GLASS & CERAMIC

SHAPING & FORMATION

 GLASS
Atomic structure →noncrystalline (or
amorphous)
Kinetics of crystallization→ On cooling the
liquid from a high temperature, two
phenomena may occur at the point of
solidification, Tm:
• If the liquid crystallizes there is a
discontinuous change in V and a
discontinuity in the rate of cooling (= heat
of crystallization).
• If no crystallization occurs the liquid passes
into a supercooled state and V decreases
at about the same rate as above
• Supercooled: condition in which a liquid
has been cooled to a temperature below Tf
that at which crystallization normally
would occur
• Glasses do not really solidify in the
traditional sense → no definite
temperature at which the liquid
transforms to a solid
• Upon cooling, a glass continues to be
more viscous with decreasing
temperature → The molecules pack closer
and closer together, becoming an
increasingly denser liquid.
• volume decreases continuously with
temperature reduction
• The slight change in slope occurs when
the molecules are essentially unable to
flow.
• This is the Glass Transition Temperature
• Tg→The temperature at which the Crystal → discountinue
transition in the amorphous regions decrease in vol at Tm
between the glassy and rubbery state
Tg: glass transition T
• Below this Tg, the material is considered
to be a glass; above, it is first a Tm: melting T for
supercooled liquid, and finally a liquid crystalline
Viscosity vs T
Specific points in glass fabrication:
 Glass Forming
• Heat RM to an elevated temperature above which melting occurs
• Most commercial glasses are of the silica–soda–lime variety
• silica (quartz)–Na2O(soda ash, Na2CO3)–CaO(limestone, CaCO3)
• Important: homogeneous and pore free
• Homogeneity → complete melting and mixing of RM
• Porosity results from small gas bubbles that are produced → these must be
absorbed into the melt or otherwise eliminated, which requires proper
adjustment of the viscosity of the molten material
• 4 methods to fabricate glass: pressing, blowing, drawing & fiber forming
 pressing
• → relatively thick-walled pieces (plates and dishes.
• The glass piece is pressed in a graphite-coated cast iron mold
with desired shape
• the mold is heated to ensure an even surface.
 BLOWING
⦿ some glass blowing is done
by hand → art object
⦿ RM →press in mold
→parison (temporary
shape); place into finishing
or blow mold & forced to
conform to the mold
contours by the pressure
created from a blast of air
⦿ Glass bottle, jar, light bulb
 DRAWING

● Form long, wide glass pieces (window glass,sheet, tubing, rod etc)
● hot rolling may applied
● Flatness & surface finish may be improved by floating the molten
glass sheet on a bath of molten tin at high T followed slowly cooled
and subsequently heat treated
Glass processing
 CERAMIC-Clay Products
• Clay are aluminosilicates →Al2O3 & SiO3 contain chemically
bound water
• Broad in physical characteristic, chemical composition,
structure
• Impurities-various: oxide of Ba, Ca, Na, K, Fe
• May contain nonplastic ingredient
• Nonclay minerals: flint, quartz, feldspar
• Quartz→relatively hard, little change in high T, ability to form
glass
 Composition
• Clay minerals play 2 roles:
1.When added water, form hydroplasticity
2.Fuse or melt over a range T→ dense & strong
ceramic during firing without complete melting;
desired shape

• Common clay mineral: kaolinite (Al2(Si2O5)(OH)4

• Most prevailing structure → layer structure
• When water is added, the water molecules fit in
between these layered sheets and form a thin
film around the clay particles.
• RM → milling & grinding → screening & sizing →
mixing all RM → shaping
 Binder & plastiziser
• Binder → a component that is added to hold the powder together while
shaping the body
• 2 functions of binder:
1) provide plasticity necessary for forming
2) provides the dry (green) shape with strength sufficient to survive the
handling process between shaping and sintering

• the binder should be able to be eliminated from the compact during the
firing process without any disruptive effect → water, polymers
• Poly (vinyl alcohol) (PVA → high green strength) and poly (ethylene glycol)
(PEG→high green density) are the two of the most popular binders for dry
pressing ceramics
 Plastic forming
• Plasticizer is the component of a binder that keeps it soft or pliable; it
improves the rheological properties
• Mixing ceramic powder with large vol of liquid to produce a mass that
deformable/plastic under P
• The binder: water, organic liquid, complex comp to achieve required
viscosity & properties

NOTE
⦿ Slurry → a suspension of ceramic particles in a liquid
• Green state: ceramic compact that is strong enough to be handled and
machined but is not fully dense and the bonds between the grains are not
strong → represents a transition state between the loose powder and the
high-density sintered product ; ceramic before fired
• Slip →fine ceramic powders (<10 um) that are suspended in fluid
 Fabricating clay product
• Clay is mixed with water to form a plastic body & formed
to desired shape → wet body
• Wet body is then dried and fired
- drying removes water from the clay → controlled rate
- fire vitrifies clay
- degree of vitrification depends on firing tempterature
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 CERAMIC SHAPING
3 methods in ceramic shaping:
⦿ Powder compaction: dry pressing, hot pressing, cold isostatic pressing,
etc
⦿ casting: using a mold with the ceramic as or containing of liquid or slurry
⦿Plastic forming: using pressure to shape the green ceramic; extrusion,
injection molding etc.
 Powder compaction
• Pressing of free flowing powder
• Pressure application depends on final product
• 2 types: dry pressed (i.e. without addition of binder) & pressed with the
addition of suitable binder
• uniaxially → simple shape, or isostaticcally → complex shape
 Dry pressing
• three basic steps: filling the die, compacting the contents, and
ejecting the pressed solid
• A particle size 20 and 200 µm; a high volume fraction of small
particles →s problems with flow and sticking of the punches.
• During pressing the powder particles must flow between the
punches →uniformly filled.
• In a double-action press → top and bottom punches are
movable
• Product example: brick
• bottom punch is in the low position a cavity →the cavity is filled with free
flowing powder ; the powder is struck off level with the top of the die.
The top punch descends and compresses the powder either to a
predetermined volume/set pressure.
• After pressing, both punches move upward →The compact is then ejected
 Hot pressing
• Pressing performed at high temperatures
• The die assembly is contained within a high temperature furnace
• During hot pressing the ceramic powders may sinter together to form a high-
density component.
• the ADVANTAGES of this process:
1 The powder does not have to be of the highest quality.
2 Large pores that are caused by non uniform mixing are easily removed.
3 densify at temperatures lower (typically half the melting temperature of the
material) than those needed for conventional pressure less sintering.
4 densify covalently bonded materials such as B4C, SiC, and Si3N4 without additives
 • Graphite is the most widely used
die material (up to 2200°C, 10 -
30 Mpa)
• Graphite properties:
1 easy to machine
2 cheap
3 strength increase with T
4 good creep resistance
5 excellent thermal conductivity
6 low coeff of thermal expansion

• DISADVANTAGE :
1 Die for high T is expensive and do
not generally last long.
2 limited simple shape: flat plates,
block, cylinder
 Cold isostatic pressing-CIP
• apply of hydrostatic pressure to a powder in a
flexible container.
• The advantage of applying pressure in all directions
→more uniform compaction of the powder and
more complex shapes
• Can be performed either with or without applied
heat.
WET BAG CIP PROCESS
ADVANTAGES:
• Wide range of shapes and sizes can be produced
• Uniform density of the pressed product
• Low tooling costs
DISADVANTAGES:
• Poor shape and dimensional control (particularly for
complex shapes)
• Long cycle times (typically between 5 and 60
minutes) → low production rates
 Casting ceramic
• In Tr, require slurry → ceramic powder particles to be suspended in a
liquid
• 2 type: slip casting & tape casting
• S lip casting → slurry is poured into porous mold that remove the liquid,
leave a particulate compact in the mold
• Tape casting → to make thick film/sheet
 Slip casting
• The slip is poured into a mold (usually plaster of Paris-
2CaSO.4H2O) that has been made by casting round a
model of the required shape
• The mold allow for the shrinkage of the cast ceramic
on drying and sintering.
• The fineness of the powder (in the slip) and the
consequent high surface area ensure that settling
does not occur.
• Na silicate (or soda ash) is added to the slip to
deflocculate the particles. The water passes, via
capillary action, into the porous plaster leaving a layer
of the solid on the wall of the mold. Once a sufficient
thickness has been cast, the surplus slip is poured out
and the mold and cast are allowed to dry.
• Drain slip casting →the process’s terminated when desired
thickness reached, pour out the excess slip.
• After dried, the mold is disassembled
• Characteristic the Slip →high specific gravity, very fluid &
pourable
• → sanitary lavatory ware, art objects
• Slip casting is a low cost way to produce complex shapes
• method for the production of teapots, jugs, and large articles
(whitewares)
• One of the t signs of slip casting ceramic is that it is hollow.
• Another variant of the slip casting process is solid/tape casting → slip is
continually added until a solid cast is made. These items will not be hollow
—relatively, they will be heavier.
• Characteristic slip: high specific gravity, very fluid, pourable (depend on
solid to water ratio), free of bubble, low drying shrinkage & high strength
• Mold properties → quality of casting
• Usually plaster of paris → ecomonical, easy to fabricate, reusable
• Solid casting →water from slip is absorbed into the mold when
poured, leaving solid layer on the mold wall (thickness, f=(t))
• May continue until entire mold cavity becomes solid
 extrusion
• Extrusion involves forcing a deformable
mass through a die orifice (like toothpaste
from a tube)
• widely used to produce ceramic
components having a uniform cross section
and a large length-to-diameter ratio such as
ceramic tubes and rods
• Extrusion is also used to produce the
alumina shells for sodium vapor lamps and
the honeycomb-shaped catalyst supports
for automotive emission-control devices
 Injection molding
• Used for ceramic powder which is added to a thermoplastic polymer.
• the polymer is usually referred to as the binder
• The ceramic powder is added to the binder and other organic materials to provide a
mass that has the desired rheological properties
• The plastic mass is first heated, at which point the thermoplastic polymer becomes
soft and is then forced into a mold cavity. The heated mixture is very fluid and is not
self-supporting (this is different from the situation encountered in extrusion). The
mixture is allowed to cool in the mold during which time the thermoplastic polymer
hardens.
• complex shapes are retained with very little distortion during sintering since the
densities, although low, are uniform.

• ADVANTAGES: used to fabricate

ceramic components with complex
shapes; cycle times can be rapid →
high-volume process.
• DISADVANTAGES: initial tooling costs
is quite high
 Drying & Firing
• Ceramic formed hydroplastically/slip casting → significant
porosity & insufficient strength, contain some liquid added in
previous operation
• Remove by drying → “green body”
• Continued with firing
• Defect may be introduced → results of nonuniform shrinkage
 drying
• early stage, clay particles surrounded & separated by thin water film
• Drying: remove some liquid remain →interparticle separation decrease
(shrinkage);
• Critical to control the rate of water removal
• Drying interior is accomplished by diffusion of water molecules to surface
where evaporation occurs
• Rate of evap>diffusion→ surface will dry faster than interior → shrink
• Nonuniform shrinkage & defect formation → thick >thin pieces
• More water content →more extensive the shrinkage; kept as low as
possible
• Particle size decrease → shrinkage increase
 Binder burnout
• removal of water from the shaped clay.
• The rest of the firing process causes structure changes and transformations in the
silicate itself.
• Expected → remove binder without cracking or distorting the ceramic compact.
• Binder burnout forms defects in the processing of a ceramic: macroscopic defects,
such as cracks and blisters → affect the mechanical strength and other properties.
• In commercial ceramic which often consists of several components→ challenging
to be controlled, different boiling points and decomposition temperatures.
• The components with low boiling points (e.g., waxes)may be removed by
evaporation at fairly low temperatures.
• The process of binder removal is kept slow to redue possibility of macrodefects
being produced.
 firing
• Fire between 900-1400 C (RM composition & desire
properties)
• During firing operation → density increase (→porosity
decrease) & mechanical strength enhance
• Complex reactions occured
• vitrification: gradual liquid glass formation that flows
into & fills pore volume ; f=(T, t, composition);
accompanied by shrinkage
• Degree of vitrification controls ceramic properties
(strength, durability & density)
• Addition of fluxing agent → reduce T of liquid phase
• Upon cooling, this fused phase forms in a dense, strong
body
• Complete vitricifation is avoided → body become too
soft, may collapse
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