Chapter 12 - Structures and Properties of Ceramics

Course Description:
The course covers the fundamental knowledge of engineering ceramics,

polymeric materials, composite materials and construction materials, as well as
corrosion/degradation of these materials. The materials microstructure,
processing, mechanical behaviour and applications are emphasized. Materials
selection is discussed with case studies.
Prerequisites: MECH 141 Engineering Materials I or equivalent course
Textbook: Materials Science and Engineering, eighth edition,
by William D. Callister, Jr. and David G. Rethwisch
Supplementary Textbooks (Reserved in the Library):
Engineering Materials 2: An introduce to Microstructures, Processing and
Design, second edition, 1998 by M. F. Ashby and D. R. H. Jones, Butterworth-
Heinemann, Oxford
Engineering Materials: Properties and Selection, 6th edition, 1999, by K.G.
Budinski and M.K. Budinski, Prentice Hall, N.J.
Materials Selection in Mechanical Design, 1st edition, by M.F. Ashby,
Butterworth-Heinemann, Oxford, 1993
MECH3420 (MECH 242) ENGINEERING MATERIALS II
Instructor: Tong-Yi ZHANG, Chair Professor
(Tel. 7192, Rm: 2546, E-mail: mezhangt@ust.hk)
Teaching Assistants:
Miss Yijing SUN (Tel. 7199, Rm: 2125, E-mail: sallysun@ust.hk)
Mr. Yu Xuan TEOH (Tel. 7461, Rm: 4599, E-mail: yxteoh@ust.hk)
Lectures: Monday & Wed 10:30-11:50 am (Room 3008)
Tutorials: Tuesday 6:00-6:50 pm (Room 2306)
Grading Policy: Homework and quizzes: 20%
Midterm exam: 35%
Final exam: 45%
All homework assignments should be handed in by the same day of the
week after the tutorial class. A late submission bears a penalty of 10%
per day of the mark.
Mid-term exam is scheduled on 24 October (Monday).
1. Engineering Ceramics (3 weeks)
Ceramic structures
Mechanical properties
Processing and applications
2. Polymers (3 weeks)
Polymer structures
Mechanical and thermomechanical behavior
Processing and applications
3. Composites (2 weeks)
Particle-reinforced composites
Fiber-reinforced composites
Structural composites
Lecture Contents
4. Corrosion and Degradation of Materials (2 weeks)
Corrosion and oxidation of metals
Corrosion of ceramics & degradation of polymers
5. Electrical Properties (2 weeks)
Electrical conductivity
Semiconduction
Electrical properties of metals, ceramics and
polymers
6. Construction Materials (2 weeks)
Cements and concrete
Wood
Lecture Contents
Chapter 12
Structures and Properties of
Ceramics
Department of Mechanical Engineering
Hong Kong University of Science & Technology
Outline of the Chapter
Why Ceramics? Applications?
Understanding the ceramic
structures
Mechanical Properties of Ceramics
Part I
Why Ceramics and Their Applications?
Characteristics of Ceramics
Ceramic = Keramikos in Greek meaning burnt stuff
General characteristics
Inorganic and non-metallic
Outstanding hardness
High mechanical strength
High dimensional stability
Resistance to wear
Other distinctive characteristics in application
specific ceramics
Piezoelectric ceramics dimensional change in response
to an electric field, or vice versa
Biocompatible ceramic coating bone implantation coating
Highlights of Ceramic Applications
Kitchenware
High performance electronic substrates
Knock sensor
To detect the
knocking of engine
due to gasoline
quality or difference
in operating
conditions
Cutting blade
Part II
Understanding the ceramic structures
Ceramic Structures Introduction (1)
Composed of at least two electrically charged
elements: cations (metallic) and anions
(nonmetallic)
Bonding: mostly ionic, some covalent
The closer the atoms are together, the greater the
degree of covalency
Degree of ionic character is determined by
electro-negativity of the atoms
Percentage of Ionic Character
% Ionic Character (IC) =
{1exp [-(0.25)(x
A
-x
B
)
2
]} x 100% (Eq.2.10)
where x
A
& x
B
are the electronegativities of the
respective elements
e.g. CaF
2
Ca ~ 1.0; F ~ 4.0 (see Table 12.1)
IC = {1exp [-(0.25)(1-4)
2
]} x 100% = 89.46%
Factors determining the crystal structure
Magnitude of the electrical charge of the
component ions electrically neutral
Relative size of the cations and anions
Stable ceramics: anions surrounding a cation are all in
contact with that cation
Coordination number:
number of the nearest
neighbors or touching atoms
Common coordination
numbers of ceramic
materials: 4,6,8
r
cation
r
anion
Coord #
< .155

.155-.225

.225-.414

.414-.732

.732-1.0
ZnS
(zincblende)
NaCl
(sodium
chloride)
CsCl
(cesium
chloride)
2

3

4

6

8
Coordination number increases with r
cation
/r
anion
Example 12.2
Q. On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation
Al
3+

Fe
2+

Fe
3+

Ca
2+

Anion
O
2-

Cl
-

F
-

Ionic radius (nm)
0.053

0.077

0.069

0.100

0.140

0.181

0.133

r
cation
r
anion
=
0.077
0.140
= 0.550
Based on this ratio,
Coordination No = 6
From Table 12.3,
Ceramic Structures AX Type (1)
Containing equal numbers of cations and
anions
3 structure types
Rock salt structure: Coordination no. = 6
Cesium chloride structure: Coordination no. = 8
Zinc blende structure: Coordination no. = 4
Coordination no.=6
FCC structure
Typical examples:
NaCl, MgO, MnS,
LiF & FeO
Rock Salt Structure
Coordination no.=8
Similar to BCC
structure, but not
exactly, due to the
involvement of two
different kinds of atoms
Typical example:
CsCl
Cesium Chloride Structure
Coordination no.=4
Tetrahedrally
coordinated
Typical examples:
ZnS, ZnTe and SiC
Zinc Blende Structure
Ceramic Structures A
m
X
p
Type
The absolute charge of
each cation does not
equal that of each anion
Florite (CaF
2
): r
cation
/r
anion
=
0.100/0.133 0.8
Coordination no.=8
Only half the cation sites
are occupied since #Ca
2+
ions = F
-
ions
Ceramic Structures A
m
B
n
X
p
Type
Containing more
than one type of
cation
Perovskite
Crystalline Structure
Typical Example:
BaTiO
3
Crystal Structures from the Close Packing
of Anions (1)
In ceramics, the close-packed planes of
anions are stacking on one another to form a
FCC (Face-Centered Cubic) or HCP
(Hexagonal Close-Packed) structure
The small cations may reside (or stay) at the
small interstitial sites in-between the planes
of anions
of Anions (2)
Tetrahedral Position: Four atoms surrounding one site
Octahedral Position: Six atoms surrounding one site
of Anions (3)
Two tetrahedral sites per anion
1/4 x 4 x 2 = 2
of Anions (4)
One octahedral site per anion
1/6 x 3 x 2 = 1
Octahedral Position
An octahedral
position for an
(interstitial) atom is
the space in the
interstices between 6
regular atoms that
form an octahedra
of Anions (3)
This is a rock salt crystal structure, in which the cations
reside in octahedral position with 6 neighbor anions
{111} plane
Ceramic density computations
Silicate ceramics
Silicates composed of Si & O
2
with Si-O covalent bonds: most
abundant on earth (e.g. soils, rocks, clays, sand)
Basic unit: (SiO
4
)
4-
tetrahedron, can be combined into different
arrangements for various silicate structures, like forsterite (Mg
2
SiO
4
)
and akermanite (Ca
2
MgSi
2
O
7
)
Basic Unit
Silicate ion structures
based on the Basic Unit
Silica: SiO
2
(1)
Silica may form a crystalline
3D network, in which atoms
are periodically arranged
and every corner oxygen in
the (SiO
4
)
4-
tetrahedron is
shared by adjacent
tetrahedrons
Electrically neutral and
stable atomic structure
Three primary polymorphic
crystalline forms are quartz,
cristobalite and tridymite.
Cristobalite crystal
Silica (2)
Quartz
Cristobalite Tridymite
They all possess the same chemical composition, SiO
2
, but they
have different structures and appearances
Low density, e.g. quartzs room density is 2.65g/cm
3
High melting point (1710C)
Silica Glasses
Non-crystalline, high
degree of atomic
randomness
Adding of CaO & Na
2
O
(network modifiers) can
lower the melting point
and viscosity of a glass
easier for shape
changing
Applications: containers,
windows
Layered Silicates
A layered structure is
produced by repeating the
tetrahedral unit of (Si
2
O
5
)
2-
In a common layered
silicates, kaolinite, the silica
tetrahedral layer is
electrically neutralized by an
adjacent Al
2
(OH)
4
2+
Bonding within this two-
layered sheet is strong and
intermediate ionic-covalent,
whereas bonding between
the adjacent sheets is weak,
van der Waals.
+ve
+ve
-ve
-ve
-ve
Carbon Diamond (1)
http://en.wikipedia.org/wiki/Diamond#Crystal_structure
Carbon exists in various
polymorphic forms, like
diamond, graphite, fullerenes
and Carbon nanotube
Diamond structure
Metastable crystal structure
at ambient temperature and
pressure
A variant of the zinc blende
Totally covalent carbon-
carbon bonds
Also called diamond cubic
crystal
Carbon Diamond (2)
Hardness: the hardest known
material
Clarity: optical transparent over a
larger range of wavelengths (from
the ultraviolet into the far infrared)
Thermal Conductivity: conducts
heat better than anything - five
times better than the second best
element, Silver!
Melting Point: possess the
highest melting point (3820K)!
Lattice Density: The atoms of
Diamond are closely packed.
Diamond or/and diamond-like thin
film coatings are used to enhance
hardness and wear properties of
other materials
Carbon Graphite (1)
Composed of layers of
hexagonally arranged
carbon atoms
Coexistence of strong
covalent bonds between
carbon atoms and a
weak van der Waals
bond between layers
The weak interplane
bond allows easy
interplanar cleavage -
excellent lubrication
properties
Carbon Graphite (2)
Characteristics
High electrical conductivity
parallel to the hexagonal
sheets
high strength and good
chemical stability at high
temperatures
high thermal conductivity
low coefficient of thermal
expansion
high resistance to thermal
shock
Applications:
heating elements; electrodes
for arc welding; metallurgical
crucible; casting moulds; high-
temp refractories; insulation in
rocket nozzle
Carbon - Fullerenes
Hollow spherical cluster of 60
carbon atoms (carbon-cage
molecules)
Each C
60
molecule consists of
groups of carbon atoms to
form hexagon (x20) and
pentagon (x12)
In the solid state, the C
60
units
form a crystalline structure and
pack together in a FCC array
Pure crystalline solid of C
60
is
electrically insulating. When
potassium (3K+ ions) is added,
the resulting material K
3
C
60
has a very high electrical
conductivity, with
characteristics of a metal.
Composed of both hexagon
and pentagon, in which no
two pentagon share a
common side
Carbon Nanotube (1)
Multi-wall carbon nanotube Department of Mechanical Engineering
A single sheet of graphite rolling into a
tube with the end cap of C
60
fullerene
hemisphere
Excellent mechanical properties
Strongest and stiffest fibers ever
known (E = 0.3 1.2 TPa; UTS =
50-200GPa)
Thermal properties
Good thermal conductor at room
temp. (higher than metals)
High decomposition temp. >600 )
Negligible CTE
Electrical conductivities
Variable electrical conductivity
(metal to semiconductor to insulator)
depending fabrication process and
structure
Low density (1.30~1.80 g/cm
3
)
Excellent chemical stability (Acid, base)
Carbon Nanotube (2)
Patterning of the carbon multi-walled
nanotubes (Dai & Mau, Adv Mater,
2001)
Single-walled nanotube (SWNT) fabricated
by Phy Dept, HKUST
Potential Applications: Light
Emitting Diode (LED) and flat
panel display, nano-scale
transistor, nanoelectronic
devices, electrical conducting
material, structural composites.
Multi-Wall Carbon Nanotubes synthesized by thermal
decomposition of hydrocarbons in the presence of catalysts and
purified in nitric acid.
Imperfections in Ceramics (1) Atomic Point
Defects
2 types of Atomic Point
Defects
Frenkel Defect: cation-
vacancy + cation-
interstitial
Schottky Defect: cation-
vacancy + anion vacancy
Condition of the Defects:
Electroneutrality should
be maintained
Equilibrium numbers of Frenkel and
Schottky defects
Equilibrium number of vacancies, N
v
|
.
|
\
|
=
kT
Q
N N
v
v
exp
(4.1)
N: the total number of atomic sites
Q
v
: the formation energy of a vacancy
k: Boltzmanns constant
T: the absolute temperature in kelvins
Equilibrium numbers of Frenkel and
Schottky defects
Equilibrium number of Frenkel defects, N
fr
,
and Schottky defects, N
s
N: the total number of lattice sites
Q
fr
: the formation energy of a Frenkel defect
Q
s
: the formation energy of a Frenkel defect
k: Boltzmanns constant
T: the absolute temperature in kelvins
|
|
.
|
\
|
=
kT
Q
N N
fr
fr
exp
|
.
|
\
|
=
kT
Q
N N
s
s
exp
Imperfections in Ceramics (2)
Stoichiometry (Valence defects)
Stoichiometry: a state for ionic compounds
wherein there is the exact ratio of cations to
anions as predicted by the chemical formula
Non-stoichiometry one of the ion types in
the ceramic showing two valence (or ions)
states
Imperfections in Ceramics Non-
stoichiometry
Example for non-
stoichiometry
Both Fe
2+
and Fe
3+
can
exist, depending on
temperature and the
ambient oxygen pressure
The electrically neutrality
is always maintained, but
the ratio of cation and
anion would not as shown
in the chemical formula
Imperfections in Ceramics (3) Impurities
Substitution impurity
will substitute for the
host ion to which it is
the most similar in
an electrical sense
Interstitial: impurity
ionic radius must be
small compared to
the anion
Ceramic Phase Diagrams
Experimentally or/and theoretically
determined
It is frequently the case that the two
components are compounds that share a
common element, often oxygen
Ceramic phase diagram may have
configurations similar to metal-metal systems
Examples: Al
2
O
3
-Cr
2
O
3 ,
MgO-Al
2
O
3 ,
ZrO
2
-CaO ,
SiO
2
-Al
2
O
3
Ceramic Phase Diagrams Al
2
O
3
-Cr
2
O
3
Same form as the
isomorphous Cu-Ni phase
diagram
Single liquid, single solid
and two-phase solid-liquid
phases
Al
2
O
3
and Cr
2
O
3
have the
same crystal structure
Al and Cr have the same
charge and similar radii
(0.053 and 0.062 nm,
respectively)
Al
2
O
3
-Cr
2
O
3
is also called as
Sapphire, which is used as
hard bearings in watches
and scientific instruments, or
dinnerware, artware, and
within the tile industries
Ceramic Phase Diagrams MgO-Al
2
O
3
(1)
Similar to Pb-Mg phase
diagram
An intermediate phase
(spinel: MgO-Al
2
O
3
=
MgAl
2
O
4
) there is a range
of composition over which
spinel is stable
Limited solubility of Al
2
O
3
in MgO below 1400C
due to the differences in
charge and radii of the
Mg
2+
and Al
3+
ions
(0.072nm, 0.053nm).
Two eutectic reactions
(on either side of spinel at
2000C)
Ceramic Phase Diagrams Eutectic and
Eutectoid Reactions
Eutectic reaction Upon cooling, a liquid
phase transforms isothermally and reversibly
into two intimately mixed solid phases
Eutectoid reaction Upon cooling, a solid
phase transforms isothermally and reversibly
into two intimately mixed, new solid phases
Ceramic Phase Diagrams ZrO
2
-CaO
One eutectic (2250C and 23wt%
CaO), two eutectoid (at 1000 and
2.5wt% CaO; and at 850C and
7.5wt% CaO) reactions
Three different crystal structures:
tetragonal (T), monoclinic (M) and
cubic (C).
Pure ZrO
2
experiences T - M phase
transformation at about 1150C, with a
large volume change (shrinkage) and
crack formation
Partially stabilized ZrO
2
(PSZ) by
adding 3-7wt% CaO (or Y
2
O
2
, MgO):
Upon cooling the C + T phases are
retained, without causing crack
formation
Ceramic Phase Diagrams SiO
2
-Al
2
O
3
Silica and Alumina are
prime refractory
materials
They are not mutually
soluble in one another
An intermediate
compound (mulite:
3Al
2
O
3
-2SiO
2
) forms at
72wt% Al
2
O
3
A single eutectic exists
(at 1587C and 7.7 wt%
Al
2
O
3
)
Part III
Brittle Fracture
At room temperature, ceramics exhibit brittle fracture without
plastic deformation in tension.
If crack growth in crystalline ceramics is along a specific
crystallographic plane, which is called cleavage.
Maximum stress at the crack tip:
Fracture Toughness
where
Y = dimensionless parameter
o = applied stress
a = surface crack length
t
= crack tip radius
)
a
( 2 =
1/2
t

o o
max
a Y =
KIc
t o
Mechanical Properties of Ceramic
Brittle Fracture: Observations (1)
#1: The measured fracture strengths
of ceramics << the strength predicted
from interatomic bonding forces
Explanation: Ceramics always
contain very small and prevalent
flaws, serving as stress raisers
#2: Considerable variation & scatter
in the fracture strength of a ceramic
Explanation: The fracture strength is
depended on the probability of the
existence of flaws initiating cracks
(Fig 12.28)
The frequency distribution of observed
fracture strengths for a portland cement
Poling direction
Specimen
Silicone oil
Loading
High Voltage
Experimental set-up
Bending strength (MPa)
0 20 40 60 80 100 120 140
0
10
20
0
10
20
0 kV/cm
0
10
20
3.3 kV/cm
P
r
o
b
a
b
i
l
i
t
y

d
e
n
s
i
t
y

(
%
)
0
10
20
6.7 kV/cm
0
10
20
10 kV/cm
0
10
20
16 kV/cm
20 kV/cm
Three-point bending tests on Lead
Zirconate Titanate Ceramics
Microflaws play an important role
On average, small samples have high
fracture strengths than large samples
because the possibility to have a
large size flaw in a small sample is
lower than in a large sample.
Ceramics appear to be stronger in
bending than in tension because the
largest flaw may not be near the
surface.
Mechanical Properties of Ceramic
Brittle Fracture: Observations (2)
#3: Brittle ceramics display much higher strengths in compression than
in tension
Explanation: For compression, no stress amplification associated with
flaws
#4: How can the fracture strength of a brittle ceramic be increased?
Explanation: By imposing residual compressive stresses at its
surface by thermal tempering
#5: Why tensile tests are not employed for brittle ceramics?
Explanation:
1. Difficult to grip brittle samples
2. Difficult to prepare samples with specific dimensions
3. Brittle ceramics fail at about 0.1% strain
Stress-strain Behavior Flexural Strength (1)
A linear relationship between stress
and strain for most ceramics
Brittle at room temperature: elastic
limit = fracture strength
Flexural strength:
Rectangular cross section
Circular cross section
3
R
L F
f
fs
t
o =
2
2
3
bd
L F
f
fs
= o
Stress-strain Behavior Flexural Strength (2)
Size effects: Higher
possibility of bigger flaws
in larger size specimens
High specific elastic
moduli for most
engineering ceramics
(Modulus: 70~500GPa )
Plastic Deformation Crystalline Ceramics
Plastic deformation is difficult to occur by the
motion of dislocations
For ionic predominant crystalline ceramics
Very few slip systems
Slip is difficult in ions of like charge because of
electrostatic repulsion
For covalent predominant crystalline ceramics
Strong covalent bonds
Limited number of slip systems
Complex dislocation structures
Plastic Deformation Non-crystalline ceramics
Plastic deformation is not
induced by dislocation motion
because of the irregular
atomic structure.
Viscous flow occurs instead
of dislocation slip: atoms or
ions slide past one another in
shear by the breaking and
reforming of interatomic
bonds.
The viscosity of glass
decreases with increasing
temperature as the
interatomic bond strength is
diminished.
dy / d
F/A
dy / d

u u
= =
Viscosity:
Effects of Porosity on Mechanical Properties
Pores or void spaces exist
between powder particles in
fabricated ceramics
Any residual pores are
deleterious because
Reduced cross-sectional area
Pores act as the stress raisers
Elastic Modulus of ceramics
containing pores of volume
fraction, P:
E = E
0
(1 1.9P + 0.9 P
2
)
Flexural strength decreases
exponentially with the volume
fraction (P) as
o
fs
= o
0
exp (-nP)
Elastic Modulus
Flexural Strength
Hardness
Hardness
Hardest known material -
beneficial mechanical
properties of ceramics that can
be utilised for abrasion and
grinding other materials.
Creep
Ceramics creep when subjected to stresses at elevated
temperatures
Time-deformation creep behaviour is similar to metals.
Creep strain at a given load and temperature.
Effects of stress and temperature
on the creep behavior

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Course Description:

The course covers the fundamental knowledge of engineering ceramics,

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