Chapter 5

Polymer solutions and blends

5.1

Introduction

5.2

Entropy of binary mixing

5.3

Energy of binary mixing

5.4

Calculation of binodal and spinodal

5.5

Polymer solutions

5.6

Scattering from polymer blends

5.7

Mechanisms of phase separation

5.1 Introduction
Role of polymer concentration

c < c*

c c*

c > c*

dilute solution

semidilute

characteristic
lengthscale:

chains start
to touch

concentrated
solution
characteristic
lengthscale:
mesh size
2

Phase diagram of polystyrene in cyclohexane

one-phase region

experimental phase diagram

of polyisoprene in dioxane
open symbols: binodals
closed symbols: spinodals
phase behavior depends
on polymer molar mass

two-phase region

133 kg/mol

cooling into the two-phase region

demixing into polymer-rich
and solvent-rich phase
upper critical solution temperature
(UCST) behavior common for
polymers in organic solvents

53.3 kg/mol
M. Rubinstein, R.H. Colby. Polymer Physics.
Oxford University Press 2003.
N. Takano et al., Polym. J. 17, 1123 (1985). 3

Phase diagram of a polymer blend

polybutadiene (PB) /
polystyrene (PS) blend
in all cases: MPB = 2350 g/mol
(a) MPS = 2250 g/mol
(b) MPS = 3500 g/mol
(c) MPS = 5200 g/mol
phase separation temperature
depends on molar mass
phase diagram of polymer blends
more symmetric than the one
of polymer solutions
From G. Strobl: The Physics of Polymers, 2nd edition, Springer 1996.
Data from R.-J. Roe and W.-C. Zin, Macromolecules 1980.

Mechanisms of phase separation

volume fractions:

(PS) =0.8

(PS) =0.5

blends of
PS and PBrxS

two ways of
demixing:

nucleation
and growth

spinodal
decomposition

From G. Strobl: The Physics of Polymers, 2nd edition, Springer 1996.

Data from G. Strobl et al., Macromolecules 1986.

Derivation of phase diagram using energy of mixing

Flory-Huggins theory: lattice model

calculate free energy of mixing per lattice site
with respect to the completely separated state:
=

reference state: before mixing

final state

5.2 Entropy of binary mixing

consider a homogeneous mixture of

low-molecular species A and B (volumes VA and VB)
neglect volume change upon mixing =

define lattice site volume v0: smallest unit

(solvent molecule or monomer)

,
+

= 1

volume of each molecule: = 0 , = 0

7

Regular solutions
regular solutions: = = 1

number of lattice sites: =

+
0

number of sites occupied by A molecules:

entropy: = ln

: number of ways to arrange molecules on the lattice

= number of conformations that a molecule can have
for each molecule: =

for each molecule A before mixing: =

8

 entropy of mixing for each molecule A:

= ln ln = ln > 0, because < 0

total entropy of mixing for all As and Bs: = +

= ln + ln

for a regular solution

Generalization to polymer solutions and polymer blends:

regular solution

polymer solution

polymer blend

Polymer solutions and polymer blends

use for generalization: , = ,

,

for regular solutions: = = 1

= ln + ln

for polymer solutions: = 1, = 1

=

ln

+ ln

for polymer blends: , 1

=

ln

+ ln

is large

is smaller

is even smaller

10

 = = 10
= 10, = 1

in all cases: > 0

thus mixing is favored

= = 1

only translational entropy considered

entropy changes due to
changes of chain conformations

were neglected

excluded volume
mixing volume
11

5.3 Energy of binary mixing

consider random arrangement of monomers A
and solvent molecules B on a lattice
assume that there are no correlations!
pairwise interaction energies: , ,
mean-field assumption:
The probability that the neighbor is A or B
is proportional to the average volume fraction
of A or B (A or B), respectively.

12

average pairwise interaction of A / B with one neighbor:

= + , = +
number of nearest neighbors: coordination number
=

avoid double counting

2 + 2 1 + (1 )2
2

13

total energy of A and B before mixing:

0 =

+ 1
2

energy change upon mixing:

0 =

1 2

= 0
energy change upon mixing per lattice site:

= 1 2

2

14

Flory-Huggins interaction parameter

=

2

2

or

2 +

is dimensionless and is a measure of the differences

in pairwise interaction energies between species
> 0 repulsion, < 0 attraction

= 1

15

Helmholtz free energy of mixing

=
=

ln

ln

ln

(1)

ln(1 ) + (1 )

of entropic origin:
promotes mixing

of enthalpic origin:
can promote or
hinder mixing

16

Flory-Huggins parameter
Flory-Huggins theory =
empirically

2

2

=+

: entropic part
/: enthalpic part
polymer
pair
PS/PMMA

0.0129

()

PS/PVME

0.103

-43.0

dPS/PS

-0.00017

1.96

0.117

only low molar masses miscible

phase-separation at high

phase separation for very high

17

Equilibrium and stability

local stability of homogeneous mixture of composition 0
Fmix

energy of two
phases , :
weighted average
of F and F
= straight line
(lever rule)

F
F

F
Fmix

F
F

0
unstable:

2
2

<0

small fluctuations are favorable

and therefore grow

locally stable:

2
2

>0

small fluctuations are unfavorable

and therefore die out again
18