Polymer blend phase behavior crystal

This book is concerned mainly with the study of the viscoelastic response of isotropic macromolecular systems to mechanical force fields. Owing to diverse influences on the viscoelastic behavior in multiphase systems (e.g., changes in morphology and interfaces by action of the force fields, interactions between phases, etc.), it is difficult to relate the measured rheological functions to the intrinsic physical properties of the systems and, as a result, the viscoelastic behavior of polymer blends and liquid crystals is not addressed in this book. 

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. 

Table 3.26 Inflijence of compatibilization in amoiphous/dystalline polymer blends (Hi the crystallization behavior of the dispersed phase ...

The miscibility limit between thermotropic liquid crystal polymers and flexible chain polymers can be predicted by calculations corresponding to the spinodal curve at constant temperature. This miscibility is increased with the increase of the degree of disorder (y/jc,) of the liquid crystal polymer and with the decrease of the degree of polymerization. Two quantitative parameters from the Hory s lattice theory can be used to estimate the phase behavior of this kind of blend at melt processing temperature the polymer-polymer interaction parameter and the degree of disorder (y/Xj). In binary polymer blends phase separation may occur for any value of degree of disorder (y/Xj)... 

In addition to the crystal forms, X-ray scattering studies indicate that when unoriented PEN fiber was drawn at 120 °C ( 7 g), a mesophase is generated. In this form, the molecular chains are in registry with each other in the meridional direction but not fully crystallized in the equatorial direction. This conclusion was based on the presence of additional meridional peaks not accounted for by the crystal structure obtained by X-ray scattering. The mesophase is a intermediate phase and its existence is strongly dependent upon the processing conditions consequently, it could have implications with respect to the properties of commercially produced fibers and films, since it appears to be stable and not easily converted to the crystalline form, even at elevated temperature [25, 26], The mesophase structures of PET, PEN and poly(ethylene naphthalate bibenzoate) were compared by Carr et al. [27], The phase behavior of PEN and PEN blends with other polymers has also been studied [28-32],... 

When two crystallizable components are blended, a more complex behavior due to the influence of both phases on each other is expected. In general, the discussion for matrix crystallization and droplet crystallization can be combined. However, crystallization of one of the phases can sometimes directly induce crystallization in the second phase. As a consequence, the discussion of blends of this type has been subdivided with respect to the physical state of the second phase during crystallization. The special case of coincident crystallization , in which the two phases crystallize at the same time, is discussed. Finally, the effect of compatibilization of crystalline/crystalline polymer blends is briefly reviewed. 

Some general principles governing the crystallization behavior of homopolymers also remain vahd for immiscible polymer blends in which the crystallizable component forms the continuous phase. 

Table 3.26. Influence of compatibilization on the crystallization behavior of the dispersed phase in amorphous /crystalline polymer blends...

Because the phases are physically separated in the melt, the theory concerning the crystallization behavior as discussed in Parts 3.4.3 (matrix crystallization) and 3.4.4 (dispersed droplet crystallization) can be combined to understand the crystallization and melting behavior of most crystalline/ crystalline polymer blends. In general, both crystal-lizable phases crystallize separately around then-characteristic bulk T-value (as long as the minor phase is not dispersed into very fine droplets). The T-values can be somewhat shifted due to... 

In the following overview, a survey of the most important topics concerning crystallization behavior in immiscible crystalline/crystalline polymer blends is given. Because the physical state of the second phase affects the crystallization mode of the phase under consideration, a distinction has been made for blends crystallizing in a melt environment and those crystallizing when the second phase has solidified. 

For most commonly studied polymer blends, crystallization of the matrix occurs in the presence of a molten dispersed phase. The crystallization behavior of the continuous phase can be compared to that found for crystalline/amorphous blend systems in which the dispersed amorphous phase was in the molten state. 

Blending offers an interesting means of tailoring product properties to specific applications. However, in the case of immiscible polymer pairs, the desired properties are not achieved readily without a compatibilizer, which enhances the phase dispersion and stability, as well as a good adhesion between the phases. This can be effectuated by physical or reactive methods [Folkes and Hope, 1993]. Compatibilization strongly affects the blend phase morphology and as such, it also may influence the crystallization behavior of the blend [Flaris et al., 1993]. Because both factors are related to the final properties of the blend, it is worth paying attention to these phenomena. 

The general influence of a compatibilizer on the crystallization behavior of an immiscible polymer blend system is stiU far from being well understood. However, abstract can be made between two main classes. A first class consists of compatibilizers that form a kind of immiscible interlayer between the two phases. Examples are given by Holsti-Miettinen et al. [1992], and... 

Concerning compatibilized blends, the interfacial behavior of the compatibilizer has an important effect upon the crystallization of the blended components as it was shown for crystaHine/crystalline polymer blends (60,65-67) and for crystalline polymer/LCP blends (32,37,38,68). For the latter blends, the enhanced phase interactions and improved interfacial adhesion could increase the above-mentioned nucleation activity of the LCP toward the crystallizable matrices. In the particular case of using polyolefin-g-LCP copolymer compatibilizer, the crystallization of the two blend phases might have a reverse effect upon the compatibilizing activity. Moreover, the miscibility (69,70) and/or cocrystallization (60) between the bulk homopolymers and corresponding segments of the copolymer could strongly influence the crystallization behavior of the blends. 

Chlorinated polymers/Copolyester-aniides Recent studies (5) of blends of chlorinated polyeAylenes with caprolactam(LA)-caprolactone(LO) copolymers have been able to establish a correlation between miscibiUty and chemical structure within the framework of a binary interaction model. In some of the blends, both components have the ability to crystallize. When one or both of the components can crystallize, the situation becomes rather more complicated. Miscible, cystallizable blends may also undergo segregation as a result of the crystallization with the formation of two separate amorphous phases. Accordingly, it is preferable to investigate thermal properties of vitrified blends. Subsequent thermal analysis also produces exothermic crystallization processes that can obscure transitions and interfere with determination of phase behavior. In these instances T-m.d.s.c has the ability to separate the individual processes and establish phase behavior. 

Avella, M., Martuscelli, E. Poly-d(-)(3-hydroxybutyrate)/poly(ethylene oxide) blends phase diagram, thermal and crystallization behavior. Polymer 29(10), 1731-1737 (1988)... 

Avella M, MartusceUi E, Greco P (1991) Crystallization behaviour of poly(ethylene oxide) from poly(3-hydroxybutyrate)/poly(ethylene oxide) blends phase structuring, morphology and thermal behavior. Polymer 32 1647-1653... 

The immiscible semicrystalline polymer blends may be classified in terms of crystalline/crystalline systems in which both components are crystallizable and crystalline/amorphous systems in which only one component can crystallize, being either the matrix or the dispersed phase (Utracki 1989). Numerous authors have been investigating the crystallization behavior of immiscible blends. In Tables 3.14 and 3.15, an overview is given of a number of important immiscible crystallizable blend systems. 

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