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Introduction
From a commercial point of view, semicrystalline polymers are of
prime importance. Among the four mostly used commodity plastics (PE,
PS, PVC and PP), only PS is completely amorphous.
The three semicrystalline polymers account for the largest volume of
the commercial polymer blends. A majority of the polymer blends
contains at least one crystalline component. Most polymer blends are
immiscible.
The immiscible semicrystalline polymer blends may be classified in
terms of:
1- Crystalline/crystalline systems in which both components are
crystallizable.
2- Crystalline/amorphous systems in which only one component can
crystallize, being either the matrix or the dispersed phase.
The properties of the finished articles made from immiscible blends are
governed by the morphology created as a result of the interplay of
processing conditions and inherent polymer characteristics, including
crystallizability.
Therefore, a scientific understanding of the crystallization behavior in
immiscible polymer blends is necessary for the effective manipulation
and control of properties by compounding and processing of these blends.
In table below, an overview is given of a number of important
immiscible crystallizable blend systems.
Factors Affecting the Crystallization Behavior of Immiscible
Polymer Blends:
The discussion on the crystallization behavior of neat polymers would
be expected to be applicable to immiscible polymer blends, where the
crystallization takes place within domains of nearly neat component,
largely unaffected by the presence of other polymers.
However, although both phases are physically separated, they can exert
a profound influence on each other. The presence of the second
component can disturb the normal crystallization process, thus
influencing crystallization kinetics, spherulite growth rate, semicrystalline
morphology, etc.
►Important factors are:
1- Molecular structure and molecular mass of the components
2- Blend composition
3- Type and degree of dispersion of the phases in T the melt state
4- Phase interactions (nature of the interface, migration of nuclei, etc.)
5- Melt history (Tmelt , tmelt , etc.),
6- Crystallization conditions (for example Tc, cooling rate, etc.),
7- Physical crystallization conditions (surrounded by melt or solidified
material).
These factors influence the crystalline morphology development,
resulting in changes of crystallization parameters such as:
1- Nucleation density (N)
2- Spherulite growth rate (G)
3- Overall crystallization rate (K)
4- Total degree of crystallinity (Xc)
5- Semicrystalline morphology, i.e., shape, size and texture of the
spherulites, interspherulitic boundaries, etc.
To discuss these topics in a systematic way, a distinction will be made
between three main blend categories, namely:
1. Blends with a crystallizable matrix and an amorphous dispersed phase,
2. Blends with an amorphous matrix and a crystallizable dispersed phase,
3. Blends containing two crystallizable components
Since in immiscible blends the phases are physically separated, the same
heterogeneities that nucleate the homopolymer at Tc,pure may nucleate the
crystallizable matrix. As a result, the crystallization temperature, Tc, of
the blend during cooling from the melt will in general not differ that
much from the Tc of the pure component.
Some general principles governing the crystallization behavior of
homopolymers also remain valid for immiscible polymer blends in which
the crystallizable component forms the continuous phase.
Important factors here are the blend composition, the interfacial tension
between both components, the melt-viscosity of both components, the
processing device and mixing conditions, the blend preparation method,
etc.
In this context, it is interesting to evaluate also the influence of
compatibilization on the crystallization behavior of the dispersed
phase.
Since compatibilization reduces the droplet size of the minor phase
even more drastically, it can be expected that this can lead to a serious
shift of the crystallization temperature towards lower temperatures,
resulting in more pronounced fractionated crystallization, or even in a
homogeneous crystallization.
However, this issue is more complex due to numerous other factors
involved in the nucleation process. Some examples from the literature are
listed in Table below. They illustrate how differently the
compatibilization can influence the crystallization behavior of the
dispersed phase.
Conclusions:
It can be stated that the crystallization behavior of a semicrystalline
polymer phase, dispersed into an amorphous matrix, is characterized by:
1- Fractionated crystallization or homogeneous nucleation if the minor
phase is finely dispersed.
2- A decrease in the overall degree of crystallinity, Xc, after cooling from
the melt, most pronounced in finely dispersed blend morphologies.
3- A slight decrease of the melting temperature due to the formation of
less perfect crystalline lamellae at higher undercoolings.