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CH8: Structure and Morphology

of Polymers

Three important phenomena of polymeric

materials are crystallization, melting, and
the glass transition.
The glass-transition phenomenon occurs
with amorphous or noncrystallizable
polymers that, when cooled from a liquid
melt, become rigid solids yet retain the
disordered molecular structure that is
characteristic of the liquid state.

Glass Transition Temperature

The glass transition temperature (Tg) is the temperature at

which an amorphous polymer ceases to be brittle and glassy
and becomes less rigid and rubbery.
Alternately, if a crystallizable material is cooled at a fast
enough rate, molecules become more or less frozen in position
and cannot rearrange themselves to form crystals. This is called
the glass transition state when material still takes on the
properties of a solid, but the arrangement of the molecules
remains disordered, as in the liquid state.

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Glass Transition Temperature

Polymers do crystallize as well as form glassy solids. But they
can not be found in gaseous state because of strong cohesive
forces.
Crystallization
depend on the
Microstructure.

Between LDPE & HDPE,

Which one would
crystallize?

Crystallization of polymer chains

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Bonding and Intermolecular

interactions

In general, interactions between non-polar molecules are

considered to be "weak" relative to those between molecules
or segments that are more polar.

Bonding and Intermolecular

interactions

Dipole dipole interaction

Hydrogen Bonding

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Chain Conformations

Single chain molecules can fold itself into various shapes called
conformations which can be generally divided into,
Ordered, such as Zig zag shape or simple helix arrangements
Disordered such as random coil
ethane

Which one has minimum potential energy?

The minimum energy conformation is
found when the hydrogens are as far away
from one another as possible, in a
conformation called trans.

Polymer Chain Conformations

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Chain Conformations

It is a 3D spatial arrangement of atoms or groups that is

changed under the effect of thermal motion, but doesnt
involve breaking of chemical bonds.

Chain Conformations
There are two gauche positions for the bond that is rotating.
These gauche conformation has a shallower minimum energy.
Essentially, at any temperature
an isolated chain will have a distribution
of conformations, so many bonds will
be trans and many will be gauche.

The symmetry of the ethane molecule

gives 3 equivalent minima and maxima
per revolution.

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Polymer Chain Conformations

Chain Conformations

Similarly n-butane (CH3-CH2-CH2-CH3) has 3 different stable

conformational states
Trans (T), gauche (G) and gauche (G)

Only rotation about middle bond can change the direction of

backbone, the rotation about two end bond do not change
conformationz

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Chain Conformations

Chain Conformations

Polymer chains exhibit in several cases a random chain

conformation, i.e. a random distribution of T and G states.
Macromolecular chains with random conformation (random
coils) are found in solutions of polymers in good solvents, in
polymer melts and in glassy amorphous polymers.
If the chain is in a melt of other chains, or in solution (i.e., has
not crystallized or frozen into a glass), then the bonds are in
constant motion, flipping between energy minima (like the trans
and gauche conformations in polyethylene).
Such random coil chains will thus have an overall number of
shapes or conformations available to them and will be
constantly shifting from one overall conformation to another.

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Chain Conformations

In the crystalline state polymers sit in their minimum energy

conformation.
If thermal energy (temperature) gets higher, it may overcome
the potential energy barrier relative to a low energy
conformation (stable state), and acquire another conformation.
Essentially, at any temperature an isolated chain will have a
distribution of conformations, so many bonds will be trans and
many will be gauche.

Number of Chain Conformations

Assume a PE chain with three local minima, like trans, gauche

and the other gauche, but have the same min. energy. Let's
also assume that a bond can only be found in one of these
three conformations.
The first bond can therefore be found in anyone of three
conformations, as can the second, the third, and so on
How many configurations are available to the first two bonds
taken together?
09 (The Pascals Traingle)

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Polymer Chain Conformations

Conformation of an Ideal Chain