28/11/2014

Thermal Transitions in Polymers

Crystallization
Melting and
Glass transition

Crystallization and Melting

What happens to a polymer when its

cooled slowly from the melting
temperature?
If the chain structure is regular, it will
crystallise below its melting temperature
with an abrupt change in volume.

G H TS
At high temperature, the overall free
energy change for crystallization is
positive and the material would not
crystallize. But at lower temperatures,
Overall G is negative and
crystallization is feasible.

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Crystallization and Melting

Tg

Tg

But if a structurally irregular polymer (atactic polystyrene) is

cooled, then crystallization cannot occur, but instead, in a
certain temperature range, there is a change in slope of the
volume/temperature curve. The mid-point of this range is
called the glass transition temperature Tg.

Crystallization and Melting

Well above Tg, the material appears to be a liquid melt, while

well below it the material is glassy in its properties (relatively
rigid and brittle). Around the transition it is sort of in-between,
a soft glass or a stiff, permanently deformable rubber.
If a polymer is cooled too rapidly it will get to the Tg and
"freeze" before it has a chance to crystallize.
It is possible to prepare all crystallizable polymers in the
glassy state by quenching from the melt.

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Crystallization of Polymers

Crystallization in polymers is process in which an ordered

structure is produced from a disordered phase, usually a melt
or dilute solution.
When temperature is reduced below the MP, there is tendency
for the random tangled molecules to become aligned and form
small ordered region called nuclei and the process itself is
called nucleation.
The second step of the crystallization is the growth whereby
crystals nuclei grow by the addition of further chains.

Nucleation and Growth of Polymers

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Crystallization and Melting

Nucleation is classified as being either homogenous or

heterogeneous.
During homogenous nucleation in a polymer melt or solution,
small nuclei form randomly throughout the melt. However most
of the cases of polymer crystallization occur by heterogeneous
nucleation on foreign bodies such as the dust particles or the
walls of the vessel.

Crystallization and Melting

When all other factors are kept constant, the number of nuclei
formed depends on temperature of crystallization (Tc).
At small undercooling, (smaller T), nucleation tends to be
scattered, and during melt crystallization a relatively small
number of large spherulites will form.
On the other hand, when undercooling is increased, many more
nuclei form and a large number of small spherulites are
obtained from the melt.

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Rate of Crystallization

The growth of the polymer crystals takes place by the addition

of the macromolecular chains within crystals which are
normally lamellar.
Crystal growth will lead to change in the lateral dimension of
the lamellar during crystallization from solution or the change
in spherulites radius during melt crystallization.
Change in linear dimension of the growing entities at a given
Tc is linear with time, so spherulites radius r will be related to
time t through an equation,
r
r vt , v
t
Where v is known as the growth rate. This equation is valid
until spherulites touch each other after certain growth. The
change in linear dimension of lamellae obeys a similar eq.

Rate of Crystallization

It is found that the growth rate v

is relatively low at crystallization
temperature just below the MP of
the polymer, but as the supercooling is increased there is a
rapid increase in v.
But there is a maximum rate of v
and further lowering of
temperature causes a reduction in
v.
Growth rate at a particular
temperature increases with
decrease in the molar mass of the
polymer.

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Rate of Crystallization
Reading the curve from left to right, the peak in v is due to two
competing effects;
The thermodynamic driving force for crystallization will
increase as the crystallization temperature is lowered.
As the temperature is reduced there will be an increase in
viscosity and transport of material to the growth point will be
more difficult and so v peaks and eventually decrease as the
temperature is reduced, even though the driving force
continues to increase.

Rate of Crystallization

The crystallization curves can be

broken down into three parts.
There is an initial induction period
during which the primary nuclei are
formed. These primary nuclei are
the smallest crystalline entities that
are stable enough to allow further
growth at that temperature.
It is followed by a period of fast spherulite growth called primary
crystallization. As the spherulites fill the volume of the sample
and impinge one another, crystallization continue at much slower
rate, this is called secondary crystallization.

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Overall Crystallization Kinetics

If a polymer melt of mass Wo is cooled below the Tc, the spherulite will
nucleate and grow with time. If nucleation is assumed homogenous, and if
the no. of nuceli formed in a unit time per unit volume (rate of nucleation) is
a constant N.
The total no. of nuclei formed in time interval dt will be NWodt/L where
L is the density of the liquid polymer.
After time t, these nuclei will have grown into spherulites of radius r. The
volume of each spherulite will be 4/3r3 OR
4
volume 3t 3 , (as r t )
3

If the density of spherulite material is s then mass of each spherulite is

M v
4
M 3t 3 s
3

The Avrami Equation

The total mass of the spherulite materials, dWs present at any

time t, and grown from the nuclei formed in the time interval,
dt, will be given by;
4
dt
dWs 3t 3 s NWo
3
L

By integration from 0-t to calculate the total

mass of the spherulites from all nuclei after time t, is given as
t

dWs 3

t s NWo

3 3

4 s NWo t
dt
3 L
0
t

Ws

Ws N 3 s t 4

Wo
3 L

dt

,which can be integrated to give

(1)

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The Avrami Equation

Alternately this can be expressed in terms of the mass of

liquid, WL remaining after time t, Since Ws+WL=Wo , i.e.
N 3 s t 4
WL
1
Wo
3 L

This analysis is simplified and equations are valid only for

early stages or primary crystallization and must be modified
to account for impingement of the spherulites.
When impingement is taken into account WL/Wo is related to
t through an equation of the form
WL
1 exp(kt 4 )
Wo

(2)

(3)

This equation is known as the Avrami equation and when t is

small, (2) and (3) have same form.

The Avrami Equation

For other nucleation and growth kinetics, the Avrami eq. takes
the forms
WL
n
(5)
1 exp(kt n )
(4) OR c (t ) 1 [exp(kt )]
Wo

Where n is called the Avrami exponent and c(t) is the

degree of crystallinity and k is a constant at a certain
temperature.
If we follow the crystallization process by measuring the
change in specimen volume rather than the mass of spherulite
material, and taking materials initial and final volumes as Vo
and Vf respectively, then

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Crystallization and Melting

Then specimen volume at time t is given by Vt as follows

Vt

WL

Ws

Wo

WL (

Vo V f

)
Wo Wo

(6)

(7 )

Combining (7) and (6),

WL Vt V f

exp(kt n )
Wo Vo V f

And since Vo=Wo/L and Vf=Wo/s , then (6) becomes

Vt V f WL (

(8)

This eq. allows crystallization process to be monitored by

measuring the specimen volume change with time. Normally this
is done by dilatometry.

Mechanism of Crystallization
The Avrami analysis somehow explain the crystallization, it
does not give any insight into the molecular process involved in
the nucleation and growth of the polymer.
The important feature that any theory must explain are the
following characteristics experimental observations.
Polymer crystals are usually thin and lamellar when
crystallised from both dilute solutions and the melt
A unique dependence is found between the lamellar thickness
and crystallization temperature and in particular, the lamellar
thickness is found to be proportional to 1/T
Chain folding is known to occur during crystallization from
dilute solution and probably occurs to a certain extent during
melt crystallization.

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Mechanism of Crystallization

The growth rates of polymer crystals are found to be highly

dependent upon the crystallization temperature and molar
mass of the polymer.
The most widely accepted approach is the kinetics by Hoffman
which has been used to explain the effects observed during
polymer crystallization.
The approach is divided into two stages. Nucleation and
growth
The main parameter for the process is the Gibbs free energy

Mechanism of Crystallization

Lets start by considering primary nucleation first to discuss the

kinetic theory of lamellar thickness and crystal growth rate.
Inorder to find the thermodynamic driving force for the
formation of a primary nucleus consider a simple lamellar
model of a primary nucleus, one whose sides are of equal
length x and whose thickness is I as shown below.

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Mechanism of Crystallization
The free energy of this crystal includes contributions from;
the bulk, i.e. inside of the lamellar where each segment of the
chain sits in an ordered array, minimizing its free energy, and
the surface free energy, e
The sides of the crystal are exposed to solvent or the melt and
thus have a higher free energy than those in the centre of the
crystal.
The top and bottom surfaces have an even higher free energy,
not only due to contact with the solvent/melt but also due to
the bond rotational angles that have a higher conformational
energy than those found in the lattice.

Mechanism of Crystallization

Let the bulk free energy of the crystal be g per unit volume.
At the equilibrium melting point g would be zero and just
below this temperature it would be negative, driving
crystallization.
If we take surface free energy terms ( and e per unit area).
These are actually excess terms, related to the amount by
which the free energy of a segment at the surface exceeds
that of a segment in the lattice.
The free energy of the primary nucleus in term of the
difference between the surface and bulk terms is given as;
Gcryst (4 xl ) (2 x 2 ) e ( x 2l )g

(5)

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Mechanism of Crystallization
During primary nucleating, s few molecules pack side by side
to form a small cylindrical crystalline embryo. This process
involved a change in the free energy since the creation of a
crystal surface which a surface energy will tend to increase G,
whereas incorporation of molecules in a crystal causes
reduction in G.
When the embryo is small the
surface/volume ratio is high and the
overall value of G increases due to
Rapid increase in surface energy.

G=Gembryo-Gmelt

Mechanism of Crystallization

As the embryo grows in size, the surface to volume ratio

decreases and the will be a critical size above which G starts
to decline and eventually free energy will be less than that of
original melt.
The peak in the curve is the energy barrier and at
crystallization temperature there will be sufficient thermal
oscillations to allow it to overcome. The growth then starts
spontaneously once a critical size is achieved as this will cause
G to further decrease.

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Mechanism of Crystallization:
Secondary Nucleation

In secondary nucleation, the growth of polymer crystals takes

place on a pre-existing crystals surface. In this way, less new
surface per unit volume of crystal is created than in the
primary nucleation and hence the activation barrier is lower.
The first step is laying down of the a molecular strand on a
smooth crystal surface.
This is followed by subsequent addition of further segments
through a chain folding process which occurs for flexible
polymer molecules. Whereas extended chains result from more
rigid molecules.
Folding occurs only when there is relatively free rotation about
the polymer back bone.

Mechanism of Crystallization:
Secondary Nucleation
The overall change in free energy for
crystallization

G Gedge G face Gbulk

Gedge 4 xl
G face 2 x 2 e
Gbulk x 2lg

Gcryst (4 xl ) (2 x 2 ) e ( x 2l )g

(5)

Crystallization will only occur when bulk term is larger than

surface terms. Also the crystal can minimize the free energy by
reducing its surface area and maximising the number of
segments within the bulk.

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