Applications and Processing of Ceramics Silicate Chains

Taxonomy of 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
• 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.

Silicate Sheets and Rings

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.

Quartz Structure along c-axis Quartz Structure

basic structure of quartz consists of spiral chains (helices)
of tetrahedra around three- and six-fold screw axes

NOT Planar:
Yellow, green and blue denote three-fold screw helix
increasing distance from the plane
of the diagram.

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 Glass Properties Glass Crystallization
• Specific volume (1/ρ) vs Temperature (T):
• Crystalline materials:
crystallize at melting temp, Tm
have abrupt change in spec. vol. at Tm
Specific volume

Supercooled Liquid
Liquid (disordered)
• Glasses:
do not crystallize
Glass change in slope in spec. vol. curve at
(amorphous solid) glass transition temperature, Tg
transparent
Crystalline no crystals to scatter light
(i.e., ordered) solid

Tg Tm Temp

Adapted from Fig. 13.6, Callister, 7e.

Glass Properties: Viscosity

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

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

η has units of (Pas)

Glass Compositions Glass Viscosity vs. T and Impurities

• sodalime glass: 70% SiO2 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 decreases with T

• Strain Point: fracture before deformation
• Annealing Point: atomic diffusion fast enough
to release strain in ~ 15 min.
• Softening Point: Impurities lower Tdeform
• Working Point: limit of easy deformation

2
 Heat Treating Glass
• Annealing:
removes internal stress caused by uneven cooling.

Tg • Tempering:

(poise)
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.

Ceramic Fabrication Methods I

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Pressing: mold is steel with graphite lining;
plates, dishes, cheap glasses
Pressing
• Fiber drawing:
Gob
operation

Parison
mold

Compressed
• Blowing: air wind up
suspended
Parison

Finishing
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.)

Sheet Glass Forming Ceramic Fabrication Methods II

• Sheet forming – continuous draw
originally sheet glass was made by “floating” glass on a pool of mercury GLASS PARTICULATE CEMENTATION
FORMING FORMING

• Milling and screening: desired particle size

• Mixing particles & water: produces a "slip"
• Form a "green" component
• Dry and fire the component

Adapted from Fig. 13.9, Callister 7e.

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 Ceramic Fabrication Methods II Clay Composition
A mixture of components used
GLASS PARTICULATE CEMENTATION
FORMING FORMING
(50%) 1. Clay
Ao (25%) 2. Filler – e.g. quartz (finely ground)
container die holder
Hydroplastic forming: force
extrude the slip (e.g., into a pipe)
ram billet extrusion Ad (25%) 3. Fluxing agent (Feldspar)
container die binds it together
Slip casting:
pour slip absorb water pour slip drain “green
into mold into mold
“green
into mold mold ceramic” aluminosilicates + K+, Na+, Ca+
ceramic”

solid component hollow component

Features of a Slip Drying

Shear • Drying: layer size and spacing decrease.
• 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 wet slip partially dry “green” ceramic

der Waals
Structure of Kaolinite Clay: bonding
4+ Drying too fast causes sample to warp or crack due to nonuniform shrinkage.
charge Si Surface tension forces tight packing. Aerogel vs. Xerogel.
3+
Adapted from Fig. 12.14, Callister 7e. neutral Al
(Fig. 12.14 is adapted from W.E. Hauth,
"Crystal Chemistry of Ceramics", American
OH
2
Ceramic Society Bulletin, Vol. 30 (4), 1951, O
p. 140.)

Shear

Firing Ceramic Fabrication Methods II

• Firing:
T raised to (900 to 1400°C).
GLASS PARTICULATE CEMENTATION
FORMING FORMING
vitrification: liquid glass forms from clay and flows between SiO2 particles.
Flux melts at lower T. Sintering: useful for both clay and nonclay compositions.
• Procedure:
produce ceramic and/or glass particles by grinding
Si02 particle place particles in mold
(quartz) press at elevated T to reduce pore size.
• Aluminum oxide powder:
micrograph of glass formed
porcelain
sintered at 1700°C
around
the particle
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
70μm Sons, Inc., 1976, p. 483.)

15 μm

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 Powder Pressing Tape Casting
Sintering powder touches forms neck & gradually neck thickens • thin sheets of green ceramic cast as flexible tape
add processing aids to help form neck • used for integrated circuits and capacitors
little or no plastic deformation
• cast from liquid slip (ceramic + organic solvent)
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.

Adapted from Fig. 13.18, Callister 7e.

Ceramic Fabrication Methods III Ceramic Fabrication Methods III

GLASS PARTICULATE CEMENTATION GLASS PARTICULATE CEMENTATION

FORMING FORMING FORMING FORMING

• Produced in extremely large quantities.

• Portland cement:
mix clay and lime bearing materials
calcinate (heat to 1400°C)
primary constituents:
tricalcium silicate
dicalcium silicate
• Adding water
produces a paste which hardens
hardening occurs due to hydration
• Forming: done usually minutes after hydration begins.

Early Cement

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 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 3Al2O32SiO2
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
mullite Region", J. American
Ceramic Society 70(10),
+ crystobalite p. 758, 1987.)
1400
0 20 40 60 80 100
Composition (wt% alumina)

Application: Refractories 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 μm 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.

Application: Cutting Tools Application: Sensors

• Example: Oxygen sensor ZrO2
• Principle: Make diffusion of ions Ca2+
• Tools:
for grinding glass, tungsten, fast for rapid response.
carbide, ceramics • Approach:
for cutting Si wafers Add Ca impurity to ZrO2: A Ca 2+ impurity
for oil drilling increases O2 vacancies removes a Zr 4+ and a
increases O2 diffusion rate O2 ion.
• Solutions:
manufactured single crystal
oil drill bits blades • Operation:
sensor
or polycrystalline diamonds coated single voltage difference
gas with an reference
in a metal or resin matrix. crystal diamonds produced when unknown, higher gas at fixed
optional coatings (e.g., Ti to help O2 ions diffuse oxygen content O2
oxygen content
diffusion
diamonds bond to a Co matrix polycrystalline from the external
diamonds in a resin surface of the sensor
via alloying)
matrix. to the reference gas.
polycrystalline diamonds +
Photos courtesy Martin Deakins, voltage difference produced!
resharpen by microfracturing GE Superabrasives, Worthington,
OH. Used with permission.
along crystalline planes.

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 Applications: Advanced Ceramics Applications: Advanced Ceramics
Heat Engines • Ceramic Armor
• Advantages: • Disadvantages:
Al2O3, B4C, SiC & TiB2
Run at higher temperature – Brittle
Excellent wear & corrosion – Too easy to have voids Extremely hard materials
resistance weaken the engine shatter the incoming projectile
Low frictional losses – Difficult to machine
energy absorbent material underneath
Ability to operate without a
cooling system
Low density

• Possible parts – engine block, piston coatings, jet engines

Ex: Si3N4, SiC, & ZrO2

Applications: Advanced Ceramics Summary

Electronic Packaging • Basic categories of ceramics:
• Chosen to securely hold microelectronics & provide glasses
heat transfer clay products
• Must match the thermal expansion coefficient of the refractories
microelectronic chip & the electronic packaging cements
material. Additional requirements include: advanced ceramics
good heat transfer coefficient • Fabrication Techniques:
poor electrical conductivity glass forming (impurities affect forming temp).
particulate forming (needed if ductility is limited)
• Materials currently used include: cementation (large volume, room T process)
Boron nitride (BN)
• Heat treating: Used to
Silicon Carbide (SiC)
alleviate residual stress from cooling,
Aluminum nitride (AlN)
produce fracture resistant components by putting
thermal conductivity 10x that for Alumina
good expansion match with Si
surface into compression.