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Processing of Ceramics
ISSUES TO ADDRESS...
• How do we classify ceramics?
Chapter 13 - 1
Classification of Ceramics
Ceramic Materials
Chapter 13 - 2
Ceramics Application: Die Blanks
Chapter 13 - 3
Ceramics Application:
Cutting Tools
• Tools:
-- for grinding glass, tungsten,
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling
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
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
O2- ions diffuse from the external unknown, higher reference
gas at fixed
surface through the sensor to the oxygen content O2-
oxygen content
diffusion
reference gas surface.
-- magnitude of voltage difference
partial pressure of oxygen at the + -
external surface voltage difference produced!
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
depress melting temperature (phase diagram):
2200 3Al2O3-2SiO2
T(ºC)
mullite
2000 Liquid
(L) alumina + L
1800
crystobalite mullite alumina
+L Fig. 12.27, Callister &
+L + Rethwisch 8e. (Fig. 12.27
1600 mullite 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: • 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
– Lower weights than to form and machine
current engines
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)
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
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/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 grain boundaries to
Adapted from Fig. 13.6,
scatter light
Callister & Rethwisch 8e.
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
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 at room temp.
cooler compression
hot hot tension
cooler compression
Chapter 13 - 15
• Ceramic Fabrication
techniques:
-- particulate forming
(hydroplastic forming, slip
casting, powder pressing, tape
casting)
-- cementation
Chapter 13 - 16
Ceramic Fabrication Methods (iia)
Ao
container die holder
force Adapted from
ram billet extrusion Ad Fig. 12.8(c),
Callister &
container die Rethwisch 8e.
Chapter 13 - 17
Ceramic Fabrication Methods (iia)
(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
900-1400ºC around
the particle
-- vitrification: liquid glass forms
from clay and flux – flows
between SiO2 particles. (Flux 70mm
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)
Chapter 13 - 22
Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size
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)
• 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
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 13 - 27