You are on page 1of 51

4.

8 APPLICATIONS AND PROCESSING

Ceramics mechanical and thermal


properties influence how they are used in
applications and how they are processed.
High hardness, very brittle, high melting
points.

These differences of physical


characteristics between metal and
ceramics influences the usage on the
different materials.
4.8.1 TYPES AND APPLICATIONS OF
CERAMICS
Ceramics are grouped into an application-
classification scheme.
4.8.1.1 GLASSES

Typical applications containers, lenses and


fiberglass.
Noncrystalline silicates containing other oxides
(CaO, Na2O, K2O, Al2O3), which influence the glass
properties.
4.8.1.2 GLASS-CERAMICS

A fine-grained polycrystalline material product


produced by a crystallization process.
High-temperature heat treatment process to
transform inorganic glasses from noncrystalline
state to a crystalline state.
Formation of the small glass-ceramics grains is a
phase formation which involves nucleation and
growth stages.
A nucleating agent (titanium oxide) is added to glass
to promote crystallization .
PROPERTIES

Designed to have the following


characteristics:
1. Relatively high mechanical strengths.
2. Low coefficients of thermal expansion.
Avoid thermal shock.
3. Relatively high temperature capabilities.
4. Good dielectric properties.
Electronic packaging applications.
5. Good biological compatibility.
6. Electrical insulators.
APPLICATIONS

Most common uses are as ovenware,


tableware, oven windows etc
Good Strength and resistance to thermal
shock.
Electrical insulators and as substrates for
printed circuit boards.
Architectural classing
Heat exchangers
Regenerators.

Ease of fabrication is the most attractive attribute.


Conventional glass-forming techniques
4.8.1.3 CLAY PRODUCTS

Inexpensive material found naturally in


abundance.
Used as mined without any further upgrading
or processing of quality.
When mixed with water in proper
proportions, a plastic mass is formed that is
easily shaped.
Further dried to remove moisture.
Dried at elevated temperature to improve
its mechanical strength and maintain its
shape.
Clay-based products are classified into 2
broad classifications:
1. Structural clay products.
1. Building bricks, tiles and sewer pipes.
2. Whitewares
1. Porcelain, pottery, tableware, china
and plumbing fixtures (sanitary ware).
2. Whiteware ceramics become white
after the high-temperature firing.
4.8.1.4 REFRACTORIES
Used in large tonnages.
Bricks are the common form.
Applications
Furnace linings for metal refining, glass
manufacturing, metallurgical heat
treatment and power generation.
Salient (important) properties
Capacity to withstand high temperature
without melting or decomposing.
Capacity to remain unreactive and inert
when exposed to severe environments.
Provide thermal insulation.
Performance of the refractory ceramic
depends on its composition.

The raw ingredients for commercial materials


consists of large and fine particles.
During firing, the fine particles are
involved in the formation of a bonding
phase which increases the strength of the
brick.
Porosity must be controlled to produce a
suitable refractory brick.
With reduced porosity;
there is an increase in:
Strength.
Load-bearing capacity.
Resistance to attack by corrosive materials.
but a reduction in:
Thermal insulation characteristics
Resistance to thermal shock.
FIRECLAY REFRACTORIES
Primary ingredients are high-purity fireclays,
alumina (23-45%) and silica mixtures.
Referring to the Figure on next slide, the highest
temperature possible without the formation of a
liquid phase is 1587C. Below this temperature,
mullite and silica (cristobalite) is present.
A small amount of liquid phase will not compromise
the mechanical integrity.
Upgrading the alumina content will increase the
maximum service temperature.
Fireclay bricks are used to confine hot atmospheres
in furnaces and to insulate structural members from
excessive temperatures.
Silica (SiO2) - Alumina (Al2O3) system.

2200
3Al2O3-2SiO2
T(C)
mullite
2000 Liquid
alumina + L
(L)

1800
mullite
crystobalite alumina
+L
+L +
1600 mullite
mullite
Adapted from Fig. 12.27,
+ crystobalite Callister 7e. (Fig. 12.27
is adapted from F.J. Klug
1400 and R.H. Doremus,
0 20 40 60 80 100 "Alumina Silica Phase
Diagram in the Mullite
Composition (wt% alumina) Region", J. American
Ceramic Society 70(10),
p. 758, 1987.)
SILICA REFRACTORIES (ACID REFRACTORIES)
Prime ingredient is silica.
High-temperature load-bearing capacity which is
applied in the arched roofs of steel/glass making
furnaces.
Resistant to slags that are rich in silica (called acid
slags).
Used as containment vessels.
But readily attacked by slags composed of a high
proportion of CaO and/or MgO (basic slags).
Note: Slag is produced during the smelting process in several ways.
Firstly, slag represents undesired impurities in the metals being
smelted, which float to the top during the smelting process. Secondly,
metals start to oxidize as they are smelted, and slag forms a protective
crust of oxides on the top of the metal being smelted, protecting the
liquid metal underneath.
BASIC REFRACTORIES
Refractories which are rich in periclase (magnesia)
(MgO).
Presence of silica is deleterious to their high-
temperature performance.
Resistant to attack by slags containing high
concentrations of MgO and CaO.
Extensively used in steel-making open hearth
furnaces.
A type of furnace where excess carbon and other
impurities are burnt out of the iron to produce
steel.
SPECIAL REFRACTORIES
Specialized refractory applications.
High-purity oxide materials with low porosity.
Alumina, silica, magnesia, beryllia (BeO), zirconia
(ZrO2) and mullite (3Al2O3-2SiO2).
Carbide compounds, graphite, carbon.
Silicon carbide used for electrical resistance heating
elements.
Crucible material - heat-resistant container in
which materials can be heated to very high
temperatures.
Internal furnace components.
Carbon and graphite have limited application
because they are susceptible to oxidation at
temperatures in excess of about 800C.
Expensive costs.
4.8.1.5 ABRASIVES
Abrasive ceramics are used to wear, grind or
cut away other (softer) material.
The prime requisite is hardness or wear
resistance.
A high degree of toughness is essential to
ensure that the abrasive materials do not
easily fracture.
Since abrasive frictional forces would
produce high temperatures, refractory
property is desirable.
Diamonds (natural and synthetic) are utilized
as abrasives but are too expensive.
Common ceramic abrasives are silicon
carbide, tungsten carbide (WC), aluminium
oxide (corondum) and silica sand.
Used in several forms:
Grinding wheels
Abrasive particles are bonded to a wheel by
means of a glassy ceramic or an organic resin.
Surface structure should contain some
porosity, a continual flow of air currents or
liquid coolants within the pores that surround
the refractory grains prevent excessive
heating.
Coated abrasives
Abrasive powder is coated on some type of
paper or cloth material, i.e. sandpaper.
Used on wood, metals, ceramics and plastics.
Loose abrasive grains
Grinding, lapping and polishing wheels often
use loose grains that are delivered in some
type of oil- or water-based vehicle.
Diamonds, corondum, silicon carbide and
rouge (iron oxide) are used in loose form over
a variety of grain size ranges.
Application: 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
Photos courtesy Martin Deakins,
resharpen by microfracturing GE Superabrasives, Worthington,
OH. Used with permission.
along crystalline planes.
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 mm 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.
4.8.1.6 CEMENTS
INORGANIC CEMENTS
CEMENTS
PLASTER OF PARIS
LIME
Produced in large quantities.
Characteristic feature of these materials is that when
mixed with water, they form a paste that
subsequently sets and hardens.
Solid and rigid structures of any shape may be
formed.
Act as bonding phase that chemically binds
particulate aggregates into a single cohesive
structure.
Cementitious bond develops at room temperature.
PORTLAND CEMENT is consumed in the largest
tonnages.
Grinding and intimately mixing clay and lime-
bearing minerals in proper proportions, and then
heating to around 1400C.
Ground into very fine powder and gypsum is
added (to retard the setting process).
Termed a Hydraulic cement because its hardness
develops by chemical reactions with water. Used
primarily in mortar (fire-proofing material) and
concrete (construction material).
Lime is a Nonhydraulic cement as compounds other
than water (e.g. CO2) are involved in the hardening
reaction.
4.8.1.7 ADVANCED CERAMICS

(a) Microelectromechanical Systems (MEMS)


Miniature smart systems consisting of a multitude of
mechanical devices that are integrated with large number of
electrical elements on a substrate of silicon.
Mechanical components consists of microsensors and
microactuators.
Microsensors collect environment information by measuring
mechanical, thermal, chemical, optical and/or magnetic
phenomena.
Microelectronic components process these inputs, and render
decisions that direct responses from the microactuator devices
(positioning, pumping, regulating). The actuating devices are of
microscopic dimensions, on the order of microns in size.
Example of current practical MEMS application is an
accelerator/decelerator sensor used in air-bag systems in
automobiles.
Potential applications include electronic displays, data storage
units, chemical detectors or even energy conversion devices.
(b) Optical Fibers
New and advanced ceramic material that is a
critical component in modern optical
communication systems.
Made of extremely high-purity silica, which
must be free of even minute levels of
contaminants and other defects that absorb,
scatter and attenuate (reduces) a light beam.
Very advanced and sophisticated processing
techniques have been developed to produce
fibers that meet rigid restrictions required for
its application.
(c) Ceramic Ball Bearings
A bearing consists of balls and races that are in contact with
and rub against one another when in use.
Standard/Traditional ball and race parts were made of bearing
steels
Very hard, corrosion resistant, polished (smooth) surface.
Past decade, Hybrid Bearings were developed
Silicon Nitride (Si3N4) were used for the ball while races still
made of steel.
Density of Si3N4 much less, therefore weight reduction.
Si3N4 has higher modulus of elasticity, therefore the balls
are more rigid and experience less deformation. Lower
levels of noise and vibrations are achieved.
Lifetimes are greater > three to five times.
Hardness is higher than steel.
Compressive strength is higher than steel, therefore
lower wear rates.
Coefficient of friction is lower, therefore less heat
generated.
Applications include electric motors, machine tool spindles,
precision medical hand tools and food processing equipment.
4.8.2 FABRICATION AND PROCESSING OF
CERAMICS

Why is the method of fabrication for


ceramics a concern?
Metal-forming operations include
casting and plastic deformation
techniques.
However for ceramic materials
have relatively high melting
temperatures, casting is not practical.
brittleness precludes deformation.
TAXONOMICAL SCHEME of CERAMIC
FABRICATION TECHNIQUES
4.8.2.1 FABRICATION AND PROCESSING OF
GLASSES AND GLASS-CERAMICS

4.8.2.1.1 GLASS PROPERTIES


Glass Properties
Specific volume (1/r) vs Temperature (T):
Crystalline materials:
Specific volume
-- crystallize at melting temp, Tm
-- have abrupt change in specific
Supercooled Liquid
Liquid (disordered)
vol. at Tm

Glass Glasses:
(amorphous solid)
-- do not crystallize
Crystalline -- no definitive temperature at which
(i.e., ordered) solid
liquid transforms to a solid
Tg Tm T -- change in slope in spec. vol. curve at
glass transition temperature, Tg
-- transparent
Adapted from Fig. 13.6, Callister, 7e.
- no crystals to scatter light
Glass Viscosity vs. T and Impurities
soda-lime glass: 70% SiO2
Viscosity decreases with T balance Na2O (soda) & CaO (lime)
Impurities lower Tdeform 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 Please refer


PAGE 473 for
annealing range further reading
10 10 and
understanding.
10 6 Tdeform : soft enough
to deform or work
10 2
Tmelt
1
200 600 1000 1400 1800 T(C)
Adapted from Fig. 13.7, Callister, 7e.
(Fig. 13.7 is from E.B. Shand, Engineering
Glass, Modern Materials, Vol. 6, Academic
Press, New York, 1968, p. 262.)
4.8.2.1.2 GLASS FORMING
Heat the raw materials above melting
temperature.
To achieve good optical transparency, glass
product needs to be homogeneous and pore
free.
Four different forming methods:
Pressing
i. Pressing. Gob
operation
Thick-walled pieces
Parison
such as plates. mold

ii. Blowing. Compressed


air
Jars, bottles and
light bulbs. suspended
Parison

Finishing
mold
iii. Drawing.
Long glass pieces such as sheets, rods, tubing or
fibers.

iv. Fiber forming.


Continuous glass fibers. Fiber drawing:

wind up
4.8.2.1.3 HEAT TREATING GLASSES
ANNEALING
When a ceramic material is cooled from an elevated
temperature, internal stresses (thermal stresses) may be
introduced as a a result of the difference in cooling rate and
thermal contraction between the surface and interior
regions.
These defects weaken the material and in some cases lead
to fracture (thermal shock).
Normally to avoid these thermal stresses, cooling is done at
a sufficiently slow rate.
Elimination or reduction can be achieved by an annealing
heat treatment.
Glassware is heated to the annealing point and slowly
cooled to room temperature.
Overall, this heat treatment method will improve the glass
durability.
GLASS TEMPERING
Glass strength may be enhanced by inducing
compressive residual surface stresses by a heat
treatment procedure called thermal tempering.
Tempered glass is used for applications in which
strength is important; such as large doors and
eyeglass lenses.
before cooling surface cooling further cooled
cooler compression
hot hot tension
cooler compression

--Result: surface crack growth is suppressed.


4.8.3 FABRICATION AND PROCESSING OF
CLAY PRODUCTS

Consists of structural clay products


and whitewares.
In addition to clay, also contain other
ingredients. During drying and firing
operations, each ingredient influences
the changes that take place.
4.8.3.1 THE CHARACTERISTICS OF CLAY

When water is added, clay becomes


very plastic, a condition termed
hydroplasticity.
Clay fuses or melts over a range of
temperatures; thus a dense and strong
ceramic piece may be produced during
firing without complete melting such
that the desired shape is maintained.
4.8.3.2 COMPOSITIONS OF CLAY
PRODUCTS

Clays (whitewares) contain some


nonplastic ingredients (flint, quartz and
feldspar).
Quartz is used as a filler material.
When mixed with clay, a flux forms a
glass that has relatively low melting
point. Feldspars act as fluxing agents.
4.8.3.3 FABRICATION TECHNIQUES

As-mined raw minerals usually go though a


milling or grinding operation in which
particle size is reduced.
2 common shaping techniques are
Hydroplasting forming
When mixed with water, clay minerals become
highly plastic.
Extrusion technique
Ao
container die holder Adapted from
--Hydroplastic forming: force
ram bille extrusion Ad Fig. 11.8 (c),
extrude the slip (e.g., into a pipe) t Callister 7e.
container die
Slip Casting
A Slip is a suspension of clay and/or other
nonplastic materials in water.
High specific gravity but also pourable.
Mold material is normally Plaster of paris.

--Slip casting:
pour slip absorb water pour slip drain green
into mold into mold into mold mold ceramic
green
ceramic

solid component hollow component

Chapter 13 - 40
4.8.3.4 DRYING AND FIRING

DRYING
As a clay-based ceramic body dries,
shrinkage occurs.
Critical to control the rate of water removal in
order for interior and exterior surfaces to dry
properly.
Shrinkage is influenced by
Body thickness.
Water content of the formed body.
Clay particle size.
Microwave energy is being used to dry
ceramic wares.
Drying below 50C.
FIRING
After drying, the body is fired up at a
temperature between 900 and
1400C.
Density is further increased and
mechanical strength enhanced.
Vitrification occurs when clay is
heated to elevated temperatures.
The gradual formation of a liquid
glass that flows into and fills some
of the pore volume.
FIRING AND VITRIFICATION
During the firing operation, the density of the finished piece
is further increased and the mechanical strength is
enhanced.
Vitrification is the process where the gradual formation of a
liquid glass flows into and fills some of the pore volume.
The degree of vitrification depends on the firing
temperature and time, as well as the composition of the
body.
Fluxing agents such as feldspar can be added to lower the
temperature at which the liquid phase form.
The fused phase flows around the remaining unmelted
particles and fills in the pores.
Upon cooling, this fused phase forms a glassy matrix that
results in a dense strong body.
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 (900-1400C)
--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.)

70mm
4.8.4 POWDER PRESSING

Used to fabricate both clay and nonclay


compositions.
A powdered mass, usually containing a small
amount of water or other binder, is compacted into
the desired shape by pressure.
Degree of compaction is maximized by using an
appropriate mixture of coarse and fine particles.
Binder acts as lubricant.
There are 3 basic powder-pressing procedures:
i. Uniaxial.
ii. Isotactic (Hydrostatic).
iii. Hot pressing.
(i)UNIAXIAL

Powder is compacted
in a metal die by
pressure that is applied
in a single direction.
Confined to relatively
simple shapes.
Inexpensive process
since high production
rates.
(ii)ISOTACTIC

Powdered material is contained in a rubber


envelope and the pressure is applied by a fluid,
isostactically (i.e. it has the same magnitude in all
directions)
More complex shapes possible than uniaxial.
More time consuming and expensive.
SINTERING
Both uniaxial and isotactic
technique requires a firing
operation after pressing
operation.
Formed piece shrinks and
reduction in porosity.
Powder particles coalescence
into a more dense mass in a
process called sintering
(iii)HOT PRESSING

Powder pressing and heat treatment are


performed simultaneously.
Used for materials that do not form a
liquid phase except at very high
temperatures.
Most expensive technique.
4.8.5 TAPE CASTING
thin sheets of green ceramic cast as flexible tape
used for integrated circuits and capacitors
cast from liquid slip (ceramic + organic solvent)

Adapted from Fig. 13.18, Callister 7e.


4.8.6 CEMENTATION
Produced in extremely large quantities.
Portland cement:
-- mix clay and lime bearing materials
-- calcinate (heat to 1400C)
-- 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.