Polymers

You may think of polymers as being a relatively

modern invention
however naturally occurring polymers have been used
for thousands of years
wood, rubber, cotton, wool, leather, silk,.. etc

Artificial polymers are, indeed, relatively recent

and mostly date from after WWII
in many cases, the artificial material is both better and
cheaper than the natural alternative

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Introduction to Polymers
styrofoam cups
contact lenses
rubber tires
telephone housings
epoxies
sandwich bags
soda bottles
rubber bands
computer keyboard keys
cables etc

COMMERCIAL Polymers: used in

large quantities for their lightweight,
corrosion-resistance, and good
formability.
- usually low strength and stiffness

ENGINEERING Polymers:
improved strength and better
elevated temperature properties.

in fact, just look around your, house, dorm or apartment room and youll
likely find plenty of examples of polymeric materials.

Polymers:
THERMOPLASTICS, THERMOSETS AND ELASTOMERS
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Different aspects of polymer science

Polymer synthesis
Polymer characterization
Polymer physical chemistry
Paul J. Flory, Nobel prize for chemistry, 1974
Polymer physics
Pierre de Gennes, Nobel prize for physics, 1991
Polymer engineering
Each of these aspects has considerable
industrial and research significance. The
successful polymer scientist has some
understanding of all of these areas.
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Definitions

Indicates a chain of n units

Polymer: long molecule made up by the repetition of small units

Synonym: macromolecule
High molecular weight (M)
Ex. polystyrene (PS)

Monomer: molecule that combines with others (identical or

different) to form a polymer
Ex. ethylene (PE polyethylene)
Oligomer: low molecular weight polymer, constituted of at least
two monomers
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Classification of polymers
Thermoplastics: can be processed by melting (several cycles of
heating and cooling are possible for thermally stabilized
polymers)
PS, PE
PP
PVC

PET
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Classification of polymers
Thermosets: cannot be melted or dissolved
to be processed: chemical decomposition
occurs before softening
Formation of a 3D network
Example: epoxy (resin and hardener)

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Vulcanization of rubber
Sulphur reacts with
chain at the double bond

This kind of
materials are
referred to as
elastomers

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Molecular forces in polymers

Intramolecular forces: generally covalent bonds
(strong)
(forces between atoms in one chain)

Intermolecular forces: Van der Waals forces (PE),

hydrogen bridges (PS) (stronger). Can become
very strong as M
(forces between two chains)

Entanglements (physical)
In the crystalline state the van der Waals bonds are very
important. In the rubbery amorphous state the
entanglements are very important.
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Basic Polymer Structure

Suppose our repeat unit is an X. Then, a linear

polymer based on X would look like the following:
--X--X--X--X--X--X--X--X--X--X--X--X--
where each X represents a mer.
Sometimes, polymers contain functional side groups,
called pendant groups:
We call the primary
linear chain the
backbone

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Homopolymers and co-polymers

Homopolymers vs. co-polymers:
-If only one type of repeat unit is present, the polymer is called
a homopolymer.
-If a second monomer is also present in the chain, the resulting
material is called a co-polymer.
Model for a homopolymer:
--X--X--X--X--X--X--X--X--X--X--XX
Model for an alternating co-polymer:
--X--W--X--W--X--W--X--W--X--W--XW
Model for a random co-polymer:
--X--X--X--W--X--W--X--X--W--X--WW
Model for a block co-polymer:
--X--X--X--X--X--X--X--X--W--W--W--W--W--W-MECH 221

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Other Copolymers
Graft: a polymer is grafted to another preformed
macromolecule
Ex. Impact resistant PS: PS branches on
polybutadiene (rubber)
Also, ABS branches of SAN on polybutadiene

Block : long sequences of different repeating units

A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-A-A-A
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Hydrocarbon molecules
Hydrocarbons
hydrogen and carbon, bonded covalently
Simplest are methane, ethane, propane, butane
CnH2n+2, the paraffin family
where each carbon shares an electron either with
another carbon or with a hydrogen
Alternatively, a carbon can share two electrons with
H H
another carbon atom
| |
a double bond
C= C
| |
hence ethylene, C2H4
H H
And triple bonds are also possible
e.g. acetylene, C2H2
HCCH
Polymers are composed of hydrocarbon basic units (mers).
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Structure of Polymers
Examples of real monomers and their resulting polymers:

Polyethylene: (the mer unit is C2H4)

ethylene

Polyethylene is used
for flexible bottles, toys,
battery parts, ice trays,
and film wrapping and
other packaging
materials.
It is tough but
possesses low strength.
Trade names: Ethron,
Fortiflex, Hi-fax, Rigidex,
Zendel.

This is an example of a linear chain homopolymer, where the

X in our model is replaced with the ethylene group.
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Structure of Polymers
Polypropylene: (the mer unit is now C3H6)
propylene

Polypropylene is used for such items as bottles, TV cabinets,

luggage.
It tends to be relatively strong and resistant to heat.
It has the trade names Herculon, Meraklon, and Profax.
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Structure of Polymers
Polyvinyl chloride: (the mer unit is C2H3Cl)

Polyvinyl chloride is a very popular, low cost rigid material

It can be made flexible by adding plasticizers.
It is used as floor coverings, pipe, garden hose, electrical
wire insulation, and (at one time) phonograph records.
Tradenames: PVC, Saran, Tygon, Darvic, Geon.
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Molecular weight
Since not all chains in a sample of material are the same
length, and so there is a distribution of molecular weights
number average, M n = xi M i

amount of polymer

Mi is mean weight in size range, i

xi is the fraction of total number of
chains in size range, i
wi is the fraction of total weight in size range, i
weight average, M w

= wi M i

molecular weight

Very large molecular weights are common for polymers

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Molecular weight
Alternative way to express average polymer chain size is degree
of polymerization - the average number of mer units in a chain:

The mer molecular weight for a co-polymer can be determined by:

m = f jm j

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fj chain fraction of mer j

mj molecular weight of mer j

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Molecular shape
If the form of the molecule was strictly determined,
polymers would be straight
in fact, the 109 bond angle in polyethylene gives a
cone of rotation around which the bond lies
109

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Molecular shape
Hence the polymer chain can bend,
twist, and kink into many shapes
adjacent molecules can intertwine
leading to the highly elastic nature of
many polymers, such as rubber

Random kinks and coils lead to

entanglement, like in the spaghetti
structure:
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Molecular structure
Linear polymers
long, flexible chains (with only 2 ends) with some van der
Waals or hydrogen bonding between chains
Branched polymers
Chain packing efficiency is reduced compared
to linear polymers (lower density)

Crosslinked polymers
cross linkage happens either during synthesis or in a separate
process, typically involving addition of impurities which bond
covalently
this is termed vulcanisation in rubber
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Molecular structure
Network polymers: 3D networks made from
trifunctional mers. Examples: epoxies,
phenolformaldehyde. These are thermosetting
materials!

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 Covalent chain configurations and strength:

secondary

bonding

Linear

Branched

Cross-Linked

Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.

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Crystallinity in polymers
Although it may at first seem surprising, Polymers can form crystal
structures (all we need is a repeating unit, which can be based on
molecular chains rather than individual atoms)
Some parts of structure align during cooling to form crystalline regions.
(Not like FCC + BCC metals - chains align alongside each other.)
Around CRYSTALLITES get AMORPHOUS regions.

% crystallinity =

c ( s a )
x100
s ( c a )

Where:
s = Density of sample
a = Density of the completely
amorphous polymer
c = Density of the completely
crystalline polymer
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Crystallinity in polymers
Most real polymers contain both
amorphous and crystalline
regions, as shown here.

% crystallinity depends on several factors:

Rate of cooling
(faster cooling less crystallinity)
Type of polymer
(simple structures more crystallinity)
(Copolymers less crystallinity)
Linear polymers more easily form crystals
- Degree of Crystallinity ranges from 5 - 95%
- The higher % Crystallinity higher strength
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Polymer Crystals

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Spherulites
When polymers are
crystallized they form
spherical structures
called spherulites

Crystalline structure of
polylactide crystallized from
bulk. 50x50 m scan
MASc thesis of Yury Yuryev, Concordia U., 2006

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Mechanical properties of polymers

- There are three typical classes of polymer stress-strain characteristic
stress (MPa)
6

brittle

plastic
highly elastic elastomeric

0
0

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strain

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Mechanical properties of polymers

Modulus of Elasticity
may be as low as 7 MPa or has high as 4x103 MPa
(compare to 48-410 x 103 MPa for metals)
TS polymers 100 MPa (metals up to 4100MPa)

Elongation
Often elongate plastically as much as 1000% (compare
to metals - rarely over 100%)

Temperature Dependence
Mechanical properties are very T dependent - even close
to room T

Strain Rate Dependence

same behavior as raising temperature
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Mechanical Properties of Polymers

Elastic modulus is very much

lower than for metals or ceramics
Beyond the yield point sample
deforms plastically.
Tensile stress (TS) is the stress
at fracture
TS may be less or greater than
the yield strength.
Schematic stressstrain curve for a
plastic polymer showing how yield
and tensile strengths are determined.

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Mechanical Properties of Polymers

Decreasing T...
--increases E
--increases TS
--decreases %EL

Effect of temperature on stress-strain

behavior of PMMA (left).

Increasing strain rate causes the same effects as decreasing T.

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Molecular Structure: Polymer Crystal Models

Chain folded
model: crystals
are actually
small platelets
of interwoven
polymer chains
In many bulk polymers crystallized
from the melt, these platelets often
arrange themselves in radiating
patterns to form spherulites.
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Mechanisms of Elastic Deformation, in

Amorphous & Semicrystalline Polymers
Elastic deformation takes place due to the
elongation of chain molecules by bond
stretching (all regions) and bond rotation
(amorphous region), along the direction of the
applied stress.
Bonds do not break and chains do not slip
past each other. If either of these happen
yielding occurs.
Inter-molecular bonding (Van der
Waals) is much weaker than other
types, hence the low yield strengths of
polymers compared to metals or
ceramics.
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stable conformation

bond stretched
and rotated

stressed conformation

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Mechanisms of Plastic Deformation

- Semicrystalline Polymers

Two adjacent chain

folded lamellae and
interlamellar
amorphous material
before deformation

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Elongation of
amorphous tie
chains

Tilting of
Separation of
lamellar chain
crystalline
folds
block segments Orientation of
block segments
and tie chains
with tensile axis
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Plastic Deformation - Semicrystalline Polymers

yield

Unlike metals, TS is
not where neck forms
Because deformation
continues outside of
neck. Neck region is
actually strengthened

Mechanism - chains slip past each other (bonds rotate to allow

this), some inter-molecular van der Waals bond breaking.
- Result is a highly oriented structure in the neck region of our
tensile specimen)
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PREDEFORMATION BY DRAWING
Drawing...
--stretches the polymer prior to use
--aligns chains to the stretching direction
Results of drawing:
--increases the elastic modulus (E) in the
stretching dir.
--increases the tensile strength (TS) in the
stretching dir.
--decreases ductility (%EL)
Annealing after drawing...
--decreases alignment
--reverses effects of drawing.

Compare to cold working in metals!

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TENSILE RESPONSE: ELASTOMER

CASE
(MPa)

60 xbrittle failure
plastic failure

40

20

elastomer

0
0

initial: amorphous chains are

kinked, heavily cross-linked.

final: chains
are straight,
still
cross-linked

Deformation
is reversible!

Compare to responses of other polymers:

--brittle response (aligned, cross linked & networked case)
--plastic response (semi-crystalline case)
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TENSILE RESPONSE: BRITTLE vs PLASTIC

Near Failure

(MPa)
brittle failure
x
60

40
Initial

onset of
necking

plastic failure

20
0
0

aligned,networked
crosscase
linked
case

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Strength in Polymers
Major factors affect strength are temperature and strain rate:
In general, decreasing the strain rate has the effect similar
to increasing the temperature.
Other Factors that influence strength
Tensile strength increases with molecular weightmore
entangled (short strings vs long)
TS = TS - A/Mn
Strength can be increased by increasing the degree of crosslinking (inhibits chain motion - makes it more brittle)
Crystallinity increases strength by increasing intermolecular
bonding
Deforming a polymer can increase its strength - so that
chains become oriented
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Strength in Polymers

Influence of degree of crystallinity and MW on strength

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Melting and Glass Transition Temperature

For amorphous and semicrystalline polymers, this is a critical
aspect of designing with polymers.
Crystalline polymers: there is a
discontinuous change in specific
volume at Tm
Amorphous polymer:
continuous, no Tm - but there is
an increase in slope at Tg, the
glass transition temperature,
Semicrystalline polymer:
intermediate to crystalline and
amorphous, show both
transistions.

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Melting and Glass Transition Temperature

Melting of a crystalline polymer
transforming solid with an ordered structure to a viscous
liquid with a highly random structure
Amorphous glass transitions
transformation from a rigid material to one that has rubberlike characteristics
temperature has large effect on chain flexibility
Below glass transition temperature, Tg, polymers are usually
brittle and glass-like in mechanical behavior.
Above glass transition, Tg, polymers are usually more elastic.
Why is That?
Bond rotations are freezing which means chains cant slip past
each other so polymer becomes brittle, (no plastic deformation)
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Polymers and Spaghetti

Amorphous polymers.hot, fresh spaghetti with not clumps
Semicrystalline polymers.hot fresh spaghetti with some clumps
Crystalline polymers.spaghetti the way my friend made it, mostly
clumps with some free strands
GlassyPolymer below Tg, three day old spaghetti- left in the
sun!

Tg is low for
simple linear
polymers
Tg and Tm
increase with
mer complexity
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Effect of temp. on tensile response of thermoplastics

Stress strain behavior of PMMA

Modulus of PS
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Polymer Additives
Mechanical, chemical, physical Properties can be modified by
additives:
Fillers
Improve tensile and compressive strengths, abrasion resistance,
toughness, and thermal stability
sand, glass, clay, talc (eg. carbon in tires)
Particle sizes range from very small (10 nm) to large (mm)

Plasticizers: small molecules which occupy positions between polymer

chains (increase distance and interactions between chains)
increases flexibility, ductility, and toughness
reduces hardness and stiffness

Stabilizers
UV resistance of C-C bonds
Oxidation resistance

Colorants and Flame Retardants

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Forming of Polymers

Polymeric materials are normally fabricated at elevated

temperatures and often by application of pressure
The technique used to form a particular polymer depends on
whether it is thermoplastic or thermosetting
the atmospheric stability of the material at which forming takes
place
the geometry and size of the final product
If the polymer is thermoplastic, the temperature at which it
softens will also dictate the process

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Thermosets
Crosslinking prevents melting and viscous flow
Hot working, such as extrusion is not possible
At high temperatures they decompose rather than melt
although they can be used at higher temperatures than thermoplastics
and are more chemically inert

Fabrication of thermosetting polymers is usually a two stage process

In the first stage a linear polymer, with a low molecular weight is
prepared
The second curing stage is carried out in a mould having the desired
shape during the addition of:
heat and/or catalysts

pressure
During the cure, chemical and structural changes take place at a
molecular level
crosslinked or network polymer formed
this is dimensionally stable and can be removed from the mould while
hot
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Compression Moulding
Both thermoplastics and thermosets can be formed by compression mould
The polymer, or mixture of resin and hardener is heated and
compressed between dies
This method is well suited to
forming of:
thermoset casings for
appliances
thermoplastic car bumpers
Since a thermoset can be
removed when hot, cycle times
can be as low as:
10 seconds for small
components
10 minutes for large thick
walled mouldings
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Injection Moulding

In injection moulding, polymer granules are

compressed by a ram or a screw
heated until molten
injected into a cold, split mould under pressure
The moulded polymer is cooled below Tg
the mould opens and the product is ejected
This process gives high precision mouldings because the
polymer cools under pressure
Cycle time is typically between 1 5minutes
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Thermoplastic Extrusion

It is a cheap continuous process for producing shapes of

constant section
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Blow Moulding
The parison is a hollow
tube of softened
plastic Its shape is
determined
by the screw speed
and/or the die opening

Eg. Container fabrication similar to glass bottle production

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