Free energy of polymer mixtures

FmixN / (kBT)

0.1

0.0017
0.0020
0.0022
0.0025
0.0030

NA = NB = 1000

0.0

free energy
for = =

-0.1

-0.2

-0.3
0.0

0.2

0.4

0.6

0.8

1.0

Volume fraction A
between inflection points: unstable, miscibility gap
outside minima: stable
between minima and inflection points: metastable

Metastability
stable for
small fluctuations

-0.02

FmixN / (kBT)

-0.04
-0.06
-0.08
-0.10
= 0.0025
-0.12
0.0
demixing for
strong fluctuations

0.2

0.4

0.6

0.8

1.0

Volume fraction A
2

Free energy of polymer blends

free energy for
certain value of ,
and for = = :

unstable:

two phases

metastable: two phases

stable:

single phase

Temperature dependence

minima and inflection points

binodal and spinodal

considered here: UCST behavior

=+

with > 0

at high temperatures, the solution/

blend is stable at all mixing ratios
at low temperatures ( < ),
miscibility gap, i.e. blend/solution
only stable for asymmetric
compositions
4

5.4 Calculation of binodal line

(1 )
ln +
ln + 1

binodal line:
between stable and metastable phase
connects the minima of the curve:

=0

ln
1 ln(1 )
1

=
+

+ 1 2

=0

for = = :

ln ln(1 )
=

+ 1 2

ln 1
=
2 1

=0

binodal line
coexistence curve

: binodal line

Spinodal line
between metastable and unstable phase
connects inflection points:

2
2

=0

1
1
2
=
+
2 = 0
2
(1 )

1 1
1
+
=0
=
2 (1 )
for = = :
: spinodal line

1
2(1)

Critical point
lowest point on spinodal curve:

1
1
1

+
=0
2
2 (1 )2

critical composition: =
=

1
2

for = = :

1
2

= ,

=0

= 2

Two phases

c is very small,

thus most polymer

blends are not stable

polymer
pair
PS/PMMA
dPS/PS

A
0.0129
-0.00017

B (K)

at 20C

1.96

0.020

0.117

0.00023

Nc at 20C
100
8722
9

5.5 Polymer solutions

= , = 1

1
2

is very low

1
2

is close to 1/2

133 000 g/mol

asymmetric phase diagram

theta temperature at =

1
2

polyisoprene solutions in dioxane:

for 133 000 g/mol at 22C:
miscibility only for
< ~0.02 and > 0.20
for 53 300 g/mol at 22C:
miscibility for all

53 300 g/mol

From Rubinstein, Colby.

Data from N. Takano et al., Polym. J. 1985
10

Upper critical solution temperature (UCST) behavior

using = +
+

with > 0

1
1
1
= +
+
2
2

12
2

1
2

(UCST behavior) and = +

1
2

1
2

highest T of two-phase region:

upper critical solution temperature (UCST)

11

UCST behavior
polystyrene in cyclohexane

270 000 g/mol

250 000 g/mol
89 000 g/mol
43 600 g/mol

PS in CHX

polyisobutylene
in diisobutyl ketone

From Rubinstein, Colby.

Data from A.R. Shultz, P.J. Flory, J. Am. Chem. Soc. 74, 4760 (1952).

12

More complete phase diagram for UCST polymer

consider = +

with

= 0, > 0
*: overlap concentration

excluded volume: = 1 2 3 =

13

Lower critical solution temperature (LCST) behavior

=+

with < 0

decreases with decreasing T

lowest T of two-phase region: lower critical solution temperature (LCST)

mixture of
polyisobutylene
and deuterated
head-to-head
polypropylene

another case: changes sign with temperature

both UCST and LCST observed

example: polystyrene in cyclopentane

From Rubinstein, Colby.

Data from N.P. Balsara: Physical Properties of Polymers Handbook, 1996

14

PNIPAM: A polymer with LCST behavior

Poly(N-isopropylacrylamide) (PNIPAM)
monomer has hydrophobic and hydrophilic groups
delicate balance of interactions with water

special for PNIPAM:

H-bonding also possible among monomers
glass transition temperature < room temperature

15

PNIPAM: A polymer with LCST behavior

N = 430
1 g/L
1 K/min

Temperature (K)

turbid

cloud point

PNIPAM5400

clear

PNIPAM concentration (wt%)

in dilute aqueous solution:

optical transmission decreases strongly at ~32 C
cloud point (binodal) determination by turbidimetry
photos courtesy of M. Philipp
Phase diagram by: Y. Okada, F. Tanaka, Macromolecules 38, 4465 (2005).

16

PNIPAM: A polymer with LCST behavior

high molar mass PNIPAM: 13 106 g/mol
at extreme dilution in H2O: 6.710-4 g/L
2 h waiting time per point

cloud point

in aqueous solution: coil collapsed single chain globule

aggregation of globules turbidity above cloud point

X. Wang, X. Qiu, C. Wu, Macromolecules 31, 2972 (1998)

17

Theoretical explanation for LCST behavior of PNIPAM

PNIPAM in H2O: H2O molecules

bind to PNIPAM in long sequences
hydration is cooperative phenomenon

steric reason:
if one H2O binds to the polar part of the side group, space is created
for next H2O molecule, it is favorable to bind to the PNIPAM monomer
which is next to the first H2O
dehydration of entire sequences of H2O at once

X. Wang,
X. Qiu,I.C.Kaneda,
Wu, Macromolecules
(1998)
F. Tanaka,
T. Koga,
F.M. Winnik,31,
J. 2972
Phys.:
Condens. Matter 23, 284105 (2011).

18

Making use of the collapse transition by cross-linking

water-soluble
water-insoluble

T. Tanaka et al.

application: permeation control

20C:

tryptophan

40C:

19

5.6 Scattering from polymer blends

composition fluctuations in blend in one-phase region scattering
= 0 = ()2

2
=
2

1
1
1
=
+
2

1
=0
determination of the -parameter by measuring = 0 by SANS

the contrast is maximum, if one component is deuterated

20

Ornstein-Zernike scattering function

Extension to finite q-values: random phase approximation
1
1
1
=
+
2
(, ) 1 (, )

where (, ) is the form factor of the ideal chain

Here, a simplified Debye function is used: , 1 +

1
1
2 2

=
+

( = 0) 12 1
more general:

(0)
1+()2

12
2 2

Ornstein-Zernike scattering function

comparison correlation length =

2 (0)
12 1

21

83C: = 9.1 nm
51C:
= 4.5 nm

SANS on blend of polyisobutylene

and poly(ethylene-r-butene) with = 0.5
1

27C:
= 3.3 nm

at high q: 2

0 increases with increasing

LCST behavior (LCST: 95C)

22