Dyeing And Finishing

ost textile materials and fabrics require pretreatment before they can be dyed and finished. The preparatory treatments needed depend on the type of fiber in the material and the dyeing and finishing treatments required for a particular fabric. Generally, fibers containing the most types and the greatest amount of impurities require the

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New developments in theory also improve the understanding of this critical step in fabric preparation.
By Warren S. Perkins Technical Editor

Advances Made In Bleaching Practice

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mobile electrons in organic compounds usually are in systems of conjugated double bonds involving carbon, nitrogen and oxygen atoms. A simple alkene can be used to illustrate the effect of oxidation on color of an organic molecule. Oxidation of an alkene can produce carbony1 compounds. The resulting break in conjugation in the molecule decreases the delocalization of electrons and produces colorless oxidation products [Figure

Editors Note: This article is based on papers presented at the 1995 AATCC International Conference and Exhibition in Atlanta. The author references the following sources: (1) E.R. Trotman, Dyeing and Chemical Technology of Textile Fibres, 6th Ed.

(2) A.M.M. Taher and D.M.

Cates, Textile Chemist and Colorist, Vo!. 7, No. 12.

(3) W.G. Steinmiller and D.M. Cates, Textile Chemist and Colorist, Vol. 8, No. 1.
92 ATI January 1996

fiber to interact with dyes. most preparation. Usually the Oxidized cellulose also is subject to preparatory treatments are done on depolymerization under alkaline the material in fabric form. Fabrics conditions, so oxidative damage can prepared for dyeing and oxidation finishing must have sufficient absorbency - C = C - C = O + O = Cand whiteness. colorless colored Fabrics destined for white end-products Figure 1. require a very high degree of whiteness. Those to be decrease strength and change other dyed pastel or very bright shades physical properties. also require a good level of whiteIndustrial bleaching of cotton is ness. most commonly done using hydrogen peroxide (peroxide). Commercially available peroxide is usually The Role Of Bleaching Cellulose and most other fibereither a 35- or 50-percent solution forming polymers are white in their in water. Hydrogen peroxide is relanatural state. However, impurities tively stable under acidic conditions in fibers may absorb light, causing and unstable in alkaline medium. the fibers to have a creamy, yelThe activity of peroxide in bleach lowed or dull appearance. baths is regulated by controlling The goal of bleaching is to decoltemperature, pH and alkalinity of orize the impurities that mask the the bath. natural whiteness of fibers. OxidizEven though hydrogen peroxide ing agents are used to bleach has been used successfully for fibers. Bleaching processes must be decades and is currently the domicontrolled closely so that color in nant agent for bleaching of textiles, the fibers is destroyed with minimal its mechanism of bleaching is damage to the fibrous material. obscure and controversial. Both ionic and free radical mechanisms Color in organic substances usually is due to the presence of have been proposed to account for mobile electrons in either inorganic bleaching with peroxide. The ionic or organic substances. These mechanism proposes that the active

species in peroxide bleaching is the perhydroxyl ion (Figure 2: see Editors Note, Reference 1). The fact that bleaching rate increases with higher alkalinity in H20, Figure 2. the bath supposedly supports this ionic mechanism, since higher alkalinity would drive the reaction in Figure 2 to the right, increasing the concentration of perhydroxyl ions. According to this mechanism, as the perhydroxyl ions are consumed in reactions with coloring matter and cellulose, they are replenished by ionization of peroxide in the bath. The free radical mechanism suggested by Cates et al. (References 2 and 3) proposes that a donor substance (D) transfers one electron to peroxide, which then forms a radical () (Figure 3). A chain reaction ensues to form new radicals that HO 2+ HO2 Figure 3. propagate the process as the free radicals react with coloring matter and cellulose. The free radical mechanism accounts for the effect of pH by proposing that perhydroxyl ions can be an electron donor substance to initiate formation of free radicals Figure 4).
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merization of cellulose under alkaline conditions. Peroxide bleaching usually is activated by addition of alkali such as caustic soda or soda ash to the bath. The bath is stabilized by addition of sodium silicate or other agents. Wetting agents and chelating agents also may be added. The time, temperature and concentration of peroxide used vary depending on the process. Continuous, batch and pad/batch processes can be used in peroxide bleaching. High temperature in the bleach bath greatly accelerates peroxide bleaching.

Mechanism Observations
At the recent AATCC International Conference, scientists from Ciba-Geigy (Drs. Dannacher and Schlenker) reported extensive laboratory research on the mechanism by which hydrogen peroxide bleaches textiles. Through a process of elimination, the paper gave a convincing argument that superoxide (0 2 -) is the active bleaching species. They discounted a theory that nascent oxygen exists in bleach baths, based on the high energy requirement for decomposition of hydrogen peroxide into water and oxygen. The ionic mechanism involving perhydroxyl ions was repudiated based on the observation that the pH of maximum bleaching effect is below the pH where maximum concentration of parasol ions should exist. Addition of hydroxyl radical

f g HO + HO- + HO 2

Another interesting paper at the conference dealt with peroxide bleaching of pigmented protein fiber. Different mordanting conditions were used in an effort to optimize bleaching of black human hair by peroxide. Iron was deposited on the fibers along with a sequestering agent to improve absorption of iron on the fibers. The treated fibers were then bleached with peroxide and tested for color removal and physical properties. Peroxide bleaching was accelerated by the presence of iron. The mechanism operating in this process is probably the action of ferric ions on peroxide to form free radicals. Initially, the hydroxyl radicals are formed followed by perhydroxy radicals. As was the case in hightemperature peroxide bleaching described above, the species most likely responsible for bleaching is superoxide. A similar free radical mechanism may account for the activation of peroxide as an oxidant (bleaching agent) by ultraviolet light. UV light homolytically severs the hydrogen peroxide molecule, forming hydroxyl radicals (Figure 6). The hydroxyl

Figure 6. radical then reacts with another hydrogen peroxide molecule, forming a perhydroxyl radical and water (Figure 7). Again, the potential exists for the active bleaching species to be superoxide.

Figure 4. The free radical mechanism is consistent with the observation that certain ions (Fe+, Ca2+, Mg2+) inhibit the decomposition of peroxide while other ions (Cu2+, Fe3+, etc.) catalyze the decomposition of peroxide. Regardless of the mechanism, the decomposition of peroxide to release the active bleaching species must be controlled to achieve optimum bleaching. Formation of molecular oxygen in the bleach bath is undesirable, since it is lost to the atmosphere. Molecular oxygen also has been associated with depoly94 ATI January 1996

bleaching, indicating that hydroxyl radicals are not responsible for the bleaching action. However, use of increasing concentrations of a superoxide scavenger, hydroquinone, caused a marked decrease in peroxide bleaching activity. The paper supports Catess free radical bleaching theory, since perhydroxyl radicals would be converted almost completely to superoxide at pH and alkalinity conditions used in peroxide bleaching

Figure 7. A paper by Bruce Evans of DuPont examined bleaching of cotton hosiery with hydrogen peroxide. Hosiery is most commonly bleached using sodium hypochlorite. But both OSHA and the EPA are concerned about use of hypochlorite in manufacturing. The paper also pointed out that hydrogen peroxide is less corrosive than hypochlorite to the continuous tunnel washers that are now the state-of-the-art equipment for hosiery bleaching. m

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