Universite dOttawa

Faculte de Genie
Departement de genie
Mecanique

University of Ottawa
Faculty of Engineering
Department of Mechanical
Engineering

MCG2361
Engineering Materials II
Week 2: CERAMIC MATERIALS

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What are Ceramics?

q Ceramics are inorganic, non-metallic and crystalline materials that are
typically produced using clays and other minerals from the earth or
chemically processed powders
q Ceramics are crystalline and are compounds formed between metallic
and non-metallic elements such as aluminium and oxygen (alumina-
Al2O3 ), silicon and nitrogen (silicon nitride- Si3 N4) and silicon and
carbon (silicon carbide-SiC).
q Glasses are non-metallic, inorganic but amorphous. They are often
considered as belonging to ceramics.

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Characteristics of Ceramics
Ceramics
q
q
q
q
q
q
q

Low density
High Tm
High elastic modulus
Brittle
Non-reactive
Good electrical and
thermal insulators
High hardness and
wear resistance

Metals
q
q
q
q
q
q

Tm: melting temperature

High density
Medium to high Tm
Medium to high elastic
modulus
Ductile
Reactive (corrode)
Good electrical and
thermal conductors

A. Ourdjini@2016

Polymers
q
q
q
q

Very low density

Low Tm
Low elastic modulus
Ductile and brittle

Structure of Ceramics
q Ceramics exhibit ionic, covalent bonding or a combination of the two
(like in Al2O3)
q Type of bonding strongly influences the crystal structure of ceramics
q Ceramics crystallise in two main groups:
1. Ceramics with simple crystal structure (e.g; SiC, MgO)
2. Ceramics with complex crystal structures based on silicate SiO4
(known as silicates)

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Structure of Ceramics
Bonding:
-- % ionic character increases with difference in electronegativity

Large vs small ionic bond character:

CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister 7e.

A. Ourdjini@2016

Structure of Ceramics
Percentage of ionic and covalent bonding for selected ceramics
Ceramic

Atoms in
bond

XA - XB

% Ionic
character

% covalent
character

MgO

Mg - O

2.3

73

27

Al2O3

Al - O

2.0

63

37

SiO2

Si - O

1.7

51

49

Si3Ni4

Si - Ni

1.2

30

70

SiC

Si - C

0.7

11

89

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Ceramic crystal structure considerations

n

Charge Neutrality
The bulk ceramic must remain electrically neutral
For example, the compound MgO2 does not exist
Mg+2 & O-2: net charge / molecule = 1(+2) + 2(-2) = -2

Coordination Number (CN)

Depends on atomic size ratio

CN increases as the RC/RA increases
CN determines the possible crystal structure,
Thus, CN determines the physical properties
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IONIC BONDING & STRUCTURE

Charge Neutrality:
--Net charge in the
structure should
be zero.
--General form:

CaF 2 :

F-

Ca 2+ +
cation

anions
F-

Am Xp

Stable structures:

m, p determined by charge neutrality

--maximize the # of nearest oppositely charged neighbors.

unstable

stable
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stable

Adapted from Fig. 12.1,

Callister 6e.

Chapter 12- 3

EX: PREDICTING STRUCTURE OF FeO

On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation
Al3+
Fe 2+
Fe 3+
Ca 2+
Anion
O 2Cl F-

Ionic radius (nm)

0.053
0.077
0.069
0.100

0.140
0.181
0.133

Answer:
r cation
r anion

0 .077
0.140
0 .550

based on this ratio,

--coord # = 6
--structure = NaCl

Data from Table 12.3,

Callister 6e.
Chapter 12- 5

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Coordination number and ionic radii

Coordination
# and Ionic Radii
r cation
Coordination # increases with r
anion

Issue: How many anions can you

arrange around a cation?
r cation
r anion
< 0.155

ZnS
(zincblende)

Coord
#
2
linear

0.155 - 0.225

triangular

0.225 - 0.414

TD

0.414 - 0.732

OH

0.732 - 1.0

cubic

Adapted from Fig.

12.4, Callister 7e.

NaCl
(sodium
chloride)

Adapted from Fig.

12.2, Callister 7e.

CsCl
(cesium
chloride)
Adapted from Fig.
12.3, Callister 7e.

Adapted from Table 12.2,

Callister 7e.

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Examples of AX type structure

Cs+

Cl-

= Na+
= Cl-

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Summary of Some Common Ceramic Crystal Structures

Common ceramic structures

Structure name

Structu
re type

Anion
packing

Coordination numbers
cation

Examples

anion

NaCl
NCl, MgO, FeO

Rock salt (sodium

chloride)

AX

FCC

Cesium chloride

AX

Simple
Cubic cubic

CsCl

Zinc Blende
(sphalerite)

AX

FCC

ZnS, SiC

Fluorite

AX2

Simple cubic

CaF2, UO2 ThO2

Perovskite

AX3

FCC

12 (A)
6(B)

BaTiO3, SrZrO3,
SrSnO3

Spinel

A2X4

FCC

4(A)
6(B)

MgAl2O4,
FeAl2O4

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CERAMICS

GLASSES

REFRACTORIES

CLAY PRODUCTS

ABRASIVES

CEMENT

ENG.
CERAMICS

Our focus is HERE !!!

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Engineering ceramics are generally

classified into the following:

Bioceramics

Cutting tools
n

Structural ceramics,

Electrical and Electronic ceramics,

Capacitors, insulators, substrates, IC

packages, piezoelectrics, magnets,
superconductors

Ceramic coatings,

Industrial wear parts, bioceramics,

cutting tools, engine components

Industrial wear parts, cutting tools,

engine components

Chemical processing & environmental

Coating
ceramics

Filters, membranes, catalysts

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Engine parts

Types of ceramics
Eng. ceramics

Traditional ceramics

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Manufacturing, Engineering & Technology, Fifth Edition, by Serope Kalpakjian and Steven R. Schmid.
ISBN 0-13-148965-8. 2006 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved.

A. Ourdjini@2016

Ceramic Components

Figure 8.1 A variety of ceramic components. (a) High-strength alumina for high-temperature
applications. (b) Gas-turbine rotors made of silicon nitride. Source: Courtesy of Wesgo Div.,
GTE.
Manufacturing, Engineering & Technology, Fifth Edition, by Serope Kalpakjian and Steven R. Schmid.
ISBN 0-13-148965-8. 2006 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved.

A. Ourdjini@2016

Properties of Ceramics

Manufacturing, Engineering & Technology, Fifth Edition, by Serope Kalpakjian and Steven R. Schmid.
ISBN 0-13-148965-8. 2006 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved.

A. Ourdjini@2016

Silicate Ceramics
Composed mainly of Si and O2.

Si-O Tetrahedron O

Bonding: 50%ionic-50%covalent
RC/RA = 0.29

Si

Important component in traditional

ceramics and glasses
Two most common silicate ceramics
are:
1.

Silica (SiO2)
If the tetrahedra are arranged in a
regular and ordered manner, a
crystalline structure is formed. Silica
have 3 different types: quartz,
crystobalite and tridymite
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Silica

Silicate Ceramics
2. Silica Glasses

If the tetrahedra are randomly arranged, a

non-crystalline structure, known as Glass is
formed.

Other oxides may also be incorporated into a

glassy SiO2 network in different ways:
1. Network formers: form glassy structures
(B2O3)
2. Network modifiers: added to terminate
(break up) the network (CaO, Na2O).
These are added to silica glass to lower
its viscosity (so that forming is easier)
3. Network intermediates: these oxides
cannot form glass network but join into
the silica network and substitute for Si
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Traditional Ceramics
Traditional ceramics contain many pores and cracks
Low modulus of elasticity (because of the glass phase
present)
Examples: bricks, pottery, china, porcelain, and refractory
ceramics
Raw materials for traditional ceramics:

Clay: Kaolinite
(Si2O5)6(OH)4

(Al2(Si2O5)(OH)4),

Feldspars: K2O.Al2O3.8SiO2

Quartz sand: silica (SiO2)

Montmorrilonite

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Al5(Na,Mg)

Traditional Ceramics - Applications

Ceramic china
Refractory ceramic

Porcelain
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Engineering Ceramics
Engineering ceramics made up of pure compounds of
oxides, carbides and nitrides
More dense ceramics with small number of cracks and
higher elastic modulus
Produced by mixing powders, formed and then sintered
(powder metallurgy)

A. Ourdjini@2016

Engineering Ceramics
Examples Include:
Al2O3, SiC, ZrO2, BeO, MgO
Abrasive ceramics: Si3N4 and SiC
Piezoelectrics and Ferroelectrics: BaTiO3, SrTiO3
Biomaterials : Hydroxyapatite (HA)

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Engineering Ceramics - Applications

Examples:
1.

Alumina (Al2O3)

2.

Silicon nitride (Si3N4)

3.

Silicon carbide (SiC)

4.

Zirconia (ZrO2)

Alumina (Al2O3)

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Oil drill bit

Engineering Ceramics

Tool inserts

Ceramic coating

Piezoceramics
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Mechanical Properties of Ceramics

Ceramics have inferior mechanical properties compared
to metals, and this has limited their applications
The main limitation is that ceramics fail in brittle
manner with little or no plastic deformation.
Fracture strength of ceramics are significantly lower than
predicted by theory because of the presence of very
small cracks in the material (stress concentrators).

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Mechanical Properties of Ceramics

Why are ceramics more brittle than metals?
Metals deform plastically by slip along slip planes
In ceramics, this slip is very difficult due to ionic and
covalent bonds higher energy is required to move one
anion past another.

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Mechanical Properties of Ceramics

Ceramics have excellent compressive strength (used in
cement and concrete in foundations for structures and
equipment)
The principal source of fracture in ceramics is surface cracks,
porosity, inclusions and large grains produced during
processing. Properties are dependent on processing
Testing ceramics using the usual tensile testing is not possible,
so a transverse bending test is used and a modulus of rupture
(MOR) is determined.
Strength of ceramics can only be described by statistical
methods and it is dependent on specimen size.
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Mechanical Properties of Ceramics

Material
Aluminum
oxide
Cubic boron
nitride
Diamond
Silica, fused
Silicon
carbide
Silicon
nitride
Titanium
carbide
Tungsten
carbide
Partially
stabilized
zirconia

Transverse
rupture
Compressive
strength
strength
(MPa)
(MPa)

Elastic
modulus
(GPa)

Hardness
(HK)

Al2O3

140240

10002900

310410

20003000

Poissons
ratio (n)
0.26

CBN

725

7000

850

40005000

3480

SiO2
SiC

1400

100750

7000
1300
7003500

8301000
70
240480

70008000
550
21003000

0.25
0.14

3500

3100

Si3 N4

480600

300310

20002500

0.24

3300

TiC

14001900

31003850

310410

18003200

55005800

WC

10302600

41005900

520700

18002400

10,00015,000

PSZ

620

200

1100

0.30

5800

Symbol

The p roperties vary widely d epending o n the condition o f the material (crack size)
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Density
3
(kg/m )
40004500

Defects in Ceramic Structures

Frenkel Defect
--a cation is out of place.
Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect:

Frenkel
Defect
Adapted from Fig. 12.21, Callister
7e.

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Defects in Ceramic Structures

Impurities must also satisfy charge balance

Ex: NaCl

Substitutional cation impurity

Substitutional anion impurity

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Adapted from Fig. 12.21,

Callister 7e.

Measuring Elastic Modulus

Room temperature behavior is usually elastic, with brittle failure.

we use 3-Point Bend Testing

cross section

d
b

rect.

L/2

L/2

R
d = midpoint

circ.

deflection

Determine elastic modulus according to:

x
slope =

linear-elastic behavior

E=

L3

4bd 3
rect.
cross
section

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L3

12 R4
circ.
cross
section
Adapted from Fig. 12.32,
Callister 7e.

Appendix AUseful solutions to standard problems

Useful solutions to standard problems

Measuring Elastic Modulus

Deflection of beams
C 1 C2

t
F

FL 3
ML 2
=
=
C 1E
C 1E

FL 2
ML
=
=
C 2E
C2 E

F
48 16

F
384 24
5

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L
t (tension)
tension, strength
means the
fracture strength, !t. sections.
In compression it
means
the
R
2
crushing strength !c, which is much larger; typically
Tension

Measuring Strength
3:3

= Mc

!c 10 to 15 !t

Strain = L/L

When
the moment
material is difficult to grip (as is a ceramic), its strength can be
um
bending
in of
bending.
The modulus of rupture or MoR (units: MPa) is the
center
cemeasured
from
specimen
surface stress in a bent beam at the instant of failure (Figure 3.5).
er maximum
fibers

3-point bend test to measure room temperature strength

nt of inertia of cross section

d load

f (compression)

d
2

bd3

3FL
2bd2

12

"R4
FL
4 Slope
"R3E = /

strength !c is 10 to 15 times greater than the tensile stre

Ceramics

Compression

Ao

t (tension)
Tension

Modulus of rupture

Ff

Force F

Stress = F/Ao

Figure 3.4 Stressstrain curves for a ceramic in tension and in comp

Force F
Deflection

t
he load at fracture, L is the distance between support
points, and
Strain
= L/L in Figure 12.32. When the cross sectionL is
ameters are as
indicated

Stressstrain curves for a ceramic in tension and in compression. The compressive

max = 3Ff L = MoR
strength !c is 10 to 15 times greater than the tensile strength !t.
Ff L
2bt 2
Circular section:
sfs !
Rectangular section: (12.7b)
3

pR

Ff

Modulus of rupture

Deflection

e specimen radius.
A. Ourdjini@2016
M.F. Ashby: Materials Selection
in Mechanical
Design
Force
F
istic flexural strength values for several ceramic materials are given

Toughening of Ceramics

Fracture strength or toughness of ceramics can be

improved only by mechanisms that influence the
crack propagation (ceramics always contain cracks).

There are various methods used to improve the

toughness of ceramics:

Transformation toughening

Microcrack induced toughening

Crack deflection & Crack bridging

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Toughening of Ceramics
1. Transformation Toughening: Partially Stabilised Zirconia (PSZ)
n

Zirconia (ZrO2) exists in 3 different crystal structures:

Melt

Cubic
2680 oC

Tetragonal
2370 oC

Monolithic
1150 oC

Transformation toughening is achieved by stabilizing the tetragonal

structure at room temperature.

This is achieved by adding other oxides such as: MgO, CaO, and Y2O3 to
zirconia.

As the crack propagates, it creates a local stress field that induces

transformation of the tetragonal structure to the monolithic structure in that
region.
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Toughening of Ceramics

This transformation is accompanied by a volume expansion, causing a

compressive stress locally and in turn a squeezing effect on the crack.

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Failure of a composite m
Toughening of Ceramics
1. Fiber fracture
2. Crack Deflection and Crack Bridging
Interfacial
debonding
Achieved by reinforcing the 2.
ceramic:
produce ceramic
based
composites (CMC)
3. Fiber pull-out
Crack bridging: fibres debond but do not break

Fibres carry stresses under load, so reduce stress at crack tip and
impede crack propagation
Toughness increases with crack extension

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Toughening of Ceramics

Crack

Crack deflection at
at
Crack deflection
weak
weak interfacial
interface bond
A. Ourdjini@2015

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Fibe

(C)

(B)

(A)

(E)

(D)

Toughening of Ceramics

(C)
(B)
(B)

3. Micro-crack Induced Toughening:

(c)

(d)

Micro-cracks are purposely

introduced by internal stresses
during processing of the
ceramics
These micro-cracks tend to
blunt the tip of the propagating
crack, thus reducing the stress
concentration at the crack tip

Improve
toughness
Figure 3. Conventional
toughening micromechanisms in composite nanoceramics. (a) Fibre toughening is realized th

the crack-bridging (AC) and crack-deflection (D) effects of second-phase fibres incorporated in a ceramic matrix. The br
effect occurs when the fibres either shed load from the crack tip while remaining intact (A) or dissipate the elastic energy
they break (B) or debond from the ceramic matrix and pull out (C). The crack deflection effect occurs when a crack tip meets
fibre that forces the crack to change direction ofA. Ourdjini@2016
its growth (D). (b) Ductile-phase toughening. Ductile inclusions provide bl

Toughening of Ceramics
Fig. (a): A, B, C
v Crack Bridging
Fig. (a): D
v Crack Deflection
Fig. (c):
v Transformation
Toughening
Fig. (d): D
v Microcrack Toughening

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I. A. Ovidko, Philosophical Transactions A, (2015)