Chapter 13: Applications and

Processing of Ceramics

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

What are some applications of ceramics?

How is processing of ceramics different than for metals?

Chapter 13 - 1
 Classification of Ceramics

Ceramic Materials

Glasses Clay Refractories Abrasives Cements Advanced

products ceramics
-optical -whiteware -bricks for -sandpaper -composites -engine
-composite -structural high T -cutting -structural rotors
reinforce (furnaces) -polishing valves
-containers/ Adapted from Fig. 13.1 and discussion in
bearings
household Section 13.2-8, Callister & Rethwisch 8e. -sensors

Chapter 13 - 2
 Ceramics Application: Die Blanks

Die blanks: die Ad

-- Need wear resistant properties! Ao tensile
force
die
Die surface: Adapted from Fig. 11.8(d),
Callister & Rethwisch 8e.
-- 4 m polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond gives uniform
hardness in all directions to reduce
wear.

Courtesy Martin Deakins, GE

Superabrasives, Worthington,
OH. Used with permission.

Chapter 13 - 3
 Ceramics Application:
Cutting Tools
Tools:
-- for grinding glass, tungsten,
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling

Materials: oil drill bits blades

-- manufactured single crystal
or polycrystalline diamonds Single crystal
diamonds
in a metal or resin matrix.
-- polycrystalline diamonds
polycrystalline
resharpen by microfracturing diamonds in a resin
along cleavage planes. matrix.
Photos courtesy Martin Deakins,
GE Superabrasives, Worthington,
OH. Used with permission.

Chapter 13 - 4
 Ceramics Application: Sensors
Example: ZrO2 as an oxygen sensor
Ca 2+
Principle: Increase diffusion rate of oxygen
to produce rapid response of sensor signal to
change in oxygen concentration
Approach: A substituting Ca2+ ion
Add Ca impurity to ZrO2: removes a Zr 4+ ion and
an O2- ion.
-- increases O2- vacancies
-- increasesO2- diffusion rate
Operation:
sensor
-- voltage difference produced when
gas with an reference
O2- ions diffuse from the external unknown, higher gas at fixed
oxygen content O2-
surface through the sensor to the diffusion
oxygen content
reference gas surface.
-- magnitude of voltage difference
partial pressure of oxygen at the + -
voltage difference produced!
external surface
Chapter 13 - 5
 Refractories
Materials to be used at high temperatures (e.g., in
high temperature furnaces).
Consider the Silica (SiO2) - Alumina (Al2O3) system.
Silica refractories - silica rich - small additions of alumina

depress2200
melting temperature (phase
3Al2O3-2SiO 2
diagram):
T(C)
mullite
2000 Liquid
(L) alumina + L

1800
crystobalite mullite alumina
+L +L +
Fig. 12.27, Callister &
Rethwisch 8e. (Fig. 12.27
1600 mullite adapted from F.J. Klug and
mullite R.H. Doremus, J. Am. Cer.
Soc. 70(10), p. 758, 1987.)
+ crystobalite
1400
0 20 40 60 80 100
Composition (wt% alumina)
Chapter 13 - 6
 Advanced Ceramics:
Materials for Automobile Engines

Advantages: Disadvantages:
Operate at high Ceramic materials are
temperatures high brittle
efficiencies Difficult to remove internal
Low frictional losses voids (that weaken
Operate without a cooling structures)
system Ceramic parts are difficult
to form and machine
Lower weights than
current engines

Potential candidate materials: Si3N4, SiC, & ZrO2

Possible engine parts: engine block & piston coatings

Chapter 13 - 7
 Advanced Ceramics:
Materials for Ceramic Armor
Components:
-- Outer facing plates
-- Backing sheet

Properties/Materials:
-- Facing plates -- hard and brittle
fracture high-velocity projectile
Al2O3, B4C, SiC, TiB2
-- Backing sheets -- soft and ductile
deform and absorb remaining energy
aluminum, synthetic fiber laminates

Chapter 13 - 8
 Ceramic Fabrication Methods (i)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Blowing of Glass Bottles: Pressing: plates, cheap glasses
Pressing -- glass formed by application of
Gob
operation
pressure
Parison
-- mold is steel with graphite
mold lining
Fiber drawing:
Compressed
air

Suspended
parison

Finishing
mold wind up
Adapted from Fig. 13.8, Callister & Rethwisch 8e. (Fig. 13.8 is adapted from C.J.
Phillips, Glass: The Miracle Maker, Pittman Publishing Ltd., London.) Chapter 13 - 9
 Sheet Glass Forming
Sheet forming continuous casting
sheets are formed by floating the molten glass on a pool of
molten tin

Adapted from Fig. 13.9,

Callister & Rethwisch 8e.

Chapter 13 - 10
 Glass Structure
Basic Unit: Glass is noncrystalline (amorphous)
4- Fused silica is SiO2 to which no
Si0 4 tetrahedron
impurities have been added
Si 4+ Other common glasses contain
O2- impurity ions such as Na+, Ca2+,
Al3+, and B3+

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

(soda glass)
Adapted from Fig. 12.11,
Callister & Rethwisch 8e.

Chapter 13 - 11
 Glass Properties
Specific volume (1) 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

Adapted from Fig. 13.6, -- transparent - no grain boundaries to
Callister & Rethwisch 8e.

scatter light
Chapter 13 - 12
 Glass Properties: Viscosity

Viscosity, :
-- relates shear stress () and velocity gradient (dv/dy):

dy dv
glass dv
dy dv / dy

velocity gradient

has units of (Pa-s)

Chapter 13 - 13
 Log Glass Viscosity vs. Temperature
soda-lime glass: 70% SiO2
Viscosity decreases with T
balance Na2O (soda) & CaO (lime)
borosilicate (Pyrex):
fu 13% B2O3, 3.5% Na2O, 2.5% Al2O3
96 yre e
so ss

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

% x
ds a
da
P

fused silica: > 99.5 wt% SiO2

-lim

ilic

10 14
Viscosity [Pa-s]

strain point
a

annealing point
10 10

10 6 Working range:
glass-forming carried out
10 2
Tmelt Adapted from Fig. 13.7, Callister & Rethwisch
8e. (Fig. 13.7 is from E.B. Shand,
1 Engineering Glass, Modern Materials, Vol. 6,
200 600 1000 1400 1800 T(C) Academic Press, New York, 1968, p. 262.)

Chapter 13 - 14
 Heat Treating Glass
Annealing:
-- removes internal stresses caused by uneven cooling.
Tempering:
-- puts surface of glass part into compression
-- suppresses growth of cracks from surface scratches.
-- sequence:
before cooling initial cooling at room temp.
cooler compression
hot hot tension
cooler compression

-- Result: surface crack growth is suppressed.

Chapter 13 - 15
 Ceramic Fabrication
techniques:

-- glass forming (pressing,

blowing, fiber drawing).

-- particulate forming
(hydroplastic forming, slip
casting, powder pressing, tape
casting)

-- cementation
Chapter 13 - 16
 Ceramic Fabrication Methods (iia)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Hydroplastic forming:
Mill (grind) and screen constituents: desired particle size
Extrude this mass (e.g., into a brick)

Ao
container die holder
force Adapted from
ram billet extrusion Ad Fig. 12.8(c),
Callister &
container die Rethwisch 8e.

Dry and fire the formed piece

Chapter 13 - 17
 Ceramic Fabrication Methods (iia)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Slip casting:
Mill (grind) and screen constituents: desired particle size
Mix with water and other constituents to form slip
Slip casting operation
pour slip absorb water pour slip drain green
into mold into mold into mold mold ceramic Adapted from Fig.
green 13.12, Callister &
ceramic Rethwisch 8e. (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 cast piece

Chapter 13 - 18
 Typical Porcelain Composition

(50%) 1. Clay
(25%) 2. Filler e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp. glass

Chapter 13 - 19
 Hydroplasticity of Clay
Clay is inexpensive Shear
When water is added to clay
-- water molecules fit in between
layered sheets charge
-- reduces degree of van der Waals neutral
bonding
-- when external forces applied clay
particles free to move past one
weak van
another becomes hydroplastic
der Waals
Structure of bonding
4+
Kaolinite Clay: charge Si
3+
Adapted from Fig. 12.14, Callister & neutral Al
-
Rethwisch 8e. (Fig. 12.14 is adapted from
W.E. Hauth, "Crystal Chemistry of
OH
2-
Ceramics", American Ceramic Society O
Bulletin, Vol. 30 (4), 1951, p. 140.)

Shear Chapter 13 - 20
 Drying and Firing
Drying: as water is removed - interparticle spacings decrease
shrinkage.
Adapted from Fig.
13.13, Callister &
Rethwisch 8e. (Fig.
13.13 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)

wet body partially dry completely dry

Drying too fast causes sample to warp or crack due to non-uniform shrinkage

micrograph of porcelain
Si02 particle
Firing: (quartz)
-- heat treatment between glass formed
900-1400C around
the particle
-- vitrification: liquid glass forms
from clay and flux flows
between SiO2 particles. (Flux 70 m
Adapted from Fig. 13.14, Callister & Rethwisch 8e.
lowers melting temperature). (Fig. 13.14 is courtesy H.G. Brinkies, Swinburne
University of Technology, Hawthorn Campus,
Hawthorn, Victoria, Australia.) Chapter 13 - 21
 Ceramic Fabrication Methods (iib)

GLASS PARTICULATE CEMENTATION

FORMING FORMING

Powder Pressing: used for both clay and non-clay compositions.

Powder (plus binder) compacted by pressure in a mold

-- Uniaxial compression - compacted in single direction
-- Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope
-- Hot pressing - pressure + heat (

Chapter 13 - 22
 Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size

Adapted from Fig. 13.16,

Callister & Rethwisch 8e.
Aluminum oxide powder:
-- sintered at 1700C Adapted from Fig. 13.17, Callister
for 6 minutes. & Rethwisch 8e. (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 - 23
 Tape Casting
Thin sheets of green ceramic cast as flexible tape
Used for integrated circuits and capacitors
Slip = suspended ceramic particles + organic liquid

(contains binders, plasticizers)

Fig. 13.18, Callister &

Rethwisch 8e.
Chapter 13 - 24
 Ceramic Fabrication Methods (iii)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Hardening of a paste paste formed by mixing cement

material with water

Formation of rigid structures having varied and complex
shapes
Hardening process hydration (complex chemical
reactionscement
Portland involving water and of:
production cement particles)
-- mix clay and lime-bearing minerals
-- calcine (heat to 1400C)
-- grind into fine powder
Chapter 13 - 25
 Summary

Categories of ceramics:
-- glasses -- clay products
-- refractories -- cements
-- advanced ceramics
Ceramic Fabrication techniques:
-- glass forming (pressing, blowing, fiber drawing).
-- particulate forming (hydroplastic forming, slip casting,
powder pressing, tape casting)
-- cementation
Heat treating procedures
-- glassesannealing, tempering
-- particulate formed piecesdrying, firing (sintering)

Chapter 13 - 26
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 13 - 27