Polymer Blends & Alloys

Blend Terminology

• Miscible / homogeneous – Mixtures whose components are soluble in

one another, and mix at the molecular level.

• Immiscible – Mixtures whose components are completely or

partially insoluble in one another, leading to multiple phases.

• Compatible – commercially attractive polymer mixtures that often

appear to be homogeneous to the eye and demonstrate properties
superior to their purest components.

• Alloy – A macroscopically uniform physical properties that comprises

a compatible blend, a miscible blend or a multiphase copolymer. It
does not refer to incompatible, immiscible blends.
Polymer Blending
• Blends are comprised of two or more polymers, and are of commercial
interest for a variety of reasons:

Reasons for blending

– If the mechanical properties required for a given application can be met by

blending two polymers (usually an expensive engineering resin with a low-
cost commodity material), then the formulation is less expensive. COST

– If you wish to recycle polymer products, you will likely encounter issues
related to blending, since your polymer sources will vary widely in terms of
purity. PURITY

– 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.
Blending is used for …
• Impact modification of brittle polymers (PVC, PS, PP).
This is done through incorporation of a minor rubbery (elastomeric
phase).
Examples: PVC with acrylonitrile butadiene rubber (NBR), high impact
polystyrene, PP with ethylene propylene rubber (EPR).

• Improvement of processability, solvent and impact resistance and cost

of engineering polymers (polycarbonate - PC, poly phenylene ether -
PPE, polyamides - PA, polyester-PET).
PC/PMMA, PC/PA, PPE/styrenics, PA/poly olefins, PET/PE, PET/PA

• Improvement of properties of bio-based polymers (starch, poly lactic

acid, poly hydroxy alkanoates).
Miscibility of Blend Components
Thermodynamically there are two classes of blends

• In immiscible blends the constituent polymers do not mix, but remain

in separate phases, leading to the formation of a dispersion of one of
the polymers in a continuous matrix of the other.

– 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.

• In miscible blends the constituent polymers mix on a molecular level, to form a

homogeneous material equivalent to a polymer-polymer solution.

The physical, chemical and mechanical properties are generally a weighted average of
the mixture components.
Miscibility of Blend Components

• Although most polymer pairs are completely immiscible, polymer

blends can exhibit a range of phase behaviour.

• LCST = lower critical solution temperature (more common of

this relatively rare phenomena).

• UCST = upper critical solution temperature (often not observed

due to interference of glass transitions).
Immiscible Blends

• In immiscible polymer blends, the composition, rheological and

interfacial properties of the components control phase
morphology.

PP/elastomer =70/30 PP/elastomer =60/40 PP/elastomer =50/50

Production of Blends

• Polymerization: Several reactors in series are used to

prepare a final product that contains a mixture of
polymers.
• Solution casting: The polymers are dissolved in a
common solvent. Blend is produced by evaporating
the solvent and precipitating the resulting polymer
mixture.
• Melt blending: High-shear mixers can generate fine
dispersions, with droplet diameters < 1 μm.
Melt Blending

• Recall the definitions of distributive and dispersive mixing .

• Distributive mixing can be achieved by providing convoluted

flow paths that split and reorient the flow repeatedly .

• Dispersive mixing can be achieved by passing the mixture

through small regions of intense deformation.

See Fig
Melt Blending: Melt mixing is a complex process involving melting of the
(solid) pellets, distributive mixing (particle elongation), dispersive mixing and
droplet coalescence.
Rheology in Melt Blending
Dispersive mixing of molten polymers occurs by
a process of droplet deformation and break-up.
Droplets tend to minimize their surface area to
volume ratio, by adopting spherical shapes.

• Droplet deformation and break-up is:

– Promoted by stresses.
– Resisted by interfacial stress.