EBT 335

Polymer blends

Presented by: PL Teh

History and Commercial Importance

Polymer blending has a long commercial history in the rubber, coatings,

and adhesives industries, and it entered the plastics industry a half
century ago.

When plastics processors first tried to blend polymers with each other,
they were shocked to find that most pairs of plastics were immiscible and
had very poor properties.

Plastics chemist reasoned that they must develop miscible

homogeneous system to achieve useful properties.

They did discover a number of polymer pairs that were completely

miscible to give a homogeneous single phase, with polymer properties
proportional to the ratio of the two polymers in the blend, and several
of these were of commercial importance.

They tended to use the terms miscibility and compatibility

interchangeable

Definition:
Term

Definition

Polymer blends

A mixture of at least two polymers or

copolymers

Miscible polymer
blend

Miscibility and homogeneity extend down to

the molecular level, so that there is no phase
separation (Mixtures whose components are
soluble in one another)

Immiscible blend

A blend in which phase separation occurs

(Mixtures whose components are completely
or partially insoluble in one another)
A process of modification of interfacial
properties of an immiscible polymer blend

Compatibilization
Polymer alloys

An immiscible polymer blend having a modified

interface and/ or morphology

Polymer blends vs Polymer alloys

Polymer A

Polymer B

Polymer blends
Miscible Immiscible

Chemical modification
Compatibilizer

Polymer alloys

Why we need blending?

Polymer blending is an alternative approach to
obtaining new materials with desirable properties
based on commercially available polymers rather than
to design and synthesize completely new polymers.
Sometimes we want a material that has the same
properties of one polymer, and some of the properties
of another.
Instead of synthesizing a brand new polymer we try to
mix two polymers together to form a blend with all the
qualities that we want.

Reasons for Blending

Dilute high-cost engineering resin with lowcost polymer

Develop broad property range materials
Form high performance blend from
synergistically interacting polymers
Adjust composition to suit customer
Recycle industrial plastics scrap

Benefits of blending:
Material related benefits:

Providing materials with full set of desired properties at the lowest price
(usually an expensive engineering resin with a low cost commodity
material)

Extending the engineering resins' performance as a market develops

Improving specific properties, eg: impact strength or solvent resistance

Some polymer combinations exhibit properties that are superior to their

parent polymers. This is called synergism, and it is widely used for
toughening of rigid plastics.

Offering the means for industrial plastics waste recycling

Manufacturing related benefits:

Improved processability, product uniformity and scrap reduction
Quick formulation changes
Plant flexibility and high productivity
Reuse of plastics scrap

Example of Immiscible
blend

LDPE/PS blend without a

compatibilizer

LDPE/PS blend with a

compatibilizer

Problems in Polymer Blends

Some of the major issues involved with polymer blending need to be
introduced.
The adverse effects are often so important that the resulting material is
most likely unusable- Immiscible
Blending two immiscible polymers necessarily leads to a phaseseparated material.
There are three inherent problems if the morphology and the
interfaces of the blend are not well controlled:
1. Poor dispersion of one polymer phase in the other.

For most polymer pairs, the interfacial tension is high

Difficult to disperse one phase in the other by melt blending
When the inclusions of the dispersed phase are large, the interfacial
contacts between the two phases are small.
When the material is subjected to a mechanical load, the two phases
are unable to show their best features in a "concerted" manner in order
to respond efficiently.

2. Weak interfacial adhesion between the two phases.

There is little penetration of polymer chains from one phase into

the other and vice versa, and consequently few entanglements are
formed across the interfaces
Failure of the interface between two polymers thus requires only
the breaking of weak Van der Waals bonds, as in the fracture of a
low-molecular-weight polymer.
When they are subjected to an external stress, the interfaces will
most likely fail well before the base polymer components.

3. Instability of immiscible polymer blends.

An immiscible polymer blend is thermodynamically unstable.

The state of dispersion of one phase in another is governed by
both thermodynamics (interfacial tension) and thermo-mechanics
(agitation).

Thermodynamically there are two main classes of blends.

Completely Miscible blends and
Completely Immiscible blends

Experimental evidence indicates that most polymer pairs are

completely immiscible

Note that blends can exhibit complete immiscibility and partial

immiscibility, just as in small molecule systems.

Polymer-polymer miscibility:
Necessary condition for mixing at temperature T
If:

If:

mix

mix

mix

mix

S mix

S mix

Miscible blend

Immiscible blend

Whereby:
H

mix

S mix

Thus

RT

AB

v AvB

2 nk ln 2

mix

Where
Hmix is the enthalpy of the system
vA and vB are volume fraction of polymer A and B
AB is the Flory-Huggins interaction parameter

2 NR ln 2

RT

AB

v AvB

usually positive

Where
Smix is the entropy of the system
n is the number of molecules for either polymer of A and B
N is the number of molecules in moles for either polymer A and B and
k is the Boltzmann constant.

easily becomes positive

immiscible!
very small value

2 NRT

ln 2

If:
If:

mix

mix

mix

mix

S mix

S mix

Miscible blend
Immiscible blend

The second law of thermodynamics:

The energy always flows from the higher to a lower level

There is a natural tendency of any isolated system to
degenerate into a more disordered state.
Example: When things change, they will change from a state
of order to a state if disorder

to change from a state of less entropy to

more entropy

Phase Diagram

Phase diagram in polymer blend:

G > 0: immiscible blend
- Phase separation with inter-phase for
compatible blends and without interphase for incompatible blends.
G 0: miscible blend

Partially miscible blend

G 0 - one phase
G > 0 - phase separation

A immiscible system
B fully miscible system
C partially miscible system

..Phase diagram in polymer blend:

0 - b1: stable composition
b1 - b2: unstable composition
b2- 100: stable composition

A phase diagram for a system exhibiting both

LCST and UCST.
LCST - Lower critical solution temperature
UCST - Upper critical solution temperature

Metastable - A system is in a metastable state when

it is in equilibrium, but it is susceptible to fall into
lower-energy states with only slight interaction.

Spinodal:
Spinodal separates metastable and
unstable regions which determine the
process of phase separation.

Binodal:
Binodal separates miscible and
immiscible.
the border line between the one and
two-phase regimes
The binodal and spinodal meet at the critical point which also represent the
highest temperature of immiscibility in polymer systems.

..Phase diagram in polymer blend:

Phase separation condition for two polymers is
not constant:
Temperature dependent
Composition dependent
Some polymer pairs the phase separate range gets
smaller as temperature increases.
As temperature keep on increasing, that range of
immiscibility will become so small that it will disappear.
The point of temperature at which this happens is called
the upper critical solution temperature (UCST)

But sometimes there are some polymer pairs the range

of immiscibility decreases with decreasing temperature.
The range of temperature gets smaller and at one point
it will disappears as temperature decreases.
This point is called the lower critical solution
temperature (LCST)

As temperature reduces

Morphology changes

T
Ostwald ripening

Coalescence of droplets

Coarser morphology

 A composition that is completely miscible at

both the processing temperature and the
service temperature presents no problems
in terms of changes in morphology and
properties due to processing.
A blend which is immiscible at both the
processing and service temperature,
however, could present difficulties, it would
lead to coalescence of droplets and the
development of a coarser morphology.