Polymer

Science II
Dr A Ndiripo

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Mechanism
and kinetics
of
crystallization

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 Crystallization depends on the number of
points mainly on
(a) Nucleation
(b) Rate of growth and also depends on
temperature, nature and structure of the
polymer i.e., branched and linear,
Mechanism and
prethermal history of melt and additives
Kinetics of
which determine the crystallization.
crystallization

There are two main processes.

(a) Nucleation and
(b) Growth.

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 (a) Nucleation: Nucleation is a process of
development of nuclei within the liquid material.
Nuclei are basically the center of growth of crystals.
There are two types of nucleation.
(i) Homogeneous nucleation: This is the most
common type of nucleation in low molecular
Mechanism weight polymer. This is spontaneous nucleation,
and Kinetics which comes about as a result of attainment of a
particular temperature of the liquid material.
of The homogeneous nucleation does not
necessarily take place throughout the process of
crystallization crystallization. Rate of crystallization, = Nt, where
N is the number of nuclei produced. In this
process not all nuclei produced will be able to
grow into crystals. Process of nucleation depends
on the thermal energy of the system.

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 (ii) Heterogeneous nucleation:
(a) Impurities of foreign bodies: Nucleation that
is based on the presence of impurities of foreign
bodies within the system i.e., minute particles of
catalyst, additives, fillers etc., Here the nucleation
Mechanism takes place through out the process. This is as a
result from the impurities becoming centers of
and Kinetics crystallization, which will take place at different
temperature. Crystals formed as a result of
of heterogeneous nucleation are weak because the
crystallization materials that form the centers of the crystals are
foreign, thus no mutual bonds are formed
between them and the material that come
around the nuclei or crystal center.

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 (b) Deliberate heterogeneous nucleation: Impurities are put into the
system, which will activate the nucleation process. These nucleation
agents are added to the system in order to cater for crystallization to
take place at lower temperatures. Generally, the impurities are added at
a particular range of temperatures that are actually suitable for the
system.
Mechanism (b) Growth: Rate of growth depends on the rate at which the
macromolecules are aligned to build the crystals. It can grow in one,
and Kinetics two or three dimension. The growth of crystals also depends on
(i) the chemical nature of the polymer,
of (ii) the temperature range of crystallization

crystallization (iii) the rate of nucleation i.e., number of nuclei that are present in the
system. The more nuclei present in the system, the smaller the size
of crystals and vice versa.
Crystals stop growing when it infringes to another growing crystal.
These little centers growing when they infringe on each other, they stick
or join to form one mass. The growth of the centers creates unit cells
which than join to form a single crystal.

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 Polymers do not undergo isothermal crystallization but
undergo non-isothermal crystallization. Isothermal
crystallization occurs in lower molecular weight substance
such as water.
Basic equation for kinetics of crystallization is the Avrami
equation.
Kinetics of It attempts to express the kinetics of crystallization. It is
only applicable to part of some non-isothermal
crystallization crystallization.
Crystallization can be divided into two categories,
(i) primary and
(ii) secondary.
Primary crystallization can be prescribed by using Avrami
equation for macromolecules.

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 The Avrami equation can be expressed as follows;
WL
=e
WO
WL = mass of melt at time t
W0 = initial mass
The amount of polymer at time t:
Kinetics of a=1–e
where a = amount of material (%) that has crystallized
crystallization Ko = rate constant
t = time
n = 1, 2, 3, 4 are called Avrami's index.
Characterized by nature of nucleation.
1 = fibril; 2 = disk; 3 = spherulite; 4 = shear

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 The Avrami equation can be expressed in terms of volume as
follows:

Vt − V
=e
V0 − V

Kinetics of Vt = Volume at time t

V∞=
crystallization
Now: 1-a = e-
ln (1 -a) = -Kotn
log [ - ln (1 - a)] = log Ko + n log t

plot a graph of log [-ln(1-a)] against log t which should look like
the graph below.

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 The Avrami equation can be expressed in terms of volume as
follows:
Vt − V
=e
V0 − V

Now: 1-a = e-

Kinetics of ln (1 -a) = -Kotn

log [ - ln (1 - a)] = log Ko + n log t
crystallization
plot a graph of log [-ln(1-a)] against log t which should look
like the graph below.

Log [-ln (1-a)

log Ko Gradient = n

log t 10
Determination of
crystallinity
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Techniques of determining
crystallinity

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X-ray diffraction
Crystalline polymers give concentric circles, which are regular as well
as very clear.
For amorphous polymers, blurred vision like a blob observed.
Linear amorphous polymers have (a) a glassy physical state and (b)
liquid physical state.
An amorphous polymer can be likened to a plate of spaghetti or
likened to a plate of worms.
The difference between these two is the motion.
In the latter, there is some form of segmental movement not a
wholesome movement.
At low temperature, the movement is slow compared to high
temperature.

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 X-ray diffraction

Amorphous Crystalline

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X-ray diffraction
The glassy state exists at lower temperature, which is described as the
amorphous state.
But as the temperature is increased, liquid form is attained, giving the
range in which amorphousness predominates.
This means amorphous state is confined within the glassy and liquid
state.
Different polymers have different Tg. The physical properties i.e., flow,
glassiness, brittleness do not change even if temperature goes below Tg.
The amorphous polymer will not crystallize even if the temperature is
lowered.
Only rapid cooling of polymer solution gives crystalline state. This type of
method called quenching.

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Determination of crystallinity
Amorphous State:
The region whereby an amorphous or semi-crystalline polymer cannot crystallize, even if
we induce such conditions as nucleation that cause crystallization.

Amorphous Linear Polymers:

There are five (5) different stages through which the polymer said to be within the
amorphous range.
These stages are peculiar to all amorphous polymers.
Any one of these five stages is indicative of amorphousness.
A study of the changes in modulus against the temperature will indicate these five changes.

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Amorphous Linear
Polymers
Region or state:(a)glass state (b)leathery state (c) rubbery
state (d) rubbery flow (e) viscous flow.
Relaxation
(a) Glassy state: Region of relatively high modulus. This is the modulus
region of lowest temperatures. There is no motion in the (Er)
polymer as far as the unit movements are concerned. The A B C D E
elastic deformation is not possible as the units are frozen. In
glass region, there is no polymer structure change, but
Glassy Leathery Rubbery Rubbery Viscous
difference in physical change. There are polymers which are state state state flow flow
processed around Tg especially those that are soft.
Temperature (K)

(b) Leathery state: Temperature in this region increases from

glassy state and in this state there is a macromolecular
motion- inter or intra molecular motion. There is a tendency
of softening and have a degree of elasticity. This region is
very small and occupies a small range of temperature. The
glass state molecules are loosening because of motion.

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Amorphous Linear
Polymers
(c) Rubbery state: Rubbery state occupies the longest range of
temperature. As the temperature is higher than glassy state, motion of
molecules has increased considerably. High degree of elasticity has Relaxation
been observed. As temperature has increased, one can assume the modulus
flow, but still at this stage viscosity is relatively high and no visible flow (Er)
has occurred. There are polymers that are processed within the
rubbery state. The wider the range of temperature for a given stage, A B C D E
easier it becomes to process the polymer.
Glassy Leathery Rubbery Rubbery Viscous
(d) Rubbery Flow Region: In this region, viscosity relatively low,
state state state flow flow
therefore polymer can flow. The temperature is higher than the
previous stages; hence the motion and elasticity increase. The graph Temperature (K)
approaches to plateau showing that there is a minimal change in
property (modulus) as the temperature increases.

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Amorphous Linear
Polymers
(e) Viscous region: The region where a lot of
processing methods are applied, since the Relaxation
modulus
polymer is now in melt form and viscous. (Er)

The temperatures are relatively high which A B C D E

lower the viscosity hence motion increases.
Glassy Leathery Rubbery Rubbery Viscous
Most common amorphous polymers will pass state state state flow flow
through all these stages. Temperature (K)

N.B. Adding plasticizer or fillers can change Tg

of a polymer.

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Amorphous Linear
Polymers
What is Tg?
It is a glass transition temperature. It
is an average temperature at which
the viscosity of the polymer reaches
about 1013 poises i.e., the viscosity of
the polymer is very high causes not to
flow.
It is a movement transition of liquid
state of aggregation to a solid state
that does not form crystals but glassy
state.

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Amorphous Linear
Polymers
Factors affecting the Tg:

1. Molecular weight
2. General structure of polymer
3. Packing density of macromolecules
4. Additives
5.Tacticity
6. Plasticizer.

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Factors affecting the Tg

1. Molecular weight:
Tg of the polymer increases with increase in
molecular weight.
In the event of polymer being flexible, additives
are added to increase the Tg, thus increasing the
molecular weight and the rigidity.

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Factors CH2 CH2 very flexible T-105°Co
g = -105°C
-105

affecting the Tg CH2 CH less flexible Tg = -10°C

o
-10°C
-10
CH3

CH2 CH
2. General structure of polymer: Linear TTg
polymer has low Tg while crossed linked rigid g = 100°C
1000
or branched polymers have high Tg.
Tg can be improved by addition of
additives. e.g., Vulcanization CH2 CH
3. Packing density of macromolecules:
COOCH3 Tg 00
Tg = 0°C
Orderly and disorderly arrangement of
macromolecules i.e., packing of the
molecules affect the Tg. Packing of the
CH3
molecules will determine the amount of CH2 C TTg 1050
g = 105°C
energy needed to break the bonds.
COOCH3

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 4. Additives: Specific additives control the Tg
of a particular polymer.
5. Tacticity: Tacticity affect the close packing
of the macromolecules, rotation of system
and thus gives a particular range of Tg.
6. Plasticizers: Plasticizers are used to
Factors affecting the increase or to decrease the Tg and must be
miscible in polymer. e.g., Tg of PVC must
Tg decrease to reduce the rigidity from 81 to 0

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Factors affecting the Tg

William, London and Ferry (WLF) looked at the Tg of a polymer

in the presence of a given plasticizer whose Tg is known.

Tg / K
Tg =
V f ( plasticiser )

Where K = solubility constant ; Vf = free volume of plasticizer

The higher the Vf, the higher the Tg.

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 Morphology of
Domain amorphous polymers
(crystalline
region)
As we have already seen in the previous lecture, the
morphology of amorphous polymer is determined by
Entanglement X-ray diffraction. There are three important things
are observed in the model. (The model is called Yeh
Tie chains motel).
Amorphous
region (a) Domain: A region of reasonable orderliness within
an amorphous system (similar to crystalline state).
(b) Tie chains: Chains that join the domains.
(c) Amorphous regions: This is the tail end of
macromolecules, which are in complete randomness.
 Softest part (or defect) of a crystalline polymer
Morphology is the amorphous region i.e., the most
venerable part of the crystal.
of amorphous This amorphous region or section has been
determined by free volume (Vf). Free volume is
polymers an unoccupied region in a crystal. The
alignment or packing of molecules determines
crystallinity (LRO) or amorphousness (SRO).
The packing of the macromolecules is
determined by the temperature at which
polymer is exposed.

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Morphology of
amorphous polymers
Vf = V T - V0

Vf = volume of macromolecules at a particular

temperature
and is described as an empty volume.
VT = volume at given temperature
V0 = volume at absolute zero
Vf = V T - VW
VW = volume of a specific mass at the same
temperature with V
VT = volume at given temperature.

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The end
Up next, Viscosity

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