Polymer structure
• The polymer chain layout determines a lot of material
properties:
• Amorphous: Crystalline:
• Polymer crystallinity
– (One of the) differences between small molecules and
polymers
– Small molecules can either totally crystallize or become an
amorphous solid
– Polymers often are only partially crystalline
• Why? Molecules are very large
• Have crystalline regions dispersed within the remaining
amorphous materials
• Polymers are often referred to as semicrystalline
Structures of Polymers
• Polymer crystallinity
– Another way to think about it is that these are two phase materials (crystalline,
amorphous)
– Need to estimate degree of crystallinity – many ways
• One is from the density
c s a
%crystallin ity 100
s c a
Factors effecting crystallinity
• Rate of cooling during solidification
• Molecular chemistry – structure matters
– Polyisoprene – hard to crystallize
– Polyethylene – hard not to crystallize
• Linear polymers are easier to crystallize
• Side chains interfere with crystallization
• Stereoisomers – atactic hard to crystallize; isotactic, syndiotactic –
easier to crystallize
• Copolymers – more random; harder to crystallize
Polymer Crystallinity
Polymers rarely 100% crystalline
• Difficult for all regions of all chains to
become aligned crystalline
region
• Degree of crystallinity
expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.
amorphous
region
3
MOLECULAR WEIGHT & CRYSTALLINITY
• Molecular weight, Mw: Mass of a mole of chains.
• Tensile strength (TS):
--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.
• % Crystallinity: % of material that is crystalline.
--TS and E often increase
with % crystallinity. crystalline
--Annealing causes region
crystalline regions
to grow. % crystallinity amorphous
increases. region
4
Polymer Crystallinity
Polymer crystals
– Chain folded-model
• Many polymers crystallize as very thin platelets (or lamellae)
• Idea – the chain folds back and forth within an individual plate
(chain folded model)
• Crystalline regions
– thin platelets with chain folds at faces
– Chain folded structure
Single Crystals
• Electron micrograph – multilayered single crystals (chain-
folded layers) of polyethylene
• Single crystals – only for slow and carefully controlled
growth rates
6
Semicrystalline Polymers
• Some semicrystalline
polymers form spherulite
structures
• Alternating chain-folder
crystallites and
amorphous regions
• Spherulite structure for
relatively rapid growth
Spherulite rates
surface
7
Structures of Polymers
• Polymer crystals
– More commonly, many polymers that crystallize from a melt form
spherulites
• One way to think of these – the chain folded lamellae have
amorphous “tie domains” between them
• These plates pack into a spherical shape
• Polymer analogues of grains in polycrystalline metals/ceramics
Photomicrograph – Spherulites in Polyethylene
Cross-polarized light used
-- a maltese cross appears in each spherulite
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Chain complexity decreases crystallinity Ordered tacticity increases crystallinity
Bigger side groups are less crystalline
Branching reduces crystallinity
Effect on geometry
Natural rubber and synthetic rubber provide an example to illustrte the effect of macromolecular
Geometry on crystallisability.Both are polyisoprenes with structures as shown below.
Natural rubber, cis isomer, Synthetic rubber, trans isomer,
bend back gives coiled str. rod like str. enables to pack
in orderly manner
Rapid conformational change due to ease of rotation around single bonds occurs if groups as
(– CO–O–), (–O–CO–O–), and (–C–N–) are introduced into the main chain.
Molecules with polar side groups (–CN, –Cl, –F, or –NO2) exhibit polar bonding. The
bonding energies of such dipoles or polarizable units are in the range between
hydrogen bonding and van der Waals bonding. If these groups occur regularly along
the chain (isotactic and syndiotactic), the resulting polymers are usually crystalline and
have higher melting points than polyethylene
Crystallinity and intermolecular forces
Intermolecular forces can be a big help for a polymer if it wants to form crystals. A good example
is nylon. You can see from the picture that the polar amide groups in the backbone chain of nylon
6,6 are strongly attracted to each other. They form strong hydrogen bonds. This strong binding
holds crystals together.
Factors Affected by Crystallinity
The degree of crystallization (volume fraction of crystalline regions in a polymer) affects the
optical, thermal, and mechanical properties of a polymer
Optical properties
• Semicrystalline polymers can be recognized easily because they are opaque,
light is not transmitted through the polymer; rather, it is reflected or scattered by the
crystalline planes
• amorphous polymers are clear: visible light can pass through them
Thermal properties – Semicrystalline polymers will have a definite melting point range at
which the crystalline volume is destroyed; amorphous polymers do not have a defined
melting range because they are already without any crystallinity
Mechanical properties – as a polymer’s crystallinity increases, so also will its level of
secondary bonding. This in turn increases the stiffness (elastic modulus) and strength of the
polymer. On the other hand, ductility declines as crystallinity increases.
Disadvantages of Crystallinity
• While crystallinity is a powerful tool for improving strength and stiffness, such
strengthening is almost always directional – that is, the properties are not the same in all
directions.
• A crystalline polymer will be much stronger in the direction of molecular alignment, and
much weaker at right angles to that alignment.
• Such materials, whose properties are not the same in all directions, are called anisotropic.
