Structure polymer single crystals

Figure 4.11 Electron micrographs of polyethylene crystals, (a) Dark-field illumination shows crystals to have a hollow pyramid structure. (Reprinted with permission from P. H. Geil, Polymer Single Crystals, Interscience, New York, 1963.) (b) Transmission micrograph in which contrast is enhanced by shadow casting [Reprinted with permission from D. H. Reneker and P. H. Geil, /. Appl. Phys. 31 1916 (I960).]...

Lotz, B. and Wittmann, J.-C. (1993) Structure of Polymer Single Crystals, in Structure and Properties of Polymers, ed. Thomas, E.L. Materials Science and Technology, A Comprehensive Treatment, eds. Cahn, R.W., Haasen, P. and Kramer, E.J. (VCH, Weinheim) p. 79. 

The fringed micelle theory has been less favoured recently following research on the subject of polymer single crystals. This work has led to the suggestion that polymer crystallisation takes place by single molecules folding themselves at intervals of about 10 nm to form lamellae as shown in Figure 3.3b. These lamellae appear to be the fundamental structures of crystalline polymers. 

Since polymer single crystals prepared these days are too small for x-ray diffraction experiments, the Crystal Structure of a polymer is generally determined from x-ray patterns of a fibre drawn from the polymer. Due to the alignment of the crystalline regions with the long axes of the molecules parallel to the fibre axis, the pattern is essentially identical to a rotation pattern from... 

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. 

Fully conjugated and fully chain-aligned polymer single crystals with planar polymer backbone are obtained, which may have the alternative acetylene (ynene) or butatriene structures of Eq. (1). From our experiment we know that the acetylene structure is dominant in the polymer molecules. Up to now the best investigated diacetylene crystals are the TS-6 monomer crystals and the corresponding polymer crystals (poly TS-6). The substituents R and the notation of further diacetylene crystals discussed below are listed in Table 1. 

Single crystals are commonly mounted on a four-circle diffractometer. This method may provide the quality of data necessary for structural refinements. However, polymer single crystals of usable sizes have been obtained only through solid-state polymerization of monomer crystals, such as in the case of poly-diacetylcnes. Oligomers and model compounds, however, have been obtained in single-crystal fonn in several cases, either from solution or from the vapour phase. 

The above results have obvious implications for the biosynthesis of cellulose mlcrofIbrlls. The parallel chain structure of cellulose I rules out any kind of regularly folded chain structure, and reveals the mlcrofibrils to be extended chain polymer single crystals, which leads to optimum tensile properties. Work by Brown and co-workers (22) on the mechanism of biosynthesis points to synthesis of arrays of cellulose chains from banks of enzyme complexes on the cell wall. These complexes produce a bundle of chains with the same sense, which crystallize almost immediately afterwards to form cellulose I mlcroflbrlls there is no opportunity to rearrange to form a more stable anti-parallel cellulose II structure. Electron microscopy by Hleta et al. (23) confirms the parallel sense of cellulose chains within the individual mlcroflbrlls stains reactive at the reducing end of the cellulose molecule stain only one end of the mlcroflbrll. 

---