Ceramics 1

Copyright The McGraw-Hill Companies, Inc.
Permission required for reproduction or display
SE2 Structural Materials
Introduction to
Engineering Ceramics
Dr. Yu Qiao
Department of Structural Engineering, UCSD
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display
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).
11-2
Venus of Doln
Vstonice (~25,000
years ago)
Year
Development
24,000 B.C.
Ceramic figurines used for

ceremonial purposes
14,000 B.C.
First tiles made in

Mesopotamia and India
9000-10,000 B.C.
Pottery making begins
5000-8000 B.C.
Glazes discovered in Egypt
1500 B.C.
Glass objects first made
1550 A.D.
Synthetic refractories
(temperature resistant) for
furnaces used to make steel,
glass, ceramics, cement
Mid 1800s
Porcelain electrical insulation

Incandescent light bulb
1920s
High-strength quartz-enriched
porcelain for insulators
Alumina spark plugs
Glass windows for
automobiles
11-2
Simple Ionic Arrangements
Packing of Ions depends upon

Relative size of ions.
Need to balance electron charges.
If the anion does not touch the
cation, then the arrangement is
unstable.
Radius ratio = rcation/ranion
Critical radius ratio for stability
for coordination numbers 8,6 and
3 are >0.732, >0.414 and > 0.155
respectively.
The number of adjacent atoms/ions
Figure 10.2
Unstable
Stable
11-4
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 ( , , ) position.
CsBr, TlCl and TlBr have similar structure.
Figure 10.5
11-5
Sodium Chloride Crystal 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
11-6
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 or ions equidistant
from central void.
There are four
octahedral sites and
eight tetrahedral sites
per unit cell of FCC.
Figure 10.9
Figure 10.11
11-7
After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976
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) ( , ,0) ( , 0, ) (0, , )
Zn Atoms
( , , ) ( , , )( ,, ) ( , , )
Tetrahedrally covalently bonded
(87% covalent character) with
CN = 8.
CdS, InAs, InSb and ZnSe have
similar structures.
Figure 10.12
11-8
Calcium Fluorite (CaF2) Crystal Structure
Ca2+ ions occupy the FCC

lattice sites while the Fions are located at eight
tetrahedral sites.
UO2, BaF2, PbMg2 have
similar structures.
Figure 10.14
Large number of unoccupied octahedral sites in UO2
allow it to be used as nuclear fuel.
Fission products are accommodated in these vacant
positions.
11-9
After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976.
Other Crystal Structures

Antifluorite: Anions occupy lattice points and cations
occupy eight tetrahedral sites of FCC.
Examples: Li2O, Na2O
Corundum: Oxygen ions in lattice
points of HCP unit cell.
Two Al3+ ions in octahedral
sites for every three O- ions
Figure 10.15
distortion of structure.
Spinel (MgAl2O4): Oxygen ions form FCC lattice and
Mg and Ml ions occupy interstitial sites .
These are nonmetallic magnetic materials.
11-10
Other 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
Graphite : Polymorphic form
of compound.
Layered structure with carbon
atoms in hexagonal arrays.
Good lubricating properties.
Figure 10.17
11-11
After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976.
Silicate Structures
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 SiO44tetrahedron.
Figure 10.18
Chain/ring structure: Two
corners of each SiO44- tetrahedron
bonds with corners of other
tetrahedron.
Figure 10.19a
11-12
After M. Eisenstadt, Mechanical properties of Materials, Macmillan, 1971, p.82.
Sheet Structures of Silicates
Sheet structure: 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
Figure 10.19b
type of sheets.
If the bondings are weak,
sheets slide over each other
easily.
Figure 10.20
11-13
After M. Eisenstadt, Mechanical properties of Materials, Macmillan, 1971, p.83.
Silicate Networks
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
11-14
Processing of Ceramics
Produced by compacting powder or particles

into shapes and heated to bond particles
together.
Material preparation: Particles and binders
and lubricants are (sometimes ground) and
blend wet or dry.
Forming: Formed in dry, plastic or liquid
conditions.
Cold forming process is predominant.
Pressing, slipcasting and extrusion are the
common forming processes.
11-15
Pressing
Dry Pressing: Simultaneous uniaxial compaction and

shaping of power along with binder.
Wide variety of shapes can be formed rapidly and
accurately.
Figure 10.25
Figure 10.24
11-16
Isolatic pressing: Ceramic powder is loaded into a

flexible chamber and pressure is applied outside the
chamber with hydraulic fluid.
Examples: Spark plug insulators, carbide tools.
After J. S. Reed and R. B Runk, Ceramic Fabrication Process, vol 9: 1976, p.74.
Slip Casting
Powdered ceramic material and a liquid mixed to

prepare a stable suspension (slip).
Slip is poured into porous mold and liquid portion is
partially absorbed by mold.
Layer of semi-hard material
is formed against mold
surface.
Excess slip is poured out
of cavity or cast as
solid.
The material in mold is
allowed to dry and then fired.
Figure 10.27
11-17
After W. D. Kingery, Introduction to Ceramics, Wiley, 1960, p.52.
Extrusion
Single cross sections and hollow shapes of ceramics can

be produced by extrusion.
Plastic ceramic material is forced through a hard steel or
alloy die by a motor driven augur.
Examples: Refractory brick, sewer pipe, hollow tubes.
Figure 10.28
11-18
After W. D. Kingery, Introduction to Ceramics, Wiley, 1960.
Thermal Treatments
Drying: Parts are dried before firing to remove water

from ceramic body.
Usually carried out at or below 1000C.
Sintering: Small particles are bonded together by solid
state diffusion producing dense coherent product.
Carried out at higher temperature but below MP.
Longer the sintering time, larger the particles are.
Vetrification: During firing, glass phase liquefies and
fills the pores.
Upon cooling liquid phase of glass solidifies and a
glass matrix that bonds the particles is formed.
11-19
Traditional Ceramics
Made up of clay, silica and fledspar.
Clay: Provide workability and hardness.
Silica: Provide better temperature resistance and MP.
Potash Fledspar: Makes glass when ceramic is fired.
Table 10.6
SEM of Porcelain
Quartz
grain
Figure 10.33
11-20
Source: F. Norton, Elements of Ceramics, 2nd ed., Addision-Wesley,1974, p.140
High-silica
glass
10
Engineering Ceramics
Alumina (Al2O3): Aluminum oxide is doped

with magnesium oxide, cold pressed and
sintered.
Uniform structure. Used for electric
applications.
Silicon Nitride (Si3N4): Compact of silicon
powder is nitrided in a flow of nitrogen gas.
Moderate strength and used for parts of
advanced engines.
Silicon Carbide (SiC): Very hard refractory
carbide, sintered at 21000C.
Used as reinforcement in composite
materials.
Zirconia (ZrO2): Polymorphic and is subject to
cracking.
Combined with 9% MgO to produce
ceramic with high fracture toughness.
11-21
Electrical Properties
Basic properties of dielectric:

Dielectric constant:Q = CV
Q = Charge
V = Voltage
C = Capacitance
Figure 10.35
C = 0A/d
0 = permeability of free space
= 8.854 x 10-12 F/m
When the medium is not free space
C = K0A/d Where K is dielectric constant of the
material between the plates
11-22
11
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 where is dielectric loss angle.
Dielectric loss factor = K tan
measure of
electric energy lost.
11-23
Ceramic Insulator Materials
Ionic and covalent bonding restricts the mobility of

ions and electrons and hence ceramics are good
insulators.
Electrical porcelain: 50% Clay + 25 % Fledspar.
Good plasticity, wider firing temperature range, cheap.
High power loss factor.
Steatite: 90% talc + 10 % clay

Good insulator, low power loss factor, impact strength
Fosterite: Mg2SiO4
no alkali ions
Higher resistivity, low electrical loss
Alumina: Al2O3
to glassy matrix.
Crystalline phase bounded
High dielectric strength, low dielectric loss

11-24
12
Ceramic Materials for Capacitors
Ceramics are used as dielectric materials for

capacitors.
Example: Disk ceramic capacitors.
BaTiO3 + additive
Very high dielectric
constant
Used in ceramic based
thick film hybrid
electronic circuit
Higher capacitance per unit area
11-25
Figure 10.38a
Courtesy of Sprague Products Co
Ceramic Semiconductors
Ceramics can be used as semiconducting materials.

Thermistor: Thermally sensitive resistor.
NTC thermistor: Conductivity raises with
temperature.
Solid solution oxides of Mn, Ni, Fe, Co and Cu are
used to obtain necessary property ranges.
By combining low conducting metal oxide with low
conducting oxides intermediate properties are
obtained.
Example: Conductivity of Fe3O4 is reduced gradually
by adding increasing amounts in solid solution of
MgCr2O4
11-26
13
Ferroelectric Ceramics
Ferroelectric Domains: If unit cells do not have center

of symmetry, dipole moments arise.
Dipole moment of unit volume = sum of all dipole
moments of cell.
Example: BaTiO3 unit cell is symmetric above 1200C
but below 1200C (Cutie temperature) dipole moment is
created due to shifting of Ti4+ and O2- ions.
If cooling takes place in
electric field, dipoles
align in the direction
of the field.
Figure 10.40
11-27
After K. M. Ralls, T. H. Courtney, and J. Wulff, An Introduction to Material Science and Engineering, Wiley, 1976, p.610.
Piezoelectric Effect
If compressive force is applied to piezoelectric ceramic,

it changes dimension and results in net dipole moment.
Change in dipole moment changes the charge
density at the ends and changes voltage
difference between the ends.
If electric field is applied to the sample, charge
density changes resulting in change of dimension
of the sample.
Peizolectric effect
Mechanical
force
Electric
response
11-28
14
Piezoelectric Materials
PZT ceramics: Solid solutions of lead zirconate

(PbZrO3) and lead titanate (PbTiO3)
Have broader range of piezoelectric properties.
High curie temperature.
Barium Titanate: ( BaTiO3 ) Commonly used.
Low curie temperature.
Applications: Piezoelectric compression accelerometer,

ultrasonic cleaning transducer and underwater sound
transmitter.
11-29
Mechanical Properties of Ceramics

Strength of ceramics vary greatly but they are generally
brittle.
Tensile strength is lower than compressive strength.
Table 10.9
11-30
15
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.
Figure 10.44
Cracking occurs at grain boundaries.
11-31
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.
11-32
16
Toughness of ceramic Materials

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 = Y f a
f = fracture stress (MPa)
a = half size of target internal flaw
Y = dimensionless constant
Figure 10.46
11-33
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.
11-34
17
Toughness of Zirconia (Cont..)

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
11-35
After A. H. Heuer, Advances in Ceramics, vol. 3, Science and Technology of Zirconia, American Ceramic Society, 1981.
Fatigue 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
11-36
After Suresh and J. R. Brockenbrough, Acta Metall. 36:1455, 1988.
18
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.
11-37
Acidic and Basic Refractories
Acidic refractories:
Silica refractories have high mechanical strength
and rigidity.
Fireclays: Mixture of plastic fireclay, flint clay and
grog. Particles vary from coarse to very fine.
High aluminum refractories: Contain 50-90%
alumina and have higher fusion temperature.
Basic refractories: consists mainly of MgO and CaO.
Have high bulk densities, melting temperature and
resistance to chemical attack.
used for lining in basic-oxygen steelmaking process.
11-38
19
Insulation for Space Shuttle Orbital
About 70% of external surface is protected from heat

by 24000 ceramic tiles.
Material: Silica fiber compound.
Density is 4kg/ft3 and withstands temperature up to
12600C.
Figure 10.51
11-39
Courtesy of NASA
Glasses
Combination of transparency, strength, hardness and

corrosion resistance.
Glass is an inorganic product of fusion that has cooled
to a rigid condition without crystallization.
Glass does not crystallize
up on cooling.
Up on cooling, it transforms
from rubbery material to
rigid glass.
Figure 10.52
11-40
20
Structure of Glasses
Fundamental subunit of glass is SiO44- tetrahedron.

Si 4+ ion is covalently ionically bonded to four oxygen
atoms.
In cristobalite, Si-O tetrahedron are joined corner to
corner to form long range order.
In simple silica glass, tetrahedra are joined corner to
corner to form loose network.
Figure 10.53
11-41
Cristobailite
Simple silica glass
Courtesy of Corning Glass Works
Glass Modifying Oxides and Intermediate Oxides
Network modifiers: Oxides that breakup the glass

network.
Added to glass to increase workability.
Examples:- Na2O, K2O, CaO, MgO.
Oxygen atom enters network and other ion stay
in interstices.
Intermediate oxides: Cannot form glass network by
themselves but can join into an existing network.
Added to obtain special properties.
Examples: Al2O3, Lead oxide.
11-42
21
Composition of Glasses
Soda lime glass: Very common glass (90%).

71-73% SiO2, 12-14% Na2O, 10-12% CaO.
Easier to form and used in flat glass and
containers.
Borosilicate glass: Alkali oxides are replaced by boric
oxide in silica glass network.
Known as Pyrex glass and is used for lab
equipments and piping.
Lead glass: Lead oxide acts as network modifier and
network former.
Low melting point used for solder sealing.
Used in radiation shields, optical glass and TV
bulbs.
11-43
Viscous Deformation of glasses.
Viscous above Tg and viscosity decreases with increase in

temperature.
Q = Activation energy
* = 0e+Q/RT
* = Viscocity of glass (PaS)

0 = preexponential constant (PaS)
1.
2.
3.
4.
Working point: 103 PaS glass

fabrication can be carried out
Softening point: 107 PaS glass
flows under its own weight.
Annealing point: 1012 PaS Internal
stresses can be relieved..
Strain point: 10 13.5 PaS glass is
rigid below this point.
Figure 10.55
11-44
After O. H. Wyatt and D. Dew-Hughes, Metals Ceramics and Polymers, Cambridge, 1974, p.259.
22
Forming Methods
Forming sheet and plate

glass:
Ribbon of glass moves out
of furnace and floats on a
bath of molten tin.
Glass is cooled by molten
tin.
After it is hard, it is
removed and passed
through a long annealing
furnace.
Figure 10.56
11-45
After D. C. Boyd and D. A. Thompson, Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., Wiley, 1980, p.862.
Blowing, Pressing and Casting
Blowing: Air blown to force molten glass into molds.

Pressing: Optical and
sealed beam lenses are
pressed by a plunger
into a mold containing
molten glass.
Casting: Molten glass
is cast in open mold.
Figure 10.57
Centrifugal casting: Glass globs are dropped into
spinning mold.
Glass first flows outward towards wall of mold and then
upward against the mold wall.
11-46
After W. Giegerich and W. Trier, Glass Machines Construction .., Spring-Verlag, 1969
23
Tempered Glass
Glass is heated into near softening point and rapidly

cooled.
Surface cools first and contracts.
Interior cools next and
contracts causing tensile
stresses in the interior
and compressive stress
Figure 10.58
on the surface.
Tempering strengthens the glass.
Examples: Auto side windows and safety glasses.
11-47
Chemically Strengthened Glass
Special treatment increases chemical resistance of

glasses.
Example:- Sodium aluminosilicate glasses are
immersed in a bath of potassium nitrate at 500C for 6
to 10 hours
Large potassium ions are induced into surface
causing compressive stress.
Compressive layer is much thinner than that in
thermal tempering.
Used for supersonic aircraft glazing and
ophthalmic lenses.
11-48
24

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SE2 Structural Materials

Ceramics are inorganic and nonmetallic.

Ceramic figurines used for

First tiles made in

Pottery making begins

Glazes discovered in Egypt

Glass objects first made

Porcelain electrical insulation

Simple Ionic Arrangements

Packing of Ions depends upon

The number of adjacent atoms/ions

Cesium Chloride Crystal Structure

Sodium Chloride Crystal Structure

Interstitial Sites in FCC and HCP Crystal Lattices

After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976

Zinc Blende (ZnS) Crystal Structue

Four zinc and four sulfur atoms.

After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976

Calcium Fluorite (CaF2) Crystal Structure

Ca2+ ions occupy the FCC

After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976.

Other Crystal Structures

Other Crystal Structures

Perovskite (CaTiO3) : Ca2+ and O2- ions form FCC unit

After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976.

Silicate (SiO44-) is building block of silicates.

After M. Eisenstadt, Mechanical properties of Materials, Macmillan, 1971, p.82.

Sheet Structures of Silicates

Sheet structure: Three corners of same planes of silicate

After M. Eisenstadt, Mechanical properties of Materials, Macmillan, 1971, p.83.

Silica: All four corners of the SiO44- tetrahedra share

After W. D. Kingery, H. K. Bowen, D. R. Uhlmann, Introduction to Ceramics,2nd ed., Wiley, 1976

Produced by compacting powder or particles

Dry Pressing: Simultaneous uniaxial compaction and

Isolatic pressing: Ceramic powder is loaded into a

Powdered ceramic material and a liquid mixed to

After W. D. Kingery, Introduction to Ceramics, Wiley, 1960, p.52.

Single cross sections and hollow shapes of ceramics can

After W. D. Kingery, Introduction to Ceramics, Wiley, 1960.

Drying: Parts are dried before firing to remove water

Source: F. Norton, Elements of Ceramics, 2nd ed., Addision-Wesley,1974, p.140

Alumina (Al2O3): Aluminum oxide is doped

Basic properties of dielectric:

Dielectric Strength and Loss Factor

Dielectric strength is measure of ability of material to

Ceramic Insulator Materials

Ionic and covalent bonding restricts the mobility of

Steatite: 90% talc + 10 % clay

Crystalline phase bounded

High dielectric strength, low dielectric loss

Ceramic Materials for Capacitors

Ceramics are used as dielectric materials for

Courtesy of Sprague Products Co

Ceramics can be used as semiconducting materials.

Ferroelectric Domains: If unit cells do not have center

If compressive force is applied to piezoelectric ceramic,

PZT ceramics: Solid solutions of lead zirconate

Applications: Piezoelectric compression accelerometer,

Mechanical Properties of Ceramics

Covalently bonded ceramics: Exhibit brittle fracture

Factors Affecting Strength

Failure occurs mainly from surface