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
solidication, 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 denite
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
TgThe temperature at which the
transition in the amorphous regions
between the glassy and rubbery state
Below this Tg, the material is considered
to be a glass; above, it is rst a
supercooled liquid, and nally a liquid

Crystal discountinue
decrease in vol at Tm
Tg: glass transition T
Tm: melting T for
crystalline

Specic points in glass fabrication:

Viscosity vs T

Glass annealing
When a ceramic material is cooled from an elevated
temperature, internal stresses, called thermal
stresses, may be introduced as a result of the
difference in cooling rate and thermal contraction
between the surface and interior regions.
These thermal stresses are important in brittle
ceramics, especially glasses, since they may
weaken the material lead to fracture
Attempts are made to avoid thermal stresses, which
may be accomplished by cooling the piece at a
sufciently slow rate
Once such stresses have been introduced, however,
elimination, or at least a reduction in their
magnitude, is possible by an annealing heat
treatment in which the glassware is heated to the

 Generally at a temperature slightly above the point at which

recrystallization occurs

Glass tempering
enhanced the strength of a glass piece by intentionally inducing
compressive residual surface stresses can be accomplished by a heat
treatment procedure called thermal tempering
the glassware is heated to temperature above the glass transition
region yet below the softening point, then cooled to room temperature in
a jet of air or, in some cases, an oil bath.
The residual stresses arise from differences in cooling rates for surface
and interior regions.
Initially, the surface cools more rapidly and, once having dropped to a
temperature below the strain point, becomes rigid. At this time, the
interior, having cooled less rapidly, is at a higher temperature (above the
strain point) and, therefore, is still plastic. With continued cooling, the
interior attempts to contract to a greater degree than the now rigid
exterior will allow.
As a consequence, after the glass piece has cooled to Tr, it sustains
compressive stresses on the surface, with tensile stresses at interior
regions.

Glass/Ceramic fabrication

Glass Forming

Heat RM to an elevated temperature above which melting

occurs
Most commercial glasses are of the silicasodalime 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 &
ber 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
nishing 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 nish 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

CLAY PRODUCTS
Composition
Clay, quartz, feldspar (KAlSi3O8 NaAlSi3O8
CaAl2Si2O8)
CLAY are aluminosilicates Al2O3 & SiO3 contain
chemically bound water
distinguished by their composition, plasticity, color,
and ring characteristics
Broad in physical characteristic, chemical
composition, structure
Impurities-various: oxide of Ba, Ca, Na, K, Fe
May contain nonplastic ingredient

 Clay minerals play 2 roles:

1. When added water, form hydroplasticity
2. Fuse or melt over a range T dense &
strong ceramic during ring without
complete melting; desired shape maintain

Common clay mineral: kaolinite

(Al2(Si2O5)(OH)4
Most prevailing structure layer structure
When water is added, the water molecules
t in between these layered sheets and
form a thin lm around the clay particles.
The particles are thus free to move over
one another, which accounts for the
resulting plasticity of the waterclay
mixture.

QUARTZ (SiO2)used primarily as a ller material, being

inexpensive, relatively hard
It experiences little change during high-temperature heat
treatment because it has a melting temperature well above
the normal ring temperature; when melted, however, quartz
has the ability to form a glass.
FELDSPAR (KAlSi3O8 NaAlSi3O8 CaAl2Si2O8)
is a source of Al2O3
Roles: improves the mechanical properties (such as its
scratch resistance and its ability to withstand thermal shock),
produces a glassy phase during ring increasing the strength
and translucency

Binder
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 sufcient to
survive the handling process between shaping and sintering

the binder should be able to be eliminated from the

compact during the ring process without any disruptive
effect water, polymers
Poly (vinyl alcohol) (PVA high green strength) and poly
(ethylene glycol) (PEGhigh green density) are the two of
the most popular binders for dry pressing ceramics

plasticizer
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

Fabrication
RM milling & grinding screening &
sizing mixing all RM shaping
Clay is mixed with water and perhaps other
ingredients to give flow characteristics that
are compatible with the particular forming
technique to form a plastic body & formed
to desired shape wet body
The formed piece must have sufcient
mechanical strength to remain intact during
transporting, drying, and ring operations.
Shaping methods: hydroplastic, casting &
powder pressing
Wet body is then dried and red

Hydroplastic
Clay minerals, when mixed with water,
become highly plastic and pliable and
may be molded without cracking;
however, they have extremely low yield
strengths.
The consistency (waterclay ratio) of the
hydroplastic mass must give a yield
strength sufcient to permit a formed
ware to maintain its shape during
handling and drying.
The most common hydroplastic forming
technique is extrusion
forcing a deformable mass through a die
orice having the desired cross-sectional
geometry
Brick, pipe, ceramic blocks, and tiles

Slip Casting ceramic

In Tr, require slurry ceramic powder particles to be
suspended in a liquid (slip)
S lip casting slurry is poured into porous mold
(commonly made of plaster of paris) that has been
made by casting, round a model of the required shape
water from the slip is absorbed into the mold (remove
the liquid), leave a particulate compact/layer on the
mold wall the thickness of which depends on the time
The nature of the slip is extremely important; it must
have a high specic gravity and yet be very fluid and
pourable depend on the solid-to water ratio and
other agents that are added.

 A satisfactory casting rate is an essential

requirement.
The properties of the mold itself influence the
quality of the casting the mold porosity may be
varied to control the casting rate.
Usually plaster of paris ecomonical, easy to
fabricate, reusable
In addition, the cast piece must be free of bubbles,
and it must have a low drying shrinkage and a
relatively high strength.
The rather complex ceramic shapes that may be
produced by means of slip casting include sanitary
lavatory ware, art objects, and specialized scientic
laboratory ware such as ceramic tubes
2 methods: drain casting & solid casting

 Drain slip casting the processs terminated when

desired thickness reached, pour out the excess slip.
After dried, the mold is disassembled
Characteristic the Slip high specic gravity, very fluid &
pourable
One of the t signs of slip casting ceramic is that it is
hollow.
low cost way to produce complex shapes
sanitary lavatory ware, art objects

 Solid casting water from slip is absorbed into the

mold when poured, leaving solid layer on the mold
wall (thickness, f=(t))
slip may continually added until a solid cast is
made. These items will not be hollowrelatively,
they will be heavier.

Powder compaction

Pressing of free flowing powder containing a small amount

of water or other binder, is compacted into the desired
shape by pressure
Pressure application depends on nal product
The degree of compaction is maximized; fraction of void
space is minimized by using coarse and ne particles mixed
in appropriate proportions.
no plastic deformation of the particles during compaction
One function of the binder is to lubricate the powder
particles as they move past one another in the compaction
process.
2 types: dry pressed (i.e. without addition of binder) &
pressed with the addition of suitable binder

Dry pressing
three basic steps: lling the die, compacting the
contents, and ejecting the pressed solid
A particle size 20 and 200 m; a high volume
fraction of small particles
problems with flows and sticking of the punches.
During pressing the powder particles must flow
between the punches uniformly lled.
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

lled 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
or set pressure.
After pressing, both punches move upward The compact
is then ejected

Hot pressing

1
2
3

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:
The powder does not have to be of the highest quality.
Large pores that are caused by non uniform mixing are easily
removed.
densify at temperatures lower (typically half the melting
temperature of the material) than those needed for conventional
pressure less sintering.
densify covalently bonded materials such as B4C, SiC, and Si3N4
without additives

DISADVANTAGE :
1 Die for high T is expensive
and do not generally last
long.
2 limited simple shape: flat
plates, block, cylinder

1
2
3
4
5
6

Graphite is the most widely

used die material (up to
2200C, 10 - 30 Mpa)
Graphite properties:
easy to machine
cheap
strength increase with T
good creep resistance
excellent thermal
conductivity
low coeff of thermal
expansion

Drying & Firing

Ceramic formed hydroplastically/slip casting
retain signicant porosity & insufficient strength,
still contain some liquid added in previous operation
Remove by drying green body
Procedure continued with ring
density and strength are enhanced as a result of a
high-temperature heat treatment or ring
Defect may be introduced during the operation
render the ware useless (e.g., warpage, distortion,
and cracks)
These defects normally result from stresses that are
set up from nonuniform shrinkage.

drying
early stage, clay particles surrounded & separated by thin water
lm
Drying: remove some liquid remain interparticle separation
decrease (shrinkage);
As a clay-based ceramic body dries, it also experiences some
shrinkage
During drying, it is critical to control the rate of water removal
Drying at interior is accomplished by diffusion of water molecules
to surface where evaporation occurs
The rate of surface evaporation = the rate of water diffusion; If
rate of evap>diffusion surface will dry faster than interior
shrink
evaporation rate may be controlled by temperature, humidity,
and the rate of airflow.

 Other factors also influence shrinkage, such as thickness,

water content, particle size
nonuniform shrinkage and defect formation are more
pronounced in thick pieces than in thin ones.
Water content of the formed body is also critical: the
greater the water content, the more extensive the
shrinkage consequently, the water content is ordinarily
kept as low as possible
Clay particle size also has an influence; shrinkage is
enhanced as the particle size is decreased.
To minimize shrinkage, the size of the particles may be
increased, or nonplastic materials having relatively large
particles may be added to the clay.

ring
Firing: heat treatment process that sinters
ceramic materials
performed in furnace called kiln
Fire between 900-1400 C (RM composition
& desire properties)
causes structure changes and
transformations in the silicate itself
Bond are developed between the ceramic
grain which lead to densication and
reduction of porosity additional shrinkage
occurs; mechanical strength increase
Expected no cracking or distorting the
ceramic compact.

 Complex reactions occurred

A glass phase forms among the crystals which act as binder
Vitrication gradual liquid glass formation that flows into
& lls pore volume ; f=(T, t, composition)
Degree of vitrication controls ceramic properties (strength,
durability & density)
O reduce T of liquid phase Add fluxing agent (compounds
to bond the materials), such metal oxides, such as sodium,
potassium and calcium as found in feldspar
This fused phase flows around the remaining unmelted
particles and lls in the pores as a result of surface tension
forces (or capillary action); shrinkage also accompanies this
process.
Complete vitricifation is avoided body become too soft,
may collapse

 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.
Upon cooling, this fused phase forms in a dense,
strong body

Glazing
Glazing: application of ceramic surface coating
to make the piece more impervious to water
and enhance its appearance
Colorants, such as iron oxide, copper carbonate
or cobalt carbonate, and sometimes opaciers
such as tin oxide or zirconium oxide, are used to
modify the visual appearance of the red glaze.
The usual processing sequence with glazed
ware is:
1. Fire the piece once before glazing to harden
the body of piece
2. Apply the glaze
3. Fire the piece a second time to harden the
glaze