POLYMERS:

An introduction
• Fundamentals of Polymer Technology
• Thermoplastic Polymers
• Thermosetting Polymers
• Elastomers (Rubbers)

Department of Metallurgy & Materials Engineering

University of Indonesia

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What is polymer?

The word polymer is derived from the Greek words poly,

poly, meaning many,
and meros (reduced to mer),
mer), meaning part.

Polymer is a compound consisting of long-
long-chain molecules, each
molecule made up of repeating units connected together.

There may be thousands, even millions of units in a single polymer
polymer
molecule. Most polymers are based on carbon and are therefore
considered organic chemicals.

Heat
Catalyst

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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.

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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,
transparent,
which makes them competitive with glass in some
applications (e.g
(e.g.. polymethyl methacrylate PMMA).

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Limitations of Polymers

• Low strength relative to metals and ceramics

• Low modulus of elasticity (stiffness)
• Low service temperatures, 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

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Types of Polymers

 In general, polymers can be separated into

plastics and rubbers
 As engineering materials, it is appropriate to
divide them into the following three
categories:
• Thermoplastic polymers
• Thermosetting polymers
• Elastomers
where (1) and (2) are plastics and (3) are
rubbers

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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.

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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.
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Elastomers (Rubbers)

• 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.
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Market Shares

• Thermoplastics are commercially the most

important of the three types,
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.

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Examples of Polymers:

• Thermoplastics:
• Polyethylene, polyvinylchloride,
polypropylene, polystyrene, and nylon
• Thermosets:
• Phenolics,
Phenolics, epoxies, and certain
polyesters
• Elastomers:
• Natural rubber (vulcanized)
• Synthetic rubbers, which exceed the
tonnage of natural rubber

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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-
chain-like structure.
• The small units, called monomers, are
generally simple unsaturated organic
molecules such as ethylene C2H4 .

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 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
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Linear, Branched, and Cross-linked

Polymers

• Linear structure – chain-

chain-like structure
• Characteristic of thermoplastic polymers

• Branched structure – chain-

chain-like but with side
branches
• Also found in thermoplastic polymers

• Cross-
Cross-linked structure
• Loosely cross-
cross-linked, as in an elastomer
• Tightly cross-
cross-linked, as in a thermoset
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 Linear structure of a thermoplastic polymer
characteristic of thermoplastics

Branched structure that includes side branches

along the chain, also a characteristic of thermoplastics

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• Loosely cross-
cross-
linked,
linked, in which primary
bonding occurs
between branches and
other molecules at
certain connection
points, as in
elastomers.
elastomers.

• Tightly cross-
cross-linked
or network structure –
resulting in the entire
mass as one gigantic
macromolecule, as in
thermosets.
thermosets.

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Effect of Branching on Properties

• Thermoplastic polymers always possess linear or

branched structures,
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

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Effect of Cross-Linking on
Properties

 Thermosets possess a high degree of cross-linking,

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.

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Polymer architecture

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Degree of Polymerization

• The mean value of n is called the degree of

polymerization (DP).
• The molecular weight (MW) of a polymer is the sum of
the molecular weights of the mers in the molecule.

- MW = n x the molecular weight of each

repeating unit.
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Molecular Weight of Polymers

DP affects properties of the polymer:

polymer:
higher DP  longer chain  heavier weight of polymer 
increases mechanical strength and viscosity in the fluid state,
which makes processing more difficult.

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 However, polymers (as a

bulk material) are
comprised of many
macromolecules each with
different length (molecular
weight) as a consequence
of different molecules in a
batch).
 Therefore, the molecular
weight of polymer must be
interpreted as an average.
average.

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Determining the molecular weight distribution:

Mn , the number average molecular weight, is

calculated from the mole fraction distribution of
different sized molecules in a sample:

Mw, the weight average molecular weight, is calculated from

the weight fraction distribution of different sized molecules.

Note:

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Simple analogous of molecular weight

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Simple analogous of molecular weight

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Simple analogous of molecular weight

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Typical Values of DP and MW for
Selected Polymers

Polymer DP(n) MW
Polyethylene 10,000 300,000
Polyvinylchloride 1,500 100,000
Nylon 120 15,000
Polycarbonate 200 40,000

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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 %.

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 Crystallized regions in a polymer:
(a) long molecules forming crystals randomly mixed in with the
amorphous material;
(b) folded chain lamella, the typical form of a crystallized region.

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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

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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.

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Low Density vs High Density Polyethylene

Polyethylene type Low density High density

Degree of crystallinity 55% 92%

Specific gravity 0.92 0.96

Modulus of elasticity 140 MPa 700 MPa

Melting temperature 115°

115°C 135°
135°C

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 Factors affecting Crystallization

Slower cooling promotes crystal formation and

growth.

Mechanical deformation,
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.

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Thermal behaviors of polymer

• Glass transition temperature (Tg)

• Melting temperature (Tm)

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Glass transition temperature (Tg) phenomenon

Introduction

There is a certain temperature (different for each polymer) called the

glass transition temperature, or Tg for short. When the polymer is
cooled below this temperature, it becomes hard and brittle, like glass.

Some polymers are used above their glass transition temperatures,

and some are used below. Hard plastics like polystyrene and
poly(methyl methacrylate), are used below their Tg’s; that is in their
glassy state. Their Tg's are well above room temperature, both at
around 100 oC. Rubber elastomers like polyisoprene and
polyisobutylene, are used above their Tg's, that is, in the rubbery state,
where they are soft and flexible.

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Amorphous and Crystalline Polymers

• Important note: the glass transition is not the same thing as melting.
• Melting is a transition which occurs in crystalline polymers. Melting
happens when the polymer chains fall out of their crystal structures, and
become a disordered liquid.
• The glass transition is a transition which happens to amorphous
polymers; i.e., polymers whose chains are not arranged in ordered
crystals, but are just strewn around in any old fashion, even though they
are in the solid state.
• But even crystalline polymers will have a some amorphous portion. This
portion usually makes up 40-70% of the polymer sample. This is why the
same sample of a polymer can have both a glass transition temperature
and a melting temperature. However, the amorphous portion undergoes
the glass transition only, and the crystalline portion undergoes melting
only.

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Simple analogous:: think of a polymer in the amorphous state as a big room full of slithering
snakes.

• Each snake represents a polymer chain.

• As cold blooded animals, so all their body heat
has to come from their surroundings. When it is
warm, the snakes are capable of slithering and
sliding with no trouble at all. They will move all
about randomly, over and around each other.
• But when the surrounding gets cold, snakes do
not move too much. They slow down without any
heat, and tend to just sit still. Now they are still all
wrapped around, over, and under each other.

• Now imagine a bulldozer is trying to move through this room full of snakes. If the
temperature is warm, and the snakes are moving, they can quickly slither out,
and the bulldozer moves through the room easily, causing a minimal amount of
snake damage. But if it is cold, one of two things will happen to the motionless
snakes, either: (a) the snakes will be stronger than the bulldozer, and the
bulldozer will not get through, and the snakes will stay put; or (B) the bulldozer
will be stronger than the snakes, and they will get squashed, still not moving
anywhere.
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Glass transition in polymers

The amorphous polymers behave in the same way…..

When the temperature is warm, the polymer chains can move around
easily. So, when the polymer is bent above its Tg, the molecules, since
they are being in motion already, have no trouble moving into new
positions to relieve the applied stress.

But if polymer sample is bent below its Tg, the polymer chains will not be
able to move into new positions to relieve the stress applied to them. Just
like in the example of a room full of cold snakes, one of two things will
happen, either:

(a) the chains are strong enough to resist the applied force, and the
sample will not bend; or

(b) the applied force will be too much for the motionless polymer chains
to resist, and being unable to move around to relieve the stress, the
polymer sample will break or shatter.
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Glass transition in amorphous polymers

The science behind the Tg phenomenon…

The change in mobility with temperature happens because the heat is a

form of kinetic energy; i.e., the energy of objects in motion. The heat
significantly affects the random motion of molecules, including polymer
chains.

So, it can be said:

a. Things are "hot" when the polymer molecules/chains have lots of
kinetic energy and move around very fast.
b. Things are "cold" when the polymer molecules/chains lack kinetic
energy and move around slowly, or not at all.

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The difference between glass transition and

melting process

Heating a crystalline polymer at a constant rate: the temperature increases following the
heat capacity; reaching the melting point (Tm), then the temperature rising stops
although the heat is still supplied  latent (hidden) heat to result in all part of the
polymer completely melted.

Once the polymer has melted (above

its Tm), the temperature begins to
rise again, but with a slower rate.
Why ? Increase in heat capacity ?.

Melting:
(i) absorption of a certain amount of
heat, the latent heat of melting;
(ii) a change in heat capacity.

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Heating an amorphous polymer at a constant rate: the temperature goes up at a rate determined by
the heat capacity; reaching the glass transition temperature (Tg), however the temperature doesn’t
stop rising  no latent (hidden) heat .
The temperature keeps going up, with an increase in heat capacity.

The glass transition temperature is between 0.5-0.8 of the melting

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Factors Affecting Tg

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Effect of free volume

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Effect
• of intermolecular forces

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 •
Effect of chain mobility

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Effect of chain length

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Factors affecting melting temperature, Tm
The melting temperature increases with the rate of heating, thickness of
the lamellae, and depends on the history of material, especially
crystallization temperature.

Melting involves breaking of the inter-chain bonds, therefore the glass and
melting temperatures depend on:

Chain stiffness (e.g., single vs. double bonds) – rigid chains have higher
melting temperatures
Size/weight of molecules - increasing molecular weight increases Tm
(range of M produces range of Tm)
Size, shape of side groups, side branches, crosslinking, defects, etc.
Ex: Tm PP = 175oC; PVC = 212oC.
Tm HDPE = 137 C; LDPE = 115oC
o

Essentially the same molecular characteristics rise and lower both melting
and glass transition temperatures.
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Typical examples

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 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-
cross-link upon heating
 By contrast, thermosets and elastomers change
chemically when heated, which cross-
cross-links their
molecules and permanently sets these polymers

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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
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 Relationship of mechanical properties,
properties, portrayed as
deformation resistance, as a function of temperature
for an amorphous thermoplastic, a 100% crystalline
(theoretical) thermoplastic, and a partially crystallized
thermoplastic
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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

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Physical Properties of Thermoplastics -2

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

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Commercial Thermoplastic
Products and Raw Materials

Thermoplastic products include molded and

extruded items, fibers, films and sheets,
packaging materials, 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

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 Thermosetting Polymers (TS)

TS polymers are distinguished by their highly

cross-
cross-linked three-
three-dimensional, covalently-
covalently-bonded
structure within the molecule

Chemical reactions associated with cross-
cross-linking
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

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General Properties and Characteristics

of Thermosets

Rigid - modulus of elasticity is two to three times

greater than TP

Brittle,
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

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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

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Elastomers
A type of 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
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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 un-
stretched
2. Degree of cross-linking is substantially less
than thermosets

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Model of long elastomer molecules, with low degree

of cross-linking:
(a) un-stretched,
(b) under tensile stress

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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-
cross-linked molecules begin to play an increasing
role in the modulus, and stiffness increases

With greater cross-
cross-linking, the elastomer becomes
stiffer and its modulus of elasticity is more linear

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Increase in stiffness as a function of strain for three

grades of rubber: natural rubber, vulcanized rubber,
and hard rubber
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Vulcanization

 Curing to cross-
cross-link most elastomers
 Vulcanization = the term for curing in the context of
natural rubber (and certain synthetic rubbers)
 Typical cross-
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-
cross-linking in
thermosets

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Natural Rubber (NR)

NR consists primarily of polyisoprene,

polyisoprene, a high
molecular-
molecular-weight polymer of isoprene (C5H8)

It is derived from latex,
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.

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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

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Natural Rubber Products

Largest single market for NR is automotive tires

Other products:
products: shoe soles, bushings, seals, and
shock absorbing components

In tires, carbon black is an important additive;
additive; it
reinforces the rubber, serving to increase tensile
strength and resistance to tear and abrasion

Other additives:
additives: clay, kaolin, silica, talc, and calcium
carbonate, as well as chemicals that accelerate and
promote vulcanization

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Synthetic Rubbers

Today, the tonnage of synthetic rubbers is more

than three times that of NR.
NR.

Development of synthetic rubbers was motivated
largely by world wars when NR was difficult to
obtain.

The most important synthetic is styrene-
styrene-butadiene
rubber (SBR), a copolymer of butadiene (C4H6) and
styrene (C8H8)

As with most other polymers, the main raw material
for synthetic rubbers is petroleum.

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Thermoplastic Elastomers (TPE)

A thermoplastic that behaves like an elastomer

Elastomeric properties not from chemical
cross-
cross-links,
links, but from physical connections

between soft and hard phases in material  a

composite?
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

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References:

1. Elias, H. G., An Introduction to Plastics,

Plastics, Willey-
Willey-VCH GmbH.,
Michigan, 2003.
2. Young, R. J., Lovell, P. A., Introduction to Polymers,
Polymers,
Chapman & Hall, 2nd Ed., 1991.
3. Fred W. [Link],
[Link], Textbook of Polymer Science,
Science, third
edition, John Wiley and Sons, New York, 1994.
4. Alfred Rudin,
Rudin, The Elements of Polymer Science and
Engineering,
Engineering, 2nd Ed., Academic Press, 1999.
5. Stephen L. Rosen, Fundamental of Polymeric Materials,
Materials,
John Wiley and Sons, New York, 1982.
6. Steven. M.P, Polymer Chemistry,
Chemistry, Oxford University Press,
Inc.
7. Fried, J. R., Polymer Science & Technology,
Technology, Prentice-
Prentice-Hall
Inc., New Jersey, 1995.

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