Thermal Transitions: Crystallization,

Melting and the Glass Transition

• This lecture: Crystallization and Melting

• Next Lecture: The Glass Transition Temperature

Today:

• Why do polymers crystallize in a chain

folded fashion?

• Why do polymers melt over a range of

temperatures?

• What are the factors that affect the Tm?

Chapter 8 in CD (Polymer Science and Engineering)

Thermal Transitions
Temperature

Viscoelastic
liquid

Glass
Crystallization Transition
Melting

Semi-crystalline
Glassy Solid
Solid
Crystallization and the
Glass Transition

Volume
Cool

Liquid
Glassy or Melt
Solid

Crystalline
Solid Temperature
Tg Tc
 Kinetics, Crystallization
and the Glass Transition
Volume

Volume
Cool Quickly
Cool Quickly
Liquid
Glassy or Melt
Solid
Does not Cool Slowly
Crystallize !

Temperature
Temperature
Tg
Tg Tg
Crystallizable Polymer
Non-Crystallizable Polymer
 Polymer Crystallization
WHAT DO WE KNOW FROM EXPERIMENTAL OBSERVATION ?

• Crystallization occurs relatively

slowly

• At high undercoolings

• And results in the formation

of chain folded lamellae
 Polymer Crystallization
SMALL MOLECULES
Specific Cool
Volume
What is
Melt undercooling ?

Heat

Tc Tm Temp
POLYMERS
Specific Cool
Volume

Semi-crystalline
Solid
Heat
Tc Tm Temp
 Crystallization Kinetics
General Features
Degree of
Crystallinity Secondary
• Induction period - formation of primary Crystallization
nuclei

• Primary crystallization - a period of fast

Primary
spherulitic growth Crystallization

• Secondary crystallization - a period of

slower crystallization that occurs once the Induction Period
spherulites have impinged on one another (Nucleation Step)

Time
Thermodynamic Considerations
The free energy of this primary nucleus is given by

∆ Gcryst = (4xl)σ + (2x )σ e - (x l)∆ g

2 2

• The last term represents the free energy that we would obtain if
all the segments were in the bulk.
• The first two terms are the excess free energy that must be
“added in” to account for those segments at the surface.

l
σe

x
σ

x
 Extended Chain Crystals
and Annealing
Thermodynamically most stable form

Courtesy of I.R. Harrison, Penn State

Crystals irreversibly thicken on annealing - so they

would like to get to the extended form
 Critical Nucleus Size

So why don‛t polymers crystallize in the

extended chain form to begin with?
To answer this let‛s calculate the critical
nucleus size.

0
Tm = T
m
 Critical Nucleus Size
The critical nucleus size is given by
the values of l and x that minimize
∆Gcryst;

∂∆G = ∂∆G = 0
∂l ∂x
Solving the two simultaneous
equations

l = 4σ e Nucleation
∗

∆g at temperature T
 Critical Nucleus Size

Substituting for ∆g;

∗ 4σ e Tm0
l =
∆h f ∆T l*

where ∆T is the undercooling;

0
∆T = T − Tc
m

Note the inverse

dependence of fold period
Critical Nucleus Size
on ∆T.
Also, at the equilibrium melting temperature, Tc = Tm0, and only
lamellae with infinite fold periods could grow.
The Rate of Primary Nucleation

An expression for the rate ∗ 4σ e Tm0 4σ e Tm0

of nucleation can also be l = =
∆h f (Tm − T ) ∆h f ∆T
0
obtained:
0 2 l** For l* large,∆T vnuc
const.σ σ e[ Tm ]
2
nuc
νnuc ~ exp− has to be small
∆h f kTc[ ∆T ]
2 2
At small ∆T
Vnuc is small
Note that the rate of
nucleation is vanishingly small
at low undercoolings. Only
nuclei with relatively short fold
periods (compared to chain
length) form at an appreciable ∆∆T
rate.
 Primary Crystallization:

• Once a nucleus has been formed

growth is predominantly in the
lateral direction.
• There is a considerable increase
in the fold period behind the
lamellar front during
crystallization from the
melt

Crystallization
 The Crystalline
Melting Temperature

Semi-crystalline
Solid

Heat

Melt
 Characteristics:
Melting Temperatures
Temperature (0 C) 40

20

Melting is Complete
0

Melting Starts
-20 Crystallization

-40
-50 -40 -30 -20 -10 0 10

Temperature of Crystallization
The Melting Temperature
of Polymer Crystals

 2σ e 
Tm = T 1 − 
0

 l∆hf 
m
Temperature

Tm0

l
 Factors that Affect the Melting
Temperature of Polymer Crystals

- CH2-
CH2
-CH2
CH2
-CH2
CH2
- Why?

-
Tm ~ 1350C

H -
O= N- -N
-

- H
C- -C

-
- =
O
Tm ~ 3700C
The Effect of Chemical Structure

∆Gf = ∆Hf - T∆Sf

And at Equilibrium
∆Gf = 0

Hence Τm = ∆Hf /∆Sf

Equilibrium
at temperature Tm
Τm = ∆Hf /∆Sf

The subscript “f” stands for fusion

Intermolecular
Interactions

- CH2 -CH2 -CH2 -

CH2 CH2 CH2
-

-
Tm ~ 1350C
O

CH2 - CH2 -CH2 C

- - =
CH2 CH2 N
-

-
-

-
H
Tm ~ 2650C

Is this nylon 6
or nylon 66 ?
 The Effect of Intermolecular
Interactions

OK, now it‛s your turn ! CH2 - CH -

A. -
Supposing you could synthesize such beasts, would

-
Cl
you expect syndiotactic poly(propylene) or
syndiotactic PVC to have the higher melting point?
B. - CH2 - CH -

-
CH3
Entropy and Chain Flexibility

Flexible Τm = ∆Hf /∆Sf

Stiff
Entropy and Chain Flexibility

∆Sf S = k lnΩ

∆Sf = k (lnΩmelt - lnΩcrystal ) = Large

Conformational Entropy and
the Melting Point

Tm = ∆Hf / ∆Sf
∆Sf = k (lnΩmelt - lnΩcrystal)
= Small
Entropy and the Melting Point

- CH2 - CH2 -
Polyethylene Tm ~ 1350C

- CH2 - CH2 - O -
Tm ~ 650C
Poly (ethylene oxide)

- CH2 - CH2 - -
Tm ~ 4000C
Poly (p-xylene)
Entropy and the Melting Point

- CH2 - CH2 -
Polyethylene Tm ~ 1350C

- CH2 - CH -

-
CH3 Tm ~ ?
Isotactic Polypropylene

- CH2 - CH -
-

Tm ~ ?

Isotactic Polystyrene
∆S1 The Effect of
Diluents

∆S2 > ∆S1

∆S2
The Effect of C o p o l y m e r i z a t i o n
and Molecular Weight