Ceramic Their Properties and

Material Behavior
EEM3212 – Materials Science
Dr Dayang Siti Hazimmah binti Ali
 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:
-- 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.
 Ceramic Bonding
• Bonding:
-- Mostly ionic, some covalent.
-- % ionic character increases with difference in
electronegativity (remember!?!).
• 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.
 Ceramic Crystal Structures
Oxide structures
– oxygen anions much larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations in the holes of the oxygen lattice
• The same ideas apply to all “ceramics”
• Principles of Ceramic Architecture:
– Size relationships Cation to Anion
– Electrical Neutrality of the overall structure
– Crystallographic Arrangements
– Stoichiometry Must Match
 Silica Glass

• A “Dense form” of amorphous silica

– Charge imbalance corrected with “counter
cations” such as Na+
– Borosilicate glass is the pyrex glass used
in labs
• better temperature stability & less brittle than sodium
glass
GLASSES – transparent and easily shaped
Noncrystalline Silicates + oxides (CaO, Na2O, K2O, Al2O3)
E.g. Soda lime glass = 70wt% SiO2 + 30% [Na2O (soda) and CaO(lime)
Table 13.1
 GLASS PROPERTIES
• Specific volume (1) vs Temperature (T):
Specific volume
• Crystalline materials:
Liquid --crystallize at melting temp, Tm
Supercooled (disordered)
Liquid --have abrupt change in spec.
Glass
vol. at Tm
(amorphous solid)
Crystalline
• Glasses:
(i.e., ordered) solid --do not crystallize
Tg Tm T --spec. vol. varies smoothly with T
Adapted from Fig. 13.5, Callister, 6e.
--Glass transition temp, Tg
• Viscosity: 
--relates shear stress & dv dy dv
velocity gradient:  glass dv
dy dy
--has units of (Pa-s)  velocity gradient

9
 GLASS VISCOSITY VS T AND IMPURITIES
• Viscosity decreases with T increase
• Impurities lower Tdeform
fus sil
96 yre e
sod ss

ed ica
gla

% x
a-l
P

si l
im

ica
s]

10 14
annealing range
Viscosity [Pa

10 10

10 6 T deform : soft enough

to deform or “work”
10 2 from E.B. Shand, Engineering Glass, Modern
Materials, Vol. 6, Academic Press, New York,
1 1968, p. 262.
200 600 10 00 1400 1800 T(°C)

10
 Important Temperatures
•Melting point = viscosity of 10 Pa.s
•Working point= viscosity of 1000 Pa.s
•Softening point= viscosity of 4x107Pa.s
Temperature above which glass cannot
be handled without altering dimensions)
•Annealing point= viscosity of 1012 Pa.s.
•Strain point = viscosity of 3x1013Pa.s
Fracture occurs before deformation

• Viscosity decreases with T

• Impurities lower Tdeform
 Silicates
– Combine SiO44- tetrahedra by having them
share corners, edges, or faces

Mg2SiO4 Ca2MgSi2O7

– Cations such as Ca2+, Mg2+, & Al3+ act to

neutralize & provide ionic bonding
 Layered Silicates
• Layered silicates (clay
silicates)
– SiO4 tetrahedra connected
together to form 2-D plane

• (Si2O5)2-
• So need cations to balance =
charge
 Layered Silicates
• Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer

Adapted from Fig.

12.14, Callister 7e.

Note: these sheets loosely bound by van der Waal’s forces

 Layered Silicates

• Can change the counterions

– this changes layer spacing
– the layers also allow absorption of water
• Micas: KAl3Si3O10(OH)2
• Bentonite
– used to seal wells
– packaged dry
– swells 2-3 fold in H2O
– pump in to seal up well so no polluted ground water seeps
in to contaminate the water supply.
– Used in bonding Foundry Sands and Taconite pellets
 Carbon Forms
• Carbon black – amorphous –
surface area ca. 1000 m2/g
• Diamond
– tetrahedral carbon
• hard – no good slip planes
• brittle – can cleave (cut) it
– large diamonds – jewelry
– small diamonds
• often man made - used for
cutting tools and polishing
– diamond films
• hard surface coat – cutting
tools, medical devices, etc.
 Carbon Forms - Graphite
• layer structure – aromatic layers

– weak van der Waal’s forces between layers

– planes slide easily, good lubricant
 Carbon Forms –
Fullerenes and Nanotubes
• Fullerenes or carbon nanotubes
– wrap the graphite sheet by curving into ball or tube
– Buckminister fullerenes
• Like a soccer ball C60 - also C70 + others

Adapted from Figs.

12.18 & 12.19,
Callister 7e.
 Defects in Ceramic Structures
• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect: Adapted from Fig. 12.21, Callister
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

QD / kT
• Equilibrium concentration of defects ~e
 Mechanical Properties

We know that ceramics are more brittle

than metals. Why?
• Consider method of deformation
– slippage along slip planes
• in ionic solids this slippage is very difficult
• too much energy needed to move one anion
past another anion (like charges repel)
 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
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  4bd 3  12  R4
slope =
 rect. circ.
cross cross
 section section
linear-elastic behavior
 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 fs (MPa) E(GPa)
1.5Ff L Ff L
 fs   Si nitride 250-1000 304
bd 2 R3 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.


fs
 Mechanical Issues:
• Properties are significantly dependent on
processing – and as it relates to the level of
Porosity:
• E = E0(1-1.9P+0.9P2) – P is fraction porosity
 fs = 0e-nP -- 0 & n are empirical values

• Because the very unpredictable nature of

ceramic defects, we do not simply add a factor
of safety for tensile loading
• We may add compressive surface loads
• We often choose to avoid tensile loading at all – most
ceramic loading of any significance is compressive (consider
buildings, dams, brigdes and roads!)
 Application: Refractories
• Need a material to use in high temperature furnaces.
• Consider the Silica (SiO2) - Alumina (Al2O3) system.
• 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,
1800 Callister 7e. (Fig. 12.27

crystobalite mullite alumina

is adapted from F.J. Klug
and R.H. Doremus,
+L +L + "Alumina Silica Phase
1600 mullite Diagram in the Mullite
Region", J. American
mullite Ceramic Society 70(10),
+ crystobalite p. 758, 1987.)
1400
0 20 40 60 80 100
Composition (wt% alumina)
 Application: Die Blanks
• Die blanks: die Ad
-- Need wear resistant properties! Ao tensile
force
die
Adapted from Fig. 11.8 (d),
Courtesy Martin Deakins, GE Callister 7e.
Superabrasives, Worthington,
OH. Used with permission.

• Die surface:
-- 4 m polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide Courtesy Martin Deakins, GE
substrate. Superabrasives, Worthington,
OH. Used with permission.
-- polycrystalline diamond helps control
fracture and gives uniform hardness
in all directions.
 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.
-- polycrystalline diamonds
Photos courtesy Martin Deakins,
resharpen by microfracturing GE Superabrasives, Worthington,
OH. Used with permission.
along crystalline planes.
 Application: Sensors
• Example: Oxygen sensor ZrO2
• Principle: Make diffusion of ions Ca 2+
fast for rapid response.
• Approach:
Add Ca impurity to ZrO2: A Ca 2+ impurity
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
oxygen content O2-
O2- ions diffuse diffusion
oxygen content
from the external
surface of the sensor
to the reference gas. + -
voltage difference produced!
 Alternative Energy – Titania Nano-Tubes
"This is an amazing material architecture for
water photolysis," says Craig Grimes, professor
of electrical engineering and materials science
and engineering. Referring to some recent finds
of his research group (G. K. Mor, K. Shankar,
M. Paulose, O. K. Varghese, C. A. Grimes,
Enhanced Photocleavage of Water Using
Titania Nanotube-Arrays, Nano Letters, vol. 5,
pp. 191-195.2005 ), "Basically we are talking
about taking sunlight and putting water on top
of this material, and the sunlight turns the water
into hydrogen and oxygen. With the highly-
ordered titanium nanotube arrays, under UV
illumination you have a photoconversion
efficiency of 13.1%. Which means, in a
nutshell, you get a lot of hydrogen out of the
system per photon you put in. If we could
successfully shift its bandgap into the visible
spectrum we would have a commercially
practical means of generating hydrogen by solar
energy.
 Ceramic Fabrication Methods-I
GLASS PARTICULATE CEMENTATION
FORMING FORMING
• Pressing: plates, dishes, cheap glasses
Pressing
Gob --mold is steel with
operation
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.)
 Sheet Glass Forming
• Sheet forming – continuous draw
– originally sheet glass was made by “floating”
glass on a pool of mercury – or tin

Adapted from Fig. 13.9, Callister 7e.

Modern Plate/Sheet Glass making:

Image from Prof. JS Colton, Ga. Institute of Technology

 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.

 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
--Hydroplastic forming: force
ram
Adapted from
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
 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+
 Features of a Slip
Shear
• Clay is inexpensive
• Adding water to clay
-- allows material to shear easily charge
along weak van der Waals bonds neutral
-- enables extrusion
-- enables slip casting

weak van
der Waals
• Structure of bonding
4+
Kaolinite Clay: charge Si
3+
Adapted from Fig. 12.14, Callister 7e. neutral Al
-
(Fig. 12.14 is adapted from W.E. Hauth,
"Crystal Chemistry of Ceramics", American
OH
2-
Ceramic Society Bulletin, Vol. 30 (4), 1951, O
p. 140.)

Shear
 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
 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
 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.
 Tape Casting
• thin sheets of green ceramic cast as flexible tape
• used for integrated circuits and capacitors
• cast from liquid slip (ceramic + organic solvent)

Adapted from Fig. 13.18, Callister 7e.

 Ceramic Fabrication Methods-III
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.
 Applications: Advanced Ceramics

Heat Engines • Disadvantages:

– Brittle
• Advantages: – Too easy to have voids-
– Run at higher temperature weaken the engine
– Excellent wear & – Difficult to machine
corrosion resistance
– Low frictional losses
– Ability to operate without
a cooling system
– Low density
• Possible parts – engine block, piston coatings, jet engines
Ex: Si3N4, SiC, & ZrO2
 Applications: Advanced Ceramics

• Ceramic Armor
– Al2O3, B4C, SiC & TiB2
– Extremely hard materials
• shatter the incoming projectile
• energy absorbent material underneath
 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