Scope of Work

The prior study dealt with the efficiency of a few wetting agents. Thereafter the application of wetting agents in the decolourisation of denim fabric is studied. Various oxidizing and reducing agents were used to either decolourise denim or change its colour. Some novel effects on Denim fabric were obtained. Below is Part 1 of the Literature study, the next part deals with Experimentation and Results.

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INDIGO AND POTASSIUM PERMANGANATE16 Indigo has been used as a dye for as much as 4,000 years but it wasnt until 1883 that its chemical structure was elucidated. However, its interaction with permanganate had not been studied in much depth until recently when E. Malik found isatin and anthranilic acid among the oxidation products that occur when indigo dye is bleached with potassium permanganate. It is also well know and documented that isatin is formed in high yield when indigo is oxidized with nitric acid or chromic acid or a mixture of the two.

The formation of isatin from indigo due to permanganate oxidation is understandable from the general reactive behaviour of KMnO4 toward carbon-carbon double bonds, which in great many cases results in the cleaving of the double bonds with the formation of carbonyl compounds. Because the central double bond is also part of indigos chromophoric group, the bleaching action of KMnO4 on this dye is also explainable. What is more difficult to understand is how free anthranilic acid can occur as the end product of permanganate oxidation in light of the fact that all aminobenzoic acids, when unprotected at the amino groups, are rapidly degraded in the presence of permanganate.

Metallic salts may combine with indigo oxidation by products such as anthranilic acid to form a latent yellowish discolouration product in acid wash denim which is wet processed by potassium permanganation. Assessments made by M. N. Larsen using atomic absorption spectrometry indicate that a reduction in some denim metallic salt levels is associated with reduced yellowing.

Potassium permanganate is one of the preferred bleaching agents for the so-called acid wash process used industrially to create special looks in denim garments. These looks can range from very slight random bleaching effects to an almost complete white out of the blue indigo dye.

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Residual chemicals from the oxidation process can certainly leave a residue behind, especially if the rinsing is inadequate. Potassium permanganate oxidation of indigo results in manganese dioxidea brown, water-insoluble compound.

3 Indigo + 2 KMnO4 + 4H2O = 6 Isatin + 2MnO2 + 2KOH 6 Isatin + 4 KMnO4 + H2O = 6 Anthranilic acid + 6CO2 + 4MnO4

Oxidation of indigo is generally achieved by using potassium permanganate solutions, resulting in products isatin and anthranilic acid. Further by-products have also been suggested by Malik. Isatin is an orange-coloured water soluble product. Anthranilic acid is a white to pale yellow crystalline powder, which is also water-soluble. With proper washing and rinsing, these chemicals should be rinsed away. The presence of high concentrations of aluminium and the fact that the yellow compound is difficult to remove has led Rucker et. al, to postulate that the aluminium can mordant with the primary amine being diazotized and coupling to form a yellow dye.

As with all wet-processes involving chemicals, a good rinse is always necessary in order to remove any chemicals which can irritate the skin of the purchaser, oxidize or photo-react to cause a problem later on. Yellowing does not occur immediately but occurs during storage. A good rinse with soap in the first rinse is always a good idea. It has also been shown in other washing and rinsing studies that several short rinses with fresh water is better than one long rinse for an equal length of time. The experience has also shown that yellow discolouration in permanganate frosted garments can be caused by incomplete removal of either the manganese dioxide or the divalent manganese in the neutralization and rinsing steps, respectively.

GARMENT WASH7,12 Over the last few decades varies garment washing techniques have been used on different material types to create special colour effects and washed looks are achieved particularly in Study on Denim treatments Part 1 Literature Survey Page 3

natural fibrous materials such as cotton, dyed with dyestuffs or pigments with good washingdown properties.

Since jean manufacturer first began offering the pre washed indigo jeans, washing techniques have expanded to an art of all of their own. The consumer literally has numerous choices of pre washed jeans to suit individual preferences. With the market expansions, wash techniques are being combined with fabric construction variation and surface finishing techniques. Now a whole new era of surface pattern effects and soft hands are emerging.

A variety of washing effects are achievable on denim goods dyed with the traditional indigo dye, which is selected on account of its brilliant blue colour and excellent fading characteristics to washing and abrasion. Depending on the dyeing method, goods dyed with indigo usually have poor colour penetration with ring-dyed yarns; thus the removal of the deeply-dyed surface fibers under mechanical abrasion causes the dyed colour to fade readily during washing. TYPES OF DENIM WASHES12 Most garment processors use the rotary drum type garment washer. These machines have advance in their capabilities by offering microprocessor controls and extraction capabilities which are tailor made for specification. As the type of product and the production capacity often decide which equipment is best suited, most machinery has the versatility to handle a wide variety of products. Features such as variable speed drum rotation, reverse direction of rotation, compartment configuration, etc. adds to the versatility.

Cotton fiber dyed with indigo have a ring dyed effect. The indigo dye is layered onto the outside of the yarn and the inside fibres are left undyed or white. This is what gives indigo denim the unique characteristic of a wash down effect to a rich blue shade when subjected to multiple launderings. Techniques such as caustic treatment of the warp yarn may be utilized to render a more pronounced core effect. This allows the garment washing to be done much faster as more dye is located on the outside. Also a salt and pepper effect can be achieved. Study on Denim treatments Part 1 Literature Survey Page 4

Traditional Washing This entails desizing the materials with enzyme (amylase) and detergent followed by washing at an elevated temperature. The degree of colour fading is comparatively slight, but uniform depending on whether the denims is a deeply dyed classic denim or only moderately dyed with poor penetration the removal of sizes imparts a much softer handle than the stiff unwashed denim.

Stone washing: Volcanic rocks or pumice stone are added to the garments during washing as abradant. Colour fading is more apparent but less uniform. The degree of colour fading depends on the washing time, stone ratio (weight of stones relative to the weight of garment), sizes of stones, liquor ratio and garment load. The major limitations of stone wash are: Process control is difficult due to variation in quality and size of stones. Yellowing of washed garments due to the presence of residues of stone washing. Machine damages are maximum due to the use of stones. The metal surface is damaged due to abrasion. The dust coming out of the stones is not eco-friendly and can cause environmental problems. Garment accessories are also damaged. The powdered dust coming out of stones gets accumulated on the garments giving a rough feel and an odd look. Fabric deterioration also takes place due to which the life of the garment is reduced.

Acid washing: Acid washing is usually done by dry tumbling the garments with pumice stones presoaked in a solution of sodium hypochlorite (5-10%) or potassium permanganate (3-6%) such that localized bleaching takes place resulting in a non uniform sharp blue/white contrast. Addition of water is

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not required. the colour contrast after tumbling can be further enhanced by a subsequent optical brightening. Soft stones that dust off easily are more suitable for this process. Acid wash is otherwise known as snow wash ice-wash, white wash, frosted wash or other terminology used to indicate the dry tumble of pre-soaked stones on garments. Some stone are better suited for this process with respect to the absorbency and softness. The stones should be soft as to dust easily when tumbled.

The presoaked stones are allowed to drain and can be tumbled in the machine with waste fabric to remove excess solution. This prevents spotting and a more even surface colour discharge. At a low weight ratio of stone (0.5:1) a light frost can be achieved. A white-out effect is accomplished by using higher ratios of stones to garments (3:1).

Some companies now offer presoaked stones to increase production and reduce labour costs. The advantages here are the elimination of pre-soaking, removal of excess solution from the stones and having stones of more uniform properties; especially when they are man-made or preformed. Carus Chemical Corporation has a unique system called Denox. This is an extruded stick or chalk or potassium permanganate that produces similar effects as soaked stones. The advantage here is that no sludge. Ocean wash incorporated offers a pre-formed stone of various hardness soaked with various concentration levels of potassium permanganate. The introduction of such products shows that this area of textiles processing is important enough to warrant research and development that will continue to give fresh, new apparel items to the consumer.

Denim bleaching In this process a strong oxidative bleaching agent such as sodium hypochlorite or potassium permanganate is added during the washing, with or without stone addition. Decolouration is usually more apparent depending on the strength of the bleaches, liquor quantity and treatment time. A strong bleach with a short treatment time is preferable owing to the better contrast of the bleached colours. The bleached goods should be adequately afterwashed to minimise subsequent yellowing and tendering of the goods. Study on Denim treatments Part 1 Literature Survey Page 6

To ensure colour uniformity after bleaching, the materials should be carefully sorted before bleaching. Denims dyed to varying degrees of colour penetration can result in apparent colour difference after bleaching.

Caustic wash This is also known as hard wash. Because of the ring dyed effect of indigo, bio washing with caustic gives a fader look. However, it is not to a wider extent as stone wash or enzyme wash.

Bata wash Hydrochloride of little higher degree of available chlorine is used for this effect thus giving a higher degree of removal of indigo.

Sand blasting This technique is applied to give the stone-wash look, by creating a localized abrasion or colour change. The degree of fading is obtained by subjecting the stone wash garments to the bombardment of sand at various pressures in certain areas such as knees and elbows. In this method blasting substance are generally sand, metal granules or particles. Another method that is employed to get the similar look is by spraying a solution containing sodium hypochloride or potassium permanganate. After sparing the desired areas on the garment, they are neutralised, rinsed, softened and dried

Stoneless Stone WashingAn innovative concept in Denim Washings8,10,11,14 Cellulase enzymes have been used for years in food processing to upgrade grains and soyabeans in human consumption, to clarify citrus fruits and to produce table juice concentrates. While not new technology, their use in the denim garment washing industry to give a stone washed look to denim without the use of pumice stones or by reducing their use is certainly new and exciting. When cotton fabric is treated with a cellulase solution under proper conditions, Study on Denim treatments Part 1 Literature Survey Page 7

certain properties are affected. Cellulase hydrolyzes cellulose by reacting to the beta 1, 4glycoside bond of the cellulose molecule. As a result the fabric surface becomes smooth with the loss of surface fibre and the hand becomes soft. There is also a loss in strength proportional to the amount of weight reduction.

Application technology: Cellulase products are available to the textile industry from at least 12 different sources. Classification of cellulases is usually by the pH range in which they are most effective. Acid stable, neutral stable and alkaline stable are the categories that are effective for textile application. Neutral stable enzymes are more effective in the 6.0-7.0 pH range, while acid stable enzymes have higher activity at pH values of 4.5 to 5.5. These currently are the two most popular enzymes used in garment and fabric applications. Alkaline stable cellulase is being incorporated into some home laundry detergent products to aid in stain removal and to improve surface after multiple launderings.

For cellulase to become active as an enzyme under normal processing conditions temperature and pH are critical factors that must be controlled. The pH should be maintained throughout the cycle by means of buffer solutions. Some fabrics or garment like indigo denim can have a high alkalinity resulting in an increase in the pH during the washing procedure. It has been reported that neutral cellulase is stable over a broader pH range. A safe operating temperature for the enzymes would be 55 to 60C. At a lower temperature a longer cycle may be necessary. Concentration of the cellulase would depend on the fabric and degree of wash down. Once the cellulase enzyme begins to react on the cellulose fibre, the surface is partially hydrolyzed.

Mechanical action between the garment and equipment, or surface-to-surface contact of the fabrics, removes the weakened surface fibres. This results in a cleaner, smoother surface appearance. In the case of indigo or other surface dyed fabrics, the colour is removed or reduced in much the same way as stones. Because there is, to a lesser degree, a difference between cellulase enzyme wash and regular stone wash, some facilities will add stones to the procedure.

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Since the cellulase enzyme is reactive only to cellulose, the starch size should be removed first using an alpha-amylase or oxidative desize.

Cellulase activities Cellulases are secreted by various fungi as complex mixtures of three major types of enzymes endoglucanases (EG), cellobiohydrolases (CBH) and (CB). A general model for the action of these different enzyme components in the hydrolysis of cellulose is that EGs cause random hydrolytic chain scission at the most accessible parts of cellulose chains, CBHs split cellubiose from the ends of cellulose chains in a stepwise manner along cellulose chains, and cellobiase hydrolyzes cellobiose to glucose. Efficient hydrolysis of crystalline cellulase by cellulases requires the synergistic action of the Egs and CBHs. Advances in bio-technology have lead to the development of recombinant DNA techniques and have made possible the manipulation of the genes of cellulase-secreting fungi. Using these techniques, new straines can be developed enabling industrial production of novel cellulase compositions. These may provide the opportunity for achieving radically new cellulase finishing effects as well as improving the existing ones.

Cellulolytic enzymes are currently applied in textile processing, where mechanical action is always present such as in jets or rotating drum washers. It is already recognized that cellulases with strong EG activity are preferred for achieving the aged look on denims and this effect is best obtained in machines that provide vigorous beating action. It is also know that a careful balance between cellulase activity and mechanical action is required to achieve to efficient fuzzfibre and pill removal without excessive fabric strength loss. These facts indicate that cellulase composition and mechanical action are key features during cellulase processing of cotton.

The characterization of cellulase enzymes poses special problems related to the multi component nature of the enzymes and their complex synergistic action in various substrates. Crystalline or amorphous forms of celluloses as well their derivatives are all degraded by cellulases. Therefore, the specific action of cellulases is related to the hydrolysis of the 1,4--Dglycosidic bonds and is incorrect just to relate them to the hydrolysis of cellulose polymers. Study on Denim treatments Part 1 Literature Survey Page 9

Substitute for stones Using cellulase as a substitute for stones prevents the damages to wash-machines and the garments, eliminates the need for disposal of the used stones, improves the quality of the wastewater and eliminates the need for labour-intensive removal of dust from the finished garment. Because stones are no longer added, the garment load can be increased by as much as 50%. Some highly-abraded finishes cannot be achieved by using cellulase alone. In such cases enzymatic stone washing can achieve the desired look. In general, enzyme fits well with existing stonewashing conditions. However, specific parameters such as pH and dose will need an adjustment to get the optimal performance from the cellulase.

Temperature control is important to obtain reproducible results. As a rule of thumb, enzyme activity doubles per 10C increase but above a certain temperature, the enzyme denatures and loses activity completely. It is found that the neutral cellulase is slightly more heat stable than the acid cellulase making it impossible to operate at 55C rather than 50C as recommended for the acid cellulase.

Buffering of the cellulase bath is very important as alkalinity is often released from the garment during the wash cycle. For the acid cellulase, buffering can be done with acetic acid and sodium hydroxide. For neutral cellulase, phosphate buffer can be prepared. In areas that cannot use phosphates other buffering systems are available.

The time needed for tumbling to obtain the desired look depends on liquor ratio, type of washing machine, as well as the jeans. The time can be reduced by using more cellulase, but only to a limited extent because the mechanical effect becomes the rate limiting factor. Too high a dose of cellulase will reduce the strength of the garment.

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The rinsing procedure depends on the desired look. A few rinses are necessary to clean away the released indigo. To clean up the colour of the garments, a detergent wash or light bleach is sometimes included. Another reason for the rinses after the cellulase wash, is to get rid of the cellulase as it will cause strength loss if left on the garments.

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References
1. Tomasino Charles, Chemistry and Technology of fabric, Preparation and Finishing, NCSU 2. http://pharmcal.tripod.com/quicklnk.htm 3. http://periodicals.wanfangdata.com.cn/qikan/periodical/jxsyhg/jxsy2001/0102/01 02mle.htm 4. Shenai V.A, Technology of Textile Processing, VOL 5, Sevak Publications, Mumbai, 2002 5. Skinkle J.H, Textile Testing, Chem. Publication Co., NY 6. Jay C Harns, Detergency Evaluation ant Testing, Interscience Publishers, Inc., NY, 1954 7. Paul R., Naik S. R., Textile Dyer and Printer, 30(5),16,1997 8. Paul R., Naik S. R., Textile Dyer and Printer, 30(5), 13,1997 9. Shelke Vinod, Colourage, 48 (1), 25, 2001 10. Schmitt B., Prasad A. K., Colourage, 45 (10), 20,1998 11. Kochavi D, Vidibaek T, Cedroni D, American Dyestuff reporter, (9), 24, 1990 12. Micheal Tyndall R., American Dyestuff Reporter, (5) ,22,1990 13. www.rossari.com 14. http://science.ntu.ac.uk/research/EnzyTex/TitleCo2.html#Contents 15. http://www.touchofcotton.com/fabricsmart 16. Paul R., Naik S. R., Textile Dyer and Printer, 30(10), 17,1997

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