Crystalline polymer definition

Figure 9.10 Schematic X-ray diffraction patterns from an unoriented and an oriented crystalline polymer. Definition of the azimuthal angle (j).

The major results described could be partially anticipated from those previously reported for linear polyethylene (17) as well as those for cis polyisoprene. (] ) For the latter polymer, by taking advantage of its crystallization kinetic characteristics, it was possible to compare the relaxation parameters of the completely amorphous and partially crystalline polymer (31% crystallinity) at the same temperature, 0°C. This is a unique situation and allows for some unequivocal comparisons. It was definitively observed that for all the carbons of cis polyisoprene the T] s did not change with crystallization. 

After a listing of some general definitions relating to crystalline polymers (Section 1), the subject is divided into sections dealing, successively, with local structural arrangements at the scale of a few bond lengths (Section 2), morphological aspects (Section 3), molecular conformation within polymer crystals (Section 4) and, finally, kinetic aspects of crystallization (Section 5). An alphabetical index of terms is provided for the convenience of the reader. 

Definitions of terms relating to crystalline polymers (lUPAC Recommendations 1988), PureAppl. Chem. 61, 769-785 (1989). Reprinted as Chapter 6, this edition. 

After an introductory chapter we review in Chap. 2 the classical definition of stress, strain and modulus and summarize the commonly used solutions of the equations of elasticity. In Chap. 3 we show how these classical solutions are applied to various test methods and comment on the problems imposed by specimen size, shape and alignment and also by the methods by which loads are applied. In Chap. 4 we discuss non-homogeneous materials and die theories relating to them, pressing die analogies with composites and the value of the concept of the representative volume element (RVE). Chapter 5 is devoted to a discussion of the RVE for crystalline and non-crystalline polymers and scale effects in testing. In Chap. 6 we discuss the methods so far available for calculating the elastic properties of polymers and the relevance of scale effects in this context. 

By definition, thermoplastics have limitations at elevated temperatures. It is in this particular property that fibrous glass can lead to remarkable improvements. However, a sharp division exists for reinforced thermoplastics. The various reinforced thermoplastics can be put in two groups relative to DTUL. These consist of amorphous and crystalline or semicrystalline polymers. The amorphous polymers such as styrene-acrylonitrile, polystyrene, polycarbonate, poly (vinyl chloride), and acrylo-nitrile-butadiene-styrene are generally limited to modest DTUL improvements, usually on the order of 20°F with 20% glass. However, crystalline polymers such as the nylons, linear polyethylene, polypropyl-... 

The character of the polymethyl methacrylate data is essentially similar to that found for systems atactic polystyrene-benzene at 25°, 35°, and 50° C. [Kishimoto, Fujita, Odani, Kurata and Tamura (1960) Odani, Kida, Kurata and Tamura (1961)] and also atactic polystyrene-methyl ethyl ketone at 25° C. [Odani, Hayashi and Tamura (1961)], and appears to be fairly general for amorphous polymer-solvent systems in the glassy state. On the other hand, the cellulose nitrate data shown in Fig. 8 appear to manifest features characteristic of crystalline polymer-solvent systems. For example, the earlier data of Newns (1956) on the system regenerated cellulose-water (in this case, water is not the solvent but merely a swelling-agent) and recent studies for several crystalline polymers all show essentially similar characters [see Kishimoto, Fujita, Odani, Kurata and Tamura (I960)]. To arrive at a more definite conclusion, however, more extensive experimental data are needed. 

Because nematic liquid-crystalline polymers by definition are both anisotropic and polymeric, they show elastic effects of at least two different kinds. They have director gradient elasticity because they are nematic, and they have molecular elasticity because they are polymeric. As discussed in Section 10.2.2, Frank gradient elastic forces are produced when flow creates inhomogeneities or gradients in the continuum director field. Molecular elasticity, on the other hand, is generated when the flow is strong enough to shift the molecular order parameter S = S2 from its equilibrium value 5 . (Microcrystallites, if present, can produce a third type of elasticity see Section 11.3.6.)... 

Molecular conformation is an important subject of concern in liquid crystalline polymers. It is also the basic subject of polymer science. The mean square end-to-end distance or the radius of gyration is often used to characterize the size of a polymer molecule. According to the definition, the end-to-end distance is the sum of each rod s vectors in sequence... 

Definitions of. Terms Relating to Crystalline Polymers lUPAC, 1989b... 

Until now there was no obvious correlation found between the monomer structure and the resulting pol qner phase. No.theorr retical structural conditions were described which would result in a liquid crystalline polymer with a definite ordered phase e.g. with a nematic a smectic or a cholesteric phase as in conventional liquid crystals. Although previous examples have established (8 9) the existence of enantiotropic liquid crystalline side chain polymers additional considerations are in order for a systematic synthesis of such polymers. 

A noncrystalline polymeric material that has no definite order or crystallinity. A polymer in which the macromo-lecular chain has a random conformation in solid (glassy or rubbery) state. On the one hand, an amorphous polymer may show a short range order, while on the other, a crystalline polymer may be quenched to the amorphous state (viz., polyethylene terephthalate (PET)). The maximum value of a periodically varying function, e.g., used to describe the energy transmitted from the ultrasonic welding horn to the weld joint. 

Fig. 2.19 displays some other typical WAXS curves. As shown [60] [EG-DBDl]jj represents a polymer with a high tendency of crystallization (Fig. 2.19 (b)) both in terms of quantity of crystalline material and the definition by the X-ray reflections. This behaviour is paralleled by the self-separation of crystalline polymer from its solution with time [69]. The [EG-MDI] (Fig. 2.19 (c)) shows only a single broad peak, rather narrower than might be expected for an amorphous halo, suggesting a rather loose association of molecular chains. This material does not crystallize from solution [60],... 

In Chapter 9 the techniques which can be used for the study of molecular interfaces were considered and provide us with the tools to ask the question What are the factors that make definition of the surface difficult In order to help our consideration of the answer it is appropriate to divide the diseussion into three types of system crystalline polymers, amorphous polymers and polymer blends. 

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