Polymer Blends and Alloys Dr.

Ammar Al-kawaz

Polymer Blends Processing

Polymer processing: is an engineering specialty concerned with the operation carried out on
polymeric materials or systems to increase their utility. This field can be divided into three
categories:

(i) Modification (including mixing).

(ii) Forming, the processes that fix the shape of the products.
(iii) Finishing, painting, joining.

Morphology development
Polymer-polymer melt blends usually start in the solid state as millimeter sized pellets,
powder, or flakes, and are then heated and sheared inside an intensive mixing device such as
an extruder or batch mixer. These millimeter size domains melt and break up into micrometer
or nanometer sized domains during the initial softening stages.

After this initial stage, depending on the composition of the two components, a processing
phase inversion may occur, i.e., the minor phase (the component in lower concentration),
softens first and becomes the matrix phase initially. After the major component softens, once
it has sufficient melt concentration, the phases invert and the minor phase becomes the
dispersed phase. If the major phase softens first and initially forms the matrix, no phase
inversion will be seen.

Figure 1 Important mechanisms in morphology development during polymer blending of nylon/ethylene-

propylene rubber blends. Initially a sheet morphology is formed, and the dispersed phase domain size decreases
sharply (note logarithmic scale for y axis). A processing phase inversion may occur before breakup and
coalescence mechanisms take over, leading to a stable drop size. The drop size can change by an order of
magnitude because of compatibilization via reactive blending or by adding premade copolymer .
Polymer Blends and Alloys Dr.Ammar Al-kawaz

In the final stage of polymer blending, a balance is established between drop breakup and
coalescence so that a stable morphology is formed and the final morphology depended on
polymer rheological properties and processing parameters. Stabilization of the morphology
during and after processing can be achieved using compatiblizers. Two main types of
compatibilizers used in polymer blends are premade block copolymers and compolymers
formed through in situ reaction between functionalized polymers. Of the two, the latter is
practiced more in industry.

Initial morphology
It was found that the dispersed phase breaks up by stretching into sheets and these sheets
subsequently broke up into smaller domains. Figure (2) is a summary of work by Scott,
Macosko, Sundararaj, and coworkers showing how a pellet deforms into a sheet and
subsequently breaks up into droplets.

Figure 2 Schematic showing morphology development mechanisms during polymer blending process. Sheets
are broken into droplets, and then the final morphology is dependent on whether compatibilization was used.

The figure also shows the effect of stabilization on final drop size. Most of the significant
morphology change occurred within one length/diameter (L/D) of extruder of the first point of
melting in a twin-screw extruder, and within the first minute of mixing in a batch mixer. For
single-screw extruders, the sheet breakup may occur over a longer section of the extruder
before droplets are seen. Once domains reach the micron size scale, they may be stretched
into filaments and are then broken into droplets. At this size scale, interfacial forces become
important and pull in the edges of the stretched domains, giving cylindrical or filament type
morphology.
Polymer Blends and Alloys Dr.Ammar Al-kawaz

The stretching and breaking up of filaments is due to the combined effect of high shear zones
and low shear zones in the mixer. The domains are stretched in the high shear zones and then
relax and break up in the low shear zones via Rayleigh type instabilities. It may be possible to
form drops directly from sheets but only at very low shear rates.

When polymer blends are prepared from a mixture of solid pellets or powder, the melting
order of the components is important in determining the morphology development. If the
component in lower concentration, the minor component, softens first, then it will initially
form the matrix surrounding the pellets of the major component. As higher temperatures are
reached during processing, the major component reaches sufficient concentration in the melt
to envelop the minor component and the major component becomes the matrix. The
mechanism of the processing phase inversion (sometimes referred to as inversion of phase
continuity during processing) is shown schematically in Figure (3).

Figure 3 Phase inversion mechanism. (a) Sheets are pulled off the softening pellets near the softening transition
of the major phase. (b) The sheets form lamellar domains inside the minor phase and (c) break up into irregular
pieces (the minor phase is also breaking up at this point) until (d) phase inversion occurs during processing
through coalescence of the major phase domains.

Scott and Joung, studied the effect of the viscosity ratio (ηr = ηminor/ηmajor) on phase inversion,
particularly at early mixing times. They reported a qualitative difference in torque traces,
depending on the viscosity ratio. For ηr > 0.1, the time to phase inversion was relatively
constant; however, for ηr <0.1, the time to phase inversion increased as the viscosity ratio
decreased.

Final morphology
For different applications, different types of morphology are sought. For example, for barrier
properties, a lamellar structure is required, whereas for impact properties, a droplet-in-matrix
Polymer Blends and Alloys Dr.Ammar Al-kawaz

morphology is preferred. Filament morphology may be desired for transport applications or

for applications where nonisotropic properties are required. Here, we will focus on droplet-in-
matrix final morphologies.

Breakup and Coalescence Balance

Tokita, suggested that an equilibrium drop diameter occurs from continuous breakup and
coalescence of the dispersed phase. Coalescence of drops is shown schematically in Figure
(4). Fortelny and coworkers, found that the amount of coalescence in blends depends on
matrix phase viscosity and dispersed phase volume fraction. However, this was for a
quiescent blend without mechanical stress.

Figure 4 Idealized depiction of coalescence in polymer blends. Drops are brought close to each other by the
shear field, and then the matrix film between the drops thins.

Effect of Copolymer on Coalescence

It has been shown that the particle size decreases when premade copolymers or reactive
polymers are used. The particle size is seen to decrease when low concentrations of
copolymer compatibilizer are added to a blend, and a critical compatibilizer concentration
exists above which there is no change in particle size. This suggests that there is a point where
the copolymer saturates the interface and the addition of any more compatibilizer will have no
effect.

When the dispersed phase concentration is increased in uncompatibilized blends, the particle
size increases, but for blends containing premade or in situ copolymers, the particle size
remains fairly constant. This observation suggests that coalescence is suppressed by the
addition of copolymers.

There were two major theories proposed to describe the suppression of coalescence.
Sundararaj and Macosko, described a steric interaction between droplets due to the copolymer
at the interface, shown in Figure (5a). Milner and Xi, suggested that a local concentration
gradient was created when two drops came together leading to a Marangoni stress that slowed
the rate of film drainage between the drops, thereby suppressing coalescence (Figure 5b).
Polymer Blends and Alloys Dr.Ammar Al-kawaz

Figure 5 Mechanisms for suppression of coalescence in compatibilized blends. The copolymer may reduce
coalescence effects by (a) steric repulsion of interacting drops or (b) creating a surface tension gradient
(Marangoni forces).

Effect of processing and material parameters on morphology

Many researchers have tried to change the blend morphology using processing parameters
such as shear rate (related to r/min), temperature, mixing time, mixer type, and composition.
Among these, the most important parameter is blend composition. The other processing
parameters, for the most part, have been found to have much less effect on morphology. Part
of the reason is that the dispersed phase size scale changes from millimeters to microns within
a very short period. The final domain size is about 1 mm for the majority of uncompatibilized
polymer blends regardless of processing conditions. However, subtle changes in particle size
can have important consequences for mechanical properties, and therefore, there have been
many studies about the effect of processing parameters on morphology.

Effect of Composition
Increasing the composition typically increased particle size up to the co-continuous
morphology region which could easily affect on the final blend properties. It was found
that increasing the composition typically increased particle size up to the cocontinuous
morphology region. Sundararaj and Macosko, showed that the particle size increased with
concentration of dispersed phase due to coalescence in uncompatibilized blends. At low
Polymer Blends and Alloys Dr.Ammar Al-kawaz

concentrations, the particles reached a limiting size. This limiting size should correspond
to the dilute solution limit; i.e., the stable size of a single drop in a matrix. At higher
concentrations, cocontinuous blend morphology is found. The concentration range of the
cocontinuous region depends on several factors, including viscosity ratio and interfacial
tension.

Effect of Shear Rate

The customary expectation is that the dispersed phase domain size will decrease with
increased shear rate. Even when considering the shear thinning nature of polymer
viscosity, the shear stress continues to increase with increasing shear rate so drop size
should decrease at higher shear rates. As the shear rate was increased. During mixing,
Plochocki et al., observed that the drop size decreased initially as the shear rate was
increased, and then the drop size actually increased at higher shear rates.

Effect of Mixing Time

Dispersed phase domain size decreases very rapidly in the initial mixing stages. After 1
min in the batch mixer, there is very little change in the morphology. Mixing for up to 10
min in the batch mixer showed very little change from the morphology seen at 1 min
Mixing for longer times actually led to coarsening, and particle size increased between 10
and 20 min of mixing.

Because the polymer blend inherently has high viscosities and low interfacial tension, the
particle size changes rapidly from millimeter size to a micron- or nanosize. However, once
it reaches this stable size, the morphology does not change significantly upon further
mixing.

Effect of Temperature
Temperature can have varying effects on the polymer morphology. Thomas and
Groeninckx, report an increase in particle size with temperature for a nylon/EP (ethylene-
propylene) rubber blend and this may be due to a decrease in the matrix phase nylon
viscosity at higher temperatures.

Polymer blend forming

For all polymers, significant changes in microstructure take place during and after
forming, affecting molecular orientation crystallinity and crystalline morphology. In
addition, in the case of polymer blends, blend morphology is usually affected. All these
changes may profoundly influence the product properties. Polymer forming involves a
number of physical and sometimes chemical changes that need to be understood.

Polymer forming began with the chemical modification of natural polymers .

In forming operations, the material must flow to be shaped, and solidify while retaining
the desired shape. Analysis of plastics forming involves defining a number of elementary
Polymer Blends and Alloys Dr.Ammar Al-kawaz

steps, viz., solids handling, melting, mixing, forming, etc. In order to analyze the
material’s behavior, three distinct stages may be considered:

1- Plastication, during which the polymer changes state from solid to liquid.
2- Forming, during which the polymer is formed into a specifi ed shape by flowing
under pressure,e.g., into molds or through dies.
3- Solidification, during which the material solidifies, and possibly undergoes other
post-forming operation such as demolding, trimming, cutting, polishing, etc.

Molten polymers show constant viscosity (a Newtonian behavior) only in the low strain
rate region. At higher shear rates, the viscosity generally decreases with increasing rate of
deformation, what is know as a pseudoplastic behavior. The viscosity of synthetic
polymers is generally high, resulting in large pressure buildups in processing equipment.
The viscoelastic nature of polymers manifests itself during processing in several ways,
e.g.,

(i) Resulting in extrudate swelling at the die exit.

(ii) Stabilizing stretching operations.
(iii) Causing flow instability leading to extrudate distortions.

Modern processing equipment usually employs an Archimedes-type screw that transfer

the solid polymer (powder or granules) and causes it to melt progressively through heat
transfer from the barrel and heat generation by viscoelastic dissipation of the energy
introduced by the screw rotation.

Figure 6 Archimedes-type screw

The processability window of a polymer system is defined as the processing conditions

that will yield acceptable products. The window is not defined by a single set of
conditions, but rather it may be represented schematically by an area on a processing
diagram.

For example, a processing window for the extrusion process is shown in Figure (7). The
curves illustrate limits of the process. Line 1 indicates the maximum screw rotation speed
of the extruder, Curve 2 represents the torque limitation of the drive system (region to the
right and below of curve exceeds the allowable torque on the drive system). Curve 3
Polymer Blends and Alloys Dr.Ammar Al-kawaz

represents the maximum temperature allowable to avoid degradation. Line 4 indicates the
minimum screw rotation speed to achieve the minimum throughput dictated by the
economics of the process.

Figure 7 Schematic representation of the processing window for the extrusion process.

Forming Polymer Blends

This section aims at discussing the behavior of blends from a general point of view, looking at
the impact of blending on processability, flow induced morphology and the effect of forming
on properties.

Processability
Blending is increasingly carried out to improve processability. When immiscible polymers are
blended, the blend viscosity rarely follows the additivity rule. For example, blending ABS
with PC improves significantly processability of the latter. Another way to reduce viscosity
and improve polymer processability is to lower molecular weight. This, however, has
detrimental effects on mechanical properties, e.g., modulus or toughness. Fortunately, in many
instances, the loss in toughness can be minimized by the addition of a second component at
little or no cost in the ease of processing. For example, if optical clarity is not essential, the
molecular weight of PC can be reduced, enabling easier processing and the toughness can be
maintained by addition of an elastomeric impact modifier.

In general, blends require tighter control over the process parameters. Processing temperature,
for example, has been shown to infl uence strongly the performance of blends. Using too high
processing temperatures was shown to affect the structure and thus to be detrimental
[Menges,1989]. Increasing the melt temperature during injection molding of a
thermoplastic/elastomer system resulted in an increase of the relaxation peak of the elastomer,
thus a decrease of impact strength.
Polymer Blends and Alloys Dr.Ammar Al-kawaz

Flow-induced Morphology
A flow field can induce a number of changes in multiphase systems. These changes will affect
either the drops or the whole system. On the one hand, drops can:

i) Undergo deformation from a spherical shape to ellipsoids or fibrils,

ii) Break up into smaller ones

or

iii) Coalesce when they collide.