CHAPTER

10
Applications and Processing of
Ceramics

8-1
Fabrication and Processing of Ceramics
 Glass

• Combination of transparency, strength, hardness and

corrosion resistance.
• Glass is an inorganic product of fusion that has cooled to a
rigid condition without crystallization.
• Glass does not crystallize
up on cooling.
• Up on cooling, it transforms
from rubbery material to
rigid glass.

Figure 10.52

11-40
 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)
• In cristobalite, Si-O tetrahedron are joined corner to
corner to form long range order.
• In simple silica glass, tetrahedra are joined corner to
corner to form loose network.
 Composition of Glass

• Soda lime glass: Very common glass (90%).

 71-73% SiO2, 12-14% Na2O, 10-12% CaO.
 Easier to form and used in flat glass and containers.
• Borosilicate glass: Alkali oxides are replaced by boric oxide in silica
glass network.
 Known as Pyrex glass and is used for lab equipments and
piping.
• Lead glass: Lead oxide acts as network modifier and network former.
 Low melting point – used for solder sealing.
 Used in radiation shields, optical glass and TV bulbs.
 Glass Modifying Oxides and Intermediate Oxides

• Network modifiers: Oxides that breakup the glass

network.
 Added to glass to increase workability.
 Examples:- Na2O, K2O, CaO, MgO.
 Oxygen atom enters network and other ion stay
in interstices.
• Intermediate oxides: Cannot form glass network by
themselves but can join into an existing network.
 Added to obtain special properties.
 Examples: Al2O3, Lead oxide.
 Glass Properties

• Specific volume (1/ρ) vs Temperature (T):

• Crystalline materials:
Specific volume
-- crystallize at melting temp, Tm
-- have abrupt change in spec.
Supercooled Liquid
Liquid (disordered) vol. at Tm

Glass • Glasses:
(amorphous solid)
-- do not crystallize
Crystalline -- change in slope in spec. vol. curve at
(i.e., ordered) solid

Tg Tm T glass transition temperature, Tg

-- transparent
- no crystals to scatter light
Adapted from Fig. 13.6, Callister, 7e.
 Viscosity

• Viscosity, η:
-- relates shear stress and velocity gradient:

τ
dy dv dv
glass dv τ=η
dy dy
τ
velocity gradient

η has units of (Pa-s)

 Viscous Deformation of Glass

• Viscosity decreases with T • soda-lime glass: 70% SiO2

balance Na2O (soda) & CaO (lime)
• Impurities lower Tdeform • borosilicate (Pyrex):
fu 13% B2O3, 3.5% Na2O, 2.5% Al2O3
96 yre e

• Vycor: 96% SiO2, 4% B2O3

so ss

se silic
gla

% x
ds a
da
P

• fused silica: > 99.5 wt% SiO2

Viscosity [Pa ⋅ s]
-lim

ilic

10 14 strain point
a

annealing range
10 10

10 6 Tdeform : soft enough

to deform or “work”
10 2
Tmelt
1
200 600 1000 1400 1800 T(°C)
• Viscous above Tg and viscosity decreases with increase in temperature.
Q = Activation energy
η* = η0e+Q/RT η* = Viscocity of glass (PaS)
η0 = preexponential constant (PaS)

• Working point: 103 PaS – glass

fabrication can be carried out
• Softening point: 107 PaS – glass
flows under its own weight.
• Annealing point: 1012 PaS – Internal
stresses can be relieved..
• Strain point: 10 13.5 PaS – glass is
rigid below this point.

Figure 10.55
 Forming Methods

• Forming sheet and plate

glass:
Ribbon of glass moves
out of furnace and floats
on a bath of molten tin.
• Glass is cooled by molten
tin.
• After it is hard, it is
removed and passed
through a long annealing
furnace.
 Blowing

• Blowing: Air blown to force molten glass into molds.

Compressed
air

suspended
Parison

Finishing
mold
 Pressing

• Pressing: Optical and sealed beam lenses are

pressed by a plunger into a mold containing
molten glass.
Pressing
Gob
operation

Parison
mold
 Casting

• Casting: Molten glass is cast in open mold.

• Centrifugal casting: Glass globs are dropped into
spinning mold.
 Glass first flows outward towards wall of mold and
then upward against the mold wall.
 Drawing

Continuous drawing
– originally sheet glass was made by “floating” glass
on a pool of mercury
• Fiber drawing:

wind up

plates, dishes, cheap glasses

--mold is steel with
graphite lining
 Tempered Glass

• Glass is heated into near softening point and rapidly

cooled.
• Surface cools first and contracts.
• Interior cools next and
contracts causing tensile
stresses in the interior
and compressive stress
Figure 10.58
on the surface.
• Tempering strengthens the glass.
• Examples: Auto side windows and safety glasses.
 Chemically Strengthened Glass

• Special treatment increases chemical resistance of

glasses.
• Example:- Sodium aluminosilicate glasses are
immersed in a bath of potassium nitrate at 500C
for 6 to 10 hours
 Large potassium ions are induced into surface
causing compressive stress.
 Compressive layer is much thinner than that in
thermal tempering.
 Used for supersonic aircraft glazing and
ophthalmic lenses.
 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.

2. Particulate Forming
 Traditional Ceramics

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+

 Traditional Ceramics

• Clay: Provide workability and hardness.

• Silica: Provide better temperature resistance and MP.
• Potash Fledspar: Makes glass when ceramic is fired.

Quartz
grain High-silica
glass
 Engineering Ceramics

• Alumina (Al2O3): Aluminum oxide is doped with

magnesium oxide, cold pressed and sintered.
 Uniform structure. Used for electric applications.
• Silicon Nitride (Si3N4): Compact of silicon powder is
nitrided in a flow of nitrogen gas.
 Moderate strength and used for parts of advanced engines.

• Silicon Carbide (SiC): Very hard refractory carbide,

sintered at 21000C.
 Used as reinforcement in composite materials.
• Zirconia (ZrO2): Polymorphic and is subject to cracking.
 Combined with 9% MgO to produce ceramic with high
fracture toughness.
 Hydroplastic 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
 Feature of 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+
neutral Al
-
OH
2-
O

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 µm
 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

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.

15 µm
 Tape Casting

• thin sheets of green ceramic cast as flexible tape

• used for integrated circuits and capacitors
• cast from liquid slip (ceramic + organic solvent)
 Cementation

• 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

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/ -bearings
household
-sensors

8-2
 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

1800
crystobalite mullite alumina
+L +L +
1600 mullite
mullite
+ crystobalite
1400
0 20 40 60 80 100
Composition (wt% alumina)
• Acidic refractories:
– Silica refractories have high mechanical strength
and rigidity.
– Fireclays: Mixture of plastic fireclay, flint clay and
grog. Particles vary from coarse to very fine.
– High aluminum refractories: Contain 50-90%
alumina and have higher fusion temperature.
• Basic refractories: consists mainly of MgO and
CaO.
– Have high bulk densities, melting temperature and
resistance to chemical attack.
– used for lining in basic-oxygen steelmaking process.
 Die

• Die blanks: die Ad

-- Need wear resistant properties! Ao tensile
force
die

• Die surface:
-- 4 µm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond helps control
fracture and gives uniform hardness
in all directions.
 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
resharpen by microfracturing
along crystalline planes.
 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!
 Insulation

• About 70% of external surface is protected from heat by

24000 ceramic tiles.
• Material: Silica fiber compound.
• Density is 4kg/ft3 and withstands temperature up to
12600C.

Figure 10.51
 Ceramic Insulator Materials
• Ionic and covalent bonding restricts the mobility of ions and electrons
and hence ceramics are good insulators.
• Electrical porcelain: 50% Clay + 25 % Fledspar.
 Good plasticity, wider firing temperature range, cheap.
 High power loss factor.
• Steatite: 90% talc + 10 % clay
 Good insulator, low power loss factor, impact strength
• Fosterite: Mg2SiO4 no alkali ions
 Higher resistivity, low electrical loss
• Alumina: Al2O3 Crystalline phase bounded to glassy
matrix.
 High dielectric strength, low dielectric loss
 Capacitors

• Ceramics are used as dielectric materials

for capacitors.
• Example: Disk ceramic capacitors.
 BaTiO3 + additive
 Very high dielectric
constant
 Used in ceramic based
thick film hybrid
electronic circuit Figure 10.38a
 Higher capacitance per unit area
 Semiconductors

• Ceramics can be used as semiconducting materials.

• Thermistor: Thermally sensitive resistor.
• NTC thermistor: Conductivity raises with temperature.
• Solid solution oxides of Mn, Ni, Fe, Co and Cu are used
to obtain necessary property ranges.
• By combining low conducting metal oxide with low
conducting oxides intermediate properties are obtained.
• Example: Conductivity of Fe3O4 is reduced gradually by
adding increasing amounts in solid solution of MgCr2O4
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
 6. Advanced Ceramics

Heat Engines
• Disadvantages:
• Advantages:
– Brittle
– Run at higher 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
• Ceramic Armor
– Al2O3, B4C, SiC & TiB2
– Extremely hard materials
• shatter the incoming projectile
• energy absorbent material underneath