Mercerized cotton, crystallinity

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. 

Strong basic solutions, such as sodium hydroxide, penetrate the crystalline lattice of a-cellulose producing an alkoxide called alkali or soda cellulose. Mercerized cotton is produced by aqueous extraction of the sodium hydroxide. 

Average Ordered Fraction (AVF) and Crystallinity (XAL) of Cotton and Mercerized Cotton Determined by Sorption... 

The effects of cellulase enzymes on cotton substrates that were dyed with various classes of dyes have been reported. It was found that vat dyes do not inhibit cellulase activity on cotton, and hydrolysis of the substrate with subsequent color removal transpires. In contrast, cellulase activity on cotton was inhibited by the presence of some direct and reactive dyes. There is the probability that a dye-enzyme complex is formed with less activity than that of the free enzyme. The increased weight loss from enzymatic treatment on untreated cellulose is associated with a slight reduction in dye sorption, and this may be because of a reduction of amorphous regions in cellulose where dye molecules are usually sorbed. Cellulase activity is more prominent on mercerized cotton than on unmercerized cotton. This is because mercerization is associated with a decrease in the crystallinity of the cellulosic structure [540]. One major negative aspect of cellulase treatment of cotton fabric is the strength loss associated with the approximately 3-5% weight reduction under normal treating conditions. Of course, this is to be expected after cellulose is hydrolyzed. Future research efforts may lead to processes in which enzymes... 

Accessibility. The extent of etherification is often determined by the accessibility of a substrate under a given environment. As Segal discussed [8], the extent of methylation with ethereal diazomethane (indicated by methoxyl contents) increased in the order hydrocellulose (5.9%) < cotton (7%) < mercerized cotton (14.9%) < cuprammonium rayon (18.6%) < ball mill-ground cotton (20.6%). Crystallinity of the cellulose was considered to be a significant factor. 

The effect and action of enzymes seems to be very limited because ol the stronger conditions of alkali of mercerizing strength. Enzymatic hydrolysis is accelerated when mercerization is carried out without tension [44]. The greater accessibility and lower crystallinity of cellulose mercerized without tension is a decisive factor in the enzymatic hydrolysis process. Mercerized cotton is generally more prone to enzymatic modification than untreated cotton. 

The Unit Cell Dimensions of the Crystallites Present. Cellulose occurs in four recognized crystal structures designated Cellulose I, II, III, and IV (27). These can be distinguished by their characteristic x-ray diffraction patterns. Cellulose I is the crystal form in native cellulosic materials. Cellulose II is found in regenerated materials such as viscose filaments, cellophane, and mercerized cotton. Cellulose III and IV are formed by treatment with anhydrous ethylamine and certain high temperatures, respectively. These four crystal forms differ in unit cell dimensions—i.e., the repeating three-dimensional unit within the crystalline regions. These dimensions are shown in Table VI for the four crystal forms. 

Crystalline Material (X) and Accessibility (A ) of Cotton and Mercerized Cotton Calculated fran Water Sorption Data ( )... 

Fig. 16. Integrated fraction of the downfield component of the C4 resonance line versus degree of crystallinity, /, determined by X-ray analysis., Native cellulose O, regenerated cellulose , mercerized cotton and ramie. (The data for regenerated cellulose samples, except for cupra rayon fibres, were reproduced from ref. 45).

An important chemical finishing process for cotton fabrics is that of mercerization, which improves strength, luster, and dye receptivity. Mercerization iavolves brief exposure of the fabric under tension to concentrated (20—25 wt %) NaOH solution (14). In this treatment, the cotton fibers become more circular ia cross-section and smoother ia surface appearance, which iacreases their luster. At the molecular level, mercerization causes a decrease ia the degree of crystallinity and a transformation of the cellulose crystal form. These fine stmctural changes iacrease the moisture and dye absorption properties of the fiber. Biopolishing is a relatively new treatment of cotton fabrics, involving ceUulase enzymes, to produce special surface effects (15). 

Cotton thread treated with concentrated NaOH shrinks and has an increased luster. Tire resulting "Mercerized" cellulose has changed into other crystalline forms. The major one is cellulose II, in which the chains in the sheets are antiparallel.693 Cellulose II may also occur to some extent in nature. Many other modified celluloses, e.g., methylcellulose, in which some -OH groups have been converted to methyl ethers70 are important commercial products. 

The most important alternative crystalline form is cellulose II. This form can result from treatment of cellulose in concentrated alkali, such as 23% NaOH, followed by rinsing in water. This is also the main form that results from crystallization of dissolved cellulose, such as regeneration of rayon. Supercritical water can also effect the transformation [216]. The treatment of cotton in milder alkali, for industrial mercerization, amounts mainly to disruption and decrystallization rather than transformation to crystalline II. Cellulose II can occur as the native state when the normal biosynthesis and subsequent crystallization is disrupted [217-219]. 

Cellulose crystallinity is not uniform. A simple experiment of immersing cellulose in cold concentrated alkali, a process used for enhancing the dye-absorbing quality of cotton fabrics called mercerization, was found already in the 1930s on the basis of X-ray diffraction to produce a cellulosic allomorph with different unit cell dimensions [13,14]. This was given the... 

Mercerization has been recognised as a method for removing immature (dead) fibres to obtain level dyeing effect on cotton fabrics. The dead fibres are underdeveloped and appear as flat or slightly twisted tapes. They are non-crystalline, convolutions are sometimes absent, cell walls are extremely thin and the lumen is collapsed and hence do not contain dye to same extent as matured fibres. 

Hydrocellulose II, cotton treated with NaOH for mercerization and then hydrolyzedwith HCa to provide a highly crystalline cellulose II powder... 

Table I, native celluloses such as ramie, cotton linters and Avicel, both before and after mercerization dissolved completely in this solvent system. More recently we have established that highly crystalline algal celluloses are also readily dissolved in this system.

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