GINEERING MATERIALS &

METALLURGY

UNIT IV

1
 Polymers

INTRODUCTION
POLYMER: Another word for a plastic material: one which has been made from chains of
molecules of one or more MONOMERS. Polymers (plastics) are ORGANIC substances of high
MOLECULAR WEIGHT, made from hundreds or thousands of molecules linked together in a
repeating chain pattern (also known as macromolecules).

THERMOPLASTIC:
A plastic material which, when softened in a mould under heat and pressure, forms a shape
which can be re softened and re moulded, e.g.: polythene, acrylic, PVC, and nylon.

THERMOSET:
A plastic which under heat and pressure polymerises into a form which cannot be re softened due
to CROSSLINKING of the molecules. It is therefore used for components such as light fittings,
saucepan handles and ashtrays.

ELASTOMERS:
More commonly known as rubber, can be defined as any material which after vulcanisation can
be extended to several times it’s original length and return to it’s original length when the force
is removed.

ADDITIVES:
Plastics used in moulding processes are normally in powder or small chips known as granules.
Before being moulded into shape they need to be mixed with additives. These come in the forms
of: Fillers, Stabilisers, Plasticizers, Lubricants, Antioxidants, Flame retardants, Colorants.

COMMON PROCESSES USING PLASTICS:

MOULDING:
The most common method for forming thermosetting resins such as BAKELITE into ashtrays,
radios etc. The moulding powder, usually with a filler is placed in the lower ' female ' part of a
two part mould. The top part closed on to it, heat and pressure are applied, the plastic flows
around the mould and the final moulding is ejected.

EXTRUSION:
Process similar to making spaghetti for moulding plastics into continuous lengths of pipes, rods
and profiles. The softened material is forced through a shaped DIE.

INJECTION MOULDING:
The most widely used high speed process for mass producing plastic articles. Granules are
heated and forced under pressure into a mould, which can be single cavity for a bucket or chair,
or multi cavity for combs and other small objects.

2
THERMOFORMING/VACCUM FORMING:
The shaping of heat softened thermoplastic sheet through heat and/ or vacuum.

POLYMERS.
v Polymers consist of large molecules that are made up of smaller repeating units, or
monomers.
v Polymers containing only one type of monomer are known as HOMOPOLYMERS,
v Polymers combining more than one type of monomer are known as COPOLYMERS.
v Two general methods exist for forming large molecules from small monomers: addition
polymerization and condensation polymerization.
v In the chemical process called addition polymerization, monomers join together without
the loss of atoms from the molecules.
v Some examples of addition polymers are polyethylene, polypropylene, polyphenylethene,
polyethenyl ethanoate, and polytetrafluoroethylene (Teflon).

v A new method of addition polymerization called group transfer polymerization was

announced.
v An activating group within the molecule initiating the process transfers to the end of the
growing polymer chain as individual monomers insert themselves in the group.
v The method has been used for acrylic plastics; it should prove applicable to other plastics
as well.

CONDENSATION POLYMERS:
THERMOSETTING PLASTICS

Ø Thermosetting plastics are plastics that cannot be remelted once they have hardened.
Ø Compression moulding forms thermosetting plastic objects in a steel mould.
Ø When heat and pressure are applied, the softened plastic squeezes into all parts of the
mould to form the desired shape.
Ø Laminating binds layers of materials together in a plastic matrix. The layers are fused
when heated plates melt the plastic and squeeze the material together
Ø This involves the elimination of water molecules during the linking up of the constituent,
this usually form thermosetting plastics in most cases organic acids are made to react
with alcohol to produce ester and water, the elimination of that water complete the
process this is usually cure by heating the resin or treating it with thermosetting agents.
Ø In condensation polymerization the repeat unit is related to the two substances forming
the polymer

R1 COOH + R2 OH – R1COOR2 + H2O

A-A-A-A
The repeat unit is the same through out the chain, the product is known as HOMO-Polymer,

3
When you have a particular group alternating or combining with the basic monomer e.g.
A - B - A - B -alternating copolymers forming alternating co-polymer, if the alternating is such
that the first define a next chain of the other is called Block Polymer e.g.
A - A - A + B - B - B

A chaining of A through out with B branching is term Graft – copolymer.

Ø Thermosetting plastics – phenol- formaldehyde first produced in 1856, this is form by
condensations phenol and formaldehyde and on curing could be suitable for water closet
(WC) seats, electrical fittings, and paints and vanishes, it is dark in colour.
Ø Urea formaldehyde – the second form of thermosetting which is white, creamy plastic
used for electrical fittings
Ø Melamine formaldehyde is almost similar to urea formaldehyde, its about the hardest
plastic around, it is used for the manufacture of plates and adhesives-araldite it can also
be impregnated with paper together with special effect in printed or colour pattern and
cure into a tough surface impervious to heat, this is called Formica.
Ø SILICONES – these are chains of alternating silicon and oxygen ion used for water-
proofing materials in the construction industry.

PROPERTIES OF POLYMERS.
1 Plastics have a specific gravity of 1 – 1.6.
2 They have low thermal conductivity
3 Are resistant to corrosion
4 They have high coefficient of expansion
5 They have high strength/weight ratio.

Polymers can be grouped on the basis of their constituent elements.

1) C, H polyolefin
2) C, H, O polyether, esters and alcohols, carbohydrates (e.g., cotton, Rayon)
3) C, H, Cl (F) PVC, chlorinated and fluorinated polyolefin
4) C, H, N polyimide
5) C, H, N, O polyamides and urethanes - synthetic
(e.g., Nylon, acryl amides); silk
6) C, H, N, O, S polyamides - natural (e.g., wool, hair)
7) C, H, N, O, S, Cl chlorinated polyamides (e.g., shrink proofed wool)

RUBBER
The raw material is a thermoplastic but when treated with sulphur (vulcanizing) it turns into a
thermosetting plastic and with addition of excess sulphur the elasticity would be lost and form a
rigid material called Ebonite which is used for decorating terrazzo floors, braking joints into
moulding.

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SYNTHETIC RUBBER
Ø Any artificially produced substance that resembles natural rubber in essential chemical
and physical properties can be called synthetic rubber.
Ø Substances are produced by chemical reactions, known as condensation or
polymerization, of certain unsaturated hydrocarbons.
Ø The basic units of synthetic rubber are monomers, which are compounds of relatively low
molecular weight that form the building units of huge molecules called polymers.
Ø The synthetic rubber is cured by vulcanization.

DEVELOPMENT OF SYNTHETIC RUBBER

Ø The origin of synthetic-rubber technology can be traced to 1860,
Ø The British chemist Charles Hanson Greville Williams determined that natural rubber
was a polymer of the monomer isoprene,
Ø It has the chemical formula CH2: C (CH 3) CH: CH2. Many efforts were made during
the next 70 years to synthesize rubber in the laboratory by using isoprene as the
monomer.
Ø Other monomers were also investigated, and during World War I German chemists
polymerized dimethylbutadiene (formula CH2: C (CH3) C (CH 3): CH2) producing a
synthetic rubber called methyl rubber, which was of limited usefulness.
Ø A breakthrough in synthetic-rubber research did not occur, however, until about 1930
Ø Synthetic-rubber research initiated in the United States during World War II led to the
synthesis of a polymer of isoprene identical in chemical composition with natural rubber.

TYPES OF SYNTHETIC RUBBER

NEOPRENE
One of the first successful synthetic rubbers resulting from Carothers's research was
neoprene, which is the polymer of the monomer chloroprene, chemical formula CH2: C
(Cl) CH: CH2.
The raw materials of chloroprene are ethyne and hydrochloric acid. Developed in 1931,
Neoprene has high resistance to heat and such chemicals as oils and petroleum.
Neoprene is used in hose for conveying petroleum and as an insulating material for cables
and in machinery.

BUNA RUBBERS
v In 1935 German chemists developed the first of a group of synthetic rubbers
called Buna, which is produced by copolymerization
v That is, the polymerization of two monomers, called co monomers
v The name Buna is derived from the initial letters of butadiene, used as one of the
comonomers, and natrium (sodium), which was used as a catalyst.
v One of these products, Buna-N, uses acrylonitrile (CH2: CH (CN)) as the other
comonomer.
v Acrylonitrile is produced from cyanide. Buna-N is valuable for uses requiring
resistance to the action of oils or abrasion.

5
BUTYL RUBBER
ü Butyl rubber, produced initially in 1940, is prepared by the
copolymerization of isobutylene with butadiene or isoprene.
ü It is plastic and can be compounded like natural rubber, but is difficult to
vulcanize. Although butyl rubber is not as resilient as natural rubber and
other synthetics,
ü It is extremely resistant to oxidation and the action of corrosive chemicals.
ü Because of its low permeability to gas, butyl rubber is used widely for
inner tubes in car tyres.

OTHER SPECIALITY RUBBERS

Ø Many other types of synthetic rubber have been developed for
purposes requiring specific properties.
Ø One such speciality rubber, called Koroseal, is a polymer of vinyl
chloride (CH2: CHCl). Vinyl chloride polymers are heat-,
electricity-, and corrosion-resistant and are unaffected by exposure
to light or by long storage.
Ø Koroseal cannot be vulcanized,
Ø Not subjected to high temperatures, it is more resistant to abrasion
than natural rubber or leather.

PET

MANUFACTURING METHOD OF CO POLYESTER FOR LOW

ACETALDEHYDE CONTENT OF PET BOTTLES,

Ø The present invention provides a manufacturing method of copolyester for low

acetaldehyde content of PET bottles.
Ø The polyethylene terephthalate (PET) polymer is added with an appropriate modifier in
order to decrease the production of acetaldehyde caused by pyrolysis side reaction during
the blow molding process of PET bottles.
Ø The modifier comprises stabilizer and primary antioxidant, wherein the stabilizer is an
inorganic phosphorous compound with an addition quantity of 0.003.about.0.5 weight %
based on the weight of the total co polyester copolymer and the primary antioxidant is a
hindered phenolic antioxidant containing Ca.sup.+2 with an addition quantity of
0.005.about.5.0 weight % based on the weight of the total co polyester copolymer.
Ø The present invention owns an improving effect of decreasing the production of side
product--acetaldehyde at least 30% than those without the addition of said modifier.
THE MANUFACTURING PROCESS OF THE PET BOTTLE CAN BE SEPARATED TO
THREE MAIN STEPS:

(1). Melted state polycondensation operation

(2). Solid state polycondensation operation

(3). Blow moulded manufacturing operation

6
The three main steps of the prior art are described respectively as follows:

(1) "Melted State Polycondensation Operation” can be Further Splitted to two Processes

(A). Continuous melted state polycondensation operation

In the continuous melted state polycondensation operation process, the terephthalic acid
(PTA) and the ethylene glycol (EG) are blended to form thick liquid;
Ø The isophthalic acid (IPA) 0.about.10 mol % is added thereafter and blended together and
then transmitted to esterification tank so as to perform direct esterification.
Ø The operation temperature of esterification is between 220.about.265.degree.C.
Ø The operation pressure of esterification is between normal pressure and 2.0 kg/cm.sup.2.
Ø The produced water and alcohols during said process should be distilled out.
Ø While the esterification has completed 95.about.98% of esterification conversion ratio,
the esterification has been stopped and the polycondensation is initiated.
Ø A catalyst should be added before polycondensation in order to expedite the rate of
polycondensation so as to shorten the polycondensation time.
Ø Antimony acetate or antimony trioxide or germanium dioxide or titanium, or their
mixture can normally be used as catalyst to expedite the completion of polycondensation.
Ø In addition, the stabilizer such as phosphoric acid, phosphorous acid, trimethyl
phosphate, triphenyl phosphate, triethyl phosphate is added.

The polycondensation of PET and its copolymer includes pre-polymerization and main-
polymerization.
Ø The operating temperature for pre-polymerization is between 70.about.280.degree.C, The
operating vacuum intensity for pre-polymerization between 250.about.15mmHg. The
operating temperature for main-polymerization is between 275.about.285.degree.C.,
Ø The operating pressure for main-polymerization is below 1 mmHg.
Ø The intrinsic viscosity of PET polymer is raised to 0.5.about.0.7 dl/g at the end of PET
melted state polycondensation.

(B). BATCH MELTED STATE POLYCONDENSATION OPERATION

Ø In the batch melted state polycondensation operation process, the dimethyl
terephthalate (DMT) and the ethylene glycol (EG) are blended;
Ø The transesterification catalyst such as manganese acetate, or zinc acetate, or titanium
is added so as to perform transesterification reaction.
Ø The operating temperature for transesterification reaction is between
140.about.260.degree.C.
Ø The methyl alcohol should be distilled out during the said process.
Ø While the transesterification reaction has completed 95.about.98% of esterification
conversion ratio, the isophthalic acid (IPA) 0.about.10 mol % is added thereafter and
blended together to form copolymer and so as to end the transesterification reaction.
A polycondensation type catalyst should be added before melted state

7
 polycondensation in order to expedite the rate of polycondensation so as to shorten
the polycondensation reaction time.
Ø Antimony acetate or antimony trioxide or germanium dioxide or titanium, or their
mixture can be used as catalyst to expedite the completion of polycondensation.
Ø In addition, the stabilizer such as phosphoric acid, phosphorous acid, trimethyl
phosphate, triphenyl phosphate, triethyl phosphate is added.

SOLID STATE POLYCONDENSATION OPERATION

The intrinsic viscosity of the PET chip made from Step Melted state
polycondensation operation" is somewhere between 0.5.about.0.7 dl/g;
Ø The molecular weight of the PET chip is too low for Blow moulded manufacturing
operation".
Ø Its strength is below enough. Moreover, the residual acetaldehyde in the PET chip is
too high to manufacture PET bottles.
Ø solid state polycondensation is a necessity to raise the intrinsic viscosity of PET chip
up to somewhere between 0.72.about.1.2 dl/g so as to obtain enough molecular
weight needed by the succeeding blow moulding process and to reduce the residual
acetaldehyde in PET chip to below 1 ppm.
Ø One of the solid state polycondensation process is the batch process, where the PET
chip is heated in a vacuum revolving tank.
Ø The other one is the continuous process, where the PET chip is treated by
crystallization and dryness, then an inert gas (such as nitrogen gas) is led into the
solid state polycondensation tank in order to raise the intrinsic viscosity and to reduce
the residual acetaldehyde in PET chip to below 1 ppm.

The solid state polycondensation is operated in an inert gas stream or vacuum

environment, the operating temperature of which is between 180.about.240.degree.C.;
Ø in general, the operating temperature is below the melting point of PET and its
copolymer to prevent stocking from taking place.
Ø In normal circumstance, the PET chip solid state polycondensation for continuous
process is operated at the exist of inert gas stream.
Ø The inert gas includes nitrogen, carbon dioxide, helium, argon, krypton, xenon gases
or their mixture.
Ø The helium gas is commonly used as inert gas.
Ø The continuous solid state polycondensation reactor includes fluidized bed and
moving bed. In most cases, a column shape polycondensation reactor is better to be
utilized, wherein the PET chip is transmitted through the reactor in a speed which fits
the needed reaction time.
Ø The column shape reactor should be high enough to allow the PET chip be
transmitted by gravity from the top to the bottom of the reactor in a speed that fits the
needed reaction retention time to obtain the required final intrinsic viscosity.

8
Ø BLOW MOULDER PROCESSES TO PRODUCE PET BOTTLES

The PET chip with high intrinsic viscosity, which has been processed by solid state
polycondensation, required by blow moulding is further processed by the ejector and
blow moulder to produce transparent PET bottles.
Ø The operating temperature of the ejector is somewhere between
260.about.285.degree.C.,
Ø The acetaldehyde content of PET chips is quickly increased by the function of this
high temperature and mechanical shear force.

CHEMICAL COMPOSITION OF PET RAW MATERIALS

(1) Dicarboxyl acid comprises Terephthalic acid (PTA), Isophthalic acid (IPA), Dimethyl
terephthalate (DMT), 2,6-naphthalenedicarboxylic acid (NDA), Dimethyl 2,6-
naphthalenedicarboxylate.

(2)Dihydric alcohol comprises Ethylene glycol, propylene glycol, 1,3-propylene glycol,

1,4-butanediol, 1,4-cyclohexanedimethanol (CHDM ).

(3)As said in (1) and (2), the mole ratio of dicarboxyl acid and dihydric alcohol is 1:1.
The other said dicarboxyl acid or dihydric alcohol also can be added in order to prepare
co polyester copolymer. At least 80 mole % of the component should be terephthalic acid
or 2,6-naphthalenedicarboxylic acid or dimethyl terephthalate or dimethyl 2,6-
naphthalenedicarboxylate.

(4) The catalyst comprises antimony acetate, antimony trioxide, germanium dioxide,
titanium, manganese acetate, zinc acetate. Based on the weight of co polyester, the
catalyst metal element manganese is between 0.about.300 ppm or titanium is between
0.about.80 ppm or titanium is between 0.about.300 ppm or germanium is between
0.about.200 ppm.

(5) The stabilizer comprises phosphoric acid, phosphorous acid, trimethyl phosphate,
triphenyl phosphate, triethyl phosphate. Based on the weight of copolyester, the
phosphorus element content is between 5.about.100 ppm, preferably 37.6 ppm.

(6) The hindered phenolic antioxidant is Irganox-1425 (Ciba merchandise name). Based
on the weight of copolyester, the calcium element is between 5.about.100 ppm,
preferably 17.3 ppm.

(7)The toner comprises tetrahydrated cobaltous acetate, cobaltous chloride, cobaltous

nitrate, salicyl cobaltous salicylate. Based on the weight of copolyester, the cobalt
element content is between 0.about.100 ppm.

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 PMMA
Ø PMMA positive resists based on special grades of POLYMETHYL METHACRYLATE
designed to provide high contrast, high resolution for e-beam, deep UV (220-250nm) and
X-ray lithographic processes.
Ø In addition, PMMA is often used as a protective layer in III-V device wafer thinning
applications.
Ø Standard products include 495,000 and 950,000 molecular weights (MW) in a wide range
of film thicknesses formulated in chlorobenzene, or the safer solvent anisole.
Ø In addition 50,000, 100,000, 200,000 and 2.2 million MW are available upon request.
Ø Copolymer resists are based on a mixture of PMMA and ~8.5% methacrylic acid.
Copolymer MMA (8.5) MAA is commonly used in combination with PMMA in bi-layer
lift-off resist processes where independent control of CD size and shape of each resist
layer is required.
Ø Standard copolymer resists are formulated in the safer solvent ethyl lactate and are
available in a wide range of film thicknesses.
Ø In addition, MMA (17.5) MAA copolymer resists are available upon request.

CERAMICS

CERAMICS

v Ceramics encompass such a vast array of materials that a concise definition is almost
impossible. One workable definition of ceramics is a refractory, inorganic, and
nonmetallic material.

Ceramics can be divided into two classes:

Traditional
Advanced

Ø Traditional ceramics include clay products, silicate glass and cement;

Ø Advanced ceramics consist of carbides (SiC), pure oxides (Al2O3),
nitrides (Si3N4), non-silicate glasses and many others.

10
Ceramics offer many advantages compared to other materials.

v They are harder and stiffer than steel;

v More heat and corrosion resistant than metals or polymers; less dense than most metals
and their alloys; and their raw materials are both plentiful and inexpensive.

Ceramic materials display a wide range of properties which facilitate their use in many different
product areas.

Product Area Product

Aerospace space shuttle tiles, thermal barriers, high
temperature glass windows, fuel cells

Consumer Uses glassware, windows, pottery, Corning®

ware, magnets, dinnerware, ceramic tiles,
lenses, home electronics, microwave
transducers
Automotive catalytic converters, ceramic filters, airbag
sensors, ceramic rotors, valves, spark
plugs, pressure sensors, thermostats,
vibration sensors, oxygen sensors, safety
glass windshields, piston rings
Medical (Bioceramics) orthopedic joint replacement, prosthesis,
dental restoration, bone implants

Military structural components for ground, air and

naval vehicles, missiles, sensors

Computers insulators, resistors, superconductors,

capacitors, ferroelectric components,
microelectronic packaging

Other Industries bricks, cement, membranes and filters, lab

equipment

Communications fiber optic/laser communications, TV and

radio components, microphones

11
 SCIENTIFIC PRINCIPLES

Ceramics have characteristics that enable them to be used in a wide variety of applications
including:

• High heat capacity and low heat conductance

• Corrosion resistance
• Electrically insulating, semi conducting, or superconducting
• Nonmagnetic and magnetic
• Hard and strong, but brittle

The diversity in their properties stems from their bonding and crystal structures.

Atomic Bonding:

o Two types of bonding mechanisms occur in ceramic materials, ionic and covalent.
o These mechanisms co-exist in the same ceramic material.
o Each type of bond leads to different characteristics.

ü Ionic bonds most often occur between metallic and non-metallic elements that
have large differences in their electro negativities.
ü Ionically-bonded structures tend to have rather high melting points, since the
bonds are strong and non-directional.
ü The other major bonding mechanism in ceramic structures is the covalent bond.
Unlike ionic bonds where electrons are transferred, atoms bonded covalently
share electrons.
ü the elements involved are non-metallic and have small electro negativity
differences.
ü Many ceramic materials contain both ionic and covalent bonding.
ü The overall properties of these materials depend on the dominant bonding
mechanism.
Comparison of % Covalent and Ionic character with several ceramic compounds’
melting points.

Ceramic Melting Point C % Covalent % Ionic character

Compound character
Magnesium Oxide 2798 27% 73%
Aluminum Oxide 2050 37% 63%
Silicon Dioxide 1715 49% 51%
Silicon Nitride 1900 70% 30%
Silicon Carbide 2500 89% 11%

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Classification:

Ceramic materials can be divided into two classes:

§ CRYSTALLINE
§ AMORPHOUS (NONCRYSTALLINE)

.
In crystalline materials, a lattice point is occupied either by atoms or ions
depending on the bonding mechanism.
These atoms (or ions) are arranged in a regularly repeating pattern in three
dimensions (i.e., they have long-range order).
In contrast, in amorphous materials, the atoms exhibit only short-range
order.
Some ceramic materials, like silicon dioxide (SiO2), can exist in either
form.
A crystalline form of SiO2 results when this material is slowly cooled
from a temperature (T>TMP @1723 C).
Rapid cooling favours noncrystalline formation since time is not allowed
for ordered arrangements to form.

Oxygen
Silicon

Crystalline Silicon dioxide Amorphous Silicon dioxide

(regular pattern) (random pattern)

Comparison in the physical structure of both crystalline and amorphous Silicon dioxide

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Thermal Properties:

The most important thermal properties of ceramic materials are heat capacity, thermal
expansion coefficient, and thermal conductivity. Many applications of ceramics, such
as their use as insulating materials, are related to these properties.

Thermal energy can be either stored or transmitted by a solid.

The ability of a material to absorb heat from its surrounding is its heat capacity.
In solid materials at T > 0 K, atoms are constantly vibrating.
The atomic vibrations are also affected by the vibrations of adjacent atoms
through bonding.
Vibrations can be transmitted across the solid.
The higher the temperature, the higher the frequency of vibration and the shorter
the wavelength of the associated elastic deformation.

The potential energy between two bonded atoms can be schematically represented by a
diagram:

Potential 2
Energy

-2

-4

0.5 1 1.5 2 2.5

Separation Distance (A) (Å)

Graph depicting the potential energy between two bonded atoms

• The distance at which there is minimum energy (potential well) represents what is
usually described as the bond length.
• A good analogy is a sphere attached to a spring, with the equilibrium position of
the spring corresponding to the atom at the bond length (potential well).
• When the spring is either compressed or stretched from its equilibrium position,
the force pulling it back to the equilibrium position is directly proportional to the
displacement (Hooke's law).

14
 • The frequency of oscillation is greatest when there is a large spring constant and
low mass ball.
• Ceramics generally have strong bonds and light atoms.
• They can have high frequency vibrations of the atoms with small disturbances in
the crystal lattice.
• The result is that they typically have both high heat capacities and high melting
temperatures.
• As temperature increases, the vibrational amplitude of the bonds increases.
• The asymmetry of the curve shows that the interatomic distance also increases
with temperature, and this is observed as thermal expansion.
• The conduction of heat through a solid involves the transfer of energy between
vibrating atoms.

Comparison of thermal properties of different ceramic materials.

Material Melting Heat Coefficient Thermal

Temp.(oC) Capacity of Linear Conductiv-
(J/kg.K) Expansion ity (W/m.K)
1/oCx10-6
Aluminum 660 900 23.6 247
metal

Copper 1063 386 16.5 398

metal

Alumina 2050 775 8.8 30.1

Fused silica 1650 740 0.5 2.0

Soda-lime 700 840 9.0 1.7

glass

Polyethylene 120 2100 60-220 0.38

Polystyrene 65-75 1360 50-85 0.13

Ø One of the most interesting high-temperature applications of ceramic materials is

their use on the space shuttle.
Ø Almost the entire exterior of the shuttle is covered with ceramic tiles made from
high purity amorphous silica fibers.
Ø Those exposed to the highest temperatures have an added layer of high-emittance
glass. These tiles can tolerate temperatures up to 1480 C for a limited amount of
time.

15
The high temperatures experienced by the shuttle during entry and ascent are shown in
Figure

955

315 Temperatures are in

650 Celsius degrees.
1465 Temps marked with
an * signify ascent
temperatures.

*1175
*425 980

*430 * 420
*405
Diagram of space shuttle's ascent and descent temperatures

v The melting point of aluminium is 660 C.

v The tiles keep the temperature of the aluminium shell of the shuttle at or below
175 C while the exterior temperatures can exceed 1400 C.
v The tiles cool off rapidly, so that after exposure to such high temperatures they
are cool enough to be held in the bare hand in about 10 seconds.
v The thickness of these ceramic tiles varies from only 0.5 inches to 3.5 inches.

maximum
1480 exposure
temperature

Temp
( C)

660
T (Aluminum)
mp
175
0.0 3.5
Tile Thickness (in)
Graph of inner temperature of tile versus tile thickness.

The shuttle also uses ceramic applications in fabrics for gap fillers and thermal barriers,
reinforced carbon-carbon composites for the nose cone and wing leading edges, and high
temperature glass windows.

16
 Tensile
Strength

Brittle fracture

Breaking
Elastic Strength

Strain Strain
(a) (b)

Tensile
Bending
Compressive

Electrical Properties:

• The electrical properties of ceramic materials vary greatly, with characteristic

measures spanning over many orders of magnitude.
• Ceramics are probably best known as electrical insulators.
• Ceramic insulators (such as BaTiO3) can be polarized and used as capacitors.
• Other ceramics conduct electrons when a threshold energy is reached, and are
thus called semiconductors.
• In 1986, a new class of ceramics was discovered, the high Tc superconductors.
• These materials conduct electricity with essentially zero resistance.
• ceramics known as piezoelectric can generate an electrical response to a
mechanical force or vice versa.

Electrical Resistivity of different materials.

Type Material Resistivity ( -cm)

Metallic conductors: Copper 1.7 x 10-6
CuO2 3 x 10-5
Semiconductors: SiC 10
Germanium 40
Insulators: Fire-clay brick 108
Si3N4 >1014
Polystyrene 1018
Superconductors: YBa2Cu3O7-x <10-22 (below Tc)

17
Anyone who has used a portable cassette player, personal computer, or other electronic
device is taking advantage of ceramic dielectric materials. . The structure of a capacitor
is shown in the diagram.

charge +q

+ + + + +
+ + + + + V
capacitor
plates - - - - - -
- - - - -
charge -q
external
battery

The charge of the capacitor is stored between its two plates. The amount of charge (q)
that it can hold depends on its voltage (V) and its capacitance (C).

q = CV

The dielectric is inserted between the plates of a capacitor, raising the capacitance of the
system by a factor equal to its dielectric constant, k.

q = (kC)V

o Using materials that have large dielectric constants allows large amounts of
charge to be stored on extremely small capacitors.
o This is a significant contribution to the continuing miniaturization of electronics
(e.g., lap top computers, portable CD players, cellular phones, even hearing
aids!).

ü The dielectric strength of a material is its ability to continuously hold

electrons at a high voltage.
ü When a capacitor is fully charged, there is virtually no current passing
through it.
ü The magnetic field strength necessary to produce breakdown of a
material is its dielectric strength.
ü Some ceramic materials have extremely high dielectric strengths.

Electrical property constants of different ceramic materials.

Material Dielectric constant Dielectric strength

at 1 MHz (kV/cm)
Air 1.00059 30
Polystyrene 2.54 - 2.56 240
Glass (Pyrex) 5.6 142

18
Alumina 4.5 - 8.4 16 - 63
Porcelain 6.0 - 8.0 16 - 157
Titanium dioxide 14 - 110 39 - 83

v Electrical current in solids is most often the result of the flow of electrons
(electronic conduction).
v In metals, mobile, conducting electrons are scattered by thermal vibrations
(phonons), and this scattering is observed as resistance.
v Thus, in metals, resistivity increases as temperature increases.
v In contrast, valence electrons in ceramic materials are usually not in the
conduction band, thus most ceramics are considered insulators.
v Conductivity can be increased by doping the material with impurities.
v Thermal energy will also promote electrons into the conduction band, so that in
ceramics, conductivity increases (and resistivity decreases) as temperature
increases.

v A superconductor can transmit electrical current with no resistance or power loss.

v For most materials, resistivity gradually decreases as temperature decreases.
Superconductors have a critical temperature, Tc, at which the resistivity drops
sharply to virtually zero.

nonsuperconductors
Electrical
Resistivity

superconductors

Tc
Temperature (K)

Ø Pure metals and metal alloys were the first known superconductors.
Ø All had critical temperatures at or below 30K and required cooling with liquid
helium. The new ceramic superconductors usually contain copper oxide planes
such as YBa2Cu3O7 discovered in 1987 with Tc = 93 K.

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 Ø They have critical temperatures above the boiling point of liquid nitrogen (77.4
K), which makes many potential applications of superconductors much more
practical.
Ø This is due to the lower cost of liquid nitrogen and the easier design of cryogenic
devices.

Copper
Oxygen

Barium

Yttrium

In addition to their critical temperature, two other parameters define the region where a
ceramic material is superconducting:
ü The critical current and
ü The critical magnetic field.

As long as the conditions are within the critical parameters of temperature,

current, and magnetic field, the material behaves as a superconductor.
Any of these values is exceeded, superconductivity is destroyed.
Applications of superconductors which rely on their current carrying
ability include electrical power generation, storage and distribution.
SQUIDS (Superconducting Quantum Interference Devices) are electronic
devices that use superconductors as sensitive detectors of electromagnetic
radiation.
Possible applications in the field of medicine include the development of
advanced MRI (Magnetic Resonance Imaging) units based on magnets
made of superconducting coils.
The magnetic applications of superconductors are also of major
importance. Superconductors are perfect diamagnets, meaning that they
will repel magnetic fields. This exclusion of an applied magnetic field is
called the Meissner effect and is the basis for the proposed use of
superconductors to magnetically levitate trains.

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Ceramic Processing:

Processing of ceramic materials describes the way in which ceramic objects (e.g., glass
windows, turbocharger rotor blades, optical fibres, and capacitors) are produced.
Processing begins with the raw materials needed to produce the finished components, and
includes many individual steps that differ significantly depending on the type of ceramic
material, crystalline versus glass.

Processing of Crystalline Ceramics Glass Processing

Raw Material Selection Raw Material Selection
Preparation Melting
Consolidation Pouring
Sintering Annealing

ü Raw material selection involves obtaining and preparing the right materials for
the final product.
ü Traditional ceramics use various forms of clay.
ü Glass makers start with primarily silica.
ü Advanced ceramics use several different raw materials depending on the
applications (i.e., properties needed).

Material
Al2O3 (aluminum oxide)
MgO (magnesium oxide)
SiO2 (Silicon dioxide)
ZrO2 (zirconium oxide)
SiC (silicon carbide)
Si3N4 (silicon nitride)
Uses
Spark-plug insulating bodies, substrates for
microelectronic packaging
electrical insulators, refractory brick
cookware, optical fibers
cubic zirconia, oxygen sensors
kiln parts, heating elements, abrasives
turbocharger rotors, piston valves

Ø For crystalline ceramics, the characteristics of the raw materials (powders) such as
their particle size and purity are very important as they affect the structure (e.g.,
grain size) and properties (e.g., strength) of the final component.
Ø Strength increases with decreasing grain size, most starting powders are milled (or
ground) to produce a fine powder (diameter < 1 µm).
Ø Dry powders are difficult to shape, processing additives like water; polymers, etc.
are added to improve their plasticity.
Ø Consolidation involves forming the ceramic mixture into the specified shape.

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There are many techniques available for this step:

P P
injection
liquid
P
powder powder powder

Rubber mold pestle Extrusion molding Injection molding

P

powder slurry
product
plaster
Slip casting
Die pressing

Ceramic processing aides.

Ø Sintering is the final step in the process.

Ø Sintering at high temperatures (800 to 1800 C) causes densification that gives
the ceramic product its strength and other properties.
Ø The individual ceramic particles coalesce to form a continuous solid network and
pores are eliminated.
Ø The microstructure of the sintered product contains dense grains, where an
individual grain is composed of many starting particles.

forming sintering

Raw powder Formed product Sintered product

Microstructure of raw, formed, and sintered ceramic products

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 GLASS PROCESSING
v Glass processing is different from crystalline processing.
v One of the considerations that must be examined is the solidifying behaviour of
glass. Glasses are most commonly made by rapidly quenching a melt.
v This means that the elements making up the glass material are unable to move
into positions that allow them to form the crystalline regularity.
v The result is that the glass structure is disordered or amorphous.
v One of the most notable characteristics of glasses is the way they change between
solid and liquid states.
v Crystals, which transform abruptly at a precise temperature (i.e., their melting
point) glasses, undergo a gradual transition.
v The melting temperature (Tm) of a substance and the so-called glass transition
temperature (Tg),
v The substance is considered a supercooled liquid.
v When glass is worked between Tg and Tm, one can achieve virtually any shape.
v The glass blowing technique is a fascinating demonstration of the incredible
ability to deform a glass.

Liquid In the area between Tg

Super- and Tm, the crystalline
Cooled material remains solid.
liquid The amorphous (glass)
specific Glass shrinkage material however,
volume due to passes through a phase
freezing known as a
super-cooled liquid.
This is when the glass
crystalline can be easily deformed
solid if the applied stresses
Tg Tm are sufficiently high.
temperature
Specific Volume vs. Temperature graph for a typical ceramic material

Ø Glass processing does not require an optimum size particle (although smaller
pieces melt faster).
Ø The selections of glass raw materials and chemical additives (which, for example,
can alter the color of the glass) are heated up (700 - 1600 C),
Ø Melted and finally poured onto or into a quick-cool form or plate.

There are four different forming techniques used to fabricate glass.

Technique Application
Pressing Table ware
Blowing Jars
Drawing Windows
Fiber forming Fiber optics

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 • During the glass formation, there may be stresses that have been introduced by
rapid cooling or special treatments that the glass needs (such as layering or
strengthening). Additional heat treatment is needed to “heal” the glass.
• Annealing, in which the glass is heated to the annealing point (a temperature just
below the softening point where the viscosity is approximately 108 Poise) and
then slowly cooled to room temperature, is one such process.

ALUMINA
GENERAL PROPERTIES
Specific Gravity: 3.90
Crystal Size: Range 2-50 Micron, Avg 15-30
Surface Finish, As Fired: 26
Surface Finish, Ground: 17
Water Absorption: None
Permeability: Gas Tight
Flexural Strength, Typical 25 oC: 331 MPa (48 kpsi)
Flexural Strength, Typical 1000 oC: 193 MPa (28 kpsi)
Compressive Strength: 2071 MPa (>300 kpsi)
Modulus of Elasticity Typical 25 oC: 345 GPa (50 x 106 psi)
Color: Ivory
Specific Heat @ 100 oC: 880 J/Kg-oK, 0.21 Cal/g/oC
Maximum Temperature
(for no load conditions): 1750 oC, 3180 oF
Thermal Conductivity, 25 oC: 29.4 W/mK
Thermal Conductivity, 100 oC: 23.0 W/mK

THERMAL COEFFICIENT OF EXPANSION:

25 - 200 oC: 6.7 x 10-6/oC
25 - 500 oC: 7.3 x 10-6/oC
25 - 800 oC: 7.8 x 10-6/oC
25 - 1000 oC: 8.0 x 10-6/oC

DIELECTRIC STRENGTH
6.35 mm: 8.7 kv/mm
3.18 mm: 11.6 kv/mm
Spec. 1.27 mm: 16.5 kv/mm

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BORON NITRIDE
GENERAL PROPERTIES
Compressive Strength 25 oC (ACMA-1) lg/in2: 15 x 10.3
Modulus of Elasticity 25 oC (sonic): 11.4 x 10.6
Modulus of Rupture lb/in2
@ 25 oC: 6350
@ 1000 oC: 6760
@ 1350 oC: 3495
Density (ASTM C20), g/cm2: 1.90
Hardness: 205
Water absorption, % weight gain: % weight gain in 168 hours
@ 25oC and 80%-100% relative humidity: 0.16

Thermal Expansion Degrees (C-1 x 10-6):

75oC - 5000C: 0.0
75oC - 1000oC: 0.0
75oC - 1500oC: 0.09
75oC - 2000oC: 1.30
Thermal Conductivity, (W/moC):
@ 100oC: 39.7
@ 350oC: 31.2
@ 700oC: 28.8
Maximum Use Temperature in
Inert or reducing atmosphere (oC): 2000
Oxidizing Atmosphere (oC): 1200

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