DSC

DSC thermograms of
semi‐crystalline
polymers illustrate
the spread in melting
points and wide
variation in degree of
crystallinity
(enthalpy).

The distinct melting

temperatures and
enthalpies are
attributed to
differences in
molecular structure.
The substantial variation
in thermal properties is
associated with the
unique aspects of
molecular structure of
the various semi‐
crystalline polymers.

Polyethylene shows the

highest degree of
crystallinity, but the
lowest melting point.
Polyacetal also has a
comparatively high
degree of crystallinity.
Both have relatively
simple structures that
can “fold” together to
create crystalline
content.
Crystallinity
• Linear polymer chains promote crystallinity. HDPE and POM
have a simple linear structure and are the highest degrees of
crystallinity.
• Stereoregularity facilitates crystallinity ‐ the greater the
order in the polymer, the higher the crystallinity. Atactic PP
and atactic PS are amorphous, but the isotactic and
syndiotactic versions are semi‐crystalline.
• Bulky sidechains impede the formation of crystals. PP has a
lower degree of crystallinity than HDPE. PVC is amorphous.
• A stiff chain backbone that can “fold” supports crystallinity.
• Strong intermolecular forces favor the formation of crystals
and promote an orderly arrangement and molecular
packing. The hydrogen bonding creates crystalline structure
within nylon polymers.
• Narrow molecular weight distribution increases crystallinity.
Melting Point
• The melting point is elevated when the flexibility of the
molecular chains is impeded. PEEK has a non‐flexible
structure and a very high melting point.
• Melting point is Increased with aromatic groups in the
chain backbone. PPA has a higher melting point than
nylon 6/6.
• Large pendant side chains foster elevation of the
melting point.
• Strong intermolecular forces ‐ Cohesion energy and
attractive forces ‐ promote higher melting points.
Nylon 6 has a higher melting point than nylon 12.
• Branching with analogous polymers reduces the
melting point due to molecular “defects”. LDPE has a
lower melting point than HDPE.
The long chain
branching within
LDPE is responsible
for the lower melting
point and the lesser
degree of
crystallinity.

The branching
inhibits crystal
formation due to
steric hindrance.

The reduction in
intermodular forces
serves to lower the
melting point.
 Nylon 6/6 has a less
orderly structure
compared with high
density polyethylene –
Polyethylene lower degree of
Nylon 6/6 crystallinity.

Nylon 6/6 has stronger

intermolecular forces
(hydrogen bonding
comparing with weak
forces for
polyethylene
(dispersion forces) –
Hydrogen bonding Dispersion forces higher melting point.
The benzene ring
in PPA results
stiffens the
polymer chain.

This results in a
higher melting
point and a lower
degree of
crystallinity
compared with
nylon 6/6.