Chain folding structure, single crystals

The sketch includes amcrphcus areas (defects), chain ends, rotated crystals, loose folds, sharp folds, areas of para-crystalline structure, extended-chain sections, voids, sheared regions, chain-kinks, single fibrils, migrating folds, and single-crystal regicns. 

TEM (Fig. 5.1a). The width can be several micrometers and the thickness only a few hundred angstroms. The electron diffraction pattern shows that only the hkO reflections are detected in the case of trigonal POM, which indicates that the chain stems stand up in the direction normal to the crystal surface. Stokes is the first to indicate the possibility of chain folding by measuring the electron diffraction patterns of unoriented trans-l,A-polyisoprene, he found that the chain axis is normal to the film plane [9]. Later, Fischer, Till, and Keller made direct observations of polymer single crystals with a chain-folded structure. The concept of chain folding originates from this experimental evidence [10]. 

The single crystal of a polymer is a lamellar structure with a thin plateletlike form, and the chain runs perpendicular to the lamella. The crystal is thinner than the polymer chain length. The chain folds back and forth on the top and bottom surfaces. Since the fold costs extra energy, this folded chain crystal (FCC) should be metastable with respect to the thermodynamically more stable extended chain crystal (ECC) without folds. 

Extrapolation of the molecular structure of an a-maltohexaose duplex com-plexed with triiodide in single crystals leads to a left-handed, 8-fold, antiparallel double-helix for amylose.90 The pitch of this idealized helix is 18.6 A, so h is only 2.33 A. Although this model is no contender to the fiber data, in terms of biosynthesis, it is doubtful that the native amylose helix favors antiparallel chains. 

One of the most remarkable features of polymer crystallization is that such chain molecules can form lamellar crystals that contain heavily folded polymer chains. In experiments, the structural analysis of these lamellar crystals became possible when polyethylene single crystals were first prepared from a solution [100-102]. It was found that the orientation of the polymer chains... 

For linear PE, the initial structure formed is a single crystal with folded chain lamellae. These quickly lead to the formation of sheaflike structures called axialites or hedrites. As growth proceeds, the lamellae develop on either side of a central reference point. They continue to fan out, occupying increasing volume sections through the formation of additional lamellae at appropriate branch points. The result is the formation of spherulites as pictured in Figures 2.15 and 2.16. 

While the lamellar structures present in spherulites are similar to those present in polymer single crystals, the folding of chains in spherulites is less organized. Further, the structures that exist between these lamellar structures are generally occupied by amorphous structures including atactic chain segments, low molecular weight chains, and impurities. 

While, in recent years, many laboratories have demonstrated that nearly every synthetic polymer can crystallize in the form of single crystals (13) consisting of lamellae formed by regular chain folding (Figure 3), it is clear that extreme condi-tions-i.e., very slow crystallization or very dilute solutions, are required for these structures to form. Under normal conditions, such as those encountered in any industrial process, the polymer usually crystallizes in the form of less ordered, large structures, called spherulites. 

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