GLASS
TRANSITION
TEMPERATURE
Have you ever left a plastic bucket or some
other plastic object outside during the winter,
and found that it cracks or breaks more easily
than it would in the summer time?
What you experienced was the phenomenon
known as the glass transition. This transition
is something that only happens to polymers,
and is one of the things which make polymers
unique.
This change in mobility with temperature happens
because of the "heat" which is really a form of kinetic
energy; that is, the energy of objects in motion. It is
actually an effect of random motion of molecules,
whether they are polymer molecules or small
molecules.
Things are "hot" when their molecules have lots of
kinetic energy and move around very fast. Things are
"cold" when their molecules lack kinetic energy and
move around slowly, or not at all.
When the temp. is warm, the polymer chains can
move around easily. So, when a piece of the polymer
is taken and bent, the molecules, being in motion
already, have no trouble moving into new positions to
relieve the stress placed on them.
But if the sample of a polymer is bent below its Tg,
the polymer chains won't be able to move into new
positions to relieve the stress which is placed on
them. So, one of two things will happen:
- Either the chains are strong enough to
resist the force applied, and the sample
won't bend
- Or the force applied 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.
The glass transition temperature, or Tg for short is
a specific temperature (different for each polymer)
below which every polymer becomes hard and
brittle, like glass. This is because at Tg all the
molecular motions such as translation, vibration
and rotation cease.
Some polymers are used above their Tg, and some are
used below.
- Hard plastics like polystyrene and poly(methyl
methacrylate), are used below their glass transition
temperatures; that is in their glassy state. Their Tg’s are
well above RT, both at around 100oC.
- Rubber elastomers like polyisoprene and
polyisobutylene, are used above their Tg's, i.e., in the
rubbery state, where they are soft and flexible. Their
Tg’s are much below room temp. (less than -50oC)
• The glass transition is not the same thing as
melting.
• Melting is a first order transition which occurs in
crystalline polymers when the polymer chains
fall out of their crystal structures, and become a
disordered liquid.
• The glass transition is a transition which occurs
only in amorphous polymers; that is, polymers
whose chains are not arranged in ordered
crystals, but are just strewn around, even
though they are in the solid state.
But even crystalline polymers have some
amorphous portion (40-70%). Hence a polymer can
have both a glass transition temp. and a melting
temp.
The amorphous portion undergoes the glass
transition only, and the crystalline portion
undergoes melting only.
But the chains that undergo melting are different
from those chains that undergo glass transition.
There is another big difference between melting
and the glass transition. When a crystalline
polymer is heated at a constant rate, the temp.
will increase at a constant rate until the polymer
reaches its melting point. At the temp. will hold
steady for awhile until the polymer has
completely melted, even though heat is being
added to the polymer.
Then the temperature of the polymer will begin
to increase once again. The temp. rising stops
because melting requires energy. All the heat
energy added to a crystalline polymer at its
melting point goes into melting, and none of it
goes into raising the temperature (latent heat of
melting).
Now once polymer has melted, the temp. begins
to rise again, but now it rises at a slower rate.
The molten polymer has a higher heat capacity
than solid crystalline polymer, so it can absorb
more heat with a smaller increase in temp.
But when an amorphous polymer is heated to its
Tg, something different happens. First as it gets
heated, the temp. goes up. It goes up at a rate
determined by the polymer's heat capacity just
like in crystalline polymers. Only the temp.
doesn't stop rising when the Tg is reached,
There is no latent heat of glass transition. The
temperature keeps going up.
But the temperature doesn't go up at the
same rate above the Tg as below it. The
polymer does undergo an increase in its heat
capacity when it undergoes the glass
transition. Because the glass transition
involves change in heat capacity, but it
doesn't involve a latent heat, this transition is
called second order transition
Factors responsible for Tg
• Chain geometry & flexibility
• Bulky pendant groups
• Intermolecular interaction
Polymer Geometry & Flexibility
Polymers with low hindrance potential to internal
rotation show very low Tg
PE -120oC
POM -85oC
Stiffer chains require higher temps for the onset of
molecular motions, hence high Tg
PET 70oC
PC 150oC
Molecular symmetry lowers Tg
PVC 87oC
PVDC -10oC
PP -18oC
Polyisobutylene -65oC
Bulky Side groups raise Tg
PE -120oC
PP -18oC
PS +100oC
Intermolecular Forces & Hydrogen Bonding
tend to raise Tg
PP (-CH3) -18oC
PVC (-Cl) +87oC
PAN (-CN) +103oC
Polytetramethylsebacate -57oC
Polyhexamethyleneadipamide 50oC
(hydrogen bonding in Nylon 6,6)
Other factors affecting Tg
(Controllable Parameters)
1. Pressure
2. Plasticizers and/or Diluents
3. Molecular Weight
4. Comonomers
5. Crystallinity
6. Tacticity
7. Crosslinking
