Regenerated celluloses, crystallinity

Accessible Cellulose in Wood Pulp, Linters and Regenerated Cellulose. Crystalline Reactivity and Yarn Properties2S... 

Sisson has traced the evolution of current concepts of the crystalline part of cellulose structures. The fiber diagram obtained by X-ray diffraction is now known to be produced by a series of elementary crystals, called crystallites, which have a definite arrangement with respect to the fiber axis. It is also known that the crystallites in regenerated cellulose may be oriented to varying degrees with respect to the fiber axis and that the crystallites in regenerated cellulose and mercerized cotton differ from those in native fibers. These hydrate type crystallites appear to be more reactive chemically than the native type. 

Regenerated cellulose Stable in most organic solvents (typically prepared from cellulose acetate as precursor) High crystalline content 4-9... 

The character of the polymethyl methacrylate data is essentially similar to that found for systems atactic polystyrene-benzene at 25°, 35°, and 50° C. [Kishimoto, Fujita, Odani, Kurata and Tamura (1960) Odani, Kida, Kurata and Tamura (1961)] and also atactic polystyrene-methyl ethyl ketone at 25° C. [Odani, Hayashi and Tamura (1961)], and appears to be fairly general for amorphous polymer-solvent systems in the glassy state. On the other hand, the cellulose nitrate data shown in Fig. 8 appear to manifest features characteristic of crystalline polymer-solvent systems. For example, the earlier data of Newns (1956) on the system regenerated cellulose-water (in this case, water is not the solvent but merely a swelling-agent) and recent studies for several crystalline polymers all show essentially similar characters [see Kishimoto, Fujita, Odani, Kurata and Tamura (I960)]. To arrive at a more definite conclusion, however, more extensive experimental data are needed. 

Fig. 9. Correlation plots of (the time corresponding to the inflection point on the differential two-stage curve) and Ct° (the initial concentration of each differential absorption) O PMMA-methyl acetate (30° C). APSt-benzene (25° C). IPSt-LC-benzene (35° C). IPSt-HC-benzene (35° C). cellulose acetate-methyl acetate (20° C). g cellulose nitrate-acetone (25° C). A regenerated cellulose-water (15° C). PMMA = polymethyl methacrylate. APSt = atactic polystyrene. IPSt-LC = isotactic polystyrene of low crystallinity. IPSt-HC = isotactic polystyrene of high crystallinity. Taken from Fujita, Kishimoto and Odani...

If the orientation process in semi-crystalline fibres is carried out well below the melting point (Tm), the thread does not become thinner gradually, but rather suddenly, over a short distance the neck. The so-called draw ratio (A) is the ratio of the length of the drawn to that of the undrawn filament it is about 4-5 for many polymers, but may be as high as 40 for linear polyolefins and as low as 2 in the case of regenerated cellulose. 

The degree of crystallinity of the fibers and the structure of the approximately 80% crystallinity, kraft with 60%, and regenerated cellulose fiber with around 50% show differing degrees of accessibility. A cotton-based paper does have longer life, under adverse conditions, than one made from rayon. However, given acid conditions, all the cellulose fibers finally do degrade and become brittle. 

Straight-line relationships were obtained between the accessibilities by the bromine method and the IR crystallinity indices and the wide angle x-ray scattering (WAXS) indices for 16 native and regenerated celluloses with accessibilities ranging from 70 to 6% (See Table 5.3 and Figure 5.21 and Figure 5.22). 

In the crystalline part, the cellobiose units are closely packed to form Cellulose I in native cellulose fibres and Cellulose II in regenerated cellulose fibres. In Cellulose I the chain molecules are parallel to one another [16]. The folded chain occurs at Cellulose II, in the crystalline regions the chain molecules are antiparallel. Thus, the basis for helical structure for Cellulose I is preferably extended to the structure of Cellulose II [17]. 

Viscose rayon is inherently a weak fibre, particularly when wet, therefore it is highly susceptible to damage if enzymatic hydrolysis is not controlled. The enzymatic hydrolysis of viscose fibres causes a decrease of the intrinsic viscosity from 250 to 140 ml/g and an increase in crystallinity from 29 to 39% after 44 h [34]. Strong changes of the structure, however, are not typical for the enzymatic hydrolysis of cellulosic materials. Neither cotton nor wood pulp show an essential decrease of the DP during enzymatic hydrolysis [35-37]. The kinetics of the enzymatic hydrolysis of regenerated cellulose fibres before and after acid prehydrolysis changes the kinetics from a monophasic to a biphasic first order reaction [38]. 

As a result of these investigations it is generally agreed that naturally-occurring cellulosic fibres contain of the order of 60 to 70 per cent of molecules orientated in crystalline structure. The regenerated celluloses contain 30 to 40 per cent, Terylene 50 per cent, and nylon between 50 and 60 per cent. 

Table 2 Crystallinity index and degree of orientation of crystals of regenerated cellulose fibers calculated from their X-ray diffraction patterns...

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