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6.10 FIBER FORMATION AND STRUCTURE The synthetic bers of today, the polyamides, polyesters, rayons, and so on, are manufactured by a process called spinning. Spinning involves extrusion through ne holes known as spinnerets. Immediately after the spinning process, the polymer is oriented by stretching or drawing. This both increases polymer chain orientation and degree of crystallinity. As a result the modulus and tensile strength of the ber are increased. Fiber manufacture is subdivided into three basic methods, melt spinning, dry spinning, and wet spinning; see Table 6.10 (159). Melt spinning is the simplest but requires that the polymer be stable above its melting temperature. Polyamide 66 is a typical example. Basically, the polymer is melted and forced through spinnerets, which may have from 50 to 500 holes. The ber diameter immediately after the hole and before attenuation begins is larger than the hole diameter. This is called die swell, which is due to a relaxation of the viscoelastic stress-induced orientation in the hole; see Section 5.4 and Figure 10.20. During the cooling process the ber is subjected to a draw-down force, which introduces the orientation. Additional orientation may be introduced later by stretching the ber to a higher draw ratio. In dry spinning, the polymer is dissolved in a solvent. A typical example is polyacrylonitrile dissolved in dimethylformamide to 30% concentration. The polymer solution is extruded through the spinnerets, after which the solvent is rapidly evaporated (Figure 6.41) (159). After the solvent is evaporated, the ber is drawn as before. In wet spinning, the polymer solution is spun into a coagulant bath. An example is a 7% aqueous solution of sodium cellulose xanthate (viscose), which is spun into a dilute sulfuric acid bath, also containing sodium sulfate and zinc sulfate (160). The zinc ions form temporary ionic cross-links between the xanthate groups, holding the chains together while the sulfuric acid, in turn,
Table 6.10 Spinning processes (159)

Solution Spinning Wet Spinning Melt Spinning Polyamide Polyester Polyethylene Polypropylene PVDC Dry Spinning Cellulose acetate Cellulose triacetate Acrylic Modacrylic Aramid Elastane PVC Vinylal Coagulation Regeneration Viscose rayon Cupro Acrylic Modacrylic Aramid Elastane PVC

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Figure 6.41 In typical dry-spinning operations, hot gas is used to evaporate the solvent in the spinning cabinet. The bers are simultaneously oriented (159).

removes the xanthate groups, thus precipitating the polymer. After orientation, and so on, the nal product is known as rayon. 6.10.1 X-Ray Fiber Diagrams For the purpose of X-ray analyses, the samples should be as highly oriented and crystalline as possible. Since these are also the conditions required for strong, high-modulus bers, basic characterization and engineering requirements are almost identical. Figure 6.42 (27,161,162) illustrates a typical X-ray ber diagram, for polyallene, CH2 C CH2 n . The actual ber orientation is vertical. The most intense diffractions are on the equitorial plane; note the 110 and 200 reections. Note the rather intense amorphous halo, appearing inside the 011 reection.

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Figure 6.42 X-ray ber diagram of polyallene (a), and its indexing (b) (27).

Because of the imperfect orientation of the polymer in the ber, arcs are seen, rather than spots. The variation in the intensity over the arcs can be used, however, to calculate the average orientation. A further complication in the interpretation of the ber diagram arises because it actually is a full rotation photograph. In these ways ber diagrams differ from those of single crystals. Vibrational analyses via infrared and Raman spectroscopy studies play an important role in the selection of the molecular model, as described above. 6.10.2 Natural Fibers Natural bers were used long before the discovery of the synthetics in the twentieth century. Natural bers are usually composed of either cellulose or protein, as shown in Table 6.11. Animal hair bers belong to a class of proteins known as keratin, which serve as the protective outer layer of the higher vertebrates. The silks are partly crystalline protein bers. The crystalline por-

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THE CRYSTALLINE STATE

Table 6.11 Chemical nature of natural bers

Cellulose Cotton Tracheid (wood) Flax Hemp Coir Ramie Jute

Protein Wool Hair Silk Spider webs

Figure 6.43 The cell walls of a tracheid or wood ber have several layers, each with a different orientation of microbrils (164). ML, middle lamella, composed of lignin; P, primary wall; S1, S2, S3, layers of the secondary wall; W, warty layer. The lumen in the interior of the warty layer is used to transport water.

tions of these macromolecules are arranged in antiparallel pleated sheets, a form of the folded-chain lamellae (163). The morphology of the natural bers is often quite complex; see Figure 6.43 (164). The cellulose making up these trachieds is a polysaccharide; see Table 1.4. The crystalline portion of the cellulose making up the trachieds is highly oriented, following the various patterns indicated in Figure 6.43. The winding angles of the cellulose form the basis for a natural composite of great strength and resilience. A similar morphology exists in cotton cellulose. The brous proteins (keratin) are likewise highly organized; see Figure 6.44 (165). Proteins are actually polyamide derivatives, a copolymeric form of polyamide 2, where the mers are amino acids. For example, the structure of the amino acid phenylalanine in a protein may be written H N H C O C (6.57)

CH2

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Figure 6.44 A wool-ber cortical cell is complex structure, being composed ultimately of proteins (165)

There are some 20 amino acids in nature, see Figure 14.29. These are organized into an a-helix in the brous proteins, which in turn are combined to form protobrils as shown. In addition to being crystalline, the brous proteins are cross-linked though disulde bonds contained in the cystine amino acid mer, which is especially high in keratin. Animal tendons, composed of collagen, another brous protein, have also been shown to have a surprisingly complex hierarchical structure (166).

6.11 THE HIERARCHICAL STRUCTURE OF POLYMERIC MATERIALS While all polymers are composed of long-chain molecules, it is the organization of such materials at higher and higher levels that progressively determines their properties and ultimately determines their applications. Table 6.12 summarizes the hierarchical structure of the several classes of polymers according to size range. The largest synthetic crystalline polymer structures are the spherulites, while the largest structures of the natural polymers are the walls of the whole (living) cell. Of course, there are many kinds of natural polymers. Starch and bread are discussed in Section 14.3, and silk bers in Section 14.4; both are semicrystalline materials. The hierarchical structure of polymers has been reviewed by