Chapter 13: Applications and

Processing of Ceramics

ISSUES TO ADDRESS...
• How do we classify ceramics?

• What are some applications of ceramics?

• How is processing different than for metals?

Chapter 13 - 1
Chapter 13 - 2
Chapter 13 - 3
Figure 13.1 classification of ceramic materials on
the basis of application

Chapter 13 - 4
 Taxonomy
Types of ofCeramics
and Applications 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.
Chapter 13 - 5
 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
mullite is adapted from F.J. Klug
crystobalite alumina 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)
Chapter 13 - 6
 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.
Chapter 13 - 7
 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.
Chapter 13 - 8
 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
-- increases O2- vacancies removes a Zr 4+ and a
-- increases O2- diffusion rate O2- ion.

• 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!

Chapter 13 - 9
 13.2glasses

Table 13.1 compositions and characteristics of some of the

common commercial glasses

Chapter 13 - 10
 13.3 glasses-ceramics

Figure 13.2continuous cooling transformation diagram for

the crystallization of a lunar glass Chapter 13 - 11
 13.4 clay products
• Structural clay product
• whitewares

Chapter 13 - 12
 13.5 refractories
Table 13.2 compositions of five common ceramic
refractory materials

方鎂石

Chapter 13 - 13
 13.6 abrasives SiC, WC, Al2O3

Figure 13.3

Chapter 13 - 14
 13.7 cements
• CLAY +LIME-bearing minerals at
1400℃calicination(鍛燒) →clinker(熔渣) →
ground into a very fine powder to which is
added a small amount of gypsum (CaSO4-
2H2O) to retard the setting process. The
product is portland cement.
• Hydration reaction 2CaO-SiO2＝2CaO-
SiO2-XH2O

Chapter 13 - 15
 13.8 advanced cermics
• 1.Microelectromechanical systems(MEMS)
Figure 13.4

線性齒條齒輪減速機構:SiC or Si3N4
。2.optical fiber
。3.ceramic ball bearings:Si3N4

Chapter 13 - 16
 Fabrication and Processing of
Ceramics
13.9 Fabrication and Processing of Glasses and Glass-Ceramics

膠結

Figure 13.5

Chapter 13 - 17
 Glass Structure
• Basic Unit: • Glass is amorphous
4- • Amorphous structure
Si0 4 tetrahedron occurs by adding impurities
Si 4+ (Na+,Mg2+,Ca2+, Al3+)
O2-
• Impurities:
interfere with formation of
crystalline structure.

• Quartz is crystalline
Na +
SiO2:
Si 4+
O2-

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

Chapter 13 - 18
 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.
vol. at Tm
Glass
(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
 glass dv
velocity gradient: dy dy
--has units of (Pa-s)  velocity gradient

Chapter 13 - 19
Figure 13.6

Chapter 13 - 20
Figure 13.7

Chapter 13 - 21
 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
fu
96 yre e
so ss

se silic
• Vycor: 96% SiO2, 4% B2O3
gla

% x
da

ds a
P

• fused silica: > 99.5 wt% SiO2

Viscosity [Pa ×s]
-lim

ilic
10 14
a
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.
(Fig. 13.7 is from E.B. Shand, Engineering
1 Glass, Modern Materials, Vol. 6, Academic
200 600 1000 1400 1800 T(°C) Press, New York, 1968, p. 262.)

Chapter 13 - 22
 glass
• The melting point corresponds to the temperature at which the
viscosity is 100P.
• The working point represents the temperature at which the
viscosity is 103P；the glass is easily deformed at this viscosity.
• The soft point, the viscosity is 4×106P,is the maximum
temperature at which a glass piece may be handled without
causing significant dimension alterations.
• The annealing point, the viscosity is 1012P,at this temperture,
atomic diffusion is sufficiently rapid that any residual stresses
may be removed within about 15 min.
• The strain point, the viscosity is 3×1013P:below the strain point,
fracture will occur before the onset of plastic deformation.

Chapter 13 - 23
 Ceramic Fabrication Methods-I

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• 1.Pressing:
Pressing
Gob 熱凝塊 plates, dishes, cheap glasses
operation
--mold is steel with
Parison graphite lining
溶漿模 mold
• 3.Fiber drawing:
Compressed
• 2.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.) Chapter 13 - 24
 Glass forming-pressing and blow

熱凝塊
溶漿模

1.Pressing:

2. blow:

Chapter 13 - 25
 4.drawing
• Sheet forming – continuous draw
– originally sheet glass was made by “floating” glass
on a pool of mercury

Figure 13.9

Adapted from Fig. 13.9, Callister 7e.

Chapter 13 - 26
 HEAT TREATING GLASSES
1• Annealing:退火
--removes internal stress caused by uneven cooling rate between the
surface and interior regions.
2• Tempering:回火
--puts surface of glass part into compression
--suppresses growth of cracks from surface scratches.
--sequence: the glassware is heated to a temperature above the Tg rg
yet below the softening point. It is then cooled to room temperature
jet of air or, in some cases, an oil bath.
before cooling surface cooling further cooled
cooler compression
hot hot tension
cooler compression
--Result: surface crack growth is suppressed.

Chapter 13 - 27
 Tempered glass plate

Figure 13.10 room-temperature residual stress distribution

over the cross section of a tempered glass plate.

Chapter 13 - 28
Figure 13.11 Typical time-versus-temperature processing
cycle for a Li2O-Al2O3-SiO2 glass-ceramic

Chapter 13 - 29
 13.10 fabrication and processing of clay products
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
--1.Hydroplastic forming: force
ram bille extrusion Ad Fig. 11.8 (c),
extrude the slip (e.g., into a pipe) t Callister 7e.
container die
--2.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
Chapter 13 - 30
 FEATURES OF CLAY
Al2O3, SiO2 Shear

• Clay is inexpensive charge

• Adding water to neutral
clay(hydroplasticity)水塑性
--allows material to shear easily
along weak van der Waals bonds weak van
--enables extrusion der Waals
--enables slip casting bonding
4+
• Structure of charge Si
3+
Kaolinite Clay:Al2(Si2O5)(OH)4 neutral Al
-
Adapted from Fig. 12.14, Callister 6e.
OH
2-
(Fig. 12.14 is adapted from W.E. Hauth, O
"Crystal Chemistry of Ceramics",
American Ceramic Society Bulletin,
Vol. 30 (4), 1951, p. 140.) Shear
Chapter 13 - 31
 Composition of Clay product
A mixture of components used:a typical porcelain

(50%) 1. Clay
(25%) 2. Filler – e.g. quartz (finely ground)
(25%) 3. Fluxing agent 助熔劑:長石(Feldspar):
binds it together
長石:含 K+, Na+, Ca+ aluminosilicates

Chapter 13 - 32
Particulate forming :1.Hydroplastic forming 2.Slip Casting
3. Powder pressing 4. Tape casting

1.Hydroplastic Forming水塑性成形
• Brick
• Pipe
• Ceramic Block

Ao
container
die holder Adapted from
force Fig. 11.7,
ram billet extrusion Ad Callister 6e.
container die

Chapter 13 - 33
2.Slip Casting:泥漿鑄造

Chapter 13 - 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焙燒:
--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 Chapter 13 - 35
 長石

莫來針狀

Figure 13.14 SEM of a fired porcelain specimen (etched 15 s, 5C,10% HF)

Chapter 13 - 36
 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 Chapter 13 - 37
 13.11 Powder Pressing
Uniaxial, isostatic and hot pressing

Procedure:
• grind to produce ceramic and/or glass
particles
• inject into mold

Chapter 13 - 38
 13.11 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.

Chapter 13 - 39
Uniaxial Pressing
Figure 13.15

Chapter 13 - 40
 Pressing sintering燒結
Sintering: During firing the formed piece shrinks, and experiences a
reduction of porosity and an improvement in mechanical integrity.
These changes occur by the coalescence of the particle into a more
dense mass.
Figure 13.16

Chapter 13 - 41
Figure 13.17

Al2O3 sintered at
1700℃ for 6 minutes

Chapter 13 - 42
 13.12 Tape Casting帶狀鑄造
• 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,Schematic diagram showing the tape-casting process using a doctor blade. Callister 7e.
Chapter 13 - 43
 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.
Chapter 13 - 44
 Summary
• Basic categories of ceramics:
-- glasses
-- clay products
-- refractories
--abrasives
-- cements
-- advanced ceramics
• Fabrication Techniques:
-- glass forming (impurities affect forming temp).
-- particulate forming (needed if ductility is limited)
-- cementation (large volume, room T process)
• Heat treating: Used to
-- alleviate residual stress from cooling,
-- produce fracture resistant components by putting
surface into compression.
Chapter 13 - 45
 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

Chapter 13 - 46
Applications: Advanced Ceramics
• Ceramic Armor
– Al2O3, B4C, SiC & TiB2
– Extremely hard materials
• shatter the incoming projectile
• energy absorbent material underneath

Chapter 13 - 47
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

Chapter 13 - 48