Crystal structures, polymers fibers

It should be noted that any defects and imperfection in structure and orientation would give rise to rather coarse points and doughnut-shaped zones in the reciprocal lattice rather than clearly defined points and circles. This is the case for oriented liquid crystals and polymer fibers. Diffused diffraction patterns are therefore obtained for these specimens. 

Figure 4.10 Crystal structure of polyethylene (a) unit cell shown in relation to chains and (b) view of unit cell perpendicular to the chain axis. [Reprinted from C. W. Bunn, Fibers from Synthetic Polymers, R. Hill (Ed.), Elsevier, Amsterdam, 1953.]...

At present, it is known that the structures of the ECC type (Figs 3 and 21) can be obtained in principle for all linear crystallizable polymers. However, in practice, ECC does not occur although, as follows from the preceding considerations, the formation of linear single crystals of macroscopic size (100% ECC) is not forbidden for any fundamental thermodynamic or thermokinetic reasons60,65). It should be noted that the attained tenacities of rigid- and flexible-chain polymer fibers are almost identical. The reasons for a relatively low tenacity of fibers from rigid-chain polymers and for the adequacy of the model in Fig. 21 a have been analyzed in detail in Ref. 65. 

The examples of polymer crystal structures shown in the previous sections are ideal structures, which can be described with the traditional concepts of the principles of equivalence and close packing or the new concepts of symmetry breaking146 and frustration.154 The models of perfect crystals are characterized by a long-range positional order for all the atoms (disregarding thermal motion). The X-ray diffraction patterns of such crystals, oriented with the chain axes along one direction (as in oriented fibers), present sharp reflections organized in layer lines. 

Structural steels, tellurium in, 24 425 Structure(s), see also Chain structure Chemical structures Cocontinuous structures Controlled structure Crystal structure Molecular structure Morphology Phase structure of carbon fibers, 26 737-739 detersive systems for, 8 413t HDPE, 20 157-162 LLDPE, 20 182-184, 203-205 polyesterether elastomer, 20 72-73 polyester fiber, 20 21 polyether antibiotics, 20 137-139 polyimide, 20 276-278 polymer, 20 395-405 protein, 20 449 PTT, 20 68t... 

In addition to the crystal forms, X-ray scattering studies indicate that when unoriented PEN fiber was drawn at 120 °C ( 7 g), a mesophase is generated. In this form, the molecular chains are in registry with each other in the meridional direction but not fully crystallized in the equatorial direction. This conclusion was based on the presence of additional meridional peaks not accounted for by the crystal structure obtained by X-ray scattering. The mesophase is a intermediate phase and its existence is strongly dependent upon the processing conditions consequently, it could have implications with respect to the properties of commercially produced fibers and films, since it appears to be stable and not easily converted to the crystalline form, even at elevated temperature [25, 26], The mesophase structures of PET, PEN and poly(ethylene naphthalate bibenzoate) were compared by Carr et al. [27], The phase behavior of PEN and PEN blends with other polymers has also been studied [28-32],... 

As a consequence of this almost perfect alignment of molecule structures, such polyamides are able to orientate in solution and to form liquid crystalline phases (see Sect. 1.3.4). Out of these solutions one obtains fibers of poly(p-phenylene terephthalamide) (PPTA) having 5-10-fold higher values for stiffness and strength as the all-mefa linked polymers. In addition, PPTA crystallizes, whereupon the fibers achieve an extraordinary temperature resistance in a nitrogen atmosphere they decompose at temperatures above 550 °C without melting. 

The recent studies of the phase structure of linear polyethylene by refined NMR analyses are reviewed. The phase structure of the polymer in various crystalline forms, including bulk-crystals, solution-crystals and drawn fibers, is discussed in terms of different modes of molecular mobilities in a wide range of temperature. 

In this article we have reviewed our recent work with NMR analysis on various kinds of linear polyethylene samples. It has become evident that the refined NMR analysis gives us much important information on the phase structure of samples in terms of molecular mobility, and establishes that there is no unified phase structure for polymer samples. The phase structure of samples varies over a very wide range, depending strongly on the sort of samples involved as well as on the mode of crystallization or the history of those samples. We should emphasize that there are significant differences in phase structure among the bulk-crystals, the solution-crystals, and the fiber samples, particularly in the conformation of molecular chains in the noncrystalline content. We should not confuse these phase structures with each other. The phase structures are evidently different, sample by sample, as their macroscopic properties also differ one from another. 

The determination of crystal structure in synthetic polymers is often made difficult by the lack of resolution in the diffraction data. The diffuseness of the reflections observed in most x-ray fiber patterns results from the small size and imperfect lattice nature of the polymer crystallites. Resolution of individual reflections is also made difficult from misorientation of the crystallites about the fiber axis. This lack of resolution leads to poor accuracy in measurement of peak positions. In particular, this lack of accuracy makes determination of layer line heights difficult with a corresponding loss of significant figures in evaluation of the repeat distance for the molecular conformation. In the case of helical conformations, the repeat distance may be of considerable length or, as we shall show, indeterminate and, in effect, nonperiodic. This evaluation requires high accuracy in measurements of layer line heights. 

In order to discuss the hydrogen bonding in polysaccharide crystal structures, two interrelated problems have to be resolved. One is to determine the intrachain hydrogen bonding, which may be inter- or intramonomer residue. This bonding must be consistent with fitting the polymer repeat unit to the length of the fiber axis, which is usually a well-defined quantity. When the fiber axis coincides with the axis of the polymer, the conformation of the polymer repeat unit must fit the symmetry of the fiber axis. 

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