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

Clay=arcilla Bricks=ladrillo Bearings = rodamientos

Chapter 13 - 2
 Ceramics Application: Die Blanks
• Die blanks (dados trefilado):
-- Need wear resistant properties!
-- necesitan alta resistencia al desgaste die Ad
Ao tensile
force
die
• Die surface: Adapted from Fig. 11.8(d),
Callister & Rethwisch 8e.
-- 4 mm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond gives uniform
hardness in all directions to reduce
wear(desgaste).

Courtesy Martin Deakins, GE

Superabrasives, Worthington,
OH. Used with permission.

Chapter 13 - 3
 Ceramics Application:
Cutting Tools
• Tools:
-- for grinding(molienda) glass,
tungsten, carbide, ceramics
-- for cutting Si wafers(discos)
-- for oil drilling(extracción de
petroleo)

• Materials: oil drill bits Blades(cuchillas)

-- 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,
reafilar por microfractura GE Superabrasives, Worthington,
a lo largo de los planos de clivaje OH. Used with permission.

Chapter 13 - 4
 https://www.youtube.com/watch?v=MN56cBWwo2k

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(enfoque): A substituting Ca2+ ion
removes a Zr 4+ ion and
Add Ca impurity to ZrO2: an O2- ion.
-- increases O2- vacancies
-- increases O2- 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 oxygen content
diffusion
reference gas surface.
-- magnitude of voltage difference
 partial pressure of oxygen at the + -
voltage difference produced!
external surface Chapter 13 - 5
 Mullita: neosilicato, del cuarzo, tridimita, coesita y stishovita, por lo
Refractories quepolimorfo es un óxido de Si. Además de los elementos de su fórmula,
suele llevar como impurezas: Fe, Ca, Al, K, Na, Ti, Mn, Mg y P.

• Materials to be used at high temperatures (e.g. in

high T˚ furnaces).
• Consider the Silica (SiO2)-Alumina (Al2O3) system.
• Silica refractories-silica rich-small additions of alumina
depress melting temperature (phase diagram):
2200 3Al2O3-2SiO2
T(ºC) Bajos
mullite incrementos de
2000 Liquid alúmina hacen
alumina + L
(L) descender la T˚
de fusión
1800
mullite alumina
crystobalite
+L +
+L Fig. 12.27, Callister &
1600 mullite Rethwisch 8e. (Fig. 12.27
adapted from F.J. Klug and
mullite R.H. Doremus, J. Am. Cer.
+ crystobalite Soc. 70(10), p. 758, 1987.)
1400
0 20 40 60 80 100
Composition (wt% alumina)
Chapter 13 - 6
 Advanced Ceramics:
Materials for Automobile Engines
• Advantages:
– Operate at high
temperatures – high
efficiencies
– Bajas pérdidas X fricción
– Operate without a cooling
system
– Pesos más bajos que
los motores actuales
• Disadvantages:
– Ceramic materials are
brittle(fragil)
– Difficult to remove
internal voids(huecos)
(that weaken-dañan-
structures)
– Ceramic parts are
difficult to form and
machine

• Potential candidate materials: Si3N4, SiC, & ZrO2

• Possible engine parts: engine block & piston coatings
(revestimientos)

Chapter 13 - 7
 Advanced Ceramics:
Materials for Ceramic Armor (armadura)
Components:
-- Outer facing plates (placas de revestimiento exterior)
-- Backing sheet (hoja de respaldo)

Properties/Materials:
-- Facing plates -- hard and brittle (placas de revestimiento duras y frágiles)
— fracture high-velocity projectile
— Al2O3, B4C, SiC, TiB2
-- Backing sheets -- soft and ductile(suaves y dúctiles)
— deform and absorb remaining energy

Chapter 13 - 8
 Ceramic Fabrication Methods (i)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Blowing of Glass Bottles: • Pressing: plates, glasses
baratos
Pressing -- glass formed by application of
trozo
operation
pressure
Parison
-- mold is steel with graphite
mold lining (revestimiento)
• Fiber drawing:
Compressed
air

Suspended
Parison(preforma

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 (laminado) – continuous casting
– las láminas de espejos se forman flotando el vidrio
fundido en un charco de estaño fundido

Adapted from Fig. 13.9,

Callister & Rethwisch 8e.

Chapter 13 - 10
 Glass Structure
• Basic Unit: Glass is noncrystalline (amorphous)
4- • La sílice fundida es SiO2 a la que
Si0 4 tetrahedron no se han agregado impurezas.
Si 4+ • Otras vidrios comunes contienen
O2- iones de impurezas tales como: 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/r) 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
glass transition temperature, Tg
Tg Tm T -- transparent - no tiene límites de
Adapted from Fig. 13.6,
grano.
Callister & Rethwisch 8e.

Slope=pendiente Chapter 13 - 12
 Glass Properties: Viscosity

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


dy dv 
glass dv
dy
h
dv / dy

velocity gradient

h 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):
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 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(ºC) 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 A T°ambiente.
cooler compression
hot hot tension
cooler compression

-- Result: Supresión de grietas superficiales.

Chapter 13 - 15
• Ceramic Fabrication
techniques:

-- glass forming (pressing,

blowing=soplado, fiber drawing).

-- particulate forming
(hydroplastic forming, slip
casting, prensado en polvo,
Colada continua
-- 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= ladrillo)

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 (relleno)– e.g. quartz (finamente molido)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp. glass
melting= derritiendo

Chapter 13 - 19
 Hydroplasticity of Clay (arcilla)

• 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: (secado) 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
• TT: (quartz)
-- heat treatment between glass formed
900-1400ºC around
-- vitrification: liquid glass forms the particle

from clay and flux – flows

between SiO2 particles. (Flux
lowers melting temperature).
70mm
Adapted from Fig. 13.14, Callister & Rethwisch 8e.
(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 ( La
sinterización ocurre durante el disparo de una pieza que ha sido en polvo presionado)

-- powder particles coalesce and reduction of pore size

Adapted from Fig. 13.16,

Callister & Rethwisch 8e.
Aluminum oxide powder:
-- sintered at 1700ºC 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 mm 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
reactions involving water and cement particles)
• Portland cement – production of:
-- mix clay and lime-bearing minerals (minerals que contienen cal)
-- calcine (heat to 1400ºC)
-- grind into fine powder (moler en polvo fino)
https://www.youtube.com/watch?v=mxIb_LkjeXg 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
-- glasses—annealing, tempering
-- particulate formed pieces—drying, firing (sintering)

Chapter 13 - 26