Polymers

~ 1m
03 . nm
10
4
chain units long molecules
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
O
CH
2
OH
HO OH
O
thin, flexible
polyethene
apolar
hydrophobic
thick, rigid
cellulose
polar
hydrophylic
~ 10nm
coiled
O
CH
2
OH
HO OH
O
O
CH
2
OH
HO OH
O
H
C
H
H
C
H
H
C
H
H
C
H
C
H
H
C
H
C
H
H
C
H
HCH
entanglement
Cross Links
cross links make a polymer insoluble
crystalline
(no diffusion)
amorphous
with some space
open, that allows
motion of permeants
0 < crystallinity < 1
depends on the
polymer and its history
dimensions ~ 10 nm
Crystalline and Amorphous
10
8
10
6
10
4
modulus of
elasticity
E
N m
2
200 300 400 500
T
g
T
m
glass rubber liquid
temperature
T
K
glass transition
melting
temperature
rigid creeping
flow
10
10
10
2
with cross
linking
Glass Transition Point
10
8
10
6
10
4
modulus of
elasticity
E
N m
2
200 300 400 500
T
g
temperature
T
K
10
10
slow cooling:
lower glass point
long in
between
short relaxation times
Freezing in
polymer (1) solvent (2)
solvent
activity
a
2
10
2
10
0
volume fraction
c
2
10
1
10
0
10
1
10
2
polymer and solvent
fit on a 3D lattice
factor 2.71
a
V
V
2 2
2
1
1
1 =
|
\

|
.
|
|
\

|
.
|
c c exp
V V
2 1
<<
linear
Flory-Huggins
V
V
2
1
10
2
10
3
10
4
solvent
activity
10
2
10
4
10
6
10
0
10
2
10
0
10
0
10
2
volume
fraction
c
2
mole
fraction x
2
a
2
activity is a simple function
of the volume fraction

strong volume and non-

ideality effects if we use
mole fractions
Do not use the
Polymer to define
Mole Fractions
a
V
V
2 2
2
1
1 1
2
1 =
|
\

|
.
|
+

(
c c _c exp
non-ideality parameter
_ > 0
solvent and polymer
dislike each other
_ = 0
solvent and polymer
are similar
solvent and polymer
attract each other
_ < 0
solvent
activity
a
2
10
2
10
0
volume fraction
c
2
10
1
10
0
10
1
10
2
_
2
1
0
-1
demixing!
Non-ideality
Swelling (1)
a B
V
V
C
2 2 1 1
2
2
1
1 3
= + +

(
c c _c c exp
B n
c
~
1
2
number of chain units
between each cross link
a cross linked polymer:
little springs under an
internal stress
solvent
Swelling (2)
1.0
0.1
0.01
0.0 1.0 2.0
0
1
2
swelling parameter
gels, protein separation media
reverse osmosis
pervaporation
gas separations
(high pressure)
_ =
c
2
B
V
V
C
2
Solubility of Vapour in Polymer
activity of vapour 2 activity of 2 in polymer
' =
-
a
p
p
2
2
2
a B
V
V
C
2 2
2
1 = + +

(
c _ exp
( )
c
1
1
equilibrium
' = a a
2 2
c
_
2 2
2
2
1
1
=
+ +

(
-
p
p B
V
V
C
exp
Henry coefficient

Distribution between Solvent and Polymer
polymer (1)
solvent (2)
solute (3)
' = c
1
0
' c
2
large
' c
3
small
c
1
c
2
c
3
equilibrium calculation:
' = a a
2 2
' = a a
3 3
a
V
V
B
V
V
C
3 3 1
3
2
2
3
1
1 3
1 = +
|
\

|
.
|
+

(
c c c c exp
swelling: Fig 15.10
' = '
|
\

|
.
|
'

(
a
V
V
3 3
3
2
2
1 c c exp
c
c
3
3
'
=constant
volume distribution
(Nernst) coefficient