.Lec. 11 Miscibility of Polymer Blends…………………………………………..….Eng. Auda Jabbar Ms.

Lec-11
Miscibility of Polymer Blends
Miscibility: Capability of a mixture to form a single phase over certain
ranges of temperature, pressure, and composition.
The miscibility term describes the homogeneity of polymer mixtures at
some temperatures. Miscibility can be influenced by various factors such
as morphology, crystalline phase, intermolecular interaction, and
reduction of surface tension.
Notes:
1. Whether or not a single phase exists depends on:
♦ The chemical structure
♦ Molar-mass distribution
♦ Molecular architecture of the components present.
2. The single phase in a mixture may be confirmed by:
♦ Light scattering
♦X- ray scattering
♦ Neutron scattering
The miscibility of two polymers is depending on the specific
interactions between polymer chains. This can be explained by the factor
of entropy in the following equation, which represents the second law of
thermodynamics.
GM = HM - TSM
where, ΔG = change in free energy, ΔH = change in enthalpy, ΔS =
change in entropy, T = absolute temperature.
For a homogeneous miscible blend the Gibbs free energy of mixing
requires a negative value. For high molecular weight polymer blends, the
gain in entropy is negligible. Hence, the free energy of mixing can only
be negative if the heat of mixing is negative. This means that the mixing
must be exothermic, which usually requires specific interactions between
the blend components. These interactions may range from strongly ionic
to weak and non-bonding, including hydrogen bonding, ion-dipole,
dipole-dipole, and donor-acceptor interactions.
Based on the miscibility, three types of blends can be distinguished;
1- Completely miscible blends
2- Partially miscible blends
3- Fully immiscible blends

Partially miscible blends, in which a part of one blend component is

dissolved in the other, exhibits normally good compatibility and fine
phase morphologies. However, fully immiscible blends exhibit a coarse
phase morphology having a sharp interface and a poor adhesion between
both blend phases. This is the reason for often observed poor properties
of immiscible blends, which strongly depend on the size and distribution
.Lec. 11 Miscibility of Polymer Blends…………………………………………..….Eng. Auda Jabbar Ms. C

of the phases.

Where: A: Immiscible system, B: Fully miscible system , C:Partially

miscible system
Miscibility Window:
Range of copolymer compositions in a polymer mixture, at least one
component substance of which is a copolymer, that gives miscibility over
a range of temperatures and pressures.
Notes:
1. Outside the miscibility window immiscible mixtures are formed.
2. The compositions of the copolymers within the miscibility window
usually exclude the homopolymer compositions of the monomers
from which the copolymers are prepared.
3. The miscibility window is affected by the molecular weights of
the component substances.
4. The existence of miscibility windows has been attributed to an
average force between the monomer units of the copolymer that
leads to those units associating preferentially with the monomer
units of the other polymers

Methods of Investigating Miscibility:

.Lec. 11 Miscibility of Polymer Blends…………………………………………..….Eng. Auda Jabbar Ms. C

Equation 1 provides an abstract definition of what miscibility means in

terms of thermodynamics; from it the state of miscibility of a polymer
pair cannot be obtained.
GM = HM - TSM…………………..(1)
In practice, the miscibility of a polymer pair is defined by the method
that is used to test it. In other words, it is defined in terms of degree of
dispersion, phase morphology or degree of interaction between the
components.
The most common method to establish polymer miscibility is
Differential Scanning Calorimetry (DSC), with which determination of
the glass transition temperature (Tg) or the depression of the melting
temperature allow one to obtain details of the mixing.
Completely miscible blends consist of one homogeneous phase. This
type of blend exhibits only one glass transition temperature (T g), which is
between the Tg s of both blend components with a close relation to the
blend composition.

In some cases, it is necessary to use other experimental techniques. The

optical microscopy is used to study the spherulitic superstructure of
polymer crystals from the melt and explain the relationship between
morphology and crystal growth rate.
In addition, Small-angle light scattering (SALS) and Small-angle X-ray
scattering (SAXS) are used to study the morphology of crystalline /
amorphous polymer blends.
The miscibility of homopolymer/copolymer blends has been successfully
described by the binary interaction model. The most common specific
intermolecular interactions occuring between two different polymer
chains are: hydrogen bond, ionic bond and dipole-dipole interactions
.Lec. 11 Miscibility of Polymer Blends…………………………………………..….Eng. Auda Jabbar Ms. C

In Table 1.1 are displayed several experimental methods used to

characterize blends. These methods can be divided in three Categories:

EXAMPLES
Ex 1: Let me use an example to illustrate. Two polymers that do actually
mix are polystyrene and poly(phenylene oxide).
As you can see, both of these polymers have aromatic rings. As you may
know, aromatic rings like to stack up like little hexagonal poker chips.
For this reason, these two polymers like to associate with each other. So
they blend very nicely. There are a few other examples of polymer pairs
which will blend. Here is a list of a few:
poly(ethylene terephthalate) with poly(butylene terephthalate)
poly(methyl methacrylate) with poly(vinylidene fluoride)
But most of the time, the two polymers you want to blend won't be
miscible. So you have to play some tricks on them to make them mix.
One is to use copolymers.
.Lec. 11 Miscibility of Polymer Blends…………………………………………..….Eng. Auda Jabbar Ms. C

 Polystyrene doesn't blend with many polymers, but if we use a

copolymer made from styrene and p-(hexafluoro-2-hydroxyisopropyl)
styrene, blending is a lot easier.
You see, those fluorine atoms are very electronegative, and they're
going to draw electrons away from all the nearby atoms. This leaves the
alcohol hydrogen very lacking in electrons, which means it is left with a
partial positive charge. So that hydrogen will form strong hydrogen bonds
with any group with a partial negative charge. Because of this, it's easy to
form blends of this copolymer with polycarbonates, poly(methyl
methacrylate), and poly(vinyl acetate)
Ex2: There's another way copolymers can be used to help polymers
blend. Let's consider a random copolymer of styrene and acrylonitrile.
This copolymer will blend with poly(methyl methacrylate) (PMMA).
This is where it gets weird. PMMA won't blend with
either polystyrene or polyacrylonitrile.
So why does the random copolymer blend with PMMA? The
explanation is something like this:  the styrene segments and the
acrylonitrile segments of the random copolymer may not like PMMA, but
they like each other even less. The styrene segments are non-polar, while
the acrylonitrile segments are very polar. So, the styrene segments and
the acrylonitrile segments blend into the PMMA to avoid coming into
contact with each other.
Making Your Own Blends
Blends are usually made in two ways. The first way is to dissolve two
polymers in the same solvent, and then wait for the solvent to evaporate.
(presuming your two polymers are miscible).
While this method works fine in the laboratory, it could get expensive if
you tried to do this industrially. Solvents aren't cheap, and if you're going
to evaporate hundreds or thousands of gallons of them, you'll be paying a
lot of money. Not to mention the effects on the environment of putting so
much of your toxic solvents into the air, or the extra cost of recapturing
all that solvent so it could be reused. So for making blends in large
amounts, you heat the two polymers together until you're above the glass
transition temperatures of both polymers. At this point they will be nice
and gooey, and you can mix them together like a cake mix. This is often
done in machines such as extruders. When your material cools, you'll
have a nice blend, again, presuming your two polymers are miscible.
.Lec. 11 Miscibility of Polymer Blends…………………………………………..….Eng. Auda Jabbar Ms. C