Semicrystalline polymers crystallization behaviors

We have adapted a commercially available x-ray diffractometer normally used for structure determinations on single crystals to operate as a very flexible device for performing x-ray pole figure determinations and related studies on polymeric materials. Descriptions of crystallite orientations, as provided by pole figures, are useful in studying many aspects of the behavior of products made from semicrystalline polymers. This paper describes the software that we have written for our pole figure facility. Except for some vendor-provided routines to drive the hardware Interface all of our software is written in FORTRAN. Menu driven operation is provided to maximize user convenience. 

The effects of morphology (i.e., crystallization rate) (6,7, 8) on the mechanical properties of semicrystalline polymers has been studied without observation of a transition from ductile to brittle failure behavior in unoriented samples of similar crystallinity. Often variations in ductlity are observed as spherulite size is varied, but this is normally confounded with sizable changes in percent crystallinity. This report demonstrates that a semicrystalline polymer, poly(hexamethylene sebacate) (HMS) may exhibit either ductile or brittle behavior dependent upon thermal history in a manner not directly related to volume relaxation or percent crystallinity. 

Poly(ethylene terephthalate) Poly(ethylene terephthalate) is a widely used semicrystalline polymer. The macroscopic properties of PET such as thermal, mechanical, optical, and permeation properties depend on its specific internal morphologies and microstructure arrangement. It can be quenched into the completely amorphous state, whereas thermal and thermomechanical treatments lead to partially crystallized samples with easily controlled degrees of crystallinity. The crystallization behavior of thermoplastic polymers is strongly affected by processing conditions [91-93]. 

Accordingly, the influence of MW on the crystallization behaviors of semicrystalline polymers has been studied in various articles. For example, linear crystal growth rates of poly(ethylene oxide) and poly(ethylene succinate) (PES) reach a minimum value at a critical MW. This value is related to the crystallization transition from an extended chain to a folded chain conformation [96,97], suggesting that high MW polymers require sufficient reconformation time to achieve an ordered structure. As evidence of this MW dependence of the semicrystalline polymer on... 

A complex melting behavior is also observed when a semicrystalline polymer exhibits two different types of crystal structure. A second crystal strucmre can be introduced by a variation in temperarnre, pressure, elongation, etc. This phenomenon is known for neat PE. Adding an amorphous polymer to a crystallizable component can result in a change of the unit cell dimensions of the crystal structure. This has been observed for... 

In the following part, a discussion on the crystallization behavior in immiscible polymer blends is given, including the nucleation behavior, spheiuhte growth, overall crystallization kinetics, and final semicrystalline morphology. Each topic is illustrated with several examples from the literature, to allow the reader to find enough references on the discussed subject for further information. 

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. 

It can be stated that the crystallization behavior of a semicrystalline polymer phase, dispersed into an amorphous matrix, is characterized by ... 

The scientific literature on crystallization in polymer blends clearly indicates that the crystallization behavior and the semicrystalline morphology... 

A large number of polymer blends contain one or two crystallizable components. The crystallization behavior of a polymer component in a blend is expected to be altered by the presence of the second blend component, whether both are completely miscible, partially miscible, or totally immiscible. Therefore, a profound scientific understanding of the crystallization behavior and the resulting semicrystalline structure in polymer blends is necessary for effective manipulation and control of their properties. 

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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