Ceramics and composites

- Dr. P. Anbarasi
Assistant Professor
Department of Metallurgical Engineering
PSG College of Technology, Coimbatore
 Chapters
• Chapter 1 – Introduction to ceramic structures and defects
• Chapter 2 – Property prediction of engineering ceramics
• Chapter 3 – Introduction to composites
• Chapter 4 – Particulate composites
• Chapter 5 – Laminar composites
Text books:
1. Kingery W D, “Introduction to Ceramics”, John Wiley, USA, 2011.
2. Chawla K K, “Composite Materials”, Springer, NewYork, 2006
References:
3. Broutman L J, Krock, “Modern Composite Materials”, Addison
Wesley Publishers, Massachusetts, 1967
4. Michael Barsoum, “Fundamentals of Ceramics”, McGraw Hill, 2002.
5. Daniel B Miracle, Donaldson S L, “ASM Handbook, Volume 21 -
Composites”, ASM International, 2008.
6. Matthews F L, Rawlings R D, “Composite Materials: Engineering and
Science”, Woodhead Publishing, 1999.
 Chapter 1 – Introduction to ceramic
structures and defects
Topics:
1. Covalent and ionic ceramics
2. Typical ceramic crystal structures: Sodium chloride,
cesium chloride, alumina, spinel and fluorite structures
- examples.
3. Problems in crystal systems (Pauling’s Rules)
4. Silicate structures, Structures of Glasses and properties
5. Simple problems involving packing fraction, critical
radius ratio and density
6. Defects in ceramics - problems
 Covalent and ionic ceramics
Ceramics – “the art and science of making and
using solid articles, which have, as their
essential component, and are composed in large
part of inorganic, nonmetallic materials”
Bonding
 Unfilled outermost electron shells
 Inert gases – full outer electron shells – stable
 Primary interatomic bonds – metallic, ionic and
covalent
 Secondary mechanism – Van der Waals bonds
 Metallic bonding
 Predominant bonding mechanism for metals
 Valence electrons are freely shared by all the atoms in the structure
 Mutual attraction of all the nuclei in the structure to this same cloud of
shared electrons results in metallic bond.
 Due to the uniform distribution of valence electrons in a metal and due
to the same size of all atoms, close packed structures results in a pure
metal
 Such close packed structures contain many slip planes, along which
movement can occur during mechanical loading, producing the ductility
for metals.
 Free movement of electrons through the metallic structure results in
high electrical conductivity and thermal conductivity
 Alkali metals (Na, K) – bonded by outer ‘s’ electrons – have low bond
energy, low strength and low melting temperatures and not very stable
 Transition metals (Cr, Fe, W) – bonded by inner electrons – have higher
bond strength, high strength, high melting temperatures and are more
stable.
 Ionic bonding
 Ionic compounds generally form between quite active metallic elements and active nonmetals
 Occurs when one atom gives up one or more electrons and another atom or atoms accept
these electrons such that electrical neutrality is maintained and each atom achieves a stable,
filled electron shell

 Ionic compounds are typically hard and brittle and are poor electrical and thermal conductors.
 Ionic bonding is restricted mostly to metals from groups 1, 2 and 3, as well as some of the
transition metals
 Crystal structure of an ionically bonded material is
determined by the number of atoms of each element
required for electrical neutrality
 Optimum packing is based on the relative size of the
ions (ionic radius)
 Ionic radius varies slightly depending on the number
and type of oppositely charged ions surrounding an
ion.
 The relative size of the ions determines the CN of ions
and the crystal structure
 For most ionically bonded structures, the anions are
positioned in a close-packed arrangement.
 The cations fit between the anions in the interstitial
positions that are closest to the size of the cations.
For cation-to-anion ratios between 0.155
and 0.225 – a CN of 3 is most probable with
anions at the corners of a triangle around
the cation
For ratios in the range of 0.225 and 0.414 –
a CN of 4 is most probable with anions at
the corners of a tetrahedron around the
cation.
Ratios of 0.414-0.732 and greater than
0.732 are most likely to result in CNs of 6
and 8, respectively.
 In MgO, Mg2+ has a CN of 6 and O2- also has a CN of 6.
 O2- ions are arranged in a cubic close packed structure with the Mg2+ ions filling the
octahedral interstitial positions

 Na+ and Cl- bond in the same way to form Nacl.

 This structure is called Rocksalt structure.
 Larger the electronegativity difference between atoms in a compound, larger the degree
of ionic character
 Monovalent ions in groups IA (Li, Na, K, etc.) and VIIA (F, Cl, Br, etc.) produce compounds
that are highly ionic – low strength, low melting temperatures and low hardness
 Ionic compounds with more highly charged ions such as Mg2+, Al3+ and Zr4+ have stronger
bonds – higher strength, higher melting temperatures and higher hardness
 Covalent bonding
• Occurs when two or more atoms share electrons such
that each achieves a stable, filled electron shell.
• Unlike metallic and ionic bonds, covalent bonds are
directional.
• Each covalent bond consists of an electron shared
between two atoms such that the probability
distribution for the electron resembles a blunt dumbbell.
• Covalent bonding occurs between atoms of similar
electronegativity that are not close in electronic
structure to the inert gas configuration.
• Atoms such as C, N, Si, Ge, and Te are of intermediate
electronegativity and form highly covalent structures.
 Ionic and covalent bond combinations
• Many ceramic materials – combination of both ionic
and covalent bonds
• Gypsum (CaSO4.2H2O) – Sulphur is covalently bonded to
oxygen to produce SO42-, which is 2 electrons short,
whereas Ca donates two electrons and is ionically
bonded to SO42- .
• Similar type of combined bonding results in many
silicate compositions that are so important to ceramic
technology.
• These silicate structures are based on SiO44- tetrahedron
and the various ways these tetrahedra can be linked.
Typical ceramic crystal structures
Rock salt structure:

•Named for the mineral NaCl.

•Structure is cubic with anions arranged in

cubic close packing with all the interstitial
octahedral sites occupied by the cations.

•Structure consists of alternating cations

and anions along each of the three unit cell
axes [100], [010], and [001] crystal
directions.

•Examples : KCl, LiF, MgO, CaO, FeO, MnO,

NiO.
Location of tetrahedral and octahedral
interstitial sites within FCC

•Number of
octahedral sites is
always equal to
the number of
atoms

•Number of
tetrahedral sites is
always double the
number of atoms.
• Fluorite structure Named after the mineral fluorite CaF2.

The cations are large and fit into the large body-
centered position formed by the simple cubic
arrangement of anions.

Because the cations have twice the charge of the

anions, only half of the cation sites are occupied.

This results in a structure with relatively large holes.

The unit cell is based on FCC packing of cations.

In fluorite structure, the co-
ordination number of cations is 8 and
the anions are in a simple cubic
arrangement.

In antifluorite structure, anions are

in FCC arrangement, while cations fill
the tetrahedral sites.

Both structures can be viewed as

two interlaced structures: an FCC and
a simple cubic.
• Cesium chloride structure
The CsCl structure
involves cations that are
too large to fit into the
octahedral interstitial site.

They fit into the larger

cavity at the center of a
simple cube with the
anions at each corner.

This is similar to the BCC

structure of a metal.

Compositions with [CsCl]

structure include CsCl,
CsBr, and CsI.
Alumina crystal structure
Hexagonal based binary ceramic
of major importance – corundum
structure.

Aluminium oxide is the most

important material with this
structure.

In single crystal form, it is referred

to as sapphire or ruby depending on
its colour.

The O2- anions are arranged in

nearly hexagonal close packing.

The cations fill two-thirds of the

octahedral interstitial sites.
 Spinel
• Ternary structure – consists of close packed
arrangement of anions with two different sizes
or charges of cations fitting into the
appropriate interstitial positions.
• Spinel – named after the naturally occuring
mineral MgAl2O4 has a general formula of
AB2O4 where the A and B cations are in the +2
and +3 oxidation states, respectively.
• Cubic structure – combination of rock salt and
zinc blende (ccp of anions with tetrahedral co-
ordination)structures.
• 1 unit cell = 8 subcells
• 1 subcell structure consists of 4 atoms, 4
octahedral interstices, and 8 tetrahedral
interstices.
• 1 unit cell consists of 32 Oxygen anions, 32
Octahedral interstices and 64 tetrahedral
interstices, among which only ½ of the
octahedral interstices and 1/8 of tetrahedral
interstices are filled.
• Therefore, 1 unit cell of spinel contains 32
oxygen ions, 16 octahedral cations, and 8
tetrahedral cations.
• When the A2+ ions exclusively occupy the tetrahedral
sites and the B3+ ions occupy the octahedral sites –
normal spinel.
• Examples: ZnFe2O4, CdFe2O4, MgAl2O4, FeAl2O4, CoAl2O4,
NiAl2O4, MnAl2O4 and ZnAl2O4.
• Inverse spinel – A2+ ions and one half of the B3+ ions
occupy the octahedral sites, while the other half of the
B3+ ions occupy the tetrahedral sites, B(AB)O4.
• Many of the important ceramic materials with
magnetic properties have the [inverse spinel] structure.
• Examples: FeMgFeO4, FeTiFeO4, Fe3O4, ZnSnZnO4,
FeNiFeO4.
 Structure of silicates
• The earth’s crust and mantle – mainly of
silicate minerals.
• The silica structures involves small cations
with a charge of 4+.
• The radius ratio is approximately 0.33, which
indicates that tetrahedral coordination is
stable for the Si4+ cation.

• In SiO2, 4 oxygen ions are almost invariably arrayed around a

central silicon, whereas, oxygen ions are coordinated with only
two silicon atoms.
• This low coordination number makes close – packed structures
impossible for SiO2. Therefore, silicates generally have more
open structures.
• SiO2 -Each 4 Oxygen atoms are shared by neighbouring SiO4
tetrahedra. Each Si atom shares ½ of the four oxygen atoms.
Therefore, Si : O = 1:2.
• Depending on the shape of the repeat units, silicate
structures have been classified as follows:

Double chains
3D network

Chains Isolated Tetrahedra

Infinite sheets
• Two types of oxygen exists in silicate structures: bridging
oxygen and nonbridging oxygen.
• Bridging oxygen – An oxygen atom that is bonded to two
silicon atoms.
• Nonbridging oxygen (NBO) – An oxygen atom that is bonded
to one silicon atom. It is formed by the addition of, either
alkali or alkali-earth metal oxides to silica.

Where, O- denotes a NBO.

• NBOs are negatively charged and the local charge neutrality is
maintained by having the cations end up adjacent to the NBOs.
• The number of NBOs is proportional to the
number of moles of alkali or alkali-earth metal
oxide added.
• The addition of alkali or alkali-earth metal
oxides to silica must increase the overall O/Si
ratio of the silicate.
• Increasing the number of NBOs results in the
progressive breakdown of the silicate structure
into smaller units.
• Therefore, a critical parameter that determines
the silicate structures is the number of NBOs
per tetrahedron, which in turn is determined by
the O/Si ratio.
Structure O/Si ratio No. Of O per Si Examples
Bridging NBO
3 Dimensional 2.00 4.0 0.0 Quartz,
network Tridymite,
Cristobalite
Infinite sheets 2.50 3.0 1.0 Kaolinite, mica,
talc
Double chains 2.75 2.5 1.5 Asbestos

Chains 3.00 2.0 2.0 Na2SiO3, MgSiO3

Isolated 4.00 0.0 4.0 Mg2SiO4 olivine,

Li4SiO4

• The number of NBO per Si = Charge on the repeat unit/no. of Si

atoms in the repeat unit
• For example, the repeat unit for double chain structure is (Si4O11)6-.
• The charge on the repeat unit is 6, and the no. of Si atoms is 4.
Therefore, number of NBO per Si is 6/4 = 1.5.
• Si-O bond is partly covalent and the
tetrahedron satisfies both the
bonding requirements of covalent
directionality and the relative size
ratio.
• Because of the high charge on Si4+ ion,
the tetrahedral units are rarely joined
edge-to-edge and never face-to-face,
but almost always share corners, with
no more than two tetrahedra sharing
one corner.
• Reason – cation separation distance
decreases in going from corner to
edge to face sharing, which in turn
results in cation-cation repulsions and
a decrease in the stability of the
structure
• The SiO4 tetrahedra can be linked in compounds such that corners are
shared in several ways.
• There are 4 general types.
(i) Orthosilicates (SiO4)4- or island silicates:
- When the O/Si ratio is 4, the structural units are isolated tetrahedra
(SiO4)4- , which cannot be joined to each other, and have four bond
positions available to link up with cations or other coordination polyhedra.

- Examples :Garnets (Mg, Fe2+, Mn, Ca)3(Cr, Al, Fe3+)2(SiO4)3 ,

Olivines (Mg, Fe2+)2SiO4 , Zircon, aluminosilicates – Kyanite,
sillimanite, andalusite and mullite.
• (ii) Pyrosilicates (Si2O7)6- :
- Two tetrahedra with one corner shared.
- Crystalline silicates containing (Si2O7)6- ions
are rare.
• (iii) Metasilicates (SiO3)2-(SiO3)n2n- :
- Involves the sharing of two corners to yield cyclic or chain
structures.
- O/Si ratio is 3.0.
- Some of the discrete cyclic ions observed are the Si3O96- and
Si6O1812- ions.
• Minerals with chain structures comprise a large group.
• Those with composition corresponding to single chain, (SiO3)n2n- are the
pyroxenes, and those with double chains, (Si4O11)n6n-, the amphiboles.
• The most notorious of chain silicates is asbestos (double chain), in which
the silicate chains are held together by weak electrostatic forces that are
easier to pull apart than the bonds holding the chains together.\
• This results in stringy, fibrous structure that embeds in human lungs with
devastating long term consequences.
• (iv) Layer structure or sheet
silicates:
- When 3 out of 4 oxygens are
shared, sheet structures results.
- (Si2O5)n layers of SiO4
tetrahedra are linked to AlO(OH)2
octahedral layers.
- O/Si ratio is 2.5.
- The structure of many minerals
have this O/Si ratio and the
differences between them is in
simply how the sheets are
connected.
- Examples: Kaolinite Al2(Si2O5)
(OH)4, talcs and mica.
• Silica:
- For SiO2, each oxygen atom is
linked to two Si atoms and
each Si is linked to four
oxygens, resulting in a three
dimensional network.

- The resulting structures are

all allotropes of silica (quartz,
tridymite and cristobalite)
which depends on the exact
arrangement of tetrahedra.

- If long range ordering is

lacking, the resulting solid is
called amorphous silica or
fused quartz
 Glass
• Glasses are supercooled liquids that solidify without crystallizing.

• Unlike a crystal, glass does not have a sharp melting point when
heated. It gradually softens and flows at high temperatures.

• If a liquid is cooled rapidly enough such that the atoms do not

have enough time to rearrange themselves in a crystalline pattern,
before their motion is arrested, a glass is formed.

• The transformation of liquid to crystalline solid occurs by the

formation of nuclei and their subsequent growth – both processes
require time.

• If the rate of removal of thermal energy is faster than the time

needed for crystallization, the latter will not occur and a glass will
form.
 Glass formation
• Two main mechanisms by which a liquid crystallizes
are: (i) Homogeneous nucleation and (ii)
Heterogeneous nucleation.
• Homogeneous nucleation – nucleation that occurs
without the benefit of preexisting heterogeneities.
• Heterogeneous nucleation – occurs at
heterogeneities in the melt, such as container walls,
insoluble inclusions and free surfaces.
• Crystal nucleation occurs almost always
heterogeneously on impurity particles, or container
walls, at relatively low ΔTs.
• Once the nuclei are formed, they will tend to grow
until they start to impinge upon each other.
 Criteria for glass formation
• The following conditions must exist for the
formation of glass:
• (i) low nucleation rate. This occurs if ΔSf is small
or the crystal/liquid interfacial energy, γsl, is high
• (ii) High viscosity, at or near the melting point, ηm
– low growth rate
• (iii) Absence of heterogeneities.
• Based on (i) and (ii), a useful criterion for the
formation of a glass is the ratio ΔSf /ηm. The
smaller this ratio, the more likely a melt will form
a glass and vice-versa.
 Glass production
• Regardless of the source of the components used to
produce a specific glass, the batch materials can be divided
into 5 categories based on their role in the process:
• (i) glass former
• (ii) flux
• (iii) property modifier
• (iv)colorant
• (v) fining agent.
• The same component may be classed into different
categories when used for different purposes.
• Example: Alumina – glass former in aluminate glasses and
property modifier in silicate glasses.
• Arsenic oxide – either glassformer or a fining agent.
• Glass former – most essential component of any glass
batch – primary source of the structure.
• Silicate glass – most of the glass former present in a
sample is silica.
• Borosilicate glass - significant amount of boric oxide is
also present in addition to silica.
• The primary glass formers in commercial oxide glasses
are silica (SiO2), boric oxide (B2O3), and phosphoric oxide
(P2O5), which all readily form single component glasses.
• Oxides such as Bi2O3, As2O3, Sb2O3, TeO2, Al2O3, Ga2O3 and
V2O5 do not readily form glasses by themselves unless
very rapidly quenched or vapor deposited, but can serve
as glass formers when mixed with other oxides.
• Vast bulk of commercial glasses are based on silica as the
glass former.
• Flux – while silica itself forms excellent glass,
the use of pure silica glass would be very
expensive due to its high melting temperature
(> 2000 °C).
• Therefore, a flux is added to silicate glasses to
reduce the processing temperature to within
practical limits (< 1600 °C).
• The most common fluxes are the alkali oxides,
especially Na2O (soda) and PbO.
• While addition of fluxes to silica lead to
decreased cost of glass formation, the addition
of large amounts of alkali oxides results in
serious degradation in many properties.
• Property modifier – the degradation in properties is
countered by the use of property modifiers, which
include the alkaline earth and transition metal
oxides, and, most importantly, aluminium oxide
(alumina).
• While these oxides partially counter the reduction in
processing temperature obtained by addition of
fluxes, they also improve many of the properties of
the resulting glasses.
• By carefully controlling the amount and
concentration of these oxides, the properties are
modified or adjusted to obtain the desired results.
• Since they are added in lesser quantities than the
fluxes, their use does not lead to excessively high
processing temperature.
• Colorants – used to control the color of the final glass.
• Mostly – oxides of either the 3d transition metals or the
4f rare earths.
• Usually present in small quantities.
• Iron oxides – common impurity in sand acts as
unintentional colorants in many products.
• When colorants are used to counteract the effect of
other colorants to produce a slightly gray glass, they are
referred to as decolorants.
• Fining agents – to remove bubbles from the melt.
• It includes the arsenic and antimony oxides, potassium
and sodium nitrates, NaCl, fluorides such as CaF 2, NaF
and Na3AlF6, and a number of sulfates.
• These materials are usually present in very small
quantities (< 1 wt %).
 Glass structure
• Any liquid will form a glass , if cooled rapidly enough. Glasses
have been formed from ionic, organic and even metallic
melts.
• Most common – inorganic glasses formed from covalently
bonded – for the most part – silicate based – oxide melts.
• These glass forming oxides – continuous 3D network of linked
polyhedra – network formers.
• Examples of network formers – silica, boron oxide, B 2O3,
phosphorous pentoxide, P2O5 and germania,GeO2.
• Since glass possess short - range order, the idea of a repeating
unit cell is inapplicable.
• Thus the best way to describe a glass is to first describe the
building block that possess the short - range order (e.g.,the
coordination number of each atom) and then describe how
these blocks are connected.
• Vitreous or silica, SiO2:
- In fused silica, v – SiO2, the structure is similar to quartz (every silica
tetrahedron is attached to four other tetrahedra), except that the network lacks
long - range periodicity - Random network model proposed by Zachariasen.

Long - range order Short - range order

- The Si-O-Si bond angle in quartz is 144 °, whereas, for v – SiO 2 it has a
distribution of ± 10% (130 to 160 °).
- The structure of fused silica is quite uniform at a short range, but that order
does not persist beyond a few tetrahedra.
 Zachariasen rules

• Zachariasen suggested 4 rules for an

oxide AmOn to form a glass readily:
• (i) The oxygen is linked to no more than
two atoms of A.
• (ii) Coordination of the oxygen about A is
small, say 3 or 4.
• (iii) Oxygen polyhedra share corners, and
not edges or faces.
• (iv) At least three corners of each
polyhedron should be shared.
• Multicomponent silicates:
• The addition of alkali or alkaline earth metal oxides
to silicate melts usually strongly modify the
properties of a glass – network modifiers.
• The resulting structure is similar to pure silica, except
that now the continuous 3-D network is broken up
due to the presence of NBOs.
• Most of the commercial glasses are silica – based.
• Alumina sometimes behaves as a glass network and
sometimes as a glass modifier.
• If the Al3+ ion substitutes for a Si4+ ion, it becomes
part of the network.
• If it results in the formation of a NBO, it is considered
a modifier.
• Network model – early stages of development of
glass theory – does not fully explain several
experimental facts.
• E.g: (i) It has been observed that significant
structural changes occur at about 10 mol% alkali
content.
• (ii) It is well documented that the molar volume of
silicate melts remains fairly constant over a wide
range of alkali concentrations.
• Both observations at odds with the simple network
model.
• Therefore, other models such as discrete polyanions
or “iceberg” model have been proposed.
• In this model, it is assumed that between 0
and 0.1 mol fraction alkali oxide, bonds are
broken by the formation of NBOs.
• Between 0.1 and 0.33 mol fraction M2O,
discrete six-member rings (Si6O15)6- exist.
• Between 0.33 and 0.5, a mixture of (Si6O15)6-
and (Si3O9)6- or (Si4O12)8- and (Si6O20)8-rings are
presumed to exist.
• In the composition range between 12 and 33
mol%, M2O and SiO2 are not completely
miscible in the liquid state.
• Multicomponent borates:
• In pure B2O3, each B atom is bonded to three O
atoms and each O to two B atoms.
• When network modifiers, such as Na2O are added,
however, they do not immediately form NBOs.
Instead rigid BO4 tetrahedra form.
• Beyond 0.2 mole fraction of the modifier oxide,
NBOs start appearing.
• This is why when the glass transition, Tg and Vickers
hardness of a series of borate glasses are plotted as
a function of Na2O mole fraction, both properties
peak around 0.2 mole fraction.
• Smekal proposed that glasses are formed from melts
which contain bonds which are intermediate in character
between purely covalent and purely ionic bonds.
• Since purely ionic bonds lack any directional
characteristics, they do not form network structures.
• Highly covalent bonds tend to form sharply-defined
bond angles, preventing the formation of a non-periodic
network.
• Glass forming substances thus fall into two categories of
either inorganic compounds, containing bonds which are
partially ionic and partially covalent, or, inorganic or
organic compounds which form chain structures, with
covalent bonds within the chains and van der Waals’
bonds between the chains.
 Properties of glass
• Mechanical properties:
• The theoretical strength of silicate glass is
around 10 Gpa – usually reduced by the
presence of surface flaws.
• Glasses are elastic but break in tension.
• They can be strengthened by creating a
compressive surface layer (by ion exchange or
tempering) or by removing the surface flaws
(acid polishing or applying a protective
coating).
• Prince Rupert’s drops - small
gobs of molten glass are
dropped into cold water to
form tadpole-shaped drops.
• The surface cools much more
rapidly than the center creating
internal residual stresses and a
very high surface tension.
• The solidified drops can be hit
with a hammer without
breaking. But if the tail is
broken off the entire drop
shatters into powder.
• Electrical properties:
• High electrical resistivity – large band gap energy.
• In cases in which they are conductive, the charge is
carried by ions, with alkali ions being the fastest.
• Thus conductivity increases significantly as T is
increased and it is different for silicate glasses, borate
glasses, and phosphate glasses because the glass
network is different.
• Mixed alkali effect – interesting phenomenon – occurs
in glasses that contain more than one different alkali
ion.
• The resulting conductivity – significantly lower than
would be expected from simply adding their individual
conductivities.
• Application: High - wattage lamps.
• Optical properties:
• Transmission in the ultraviolet (UV), visible,
and infrared (IR) depends on several factors
including Rayleigh scattering, which is
determined by impurities.
• The IR edge and UV edge are the values where
transmission of these frequencies cut off.
• A UV edge blocker removes the UV while a UV
edge transmitter allows it through.
• The refractive index of SiO2 glass can be raised
by adding GeO2 – fabrication of optical fibers.
• An effective way of reducing the reflectivity of a glass
surface is to coat it with an antireflection coating
(ARC).
• The coating is applied onto the glass surface so that
its thickness is one – quarter of the wavelength of
the incident light.
• Light reflected from the top surface of the coating is
exactly out of phase with light reflected from the
glass surface, and so there is destructive
interference and no net reflected beam.
• MgF2 – widely used ARC material and is usually
applied onto the glass surface by PVD process.
• A single layer of MgF2 will reduce the reflectance of
glass from about 4% to a little more than 1% over the
visible spectrum.
• Thermal properties:
• Expansion coefficients of glass are generally smaller
than for metals.
• But often we want to make the following
connections to metals:
• Glass-to-metal seals: an obvious important
technological process
• SiO2: metal/insulator junctions for the electronic
industry
• Graded seals: for example, a graded seal structure
can be constructed by joining a series of glass
pieces, each of which has a slightly higher thermal
coefficient of expansion (α).
• Thermal conductivity is -1% of that of a metal.
 Pauling’s rules

• Ceramic materials are often thought of as being

ionically bonded and ions thought of as being
charged spheres.
• Many important ceramics are oxides in which
the oxygen anion is much larger than the cation.
• The crystal structure adopted by the material is
based on a balance between the attractive and
repulsive forces in the crystal.
• The electrostatic attractive force between ions of
unlike charges implies that an ion with a high CN
would be more stable than an ion with a low CN,
that is the electrostatic attraction is maximized.
• However, if too many ions of the same charge are
clustered around an individual ion of the opposite
charge, they begin to interfere with one another, that
is, the electrostatic repulsion is maximized.
• There exists a CN where the attraction is maximized
and the repulsion is minimized.
• This number is determined by the ratio of the radii of
the two ions.
• Pauling proposed a set of rules to use when
discussing topics such as: why certain oxides have
the structure they do and how this affects mixing or
doping of oxides.
• The idea is simply that ions of opposite sign pack
together in such a way as to keep ions of like sign
apart.
• Rule 1: A coordinated polyhedron of anions is formed about
each cation. The cation-anion distance is determined by the
sum of the two radii and the CN is determined by the radius
ratio (rM/rX).
• A central cation of given size cannot remain in contact with all
surrounding anions if the radius of the anion is larger than a
certain critical value.

• A given CN is thus stable only when the ratio of cation to

anion radius is greater than some critical value.
• In a crystal structure the anion is also surrounded by a
coordination polyhedron of cations.
• Critical radius ratios also govern the coordination of
cations about anions.

• Since anions are generally larger than cations, the critical

radius ratio for a structure is almost always determined
by the coordination of anions about the cations.
• In many well known ceramics, the cation coordination
polyhedron is the basic building block.
• Rule 2: In a stable structure, the total
electrostatic strength of the bonds, S, that
reach an anion in a coordination
polyhedron from all neighboring cations
should be equal to the charge of the anion.
S = ZM/CN
where ZM is the charge on the cation.
• For example, in cristobalite, the Si4+ are
surrounded by four O2- ions in a
tetrahedral arrangement.
• Silicon, with valence 4 and tetrahedral
coordination, has bond strength 4/4 = 1.
• Two bonds of strength 1 reach the shared
oxygen ion from the surrounding silicon
ions.
• In corundum, Al3+ with
octahedral coordination
has bond strength 3/6 =
1/2.
• The Al3+ is surrounded by
six O2- ions in an
octahedral arrangement.
• Each O2-ion is surrounded
by four Al3+, each with a
bond strength of ½.
• The fundamental idea is
that the crystal must be
electrically neutral.
• Rule 3: The polyhedra in a
structure tend not to share
edges or faces.
• If the edges are shared, the
shared edges are shortened.
• We can think of this
shortening as concentrating
more anions between
cations, which are too close
together.
• If there is an apparent
violation, it is likely that the
bonding is not ionic.
• Shared faces are the least
favorable.
• Rule 4: Crystals containing different cations of high
valence and small CN tend not to share polyhedron
elements with each other.
• Sharing parts of polyhedra decreases the stability
of the structure.
• Eg. In CaTiO3, [CaO12] polyhedra share edges and
[TiO6] polyhedra share corners.
• The Ti4+ cation is more highly charged than the Ca2+
cation, so the CN is smaller. The electrostatic bond
strength for this cation with the anion will be large.
• Rule 5: The number of essentially different kinds of
constituents in a crystal tends to be small.
 Defects in ceramics

• Ceramics usually have mixed bonding, that is,

a combination of ionic and covalent bonding.
• So, when we introduce defects, we usually
change the local distribution of charge or
break bonds, depending on which type of
bond predominates.
• Any change in charge distribution can produce
long-range effects.
• A broken covalent bond is known as a dangling
(unpaired electron) bond that also behaves
like a localized charge.
• When we create defects in a crystal we can create new
polyhedra that are not found in the perfect crystal.
• Grain-boundary movement in ceramics usually involves the
movement of point defects.
• Many of the properties are strongly affected by the
presence or absence of point defects.
• An overriding constraint operative during the formation of
ceramic defects is the preservation of electroneutrality at
all times.
• Consequently, the defects occur in neutral bunches and fall
in one of three categories:
(i) Stoichiometric defects
(ii) Nonstoichiometric defects
(iii) Extrinsic defects
Stoichiometric defects:
• These are defined as ones in which the crystal
chemistry, i.e., the ratio of the cations to
anions, does not change, and they include,
among others, Schottky and Frenkel defects

Schottky defect Frenkel defect

Nonstoichiometric defects:
• These defects are formed by the selective
addition, or loss, of one (or more) of the
constituents of the crystal and consequently
lead to a change in crystal chemistry.
• A material accommodates compositional
changes by selectively losing one of its
constituents to its environment that in turn
creates or eliminates defects.
• Therefore, a compound will adjust its
composition to reflect the externally imposed
thermodynamic parameters.
• This leads to the idea of nonstoichiometry where
the simple ratio between the numbers of the
constituent atoms of a compound breaks down.
• E.g. If an MO oxide is annealed in a high oxygen
partial pressure, Po2, it would be fair to assume
that the number of O anions would be relatively
greater than the number of M cations.
• Conversely, if the Po2 is very low, one would
expect the cation concentration to be higher.
• Many physical properties such as color, diffusivity,
electrical conductivity, superconductivity,
photoconductivity and magnetic susceptibility can
vary markedly with small changes in composition.
Extrinsic defects:
• Most crystals are far from pure, and their properties, especially
electrical and optical , are often dominated by the presence of trace
amounts of impurities.
• These impurities cannot be avoided; and even if the starting materials
are exceptionally pure, it is difficult to maintain the purity levels
during subsequent high-temperature processing.
• Impurity incorporation reactions – simple guidelines:
 Impurities usually substitute for the host ion of electronegativity
nearest their own, even if the sizes of ions differ.
 In other words, cations substitute for cations and anions for anions.
E.g. In NaCl, Ca and O would occupy cation and anion sites
respectively.
 In more covalent compounds, where the electronegativities may be
similar, size may play a more important role.
 Whether an impurity will occupy an interstitial site is more difficult to
predict.
 Most interstitial atoms are small, but even large ions are sometimes
 Point defects and their notation
• Kroger – Vink notation – to describe the formation of point
defects and their interaction in ceramics.
• The defect is represented by a main symbol followed by a
superscript and a subscript.
• Main symbol: The main symbol is either the species involved,
i.e., chemical symbol of the element, or the letter V for
vacancy.
• Subscript: The subscript is either the crystallographic position
occupied by the species involved or the letter i for interstitial
• Superscript: The superscript denotes the effective electric
charge on the defect, defined as the difference between the
real charge of the defect species and that of the species that
would have occupied that site in a perfect crystal.
• The superscript is a prime for each negative charge, a dot for
every positive charge or an X for a zero effective charge.
• Example: The possible defects that can occur in a pure
NaCl crystal.
 Vacancy on the Na+ sublattice: V’Na. The superscript is a
prime – representing a single negative charge – because
the effective charge on the vacancy is 0 – (+1) = -1.
 Vacancy on the Cl- sublattice: V˙Cl . In this case, the
superscript is a small dot (which denotes a positive
charge) because the effective charge on the vacancy is 0
– (-1) = +1.
 Interstitial on Na sublattice: Na˙i. The main symbol here
is the misplaced Na ion; the subscript i denotes the
interstitial position; the effective charge is: +1-0 = +1.
 Interstitial on Cl sublattice: Cl’i The main symbol here is
the misplaced Cl ion; the subscript i denotes the
interstitial position; the effective charge is: -1+0 = -1.