Crystalline birefringence

Figure 2. Polarized light micrograph of transverse section of white oak from Krabbendijke, a marine wreck from the late Middle Ages in the Netherlands. Persistent birefringent crystalline cellulose is restricted to the primary wall-middle lamella complex of fibers and small vessels.

Many ceUulosic derivatives form anisotropic, ie, Hquid crystalline, solutions, and cellulose acetate and triacetate are no exception. Various cellulose acetate anisotropic solutions have been made using a variety of solvents (56,57). The nature of the polymer—solvent interaction determines the concentration at which hquid crystalline behavior is initiated. The better the interaction, the lower the concentration needed to form the anisotropic, birefringent polymer solution. Strong organic acids, eg, trifluoroacetic acid are most effective and can produce an anisotropic phase with concentrations as low as 28% (58). Trifluoroacetic acid has been studied with cellulose triacetate alone or in combination with other solvents (59—64) concentrations of 30—42% (wt vol) triacetate were common. 

A common measurement usehil in predicting threadline behavior is fiber tension, frequentiy misnamed spinline stress. It is normally measured after the crystallization point in the threadline when the steady state is reached and the threadline is no longer deformed. Fiber tension increases as take-up velocity increases (38) and molecular weight increases. Tension decreases as temperature increases (41). Crystallinity increases slightiy as fiber tension is increased (38). At low tension, the birefringence increases as tension is increased, leveling off at a spinline tension of 10 MPa (1450 psi) (38). 

Optical Properties. When light falls on an object, it is either partially absorbed, reflected, or transmitted. The behavior of the object as it relates to each of these three possibiUties determines visual appearance. Optical properties of fibers give useful information about the fiber stmcture refractive indexes correlate well with fiber crystalline and molecular orientation and birefringence gives a measure of the degree of anisotropy of the fiber. 

These phenomena are most rapid and easiest to observe in fairly concentrated aqueous detergent solutions, that is, minimally 2—5% detergent solutions. In a practical quaHtative way, this is a familiar effect, and there are many examples of the extraordinary solvency and cleaning power of concentrated detergent solutions, for example, in the case of fabric pretreatment with neat heavy-duty Hquid detergents. Penetration can also be demonstrated at low detergent concentrations. As observed microscopically, the penetration occurs in a characteristic manner with the formation of a sheathlike stmcture, termed myelin they are filled with isotropic Hquid but have a Hquid crystalline birefringent skin. 

Annealing temperature rc) Annealing time (min) Birefringence (An) Anid Volume crystallinity (%) TTM fraction Critical dissolve time (s) Amorphous orientation function (/ )... 

Fig. 9. a Density vs. birefringence (proportional to preorientation f ) for a polyethylene melt, b Degree of crystallinity vs. f vor polychloroprene... 

Techniques for differentiating between amorphous and crystalline are (i) sharp melting point, (ii) sharp peaks in the solid state infrared fingerprint region, (iii) optical birefringence observed when solid is viewed in a phase contrast microscope and (iv) sharp peaks in the powder X-ray diffraction pattern. 

The physical properties (7-10) of our E-V copolymers are sensitive to their microstructures. Both solution (Kerr effect or electrical birefringence) and solid-state (crystallinity, glass-transitions, blend compatibility, etc.) properties depend on the detailed microstructures of E-V copolymers, such as comonomer and stereosequence distribution. I3C NMR analysis (2) of E-V copolymers yields microstructural information up to and including the comonomer triad level. However, properties such as crystallinity depend on E-V microstructure on a scale larger than comonomer triads. 

The main limitation of birefringence is that it only provides an averaged orientation value without any discrimination between amorphous and crystalline phases, or between the components in polymer blends, copolymers, and... 

Figure 18 shows the percent crystallinity obtained by birefringence measurements for NR at various elongations as a function of temperature. The relative shapes of the curves in this Figure show the pronounced temperature and strain dependence on the strain induced crystallization of NR. Of particular importance is the relatively high amounts of crystallinity that develop at room temperature. 

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