CHAPTER

9
Structure and Properties of
Ceramics

8-1
 INTRODUCTION

• Ceramics are inorganic and nonmetallic.

• Bounded by ionic or covalent bonds.
• Good electrical and heat insulation property.
• Brittle, and lesser ductility and toughness than
metals.
• High chemical stability and high melting
temperature.
• Traditional Ceramics: Basic components (Clay
and Silica).
• Engineering Ceramics: Pure compounds (Al2O3,
SiC).

8-2
 Ionic and Covalent Bonding in Simple Ceramics

• Mixture of Ionic and Covalent Types.

• Depends on electronegativity difference.
CaF2: large
SiC: small
 Ionic Bonding

Which sites will cations occupy?

1. Size of sites
– does the cation fit in the site
1. Stoichiometry
– if all of one type of site is full the
remainder have to go into other types of
sites.
1. Bond Hybridization
 1. Size of Sites
1. Size - Stable structures:
--maximize the # of nearest oppositely charged neighbors.

- - - - - -
+ + +
- - - - - -
unstable stable stable
• Charge Neutrality:
--Net charge in the F-
structure should CaF 2 : Ca 2+ +
cation anions
be zero.
F-
--General form: A m Xp
m, p determined by charge neutrality
 Coordination Number and Ionic Radii
r cation
• Coordination number increases with r
anion
Issue: How many anions can you
arrange around a cation?
r cation Coord ZnS
r anion # (zincblende)
Adapted from Fig.
< 0.155 2 linear 12.4, Callister 7e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 TD chloride)
Adapted from Fig.
12.2, Callister 7e.

0.414 - 0.732 6 OH CsCl

(cesium
0.732 - 1.0 8 cubic chloride)
Adapted from Fig.
Adapted from Table 12.2, 12.3, Callister 7e.
Callister 7e.
 Cation Site Size

• Determine minimum rcation/ranion for OH site (C.N.

= 6)
2ranion +2rcation =2a

a = 2ranion

2ranion +2rcation =2 2ranion

ranion +rcation =2ranion rcation =( 2−

1)ranion

rcation
= 0.414
ranion
 2. Stoichiometry

1. Stoichiometry
– If all of one type of site is full the remainder have
to go into other types of sites.

Ex: FCC unit cell has 4 OH and 8 TD sites.

If for a specific ceramic each unit cell has 6

cations and the cations prefer OH sites
4 in OH
2 in TD
 3. Bond Hybridization

• Bond Hybridization – significant covalent

bonding
– the hybrid orbitals can have impact if significant
covalent bond character present
– For example in SiC
• XSi = 1.8 and XC = 2.5
% ionic character = 100 {1 - exp[-0.25( X Si − X C )2 ]} = 11.5%
• ca. 89% covalent bonding
• both Si and C prefer sp3 hybridization
• Therefore in SiC get TD sites
 Example: Predicting Structure of FeO

• On the basis of ionic radii, what crystal structure

would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069 = 0.550
Ca 2+ 0.100
based on this ratio,
--coord # = 6
Anion
--structure = NaCl
O2- 0.140
Cl - 0.181
F-
Data from Table 12.3,
0.133 Callister 7e.
 Ceramic Crystal Structure
• AX Crystal Structure
– E.g. NaCl, CsCl, Zinc Blende
• AX2 Crystal Structure
– E.g. Fluorite
• ABX3 Crystal Structure
– E.g. Perovskite
• Silicate
– E.g. Silica, Glass, Silicates
• Carbon
– E.g. Diamond, Graphite
 SodiumAX
Chloride
CrystalCrystal
Structure
Structure

• Highly Ionically bonded

with Na+ ions occupying
interstitial sites between
FCC and Cl- ions.
• Radius ratio = 0.56, CN =
6.
• MgO, CaO, NiO and FeO
have similar structures.

Figure 10.7
 rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

∴ cations prefer OH sites

 Cesium Chloride Crystal Structure

• CsCl is ionically bonded with radius ratio

= 0.94 and CN = 8.
• Eight chloride ion surround a central
cesium cation at the ( ½ , ½ , ½ ) position.
• CsBr, TlCl and TlBr have similar
structure.

Figure 10.5
Cesium Chloride structure:

rCs + 0.170
= = 0.939
rCl− 0.181

∴ cubic sites preferred

So each Cs+ has 8 neighboring Cl-

Adapted from Fig.
12.3, Callister 7e.
 Zinc Blende (ZnS) Crystal Structue

• Four zinc and four sulfur atoms.

• One type (Zn or S) occupies lattice points and another
occupies interstitial sites of FCC unit cell.
• S Atoms (0,0,0) ( ½ ,½ ,0) ( ½ , 0, ½ ) (0, ½ , ½ )
Zn Atoms ( ¾ ,¼ ,¼ ) ( ¼ ,¼ ,¾ )( ¼ ,¾,¼ ) ( ¾ ,¾ ,¾ )
• Tetrahedrally covalently bonded
• (87% covalent character) with
CN = 8.
• CdS, InAs, InSb and ZnSe have
similar structures.

Figure 10.12
 Zinc Blende structure rZn2+ 0.074
= = 0.529 ⇒ OH ??
rO 2− 0.140

• Size arguments predict Zn2+

in OH sites,
• In observed structure Zn2+
in TD sites
• Why is Zn2+ in TD sites?
– bonding hybridization of
zinc favors TD sites

So each Zn2+ has 4 neighboring O2-

Adapted from Fig.
12.4, Callister 7e.

Ex: ZnO, ZnS, SiC

 MgO and FeO

MgO and FeO also have the NaCl structure

O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

∴ cations prefer OH sites

Adapted from Fig.

12.2, Callister 7e.

So each oxygen has 6 neighboring Mg2+

 AX2 Crystal Structure
Calcium Fluorite (CaF2) Crystal Structure

• Ca2+ ions occupy the FCC

lattice sites while the F-
ions are located at eight
tetrahedral sites.
• UO2, BaF2, PbMg2 have
similar structures.
• Large number of unoccupied octahedral sites in UO2Figure
allow 10.14

it to be used as nuclear fuel.

• Fission products are accommodated in these vacant
positions.
Fluorite structure
• Calcium Fluorite (CaF2)
• cations in cubic sites

• UO2, ThO2, ZrO2, CeO2

• antifluorite structure –
cations and anions
reversed
Adapted from Fig.
12.5, Callister 7e.
 ABX3 Crystal Structures

• Perovskite (CaTiO3) : Ca2+

and O2- ions form FCC unit cell.
• Ca2+ Ions
occupy corners
• O2- Ions occupy
face centers.
• Ti4+ ions are at
octahedral sites.

Figure 10.16
• Perovskite

Ex: complex oxide

BaTiO3

Adapted from Fig.

12.6, Callister 7e.
 Silicate Ceramics

Most common elements on earth are Si & O

Si4+

O2-

Adapted from
Figs. 12.9-10,
Callister 7e. crystobalite
• SiO2 (silica) structures are quartz, crystobalite, &
tridymite
• The strong Si-O bond leads to a strong, high melting
material (1710ºC)
 Amorphous Silica

• Silica gels - amorphous SiO2

– Si4+ and O2- not in well-ordered
lattice
– Charge balanced by H+ (to form
OH-) at “dangling” bonds
• very high surface area > 200 m2/g
– SiO2 is quite stable, therefore
unreactive
• makes good catalyst support

Adapted from Fig.

12.11, Callister 7e.
 Silica Glass

• Dense form of amorphous silica

– Charge imbalance corrected with “counter
cations” such as Na+
– Borosilicate glass is the pyrex glass used in
labs
• better temperature stability & less brittle than sodium
glass
 Silicates

Simple Structure
– Combine SiO44- tetrahedra by having them share
corners, edges, or faces

Adapted from Fig.

12.12, Callister 7e.

Mg2SiO4 Ca2MgSi2O7

– Cations such as Ca2+, Mg2+, & Al3+ act to neutralize

& provide ionic bonding
• Silicate (SiO44-) is building block of silicates.
• 50% Ionic and 50% covalent.
• Many different silicate structures
can be produced.
• Island structure: Positive ions
bond with the oxygen of SiO44-
tetrahedron.
• Chain/ring structure: Two Figure 10.18
corners of each SiO44- tetrahedron
bonds with corners of other
tetrahedron.

Figure 10.19a
 Layered Silicates

• Three corners of same planes of silicate tetrahedron bonded

to the corners of three other silicate tetrahedra.
• Each tetrahedron has one
unbounded oxygen and hence
chains can bond with other
type of sheets.
Figure 10.19b
• If the bondings are weak,
sheets slide over each other
easily.

Figure 10.20
• Layered silicates (clay
silicates)
– SiO4 tetrahedra connected
together to form 2-D plane

Adapted from Fig.

12.13, Callister 7e.
=
• (Si2O5)2-
• Kaolinite clay alternates (Si2O5)2- layer with
Al2(OH)42+ layer

Adapted from Fig.

12.14, Callister 7e.

Note: these sheets loosely bound by van der Waal’s forces

• Can change the counterions
– this changes layer spacing
– the layers also allow absorption of water
• Micas KAl3Si3O10(OH)2
• Bentonite
– used to seal wells
– packaged dry
– swells 2-3 fold in H2O
– pump in to seal up well so no polluted ground water
seeps in to contaminate the water supply.
 Silicate Network

• Silica: All four corners of the SiO44- tetrahedra share

oxygen atoms.
• Basic structures: Quartz, tridynute and cristobarlite.
• Important compound
of many ceramic and
glasses.
• Feldspars: Infinite 3D
networks.
• Some Al3+ Ions replace
Si4+ Ions Net negative charge.
• Alkaline and alkaline fit into interstitial sites.
Figure 10.22
 Carbon

• Carbon black – amorphous –

surface area ca. 1000 m2/g
• Diamond
– tetrahedral carbon
• hard – no good slip planes
• brittle – can cut it
– large diamonds – jewelry
– small diamonds
• often man made - used for
cutting tools and polishing
– diamond films
• hard surface coat – tools, Adapted from Fig.
12.15, Callister 7e.
medical devices, etc.
 Graphite

• layer structure – aromatic layers

Adapted from Fig.

12.17, Callister 7e.

– weak van der Waal’s forces between layers

– planes slide easily, good lubricant
 Fullerenes and Nanotubes

• Fullerenes or carbon nanotubes

– wrap the graphite sheet by curving into ball or tube
– Buckminister fullerenes
• Like a soccer ball C60 - also C70 + others

Adapted from Figs.

12.18 & 12.19,
Callister 7e.
 Imperfections in Ceramics

• Atomic Point Defect

– Schottky, Frenkel

• Impurities
– Interstitial, Substitutional
 Atomic Point Defect

• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect: Adapted from Fig. 12.21, Callister
7e. (Fig. 12.21 is from W.G.
Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Frenkel
Defect

−QD / kT
• Equilibrium concentration of defects ~e
 Impurities

• Impurities must also satisfy charge balance = Electroneutrality

• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry

• Substitutional anion impurity anion vacancy

O2-

Cl - Cl -
initial geometry O2- impurity resulting geometry
 Interstitial Sites in FCC and HCP Crystal Lattices

• Octahedral interstitial
sites: Six nearest atoms or
ions equidistant from
central void.
• Tetrahedral Interstitial
Sites: Four nearest atoms Figure 10.9
or ions equidistant from
central void.
• There are four octahedral
sites and eight tetrahedral
sites per unit cell of FCC.

Figure 10.11
 Mechanical Properties

• Strength of ceramics vary greatly but they are generally

brittle.
• Tensile strength is lower than compressive strength.
 Mechanism of Deformation

• Covalently bonded ceramics: Exhibit brittle fracture due to

separation of electron-pair bonds without their subsequent
reformation.
• Ionically bonded ceramics: Single crystal show considerable plastic
deformation. Polycrystalline ceramics are brittle.
• Example: NaCl crystal
 Slip in {100} family
of planes is rarely
observed as same
charges come into contact.
 Cracking occurs at grain boundaries.

Figure 10.44
 Factors Affecting Strength

• Failure occurs mainly from surface defects.

• Pores gives rise to stress concentration and
cracks.
• Pores reduce effective cross-sectional area.
• Flaw size is related to grain size.
• Finer size ceramics have smaller flaws and hence
are stronger.
• Composition, microstructure, surface condition,
temperature and environment also determine
strength.
 Strength of Ceramics

• 3-point bend test to measure room T strength.

cross section F
L/2 L/2 Adapted from Fig. 12.32,
Callister 7e.
d R
b d = midpoint
rect. circ.
deflection
location of max tension

• Flexural strength: • Typ. values:

Material σfs (MPa) E(GPa)
1.5Ff L Ff L
σ fs = = Si nitride 250-1000 304
bd 2 πR3 Si carbide 100-820 345
F rect. Al oxide 275-700 393
Ff x glass (soda) 69 69
Data from Table 12.5, Callister 7e.

δ
δfs
 Elastic Modulus

• Room T behavior is usually elastic, with brittle failure.

• 3-Point Bend Testing often used.
--tensile tests are difficult for brittle materials.
cross section F
L/2 L/2 Adapted from Fig. 12.32,
Callister 7e.
d R
b d = midpoint
rect. circ.
deflection
• Determine elastic modulus according to:
F F L3 F L3
x E= =
F δ 4bd 3 δ 12 π R4
slope =
δ rect. circ.
cross cross
δ section section
linear-elastic behavior
 Creep

• Elevated Temperature Tensile Test (T > 0.4 Tm).

creep test
ε
σ
x
.
slope = εss = steady-state creep rate

σ
time
 Toughness of Ceramic

• Ceramics have low strength.

• Research has been conducted to improve toughness.
• Hot pressing with additives and reaction bonding improve
toughness.
• KIC values obtained by four point bend test.

K IC = Yσ f πa
σ f = fracture stress (MPa)

a = half size of target internal flaw

Y = dimensionless constant

Figure 10.46
 Transformation Toughening of Partially Stabilized ZrO2

• Transformation of Zirconia combined with

some other refractory oxides (MgO) can
produce very high toughness ceramics.
• ZrO2 exists in 3 structures.
 Monoclinic Up to 11700C
 Tetragonal 1170 – 23700C
 Cubic above 23700C
• Adding 10% mol of MgO stabilizes cubic
form so that it can exist in metastable state
in room condition.
• If a mixture of ZrO2 – 9 mol% MgO is sintered at about
18000C and rapidly cooled, it will be in metastable state.
• If reheated to 14000C and
held for sufficient time
tetragonal structure
precipitates.
• Under action of stress,
this tetragonal structure
transforms to monoclinic
increasing volume and
hence retarding crack
growth.
Figure 10.47a
 Failure

• Fatigue fracture in ceramics is rare due to absence of plastic

deformation.
• Straight fatigue crack in
has been reported in
alumina after 79,000
compression cycles.
Figure 10.48
• Ceramics are hard and can be used as abrasives.
• Examples:- Al2O3, SiC.
• By combining ceramics, improved abrasives can be
developed.
• Example:- 25% ZrO2 + 75% Al2O3
 Thermal Properties of Ceramics

• Low thermal conductivity and high heat

resistance.
• Many compounds are used as industrial
refractories.
• For insulating refractories, porosity is desirable.
• Dense refractories have low porosity and high
resistance to corrosion and errosion.
• Aluminum oxide and MgO are expensive and
difficult to form and hence not used as
refractories.
 Porosity

• Exist between powder particles due to

forming processes.
• Heat treatment will eliminate porosity but
some residual porosity will remain.
• Influence the elastic properties and strength.
• Porosity reduce strength because:
– Pores reduce cross sectional area
– Act as stress concentrator
 Hardness

• High hardness
• Suitable for abrasive materials
 Electrical Properties

• Basic properties of dielectric:

 Dielectric constant:-
Q = CV
Q = Charge
V = Voltage
C = Capacitance
C = ε0A/d ε0 = permeability of free space Figure 10.35
= 8.854 x 10-12 F/m
• When the medium is not free space
C = Kε0A/d Where K is dielectric constant of the
material between the plates
 Dielectric Strength and Loss Factor

• Dielectric strength is measure of ability of material to hold

energy at high voltage.
 Defined as voltage gradient at which failure
occurs.
 Measured in volts/mil.
• Dielectric loss factor: Current leads voltage by 90 degrees
when a loss free dielectric is between plates of capacitor.
• When real dielectric is used, current leads voltage by 900 –
δ where δ is dielectric loss angle.
• Dielectric loss factor = K tan δ measure of
electric energy lost.