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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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MECH 221 PM Wood-Adams fall 2008
Introduction to Polymers

styrofoam cups
COMMERCIAL Polymers: used in
contact lenses large quantities for their lightweight,
rubber tires corrosion-resistance, and good
telephone housings formability.
epoxies - usually low strength and stiffness

sandwich bags
soda bottles ENGINEERING Polymers:
rubber bands improved strength and better
computer keyboard keys elevated temperature properties.
cables … etc
in fact, just look around your, house, dorm or apartment room and you’ll
likely find plenty of examples of polymeric materials.
Polymers:
THERMOPLASTICS, THERMOSETS AND ELASTOMERS 2
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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. Æ polystyrene (PS)

• Monomer: molecule that combines with others (identical or


different) to form a polymer
Ex. Æ 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--X—X
Model for an alternating co-polymer:
--X--W--X--W--X--W--X--W--X--W--X—W
Model for a random co-polymer:
--X--X--X--W--X--W--X--X--W--X--W—W
Model for a block co-polymer:
--X--X--X--X--X--X--X--X--W--W--W--W--W--W-- 10
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Other Copolymers
• Graft: a polymer is grafted to another preformed
macromolecule
Ex. Æ Impact resistant PS: PS branches on
polybutadiene (rubber)
Also, ABS Æ 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
another carbon atom H H
| |
– a double bond C= C
| |
– hence ethylene, C2H4 H H
• And triple bonds are also possible
– e.g. acetylene, C2H2 H–C≡C–H

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)
ƒ Polyethylene is used
ethylene for flexible bottles, toys,
battery parts, ice trays,
and film wrapping and
other packaging
materials.
ƒ It is tough but
possesses low strength.
ƒ 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. 13
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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

Mi is mean weight in size range, i


xi is the fraction of total number of
chains in size range, i
amount of polymer

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 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
ƒ adjacent molecules can intertwine
ƒ 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.

ρc ( ρ s − ρa )
% crystallinity = x100
ρ s ( ρc − ρa )
Where:
ρs = Density of sample
ρa = Density of the completely
amorphous polymer
ρc = 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 μm 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

4 plastic

highly elastic – elastomeric


2

0 strain
0 2 4 6 8

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MECH 221 PM Wood-Adams fall 2008
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 stress–strain 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.
stable conformation
Bonds do not break and chains do not slip
past each other. If either of these happen
yielding occurs. bond stretched
and rotated
Inter-molecular bonding (Van der
Waals) is much weaker than other
types, hence the low yield strengths of
polymers compared to metals or
ceramics. “stressed” conformation

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Mechanisms of Plastic Deformation
- Semicrystalline Polymers

Two adjacent chain


folded lamellae and Elongation of Tilting of Separation of
interlamellar amorphous tie lamellar chain crystalline
amorphous material chains folds block segments Orientation of
before deformation block segments
and tie chains
with tensile axis
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Plastic Deformation - Semicrystalline Polymers

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

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
σ(MPa)
60 xbrittle failure

plastic failure
40 x

20 x
elastomer
final: chains
0
0 2 4 6 ε 8
are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, heavily cross-linked. 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 σ(MPa)


xbrittle failure
60
onset of
necking plastic failure
40 x
Initial
20

0
ε
0 2 4 6 8
aligned,networked
cross- case
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 weight…more
entangled (short strings vs long)
• TS = TS∞ - A/Mn
– Strength can be increased by increasing the degree of cross-
linking (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 rubber-
like 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 can’t 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
• …Glassy…Polymer 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 43
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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
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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
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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 48
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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 It’s shape is
determined
by the screw speed
and/or the die opening

Eg. Container fabrication similar to glass bottle production 50


MECH 221 PM Wood-Adams fall 2008