Ceramics

Ceramics
Ceramics
A wide-ranging group of materials whose
ingredients are clays, sand and feldspar.
Clays
Contain some of the following:
Silicon & Aluminium as silicates
Potassium compounds
Magnesium compounds
Calcium compounds
Sand contains Silica and Feldspar or Aluminium
Potassium Silicate.
Comparison metals vs ceramics
Bonded Clay Ceramics
Made from natural clays and mixtures
of clays and added crystalline ceramics.
These include:
Whitewares
Structural Clay Products
Refractory Ceramics
Whitewares
Crockery
Whiteware: Bathrooms
Whitewares
Floor and
wall tiles
Sanitary wares
Whitewares
Electrical
porcelain
Whitewares
Decorative ceramics
Slip Casting
Whitewares
Refractories
Firebricks for furnaces and ovens. Have
high Silicon or Aluminium oxide content.
Brick products are used in the
manufacturing plant for iron and steel, nonferrous metals, glass, cements, ceramics,
energy conversion, petroleum, and chemical
industries.
Refractories
Used to provide thermal protection of other
materials in very high temperature
applications, such as steel making
(Tm=1500C), metal foundry operations, etc.
They are usually composed of alumina
(Tm=2050C) and silica along with other
oxides: MgO (Tm=2850C), Fe2O3, TiO2, etc.,
and have intrinsic porosity typically greater
than 10% by volume.
Specialized refractories, (those already
mentioned) and BeO, ZrO2, mullite, SiC, and
graphite with low porosity are also used.
Refractory Brick
Amorphous Ceramics
(Glasses)
Main ingredient is Silica (SiO2)
If cooled very slowly will form crystalline
structure.
If cooled more quickly will form amorphous

structure consisting of disordered and linked
chains of Silicon and Oxygen atoms.
This accounts for its transparency as it is the
crystal boundaries that scatter the light,
causing reflection.
Glass can be tempered to increase its
toughness and resistance to cracking.
Glass Types
Three common types of glass:
Soda-lime glass - 95% of all glass, windows
containers etc.
Lead glass - contains lead oxide to improve
refractive index
Borosilicate - contains Boron oxide, known as
Pyrex.
Soda lime glass
Lead glass
Borosilicate Glass
Glasses
Flat glass (windows)
Container glass (bottles)
Pressed and blown glass (dinnerware)
Glass fibres (home insulation)
Advanced/specialty glass (optical fibres)
Glasses
Glasses
Glasses
Glass Containers
Assignment:
Discuss the process of making a glass.
Pressed Glass Processing
Blow Molding
Glass in Buildings
Plate Glass Drawing Processes
Tempered Glass
The strength of glass can be enhanced
by inducing compressive residual stresses at
the surface.
The surface stays in compression closing small scratches and cracks.
Hardening Processes
Tempering:
Glass heated above Tg but below the softening
point
Cooled to room temp in air or oil
Surface cools to below Tg before interior

when interior cools and contracts it draws the
exterior into compression.
Chemical Hardening:
Cations with large ionic radius are diffused into
the surface
This strains the lattice inducing compressive
strains and stresses.
Armoured Glass
Many have tried to gain access with golf clubs
and baseball bats but obviously the glass
remains intact ! From time to time a local TV
station intends to show videos of those trying
to get at the cash!!
Leaded Glass
Crystalline Ceramics
Good electrical insulators and refractories.
Magnesium Oxide is used as insulation material
in heating elements and cables.
Aluminium Oxide
Beryllium Oxides
Boron Carbide
Tungsten Carbide.
Used as abrasives and cutting tool tips.
Abrasives
Natural (garnet, diamond, etc.)
Synthetic abrasives (silicon carbide, diamond,
fused alumina, etc.) are used for grinding,
cutting, polishing, lapping, or pressure blasting
of materials
Glasses
Cements
Used to produce concrete roads, bridges,
buildings, dams.
Advanced Ceramics
Advanced ceramic materials have been
developed over the past half century
Applied as thermal barrier coatings to protect
metal structures, wearing surfaces, or as
integral components by themselves.
Engine applications are very common for this
class of material which includes silicon nitride
(Si3N4), silicon carbide (SiC), Zirconia (ZrO2)
and Alumina (Al2O3)
Heat resistance and other desirable properties
have lead to the development of methods to
toughen the material by reinforcement with
fibers and whiskers opening up more
applications for ceramics
Advanced Ceramics
Structural: Wear parts, bioceramics, cutting
tools, engine components, armour.
Electrical: Capacitors, insulators, integrated
circuit packages, piezoelectrics, magnets and
superconductors
Coatings: Engine components, cutting tools,

and industrial wear parts
Chemical and environmental: Filters,
membranes, catalysts, and catalyst supports
Engine Components
Turbocharger
Ceramic Brake Discs
McLaren Mercedes Benz
Silicon Carbide
Automotive Components in Silicon
Carbide
Chosen for its heat and wear resistance
Ceramic Armour
Ceramic armour systems are used to protect
military personnel and equipment.
Advantage: low density of the material can
lead to weight-efficient armour systems.
Typical ceramic materials used in armour
systems include alumina, boron carbide, silicon
carbide, and titanium diboride.
The ceramic material is discontinuous and is
sandwiched between a more ductile outer and
inner skin.
The outer skin must be hard enough to shatter
the projectile.
Most of the impact energy is absorbed by the
fracturing of the ceramic and any remaining
kinetic energy is absorbed by the inner skin,
that also serves to contain the fragments of the
ceramic and the projectile preventing severe
impact with the personnel/equipment being
protected.
Alumina ceramic/Kevlar composite system in
sheets about 20mm thick are used to protect
key areas of Hercules aircraft (cockpit
crew/instruments and loadmaster station).
This lightweight solution provided an efficient
and removable/replaceable armour system.
Similar systems used on Armoured Personnel
Carriers.
Ceramic - Composite Armor
Silicon Carbide
Body armour and other components
chosen for their ballistic properties.
2002 John Wiley & Sons, Inc. M. P. Groover,
Fundamentals of Modern Manufacturing 2/e
POLYMERS
Fundamentals of Polymer Technology
Thermoplastic Polymers
Thermosetting Polymers
Elastomers
Guide to the Processing of Polymers
Polymer
A compound consisting of long-chain
molecules, each
molecule made up of repeating units
connected
together
There may be thousands, even millions of
units in a
single polymer molecule
The word polymer is derived from the Greek
words
poly, meaning many, and meros (reduced to
mer),
meaning part
Most polymers are based on carbon and are
therefore considered organic chemicals
Types of Polymers
Polymers can be separated into plastics and
rubbers
As engineering materials, it is appropriate to
divide
them into the following three categories:
1. Thermoplastic polymers
2. Thermosetting polymers
3. Elastomers
where (1) and (2) are plastics and (3) are
rubbers
Thermoplastic Polymers - Thermoplastics
(TP)
Solid materials at room temperature but
viscous
liquids when heated to temperatures of only a
few
hundred degrees
This characteristic allows them to be easily
and
economically shaped into products
They can be subjected to heating and cooling
cycles
repeatedly without significant degradation
Thermosetting Polymers - Thermosets
(TS)
Cannot tolerate repeated heating cycles as
thermoplastics can
When initially heated, they soften and flow for
molding
But elevated temperatures also produce a
chemical reaction that hardens the material
into an
infusible solid
If reheated, thermosets degrade and char
rather
than soften
Elastomers
Polymers that exhibit extreme elastic
extensibility when
subjected to relatively low mechanical stress
Also known as rubber
Some elastomers can be stretched by a

factor of 10
and yet completely recover to their original
shape
Although their properties are quite different
from
thermosets, they share a similar molecular
structure
that is different from the thermoplastics
Market Shares
Thermoplastics are commercially the most
important
of the three types, constituting around 70% of
the
tonnage of all synthetic polymers produced
Thermosets and elastomers share the
remaining
30% about evenly, with a slight edge for the
former
On a volumetric basis, current annual usage
of
polymers exceeds that of metals
Examples of Polymers
Thermoplastics:
Polyethylene, polyvinylchloride, polypropylene,
polystyrene, and nylon
Thermosets:
Phenolics, epoxies, and certain polyesters
Elastomers:
Natural rubber (vulcanized)
Synthetic rubbers, which exceed the tonnage
of
natural rubber
Reasons Why Polymers are Important:
Plastics can be formed by molding into
intricate part
shapes, usually with no further processing
required
Very compatible with net shape processing
On a volumetric basis, polymers:
Cost competitive with metals
Generally require less energy to produce than
metals
Certain plastics are translucent and/or
transparent,
which makes them competitive with glass in
some
applications
General Properties of Polymers
Low density relative to metals and ceramics
Good strength-to-weight ratios for certain
(but not all)
polymers
High corrosion resistance

Low electrical and thermal conductivity
Limitations of Polymers as Engineering
Materials
Low strength relative to metals and ceramics
Low modulus of elasticity (stiffness)
Service temperatures are limited to only a
few
hundred degrees
Viscoelastic properties, which can be a
distinct
limitation in load bearing applications
Some polymers degrade when subjected to
sunlight
and other forms of radiation
Synthesis of Polymers
Nearly all polymers used in engineering are
synthetic
They are made by chemical processing
Polymers are synthesized by joining many
small
molecules together into very large molecules,
called
macromolecules, that possess a chain-like
structure
The small units, called monomers, are
generally
simple unsaturated organic molecules such as
ethylene C
2
H
4
Figure 8.1 - Synthesis of polyethylene from
ethylene monomers:
(1) n ethylene monomers yields (2a)
polyethylene of chain
length n; (2b) concise notation for depicting
the polymer
structure of chain length n
Polymerization
As a chemical process, the synthesis of
polymers
can occur by either of two methods:
1. Addition polymerization
2. Step polymerization
Production of a given polymer is generally
associated with one method or the other
Addition Polymerization
In this process, exemplified by polyethylene,
the
double bonds between carbon atoms in the

ethylene
monomers are induced to open up so that they
join
with other monomer molecules
The connections occur on both ends of the
expanding macromolecule, developing long
chains of
repeating mers
It is initiated using a chemical catalyst (called
an
initiator) to open the carbon double bond in
some of
the monomers
Figure 8.2 - Model of addition (chain)
polymerization: (1) initiation,
(2) rapid addition of monomers, and (3)
resulting long chain
polymer molecule with n mers at termination of
reaction
Step Polymerization
In this form of polymerization, two reacting
monomers
are brought together to form a new molecule of
the
desired compound
As reaction continues, more reactant
molecules
combine with the molecules first synthesized to
form
polymers of length n = 2, then polymers of
length n =
3, and so on
In addition, polymers of length n
1
and n
2
also
combine to form molecules of length n = n
1
+n
2
, so
that two types of reactions are proceeding
simultaneously
Figure 8.4 - Model of step polymerization
showing the two types of
reactions occurring: (a) n-mer attaching a
single monomer to
form a (n+1)-mer; and (b) n
1
-mer combining with n
2
-mer to form
a (n
1
+n
2
)-mer
Sequence is shown by (1) and (2)
Some Examples
Polymers produced by addition
polymerization:
Polyethylene, polypropylene, polyvinylchloride,
polyisoprene
Polymers produced by step polymerization:
Nylon, polycarbonate, phenol formaldehyde
Degree of Polymerization
Since molecules in a given batch of
polymerized
material vary in length, n for the batch is an
average;
its statistical distribution is normal
The mean value of n is called the degree of
polymerization (DP) for the batch
DP affects properties of the polymer: higher
DP
increases mechanical strength but also
increases
viscosity in the fluid state, which makes
processing
more difficult
Molecular Weight
The molecular weight (MW) of a polymer is
the sum
of the molecular weights of the mers in the
molecule;
MW = n times the molecular weight of each
repeating unit
Since n varies for different molecules in a
batch,
the molecule weight must be interpreted as an
average
Typical Values of DP and MW for
Selected Polymers
MW
300,000
100,000
15,000
40,000
DP(n)
10,000
1,500
120
200
Polymer
Polyethylene
Polyvinylchloride
Nylon
Polycarbonate
Linear, Branched, and Cross-linked
Polymers
Linear structure chain-like structure
Characteristic of thermoplastic polymers
Branched structure chain-like but with side
branches
Also found in thermoplastic polymers
Cross-linked structure
Loosely cross-linked, as in an elastomer
Tightly cross-linked, as in a thermoset
Linear structure of a thermoplastic polymer
Figure 8.7 - Various structures of polymer
molecules:
(a) linear, characteristic of thermoplastics
Branched structure that includes side branches
along
the chain
molecules: (b) branched
Loosely cross-linked, in which primary bonding
occurs
between branches and other molecules at
certain
connection points
molecules:
(c) loosely cross-linked as in an elastomer
Tightly cross-linked or network structure - in
effect, the
entire mass is one gigantic macromolecule
molecules:
(d) tightly cross- linked or networked structure
as in a thermoset
Effect of Branching on Properties
Thermoplastic polymers always possess
linear or
branched structures, or a mixture of the two
Branches increase entanglement among the
molecules, which makes the polymer:
Stronger in the solid state
More viscous at a given temperature in the
plastic
or liquid state
Effect of Cross-Linking on Properties
Thermosets possess a high degree of crosslinking,

while elastomers possess a low degree of
cross-linking
Thermosets are hard and brittle, while
elastomers are
elastic and resilient
Cross-linking causes the polymer to become
chemically set
The reaction cannot be reversed
The polymer structure is permanently changed;
if
heated, it degrades or burns rather than melt
Crystallinity in Polymers
Both amorphous and crystalline structures
are
possible, although the tendency to crystallize is
much
less than for metals or non-glass ceramics
Not all polymers can form crystals
For those that can, the degree of crystallinity
(the
proportion of crystallized material in the mass)
is
always less than 100%
Figure 8.9 - Crystallized regions in a polymer:
(a) long molecules
forming crystals randomly mixed in with the
amorphous material;
and (b) folded chain lamella, the typical form of
a crystallized
region
Crystallinity and Properties
As crystallinity is increased in a polymer:
Density increases
Stiffness, strength, and toughness increases
Heat resistance increases
If the polymer is transparent in the amorphous
state, it becomes opaque when partially
crystallized
Low Density vs. High Density
Polyethylene
135 C
(275 F)
115 C
(239 F)
Melting temperature
700 MPa
(100,000 lb/in
2
)
140 MPa
(20,000 lb/in
2
)
Modulus of elasticity
0.96 0.92 Specific gravity
92% 55% Degree of crystallinity
High density Low density Polyethylene type
Some Observations About Crystallization
Linear polymers consist of long molecules
with
thousands of repeated mers
Crystallization involves folding back and forth
of
the long chains upon themselves to achieve a
very
regular arrangement
The crystallized regions are called crystallites
Crystallites take the form of lamellae
randomly mixed
in with amorphous material
A polymer that crystallizes is a two-phase
system - crystallites interspersed throughout
an
amorphous matrix
Factors for Crystallization
Slower cooling promotes crystal formation
and
growth
Mechanical deformation, as in the stretching
of a
heated thermoplastic, tends to align the
structure and
increase crystallization
Plasticizers (chemicals added to a polymer to
soften
it) reduce the degree of crystallinity
Additives
Properties of a polymer can often be
beneficially
changed by combining it with additives
Additives either alter the molecular structure
or
Add a second phase, in effect transforming
the
polymer into a composite material
Types of Additives by Function
Fillers to strengthen polymer or reduce cost
Plasticizers to soften polymer and improve
flow
Colorants pigments or dyes
Lubricants to reduce friction and improve
flow
Flame retardents to reduce flammability of
polymer
Cross-linking agents for thermosets and

elastomers
Ultraviolet light absorbers to reduce
degradation
from sunlight
Antioxidants to reduce oxidation damage
Thermoplastic Polymers (TP)
A thermoplastic polymer can be heated from
a solid
state to a viscous liquid state and then cooled
back
down to solid
This heating and cooling cycle can be repeated
multiple times without degrading the polymer
The reason is that TP polymers consist of
linear
(and/or branched) macromolecules that do not
cross-link upon heating
By contrast, thermosets and elastomers
change
chemically when heated, which cross-links their
molecules and permanently sets these
polymers
Mechanical Properties of Thermoplastics
Low modulus of elasticity (stiffness)
E is two or three orders of magnitude lower
than
metals and ceramics
Low tensile strength
TS is about 10% of the metal
Much lower hardness than metals or ceramics
Greater ductility on average
Tremendous range of values, from 1%
elongation
for polystyrene to 500% or more for
polypropylene
Figure 8.11 - Relationship of mechanical
properties, portrayed as
deformation resistance, as a function of
temperature for an
amorphous thermoplastic, a 100% crystalline
(theoretical)
thermoplastic, and a partially crystallized
thermoplastic
Physical Properties of Thermoplastics
Lower densities than metals or ceramics
Typical specific gravity for polymers are 1.2
Ceramics specific gravity = 2.5
Metals specific gravity = 7.0
Much higher coefficient of thermal expansion
Roughly five times the value for metals and 10
times the value for ceramics
Much lower melting temperatures

More Physical Properties of
Thermoplastics
Specific heats two to four times those of
metals and
ceramics
Thermal conductivities about three orders of
magnitude lower than those of metals
Insulating electrical properties
Commercial Thermoplastic
Products and Raw Materials
Thermoplastic products include molded and
extruded
items, fibers, films and sheets, packaging
materials,
and paints and varnishes
The starting plastic materials are normally
supplied to
the fabricator in the form of powders or pellets
in
bags, drums, or larger loads by truck or rail car
Thermosetting Polymers (TS)
TS polymers are distinguished by their highly
cross-linked three-dimensional, covalentlybonded
structure within the molecule
Chemical reactions associated with crosslinking are
called curing or setting
In effect, the formed part (e.g., pot handle,
electrical
switch cover, etc.) becomes one large
macromolecule
Always amorphous and exhibits no glass
transition
temperature
General Properties and Characteristics
of Thermosets
Rigid - modulus of elasticity is two to three
times
greater than TP
Brittle, virtually no ductility
Less soluble than TP in common solvents
Capable of higher service temperatures than
TP
Cannot be remelted - instead they degrade or
burn
How Cross-Linking is Done in TS Polymers
Three categories:
1. Temperature-activated systems
2. Catalyst-activated systems
3. Mixing-activated systems
Curing is accomplished at the fabrication

plants that
make the parts rather than the chemical plants
that
supply the starting materials to the fabricator
Temperature-Activated Systems
Curing is caused by heat supplied during part
shaping
operation (e.g., molding)
Starting material is a linear polymer in
granular form
supplied by the chemical plant
As heat is added, the material softens for
molding,
but continued heating results in cross-linking
Most common TS systems
The term thermoset" applies best to these
polymers
Catalyst-Activated Systems
Cross-linking in these systems occurs when
small
amounts of a catalyst are added to the polymer
which
is in liquid form
Without the catalyst, the polymer remains
stable
Once combined with the catalyst it changes
into solid
form
Mixing-Activated Systems
The mixing of two chemicals results in a
reaction that
forms a cross-linked solid polymer
Elevated temperatures are sometimes used
to
accelerate the reactions
Most epoxies are examples of these systems
Thermosetting vs. Thermoplastic
Polymers
TS plastics are not as widely used as the TP
One reason is the added processing costs and
complications involved in curing
Largest market share TS = phenolic resins
with 6%
of the total plastics market
Compare polyethylene with 35% market
share
TS Products: countertops, plywood adhesives,
paints,
molded parts, printed circuit boards and other
fiber
reinforced plastics

Elastomers
Polymers capable of large elastic deformation
when
subjected to relatively low stresses
Some can be extended 500% or more and
still
return to their original shape
Two categories:
1. Natural rubber - derived from biological
plants
2. Synthetic polymers - produced by
polymerization
processes similar to those used for
thermoplastic
and thermosetting polymers
Characteristics of Elastomers
Elastomers consist of long-chain molecules
that are
cross-linked (like thermosetting polymers)
They owe their impressive elastic properties
to two
features:
1. Molecules are tightly kinked when
unstretched
2. Degree of cross-linking is substantially less
than
thermosets
Figure 8.12 - Model of long elastomer
molecules, with low degree
of cross-linking: (a) unstretched, and (b) under
tensile stress
Elastic Behavior of Elastomer Molecule
When stretched, the molecules are forced to
uncoil
and straighten
Natural resistance to uncoiling provides the
initial
elastic modulus of the aggregate material
Under further strain, the covalent bonds of
the
cross-linked molecules begin to play an
increasing
role in the modulus, and stiffness increases
With greater cross-linking, the elastomer
becomes
stiffer and its modulus of elasticity is more
linear
Figure 8.13 - Increase in stiffness as a function
of strain for three grades
of rubber: natural rubber, vulcanized rubber,
and hard rubber

Vulcanization
Curing to cross-link most elastomers
Vulcanization = the term for curing in the
context of
natural rubber (and certain synthetic rubbers)
Typical cross-linking in rubber is one to ten
links per
hundred carbon atoms in the linear polymer
chain,
depending on degree of stiffness desired
Considerable less than cross-linking in
thermosets
Natural Rubber (NR)
NR consists primarily of polyisoprene, a high
molecular-weight polymer of isoprene (C
5
H
8
)
It is derived from latex, a milky substance
produced
by various plants, most important of which is
the
rubber tree that grows in tropical climates
Latex is a water emulsion of polyisoprene
(about 1/3
by weight), plus various other ingredients
Rubber is extracted from latex by various
methods
that remove the water
Vulcanized Natural Rubber
Properties: noted among elastomers for high
tensile
strength, tear strength, resilience (capacity to
recover
shape), and resistance to wear and fatigue
Weaknesses: degrades when subjected to
heat,
sunlight, oxygen, ozone, and oil
Some of these limitations can be reduced
through
the use of additives
Market share of NR 22% of total annual
rubber
volume (natural plus synthetic)
Rubber volume 15% of total polymer market
Natural Rubber Products
Largest single market for NR is automotive
tires
Other products: shoe soles, bushings, seals,
and
shock absorbing components
In tires, carbon black is an important

additive; it
reinforces the rubber, serving to increase
tensile
strength and resistance to tear and abrasion
Other additives: clay, kaolin, silica, talc, and
calcium
carbonate, as well as chemicals that accelerate
and
promote vulcanization
Synthetic Rubbers
Today, the tonnage of synthetic rubbers is
more than
three times that of NR
Development of synthetic rubbers was
motivated
largely by world wars when NR was difficult to
obtain
The most important synthetic is styrenebutadiene
rubber (SBR), a copolymer of butadiene (C
4
H
6
) and
styrene (C
8
H
8
)
As with most other polymers, the main raw
material
for synthetic rubbers is petroleum
Thermoplastic Elastomers (TPE)
A thermoplastic that behaves like an elastomer
Elastomeric properties not from chemical
cross-links,
but from physical connections between soft
and hard
phases in material
Cannot match conventional elastomers in
elevated
temperature strength and creep resistance
Products: footwear; rubber bands; extruded
tubing,
wire coating; molded automotive parts, but no
tires
Guide to the Processing of Polymers
Polymers are nearly always shaped in a
heated,
highly plastic state
Common operations are extrusion and
molding
Molding of thermosets is more complicated
because
of cross-linking
Thermoplastics are easier to mold and a
greater
variety of molding operations are available
Rubber processing has a longer history than
plastics,
and rubber industries are traditionally

separated from
plastics industry, even though processing is
similar

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Ceramics

If cooled more quickly will form amorphous

Surface cools to below Tg before interior

Coatings: Engine components, cutting tools,

Some elastomers can be stretched by a

High corrosion resistance

double bonds between carbon atoms in the

Thermosets possess a high degree of crosslinking,

Cross-linking agents for thermosets and

2002 John Wiley & Sons, Inc. M. P. Groover,

Curing is accomplished at the fabrication

2002 John Wiley & Sons, Inc. M. P. Groover,

2002 John Wiley & Sons, Inc. M. P. Groover,

In tires, carbon black is an important

and rubber industries are traditionally

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