GLASS & CERAMIC

SHAPING & FORMATION

 GLASS
Atomic structure noncrystalline (or
amorphous)
 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 transition
in the amorphous regions between the glassy Crystal  discountinue
decrease in V at Tm
and rubbery state
Tg: glass transition T
• Below this Tg, the material is considered to be
Tm: melting T for
a glass; above, it is first a supercooled liquid,
crystalline
and finally a liquid
Specific points in glass fabrication:
Viscosity vs T
Glass/Ceramic 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
 Glass tempering
• enhanced the strength of a glass piece 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 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.
• use in automobile windshields, glass doors, eyeglass lenses
• compressive stress that gives the toughened glass increased strength. This
is because any surface flaws tend to be pressed closed by the retained
compressive forces
 CLAY PRODUCTS-
COMPOSITION
• Compisition : Clay, quartz, feldspar

CLAY are aluminosilicates Al2O3 & SiO3 contain chemically bound water
• distinguished by their composition, plasticity, color, and firing characteristics
• Broad in physical characteristic, chemical composition, structure
• Impurities-various: oxide of Ba, Ca, Na, K, Fe
• When water is added  form a thin film around the clay particles.
• Common clay mineral: kaolinite (Al2(Si2O5)(OH)4

• 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 maintain
QUARTZ (SiO2)used primarily as a filler material,
being inexpensive, relatively hard
• It experiences little change during high-
temperature heat treatment because it has a
melting temperature well above the normal
firing temperature; when melted, however,
quartz has the ability to form a glass.

FELDSPAR  (KAlSi3O8 – NaAlSi3O8 – CaAl2Si2O8)

• fluxing agents  forms a glass that has a
relatively low melting point
• a group of aluminosilicate materials that
contain K+,Na+, and Ca2+ ions.
• Roles: improves the mechanical properties
(such as its scratch resistance and its ability to
withstand thermal shock), produces a glassy
phase during firing 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 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
 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 sufficient mechanical
strength to remain intact during transporting,
drying, and firing operations.
• Shaping methods: hydroplastic, casting & powder
pressing
• Wet body is then dried and fired
 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 (water–clay ratio) of the
hydroplastic mass must give a yield strength
sufficient 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
orifice 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
specific gravity and yet be very fluid and pourable depend on the
solid-to water ratio and other agents that are added.
Drain casting
• 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 scientific laboratory ware such as
ceramic tubes
• 2 methods: drain casting & solid casting
• 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
• 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
• 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 hollow—relatively, 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 final product
• The degree of compaction is maximized; fraction of void space is
minimized by using coarse and fine 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: 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
• problems with flows 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
 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
• Graphite is the most widely used die material (up to 2200°C, 10 - 30 Mpa)

• 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
• DISADVANTAGE :
1 Die for high T is expensive and do not generally last long.
2 limited simple shape: flat plates, block, cylinder
 Drying & Firing
• Ceramic formed hydroplastically/slip casting  retain
significant porosity & insufficient strength, still contain some
liquid added in previous operation
• Remove by drying  “green body”
• Procedure continued with firing
• density and strength are enhanced as a result of a high-
temperature heat treatment or firing
• Defect may be introduced during the operation (e.g crack)
render the ware useless
• These defects normally result from stresses that are set up
from nonuniform shrinkage.
 drying
• early stage, clay particles surrounded & separated by thin water film
• 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.
 firing
• 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 densification 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
• Vitrification  gradual liquid glass formation that flows into & fills
pore volume ; f=(T, t, composition)
• Degree of vitrification 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
fills 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 opacifiers such as
tin oxide or zirconium oxide, are used to modify the
visual appearance of the fired 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