CHAPTER 8:Ceramics:

. Structures,
Properties and processing

1
 ISSUES TO ADDRESS...

ISSUES TO ADDRESS...

• How do we classify ceramics?

• What are some applications of ceramics?

• How is processing different than for metals?

2
 Examples of CERAMICS

Ceramics: structures, properties and processing 3

 Examples of CERAMICS

Ceramics: structures, properties and processing 4

 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.

 Always combined more than one elements

Ceramics: structures, properties and processing 5
 Ceramic Bonding
 Bonding:
- Mostly ionic, some covalent.
- % ionic character increases with difference in electronegativity.
 Ionic character of various common ceramics
Materials % of ionic Materials % of ionic
character Character Adapted
from table.
CaF2 89 SiO2 51 12.1,
Callister 7e.
MgO 73 Si3N4 30
NaCl 67 ZnS 18
Al2O3 63 SiC 12

 Ceramics: higher ionic character  higher ionic properties

 Ceramics with oxide structure: cations in the hole of oxygen
lattice
• Oxygen lattice: usually FCC

Ceramics: structures, properties and processing 6

 Ceramics: feature properties and classification

 Generally hard and brittle

 Generally electrical and thermal insulators, especially high
temperature corrosion-resistance
 Can be totally opaque, semi- transparent or transparent.
 Classification:
• Traditional ceramics: based on clay (porcelain, bricks,…) and
glasses..
• Advanced ceramics: products for electronic, computer,
aerospace industry, human transplanted devices.

Ceramics: structures, properties and processing 7

 Ionic bonding & structure
1. Charge & Size
 Charge Neutrality: F-
- Net charge in the CaF 2 : Ca 2+ +
cation anions
structure should
be zero. F-
- General form: A m Xp
m, p determined by charge neutrality
 Ionic radius ratio

- - - - - - - -
+ + +
- - - - - - - -
Hole in anion stable
lattice
unstable stable
Charge & anion cation radius ration  stable structure
Ceramics: structures, properties and processing 8
 Tetrahedral and octahedral voids
Formed by 6 atoms

Formed by 4 atoms

Ceramics: structures, properties and processing 9

 Bonding & structure
2. Stoichiometry
If all of one type of site is full the remainder have to go into other
types of sites.
Ex: FCC structure has 4 octahedral holes (OH) and 8 tetrahedral holes TD. If for a
specific ceramic each unit cell has 6 cations and the cations prefer OH sites
4 in OH
2 in TD

Ceramics: structures, properties and processing 10

 Ionic radius and coordination number
 Coordination number increases with r cation/ r anion
 Issue: How many anions can you arrange around a cation
 Stable structure?

r cation ZnS
r anion Coord Nu (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 Tetrahedral chloride)
Adapted from Fig.
12.2, Callister 7e.

0.414 - 0.732 6 Octahedral CsCl

(cesium
0.732 - 1.0 8 cubic chloride)
Adapted from Fig.
12.3, Callister 7e.

Ceramics: structures, properties and processing 11

 Bonding & structure
3. Bond hybridization: in case of covalent bonding
 Orbitals of different elements interact  hybrid orbitals such as sp2, sp3 
impact on possibility of a cation insertion into hole

Ceramics: structures, properties and processing 12

 Bonding & structure
Ionic radii of several cations and anions (for coordination
number 6)

Copied from table .12.3, Callister 7e.

Ceramics: structures, properties and processing 13

 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,
- Coordination number =
Anion
6
O2- 0.140 - structure = NaCl
Cl - 0.181
Data from Table 12.3,
F- 0.133 Callister 7e.

Ceramics: structure, properties and processing 14

 Rock salt structure: NaCl

rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
cations prefer OH sites

 Coordination number of both Na+ and Cl- is 6

 NaCl crystal structure is considered as two
interpreting FCC lattice: Na+ and Cl- . So, its unit
cell is comprised of 4 cations and 4 anions
 Na+: (1/2, ½, ½), Cl- : (0,0,0)
 Some ceramics as MgO, FeO, MnS, LiF have same
structure of NaCl
Ceramics: structure, properties and processing 15
 Cesium Chloride (CsCl) structure

rCs 0.170
  0.939
rCl 0.181

Adapted from Fig.

12.3, Callister 7e.  So each Cs+ has 8 neighboring Cl-
 CsCl crystal unit cell contains 1 Cs+ and 1 Cl-;
however, CsCl structure is not BCC structure
 CsBr, CsI, have same structure of CsCl

Ceramics: structures, properties and processing 16

 Zinc Blende (ZnS) – Sphalerite structure

rZn 2  0.074
  0.402
rS2  0.184
Adapted from Fig. 12.4, Callister 7e.

 Each Zn2+ has 4 neighboring O2-

 Zn 2+ fills tetrahedral holes of FCC lattice of O2-. Each crystal unit cell
processes 4 Zn2+ ions and 4 O2- ions.
 Ceramic compounds with highly covalent bonding exhibit the Zinc blende
structure
Ceramics: structures, properties and processing 17
 Rutile (TiO2) structure
rTi 4 0.061
  0.435
rO 2 0.140

 Each Ti4+ has 6 neighboring O2- whilst O2-

has 3 neighboring Ti 2+
 Tetragonal unit cell, but not closed
packed. Each oxygen is surrounded by 3
planar Titanium.
 CoF2, FeF2, CrO2, PbO2, SnO2, TeO2,
WO2 have Rutile structure.

Ceramics: structures, properties and processing 18

 Perovskite (ABX3) structure
 Materials have a perovskite structure
possessing an interesting electromechanical
properties.
 Take an example with BaTiO4, unit cell
contains 8 Ba4+ located in the corner of
cubic, 6 O2- situated at the center of each of
six faces, and Ti4+ positioned at the center of
cubic.
 Ionic ratio of perovskite compounds with
cubic structure follows equation:
Adapted from Fig. 12.6, Callister 7e.
rA  rB
0,75  t  1 . t 
2 (rB  rX )

Ceramics: structures, properties and processing 19

 Summary of some common ceramic structures

Copied from Tab. 12.4, Callister 7e.

Ceramics: structures, properties and processing 20

 Glass and Simple Silicate Structure
• Basic Unit: • Glass is amorphous
• Amorphous structure occurs by adding
Si044- tetrahedron impurities (Na+,Mg2+,Ca2+, Al3+)
• Impurities: interfere with formation of
Si 4+ crystalline structure. Na+
O2-
Si4+
O2-

(soda glass)
Adapted from Fig. 12.11, Callister,
7e.

• Quartz is crystalline
SiO2:

Ceramics: structures, properties and processing 21

 Layered Silicate structure: Clay Minerals, Talc…
Shear
Structure of Kaolinite clay
Al2(Si2O5)(OH)4 : Al2(OH)42+
 A single kaolinite sheet is layer
Charge neutral
constructed by Al2(OH)42+ layer
and (Si2O5)2- layer (Si2O5)2-
 Different sheets of clay are layer
bounded by weak hydro or Van
der Waals bonding  easily to
weak van
shear or absorb water der Waals
 Crystal of Kaolinite is made of bonding
series of these sheets stacked 4+
charge Si
parallel each other. 3+
neutral Al
 Diameter of a Kaolinite crystal is -
OH
typically less than 1m 2-
O

Shear
Ceramics: structures, properties and processing 22
 Taxonomy of Ceramics
Taxonomy of Ceramics

Glasses Clay Refractories Abrasives Cements Advanced

products ceramics
-optical -whiteware -bricks for -sandpaper -composites engine
-composite -bricks high T -cutting -structural -rotors
reinforce (furnaces) -polishing -valves
-containers/ Adapted from Fig. 13.1 and discussion in
-bearings
household Section 13.2-6, Callister 7e.
-sensors
• Properties: -biomedical
devices
- Tm for glass is moderate, but large for other ceramics.
- Small toughness, ductility; large moduli & creep resist.
• Applications:
- High T, wear resistant, novel uses from charge neutrality.
• Fabrication
- some glasses can be easily formed
- other ceramics can not be formed or cast.
Ceramics: structures, properties and processing 23
 Application: Refractories
• Need a material to use in high temperature furnaces.
• Consider the Silica (SiO2) - Alumina (Al2O3) system or
MgO…
• Phase diagram shows:
mullite, alumina, and crystobalite as candidate refractories.

2200 3Al2O3-2SiO2
T(°C)
mullite
2000 Liquid
(L) alumina + L
Adapted from Fig. 12.27,
Callister 7e. (Fig. 12.27
1800 is adapted from F.J. Klug
crystobalite mullite alumina and R.H. Doremus,
+L "Alumina Silica Phase
+L + Diagram in the Mullite
1600 mullite Region", J. American
mullite Ceramic Society 70(10),
p. 758, 1987.)
+ crystobalite
1400
0 20 40 60 80 100
Composition (wt% alumina)

Ceramics: structures, properties and processing 24

 Application: Cutting Tools

• Tools:
- for grinding glass, tungsten,
carbide, ceramics
- for cutting Si wafers
- for oil drilling

• Solutions: oil drill bits blades

- manufactured single crystal
or polycrystalline diamonds coated single
crystal diamonds
in a metal or resin matrix.
- optional coatings (e.g., Ti to help
diamonds bond to a Co matrix polycrystalline
diamonds in a resin
via alloying)
matrix.
Photos courtesy Martin Deakins,
GE Superabrasives, Worthington,
OH. Used with permission.

Ceramics: structures, properties and processing 25

 Mohs scale of Mineral hardness
Mohs
Mineral Chemical formula Image
hardness
10 Diamond C

9 Corundum Al2O3

8 Topaz Al2SiO4(OH−,F−)2

7 Quartz SiO2

6 Orthoclase feldspar KAlSi3O8

5 Apatite Ca5(PO4)3(OH−,Cl−,F−)

4 Fluorite CaF2

3 Calcite CaCO3

2 Gypsum CaSO4·2H2O

1 Talc Mg3Si4O10(OH)2

Ceramics: structures, properties and processing 26

 Application: Sensors
• Example: Oxygen sensor ZrO2
• Principle: Make diffusion of ions Ca 2+
fast for rapid response.
• Approach:
A Ca 2+ impurity
Add Ca impurity to ZrO2:
removes a Zr 4+ and a
- increases O2- vacancies
O2- ion.
- increases O2- diffusion rate

• Operation:
sensor
- voltage difference
gas with an reference
produced when unknown, higher gas at fixed
O2- ions diffuse oxygen content O2-
oxygen content
diffusion
from the external
surface of the sensor
to the reference gas. + -
voltage difference produced!

Ceramics: structures, properties and processing 27

 Ceramic Fabrication Methods (I)
Ceramic Fabrication Methods

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Pressing: plates, dishes, cheap glasses
Pressing
Gob
operation -mold is steel with
graphite lining
Parison
mold
• Fiber drawing:
Compressed
• Blowing: air

suspended
Parison

Finishing wind up
mold
Adapted from Fig. 13.8, Callister, 7e. (Fig. 13.8 is adapted from C.J. Phillips,
Glass: The Miracle Maker, Pittman Publishing Ltd., London.)

Ceramics: structures, properties and processing 28

 Sheet Glass Forming
• Sheet forming – continuous draw
– originally sheet glass was made by “floating” glass
on a pool of tin

Adapted from Fig. 13.9, Callister 7e.

Ceramics: structures, properties and processing 29

 Glass Properties
• Specific volume (1/r) vs Temperature (T):
Specific volume
• Crystalline materials:
Liquid
- crystallize at melting temp, Tm
Supercooled
Liquid (disordered) - have abrupt change in spec.
vol. at Tm

Glass • Glasses:
(amorphous solid) - do not crystallize
Crystalline
- change in slope in spec. vol. curve at
(i.e., ordered) solid glass transition temperature, Tg
T - transparent
Tg Tm
- no crystals to scatter light
• Viscosity, h:
- relates shear stress and velocity gradient:

dy dv dv
glass dv h h has units of (Pa-s)
dy dy

velocity gradient
Ceramics: structures, properties and processing 30
 Glass Viscosity vs. T and Impurities
• soda-lime glass: 70% SiO2
• Viscosity decreases with T balance Na2O (soda) & CaO (lime)
• Impurities lower Tdeform • borosilicate (Pyrex):
13% B2O3, 3.5% Na2O, 2.5% Al2O3
• Vycor: 96% SiO2, 4% B2O3
• fused silica: > 99.5 wt% SiO2
Viscosity [Pa ×s]

10 14 strain point
annealing range
10 10

10 6 Tdeform : soft enough

to deform or “work”
10 2
Tmelt Adapted from Fig. 13.7, Callister, 7e.
1 (Fig. 13.7 is from E.B. Shand, Engineering
200 600 1000 1400 1800 T(°C) Glass, Modern Materials, Vol. 6, Academic
Press, New York, 1968, p. 262.)

Ceramics: structures, properties and processing 31

 Heat Treating Glass
• Annealing:
-removes internal stress caused by uneven cooling.
• Tempering:
-puts surface of glass part into compression
-suppresses growth of cracks from surface scratches.
-sequence:
before cooling surface cooling further cooled
cooler compression
hot hot tension
cooler compression

-Result: surface crack growth is suppressed.

Ceramics: structures, properties and processing 32

 Ceramic Fabrication Methods (IIA)
Ceramic Fabrication Methods-IIA

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Milling and screening: desired particle size
• Mixing particles & water: produces a "slip"
• Form a "green" component Ao
container die holder Adapted from
-Hydroplastic forming: force
ram bille extrusion Ad Fig. 11.8 (c),
extrude the slip (e.g., into a pipe) t Callister 7e.
container die
-Slip casting:
pour slip absorb water pour slip drain “green
into mold into mold into mold mold ceramic” Adapted from Fig.
“green 13.12, Callister 7e.
ceramic” (Fig. 13.12 is from
W.D. Kingery,
Introduction to
Ceramics, John
Wiley and Sons,
Inc., 1960.)
solid component hollow component
• Dry and fire the component
Ceramics: structures, properties and processing 33
 Ceramic Fabrication Methods (IIA): materials
Clay Composition
A mixture of components used

(50%) 1. Clay
(25%) 2. Filler – e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
binds it together

aluminosilicates + K+, Na+, Ca+

Ceramics: structures, properties and processing 34

 Drying and Firing
• Drying: layer size and spacing decrease. Adapted from Fig.
13.13, Callister 7e.
(Fig. 13.13 is from
W.D. Kingery,
Introduction to
Ceramics, John
Wiley and Sons,
Inc., 1960.)

wet slip partially dry “green” ceramic

Drying too fast causes sample to warp or crack due to non-uniform shrinkage
• Firing:
-T raised to (900-1400°C)
-vitrification: liquid glass forms from clay and flows between
SiO2 particles. Flux melts at lower T.
Adapted from Fig. 13.14,
Si02 particle Callister 7e.
(quartz) (Fig. 13.14 is courtesy H.G.
Brinkies, Swinburne
micrograph of glass formed University of Technology,
porcelain around Hawthorn Campus,
the particle Hawthorn, Victoria,
Australia.)

70m

Ceramics: structures, properties and processing 35

 Ceramic Fabrication Methods-IIB
Ceramic Fabrication Methods-IIB

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Sintering: useful for both clay and non-clay compositions.
• Procedure:
- produce ceramic and/or glass particles by grinding
- place particles in mold
- press at elevated T to reduce pore size.
• Aluminum oxide powder:
- sintered at 1700°C
for 6 minutes.
Adapted from Fig. 13.17, Callister 7e.
(Fig. 13.17 is from W.D. Kingery, H.K.
Bowen, and D.R. Uhlmann, Introduction
to Ceramics, 2nd ed., John Wiley and
Sons, Inc., 1976, p. 483.)

15 m

Ceramics: structures, properties and processing 36

 Powder Pressing
Sintering - powder touches - forms neck & gradually neck thickens
– add processing aids to help form neck
– little or no plastic deformation
Uniaxial compression - compacted in single direction
Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope

Hot pressing - pressure + heat

Adapted from Fig. 13.16, Callister 7e.

Ceramics: structures, properties and processing 37

 Ceramic Fabrication Methods-III
Ceramic Fabrication Methods-IIB

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Produced in extremely large quantities.
• Portland cement:
- mix clay and lime bearing materials
- calcinate (heat to 1400°C)
- primary constituents:
tri-calcium silicate
di-calcium silicate
• Adding water
- produces a paste which hardens
- hardening occurs due to hydration (chemical reactions
with the water).
• Forming: done usually minutes after hydration begins.

Ceramics: structures, properties and processing 38

 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.
cross section F Adapted from Fig. 12.32,
L/2 L/2 Callister 7e.
d R
b Measuring Elastic Modulus 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

Ceramics: structures, properties and processing 39

 Measuring Strength
• 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 sfs (MPa) E(GPa)
1.5Ff L Ff L
s fs   Si nitride 250-1000 304
bd 2 pR3 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.

d
dfs
Ceramics: structures, properties and processing 40
 Measuring Elevated T Response
• Elevated Temperature Tensile Test (T > 0.4 Tm).

creep test
e
s
x
.
slope = ess = steady-state creep rate
s
time

Ceramics: structures, properties and processing 41

 Applications: Advanced Ceramics
Heat Engines
• Advantages: • Disadvantages:
– Run at higher – Brittle
temperature – Too easy to have voids-
– Excellent wear & weaken the engine
corrosion resistance – Difficult to machine
– Low frictional losses
– Ability to operate without
a cooling system
– Low density

• Possible parts – engine block, piston coatings, jet engines

Ex: Si3N4, SiC, & ZrO2

Ceramics: structures, properties and processing 42

 Applications: Advanced Ceramics
Electronic Packaging
• Chosen to securely hold microelectronics & provide
heat transfer
• Must match the thermal expansion coefficient of the
microelectronic chip & the electronic packaging
material. Additional requirements include:
– good heat transfer coefficient
– poor electrical conductivity
• Materials currently used include:
• Boron nitride (BN)
• Silicon Carbide (SiC)
• Aluminum nitride (AlN)
– thermal conductivity 10x that for Alumina
– good expansion match with Si

Ceramics: structures, properties and processing 43