Fiber crystallites

Figure 18.14 The diffraction pattern of helices in fiber crystallites can be simulated by the diffraction pattern of a single slit with the shape of a sine curve (representing the projection of a helix). Two such simulations are given in (a) and (b), with the helix shown to the left of its diffraction pattern. The spacing between the layer lines is inversely related to the helix pitch, P and the angle of the cross arms in the diffraction pattern is related to the angle of climb of the helix, 6. The helix in (b) has a smaller pitch and angle of climb than the helix in (a). (Courtesy of W. Fuller.)...

Biological fibers, such as can be formed by DNA and fibrous proteins, may contain crystallites of highly ordered molecules whose structure can in principle be solved to atomic resolution by x-ray crystallography. In practice, however, these crystallites are rarely as ordered as true crystals, and in order to locate individual atoms it is necessary to introduce stereochemical constraints in the x-ray analysis so that the structure can be refined by molecular modeling. 

As we have seen, the orientation of crystallites in a thin film can vary from epitaxial (or single crystalline), to complete fiber texture, to preferred orientation (incomplete fiber texture), to randomly distributed (or powder). The degree of orientation not only influences the thin-film properties but also has important consequences on the method of measurement and on the difficulty of identifying the phases present in films having multiple phases. 

PAN fibers develop a structure with little point-to-point relationship between atoms in neighboring basal planes. This structure is labeled the turbostratic configuration and is characterized by interplanar spacing values greater than 0.344 nm. The crystallite size in the direction normal to the basal planes, or stack height (L, ), in turbostratic graphite is typically less than 5 nm. 

Figure 2 The lamellar substructure of a fibril. (a) Reciprocal positions of crystalline lamellae as a result of fiber annealing. (b) The situation after relaxation of stress affecting TTM. ai.2 - average angle of orientation of TTM CL - crystalline lamellae CB - crystalline blocks (crystallites) mF -border of microfibrils and F - fibril. In order to simplify it was assumed that (1) there are the taut tie molecules (TTM) only in the separating layers, (2) the axis of the fibril is parallel to the fiber axis.

Crystallites occurring in PET fibers can assume two kinds of morphological forms. The first form represents the crystallite formed by molecules of folded conformation, while the other is formed from molecules of extended-chain conformation. The first form is sometimes called a flexural morphological form, whereas the other is called a straightened morphological form. The flexural form is the typical and prevailing morphological form in PET fibers. However, it should be stressed that no... 

The numerical data, as determined by the authors, characterizing the dependence of the degree of crystallinity and the size of crystallites on the draw ratio of the fiber, are presented in Table 4. 

Table 4 Degree of Crystallinity and Average Crystallite Size of Differently Drawn PET Fibers...

The development of the internal orientation in formation in the fiber of a specific directional system, arranged relative to the fiber axis, of structural elements takes place as a result of fiber stretching in the production process. The orientation system of structural elements being formed is characterized by a rotational symmetry of the spatial location of structural elements in relation to the fiber axis. Depending on the type of structural elements being taken into account, we can speak of crystalline, amorphous, or overall orientation. The first case has to do with the orientation of crystallites, the second—with the orientation of segments of molecules occurring in the noncrystalline material, and the third—with all kinds of structural constitutive elements. 

The parallelization of crystallites, occurring as a result of fiber drawing, which consists in assuming by crystallite axes-positions more or less mutually parallel, leads to the development of texture within the fiber. In the case of PET fibers, this is a specific texture, different from that of other kinds of chemical fibers. It is called axial-tilted texture. The occurrence of such a texture is proved by the displacement of x-ray reflexes of paratropic lattice planes in relation to the equator of the texture dif-fractogram and by the deviation from the rectilinear arrangement of oblique diffraction planes. With the preservation of the principle of rotational symmetry, the inclination of all the crystallites axes in relation to the fiber axis is a characteristic of such a type of texture. The angle formed by the axes of particular crystallites (the translation direction of space lattice [c]) and the... 

The ordering of crystallites in the fiber texture is best and univocally described in the quantitative manner... 

The quantitative assessment of the degree of crystallite orientation by x-ray examination is not free of ambiguity. From a comparative analysis [23] in which results obtained from the consideration of (105) and from three different variations of equatorial reflection were compared, the conclusion was that the first procedure can lead to underrated results, i.e., to the underestimation of the orientation. However, it can be assumed that this does not result from an incorrect procedure, but from ignoring the fact that the adjacent (105) reflex can overlap. The absence of the plate effect of the orientation is characteristic of the orientation of crystallites in PET fibers. The evidence of this absence is the nearly identical azimuthal intensity distributions of the diffracted radiation in the reflexes originating from different families of lattice planes. The lack of the plate effect of orientation in the case of PET fiber stretching has to do with the rod mechanism of the crystallite orientation. 

The orientation of crystallites in PET fibers can also be assessed quantitatively by means of IR spectro-graphic examination. In this case, the basis for the assessment are the values of dichroic ratio (R) of the crystalline absorption bands in the fiber spectrogram. The determination of the values of fc is made using Fraser s dependence [24,25] modified by Chranowski [26] ... 

The crystallite orientation in PET fibers depends first and basically on the applicated draw ratio and sec ond on the stretching rate. The values off. characteristics for PET fibers as established by the authors are in Table 5. 

The tensile strength of PET fibers depends on their superstructure and internal orientation. The results from the investigations by one of the authors [54], show that the value of the tensile strength (o-j) is affected by the fraction of taut tie molecules ()3), the crystallites orienta-... 

The low electrical conductivity of PET fibers depends essentially on their chemical constituency, but also to the same extent on the fiber s fine structure. In one study [58], an attempt was made to elucidate the influence of some basic fine structure parameters on the electrical resistivity of PET fibers. The influence of crystallinity (jc) the average lateral crystallite size (A), the mean long period (L), and the overall orientation function (fo) have been considered. The results obtained are presented in the form of plots in Figs. 9-12. 

Figure 15 Electrostatic charge of PET fiber versus average crystallite size perpendicular to the chain direction.

Fibers are thin threads produced by extruding a molten polymer through small holes in a die, or spinneret. The fibers are then cooled and drawn out, which orients the crystallite regions along the axis of the fiber and adds considerable tensile strength (Figure 31.3). Nylon, Dacron, and polyethylene all have the semicrystalline structure necessary for drawing into oriented fibers. 

Active Figure 31.3 Oriented crystallite regions in a polymer fiber. Sign in at www.thomsonedu.com to see a simulation based on this figure and to take a short quiz. 

Nylon fibers are semicrystalline, that is, they consist of crystallites separated by amorphous regions. Hydrogen bonding is an important secondary valence interaction in nylon-6 and nylon-6,6. Individual chains in the microcrystalline regions of nylons are held together by hydrogen bonds. Nylons are resistant to aqueous alkali but deteriorate more readily on exposure to mineral acids. 

---