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Introduction

Ceramic materials divide into three categories:

1. Glasses – melting & solidification processing

2. Traditional ceramics – particulate processing

3. New ceramics – particulate processing

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 Glass
 Glass is one of three basic types of ceramics. Glass is
distinguished by its amorphous (noncrystalline) structure.
 Structure : Network formers
Molecules that link up with each other to form long chains and
networks. Hot glass cools, chains unable to organize into a
pattern. Solidification has short-range order only.
 Amorphous structure occurs by adding impurities (Na+,Mg2+,Ca2+, Al3+).
 Impurities: interfere with formation of crystalline structure

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 Glass
 Raw Materials

1. Glass forming oxides: usually the dominant constituent

SiO2, B2O3, P2O5, etc.
2. Fluxes: reduce melting temperatures
Na2O, PbO, K2O, Li2O, etc.
3. Property modifiers: added to tailor chemical durability,
expansion, viscosity, etc.
CaO, Al2O3, etc.
4. Colorants: oxides with 3d, 4f electron structures; minor
additives (<1 wt%)
5. Fining agents: minor additives (<1 wt%) to help promote bubble
removal
As-, Sb-oxides, KNO3, NaNO3, NaCl, fluorides, sulfates
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 Glassmaking

1. The ingredients for glass are mixed, and along with a proportion of
cullet (broken glass), are added to a bath furnace, where they are
heated to about 1500°C and fused together.
2. Molten glass is fed as ‘gobs’ to an automatic bottle or jar making
machine.
3. A hot gob is first made into a parison or blank shape (by either pressing
or blowing), which is then blown to the final bottle or jar shape. Surface
coatings (sc) may be applied while hot. 5
4. The bottles or jars pass into a lehr (an annealing oven), where they
are first reheated to soften the glass to remove stresses, and then
cooled gradually to prevent stresses developing.
5. The bottles or jars are inspected and tested to meet quality
standards. Bottles not passing the quality checks are broken and
returned to the furnace as cullet. Cullet reduces the amount of
energy required to melt the glass ingredients.
6. Bottles passing inspection and testing are packed for dispatch to
where they will be filled, capped, and labeled.

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Shaping Processes in Glassmaking
 Shaping processes to fabricate these products can be
grouped into three categories:

1. Discrete processes for piece ware (bottles, jars,

plates, light bulbs)

2. Continuous processes for making flat glass (sheet

and plate glass) and tubing (laboratory ware,
fluorescent lights)

3. Fiber-making processes to produce fibers (for

insulation and fiber optics)

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 Shaping of Piece Ware
 Ancient methods of hand-working glass included glass blowing.
 Handicraft methods are still used today for making glassware items of
high value in small quantities. However, most modern glass shaping
processes are highly mechanized technologies for producing discrete
pieces in high quantities.
 Piece Ware Shaping Processes
1. Spinning – similar to centrifugal casting of metals
2. Pressing – for mass production of flat products such as dishes, bake
ware, and TV tube faceplates
3. Press-and-blow – for production of wide-mouth containers such as
jars
4. Blow-and-blow - for production of smaller-mouth containers such as
beverage bottles and incandescent light bulbs
5. Casting – for large items such as large astronomical lenses that
must cool very slowly to avoid cracking. 8
Spinning of funnel-shaped glass parts such as back sections of cathode
ray tubes for TVs and computer monitors:
(1) gob of glass dropped into mold; and
(2) rotation of mold to cause spreading of molten glass on mold surface
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Pressing of flat glass pieces:
(1) glass gob is fed into mold from furnace;
(2) pressing into shape by plunger; and
(3) plunger is retracted and finished product is removed (symbols v
and F indicate motion (velocity) and applied force)

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1. A gob of hot glass drops into the blank (parison) mould.
2. The mould is sealed shut by a ‘base’ part and a plunger pushes the glass
into the mould (made from iron).
3. The glass is shaped into a ‘blank’ and also pushed into the neck finish by
the plunger. This part of a jar or bottle is finished to its final shape at this
stage.
4. The blank shape (parison) is removed, rotated 180°, and transferred to
the blow (finishing) mould.
5. This mould is in two halves, made from fine-grain cast iron, and is highly
polished.
6. Air is blown into the hot parison to expand it tightly against the mould
walls.
7. The mould opens, the bottle is removed, annealed in the lehr, inspected 11
and tested, and shipped for filling.
1. A gob of hot glass drops into the blank (parison) mould.
2. The end is sealed and a puff of air pushes glass into the neck (finish).
3. A puff of air from below pushes glass into the mould and shapes it into
a ‘blank’ or parison, a thick-walled bottle looking vaguely like the final
bottle shape.
4. The blank shape (parison) is removed, rotated 180°, and transferred to
the blow (finishing) mould.
5. This mould is in two halves, made from fine-grain cast iron, and is
highly polished.
6. Air is blown into the hot parison to expand it tightly against the mould
walls.
7. The mould opens, the bottle is removed, annealed in the lehr, inspected
and tested, and shipped for filling. 12
 Casting
 If molten glass is sufficiently fluid, it can be poured into a
mold.
 Relatively massive objects, such as astronomical lenses
and mirrors, are made by this method.
 After cooling and solidifying, the piece must be finished by
lapping and polishing.
 Casting of glass is not often used except for special jobs.
 Smaller lenses are usually made by pressing.

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Shaping of Flat and Tubular Glass
 Processes for producing flat glass such as sheet and plate glass:

Rolling of Flat Plate

Starting glass from melting furnace is squeezed through
opposing rolls whose gap determines sheet thickness, followed
by grinding and polishing for parallelism and smoothness

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Float Process

Molten glass flows onto the surface of a molten tin bath,

where it spreads evenly across the surface, achieving a
uniform thickness and smoothness - no grinding or
polishing is needed.

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Danner Process

Molten glass flows around a rotating hollow mandrel

through which air is blown while the glass is drawn.

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 Forming of Glass Fibers
Glass fiber products can be divided into two categories, with
different production methods for each:

1. Fibrous glass for thermal insulation,

acoustical insulation, and air filtration, in
which the fibers are in a random, wool-
like condition. Centrifugal spraying

2. Long continuous filaments suitable for

fiber reinforced plastics, yarns, fabrics,
and fiber optics. Drawing

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 Heat Treatment
 Annealing of Glass

Heating to elevated temperature and holding for a time to eliminate

stresses and temperature gradients; then slow cooling to suppress
stress formation, followed by more rapid cooling to room
temperature. Annealing temperatures are around 500°C.

 Tempering of Glass

Heating to a temperature somewhat above annealing temperature

into the plastic range, followed by quenching of surfaces, usually by
air jets. When the surfaces cool, they contract and harden while
interior is still plastic. As the internal glass cools, it contracts,
putting the hard surfaces in compression. Tempered glass is more
resistant to scratching and breaking due to compressive stresses
on its surfaces. 18
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 Ceramics Particulate Processing
 Traditional ceramics are made from minerals occurring in nature.
Products include pottery, porcelain, bricks, and cement
 New ceramics are made from synthetically produced raw materials.
Products include cutting tools, artificial bones, nuclear fuels, and
substrates for electronic circuits
 The starting material for all of these items is powder.
 For traditional ceramics, the powders are usually mixed with water
to temporarily bind the particles together and achieve the proper
consistency for shaping.
 For new ceramics, substances other than water are used as binders
during shaping.
 After shaping, the green parts are fired (sintered). 20
Usual steps in traditional ceramics processing:
(1) preparation of raw materials, (2) shaping, (3) drying, and (4) firing
Part (a) shows the workpart during the sequence, while (b) shows
the condition of the powders

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 Traditional Ceramics
 Shaping processes for traditional
ceramics require the starting material
to be a plastic paste.
 Main Ingredients of Ceramic Paste
1. Clay (hydrous aluminum silicates) -
usually the main ingredient because
of ideal forming characteristics when
mixed with water.
2. Water – Adding water to the
clay particles produces a "slip":-
allows material to shear easily
along weak van der Waals bonds
– Hydroplastic (suitable plasticity
for shaping. 22
 Shaping of Ceramics
 Slip casting
– The clay-water mixture is a slurry.
 Plastic forming methods
– The clay is plastic.
 Semi-dry pressing
– The clay is moist but has low plasticity.
 Dry pressing
– The clay is basically dry (less than 5% water) and
has no plasticity.
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 Slip Casting
 A suspension of ceramic powders in water, called a slip, is
poured into a porous plaster of paris mold so that water from the
mix is absorbed into the plaster to form a firm layer of clay at the
mold surface.
 The slip composition is 25% to 40% water.
 Two principal variations:
– Drain casting - the mold is inverted to drain excess slip after a
semi-solid layer has been formed, thus producing a hollow
product.
– Solid casting - to produce solid products, adequate time is
allowed for entire body to become firm.

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 Drain casting

Sequence of steps in drain casting, a form of slip casting:

(1) slip is poured into mold cavity,
(2) water is absorbed into plaster mold to form a firm layer,
(3) excess slip is poured out, and
(4) part is removed from mold and trimmed
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 Solid casting

Sequence of steps in solid casting:

(1) slip is poured into mold cavity,
(2) water is absorbed into plaster
mold to form a product,
(3) part is removed from mold and
trimmed
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 Plastic Forming
 The starting mixture must have a plastic consistency, with 15%
to 25% water.

 Plastic Forming Methods:

 Hand modeling (manual method)

 Jiggering (mechanized method)

 Pressing

 Isostatic pressing

 Extrusion

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 Hand Modeling
 Creation of the ceramic product by manipulating the mass of
plastic clay into the desired geometry.
 Hand molding - similar only a mold or form is used to define
portions of the part geometry.
 Hand throwing on a potter's wheel is another refinement of
handcraft methods.
– Potter's wheel = a round table that rotates on a vertical spindle,
powered either by motor or foot-operated treadle.
– Products of circular cross-section can be formed by throwing
and shaping the clay, sometimes using a mold to provide the
internal shape

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 Jiggering
 Similar to potter's wheel methods, but hand throwing is replaced
by mechanized techniques.

Sequence in jiggering:
(1) wet clay slug is placed on a convex mold;
(2) batting; and
(3) a jigger tool imparts the final product shape
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 Pressing
 Forming process in which a plastic clay slug is pressed between
upper and lower molds contained in metal rings.
 Molds are made of porous material such as gypsum, so when a
vacuum is drawn on the backs of the mold halves, moisture is
removed from the clay.
 The mold sections are then opened, using positive air pressure to
prevent sticking of the part in the mold.
 Advantages: higher production rate than jiggering and not limited
to radially symmetric parts.

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 Isostatic pressing
 A powdered material can be compacted by loading it into a
flexible, air-tight container and placing it into a closed vessel filled
with a fluid to which pressure (> 150 MPa) is applied.
 Wet bag molds are independent of the press construction. Wet-
bag served as a carrying case and controls the shape of pressed
item.

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 Extrusion
 Compression of clay through a die orifice to produce long
sections of uniform cross-section, which are then cut to required
piece length.
 Equipment utilizes a screw-type action to assist in mixing the clay
and pushing it through die opening.
 Products: hollow bricks, shaped tiles,
drain pipes, tubes, and insulators
 Also used to make the starting clay slugs for
other ceramics processing methods such as
jiggering and plastic pressing.

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 Semi-dry
Pressing
 Uses high pressure to overcome the clay’s low plasticity and force
it into a die cavity.

Semi-dry pressing:
(1) depositing moist powder into die cavity,
(2) pressing, and (3) opening the die sections and ejection
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 Dry Pressing
 Process sequence is similar to semi-dry pressing - the main
distinction is that the water content of the starting mix is typically
below 5%.
 Dies must be made of hardened tool steel or cemented carbide to
reduce wear since dry clay is very abrasive.
 No drying shrinkage occurs, so drying time is eliminated and
good dimensional accuracy is achieved in the final product.
 Typical products: bathroom tile, electrical insulators, refractory
brick, and other simple geometries.

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 Clay Volume vs. Water Content
 Water plays an important role in most of the traditional ceramics
shaping processes. It must be removed from the clay piece before
firing.
 Shrinkage is a problem during drying because water contributes
volume to the piece, and the volume is reduced when it is
removed.
 Drying : The drying process occurs in two stages:
• Stage 1 - drying rate is rapid and constant as water evaporates
from the surface into the surrounding air and water from the
interior migrates by capillary action to the surface to replace it.
• Stage 2 - the moisture content has been reduced to where the
ceramic grains are in contact.
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 Firing of Traditional Ceramics
 Heat treatment process that sinters the ceramic material.
 Performed in a furnace called a kiln.
 Bonds are developed between the ceramic grains, and this is
accompanied by densification and reduction of porosity.
 Therefore, additional shrinkage occurs in the polycrystalline
material in addition to that which has already occurred in drying.
 In the firing of traditional ceramics,
a glassy phase forms among the
crystals which acts as a binder.

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 Shrinkage during Sintering
 Sintering shrinkage depends on
initial green density.
 Shrinkage from green body to final
form may be as much as 30%(linear)
: problems in predicting final
product size and shape.
 Differential shrinkage is a serious
problem : hence use of lubricants
etc to get good flow in compaction
to green body → uniform green
density.
 If there is a difference in density
across a component distortion
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occurs.
 Refractories
 Refractory ceramics should withstand to high temperatures
without melting or decomposing, and remain unreactive and inert
when exposed to severe environments.
 Porosity is important factor to produce a suitable refractory
material.
- less thermal expansion/contraction upon thermal cycling
- Resistance to thermal shock
- Increased insulation
- Lighter
 Disadvantages: – Worse resistance to Chemical attack
– Weaker load bearing capability
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 Processing of New Ceramics
 The manufacturing sequence for the new ceramics can be
summarized in the following steps:
1. Preparation of starting materials
2. Shaping
3. Sintering
4. Finishing
 Preparation of Starting Materials : Strength requirements are
usually much greater for new ceramics than for traditional
ceramics. Therefore, the starting powders must be smaller and
more uniform in size and composition, since the strength of the
resulting ceramic product is inversely related to grain size.
 Powder preparation includes mechanical and chemical methods.
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 Shaping of New Ceramics
 Many of the shaping processes for new ceramics are borrowed from
powder metallurgy and traditional ceramics.
 The processes described here are not normally associated with the
forming of traditional ceramics.
 Hot Pressing : Similar to dry pressing except it is carried out at
elevated temperatures so sintering of the product is accomplished
simultaneously with pressing. This eliminates the need for a
separate firing step.
 Powder Injection Molding (PIM) : Ceramic particles are mixed with a
thermoplastic polymer, then heated and injected into a mold cavity.
The polymer acts as a carrier and provides flow characteristics for
molding. Upon cooling which hardens the polymer, the mold is
opened and the part is removed. The plastic binder is removed and
the remaining ceramic part is sintered. 44
Engineering Ceramics

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 Heat engine applications
 Ceramic materials are used in automobile internal combustion
engines.
 The advantage over the metal alloys:
- The ability to withstand higher operating temperatures, thereby
increasing fuel efficiency;
- excellent wear and corrosion resistance;
- the ability to operate without a cooling system;
- low densities (lower engine weight).

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Electrical/electronic applications

Materials Applications
Alumina (Al2O3)
Beryllium oxide (BeO) Insulators, substrates,
Boron nitride (BN) structural components,
Silicon carbide (SiC) etc.

Aluminum nitride (AlN)

Barium titanate (BaTiO3) Capacitors, sensors, etc.
Zirconia (ZrO2) Sensors

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Bioceramics

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 Ceramic-matrix composites
(CMCs)
 Strength and fracture toughness of ceramics have been improved
significantly by the development of ceramic-matrix composites.
 CMCs are believed to be toughened by three main mechanism, all of
which result from the reinforcing fibers interfering with crack
propagation in the ceramic as follows :
1. Crack deflection
2. Crack bridging 3. Fiber pullout

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1. Crack deflection
Upon encountering the reinforcement, the crack is deflected,
making its propagating path more meandering, thus higher
stresses are required to propagate the crack.
2. Crack bridging
Fibers can bridge the crack and help keep the material together,
thus increasing the stress level needed to cause further cracking.
3. Fiber pullout
The friction caused by fibers being pulled out of the cracking
matrix absorbs energy, and thus higher stresses must be applied to
produce further cracking. Therefore, a good interfacial bond is
required between the fibers and the matrix for higher strengths.

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 Ceramic-matrix composites
 Transformation toughening
Stress promotes transformation from one phase to another with a higher
volume, causing a compressive stress.
– Partially stabilized zirconia particles (tetragonal phase made to be stable
at ambient conditions instead of the expected and higher volume
monoclinic phase). An approaching crack can be pinched shut.

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 Cement and concrete
 Cement is a mixture of compounds made by burning limestone and
clay together at very high temperatures (1400 to 1600 oC).
 Portland cement : it is consumed in the largest amount.
 The major constituents of Portland cement are tricalcium silicate
(3CaO-SiO2), and dicalcium silicate (2CaO-SiO2).
 Concrete is a composite material consisting of aggregate particles
(sand and stone) bound together in a solid body by a cement.
 Water is the key ingredient, which when mixed with cement, forms a
paste that binds the aggregate together. The water causes the
hardening through a process called hydration.
Tricalcium silicate + Water Calcium silicate hydrate + Calcium hydroxide + heat

2 (3CaO-SiO2) + 7 H2O → 3 CaO-2SiO2-4H2O + 3 Ca(OH)2 + 173.6kJ

 The hydration will continue as long as water is present and there are
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still unhydrated compounds in the cement paste.
 Cement and concrete
 The reaction of water with the cement in concrete is extremely
important to its properties and reactions may continue for many
years. When concrete dries, it actually stops getting stronger.
Concrete with too little water may be dry but is not fully reacted.
 Advantages of concrete
- Economic benefits : long life and low maintenance requirements
- Resistant to wind, water, rodents, and insects
- Concrete has the ability to be molded or cast into almost any
desired shape on the work-site.
- Non-combustible material
 Disadvantages of concrete
- Relatively low tensile strength
- Low strength-to-weight ratio
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- Susceptible to cracking
 Reinforced concrete
 Reinforced concrete is concrete containing steel reinforcements in
the form of rods, wire, wire mesh, etc.
 In the reinforced concrete, the tension forces are transferred from
the concrete to the steel reinforcement through bonding.

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 Pretensioned
concrete
 The tensile strength of reinforced concrete can be further improved
by introducing compressive stresses into the concrete by
pretensioning or posttensioning using steel reinforcements called
tendon.
Pretensioned (prestressed) concrete

Posttensioned concrete 55
 Pretensioning :
1. Steel tendons are stretched between external tendon anchorage
and adjustable jack for applying tension.
2. Concrete is poured over the tendons.
3. When the concrete reaches the required strength, the jack
pressure is released.
 Posttensioning :
1. Hollow conduits containing steel tendons are placed in concrete.
2. When concrete is sufficiently strong, tendon is anchored at one
end and jacking tension is applied at the other end.
3. When jacking pressure is sufficiently high, a fitting is replaced the
jack.
4.The space in conduits is filled by cement grout by forcing.
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 Colorant Color
Ironoxides greens, browns
Manganese oxides deepamber, amethyst, decolorizer
Cobalt oxide deepblue
Goldchloride rubyred
Seleniumcompounds reds
Carbonoxides amber/brown
Mixof mangnese, cobalt, iron black
Antimonyoxides white
Uraniumoxides yellowgreen(glows!)
Sulfur compounds amber/brown
Copper compounds light blue, red
Tincompounds white
Leadwithantimony yellow 57