Crystallization
Melting and
Glass transition
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.
28/11/2014
Tg
Tg
28/11/2014
Crystallization of Polymers
28/11/2014
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.
28/11/2014
Rate of Crystallization
Rate of Crystallization
28/11/2014
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
28/11/2014
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
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
28/11/2014
(2)
(3)
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
28/11/2014
WL
Ws
Wo
WL (
Vo V f
)
Wo Wo
(6)
(7 )
exp(kt n )
Wo Vo V f
(8)
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.
28/11/2014
Mechanism of Crystallization
Mechanism of Crystallization
10
28/11/2014
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)
11
28/11/2014
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
12
28/11/2014
Mechanism of Crystallization:
Secondary Nucleation
Mechanism of Crystallization:
Secondary Nucleation
The overall change in free energy for
crystallization
Gedge 4 xl
G face 2 x 2 e
Gbulk x 2lg
Gcryst (4 xl ) (2 x 2 ) e ( x 2l )g
(5)
13