Introduction to Multi-Component

Polymer Systems

[Link] – Polymer Engineering

Shenkar College of Engineering & Design

Mixing and Blends Chee 490 19.1

 Polymer Blending & Mixtures
Blends or mixtures are comprised of two or more polymers (and other
materials), and are of commercial interest for a variety of reasons:

– 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.

– 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.

– 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.
Mixing and Blends Chee 490 19.2
 Mixing Low and Synergism

Mixing and Blends Chee 490 19.3

 Introduction
• Polymer mixtures are an important part of many industrial processing applications:
- Polymer melt compounding (mixing)
- Additives and concentrates
- Membrane formation
- Paints and coatings
- Polymer composites
- Toughening of engineering polymers
- Polymer- solvent solutions
- Others

• Interpreting the binary phase diagram predicted by Florry-Huggins theory, review the
importance use of the solubility parameters and the calculated χ parameters

• Looking at de-mixing processes:

– Nucleation and growth
– Spinodal decomposition

• Short view on polymer blends terminology

• Deal with some kinetic and chemical aspects in mixing processes of polymer blends

Mixing and Blends Chee 490 19.4

 FH free energy and phase diagrams

• Polymers are generally immiscible

• This is because the entropy of mixing is greatly reduced compared to

mixing of simple solutions as polymers are 3D objects not point-like
particles

• Note that for coexistence χ ≥ 0.5/M, so the slightest degree of

unfavourable interactions between certain two polymers will cause
phase separation

• Immiscibility of polymers has implications for industrial processes such

as joining, as polymer-polymer interfaces tend to be very weak

Mixing and Blends Chee 490 19.5

 Aside on polymer interfaces

w = 10-30 Å

Mixing and Blends Chee 490 19.6

 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 COMPLETELTY IMMISCIBLE.
– Note that some can exhibit complete miscibility and partial
miscibility, 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.

Mixing and Blends Chee 490 19.7

 Miscibility of Blend Components
Although most polymer pairs are
completely immiscible, polymer
blends can exhibit a range of
phase behavior.

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).

Mixing and Blends Chee 490 19.8

 Miscibility of Blend Components
Phase diagram for polystyrene
(Mw=42,000 to 320,000) +
polycarbonate (TMPC;
Mw=41,000) mixtures as a
function of the weight fraction of
TMPC.

This system exhibits LCST’s

that are a function of
polystyrene molecular weight.

Possible existance of partial

miscibility behavior.

Mixing and Blends Chee 490 19.9

 Blend & mixture Terminology
• Miscible / homogeneous – Mixtures whose components are soluble in
one another, and therefore mix at the molecular level.

• Immiscible – Mixtures whose components are completely or partially

insoluble in one another, leading to multiple phases.

• Compatible – An ill-defined term used for commercially attractive

polymer mixtures that often appear to be homogeneous to the eye
and demonstrate properties superior to their pure components.
Sometimes terms: partial-miscible blends

• 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.

Mixing and Blends Chee 490 19.10

 Immiscible Blends
In immiscible polymer blends, the composition, rheological and
interfacial properties of the components control phase morphology.
This ranges from the more common droplet morphology, to the co-
continuous structures that can be induced in some blends

HDPE + 30 wt% Nylon 6 EPR + 30 wt% PP

Mixing and Blends Chee 490 19.11
 Nucleation vs. Spinodal decomposition

Very characteristic microstructures can be observed in polymer blends which

have separated by the two means:

Nucleation and growth Spinodal decomposition

Mixing and Blends Chee 490 19.12

 Coarsening during Spinodal decomposition

Linerised approximation breaks down leading to increasing length scale

of phase separation

Mixing and Blends Chee 490 19.13

 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.

Mixing and Blends Chee 490 19.14

 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.

Mixing and Blends Chee 490 19.15

 Melt Blending
Melt mixing is a complex process involving melting of the (solid)
pellets, distributive mixing (particle elongation), dispersive mixing and
droplet coalescence.

From Scott and Macosko (1991), Polym. Bull., 26, 341

Mixing and Blends Chee 490 19.16
 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, τ, generated by the flow field
– Resisted by interfacial stress, σ/R of the new smaller droplets

The capillary number, Ca, describes whether a droplet will disperse or

remain stable within a flow field:
τR
Ca =
σ

Mixing and Blends Chee 490 19.17

 Droplet Deformation and Break-up
The value of Ca decreases throughout the melt mixing process, as the
size scale, R of the dispersed phase reduces from that of the original
granule (mm scale) to a that of a fine dispersion (µm scale).
• Dispersion occurs if the
capillary number reaches a
critical value, Cacrit, at
which point the shear
stress begins to compete
with the interfacial stress.

• Residence time within a

given deformation process
must be sufficient to allow
break-up to occur.

Mixing and Blends Chee 490 19.18

 Droplet Deformation and Break-up
The rate of droplet deformation achievable during melt blending is
dependent on the viscosity ratio, λ, between the component
polymers:
ηdispersed
λ=
ηmatrix

Mixing and Blends Chee 490 19.19

 Droplet Coalescence – Structure Stabilization
Holding an immiscible polymer blend above the melting points leads to
a coarser morphology due to droplet coalescence.

Scanning Electron Microscope photographs of the structural coarsening of a blend (holes

have been produced by “etching” (dissolving) the dispersed rubber phase using a solvent)
Mixing and Blends Chee 490 19.20
 Structure Stabilization - Compatibilization

One of the strategies commonly

followed to stabilize the blend
structure, is to prevent coalescence
by adding a block copolymer. Each
block interacts with one of the
homopolymers in the blend, thus
reducing surface tension and
promoting adhesion of the
dispersed phase in the matrix. This
procedure is called
compatibilization and the resulting
blends called “compatibilized”
blends, or “alloys”.
• In-situ reactive compatibilization
within an extruder is a very common
practice
Mixing and Blends Chee 490 19.21
 Structure Stabilization - Compatibilization

LDPE/PS blend without a

compatibilizer

LDPE/PS blend with a

compatibilizer

Mixing and Blends Chee 490 19.22