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emphasized, that the experiments do not yield the crystal structure; only researchers imagination and hard work yield that. However, it is possible to simplify the task. Natta and Corradini (23) postulated three principles for the determination of crystal structures, which introduce considerable order into the procedure. These are: 1. The Equivalence Postulate. It is possible to assume that all mer units in a crystal occupy geometrically equivalent positions with respect to the chain axis. 2. The Minimum Energy Postulate. The conformation of the chain in a crystal may be assumed to approach the conformation of minimum potential energy for an isolated chain oriented along an axis. 3. The Packing Postulate. As many elements of symmetry of isolated chain as possible are maintained in the lattice, so equivalent atoms of different mer units along an axis tend to assume equivalent positions with respect to atoms of neighboring chains. The equivalence postulate is seen in the structures given in Figure 6.6. Here, the chain mers repeat their structure in the next unit cell. Energy calculations made for both single molecules and their unit cells serve three purposes: (a) they clarify the factors governing the crystal and molecular structure already tentatively arrived at experimentally, (b) they suggest the most stable molecular conformation and its crystal packing starting from the individual mer chemical structure, and (c) they provide a collection of reliable potential functions and parameters for both intra- and intermolecular interactions based on well-dened crystal structures (27). An example of intermolecular interactions is hydrogen bonding in the polyamide structures described in Figure 6.8. The packing postulate is seen at work in Figure 6.7, where enantiomorphic structures pack closer together in space than if the chains had the same sense of helical twist. Last, one should not neglect the very simple but all important density. The crystalline cell is usually about 10% more dense than the bulk amorphous polymer. Signicant deviations from this density must mean an incorrect model. Because of the importance of polymer crystallinity generally, and the unit cell in particular, the subject has been reviewed many times (17,21,27,3141). 6.4 6.4.1 STRUCTURE OF CRYSTALLINE POLYMERS The Fringed Micelle Model

Very early studies on bulk materials showed that some polymers were partly crystalline. X-ray line broadening indicated that the crystals were either very

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STRUCTURE OF CRYSTALLINE POLYMERS

257

Figure 6.9 The fringed micelle model. Each chain meanders from crystallite to crystallite, binding the whole mass together.

imperfect or very small (42). Assuming the latter, in 1928 Hengstenberg and Mark (43) estimated that the crystallites of ramie, a form of native cellulose, were about 55 wide and over 600 long by this method. It had already been established that the polymer chain passed through many unit cells. Because of the known high molecular weight, the polymer chain was calculated to be even longer than the crystallites. Hence it was reasoned that they passed in and out of many crystallites (32,44,45). Their ndings led to the fringed micelle model. According to the fringed micelle model, the crystallites are about 100 long (Figure 6.9). The disordered regions separating the crystallites are amorphous. The chains wander from the amorphous region through a crystallite, and back out into the amorphous region. The chains are long enough to pass through several crystallites, binding them together. The fringe micelle model was used with great success to explain a wide range of behavior in semicrystalline plastics, and also in bers. The amorphous regions, if glassy, yielded a stiff plastic. However, if they were above Tg, then they were rubbery and were held together by the hard crystallites. This model explains the leathery behavior of ordinary polyethylene plastics, for example. The greater tensile strength of polyethylene over that of low-molecular-weight hydrocarbon waxes was attributed to amorphous chains wandering from crystallite to crystallite, holding them together by primary bonds. The exible nature of bers was explained similarly; however, the chains were oriented along the ber axis (see Section 6.3). The exact stiffness of the plastic or ber

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was related to the degree of crystallinity, or fraction of the polymer that was crystallized. 6.4.2 Polymer Single Crystals

Ideas about polymer crystallinity underwent an abrupt change in 1957 when Keller (19) succeeded in preparing single crystals of polyethylene. These were made by precipitation from extremely dilute solutions of hot xylene. These crystals tended to be diamond-shaped and of the order of 100 to 200 thick (see Figure 6.5) (21). Amazingly electron diffraction analysis showed that the polymer chain axes in the crystal body were essentially perpendicular to the large, at faces of the crystal. Since the chains were known to have contour lengths of about 2000 and the thickness of the single crystals was in the vicinity of 110 to 140 , Keller concluded that the polymer molecules in the crystals had to be folded upon themselves. These observations were immediately conrmed by Fischer (47) and Till (48). 6.4.2.1 The Folded-Chain Model This led to the folded-chain model, illustrated in Figure 6.10 (41). Ideally the molecules fold back and forth with hairpin turns. While adjacent reentry has been generally conrmed by smallangle neutron scattering and infrared studies for single crystals, the present understanding of bulk crystallized polymers indicates a much more complex situation (see below). Figure 6.10 uses polyethylene as the model material. The orthorhombic cell structure and the a- and b-axes are illustrated. The c-axis runs parallel to the chains. The dimension is the thickness of the crystal. The predominant fold plane in polyethylene solution-grown crystals is along the (110) plane. Chain folding is also supported by NMR studies (see Section 6.7) (4951). For many polymers, the single crystals are not simple at structures. The crystals often occur in the form of hollow pyramids, which collapse on drying. If the polymer solution is slightly more concentrated, or if the crystallization rate is increased, the polymers will crystallize in the form of various twins, spirals, and dendritic structures, which are multilayered (see Figure 6.11) (34). These latter form a preliminary basis for understanding polymer crystallization from bulk systems. Simple homopolymers are not the only polymeric materials capable of forming single crystals. Block copolymers of poly(ethylene oxide) crystallize in the presence of considerable weight fractions of amorphous polystyrene (see Figure 6.12) (52). In this case square-shaped crystals with some spirals are
The early literature reveals signcant premonitions of this discovery. K. H. Storks, J. Am. Chem. Soc., 60, 1753 (1938) suggested that the macromolecules in crystalline gutta percha are folded back and forth upon themselves in such a way that adjacent sections remain parallel. R. Jaccodine, Nature (London), 176, 305 (1955) showed the spiral growth of polythylene single crystals by a dislocation mechanism.

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STRUCTURE OF CRYSTALLINE POLYMERS

259

Figure 6.10 Schematic view of a polyethylene single crystal exhibiting adjacent reentry. The orthorhombic subcell with dimensions a and b, typical of many n-parafns, is illustrated below (41).

Figure 6.11 Single crystal of polyamide 6 precipitated from a glycerol solution. The lamellae are about 60 thick. Black marks indicate 1 mm (34).

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Figure 6.12 Single crystals of poly(ethylene oxide)blockpolystyrene diblock copolymers. (a) Optical micrograph. (b) Electron micrograph. Mn (PS) = 7.3 103 g/mol; Mn (PEO) = 10.9 103; weight fraction polystyrene is 0.34 (52).

seen. The crystals reject the amorphous portion (polystyrene), which appears on the surfaces of the crystals. Amorphous material also appears on the surfaces of homopolymer single crystals. As will be developed below, causes of this amorphous material range from chain-end cilia to irregular folding. 6.4.2.2 The Switchboard Model In the switchboard model the chains do not have a reentry into the lamellae by regular folding; they rather reenter more or less randomly (53). The model more or less resembles and old-time telephone switchboard. Of course, both the perfectly folded chain and switchboard models represent limiting cases. Real systems may combine elements of both. For bulk systems, this aspect is discussed in Section 6.7.

6.5 6.5.1

CRYSTALLIZATION FROM THE MELT Spherulitic Morphology

In the previous sections it was observed that when polymers are crystallized from dilute solutions, they form lamellar-shaped single crystals. These crystals exhibit a folded-chain habit and are of the order of 100 to 200 thick. From somewhat more concentrated solutions, various multilayered dendritic structures are observed.