Structure and Morphology

?
Into what types of overall shapes
or conformations can polymer
chains arrange themselves?

How do polymer chains interact
with one another.

Into what types of forms or
morphologies do the chains organize

What is the relationship of
conformation and morphology to
polymer microstructure.

What is the relationship of
conformation and morphology
to macroscopic properties.
Gas
Liquid
Solid
(Crystalline)
Solid
(Glass)
Evaporation
Condensation
Crystallization
Melting
Glass
Transition

Temperature
States of
Matter
Solids
Liquids
Gases
Usually consider;
1st-Order Transitions
Gas
Liquid
Solid
(Crystalline)
Small Molecules
States of Matter
V
o
l
u
m
e

Temperature T
c
Cool
Gas
Liquid
Solid
Polymers
No Gaseous
State
Viscoelastic
liquid
Semi-crystalline
Solid
Glassy Solid
Crystallization
Melting
Glass
Transition

Temperature
More complex
behaviour
Crystallizable materials can form metastable glasses.
What about polymers like atactic polystyrene that cannot crystallize?
Observed Behavior depends on:
Structure
Cooling Rate
Crystallization Kinetics
The Glassy State
Glass Transition
Liquid
Gas
Glass
Crystal
V
o
l
u
m
e

Temperature
T
g
T
c
Cool
Liquid
or Melt
Glassy
Solid
Crystalline
Solid
The Issues
Bonding & the Forces between Chains
Conformations
Ordered
Disordered
Stacking or Arrangement of Chains in
Crystalline Domains
Morphology of Polymer Crystals (and things
like Block Copolymers)
Polymer Structure
Bonding and
Intermolecular
Interactions
What are the forces
between chains that provide
cohesion in the solid state?
What determines
how close these
chains pack?
Get out of my space
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

0
Distance
I cant feel you
This is awesome
Repulsive and
Attractive Forces
Potential due to
Repulsive Forces
Potential due to
Attractive Forces
Need to consider balance
between;
Attractive and repulsive
forces
Attractive forces and
thermal energy (motion).
This will be discussed later.
Get out of my space
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

0
Distance
I cant feel you
Potential due to
Attractive Forces
Potential due to
Repulsive Forces
This is awesome
Not as well understood as
attractive forces.
Often assumed that the repulsive part
of the potential varies as 1/r
12
.
Repulsive Forces
Repulsive and
Attractive Forces
Better understood
In many non-polar or weakly polar
systems the potential goes as -1/r
6
.


Attractive Forces
Dispersion Forces
Dipole/dipole Interactions
Hydrogen Bonding
Coulombic Interactions
Increasing Interaction
Strength
Intermolecular and
Intersegmental Interactions
Non Polar
Highly Polar
Polar Forces
- CH - CH
2
-
-

C



N

-

-

-

!-
!+
- CH
2
- CH -
-

C



N

-

-

-

!+
!-
Segments of poly(acrylonitrile)
chains
Dispersion Forces
!+ !- !+ !-
!+ !-
!+ !-
No change in shape of a
symmetric electron distribution
Instantaneous fluctuation
inducing a dipole in a neighbor

Hydrogen Bonds
H - N
C = O
H - N
C = O
H - N
C = O
There is no simple, universally accepted definition of a hydrogen bond, but
the description given by Pauling
**
comes close to capturing its essence;

. . . under certain circumstances an atom of hydrogen is
attracted by rather strong forces to two atoms instead
of only one, so that it may be considered to be acting as
a bond between them. This is called a hydrogen bond

The N-H and C=O groups of nylon (and the polypeptides and proteins)
interact in this manner;
** L. Pauling, The Nature of the Chemical Bond. Third Edition. Cornell University Press, Ithaca, New York, 1960.

O - H O - H O - H
O - H
- C
H - O
C -
Hydrogen bonds form between
functional groups AH and B such
that the proton usually lies on a
straight line joining AH -- B. The
atoms A and B are usually only the
most electronegative, i.e., fluorine,
oxygen and nitrogen
Hydrogen Bonds
H - N
C = O
H - N
C = O
The hydrogen bond is largely
electrostatic in nature
- CH
2
- C -
CH
3

-
-
C
- CH
2
- C -
CH
3

-
-
C
-
Zn
++

- CH
2
- C -
CH
3

-
-
C
-
Zn
++

Coulombic Interactions - Ionomers
+
-
-
-
+
+
+
-
-
-
+
+
+
-
-
-
+
+
+
-
-
-
+
+
The structure of ionomers is actually
far more complicated than this and
the ionic domains phase separate
from the non - polar parts of the
chains into some form of cluster.
Ionomers
Type of Type of
Interaction Interaction
Characteristics Characteristics
Approximate Approximate
Strength Strength
Examples Examples
Dispersion Forces
Dipole/dipole Interactions
(Freely Rotating)
Strong Polar Interactions
and Hydrogen Bonds
Coulombic Interactions
(Ionomers)
Short Range
Varies as -1/r
6
Short Range
Varies as -1/r
6
Complex Form
but also
Short Range
Long Range
Varies as 1/r
About
0.2 - 0.5 kcal/mole
About
0.5 - 2 kcal/mole
About
1 - 10 kcal/mole
About
10 - 20 kcal/mole
Poly(ethylene)
Polystyrene
(simple hydrocarbon polymers)
Poly(acrylonitrile)
PVC
Nylons
Poly(urethanes)
Surlyn
Increasing Interaction Strength Increasing Interaction Strength
SUMMARY
Conformations
Ordered
Disordered
Staggered
Eclipsed
Staggered Staggered Staggered
Eclipsed
Eclipsed
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

(
A
r
b
i
t
r
a
r
y

U
n
i
t
s
)

-180 -120 -60 0 60 120 180
Rotation Angle
Conformations
Conformations;
Or how do Chains
Fold
gauche
trans
trans
trans
Polyethylene
trans
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y


(
A
r
b
i
t
r
a
r
y

U
n
i
t
s
)

-180 -120 -60 0 60 120 180
Rotation Angle
gauche
gauche
Why Doesn't
the Chain
Just Sit in its
Minimum
Energy
Conformation?
e.g. polyethylene
What is the Effect of Thermal Motion ?
How Many Shapes or Conformations are Available to
a Chain ?
Interesting Questions
gauche
trans
trans
trans
How Many Shapes or
Conformations are Available to
a Chain ?

Assume each bond in the chain is only
allowed to be in one of three
conformations, trans, gauche and the
other gauche

Assume each of these conformations
has the same energy

A Simple Estimate
Just one of many conformations or
configurations
How Many Conformations are
Available to a Chain?
The first bond can therefore be found
in any one of three conformations, as
can the second, the third, and so on.
How many configurations are available
to the first two bonds taken together
(ignoring redundancies).

A. 3+3=6
B. 3x3=9
This has 3
possible
conformations
So has this
And this
Another 3
And another
3
3 3
3
3
This has 3
possible
conformations
So has this
And this
Another 3
And another
3
3 3
3
3
How Many Conformations are
Available to a Chain?
Pascals triangle
Bond 1
G
T
G

G
G

T
G
G

T
G
G

T
Bond 2
How many arrangements are there
for a chain with 10,000 bonds ?
For this chain of 10 bonds there are
3.3.3.3.3.3.3.3.3.3 = 3
10
possible
arrangements. Or have we over-
counted?
How Many Conformations are Available
to a Chain Consisting
of 10,000 Bonds ?
The answer would seem to be simple;

3
10,000
=10
4,771

But you have to be careful in doing these types of calculations. You have to
account for redundancies.

Crucial Point; even after accounting for redundancies there are one
hell of a lot of (distinguishable) congurations available to a chain.
So, how on earth can we relate structure, or in this case the absence
of structure, to properties?
The Chain End-to-End Distance
R
It is the enormous number that saves
us as it permits a statistical approach.

But we will need a parameter that
tells us something about the shape of
the chain.
The Chain End-to-End Distance
R
R
The distance between the ends will be equal to the chain length if the
chain is fully stretched out;

But may approach zero if the chain is
squished in on itself forming a compact
ball.

Intuitively, one would expect most chains to lie somewhere between
these extremes.

Redrawn from J. Perrin, Atoms, English translation by
D. L. Hammick, Constable and Company, London, 1916.
.

Random Walks and Random Flights
What is the distance
between the starting
point (first
observation) and the
finishing point (last
observation) after a
walk of N steps ?

Random Walks and Random Flights
R
Random Walks and Random Flights
Consider steps of equal length,
defined by the chemical bonds.
For a polymer chain;
Complications;
A polymer chain is sterically
excluded from an element of
volume occupied by other bits of
itself.

The steps taken by a chain are
constrained by the nature of the
covalent bond and the steric
limitations placed on bond
rotations.


The Freely Jointed Chain
Freely
Hinge
Rotate
What we will assume and
still get the right
answer . . . more or less
The way it really
is . . . more or less
Fix
Rotate
To begin with we are only going to consider
a one- dimensional walk.

Actually, that is all we really need.
Imagine a three dimensional walk projected
onto (say) the x-axis of a Cartesian system

There will be some average value of the
bond length <l>, that we can use*.

We can then sum the contributions of
projections in all three spatial directions
(remember Pythagoras ?) to get the end -to
- end distance R
* This is actually calculated using the same arguments as we are going to use for the random walk!
Random Walks and Random Flights
WEST EAST
+R -R
Ye Olde
English Pub
A One-Dimensional Drunken Walk
What is the average distance
traveled from the Pub for
drunken walks of N steps?
(Assume each step is 1 unit in
length).
Q:
WALK R

1 +30
2 +50
3 -40
4 -50
5 +40
6 -30
. .
. .



.
.
500 300 100 -100 -300 -500
0
100
200
300
400
500
600
R
N
u
m
b
e
r

o
f

W
a
l
k
s

o
f

d
i
s
t
a
n
c
e

R



0
<R> = 0
Intuitive Answer
500 300 100 -100 -300 -500
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
R
P
(
R
)


=

A

e
x
p
(
-
B
R
2
)


x

1
0
4


0
<R> = 0
Probability Distributions
Another way to graph this
is to plot the fraction of
walks that end up a
distance R from the pub.

Each of these values then
also represents the
probability that a walk of
N steps will have an end -
to-end distance R.

This is a probability
distribution, P(R), and if
you know some statistics
you may guess that the
shape of the curve will be
Gaussian (for large N).
(See equation on y-axis).
Well come back to this.
What We Need To Do
+R
-R
START
Determine Distance Traveled
Regardless of Direction
Method:
Determine R for a Whole
Bunch of Walks
Determine <R
2
>
Calculate <R
2
>
0.5

The Root-Mean-Square
End-to-End Distance*
*See Feynman, Lectures on Physics, Vol. 1, Chapt. 6
ONE DIMENSIONAL WALK
For a Walk of One Step:
For the N
th
Step:
<R
2
1
> = 1
or
R
N
= R
N-1
+ 1
R
N
= R
N-1
- 1
R
N-1

or
Feynmans Method
<R
2
N
> = <R
2
N-1
> +1
Square:
Average of Squares:
Recalling:
Then:
<R
2
1
> = 1
<R
2
2
> = <R
2
1
> + 1 = 2
<R
2
3
> = 3 - - - etc.
<R
2
N
> = N
R
2
N
= R
2
N-1
+ 2R
N-1
+ 1
R
2
N
= R
2
N-1
- 2R
N-1
+ 1
One dimensional walk
The Root-Mean-Square
End-to-End Distance
<R
2
>

= N l
2

<R
2
>
0.5
= N
0.5
l
If N = 10,000, l = 1;
<R
2
>
0.5
= 100 ! ! !
R
Random Coils and Rubber Elasticity
What is the most
probable
state ?
How do we calculate a
probability distribution
for the end - to - end
distance regardless of
direction ?
The Radial Distribution Function
A distribution function that describes the
end-to-end distance regardless of direction
can be obtained by fixing one end of the
chain at the origin of a coordinate system
and then finding the probability that the
other end lies in an element of volume
4#R
2
dR. This is the radial distribution
function and is simply given by



R
dR
W(R) = P(R). 4#R
2

The Radial Distribution Function
If a chain in its most
probable state is
stretched, then it
enters a less probable
state
An entropic driving
force to return the
chain to its most
probable state is
created
More on this in
mechanical properties !
500 400 300 200 100 0
0.000
0.001
0.002
0.003
0.004
R
<R >
2
1/2
P ( R )
x
1 0
4
o r
W ( R )
P ( R )
W ( R ) = 4 # R
2
P ( R )
We have figured out a way to
Describe a collection of random
Chains

A qualitative understanding of
Rubber elasticity immediatly
follows

A pathway to more rigorous and
quantitative work is opened up
Crucial Points
Real Chains
< R
2
> = Nl
2
1
+
cos
!
1
-
cos
!
$
%
&
'
(
)
1
+ "
1
- "
$
%
&
&
'
(
)
)
< R
2
> = Nl
2
1
+
cos
!
1
-
cos
!
$
%
&
'
(
)
Fix
(*)
Freely
Rotate
Fix
Hindered
Rotation
Even sterically allowed bond rotation
angles will not be independent of one
another. Local overlap can occur
Real Chains
Overlap - ouch!
Incorporate corrections (using the
Rotational Isomeric States Model)
into a general factor C
+
,
and we can
now write;

< R
2
>= C
+
Nl
2
The Kuhn Segment Length
C
+
=
<
R
2
>
Nl
2
The Flory characteristic ratio

The Kuhn segment length
KUHN SEGMENT
N
K
l
K
2
= < R
2
> = C
+
Nl
2
But what about overlap between parts of the
chain that are topologically distant?
R
Self-Avoiding Walks and
Intramolecular Excluded Volume
A one dimensional self - avoiding walk
R = Nl
R
A two dimensional self - avoiding
walk
R = Nl
<R
2
>
0.5

=
N
0.75
l
Self-Avoiding Walks and
Intramolecular Excluded Volume
While in three dimensions;
In general;
< R
2
>
SAW
0 . 5
=
cons tant. N
v
Where;
v
=
3
d
+
2
<R
2
>
0.5

=
N
0.6
l