EME 2176

MATERIALS ENGINEERING

Chapter 4
Ceramics & Glasses
-CERAMICS MATERIALS-STRUCTURES AND
PROPERTIES (Textbook Chapter 12)
-CERAMIC MATERIALS-APPLICATIONS AND
PROCESSING (Textbook Chapter 13)
1
Midterm test
Date: 11-08-2015
Time: 8.00 pm - 10.00 pm
Venue: MAMR 2001
Topics:
Chapter 1 Electrical properties
Chapter 2 Magnetic properties
Chapter 3 Optical properties
Instructions: Answer all 3 questions
2
 CLASSIFICATION OF MATERIALS

Solid materials are conveniently grouped

into 3 basic classifications
METALS
CERAMICS
POLYMERS
COMPOSITES (Combination of two or more
of the above 3 basic materials)

3
 4. CERAMICS

Compounds between metallic and

nonmetallic elements
Oxides, nitrides, carbides
Aluminium oxide/ Alumina (Al2O3)
Silicon dioxide/Silica (SiO2)
Silicon carbide (SiC)
Traditional ceramics
Clay minerals (porcelain)
Cement
Glass
4
 4.1 CERAMIC PROPERTIES
Mechanical behavior
Stiff (Figure 1.4)
Strong (Figure 1.5)
Very Hard
Extremely Brittle
Susceptible to Fracture (Figure 1.6)
Insulative to the passage of heat & electricity (Figure 1.7)
More resistant to high Temperatures and harsh
environments (than metal & polymer)
Optical
Transparent
Translucent
Opaque
Some oxide ceramics(Fe3O4) exhibit Magnetic behavior
5
 CERAMIC BONDING
Bonding:
-- Mostly ionic, some covalent.
-- % ionic character increases with difference in
electronegativity.
Large vs small ionic bond character:
CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University. 6
 4.2 CRYSTAL STRUCTURES
The metallic ions (cations) are positively
charged because given up valence electrons
to the nonmetallic ions (anions) which are
negatively charged.
2 characteristics of the component ions in
the crystalline ceramic materials influence
the crystal structure:
Magnitude of the electrical charge on each
of the components ions.
The relative sizes of the cations and
anions.
7
 CRYSTAL STRUCTURES
Since metallic elements give up electrons
when ionized, cations are ordinarily smaller
than anions.
Cation-Anion Radius Ratio is less than
unity.
Stable ceramic crystal structures form when
those anions surrounding a cation are all in
contact with that cation.

8
 Ionic Bonding & Structure
1. Size - Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - -
+ + +
Adapted from Fig. 12.1,
Callister 7e.
- - - - - -
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
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 CRYSTAL STRUCTURES
The
coordination
number (i.e.,
number of
anion
nearest
neighbors
for a cation)
is related to
the cation-
anion radius
ratio.
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 Coordination # and Ionic Radii
r cation
Coordination # 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.
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 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
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 CRYSTAL STRUCTURES
1) AX-Type Crystal Structures
i. Some common ceramic materials where there are equal
number of cations and anions.
ii. A denotes the cation and X the anion.
2) AmXp-Type Crystal Structures
i. When charges of the cation and anion are not the same.
ii. m and/or p 1.
3) AmBnXp-Type Crystal Structures
i. Ceramic compounds having more than one type of cation.
ii. A and B represents the 2 types of cation.

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 1) AX-Type Crystal Structures
Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: Sodium Chloride NaCl (rock salt) structure
rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

cations prefer OH sites

14
 MgO and FeO
Magnesium Oxide (magnesia) MgO and
Ferrous Oxide FeO also have the NaCl
structure. O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

cations prefer OH sites

So each oxygen has 6 neighboring Mg2+ 15

 AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

rCs 0.170
= = 0.939
rCl 0.181

cubic sites preferred

So each Cs+ has 8 neighboring Cl-

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 AX Crystal Structures
rZn 2 0.074
Zinc Blende (sphalerite) structure = = 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-
Ex: ZnO, ZnS, SiC
17
 2) AmXp-Type Crystal Structures
AX2 Crystal Structures
Fluorite structure
Calcium Fluorite (CaF2)
Cations in cubic sites
Ionic radii ratio rC/rA is
about 0.8
From Table 12.2,
Coordination # 8
Examples of other
compounds: UO2, ThO2,
ZrO2, CeO2

Adapted from Fig. 12.5,

Callister 7e. 18
 3) AmBnXp-Type Crystal Structures
ABX3 Crystal Structures

Perovskite crystal
structure

Ex: complex oxide

Barium titanite BaTiO3

Adapted from Fig. 12.6,

Callister 7e.

19
 Example Problem 12.2: Predicting
Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm)
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069 = 0.550
Ca 2+ 0.100

Anion
O2- 0.140
Cl - 0.181
Data from Table 12.3,
F- 0.133 Callister 7e.
20
 Example Problem 12.2: Predicting
Structure of FeO
Table 12.4

Table 12.2

Based on this ratio,

--coord # = 6
--structure = NaCl 21
 Ceramic Density Computation
Theoretical density of a
crystalline ceramic material :

Number of formula units/unit cell

n(AC AA )
=
VC N A

Volume of unit cell

AC = Atomic weights of cations
AA = Atomic weights of anions
NA = Avogadros number, 6.023 X 1023
formula units/mol

EXAMPLE PROBLEM 12.3 PAGE 425 22

Where:
n' = the number of formula units within the unit cell (eg.BaTiO3: 1, 2 ,3)
AC = the sum of the atomic weights of all cations in the formula unit
AA = the sum of the atomic weights of all the anions in the formula unit
VC = the unit cell volume
NA = Avagadros number
Compute the theoretical density of NaCl on the basis of crystal structure.
How does this compare with its measured density?
n' = 4/unit cell
AC = ANa = 22.99 g/mol
AA = Acl = 35.45 g/mol
Vc = a3
a = 2(rNa + rcl)
rNa= 0.102 nm rcl =0.181nm

=2.14 g/cm3 (Expected value: 2.16 g/cm3)

 4.3 SILICATE CERAMICS
Silicates are materials composed primarily of
silicon and oxygen
2 most abundant elements in earths crust.
Example: soils, rocks, clays, sand.
Crystal structures in various arrangements of
an SiO44- tetrahedron:

Si4+

O2-

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 4.3.1 SILICA
Chemically the most simple silicate material is silicon dioxide
(silica) SiO2.
3 primary polymorphic crystalline forms of silica: quartz,
crystobalite, & tridymite
Structures are relatively complicated and comparatively open.
Relatively low densities.
The strong interatomic Si-O bond leads to a strong, high
melting material (1710C)

Crystobalite (a polymorph of SiO2)

25
 4.3.2 SILICA GLASSES
Fused silica / Vitreous silica
Noncrystalline solid or glass
High degree of atomic randomness (liquid
character)

Figure 3.22: 2D schemes of the structure of (a) crystalline silicon dioxide

and (b) noncrystalline silicon dioxide
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 4.3.2 SILICA GLASSES
Network formers are silica materials (i.e. B2O3 ,GeO2)
that form glassy structures (and polyhendral oxide
structures such as Figure 12.9)
Common inorganic glasses (containers and windows)
are added other oxides (CaO, Na2O) called network
modifiers. Purpose is to modify the tetrahedron
networks.
Intermediate oxides such as TiO2 and Al2O3 do not
function as network formers but substitute for silicon and
become part of the network.
Basically, the addition of modifiers and intermediates
lower the melting point and viscosity of a glass.

27
 4.3.3 THE SILICATES
Various silicate materials, one, two or three of
the corner oxygen atoms of the tetrahedra are
shared by other tetrahedra to form rather
complex structures.
Positive charged cations such as Ca2+, Mg2+ and
Al3+ function to :
Compensate the negative charges from the
tetrahedra, to achieve neutrality.
Ionically bond the tetrahedra together.

29
 4.3.3.1 SIMPLE SILICATES
Combine SiO44- tetrahedra by having them share
corners, edges, or faces

Mg2SiO4

Forsterite Mg2SiO4 has the equivalent number of

two Mg2+ ions associated with each tetrahedron in
such a way that every Mg2+ ion has six oxygen
nearest neighbors.
30
 4.3.3.2 LAYERED SILICATES
A 2D sheet or layered sheet structure can be
produced by sharing of three oxygen ions in
each of the tetrahedra .
Repeating unit formula is (Si2O5)2-
Net negative charge due to unbonded
oxygen atoms.
Electroneutrality is established by a second
palanr sheet having an excess of cations
which bond to those unbonded oxygen
atoms from (Si2O5)2 sheet
This basic structure is characteristic of clays.

31
 Layered Silicates
Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+
layer

Note: these sheets loosely bound by van der Waals forces

32
 4.4 CARBON
Exists in various polymorphic forms and amorphous
state.
Does not really fall within any one of traditional metal,
ceramic and polymer classification schemes.
Graphite (polymorphic form of carbon) is classified as
ceramic.
Crystal structure of diamond (polymorph form) is similar
to zinc blende.

33
 4.4.1 DIAMOND
Metastable carbon polymorph with a crystal structure
variant of zinc blende.
Each carbon bonds covalently to 4 other carbons and is
called diamond cubic crystal structure.
Properties
Hardest known material
Low electrical conductivity
High thermal conductivity
High index of retraction
Large diamonds gems and jewelry
Small diamonds - used for cutting tools and polishing
Diamond films made by film growth techniques coatings
for tools, medical devices or bearings to increase surface
hardness. 34
 4.4.2 GRAPHITE
Another polymorph of carbon.
Crystal structure.

Graphite structure composed of layers of hexagonally

arranged carbon atoms. Within the layers, each carbon
atom is bonded to three coplanar neighbor atoms by
strong covalent bonds. The 4th bonding electron
functions as weak van der Waals forces between layers
Excellent lubricative properties.
35
 4.4.2 GRAPHITE
DESIRABLE PROPERTIES
1) Excellent lubricative
properties.
2) More stable than diamond at
ambient temperature and
pressure.
3) High strength and good
chemical stability at elevated
temperatures and in
nonoxidizing atmospheres.
4) High thermal conductivity.
5) Low coefficient of thermal
expansion
6) High resistance to thermal
shock.
7) High adsorption of gases.
8) Good machinability.
9) Electrical conductivity is
relatively high in
crystallographic directions
parallel to the hexagonal
sheets.
COMMON APPLICATIONS
1) As Heating elements for
electric furnaces.
2) As Electrodes for arc
welding.
3) In Metallurgical crucibles.
4) In Casting molds for metal
alloys and ceramics.
5) For High-temperature
refractories and insulations.
6) In Rocket nozzles.
7) In Chemical reactor
vessels.
8) For Electrical contacts,
brushes and resistors.
9) As electrodes in batteries.
10) In Air purification devices.
36
 4.5 IMPERFECTIONS IN CERAMICS
Both vacancies and interstitials defects
are possible.

39
 4.5.1 ATOM POINT DEFECTS
DEFECT STRUCTURE
expression used to designate the types
and concentration of atomic defects in
ceramics.
ELECTRONEUTRALITY
the state that exists when they are
equal numbers of positive and negative
charges from the ions.
Therefore, defects in ceramics do not
occur alone.

40
 FRENKEL AND SCHOTTKY DEFECT
Shottky Adapted from Fig. 12.21, Callister
Defect: 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

FRENKEL DEFECT
Type of defect that involves a cation-vacancy and a cation-
interstitial site.
A cation leaving its normal position and moving into an
interstitial site.
No change in charge.
SCHOTTKY DEFECT
Type of defect found in AX materials which is a cation vacancy-
anion vacancy pair.
Removing one cation and one anion from the interior of the
crystal and placing both at an exterior surface. 41
Charge neutrality maintained.
 STOICHIOMETRY
Defined as a state for ionic compounds wherein there is the
exact ratio of cations to anions as predicted by the chemical
formula.
For example, NaCl is stoichiometric if the ratio of Na+ ions to Cl-
ions is exactly 1:1.
Therefore a Frenkel or Schottky defect does not result in the
material being nonstoichiometric since the ratio is not altered.
Nonstoichiometry occurs for some ceramics in which two
valence (or ionic) states exist for one of the ion types.
For example, Iron oxide (FeO) in which the iron can be present
as Fe2+ or Fe3+ states.
Fe3+ ion disrupts the electroneutrality
of the crystal by an excess +1 charge.
To offset this, formation of one Fe2+
vacancy for every two Fe3+ formed.

42
 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 43
 FRENKEL DEFECTS
Number of cation-vacancy/cation interstitial
defect pairs Nfr

Qfr
Nfr = N exp( )
2kT

Qfr = energy required for the formation of each Frenkel defect

N = total number of lattice sites
k = Boltzmanns constant Qv
Nv = N exp( )
t = absolute temperature kT
Note: Factor 2 is present in the denominator of the exponential because two
defects (a missing cation and an interstitial cation) in Frenkel defects.
44
 SCHOTTKY DEFECTS
The equilibrium number Ns (in a AX-type
Compound)

Qs
Ns = N exp( )
2kT

Qs = Schottky defect energy of formation.

45
 4.5.2 IMPURITIES IN CERAMICS
Impurity atoms can form solid solutions in ceramic materials.
Both substitutional and interstitial types are possible.
For interstitial, the ionic radius of the impurity must be
relatively small in comparison to the anion.
For example, in sodium chloride NaCl, impurity Ca2+ and O2-
ions would most likely substitute for Na2+ and Cl- ions
respectively.

46
 4.7 MECHANICAL PROPERTIES OF
CERAMIC MATERIALS
4.7.1 BRITTLE FRACTURE OF
CERAMICS
At room temperature, both crystalline and noncrystalline ceramics almost
always fracture before any plastic deformation can occur when applied a
tensile load.
The brittle fracture process consists of the formation and propagation of
cracks through the cross section of material in a direction perpendicular to
the applied load.
Measured fracture strengths of ceramic materials are lower than predicted
by theory from interatomic bonding forces. This is due to very small flaws
in the material that serves as stress raisers points at which the
magnitude of an applied tensile stress is amplified.
For compressive stresses, there is no stress amplification associated with
any existence flaws.
Therefore, brittle ceramics display much higher strengths in compression
than in tension. 50
 4.7.2 STRESS-STRAIN BEHAVIOR
Normal/Standard Tensile Test

Stress-strain behavior of brittle ceramics not usually ascertained by

above method due to:
Difficult to prepare and test specimens having the required
geometry.
Difficult to grip brittle materials without fracturing them.
Ceramics fail after only about 0.1% strain. Need to be perfectly
aligned to avoid bending stresses.
51
 4.7.2.1 FLEXURAL STRENGTH
A more suitable transverse bending test is mostly employed.
A rod specimen (circular/rectangular cross-section) is bent until fracture
using a three/four point loading technique.

52
 4.7.2.1 FLEXURAL STRENGTH
Stress is computed from the specimen thickness, the bending moment
and the moment of inertia.
Maximum tensile stress exists at the bottom specimen surface directly
below the point of load application.
Since the tensile strengths of ceramics are about one-tenth of their
compressive strengths, and since fracture occurs on the tensile specimen
face, this flexure test is a reasonable substitute ofr the tensile test.
The stress at fracture is known as Flexural Strength (modulus of rupture,
fracture strength or bend strength).
F
cross section L/2 L/2
d R
b
d = midpoint
rect. circ.
deflection
location of max tension

53
 Flexural strength:

1.5Ff L Ff L
s fs = = Typ. values:
bd 2 pR3 Material sfs (MPa) E(GPa)
F Rect. Circ.
Ff x Si nitride 250-1000 304
Si carbide 100-820 345
d Al oxide 275-700 393
dfs glass (soda) 69 69
Data from Table 12.5, Callister 7e.

The magnitude of flexural strength for a specific ceramic material will be

greater than its fracture strength measured from a tensile test.
The entire tensile specimen is under tensile strength
Only a small volume fraction of a flexural specimen is subjected to tensile
stresses.
54
 Measuring Elastic Modulus
Room T behavior is usually elastic, with brittle failure.
3-Point Bend Testing often used.
--tensile tests are difficult for brittle materials.
F
cross section 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 d 4bd 3 d 12 p R4
slope =
d rect. circ.
cross cross
d section section
linear-elastic behavior
55
4.7.4 MISC MECHANICAL CONSIDERATIONS
1. POROSITY
For some ceramic fabrication techniques, the precursor
material is in the form of powder. Subsequent to
compaction or forming of these powder particles into
desired shape, pore or/and voids will exist between these
powder particles. Although heat treatment will eliminate
much of the porosity but incomplete pore elimination and
residue porosity will remain.
a) INFLUENCE OF POROSITY ON ELASTIC PROPERTIES OF
CERAMICS
It is observed that for some ceramic materials, the
magnitude of the modulus of elasticity E decreases with
volume fraction porosity P according to:

For some ceramic materials: E = E0(1 - 1.9P + 0.9P2)

where:
E0 is the modulus of elasticity on the nonporous material
P is the volume fraction porosity
58
Magnitude of the modulus of elasticity E decrease with volume fraction
porosity P for aluminium oxide at room temperature.

59
b) INFLUENCE OF POROSITY ON FLEXURAL
STRENGTH OF CERAMICS
Porosity if deleterious to the flexural strength for
two reasons:
(a) pores reduce the cross-sectional area across
which a load is applied
(b) pores act as stress concentrators. Example, for
an isolated spherical pore, an applied tensile
stress is amplified by a factor of 2.

60
 Experimentally it has been shown that the flexural
strength decreases exponentially with the volume
fraction porosity (P) as

sfs = s 0 exp( nP)

s 0 = experiment al constant
n = experiment al constant
61
2. HARDNESS
This beneficial mechanical property is often utilized when an abrasive or
grinding action is required.
Hardest known materials are ceramics.

Normally ceramics having Knoop hardness of about 1000 or greater are

utilized for their abrasive characteristics.

62