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Crystallinity in Polymers

Not all polymer can form crystal

For those that can, the degree of

crystallinity is always less than 100%

Amorphous Solids: Amorphous Retrieved from
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Crystalline Solids: Crystalline solids

have definite and regular geometry
due to the orderly arrangement of
atoms or ions.
Crystalline Polymer Structure

(a) long molecules

forming crystals randomly
mixed in with the
amorphous material

(b) folded chain lamella,

the typical form of a
Retrieved from : on 24th September
2017 crystallized region
Crystallinity and Properties

As crystallinity is increased in a polymer

Density increases
Stiffness, strength, and toughness increases
Heat resistance increases
If the polymer is transparent in the amorphous
state, it becomes opaque when partially
Low Density & High Density
Observations About

Linear polymers consist of long molecules with

thousands of repeated monomers
Crystallization involves folding back and forth of
the long chains upon themselves
The crystallized regions are called crystallites
Crystallites take the form of lamellae randomly
mixed in with amorphous material
A crystallized polymer is a two-phase system
Crystallites interspersed in an amorphous matrix
Factors for Crystallization

moderate solubility is the best
supersaturation leads to sudden precipitation and smaller
crystal size
Factors for Crystallization

Nucleation fewer nucleation sites are better.

Too many nucleation sites lower the average
crystal size.
Source of formation of crystal
Factors for Crystallization

Mechanics- mechanical disturbance are bad

nucleation is severely affected by the
mechanical disturbance.
A lot nucleation sites, not good for
Factors for Crystallization
Time- faster crystallization is not good as slow
Faster crystallization yield poor quality of
crystal because it traps other solute/solvent
inside the lattice crystal structure.
Thermal Behavior of Polymers

(density)-1 as
a function of

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Properties of a polymer can often be

beneficially changed by combining it with
Additives either alter the molecular structure or
Add a second phase, in effect transforming the
polymer into a composite material
Types of Additives by Function

Fillers strengthen polymer or reduce cost

Plasticizers soften polymer and improve flow
Colorants pigments or dyes
Lubricants reduce friction and improve flow
Flame retardents reduce flammability of polymer
Cross-linking agents for thermosets and elastomers
Ultraviolet light absorbers reduce degradation from sunlight
Antioxidants reduce oxidation damage
Thermoplastic Polymers (TP)
Thermosoftening plastic, is a polymer, that
becomes moldable above a specific
temperature and solidifies upon cooling.
Reason: TP polymers consist of linear and/or
branched macromolecules that do not cross-link
upon heating
Thermosets and elastomers change chemically when heated,
which cross-links their molecules and permanently sets these
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Mechanical Properties of
Low modulus of elasticity (stiffness)
E is much lower than metals and ceramics
Low tensile strength
TS is about 10% of metal
Much lower hardness than metals or ceramics
Greater ductility on average
Tremendous range of values, from 1% elongation
for polystyrene to 500% or more for
Physical Properties
of Thermoplastics
Lower densities than metals or ceramics
Typical specific gravity for polymers are 1.2 (compared
to ceramics (~ 2.5) and metals (~ 7)
Much higher coefficient of thermal expansion
Roughly five times the value for metals and 10 times the
value for ceramics
Much lower melting temperatures
Insulating electrical properties
Higher specific heats than metals and
Thermoplastic Application