Application of polymers

Basics II

linear polymer

crosslinked polymer

star polymer

branched polymer
dendrimer
HW 1 Plastic Recycling Symbols
 Polymer Structure I

Why most? Because a few

types of polymers may do
under certain circumstances
(we will see how)

amorphous semi-crystalline
polymer polymer

MOST CRYSTALLINE POLYMERS ARE

NOT ENTIRELY CRYSTALLINE !!!
They are either amorphous or semi-crystalline.
The degree of crystallinity varies (From 0 to 90-95 %).
 Polymer Structure II

Shish-kebab morphology

SEM image of a spherulite

SEM image of a chain having
shish-kebab morphology
 Polymer Structure III

Crystallinity of polymers is affected by:

All about the Chemical structure

chain properties Stereochemistry
Molecular weight Hmm…
Temperature
External effects
Processing conditions
 Polymer Structure IV
STEREOCHEMISTRY
(Tacticity)

This is the white, plastic coffee cup

Is polystyrene flat like this?
used everywhere like Fassane.
Strafor kopuk Absolutely NO!
 Polymer Structure V
STEREOCHEMISTRY
(Tacticity)
In the previous picture you see all the phenyl groups are located on the same side of the
polymer chain. But they don't have to be this way. To illustrate let's look at a chain of
polystyrene from above. You can see that the pendant phenyl groups can be either on the
right or left side of the chain.

All phenyl groups Phenyl groups on Phenyl groups

on the same side alternating sides distributed randomly
 Polymer Structure V
STEREOCHEMISTRY
(Tacticity)

The question is, how tacticity helps crystallinity

CRYSTALLINITY ↔ LONG RANGE ORDER ↔ PACKING

Syndiotactic polystyrene: Highly crystalline

Atactic polystyrene: Highly amorphous

Similarly, a linear polymer can pack well, whereas a branched isomer cannot

Highly crystalline Highly amorphous

Polymer Structure VI
Intermolecular forces and crystallinity

(Aromatic ring stacking)

 Polymer Structure VII
• Fibers
– Polymers with regular structure can align themselves very closely for effective
utilization of the secondary intermolecular bonding forces.
– Already stretched out fully, up to 95% crystallinity
– High symmetry, high intermolecular forces.
– Characterized by high modulus, high tensile strength, and moderate extensibilities

Can you stretch this structure???

 Polymer Structure VIII
• Elastomers (rubbers)
– Polymers with irregular structure, weak intermolecular attractive forces and
flexible chains.
– Can undergo local mobility, but gross mobility of chains is restricted.
– Characterized by high extensibility, low initial modulus in tension but they stifen
when strecthed.

stretch

leave

ENTROPY WORK!
 Polymer Structure IX
• Plastics
– Fall between the elastomers and fibers. However there is no exact boundary
– Harder to stretch than elastomers (Because of crystalline regions?). But preserve
their shape when stretched unlike elastomers (Strain induced crystallization, stiff
chains)
– They are pliable, that is, they can be shaped and molded easily
– Thermoplastics: Melt when heated and can be melted again after cooling
– Thermosets: Undergoes crosslinking when heated, so does not melt again,
decomposes if heated further
– Flexible plastics: Plastics above their Tg. Flexible, soft
– Rigid plastics: Plastics below their glass transition temperature (Tg). Brittle, hard

What are Tg, crosslinking and “melting for polymers” ?

 Polymer Structure X
Glass transition temperature (Tg)

• Different polymers have different segments on their backbones. The ease of movement of these
segments (portions of the chain) depends on the structure, physical environment of the chain etc.
of the segment.

• Any movement of these segments require energy which is kinetic in this case, right? Then each
different polymer would have different energy requirement for the movement of these segments
(different polymer = different structure, different physical environment of the chain etc).

• Below glass transition temperature, these segments do not have sufficient energy to move. So, if
you apply some stress, say if you try to bend a polymer which is below its Tg then the segments
won’t be able to move into new positions to relieve the stress which you have placed on them;
which will make the polymer brittle. Above Tg they would, so they would be flexible.

• Always keep this in mind: Tg IS A PROPERTY RELATED WITH THE AMORPHOUS

REGIONS OF THE POLYMER, NOT CRYSTALLINE!

• So it should now be obvious that elastomers are elastomers above their Tg. Below, they are not
elastomers, they are glassy, because they are not flexible anymore (Remember my experiment
with rubber glove and liquid nitrogen during the lecture).
 Polymer Structure XI
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.

• Always keep this in mind: MELTING IS A PROPERTY RELATED WITH THE

CRYSTALLINE REGIONS OF THE POLYMER! So do you think you can melt atactic
polystyrene? (No, because it is not crystalline)

Question: What if I see both

melting and glass transition in the
differential scanning calorimeter
(DSC) spectrum of a polymer
sample???

It is absolutely OK. Remember,

most polymers are semi-
crystalline, i.e. have both
amorphous and crystalline regions
1. Glassy
2. glassy transition
3. rubbery plateau
4. Rubbery flow
5. Viscous flow
 Polymer Structure XII
Poly (1,4-butadiene)
Crosslinking

Crosslinking
with sulphur
(vulcanization)
Synthetic rubber

This is the tire of your car

Thus, it is possible to produce elastomers via crosslinking!

(In fact, it is not only possible but also the very common way of making elastomers, i.e. rubber)
 Mechanical properties

Now, I am sure that you can

rationale the mechanical behavior
of various types of polymers
shown in this image.
 How to make polymers

Chain growth Step growth

(Addition) (Condensations)
Monomer Monomer
Initiator Monomer (ethylene)

H2O out
Monomer

Polyethylene
This is the plastic bag
• Free radical given in the supermarket (PET)
• Ionic This is the bottle of your 1 lt coke
Ring opening

This is the breast implant of your

favorite female model
Poly(dimethyl siloxane)
 Molecular weight
• Not all of the chains of a polymer are of same length. Their size differ most of the time.

• Remember: A chain is a polymer molecule (in fact the chain is the polymer itself), so the
molecular weight of a polymer should in fact be the molar mass of a single polymer chain.
However, since chains have different lengths (that is why we call polymers as polydisperse)
we can only talk about averages

• Number average molecular weight =

Ni is the number of chains having
molecular weights Mi
• Weight average molecular weight =

• Polydispersity index = Mw / Mn
Configuration (Chain Structure)
Copolymer
(repeating units are more than
one monomer type)

homopolymer
(repeating unit is always
same monomer)
 When the chains get up to
500,000 carbons long, they
are tough enough for
synthetic ice, replacement
joints, and bullet-proof vests.
Think about it. You start
with ethylene gas molecules
that can't stop a feather from
passing through them. But
after the double-bond of one
ethylene molecule breaks, it
causes a chain reaction that
connects thousands to it. In
less than a second, these
long straight chains of
carbon and hydrogen are
strong enough to stop a
bullet or play ice hockey on.
Isn't chemistry wonderful.
Examples
Examples
Mechanical Testing
Temperature Dependence of
Deformation
 Processing

Injection molding: http://www.bpf.co.uk/downloads/files/InjectionMoulding.swf

Blow molding: http://www.pct.edu/prep/bm.htm
http://www.youtube.com/watch?v=vSabFFQUr9E
Compression molding: http://www.ticona.com/index/tech/processing/compression_molding.htm