Ceramics

Introduction
Traditional ceramics tend to be fragile and very brittle due to them
being quite porous. Most ceramics are electrically insulating. Clay
when added with water becomes hydro plastic, which is easily
formed. There are ceramics, which are covalently bonded, in reality
most ceramics are ionically bonded. A sintering process that
converts the material in a non-hydro plastic material with sufficient
strength and rigidity. Glass is an amorphous ceramic and it falls
under a big family of ceramics Silicates. There are the engineering
ceramics, which have superconductivity, exhibit magnetism, they
can also exhibit some order in the crystal structure and change their
dimensions and there are also ceramics, which can be used as
bearing materials and surfaces. Most ceramics are compound which
contain carbon.
Typical Properties
High hardness associated with their very strong bonding. The atoms
within a ceramic are bonded very well together. Traditional ceramics
are largely brittle however nowadays a lot of ceramics through very
controlled process can achieve high toughness. Electrons within the
ceramic are free to move, they cannot transport electricity from one
side to another they are electrically insulating. They also have
good thermal insulating properties not all of the ceramics display
such a property. They are chemically stable good resistance to
chemical attacks. At least they are not susceptible to
electrochemical corrosion. They are generally durable and non
magnetic. There are ceramics that display extremely high
magnetism.
Can be crystalline and amorphous. In ceramics generally the
bonding includes both ionic and covalent. Most ceramics include a
mixture of ionic and covalent bonding. The equation gives us the
percentage ionic character
The crystal structure of the ceramic is going to be affected by the
magnitude of the electric charge of the ions. The cations are the
components that are giving the electron while the anions are the
components that are accepting the electron. All the surrounding
anions must be in contact with the cations for the structure to be
stable. The radius of the ions depends on the valence and the
number of anions surrounding the cation.
Ceramic crystal structures
AX type where the number of cations is equal to the number of
anions.
*Know how to sketch certain structures such as Flourite unit cell.

Silicates
Silicate materials can be amorphous and some also crystalline. An
amorphous ceramic is a random structure, the ion constituting the
material are placed in a random fashion there is a no long-range
order. A crystalline ceramic is ordered, a repeat order throughout
the material. The atoms are in an ordered configuration.
The basic building block is the SiO4 tetrahedron. The tetrahedron on
its own is not neutral- 8 negative charges and 4 positive. There are
certain silicate material called island silicates can be considered as
consisting of islands of these individual tetrahedra that do not share
any oxygen atoms (unbridged) and the various individual tetrahedra
are bonded together via interstitial cations. Typical island silicates
are garnets.
Linear silicates have two bridging oxygens and two non-bridging
oxygens. They are joined together by interstitial cations that
ionically bond linear silicates together.
Sheet or layered silicates have 3 bridging oxygens and 1 nonbridging oxygen. Each 2 silicon cations would have 5 silicon anions Si2O5 with a net negative charge of 2- since there are 8 positive
charges and 10 negative charges. Example: clays.
*A 3D crystal structure of SiO2 (quartz) see slide 29. For quartz all
the oxygen atoms are bridged. For each silicon there are 4 halves
thus SiO2. Silica based materials are considered to be covalently
bonded but silicates are considered to be mainly covalent but then
sheet silcates, island and linear are joined together via ionic
bonding.
Glass is an amorphous silicate material. Different glasses are all
based on the silica tetrahedra.
SiO2 can exist in an amorphous state (fused silica is used where the
application temp. is high, where the optical properties are
important). Three polymorphs (quarts, cristobalite, tridymite) are all
composed of crystalline silica. Quartz in itself has a relatively low
density around 2.6g/cm3. It is used a lot for its appearance and also
for its hardness (kitchen tops over 95-96% quartz). Its very popular
since when it is given a charge it can vibrate at a very specific
frequency that is very precise and can be translated in to an
electrical signal that is why it is used in watches (Piezoelectric
effect).
Amorphous silicates also called fused or vitreous. These are
materials, which do not have any order within their structure. The
silica tetrahedra are arranged in a random fashion. In pure silica

(amorphous) all the oxygens are bridged thus making the material
rigid, highly viscous and having a high melting temperature.
Adding other oxides such as calcium oxide and sodium oxide
modifies commercial glasses. These oxides modify the network by
leaving interstitial cations. Other oxides that produce cations are
also added to replace the silca cations - these are called
intermediates. Network formers - other oxides that form networks
like silica. Example: Boron oxide. Adding oxides lowers the melting
temperature and changes the viscosity of the glass.
Sheet/layered silicates. Sheets of silica tetrahedra are formed by
sharing 3 out of the 4 oxygen ions. Kaolinite clay is a sheet silicate
material. This silicon cation is occupying the space between 4
oxygen anions and thus we call it a tetrahedral sheet. It has a net
negative charge largely associated with the oxygen protruding out
of the sheet. A tetrahedral sheet bonded to an octahedral sheet
with an anion midplane. For kaolinite clay the net negative charge is
balanced by an adjacent sheet that is composed by Al 2(OH)4 has 6
positive charges and 4 negative charges therefore 2+. Each Al is
surrounded by 6 anions (OH) and this is called an octahedral sheet.
For kaolinite clay in the presence of water the H2O between the
sheets makes the material hydroplastic. Not all sheet silicate
materials are hydroplastic an example is mica. It is very popular and
is used in furniture. It is also wear resistant.
Mica contains
potassium. Aluminum in mica replaces one of the silicon cations and
having potassium between the sheets bonds strongly the two sheets
together making the material non-hydroplastic.
Schematic Diagram: TOT k TOT
The tetrahedral and octahedral sheets are neutral.
Deformation in Ceramics
There are 2 main classes: crystalline and amorphous. Crystalline are
composed of ions placed in a regular manner. As stress is applied
the bonds are stretched leading to elastic deformation. To plastically
deform slip must occur. Especially in ionic ceramics the structure is
made out of ions and slip is not easy since repulsion occurs. Very
few slip systems in these materials and the charged ions repel each
other as they come close to each other making it difficult for slip to
occur resulting in a brittle material. For covalent ceramics the
component atoms within the material are strongly bonded together
through covalent bonds. For slip to occur a lot of force is required
which exceed the fracture strength of these ceramics. For non
crystalline ceramics there are no slip planes, no order, so definitely
slip cannot occur in amorphous ceramics. They can deform in the
same fashion as a liquid. The higher the energy of the bonds, the
higher the viscosity. Viscous flow would not happen near RT because
the viscosity of materials near RT is extremely high. The viscosity of

these amorphous materials is extremely high on the tune of 10 14

Pas, the non crystalline material wont be able to deform plastically.
Fracture in Ceramics
A ceramic material is composed of ions and as other materials it
contains defects such as pores, micro cracks at the surface, internal
micro cracks. As stress is applied the ceramics would not plastically
deform and thus the defects would act as stress concentrators. This
leads to premature failure. Thus, the fracture strength depends on
the manufacturing process, on the heat treatment (ex: sintering), on
the geometry and on the size of the component (a larger component
displays a lower fracture strength because of the higher probability
of finding a flaw).
With ceramics their ability to resist fracture is best described via
fracture toughness. Fracture toughness such as plane strain is
measured by pulling a block of material with a crack in tension.
a is the crack length(external crack)
a is half the crack length (internal crack)
y is a dimensionless value that depends on the specimen and the
crack geometry
k (MPam1/2)
kic=sigma y (pi a)1/2
When the RHS gets bigger than the k ic, the crack will propagate and
the component will fail catastrophically.
A ceramic exposed to a static load and after some time the ceramic
fails. This is very common with silicate materials. It is commonly
referred to static fatigue. The ceramic is in an environment under a
static stress, and the environment (ex: water) will sharpen existing
cracks within the material by interacting with the ionic bonds of the
crack. This is displayed especially in silica glasses. It is a brittle
failure and it is catastrophic.
The brittle fracture of ceramics can be explained through the aspect
that these ceramics
Do not plastically deform,
The presence of flaws within the material act as stress
concentrators cause failure at even lower stresses and
The fracture strength depends not only on the material but on
the manufacturing processes, heat treatments, geometry and
size of components.
For a SiN material the frequency distribution shows a range of
fracture strengths because it is the probability of finding a defect.
The smaller the volume of material the lower the probability to
find a flaw. In compression the flaws within a ceramic do not act

as stress concentrators therefore in compression the strength is

higher.
Ceramics usually display up to 0.001 strain before they fail. Due
to the brittle behavior, the properties, the stress-strain
characteristics are obtained using a flexural test. Given the
difficulty in preparing a ceramic component a flexural test is
normally used since the component is either a bar or a rod.
Another reason why a flexural test is used is that the specimen is
just supported and not gripped therefore avoiding breaking of the
specimen. Since ceramics fail with a very small amount of strain,
a slight misalignment could affect the result. The flexural
strength (modulus of rupture) and the tensile strength are
related. In a flexural test, from the neutral axis upwards the
specimen is under compression while from the neutral axis
downwards the specimen is under tension. Therefore, failure is
more likely to occur at the bottom. In a tensile test the specimen
is under tension only and thus it will exhibit less strength than in
the flexural test.
Defects in Ceramics
Bulk defects act as stress concentrators and affect the
strength of the ceramic.
Planar defects also act as stress concentrators and affect the
properties the strain in particular.
Linear defects such as dislocations in crystalline ceramics
Point defects such as vacancies or interstitial atoms:
Frenkel defect where a cation leaves a vacancy and
then resides somewhere nearby.
Schottky defect creates a vacancy pair where a cation
and anion migrate to a free surface. They migrate
together to keep the charge balanced: charge
neutrality. Are possible in ax compounds.
Stoichiometric defect the defect does not alter the chemical
formula of the compound.

Anti-structure disorder occurs where the ceramics are

predominantly covalent, the cation will reside in anion
position and vice versa

Non-stoichiometric defect where one of the ions can take

multiple valances.

Electronic defects occur in semiconductors such as ceramics

like GaAs (Gallium Arsenide). These defects are increased by
doping to form a p type or an n type semiconductor.

Hardness and Porosity

Ceramics are used as coating on metals and grit for polishing
abrasive materials (sand paper).
Higher porosity tends to negatively impact the properties of the
material: lowers strength, toughness, thermal and shock resistance.
As porosity is increased in alumina both the fracture and the
strength decrease.
Glass
It is a class of ceramics that is very important mainly due to its
optical properties and is used in the form optic fibres and lenses.
Additives are added to the pure silica to control the viscosity
temperature relationship for that particular glass. Different types of
glass include: soda-lime glass, pyrex etc.
The specific volume vs. temperature of glass
At high temperature the glass is liquid and the viscosity is low. As
the temp decreases the density decreases and at the tg the atoms
become much less mobile and thus the glass becomes solid. Above
tg the glass is called supercool glass.
Slide 47 all glasses are amorphous except for glass-ceramic. Fused
silica is composed entirely of silica. It has a very high melting
temperature and is very difficult to process. It also has a low thermal
coefficient of expansion therefore it has a much higher resistance to
thermal shock and it is very expensive. It is transparent to UV and is
used a lot in UV lamps.
Vycor is very expensive. It is high in silica content. It is more
chemically resistant than normal glass. It consists of 4% network
former. Used a lot in lab ware.
Pyrex Borosilicate contains a lot of boron oxides, which control the
viscosity and make the material resistant to thermal shock. Used in
ovens. Much easier to form compared to fused silica.
Soda lime or normal glass, it has a working temperature which is
must lower than the rest, a low melting temperature and cheap to
produce artifacts from it. Does not have good thermal shock
resistance.
Viscosity-temperature curves. This relationship is related to how
these materials will flow around the melting temperature. The
viscosity of water is 10-3.
The melting point- the temp at which the glass would have a
viscosity of 10Nsm-2
The working range-the glass can be very easily deformed.
Glass is formed in this region. Materials like fused silica are

much more difficult and expensive to work since the working

temperature is much higher. *see graph
The softening point-the temperature at which the glass can be
handled without deformation
The annealing point-the glass is held at the annealing point so
that any residual stresses in the glass would be eliminated.
The strain point-below this temperature fracture will occur
before any plastic deformation takes place
The network formers, additives affect the viscosity temperature
relationship.
Glass forming
Pressing thick pieces pressed in dies
Blowing a gob of glass is given a preliminary shape and
blown into a die. It is a fast and rather cheap process.
Drawing pulling the glass through a die. Easily performed
with soda lime.
Sheet forming- float process- a process in which glass sheets
are produced. A furnace filled with the required ingredients
and melted, this molten glass flows on tin and surface tension
effects will encourage the glass to spread over the bar of
liquid tin. The heater heats the glass at a temperature within
the working range of the glass in order to enable the glass to
flow and form a flat polished surface. The glass is then cut into
several sheets. Glass sheets used to be very expensive
Fibre drawing raw material will also include modifiers,
placed inside a furnace, molten, homogenized, refined and
goes into channels-forehearths- each die will have hundreds of
holes where glass comes out as fibres which are wound on
various spools, The velocity of the spool is much higher than
the velocity of the glass coming out resulting in tension in
fibres.
Annealing and tempering
Annealing to relieve the thermal stresses. Tempering is very
different from annealing and has nothing to do with the tempering
of steels. The heat treatment process leads to compressive stresses
at the surface and tensile stresses at the core. During cooling the
surface of the glass will shrink since it cools first. As the core cools
down it tries to shrink and it compresses the surface. The core of
the sheet will be in tension while the surface of the sheet will be in
compression. This makes the glass stronger since as the glass is
being bent, any crack in the surface has to first overcome the
residual compressive strength.
Glass ceramics are not entirely amorphous. Produced by the
crystallization of inorganic glass by heat treatment. Titanium dioxide

acts as a nucleant that promotes crystallization during heat

treatment. Much more resistant to fracture, since the start material
is glass which leads to less deformations than if it were powder.
Have a low coefficient of thermal expansion. Most of the glass used
on oven doors is made out of a glass ceramic. Even more the glass
covers on electric hobs are made out of glass ceramic. As the temp
is increased the crystalline phase has a characteristic where it
shrinks while the amorphous phase expands thus they balance out
each other.
At the working range the material is formed. Up to this pint it is still
amorphous. At the nucleation crystallites start to form and the
atoms form a crystalline phase. The lower the temperature the
more nucleation sites that is why the nucleation temperature is low.
Clay
Clays are hydro plastic when water is added i.e. easily deformed at
RT. Another characteristic is that when sintered or fired they start to
melt over a range of temperatures.
Non-plastic ingredients are added:
Quartz
Fluxes feldspars
Slip Casting is a very cheap way to produce ceramics. The final
product is normally glazed so that it would seal and be non porous.
Plaster of paris as the mold.
Abrasives and Erodents
Since ceramics are hard materials they are used as abrasives.
Ceramic abrasives are used in grinding wheels.
Other ceramics are used as erodents such as alumina and garnets.
Garnets tend to break on impact and thus exposing sharp edges
after every impact. This makes them reusable
Pressing and Sintering
Common techniques to produce ceramic components. The starting
material will be a powder ceramic that is mixed with a binder (ex:
polymer). When pressed, the green part is then placed in a furnace,
the binder is allowed to escape. The most conventional way is
uniaxial pressing. Other techniques include hot pressing or hot
isostatic pressing where pressure is applied all around the part.