chemical industry.
5. Low alkali (E-glass)
Widely used as fibres in composites.

Figure 5 shows the arrangement of

oxygen, silicon and sodium in soda glass.
There is short range order in that every
oxygen forms two bonds to a silicon and
every silicon has four bonds to an
oxygen. There is no long range order so
glass has an amorphous structure. The
sodium ions penetrate the network and
lower the melting point, making the glass
7 easier to work with.
Self-test question - What are the advantages and disadvantages of using glass as a
packaging material?

1.9 Strengthening Ceramics

Ceramics have a very poor fracture toughness which can limit the scope of their application.
There are a number of ways of improving the toughness of ceramics. One is to incorporate a
softer, tougher matrix material into the brittle ceramic matrix. This type of material is
referred to as a CERMET. An example is the incorporation of a cobalt metal matrix into
tungsten carbide (WC) which is used for cutting tools and abrasives. The material retains the
hardness and cutting ability of tungsten carbide while the softer ductile cobalt deforms and
absorbs energy.

Because of the inherent porosity, structural defects and impurities that can exist in a ceramic
structure, the strength of a particular ceramic can vary significantly even with supposedly
identical pieces. It is this phenomenon that poses a serious problem to designers, particularly
where they are going to be used to carry load. How does the designer evaluate the strength of
ceramics with such a scatter in strength values?
The Weibull distribution is a statistical means of describing the fraction of ceramic samples
that will fail under a particular applied stress. Most ceramics fail at an intermediate applied
stress with some failing at lower and higher applied stresses. But there is still the problem
that there is a good probability of failure at low stresses and it is this uncertainty that limits
the use of ceramics in critical applications. In order to produce more reliable ceramics, high
purity raw materials and complex processing is essential which makes the final product
expensive. Smaller particle size and accurate characterisation of particle shape is essential to
decrease the possibility of microcracks and porosity. Techniques have been developed based
on injection moulding which squeezes the powders together under high pressures and leads to
better consolidation.

So what can the engineer do to improve the variability in strength of components?

DON'T * use sharp corners or notches which can act as stress raisers

DO * ensure good surface finishes

* utilise compressive joints and connections rather than flanges etc.
* allow for thermal expansion mismatch, particularly with metals
* take into account batch to batch variations
* be aware of the effect processing can have on the structure and
properties of a component

1.10 A Few More Applications of Advanced Ceramics

Application Property required Ceramic

Bearings Excellent surface finish Zirconia, Alumina

Wear resistance Silicon carbide

Cutting blades Excellent surface finish Sialon, zirconia

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 High strength

Abrasive wheels High strength, wear resistance Sialon, Alumina

Good toughness Silicon carbide

Prostheses High strength, wear resistance Alumina, zirconia

excellent surface finish,
biocompatible

Gas turbine blades High temperature strength Silicon nitride

Creep resistance, thermal shock
resistance.

Engine components Thermal insulation, wear resistance Zirconia, alumina

silicon carbide.

1.11 Summary
Ceramics are brittle materials but very strong and wear resistance. They can be used at high
temperatures and don’t corrode easily. Most ceramics occurring naturally are crystalline,
except for the glasses which have an amorphous structure. They can be cheap as in building
materials but special ceramics, like superconductors, can be very expensive. Their processing
is difficult and expensive and usually involves a powder route. The powders are compressed
into the desired shape and then sintered at high temperature. The powders consolidate but
small pores and cracks can remain, which weakens the structure. Ceramics break well below
the strengths predicted by their atomic bonding.