Chapter 10

Spinodal Decomposition in Binary Polymer Blends

Mat E 454 | April 22nd, 2014

MOHAMMED ALZAYER
EDWARD BRUNS
XIAOLIN BI

Outline
Introduction
Theory:
Ideal Solution Model
Regular Solution Model
Flory-Huggins Theory
The Cahn-Hilliard Model
Fox Equation

Binary Systems Exhibiting SD:

PMMA/ PMSAN
PMMA/SAN
PEH/PEB
PMMA/PLLA
Incommensurate Films
Composition-dependent heat conductivity system
Conclusion

Introduction [1]

Describing t
ypical
polymer ble
nds phase
diagrams

Lower Boundary:
thermally induced
mixing
Upper Boundary:
thermally induced
demixing
Maximum: Highest T
for mixing (UCST)
Minimum: Lowest T
for demixing (LCST)
[1] Simmons, D. S. (2009).Phase and conformational behavior of lcstdriven stimuli responsive polymers. (Doctoral dissertation, University of

Introduction [1]

Other Behaviors: LCST is the most

There are others:
common but..
(a), UCST only (b),
LCST and UCST curves
with multiple extrema
(c and d). merged LCST
and UCST (e), closed
immiscibility loops (f),
and combinations of
LCST, UCST, and closed
immiscibility loop
behavior (g and h).
Curves may represent
either spinodal or
binodal curves.

[1] Simmons, D. S. (2009).Phase and conformational behavior of lcstdriven stimuli responsive polymers. (Doctoral dissertation, University of

Introduction

To be immiscible, i.e. spinodal

decomposed:
Criteria #1:
2 or more chemically different polymers in in a
shared volume
Criteria #2:
Phase separation between the polymers,
macro-sized regions of similar-chemical
polymer, or single polymer rich regions
dispersed throughout homogenous mixture

The Ideal Solution Model [2]

Obeys Raoults:

1 (solvent) while 2 (solute). a is the activity of the

component, X is the mole fraction, Pi is the vapor
pressure of the solvent before mixing, and Pf is the
vapor pressure of the solvent after mixing

Enthalpy and entropy of

mixing:

[2] Murat, S. (2010).Physical chemistry of polymers:

Thermodynamics of solutions of high polymers. (Doctoral

The Ideal Solution Model [2]

Why does it fail to describe

polymer
blends?
A solution
with a very small solute
weight fraction as well as a small
mole fraction () can hardly deviate
from the ideality.
Polymer solutions consist of
polymeric solutes with high
molecular weights and mole
fractions (99%!)
[2] Murat, S. (2010).Physical chemistry of polymers:
Thermodynamics of solutions of high polymers. (Doctoral

The Regular Solution Model

[3][4]
How does it describe
SD?
Formation of uni-polymer
rich regions or phase
separation of polymers from
a seemingly uniform
matrix/mixture.
Why does it happen?
SD occurs as a result of
compositions lowering
blends Gibbs free energy
[3] Martin, B. (2011).Phase transformations: Nucleation and
spinodal decomposition. MIT. [4] Zang, L.Spinodal Decomposition:
Part 1: General Description and Practical Implications. The

The Regular Solution Model

[3][4]
Notes on the model:
Points where = 0
called spinodes
(inflection points).
Spontaneous phase
separation faces no
thermodynamic barrier.
i.e. controlled solely by
diffusion.
[3] Martin, B. (2011).Phase transformations: Nucleation and
spinodal decomposition. MIT. [4] Zang, L.Spinodal Decomposition:
Part 1: General Description and Practical Implications. The

Flory-Huggins Theory [5][6]

considers a low MW solvent and
a high MW polymer in a lattice:

Where
xi is molar fraction of the component, Z is
coordination number (nearest # of neighbors in lattice), N is
total number of lattice sites, is ~ energy of formation, and
is fraction of lattice sites occupied.

And the Flory Parameter is:

[5] Frank, C. (2001).Flory-huggins model for polymer solutions.

Stanford University. [6] Andersson, C. (2008).Flory-huggins
theory applied in atmospheric aerosol modelling. (Master's

Flory-Huggins Theory [5][6]

Why is commonly used?
It is independent of concentration
It gives a better approximation of a:

Where
is activity of water, is volume fraction
of polymer, and r is chain segment number
(polymer volume to water volume ratio).

[5] Frank, C. (2001).Flory-huggins model for polymer solutions.

Stanford University. [6] Andersson, C. (2008).Flory-huggins
theory applied in atmospheric aerosol modelling. (Master's

The Cahn-Hilliard Model [7]

Why another model?

1) Regular & ideal too simple to model
real cases
2) It considers chemical kinetics
The difference in concentration is
given by

where
c is the concentration , is the amplification
factor of the fastest growing wavelength, t is time, is
wavenumber, and is the dominate wavenumber
during system decomposition.
[7] Bukusoglu, E., Pal, S. K., De Pablo, J. J., & Abbott, N. L.
(2014). Colloid-in-liquid crystal gels formed via spinodal
decomposition.Soft Matter, (10), 1602-1610.

The Cahn-Hilliard Model [7]

Why another model?
Dynamics of the SD modeled as a
function of the depth of the thermal
quench ():

[7] Bukusoglu, E., Pal, S. K., De Pablo, J. J., & Abbott, N. L.

(2014). Colloid-in-liquid crystal gels formed via spinodal
decomposition.Soft Matter, (10), 1602-1610.

Fox Equation [8]

What is it?
Fox Equations among others utilized to
predict Tg

[8] Madbouly, S. A. (2014).Mat E 454: Polymer composites and

processing (Lectures). Iowa State University.

Fox Equation [8]

What is it?
Fox Equations among others utilized to
predict Tg

[8] Madbouly, S. A. (2014).Mat E 454: Polymer composites and

processing (Lectures). Iowa State University.

PMMA/ PMSAN [9]

Preparation:
1) Drying at r.t., 3 days, cast solution in
Petri.
2) Further dried by vacuum for 3 days
at 90 C.
tetrahydrofuran
PMMA on a hot
PMSAN
(31 wt% at
3)
Meltpressing
chamber,
acrylonitrile)
constant
T.
, PDI
14000 g/mol,
96500 g/mol, 2.26
4)
After annealing,
thinDSC
film(10
obtained,
2.1 Optical,
Techniques:
t=40
mm.
C/min),
Time-resoloved light
scattering (632.8 nm He-Ne)
[9] Madbouly, S. A., & Ougizawa, T. (2004). Spinodal decomposition
in binary blend of PMMA/ PMSAN: Analysis of early and late stage
demixing.Macromolecular Chemistry and Physics,205(7), 979986.

PMMA/ PMSAN [9]

Some observations: Near critical

composition 75:25. 1-phase (150 C)
to 2 phases (180 C). Connectivity not
clear until 20 mins. Annealing time
increased, contrast of 2-phase
increased. Late stage of SD (50 mins),
co-continuity lost result of coarsening.
fragmented particles.
10 min

20 min

50 min

[9] Madbouly, S. A., & Ougizawa, T. (2004). Spinodal decomposition

in binary blend of PMMA/ PMSAN: Analysis of early and late stage
demixing.Macromolecular Chemistry and Physics,205(7), 979986.

PMMA/ PMSAN [9]

Notes: LCST, miscible at a limited T

range, miscible at entire w range (1
common , Fox), increases a lot with T
(slope shift from negative to a small
positive) agrees with LCST.

[9] Madbouly, S. A., & Ougizawa, T. (2004). Spinodal decomposition

in binary blend of PMMA/ PMSAN: Analysis of early and late stage
demixing.Macromolecular Chemistry and Physics,205(7), 979986.

PMMA/SAN [10]

Why add nanoparticles?

Ability to control morphology, improve
electrical properties, change phase
separation T and phase diagram.
Behavior becomes more complicated.
One of the polymers absorbs the other,

PMMA
SAN
changing
the thermodynamics.
, PDI

, 1.64

, 2.08

96

105

[10] Gao, J., Huang, C., Wang, N., Yu, W., & Zhou, C. (2012). Phase
separation of PMMA/SAN blends in the presence of silica

PMMA/SAN [10]

Ajji and Choplins Equation to get

Ts and Tb:

[10] Gao, J., Huang, C., Wang, N., Yu, W., & Zhou, C. (2012). Phase
separation of PMMA/SAN blends in the presence of silica

PMMA/SAN [10]
Effect of size: The bigger the particle,
the lower the Tb. Micron sized hardly
have an effect (Tb ~ Tb pure). Tb increases
with more particles added.
SiO2 content
SiO2 diameter

3%
12

3%
30

(nm)
Tb (C)

172. 171.8

3%
1000

1%
30

5%
30

169

167

171.3

174.5

[10] Gao, J., Huang, C., Wang, N., Yu, W., & Zhou, C. (2012). Phase
separation of PMMA/SAN blends in the presence of silica

PEH/PEB [11]

Contains
Contains
Thickness and
Thickness and
shape
shape

PEH
110000g/mol
110000g/mol
2 mol% hexane
2 mol% hexane
0.5 mm
0.5 mm

PEB
70000g/mol
70000g/mol
15 mol% butane
15 mol% butane
dog bone
dog bone

Preperation: Heat treatments

(separation at 130 oC), quenched into
liquid nitrogen causing fracture, etched
by 1% potassium permanganate in a
mixture of sulfuric acid and
orthophosphoric acid for contrast.
[11] Yang, L., Yanhua, N., Wang, H., & Wang, Z. (2009). Effects of
spinodal decomposition on mechanical properties of a polyolefin
blend from high to low strain rates.Polymer,50(13), 29902998.

PEH/PEB [11]
High strain rate (0.01s-1): interfacial
relaxation between phase domains
cannot be detected.
Low strain rate (0.001s-1): drop of
tensile properties with separation when
Tc is low. The effect disappears at high
Tc.
[11] Yang, L., Yanhua, N., Wang, H., & Wang, Z. (2009). Effects of
spinodal decomposition on mechanical properties of a polyolefin
blend from high to low strain rates.Polymer,50(13), 29902998.

PMMA/PLLA [12]
In the figure: Tappingmode AFM images of
monolayers mixtures
(25/75,50/50, and 75/25
weight fraction) deposited
on mica at surface
pressure 1, 5, 10, and 12
mN/m. Fibrils at surface
pressure higher than 10
mN/m are crystallized
[12] Sato, G., Nishitsuji, S., & Kumaki, J. (2013). Two-dimensional phase
PLLA
lamella.
separation
of a poly(methyl
methacrylate)/poly(l-lactide) mixed
langmuir monolayer via a spinodal decomposition mechanism.The

PMMA/PLLA [12]
2D: Analogous to 3Ds nucleation and
growth
Spinodal ring: FFT shows doughnut
like pattern in inserts. Phase-separated
structures possess concentration
fluctuation with a specific :
Early Stage: wavelength of dominant
mode is independent of t, whereas the
concentration
fluctuations,
(t),
grow
[12] Sato,
G., Nishitsuji, S., & Kumaki,
J. (2013). Two-dimensional
phase
separation of a poly(methyl methacrylate)/poly(l-lactide) mixed
with
time
langmuir
monolayer
via a spinodal decomposition mechanism.The

PMMA/PLLA [12]

Intermediate stage: described by

both and (t) growing with time.
Final stage: increases with time,
while (t) already saturates to its
equilibrium value.

[12] Sato, G., Nishitsuji, S., & Kumaki, J. (2013). Two-dimensional phase
separation of a poly(methyl methacrylate)/poly(l-lactide) mixed
langmuir monolayer via a spinodal decomposition mechanism.The

Incommensurate Films [13]

Top: 2.5 m of film

surface at 160 min,
majority
perpendicular
lamellar morphology
(PS dark, PMMA light)

Bottom: SCFT calculation of mixed

morphology intermediate state.
[13] Peters, R. D., Pawel, S., Matsen, M. W., & Dalnoki-Veress, K.
(2013). Morphology induced spinodal decomposition at the surface of
symmetric diblock copolymer films.ACS Macro Letters,2(5), 441

Composition-dependent Heat
Conductivity Systems [14]
Quench conditions: structure
resulting from SD varies with quench
condition.
Example: in the figure, the left wall is
quenched, while the right wall is
insulated

[14] Molin, D., & Mauri, R. (2008). Spinodal decomposition of binary

mixtures with composition-dependent heat conductivities.Chemical
Engineering Science,63(9), 24022407.

Composition-dependent Heat
Conductivity Systems [14]
stands for heat
conductivity
ratio, while is
a characteristic
length and D is a
mass diffusivity
parameter.
Overall, the 105
2/D translates
between 1-10
seconds. NLE, the
lewis number,
stands for the
ratio of thermal
to mass
diffusivity.
[14] Molin, D., & Mauri, R. (2008). Spinodal decomposition of binary
mixtures with composition-dependent heat conductivities.Chemical
Engineering Science,63(9), 24022407.

Conclusion
From this presentation: we
can conclude that spinodal
decomposition is important in
polymers science.
We can take it further:
improve the miscibility of
blends by introducing a third
polymer (compatibilizar).
Its beyond this chapter:
no longer binary, but rather
ternary.