Semicrystalline region

Thus the factor (Mc — M )/(Mn — M ) may be thought of as the sieving term mentioned in the theory of Yasuda et al. [150], In the Peppas-Reinhart theory, the sieving mechanism takes an understandable form which is a function of the structure of the network. It must be noted that the presence of semicrystalline regions in the polymer membrane leads to deviations from the predicted dependencies in this theory. These researchers found that as the crosslinking density in the polymer membrane increased, the solute diffusion coefficient decreased, further illustrating the importance of structural parameters of the polymer network in predicting the solute diffusion coefficient [156],... 

Crystallizable Block Copolymer Morphologies While the largest part of the block copolymer literature describes totally amorphous materials, one or more of the blocks may form semicrystalline regions. Examples include polyester-polyether block copolymers (39), where the poly(tetramethylene terephthalate) polyester blocks crystallize, and the thermoplastic polyurethane elastomers, where the polyurethane hard blocks crystallize (40). 

Fig. 2.5. Chain molecules in (A) amorphous, (B) crystalline and (C) semicrystalline regions of polymers (fringed micelle model).

Polymer morphology (amorphous and semicrystalline regions) plays an evident role in oxidation and/or photo-oxidation reactions. 

Crystallinity. Generally, spider dragline and silkworm cocoon silks are considered semicrystalline materials having amorphous flexible chains reinforced by strong stiff crystals (3). The orb web fibers are composite materials (qv) in the sense that they are composed of crystalline regions immersed in less crystalline regions, which have estimates of 30—50% crystallinity (3,16). Eadier studies by x-ray diffraction analysis indicated 62—65% crystallinity in cocoon silk fibroin from the silkworm, 50—63% in wild-type silkworm cocoons, and lesser amounts in spider silk (17). 

Mechanical Properties. Although wool has a compHcated hierarchical stmcture (see Fig. 1), the mechanical properties of the fiber are largely understood in terms of a two-phase composite model (27—29). In these models, water-impenetrable crystalline regions (generally associated with the intermediate filaments) oriented parallel to the fiber axis are embedded in a water-sensitive matrix to form a semicrystalline biopolymer. The parallel arrangement of these filaments produces a fiber that is highly anisotropic. Whereas the longitudinal modulus of the fiber decreases by a factor of 3 from dry to wet, the torsional modulus, a measure of the matrix stiffness, decreases by a factor of 10 (30). 

Fibers are thin threads produced by extruding a molten polymer through small holes in a die, or spinneret. The fibers are then cooled and drawn out, which orients the crystallite regions along the axis of the fiber and adds considerable tensile strength (Figure 31.3). Nylon, Dacron, and polyethylene all have the semicrystalline structure necessary for drawing into oriented fibers. 

Nylon fibers are semicrystalline, that is, they consist of crystallites separated by amorphous regions. Hydrogen bonding is an important secondary valence interaction in nylon-6 and nylon-6,6. Individual chains in the microcrystalline regions of nylons are held together by hydrogen bonds. Nylons are resistant to aqueous alkali but deteriorate more readily on exposure to mineral acids. 

The nature of the heat of fusion AHu deserves particular attention, for it represents the heat required to melt one mole of crystalline units it does not refer to the latent heat AJT required to melt such crystallinity as may occur in a given semicrystalline polymer. The depression of the melting point Tm, already defined as the maximum temperature at which crystalline regions may coexist with amorphous poly-... 

The properties of a semicrystalline polymer are controlled by its degree of crystallinity, the alignment of crystallites relative to one another, the number and type of links between the crystallites and amorphous regions, and the overall orientation of molecules within the material. 

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