Dyeing with Indigo - Natural Fermentation Vat

Why Indigo? Indigo is a dye different than any other. It does not require any mordant. Rather it is dyed through a living fermentation process. The process "reduces" the Indigo, changing it from blue to yellow. In this state, it dissolves in an alkaline solution. The fibre is worked in the solution, or "vat". When brought out to the air, it is a bright green. Slowly the air changes it to the beautiful deep and rich blue of Indigo.

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click to enlarge Buy Indigo

Indigo in some form is used in all traditional cultures, for it is the only clear and fast natural blue. Indigo dyeing was one of the first speciality professions. Yet it is easy to keep a home pot going, and most colonial homesteads had one. This recipe is the one most commonly used for home dyeing. It contains no harsh chemicals nor toxic metals. It can be used to dye any natural fibre. An additional beauty of dark Indigo is that when ironed or pounded, the blue cloth takes on a beautiful coppery sheen - the same sheen that is seen on the well reduced Indigo vat, when it is ready for dyeing. Indigo: Natural Vermentation Vat NOTE: requires advance preparation of about one week.

4 oz. ground Indigo 2 oz. ground Madder 2 oz. wheat bran (buy at any health food store) 12 oz. washing soda ("soda ash")

(above amounts are by weight ounces, not volume ounces.) Combine in about a three gallon pot of warm water. Always add these amounts in proportion. A larger vat can be made, for example with: 1 lb. ground indigo, 1/2 lb ground madder, 1/2 lb ground bran and 3 lbs washing soda in about a 10 gallon plastic tub. However, I advise starting small, till you are comfortable with the process. The size of the pot is determined by the amount of fobre you need to dye at one time. A three gallon pot is good for yarn skeins of 4 to 6 oz., while a 10 gallon or larger tub will be needed for yards of fabric. WARMTH: It is necessary to keep the vat warm, but not hot, around 100 - 110 Fahrenheit. It is the same temperature for raising bread or making yogurt. It should feel pleasantly warm to the hand.

To keep it warm, a light bulb in a reflector can be put under the vat, with a blanket over it to keep in the heat. (See illustration, next page.) In a warm climate no additional heat is needed, but be sure the vat is out of direct sun so it does not overheat. TIME is very important. It takes time for the vat to ferment and it does no good to try to rush the process. The first time, it takes about a week for the vat to ferment and be ready to dye. With "renewals" the time needed is a bit less, four or five days. It takes time to do the dyeing. The fibre is "dipped" several times to build up a dark color, with airing between each dip. The vat itself lasts a long time. I have had my current vat over fifteen years. In traditional cultures there are vats over 100 years old. The vat is "renewed" with more Indigo and the other ingredients in proportion, whenever the dye value weakens. Then let sit a few days to re-ferment. Indigo dyeing by this natural fermentation method is a slow-steady process. It is good meditation. Stir the vat once a day. The idea is to integrate the undissolved Indigo, madder and bran that settles to the bottom, back into solution. And to do this without incorporating air into the vat. So stir gently. Keep the vat covered. Air is the enemy of a good Indigo vat. The level of liquid in the pot should just allow room for the yarn dyeing, without spilling. The less air between surface and lid the better. I use a domed lid, turned upside down. If you leave more than 2" of air at the top of the vat, it will not reduce properly. The vat is ready for dyeing when:

It develops a coppery film on the top of the vat. The liquid, lifted carefully in a glass jar, will appear green. A test piece of fibre or paper will emerge green and turn blue in the air.

Now is the exciting time to begin Indigo dyeing! 1. Wet your fibre out very well in warm water. It must be well wet out. Any air remaining in the fibre will oxidize Indigo in the vat, and this must be avoided. 2. Put on rubber gloves! You don't want to scare people with blue hands; also the strongly alkaline vat may irritate your skin. 3. Enter the fibre (yarn/fabric) into the vat very carefully, to avoid adding any air to the vat. Now the fibre must be "worked" in the vat, under the surface. It should not be stirred, but with your gloved hands, gently, slowly and deliberately squeeze the liquid through the fibre while you hold it under the surface. Any time you break the surface you introduce

air into the vat and this you do not want to do. 4. After you have worked it several minutes, carefully and slowly raise it out of the vat, squeezing the excess Indigo solution back into the vat. Do this squeezing as close to the surface as you can, as dropping liquid will bring air into the vat. 5. The fibre should be a bright clear green. It will start to turn blue in the air immediately. Lay it out on newspaper and let it air for 20 minutes. Repeat the dips up to five times for dark Indigo Blue. Air between each dip. For lighter shades, fewer dips are needed. 6. Rinse well. Then leave the fibre to air overnight. Soak and do a final rinse in the morning. The vat lasts indefinitely. It is begun with a certain amount of Indigo, and all other ingredients as given, in proportion. Dyeing is begun, with the darkest color dyed first, then medium, then lights. Between dyeings the vat must rest overnight or an extra day. This is because, during dyeing a certain amount of the Indigo is oxidized in the vat. Allowing it to rest lets it re-reduce that Indigo. An oxidized (blue colored) vat won't dye well. The Indigo color will only wash out and rub off too quickly. When the vat is "exhausted", and will only dye light shades, it is time to renew it. All ingredients are again added, again in correct proportion. The vat is let to ferment for several days, and is ready to dye when it shows the proper signs. In this way a vat can be kept going for many years. If one wishes to rest from dyeing for several weeks, simply turn off the heat source, and keep the vat cool for that period. Stir it vigorously on occasion. When ready to dye again, warm it up, renew it with the ingredients, and proceed as before. It is not good to leave a vat unused for too long, as it is a living process and may then get cranky about starting up again. Also it is important to exhaust the vat before leaving it, or it may over-ferment and ruin any Indigo remaining in it. Over time a deposit of sludge will develop at the bottom of the vat. You may want to gently lower a screen into the vat before dyeing, to keep your fibre from pickinging itup during the dye process. Be sure to remove the screen after the day's dyeing, so you can stir the vat before closing it. For greens, dye you fibre Indigo first, then rinse well and overdye with alum mordant and your chosen yellow dye. For purples, dye the Indigo first, rinse well, then mordant and dye over with any red dye. The indigo vat is very alkaline. It is important to rinse out all the alkalinity. Just to be on the safe side, I always double rinse my indigo dyed textiles. First I rinse well just after dyeing, then I let air overnight. Next day I soak in two successive waters for about an hour each time, rinse again, wring and dry.

Squeeze solution through yarn for best penetration. Always work under the surface of the vat. Always wear rubber gloves. More About Indigo Indigofera is a legume. The plant looks similar to alfalfa, but is usually larger. It is an excellent rotational crop for increasing soil fertility. In southern Mexico, where some of the current Indigo of commerce originates, it is naturalized and grows in fallow fields, so no effort is spent cultivating it. Indigo dye must be prepared from the fresh plant in an exacting and elaborate process that takes about a month. The Indigo plants are harvested and brought to a central location. They are soaked in water and allowed to ferment. This separates the dyestuff from the plant. The solution is then beaten to oxidize and precipitate the Indigo. Excess water is poured off and the sludge is dried. This sludge, packed into balls or patties and fully dried, is the Indigo dye of commerce. This Indigo comes to us in the form of a hard, dark blue colored cake. It must be ground to be used for dyeing. Very small amounts can be ground in a mortar and pestle. Use a bit of water to facilitate grinding and keep down the dust. A Corona Corn mill is what I use. Meat grinders also work. A zip-loc baggie cinched over the grinding plates catches all the powder and keeps blue dust from getting everywhere. In most traditional cultures, the color(s) of ones clothing indicates ones status or class. Indigo blue has long been associated with the less than aristocratic classes. Indigo blue has still the association of "The Working Class". We use the distinction as "Blue Collar Workers" and "Blue Jeans". These clothes were originally dyed with indigo. In the past, Indigo has been a prolific dyestuff. It is relatively easy to grow and dye, and is quite fast. It withstands well the many washings that work clothes require. In most cultures, Indigo dyeing is or was a specialty. The dye process is unique, and the facilities require a stable set-up. Vats made of great clay pots set in the ground are commonly used in warmer climates. If more heat is needed, pits for burning charcoal are placed between clusters of the vats. Indigo dyeing is practiced today in Japan, Southern China, Tibet, India, Indonesia, Indo China, Africa, especially Nigeria, Southern Mexico and Guatemala, and it has recently been reintroduced to Turkey. Traditional fermentation methods are used. However, many of these cultures now use synthetic Indigo, manufactured from coal tar or petroleum. Natural Indigo contains several related dye chemicals that give different shades of blue. As much as twenty percent of the dye may be a violet tone called Indigo Red. These complexities give Natural Indigo nuances and depths that cannot be

achieved with the synthetic substitute. Here is a page with more about the chemical properties of indigo. An additional beauty of dark Indigo Blue, is that when ironed or pounded, cloth so dyed takes a coppery sheen - the same sheen we see on the top of the well reduced Indigo vat.

PO Box 14 Somerset, MA 02726 orders 1-800-2-BUY-DYE technical support 508-676-3838 fax 508-676-3980 e-mail promail@prochemical.com www.prochemical.com

Indigo
Please read the directions carefully before starting. Indigo belongs to a class of dyes called vat dyes, which are among the oldest natural coloring substances used for textiles. Until the beginning of this century, indigo could be obtained only from plants. Two things are required to make indigo work, Thiox, the reducing agent, and Lye, the alkali. The dye vat is prepared in two steps: The stock solution and the dye vat. The stock solution then added to the dye vat. Always do test samples before working on a large project.
While Indigo and the chemicals used are comparatively safe and non-toxic, it is best to treat them all with caution. Wear rubber gloves to minimize contact with hands. Eye protection is urged as you are working with alkalies and strong reducing agents. Always work in a well ventilated area. Good house-keeping is essential to good results. Utensils used for dyeing should never be used for food preparation. See caution for Lye (Sodium Hydroxide) below.

Supplies: For Cotton, linen, rayon, and silk PRO Indigo grains For Wool PRO Indigo grains

Lye (Sodium Hydroxide) Thiox (Thiourea Dioxide) Metaphos Non-Iodized Salt Distilled White Vinegar Ivory Bar Soap or Ivory Flakes

Lye (Sodium Hydroxide) Thiox (Thiourea Dioxide) Synthrapol SP Unflavored Gelatin Clear Household Ammonia Distilled White Vinegar Ivory Bar Soap or Ivory Flakes

Procedure for dyeing cotton, linen, rayon and silk 1. Determine whether you wish to make a 20 gallon (80 liter) full size vat or 4 gallon (16 liter) mini vat and prepare the stock solution. Full size vat PRO Indigo 1 cup (70 gm) Cold water 6 cups (1.5 liters) Lye 1 cup (215 gm) Thiox 2 Tbl (25 gm) Mini vat 3 Tbl (15 gm) 1 cups (375 ml) 5 tsp (23 gm) 1 tsp (4 gm)

2. Mix Indigo with enough luke warm water to make a lump free paste. 3. Measure the COLD water into a separate container. Carefully add the lye and set aside to cool. 4. In a third container, add the Thiox to 1 cup (250 ml) of warm water (Mini Vat use cup (125 ml) water). Stir gently to dissolve. 5. Slowly add the lye solution to the pasted Indigo and stir to make a smooth mixture. 6. Next, slowly add the thiox solution. Avoid creating air bubbles. 7. Stir this mixture gently from time to time, until reduction is complete. Reduction is complete when the stock solution turns yellow. Otherwise the surface is a deep blue from oxygen coming in contact with the dye. Set the jar of stock solution in a pan of HOT Water, if necessary. Raise the temperature no higher than 135oF (57oC) for 15 to 30 minutes or until reduction takes place.

8. Make the dye vat. Full Size Vat Warm Water 120oF(49oC) 20 gallons (80 liters) Metaphos 3 Tbl (63 gm) Salt 2 cups (600 gm) Thiox 4 tsp (15 gm) Mini Vat 3 gallons (12 liters) 1 tsp (7 gm) 1/4 cup (75 gm) tsp (2 gm)

9. Measure warm water into dye vat container. 10. Stir in the Metaphos and salt. 11. Dissolve the Thiox in a small amount of warm water and add it to the dye vat. 12. Add reduced stock solution by carefully lowering the container into the Dye Vat and sliding the liquid out at an angle. Stir gently. 13. After 30 to 60 minutes the vat should be clear greenish-yellow with a shiny, dark blue metallic surface. The vat is then ready to use. If the vat is not clear and greenishyellow in color wait an additional 30 to 60 minutes. It can take as long as 6 hours for proper reduction.

Maintaining the Indigo vat * Every precaution MUST be taken to keep oxygen out of an Indigo vat!!! * For your vat, use a deep vessel with a narrow top to minimize exposure to air. * When adding additional Stock Solution or dissolved chemicals to the vat, do not pour them in. Lower the container into the vat and slide the liquid out at an angle. Using the Indigo vat *Before dyeing, machine wash the fabric on HOT cycle with a minimum temperature of 140oF (60oC) water OR by hand in a pot on the stove with tsp (2 gm) PRO Dye Activator or Soda Ash and tsp (2.5 ml) Synthrapol per pound (454 gm) of fabric. Rinse thoroughly.

* Thoroughly wet fabrics before dipping in vat. A warm water soak for 15 to 30 minutes is recommended. Wearing gloves, squeeze out excess water evenly. * Gently push the dark blue scum aside before entering fabric in the vat. Where scum clings to the cloth it will look dark blue. However, after dyeing is finished the spot will wash off the surface, leaving a light undyed spot. * Lower fabric into the vat very gently, without splashing. * Slowly manipulate the cloth while working below the surface of the vat. This helps the dye penetrate. Keep fabric submerged for the duration of each dip, 2 to 3 minutes. DO NOT SWISH the fabric around in the vat. * Gently squeeze out excess dye BELOW the surface and remove fabric from the dye vat. DO NOT allow fabric to drip into the vat after dyeing. *Let fabric oxidize (turn blue) for approximately 15 minutes. Repeat dipping and oxidizing until youve reached the desired depth of blue. If youve gotten some of the dark blue scum on your fabric, then give it a rinse in plain room temperature water. This way the fabric that is underneath the scum can oxidize. Let the fabric air dry before washing. Remember that after washing, the final color will be one to two shades lighter. If youve done a bound resist dyed fabric its best to let the fabric dry completely before untying so the threads wont rip the fabric. Washing the fabric Wash the fabric in hot 135oF to140oF (57oC to 60oC) water for 10 minutes in a generous bath of Ivory bar soap or Ivory Flakes. With a knife, its easy to flake off a 1/8 inch thick peel of soap. Stir the wash bath occasionally and rinse the fabric until the water runs clear. Hang cotton and rayon to dry. If youre dyeing silk then soak it for 10 minutes in a bucket of acid soak. Make the acid soak by mixing 2 Tbl (30 ml) of White Distilled Vinegar in 1 gallon (4 liters) of room temperature water. Then rinse the silk thoroughly in plain water. Troubleshooting the dye vat * If the vat appears grayish and watery, it is exhausted. This means that all the indigo has been used. An addition of Stock Solution is needed. * If the vat has been left for a few days, it may need to be "Sharpened" with a small amount ( tsp (2 gm) for full size vat) Thiox, dissolved in water. * If the vat changes from yellow-green to blue, or if blue specks appear, more Thiox is needed. Add a small amount ( tsp (2 gm) for full size vat) Thiox, dissolved in water. Stir gently. Wait 15 minutes and check vat again before dyeing.

* If white specks appear or the vat appears "milky" add small amount (1 tsp for full size vat) of Lye, dissolved in cup water. Stir gently. Wait 15 minutes and check vat again before dyeing. * Occasionally, more than one addition is required to revive a vat. Use small amounts, and wait 15 to 20 minutes between additions, testing each time. Excess alkali or reducing agent can unbalance the vat, making it impossible to build up deep shades. Be patient, and the vat will have a long life. * Always dissolve Thiox and Lye in water BEFORE adding to the dye vat. DO NOT add dry flakes. * Cover with a tight fitting lid when not in use. Troubleshooting fabric * Dye washes off of fabric: too little reducing agent. * Crocking off (Dye rubs off): too little alkali Procedure for dyeing wool 1. Prepare the stock solution. Mini Vat PRO Indigo 3 Tbl (15 gm) Lye 5 tsp (23 gm) Thiox 1 tsp (4 gm) 2. Mix Indigo with enough luke warm water to make a lump free paste. 3. Measure 1 cups (375 ml) of COLD water into a separate container. Carefully add the lye and set mixture aside to cool. 4. In a third container add the Thiox to cup (60 ml) water. Stir gently until its dissolved. 5. Slowly add the Lye solution to the pasted Indigo and stir to make a smooth mixture. 6. Add the Thiox solution slowly to avoid making air bubbles. 7. Stir gently from time to time until reduction is complete. Reduction is complete when the stock solution turns yellow. If necessary set the jar of stock solution in a pan of HOT

Water. Raise the temperature no higher than 135oF (57o) for 15 to 30 minutes or until reduction takes place. 8. Make the dye vat. Mini Vat Warm Water 120oF (49oC) 3 gallons (12 liters) Unflavored Gelatin powder 1 tsp (2 gm) Synthrapol 1 tsp (5 ml) Clear Household Ammonia 2 Tbl (30 ml) Thiox 1 tsp 4 gm) 9. Measure warm water into dye pot. Use non-reactive metal such as stainless steel or un-chipped enamel as your dye pot. 10. Mix the remaining ingredients in the order listed above making certain each item is thoroughly mixed before adding the next. 11. Add reduced stock solution by carefully lowering the container into the dye vat and sliding the liquid out at an angle. Stir gently. 12. After 30 to 60 minutes the vat should be clear greenish-yellow with a shiny, dark blue metallic surface. The vat is now ready to use. 13. Maintain a 120oF(49oC) temperature throughout the dye process. Soak your wool for at least 15 minutes in 1 gallon (4 liters) of 120oF (49oC) water with 1 tsp (5 ml) of Synthrapol. The wool should sink in the Synthrapol soak, not float. Squeeze out excess water evenly from the wool. Gently push the dark blue scum aside before putting your wool into the vat. Wool that is not thoroughly wet carries large quantities of air which quickly oxidize the reduced Indigo and destroy the vat. 14. Soak the wool in the dye vat for 30 minutes with gentle, intermittent stirring, making sure all the wool remains below the surface of the vat. 15. After 30 minutes, remove the wool, squeeze excess liquid back into the vat while holding the wool close to the surface to avoid introducing air into the vat. 16. Let the wool oxidize (turn blue) for approximately 15 minutes. 17. Repeat dipping and oxidizing until the desired depth of blue is obtained.

18. After the final dip and the fiber is fully oxidized, gently wash the wool in a warm 120oF (49oC) water bath for 10 minutes in a generous bath of Ivory bar soap or Ivory Flakes. With a knife, its easy to flake off a 1/8 inch thick peel of soap. Gently stir the wash bath occasionally and rinse the fiber until the water runs clear. Then soak the wool for 10 minutes in a bucket of acid soak. Make the acid soak by mixing 2 Tbl (30 ml) of White Distilled Vinegar in 1 gallon (4 liters) of room temperature water. Then rinse the wool thoroughly in plain water and hang to dry. Copyright 2002
http://www.denimsandjeans.com/denim/manufacturing-process/indigo-dyeing-methods-engineeringcolor-wash-fastness-and-fashion-effects/

Indigo Dyeing Methods Engineering Color, Wash Fastness And Fashion Effects

Indigo Dyeing

Indigo dyeing is unique and because of the complex chemical reactions should be correctly viewed a a form of chemical engineering. Only Indigo dyeing requires multiple dye applications for a dark shade. Color consistency of Indigo in recent decades has been unsatisfactory as a result of machine designs that do not apply basic principles of fluid mechanics properly and unstable dye mixes. Commonly, a single dye lot will have between 8 and 15 visually different shades from beginning to end and also have shade differences from one side to the other.

Indigo Dyeing Methods

Indigo dyeing follows the same basic steps regardless of machine design. Scour or dye bottoming in a heated tank, washing tanks, dyeing(1-20),a heated tank for topping (optional) and wash tanks. In different areas of the world,the same color is produced using 1.8, 2.0 or 4% Indigo depending on dyeing method.

Dark Indigo(1.8%)

1. 15% caustic cold 2.Wash 60C 3.Wash 60C 4. Wash cold Drying cylinders hot Steamer cold Boxes 5-12 Indigo Steamer cold 13.Wash 50C 14. Wash 50C 15. Wash 50C 16.Wash 50C /Softener Chemical Feed 120 g/l 50% caustic 60g/l Hydro powder Feed 1.4 liters per minute

Stock Mix 80 g/l Indigo Pure 100 g/l 50% Caustic 70 g/l Hydro powder.

Dark Indigo Color

This was an example of a typical method used in the U.S. for a very dark shade. In order to produce the same depth of color as 1.2% in the U.S., in Latin America 2.0% is used and in Asia from 2.4 to 2.8%. The U.S. method results in more surface (ring dyeing), which loses color faster.

Darkest Indigo Shades

Very dark shades of Indigo are in demand currently around the world. Many companies use 4% or more Indigo on weight of yarn, which is expensive. 2% Indigo will produce the same depth if low levels of caustic are used(0-0.4%) For dark Indigo that does not lose color 2% applied normally, with an Indigo bottom.

Light Indigo Shades

Dyeing Indigo in light shades results in a sky-blue impossible with any other dye. This is useful for shirting fabrics that are not strong enough for stonewashing, bleaching or cellulase treaments. Special procedures are necessary in order to avoid colorfastness problems.

Light Indigo 0.4%

1. 4% caustic 90C 2.Wash 60C 3.Wash 60C 4. Wash 60C Bypass drying cylinders Bypass steamer Close off boxes 5-8 Boxes 9-12 Indigo 13. Wash 50C 14. Wash 50C 15. Wash 50C 16.Wash 50C/softener

Control Of Sulphur Bottoming

The typical methods used for dyeing sulfur bottoms result in denim shade differences. When applied as light colors, sulfur dyes should be dyed at temperatures <60 C, If dextrin reducing agents are used, which require 85 C, there will be variation. Sulfur bottoms are an exception to the normal pH for sulfurs(11), requiring 12.

Sulfur Bottom

1. Pad sulfur(cold) Steamer hot 2.Wash cold 3.Wash 50C 4.Wash 50C Boxes 5-10 Indigo 11. Indigo or wash 50C 12. Indigo or wash 50C Bypass steamer 13. Wash 50C 14. Wash 50C 15. Wash 50C 16.Wash 50C or softener

Sulphur Topping

In topping the sulfur dye is applied after the Indigo dyeing. Sulfur topping permits much darker color than a sulfur bottom, but is duller. Sulfur topping colors include black, blue-black, yellow brown and green. Sulfur toppings are used to produce slub appearances in normal yarn.

Sulfur Top

1. Pre-wet 2% caustic 90C 2.Wash 60C 3.Wash 60C 4. Wash cold By pass drying cylinders

Bypass steamer Boxes 5-10 Indigo 11. Wash 60C 12. Pad sulfur topping Steamer hot 13. Wash cold 14. Wash 50C 15. Wash 50C 16.Wash 50C/Softener

Reactive Dyes in Indigo Dyeing

Reactive dyes can be applied on specially-Designed Indigo machines. Small 150 liter boxes are inserted inside the larger dye tanks for Indigo and sulfur. Steamers, drying units near the front of the machine and high-quality dye padders are required for quality dyeing.

Pad-Dry Chempad- Steam Reactives

1. Pre-scour wetter plus chelate 90C 2.Wash 50C 3. Pad monochlortriazine dye cold, neutral pH Drying cylinders hot Pad caustic in salt brine Steamer hot Bypass boxes 5-10 11. Soap 90C 12. Soap 90C Steamer hot 13. Wash 60C 14. Wash 60C 15. Wash cold 16.Wash cold/softener

Pad Steam Reactive Topping 1. Pre-wet 10% caustic 90C 2.Wash 60C 3.Wash 60C 4. Wash cold By pass drying cylinders Bypass steamer Boxes 5-10 Indigo 11. Wash 60C 12. Pad Dichorotriazinyl cold with bicarbonate Steamer hot 13. Wash cold 14. Wash 50C 15. Wash 50C 16. Wash 50C / softener

Control Of Indigo Dyeing

The Indigo dyeing process begins with a concentrated mixture of Indigo, sodium hydroxide and reducing agent. This concentrated mixture (70-90 g/L Indigo) is delivered by pipes to the Indigo dye tanks where the dye concentration is reduced to 1-4 g/L for dyeing the cotton.

Dye Mixing Procedures

Many denim companies find it difficult to control original and washed Indigo shades. The primary source of color differences is the instability and inconsistency of Indigo mixtures. As the concentration of reducing agent going to the dye machine changes, the color changes.

Uniform Indigo Mixtures

For consistent Indigo dyeing, the mixture must have consistent concentrations of Indigo, sodium hydroxide and reducer from the top of the mixture to the bottom. The main cause of inconsistent Indigo mixtures relates to concentration levels. Instability of Indigo mixtures results from the decomposition of sodium hydrosulfite.

Consistency of Concentration

There is a limit to the amount of any chemical that can be dissolved in water. When the limit of solubility of any chemical In water is exceeded, precipitation occurs. Indigo mixes should not have more than 20% solids. At higher levels, chemicals and dye sink to the bottom of the tank.

Improving Dyeing Consistency

When reducing agent sinks to the bottom of the tank, there is a higher concentration than in the top of the tank. As the dye enters the machine, the higher concentration results in a lighter, greenercolor and as the dye from the top of the tank enters the machine, the color is darker and redder.

Dye Control In Feeding Tank

Stirring the tank for 2 minutes will improve dye uniformity between top and bottom. To avoid settling of dye and chemicals the total solids should not exceed 20%. The glass plate test can be used to test concentrations of hydrosulfite in the top and bottom. If dye requires 50 seconds to oxidize, there is about 50 g/L of reducer.

Buffers In Indigo Dyeing

Alkaline buffers have been used to make very dark shades of Indigo with as little as 1% dye, more ring-dyed, faster fading. Reductive buffers can eliminate color differences in Indigo-dyed denims and can reduce hydrosulfite use by 30-50%.

Indigo Dyeing Problems And Potential -Part 1

October 24th, 2011 by Harry Mercer | Filed under Manufacturing Process.
This is a highly technical article on Indigo dyeing by Harry Mercer. Read on if you are technically oriented.. This is the first of a series of 4 articles addressing the problems and potential of Indigo dyeing. The Indigo color is the principal source of the almost magical appeal of denim. The dyeing process is unique among all methods of commercial dyeing, with the unusual design that is necessary for cotton dyeing with Indigo. Indigo has been used for thousands of years, principally on wool and silk

fibers for which Indigo is more suitable The difficulties in dyeing cotton with Indigo are apparent with the numerous different shades that result, up to 15 per dye lot and also with side-center side variation. Elimination of this variation has been accomplished, but it requires a deep understanding of the unusual variables of Indigo dyeing. The 2 keys to success in manufacturing denim is firstly the dyeing, then the finishing, both of which are more complex to conduct at a high level of quality. The failure of most denim companies to overcome the challenges in denim wet-processing is the reason why they are held hostage to low profit margins. Part 1 of 4 MACHINERY Indigo dyeing is a unique process that makes denim special and distinguishes denim operations from all other types of cotton fabrics. No other method of cotton textile dyeing requires the multiple application of dye to achieve a dark color, thousands of liters of dye bath, slow production speeds and extremes of color variation and color-fastness. Indigo dyeing has been conducted without these problems. The 2 most significant sources of Indigo dyeing are the

control of chemical concentrations, which will be addressed in future articles, and the machine itself.

Machine factors that affect Indigo dyeing results

1) Circulation system design: Indigo dye in its reduced form consists of dye particles that have been partially solubilized and exists in the form of charged colloidial particles. Colloidial dispersions will sink due to the influence of gravity and require some agitation to keep them uniformly dispersed in the dye box. If sample are collected from different parts of an Indigo dye box(top, bottom, front and back), the concentrations are usually different. The uneven distribution of dye in the box as the machine operates contributes to color variation. For many years, BASF, a leader in indigo dye for most of the 20th century, recommended that the volume of the dye box be turned over 2 or 3 times an hour. This means that if the box volume is 2000 liters that 4-6000 liters of flow into and out of the dye box is needed to prevent low concentrations in part of the box and high in others. Indigo machines produced in recent decades have been furnished with pipes that are too small to deliver the right kind of flow. In terms of Reynolds number , the flow should be slightly beyond laminar, in the low transitional range to ensure uniform disper-sion while avoiding turbulence that would destabilize the dye. Also, for uniform dispersion of Indigo, the entry line should be positioned in the yarn exit side of the box near the top, while the exit line should be at the yarn entry side near the bottom. Many Indigo machines have the dye entry line on one side and the exit line at the yarn entry, which is a

cause of cross-shade variation.

2) Dye box design: In a previous article I discussed the effect of dye box design on the color consistency of Indigo. In most indigo machines the box design is responsible for massive losses of hydrosulfite at the surface of the dye boxes during operation which results in economic losses as well as variations in hydrosulfite concentrations in the machine which leads to color variation. The principle is known as Specific Surface Area which means that the larger the surface area of the Indigo box to the volume, the faster the hydrosulfite is lost. So, in a 2000 liter box with 2 square meters of surface area , the hydrosulfite will decompose at twice the rate of a 2000 liter box with 1 square meter of surface area. The total hydrosulfite losses in a typically larger box of a rope range will average around 15%, while in the smaller boxes of a typical sheet range the losses will be from 4570%. 3) Tension Control: High yarn tensions on continuous Indigo dyeing machines has 2 significant effects- the yarn loses strength and the ability of the dye to penetrate the cotton fibers is reduced. The loss in yarn strength results in higher warp breaks in weaving, meaning lower efficiency and higher weaving off-quality. The reduced penetration of Indigo into the fibers results in rubbing fastness problems and a higher per cent Indigo on weight of yarn for a specific depth of shade. 4) Immersion time: Indigo dyeing is a form of wet-on wet processing. The yarn is normally scoured and washed before entering the dyeing section, which means that it is already wet. In order for the Indigo dye to enter the wet yarn efficiently a process known as liquor exchange is necessary in which the Indigo dye/water displaces the water already in the yarn. This is a slow process and the longer the immersion time , the more easily the dye penetrates into fibers and yarn, resulting in better colorfastness and darker color. Until the 1970s, Indigo machines operated at speeds of 12 meters per minute through the much larger boxes of rope ranges, so the immersion time was 2-3 times longer than on modern sheet ranges. The dye penetration was complete which resulted in the darkest possible color with 3% Indigo and that would never fade.

http://www.denimsandjeans.com/denim/manufacturing-process/indigo-dyeing-problems-andpotential/

Indigo Dyeing : Problems And PotentialPart 2

November 11th, 2011 by Harry Mercer | Filed under Manufacturing Process.
This is a guest post by Harry Mercer on Indigo dyeing. It is second part of the article in series. The first part can be seen by clicking here

Preparation For Dyeing

In the previous article, the basic machine factors in Indigo dyeing were discussed. There are many other details required to achieve the highest quality Indigo dyeings , but ultimately the most important factors involve the preparation of Indigo and chemical feeds to the machine. Approximately 80% of Indigo dyeing control depends on the stability and consistency of the dye and chemicals being sent to the machine. 1) Raw materials: The basic ingredients for Indigo dyeing are the Indigo dye, sodium hydroxide and the hydrosulfite (sodium dithionite). Indigo is an insoluble vat dye which means that it cannot enter the cotton fiber until it is made soluble by the process of reduction .Reduction is basically a process where hydrogen is produced which opens up the Indigo dye molecule allowing it to attach to a water molecule which carries the vat dye into the fiber. The most commonly-used 2) The reducing chemical is known as sodium hydrosulfite, but this nomenclature is incorrect because the molecule does not contain hydrogen. The hydrosulfite acts on the sodium hydroxide to split it into NaO and hydrogen, both of which attach to the dye molecule in the reduction process. 3) The reduction of Indigo with sodium hydroxide and sodium dithionite is known as vatting and has been used for thousands of years. Vatting refers to mixing the dye and chemicals into a tank or vat with some stirring and then waiting from 1-4 hours usually for the complete reduction of the dye to occur which is noted when the solution color is a clear, yellow-brown.. The solution then is referred to as leuco Indigo, a Greek word meaning without color. The concentrated Indigo mix is then ready to pump into the dye machine for dyeing. 4) Most of the variation in Indigo dyeing is a result of instability in this concentrated mix. Sodium dithionite can be extremely unstable, with the concentrations in this feeding mixture becoming smaller with the

passage of time. For example, the initial recipe may specify 100 grams per liter of sodium dithionite, but by the time the last liter goes into the machine, the concentration often drops to 20 to 30 grams per liter and each 5 gram per liter loss in dithionite concentration produces a small Indigo color variation. This is evidenced in many denim operations that suffer 10-15 colors after fabric washing per dye lot. 5) There are several causes for the decomposition and strength losses of the reducing agent in the feeding mix: Oxidation at the surface of the tank, unnecessary stirring and high concentrations of ingredients. The stirring should be only enough to maintain consistent concentrations of dye and chemicals from the top of the feeding tank to the bottom. Stirring beyond that will result in more reducing agent being oxidized. Also, in many Indigo operations the stirring units are badly designed with small propellers that turn at high speeds. The Indigo feeding mix is of very high viscosity and in order to stir the entire mix out to the edge of the tank, large propellers that cover the tank diameter are needed. These stirrers should turn at only 10-15 RPM in order to avoid turbulence that would lower the strength of the mix. With regard to concentrations, if the viscosity of the dye mix is too high, the reduced Indigo will not disperse uniformly resulting in areas of varying concentration in the tank that will cause color change as the mix is fed to the machine. Concentrations above 23% solid have a tendency to settle, so that there are very high concentrations of reducer in the bottom of the tank, making a greener Indigo tone when pumped to the dye boxes, and lower concentrations of reducer at the top of the tank, making a redder Indigo tone later in the dyeing. No more than 80 grams per liter of indigo should be added to a feeding mix as this is the maximum amount that has long been proven that can be completely reduced. The amount of reducing agent should also be limited to 80 grams per liter since greater amounts will cause more rapid decomposition due to aerobic and anerobic decay. 6) The concentrations of indigo and reducing agent must be actively managed so that the same concentrations of dye and reducer are feeding to the machine every minute,otherwise the color will change. Management of the feeding mix requires an understanding of the chemistry of reduced dye solutions, measurement of concentrations and skill in correcting strength losses of ingredients in the feeding mix especially of reducing agent and alkali. There are 2 simple , but special test methods to measure the concentration of alkali and sodium dithionite in the feeding mix: a 2-endpoint titration for alkali and the glass plate test which have been in use by the best denim companies for over a century and will be covered in a future article.

Conclusion:
The problem of Indigo color variations is principally a result of inconsistent dye and chemical concentrations going to the machine. A glance at the design of flow of dye and chemicals into Indigo dye machines should make this obvious. The multiple dye box arrangement and circulation in the dyeing section of indigo machines allow the blending of indigo and reducing agents, so the problem of variation obviously starts at the mixing tank. Sponsored Link:

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Indigo Dyeing With Loop Dyeing Machinery

November 4th, 2010 by Harry Mercer | Filed under Manufacturing Process.

The name Loopdye results from the method of skying or air passage for oxidizing the Indigo-dyed yarn and the method of passing through the Indigo dye. On the other 2 important Indigo machine types, the dyed yarn is passed through from 6-8 Indigo boxes on rope machines or 6-20 Indigo boxes on slasher (sheet) Indigo machines, multiple dye boxes being necessary for dark shades because only a small amount of Indigo can be applied in each immersion. After immersion in each Indigo dye box, the yarn is conducted through the air after each box, where the reduced Indigo (yellow-green) is oxidized or fixed by oxygen in the air returning to the original blue, then the yarn enters the next dye box, passes into the air and so forth until the required depth of shade is developed. In the case of rope and sheet ranges, this oxidation takes place above each dye box. In the Loopdye process, there is only a single Indigo box through which the yarn passes 4-5 times. The white cotton is pulled into the front of the machine and passes first through the pre-treatment boxes, then moves through a reactor which can be used for steaming or additional reaction time for sulfurbottoming or Mercerization, followed by washing. The wet yarn then enters the Indigo dye box. When the yarn exits the dye box, instead of moving forward, the yarn is carried to the rear of the machine, around the top and rear of the yarn creel from where it started, passes under the yarn creel where it is returned to the Indigo box for another dye passage. This continuous passage of yarn between the yarn creel and the dye box is in the form of a loop which is almost circular. After making multiple loops through the Indigo dye box the yarn is conducted through wash boxes and on to drying cylinders. The Loopdye machine is a simplified version of a sheet or slasher Indigo machine. After drying the Indigo-dyed yarn, the yarn passes directly to sizing where the yarn is prepared for weaving. Because the sizing part of the machine must stop in order to remove a completed weaving beam, in order to prevent the dyeing unit from stopping as well, there is a yarn accumulator between the drying cylinders at dyeing and the wet-size boxes. When the yarn stops moving on the sizing unit, a series of parallel cylinders begin to move apart allowing the yarn from the dye unit to continue through dyeing and allows the size machine approximately 2 minutes of time to install an empty weaving beam and re-start the sizing machine.

Loopdye Machines in the Denim Industry

In the early 1990s, thee were approximately 30 Loopdye machines in use. Currently, the number is reported to be 60 or so. The biggest concentration of these machines is in Brazil. Vicunha employs 11 of these machines, Canatiba, Santana and Cedro have 2 units each, while Tavex, Tear, Textil Kafi, Santista have 1 each. There are 9 of these machines that have been equipped with nitrogen units which use nitrogen gas as protective blanket over the surface of the Indigo dye. The nitrogen gas prevents oxygen in the air from attacking sodium hydrosulfite resulting in more consistent dyeing and reducing consumption of hydrosulfite, lowering costs and pollution. There are other claimed advantages such as higher speeds and darker Indigo color. Advantages and Disadvantages

1.

2.

3. 4.

5.

6.

7.

8.

Productivity When compared to a multi-box slasher machine, productivity is essentially equivalent since the yarn loading, start-up times and speeds are similar. Rope dyeing machines can produce up to 4 times as much dyed yarn. Capital Investment The Loopdye machine has the lowest initial costs of continuous Indigo dyeing machinery, currently reported to be approximately 25% less than 8 dyebox slasher machine. Operating Costs Maintenance and energy costs are reported to be approximately 20% lower with Loopdye when compared with slasher dyeing and even lower than with rope dyeing. Space requirements The Loop machine with a single dye box requires less floor space than either sheet dyeing or rope dyeing. Rope machines also require higher ceilings because of the design of the airing arrangement. Indigo Dyeing Quality The newer designs of Loopdye are reported to have little of the problems with Cross-Shade (side-to-side) shading than with slasher dyeing equipment. Indigo consistency from the start-to-finish of dyeing can be expected to be better with the inclusion of nitrogen units. Rope machines still have an overall advantage in terms of Indigo dyeing quality, but this may be overcome by employing improved chemical blending. Sulfur dyeing The Loopdye machine can be equipped with a steamer for cold-pad sulfur bottoming which will provide greater consistency than a hot application in the 1st box. The Loop machine is not provided with enough boxes after Indigo dyeing for sulfur topping as the slasher dyeing is. With the newer methods for cold-sulfur dyeing, the Loop machine is ideal for sulfur colors since it the dye can be applied in only one box, which allows for faster color changes and less dye discarded after the dye lot is finished. Rope machines still have the greatest flexibility with regard to producing a full range of denim colors. Weaving Efficiency The methods of dyeing, especially of sulfurs, has a direct effect on warp yarn breakage in weaving, which lowers operating efficiency as well as fabric and garment quality. Experience with the older design of Loopdye machines demonstrated higher levels of warp breaks in weaving than other Indigo machines. Rope dyeing results in the lowest-level of weaving stops, largely because yarn breaks in dyeing can be repaired at long-chain re-beaming. Versatility In the higher denim fashion market, some companies like Vicunha have had success using a combination of Loopdye and slasher dyeing. Overall, the slasher dyeing with its greater number of application boxes offers more flexibility in product development, while rope dyeing provides the greatest flexibility for denim product development.

http://www.denimsandjeans.com/denim/manufacturing-process/indigo-dyeing-with-loop-dyeingmachinery/

Rope Dyeing Vs Slasher (Sheet) Dyeing

May 19th, 2011 by Harry Mercer | Filed under Manufacturing Process.
This is a guest post by Harry Mercer Until 1915, most Indigo dyeing was conducted in skein machines for cotton or loose fiber dyeing for wool. Skein dyeing of Indigo is still the best method for dyeing Indigo on very fine yarns for the delicate high-fashion fabrics. In 1915, the first rope dyeing machine appeared and only in the 1970s was sheet dyeing introduced. The relative advantages of rope as opposed to sheet Indigo machines is a common subject of debate. Based on my 30 years of experience in this area, including as a consultant in about 40 denim operations worldwide, here are some basic observations that I have

made in companies that had only sheet or rope dyeing, but also in many denim companies that employed both. These evaluations included mass-balance studies, benchmarking, weaving efficiency and overall fabric quality.

A. Lower consumption of reducing agent per kilogram of yarn.

The primary reducing agent utilized in Indigo dyeing is sodium dithionite, commercially known as sodium hydrosulfite. The amounts of this reducer that are consumed in Indigo dyeing are greatly in excess of what is necessary for the Indigo dyeing itself. In explanation, in order to reduce 100 kilograms of pure Indigo so that dyeing can proceed, only about 66 kilograms of 100% hydrosulfite are required for the basic reaction. The amount of hydrosulfite actually consumed in Indigo dyeing is often3 or 4 times this amount. There is often hydrosulfite wasted incurred in the initial mixing of the stock mix, due to excessive stirring or concentrations of hydrosulfite greater than 80 grams per liter which promotes anerobic decomposition. A great deal of hydrosulfite is lost because of contact with atmospheric oxygen at the surface of Indigo dye boxes as a result of aerobic decomposition. The surface losses of hydrosulfite are related to the volume and surface area of the dye boxes, with approximately 15% loss in larger Indigo boxes found on rope ranges and 50% or more in the smaller dye boxes found on sheet ranges. The scientific explanation for this phenomenon is related to what is known as Specific Surface Area (SSA). The greater the SSA (the quotient of the surface area and volume), the more rapidly the sodium hydrosulfite is oxidized. The time for half-oxidation (50% loss) is inversely proportional to the SSA, which means that decomposition is slowest in a large dye tank with a relatively small surface area. There are other factors involved such as the initial concentration of hydrosulfite in the dye boxes a higher initial concentration decomposes more slowly. However the most significant source of loss is through surface contact and air brought into the dye tank by yarn. The instability of hydrosulfite in smaller Indigo boxes is also the primary cause of color variation in Indigo dyeing, which on rope ranges is much better controlled. It should also be noted that rope ranges have the advantage in regards to Cross Shade Variation(CSV), which refers to differences in color from side-to-side in the fabric. CSV is basically a result of dye circulation system design where the Indigo enters the dye box from the side instead of the front. In rope ranges that are designed with that style of circulation there is also some difference in the yarn color from to side-to-side, but unlike sheet ranges where the yarns are fixed in their final fabric position, the yarn ropes can be blended to remove the side to side effects. There have been some newer designs of Loop indigo machines which have greatly improved CSV.

B. VERSATILITY IN DENIM PRODUCT DEVELOPMENT

Rope ranges have been designed to apply the widest range of dyeing techniques. For example, the Spectrum Dye Machine available from Morrison contains features like additional steamers and drying sections that allow not only the standard dyeing techniques of sulfur bottoming and topping, but also consistent application of all other cotton dyes such as vats, reactives and directs in combination with Indigo or dyeing yarns with these dye classes only.

Also available are specially designed dye boxes that allow the simultaneous dyeing of 2 different sulfur applications, such as one set of yarn with a sulfur topping and the other set without topping, or with only a sulfur color, which allows flexibility in production. Rope ranges are also easily adaptable for random effects such as space dyeing of yarn. With the rope design, yarns from different dyeings such as Indigo only and sulfur only, can be blended for producing stripe patterns.

C. HIGHER PRODUCTION AND FABRIC QUALITY

Common methods of operating Indigo machines have a damaging effect on yarn quality which results in very high warp breaks in weaving, lowering efficiency and increasing off quality. Yarn on the machines is made weaker as yarn tension increases. Sheet Indigo machines, because they are attached to size machines, have very high levels of yarn tension and therefore higher weaving breaks than yarn dyed on rope ranges. A yarn quality that would result in 10 warp breaks per million weft insertions without Indigo dyeing often will have around a break level of 200 with sheet dyeing, but as low as 15 if processed on rope machines. This is because tension on rope machines is much lower and can be easily controlled at very low levels. Another important cause of high weaving breaks in denim is dirty yarn the cleaner the yarn the higher the weaving efficiency. This is because chemicals not washed from the yarn after Indigo dyeing result in bad sizing and lower protection of warp yarns. Wash boxes on rope ranges are typically more efficient than the smaller wash boxes on sheet ranges that use overflow washing methods. The importance of washing the yarn dictates that it is better not to apply softeners in the final box for rebeaming efficiency which is optimal though improved washing and moisture control after drying. The need for a separate rebeaming step in rope dyeing is often considered objectionable in rope dyeing, but this is actually an important advantage, since yarn breaks can be repaired at rebeaming

resulting in higher weaving efficiencies. Yarn breaks from warping and dyeing cannot be repaired in sheet machines because they are passed directly from dyeing to sizing.

D. FLEXIBILITY IN PRODUCTION
Sheet ranges are usually limited to producing yarn for only 1 weaving set at a time. In a rope range, normally 12 ropes will produce enough yarn for a weaving set and because rope ranges do not pass the yarn directly to the size machine, from 1 to 50 ropes can be dyed at one time. Any combination of yarns can be processed for completely different fabric constructions at the same time and dyed with the same Indigo color. Also, rope ranges can be operated continuously without stopping, which avoids the waste of yarn which occurs when sheet ranges must stop in order to change yarn lots. Because the yarn is sized separately.higher priority fabric orders can be processed without delays resulting from the need to complete a dye set as with sheet dyeing.

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Dyeing Process basically discusses what you do with the dyes. There are today available latest and state-ofthe-art dyeing methods that effectively colour the various substrates. This is a very critical operation carried out in the Dye houses in a series of steps. The pages here gives precious information regarding the various dyeing processes in different industries.

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Dyeing Process Continuous Dyeing Process

Batch Dyeing Process Continuous Dyeing Process Semi-continuous Dyeing Process Pigment Dyeing Process

The working of a continuous dyeing process is described here. The textile substrates are feeded continuously into a dye range. The speeds can vary between 50 to 250 meters per minute. According to Industry estimates Continuous dyeing is a popular dyeing method and accounts for around 60% of total yardage of the products that are dyed. A Continuous dyeing process typically consists the following. Dye application, dye fixation with heat or chemicals and finally washing. Continuous dyeing has been found to be most suitable for woven fabrics. Mostly continuous dye ranges are designed for dyeing blends of polyester and cotton. The step of padding plays a key role in the operation of continuous dyeing. Sometimes Nylon carpets are also dyed in continuous processes, but the design ranges for them is unlike that for flat fabrics. Warps are also dyed in continuous process. Very good examples of such warp dyeing are long chain warp dyeing and slasher dyeing using indigo. A continuous dye range has been found useful and economically sustainable for dyeing long runs of a given shade. One important factor that separates continuous dyeing from batch dyeing is the tolerance factor for color variation. That is more for continuous dyeing as compared to batch dyeing. This is so because of two reasons a) the speed of the process. b) presence of a large number of process variables which affects dye application. The process that is illustrated below is designed for dyeing of blended fabric of polyester and cotton.

Some of the popular methods in continuous dyeing process are Pad-steam, Wet-steam, thermosol dyeing, TAK dyeing, space dyeing, and pad-steam dyeing long chain warp dyeing etc.

Optimizing the Continuous dyeing Process

Continuous and to some extent semi-continuous dyeing processes both are less prone to water consumption than batch dyeing, but results in high concentration of residues. If some strict control measures are taken up it is possible to reduce this losses of concentrated liquor. The following steps may prove useful.

Applying low add-on liquor application systems along with minimising of volume capacity of the dip through when pad dyeing techniques are in operation. Adoption of latest dispensing systems, where the chemicals get dispensed on-line as separate streams. They gets mixed only at the moment just before the delivery to the applicator. Using any of the following systems for dosing of the padding liquor. Important to know that it should be strictly according to the measurement of the pick up: o A proper measurement of the dyeing liquor quantity consumption in comparison to the processed fabric. The resulting values thus obtained are processed automatically and applied in preparing the next comparable batch.

Application of the technique of rapid batch dyeing. Here the dyestuff solution is prepared just in time, with steps that are based on on-line measurement of the pick up. This proves better than those dyestuff that is kept prepared already for the whole batch before the commencement of the dyeing batch.

To increase washing efficiency based on the proven principles like reduction of carry-over and countercurrent washing.

What gives Carpet its vibrant colour?

The carpets that you see in different colour and hues is dyed by a continuous dyeing. A continuous dye range for carpet typically consist of a steamer and a dye applicator. Generally acid dyes are used. Carpet manufacturers are very adept in application of dye for producing special color effects on their product. As a result of this, many variations of dye applicators exist. Under normal circumstances, a very high liquor ratio is must to produce good quality dyeing of carpet. Typically, application method is used to meter the dye solution into the carpet. Patterned effects are produced when the stream of dye that is metered onto the carpet are momentarily interrupted. Streams of variety color dyes are applied in different patterns to create those special effects.

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Continuous Processing of Cotton woven fabric: A general process sequence may be as below:

PRETREATMENT PART: 1. Singe & Desize (Semi Continuous process) 2. Scouring or Boiling 3. Peroxide Bleaching 4. Neutralization 5. Drying 6. Mercerising and washing off to a pH of 6 7. Neutralizing 8. Drying 9. Ready For Dyeing (RFD stage). Singeing & Desizing: Recipe: Bactosol HC = 5 g/l Common Salt = 5 g/l Wetting Agent (100%)= 3 g/l i. Do cold padding with the above chemicals, batch, and keep rotating the batch for 8 hours; ii. Desize washing in 4 compartments @ 90mts/minute speed. 2. Bleaching (Continuous Process)a. Caustic Impregnation: i. Recipe: 1. Caustic Soda = 70gram/liter 2. Lissopal D paste = 10 gram/liter a. 4 dips 1 nip @ 90 mtrs/minute speed. b. Steaming @ 105C for 45 minutes in the steaming chamber. c. Cold Wash in 2 compartments (4 dips 1 nip) x 2 b. J-BOX Bleaching optional i. Recipe: 1. Sodium Hypochlorite = 2 g/l Avl Cl2 2. Dwell time in J box 30 to 45 minutes at room temp. 3. No washing c. Peroxide Impregnation: i. Recipe: 1. Hydrogen Peroxide(50%) = 3 ml/liter 1. a. b. c.

2. Stabilizer = 0.5 gram/liter a. 4 Dips 1 Nip at cold. b. Steam in Peroxide Steamer for 45 minutes. 3. Washing in 5 compartments with each 4 dip and 1 nip. 4. Dry and batch on A frame roller. 3. Mercerisation: (Chainless Merceriser) i. Recipe: 1. Caustic Soda = 280 to 300 gpl 2. Permenol N = 10 g/l a. Cold Padding Speed: i. Bleached Fabric = 25 mtrs/minute ii. Grey Fabric = 15 mtrs/minute iii. Scoured Fabric = 20 mtrs/minute b. Mangle Pressure: 3.2 to 4 kg/cm2 c. Liquor Pickup : 110% d. Recuperation: i. 1
st

compartment strength = 8 to 27 gpl ii. 1

st

compartment temp = 90 to 95C 2 2

iii. compartment strength = 1.6 to 6.4 gpl iv. nd compartment temp = 65 to 95C e. Wash Tanks: i. ank 1 50 to 55C ii. ank 2 Acetic Acid Neutralizing iii. Tank 3 60 to 70C iv. Wetting Agent room temp f. Final fabric pH 5.5.to 6.0 g. Drying:
nd

T T

i. F abric is dried in cylinder or stenter and batched as RFD. 4. Continuous Dyeing Method for 100% Cellulose: a. There are 3 methods: i. Pad Dry Chemical Pad Steam 1. Dye Liquor Preparation & recipe: a. Cotfix Dyestuff = x grams/liter b. Wetting Agent = 2-3 gram/liter c. Antimigartion agent = 8-10 gram/liter d. Mild Oxidizing Agent = 5-10 gram/liter 2. Padding Temperature should be < 35C 3. Liquor Pick up% = 60 to 80 4. Chemical Pad Recipe: Dyestuff G/L Caustic Soda Salt (g/l) Soda Ash (g/l) < 20 Nil 200 20 30 40 Nil 250 20 > 40 Nil 250 20 5. Chemical Padding Temperature < 35C 6. Liquor Pickup 70 to 80% 7. Steaming 45-90 seconds with Saturated steam (101 to 105) the steam should be free from acid. ii. Pad-Dry-Steam: 1. This is carried out on a padding mangle attached with either Hot Flue or Flow Dried. To fix the dyestuff, the dried material is steamed in the normal continuous steamer for 4 to 7 minutes at 100 to 103C. 2. PAD LIQUOR PREPARATION for VS dyes: G/L 10 20 30 40 50 >50 G/L 0~50 0~50 0~50 50~70 50~75 50~75 G/L 5 10 15 15-18 20 20-25 10 10 10 10 10 10

Dyestuff Urea Sodium Bicarbonate Resist Salt G/L

3. Take all the precautions and conditions mentioned for Pad DryChemical Pad-Steam. iii. Pad-Dry-Thermo fix Process: 1. Here again there are 2 processes: a. Soda Ash Method b. Sodium Bicarbonate Method PAD LIQUOR PREPARATION for VS dyes Dye G/L 2 10 20 40 60 Urea G/L 15 30 45 60 80 Soda G/L 8 12 17 25 33 Ash(OR) Sodium G/L 12 18 27 36 45 Bicarbonate

The material is padded in the above liquor at room temperature, dried & thermo fixed as follows: Temperature 100C 120C 140C Soda Ash Process 4-6 minutes 2-4 minutes 40-60 seconds Sod.Bicarnonate process 5-7 minutes 3-5 minutes 60-90 seconds

5. After treatment: a. Overflow Cold wash in soapers 4 dip 1 nip in 2 compartments b. Neutralization with Acetic Acid in the soaped at cold with 2 ~3 g/l Acetic acid. c. Hot wash in one compartment (soaper) @ 80 , 4 dip 1 nip in d. Soaping with 2 g/l of soaping agent (Sandopur RSK) at 90C e. 2nd soaping with 1 g/l soaping agent (Sandopur RSK) at 90C f. Hot Wash g. Hot Wash h. Cold Wash i. Acetic Acid Treatment 1 g/l or Formic Acid treatment 0.5 g/l j. Squeezed on the last mangle and either plaited or wound on a batcher and taken for drying.

Possible Faults that may occur during the above process and check points/rectification: 1. Tailing: The Alkalinity in the mercerized fabric would be un-uniform ranging from 0.25 to 1 and above gram/liter due to inefficient recuperation. That means more and more alkalinity would be carried over on the mercerized cloth and that can be checked in lab by titration. Any variation in the alkalinity of the mercerized fabric can show up through the length by the dye affinity difference and that is tailing. a. Check Point: i. Alkalinity of the mercerized cloth has to be quantitatively checked in the lab at intervals of 500 meters. It must be uniform.

2. a. b.

C/S Variation may arise due to

1. 2. 3.

4.

Desizing Expression of the squeezing mangle is to be checked at frequent intervals. Caustic Impregnation - Expression of the squeezing mangle is to be checked at frequent intervals. c. Peroxide Bleaching: i. S team Pressure ii. S team Temperature iii. Time duration of the steaming are to be controlled. ii. Mercerising Impregnation Mangle expression has to be checked. Recuperator Efficiency has to be checked at every 1000 meters. Final Alkalinity of the mercerized fabric should be less than 0.25 g/l of caustic. Soaper washing Acid for neutralization should be prepared in volume and should be fed in to the neutralization tank continuously. To counter check, the fabric absorbency may be checked in the center and the two selvedges at regular intervals.

3. Face to back variation a. Mangle Expression in the dye padding should be 70% and chemical padding should be 80%. b. Thermosol temperature difference between faces may result in migration of dyestuff. c. In a 2 dip 2 nip mangles, if the expression of both the mangle are not identical, then back to face variation is possible at any stage, dyeing, finishing etc. d. In stenters, if the hot air blowers are not functioning, there may be face to back variation. e. In jigger dyeing machine, out of the two bottom rollers, one is not rotating properly then back to face variation is possible. 4. Specky Dyeing: a. Improper dissolution of dyestuff: i. The quantity of the dyestuff is to be pasted, say for 1 kg of dyestuff, 5 liters of soft water should be used for pasting. Then 1 kg of urea is dissolved in 5 liters of water and this solution is added in the paste and stirred well to make a uniform lump less slurry. About 40 liters of hot water at 85C is added to the slurry which is kept under a high speed stirrer. The hot water should be added slowly to the rotating vertex of the dye slurry. The filter this dissolved dyestuff through a fine gauze. ii. Temperature of dissolution: 1. M-Brand = 50C 2. V.S = 80C 3. ME, XL, HE = 80C. iii. The dissolved dyestuff may be spotted on a filter paper - a uniform circle shows proper dissolution.

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Dyeing of Reactives by Exhaust Method

DYEING OF REACTIVE DYES BY EXHAUST METHOD REACTIVE DYES EXHAUSTION PHASE Primary Exhaustion Phase

Adsorption Diffusion Substantivity

REACTIVE DYES AND DIRECT COTTON DYES

Direct Cotton Dye Reactive Dyes Role of Electrolyte Partition /Distribution Coefficient and Degree of Exhaustion Liquor Ratio Temperature Influence of pH. Influence of Substantivity
Migration phase Secondary Exhaustion Hydrolysis of Reactive dyes Typical Examples REACTIVE DYES Choice of Reactive class of Dyes has become indispensable for application of colours on the cellulosics to provide bright range of shades with reasonably good fastness features. No other class of colours can boast of the versatile range of shades with unmatched brilliance, yet economically viable and cost effective that this class of dyes can offer. Even as Reactive dyes are most popular for dyeing solid shades it is equally sought after for various resist and discharge printing styles, thanks to its suitability to be resisted or discharged readily and effectively The reaction mechanism is apparently simple in that on just altering the pH after exhaustion, formation of covalent bonds between the reactive group of the dye and the OH of cellulose proceeds. For the same reason of ready reactivity with Cell OH groups, it reacts with Water also to get hydrolyzed in which state the dye behaves no better than a direct cotton dye. The

management of the various factors/variables that govern the transport of dye uniformly from an aqueous bath to the cellulose substrate and its preferential reactivity to the fibre than to water is far more complex and critical to perform to obtain a satisfactory dyeing. As the shades invariably are tertiary matchings, the behaviour of individual dyes with different exhaustion and reactivity characteristics, all the more compounds the complexity of the problems of differential shade build up, variations, uneven dyeings, reproducibility, fastness etc multifold. Though there are other methods of dyeing Reactives like pad batch, pad dry-cure or pad-dry-steam etc exhaust dyeing is practiced widely because of its flexibility to process fabrics in rope form and in the case of yarn and other packages, exhaust dyeing is the only alternative as on date. Tubular knit-ware, by its very physical form is more amenable to exhaust dyeing in ropes form; however, advanced machineries obtainable in recent years claim satisfactory open width dyeing by Pad Batch technique. The exhaust method of dyeing would include the following phases 1. Primary exhaustion phase /Migration 2. Secondary exhaustion phase, 3. Fixation (Reaction) phase -Secondary exhaustion and Fixation can run concurrently/over lapping. 4. Washing off phase.

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EXHAUSTION PHASE Primary Exhaustion Phase Exhaustion of dye from the dye bath to the cellulose during Primary Exhaustion phase is governed by the following three physical processes and the phenomenon of substantivity

Adsorption Diffusion, Absorption/ Exhaustion/Migration

Adsorption It would be relevant to briefly look at cellulose structure with respect to its Hydrogen bonding behaviour at the surface layers and in the interiors of the cellulose micro fibrils The interior layers contain both forms - 1Alpha and 1 Beta of Cellulose molecular chains that are packed compactly and there are intra molecular Hydrogen bonding parallel to the 1.4 Beta Glucoside link (OH of #2 to #6 of the succeeding glucose unit and #3 OH with the ring O of the preceding Glucose Unit) that stabilize the cellulose chain.

The other four hydroxyl groups are fully free for Hydrogen bonding. At the surface layers of cellulose even the O-3 (OH) and 2-6 Hydrogen bondings are reported to be absent and therefore all the six Hydroxyl groups in the Cellobiose repeat units at the surface are free to attract Hydrogen bonding with the water molecules.

Adsorption in an exhaust dyeing process is fundamentally the inter-phase phenomenon of a dye (solute) in its solution in water coming in to surface contact with the substrate and forming a surface layer/ coating. That is the starting phase for the rest of the diffusion and absorption phenomenon. In the case of Cellulose exposed to a dye solution in water at slightly acidic pH there is no ionization of cellulose. However, with abundance of free OH groups available at the surface (six numbers in each of the repeat Cellobiose unit), water molecules are drawn in clusters around the cellulose molecules to form hydrogen bonds causing an overall charge separation. Resultant surface thus carries a negative charge known as the zeta potential This surface negative charge would repel the advances of the negatively charged ionized dyestuff anions. The zeta potential is partially overcome due to the presence of large amount of dye anions, some of which are forced across the electron cloud through increase in energy (raise in temperature) or through mechanical agitation to come within the effective distance for the inter molecular forces like Wander Vaals forces/secondary valence forces to facilitate the dye anion to get adsorbed on the surface of cellulose. Presence of electrolyte also helps in providing the positive charge that can effectively neutralize the zeta potential and improve the adsorption. (Discussed under Role of Electrolyte)

Diffusion phenomenon takes over followed by the absorption and migration of dyestuff across the cellulose membrane. Diffusion is influenced by the concentration gradient across the interface of cellulose surface and dye bath, the surface area of the cotton substrate in contact with the dye bath, temperature and time and the physical characteristics of the substrate. This is termed as the primary exhaustion phase. The term exhaustion would include the collective phenomenon of adsorption, absorption diffusion and migration in that order.

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Diffusion Diffusion process is explained by the relationship (Ficks Law of Diffusion in its simplest form.) F= -D (C1-C2) / L And D = Do e -E/RT Where F = Mass flow of dye gms/cm2 sec D = Diffusion coefficient of the dye m2/sec D0 = Diffusion Coefficient at Infinite Temperature C1 = Concentration of dye in the dye bath g/cm3 C2 = Concentration of dye on surface of the fiber g/cm3 L = Thickness of the layer cm e, E, R = Constants (E activation Energy; e exponential; R Universal Gas Constant) T = Temperature Kelvin Applying the above relationship the following dynamics may be inferred during the diffusion / exhaustion stages of the dye to the cotton substrate. F is the dyestuff sorbed across Unit area of the fiber surface in unit time (Rate) (C1-C2) concentration gradient during the process of diffusion. Greater the surface area of the fiber in contact with the dye bath greater is the dyestuff sorbed. The concentration gradient at the initial stages would be higher and therefore the rate of dyestuff transport to the fibre phase will be correspondingly higher tending towards zero at equilibrium. Higher the Diffusion coefficient, lesser the time taken to reach the equilibrium. Time taken for dyeing 50% of the equilibrium depth of shade is an index of the speed Increase in Temperature increases Diffusion coefficient.

D Diffusion coefficient

Temperature

Since surface area is a factor, the characteristics of the fiber and construction would influence the diffusion. Nature of cotton from different sources would have different shape, cross section, micronaire, fineness, impurities, etc and different packing densities of the cellulose molecular chains thus altering the surface area characteristics. The corollary is that thinner the fibre/count and lower the density factor greater is the surface area available and better would be the diffusion.

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The term substantivity is primarily a measure of the amount of the molecular dye chromophore that can penetrate/diffuse into the interstices of cellulose micro fibrils assisted by physical forces from an aqueous dye bath. This is influenced by the salt concentration in the dye bath, the liquor ratio, the temperature and the fibre surface area characteristics, besides the chemistry of the dye chromophore. Substantivity ratio is the unit concentration of dye on the fibre to the unit concentration of dye in the bath at the equilibrium state (both expressed in the same units)

The process of primary exhaustion proceeds to its limiting values dictated by the substantivity beyond which it ceases. In the absence of salt, the dye uptake by substantivity phenomenon as stated above is around 20 to 40% of the starting bath concentration or lower, a figure far too low to have any significant economically feasible colour yield. Therefore, as a general rule, without salt additions, substantvity by primary exhaustion of Reactive dye to cellulose cannot be improved or maximized, at the present status of Colouration technology.

[Efforts are on for reduced salt /salt-less systems based on changes in the chemistry of the dyes to exhibit reduced anionic behaviour, fibre substrate modification/sensitization to display cationic behavior to induce exhaustion with less/no salt, while retaining the reactive system for the ultimate fixation. Such developments are still in the R&D Labs and not presently available for bulk]

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REACTIVE DYES AND DIRECT COTTON DYES Reactive and Direct Cotton dyes sport similar dye chromophoric structures but for the Reactive groups present in the Reactive dyes as opposed to Direct cotton dyes. The Reactive dyes are smaller sized more akin to Acid class of dyes (not necessarily as a general rule) with Reactive groups. Direct Cotton Dye Direct Cotton Dyes molecules are engineered to include some or all of the important features listed below 1. More number of hydrogen bonding groups, groups that would facilitate inter molecular attraction / diminish repelling forces and groups that can chelate with hydroxyl groups of the Cellulose 2. Molecules of sufficiently large enough size and shape that on aggregation could get trapped in the interstices of the Cellulose molecular chains thus difficult to be removed/washed off.. 3. Optimized number of solubilizing groups (invariably -SO3Na), just enough for the dye to go in to aqueous solution. Dyeing is invariably carried out at boil, to provide the heat energy to facilitate diffusion and migration. Higher temperatures can also cause de-aggregation and consequent de-sorption Since the dyes have good substantivity due to affinity caused by physical forces like Hydrogen bonding, metal chelation etc. there is less propensity to desorb and higher

temperatures facilitates migration within the substrate forming the same physical bonding at new sites (High substantivity always causes an initial strike aggregation of colour in most favourable loosely packed sites and migration to other sites to increase uniformity in dyeing is facilitated only by imparting energy.) Fastness characteristics are just adequate even for the most satisfactory dyes of its class due to bonding only by physical forces that are relatively week to the more powerful covalent bonds.

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Reactive Dyes Reactive Dyes are capable of forming chemical covalent bonds with the Hydroxyl groups of cellulose fibre and therefore, better anchored to the substrate and not depend on the relatively weak physical forces to give better levels of fastness. All of the features that are desirable for a reasonably fast to wash Direct Cotton dyes are not essential for Reactive class of dyes (because of the more strong covalent bond), though cannot be totally discarded as undesirable. Some of them could be counter productive. For example, Reactive Dyes with features listed under I and 2 of the Direct cotton dyes would exhibit problems of low migration and or difficulty to wash off the hydrolyzed dye. Certain quantity of Hydrolyzed dye is inevitable after the fixation stage and non removal of such unfixed dye would entail bleeding/staining of white during washing. Migration is facilitated by increase in temperature; but higher temperatures induce hydrolysis of Reactive dye during the fixation phase and therefore it would be necessary to bring down the temperature to the most favourble temperature for the reaction between dye stuff and substrate before alkalie addition can be made. There fore, in the case of Reactive dyes the following aspects are most important 1. Degree of Exhaustion of the dye bath on to the fibre (both primary and secondary) that is directly related to the substantivity should be maximized /optimized (assisted more by salt addition than by the physical forces). 2. The migration of the dye within the substrate during the primary exhaustion phase should be maximized. 3. Efficiency of reaction of the exhausted dye to the fibre should be maximized during fixation phase. 4. The kinetics of reactivity has the final influence on the success of dyeing, irrespective of high levels of success achieved in the exhaustion stages, though exhaustion is an important (primary and or secondary) pre-requisite... 5. The above four aspects need to be performed within a reasonable span of time. 6. The corollary here is that the extent of hydrolysis of the dye during exhaustion and fixation stages needs to be minimized.

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Role of Electrolyte Addition of electrolyte induces exhaustion both its rate and extent. Where

the substantivity is lower the prime driving mechanism for diffusion /exhaustion of dye into the fibre is the concentration gradient across fibre/liquor interface and presence of common ion- i.e. electrolyte (Salt). The electrolyte, say, Sodium Chloride dissociates in water into Na+ and Cl and Na+ has higher propensity to travel to the fibre /water interface and neutralize the negative charge thus facilitating the free transport of dye anion to be adsorbed onto the surface of the fibre and the subsequent diffusion/ absorption (exhaustion) to take place. Secondly, the dissociated NaCl ions are more associated with water than with the large molecular dye Chromophore with a few SO3Na or other solubilizing groups and thus occupy the limited available sites in the water effectively displacing the dye Chromophore.The distribution coefficient of dye therefore shifts towards fibre. It is not the quantity of the salt but its concentration that influences the degree of exhaustion. The degree of exhaustion increases with increasing concentrations of Salt to a limiting concentration. Higher concentrations of Salt result in aggregation of the dye in the dye bath itself and hence it is salted out much in the same manner as in the manufacture of the dyestuff and less and less monomolecular dyes are available for reaching the fibre phase The optimal quantity of Salt in terms of concentration depends on the chemistry of the dye, its molecular size, its solubilizing groups, quality of water and the fibre substrate etc. Secondly, dyes displaying higher substantivity in the absence of salt would need lesser salt concentrations.

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Partition /Distribution Coefficient and Degree of Exhaustion At a given liquor ratio and bath concentration of dyestuff and salt, the exhaustion of the dye proceeds from the liquor phase to the solid phase (cellulose) until it reaches an equilibrium. This state would be different for different solutes (dyestuffs) and the factors that contribute to this variability are their molecular size, ionic character, extent of hydrogen bonding groups, inter molecular forces, temperature etc. Such equilibrium, where the number of molecules absorbed is equal to the number of molecules desorbed at the cellulose/dye liquor interface, can safely be assumed to have been reached in a time span of infinity, i.e. at the end of Exhaustion phase or Partition of the dye from the liquor phase to the solid phase at a notional infinite time It is desirable that the exhaustion proceeds at a satisfactory rate to achieve close to equilibrium exhaustion within a manageable /practicable time span a condition that is influenced by diffusion coefficient. Higher the diffusion coefficient faster the exhaustion as discussed earlier under diffusion... The Partition/Distribution coefficient of a solute between two phases is calculated as the ratio of the concentration of the solute in one phase to the concentration of the solute in the other phase under equilibrium conditions

Interestingly, at the equilibrium state of exhaustion where the concentrations of dye on fibre and in the final bath tend to become steady and constant, it is an established fact that as the dye bath concentration is increased, the concentration in fiber phase at equilibrium though increases, does not do so linearly but progressively diminishes giving relatively lower distribution coefficient values. Degree of exhaustion is the ratio of the total amount of dye present in the cellulose at the end of exhaustion to the amount of dye present in the original bath before the start of the exhaustion process. Degree of Exhaustion in terms of distribution coefficient and liquor ratio is given by the relationship

Where E Degree of Exhaustion K Partition coefficient L Material Liquor Ratio

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Liquor Ratio Recipe of x% owf (on weight of fabric) in terms of absolute quantity would be present in the starting dye bath but its concentration in the dye bath would vary depending on the liquor ratio The recipe equivalent dye % on the fabric after the completion of dyeing would not be x% but would tend towards x% - depending on the efficiency of dyeing/the substantivity /reactivity of the dye. In an ionic kind of reactions like Acid dyes on wool the degree of exhaustion would proceed to almost to .100% subject to the dye present in the dye bath does not exceed the saturation capacity of the reacting sites present in the substrate.- the limiting degree of exhaustion in this case. In a model scenario where the liquor ratio is changed to a higher one: Amount of dyestuff expressed owf, when present in the higher liquor

ratio would register proportionately a lower concentration of the dye in the starting bath and consequently lower concentration gradient at the fibre liquor interface resulting in lesser rate of diffusion of the dye from liquor phase to fiber phase Numerical Example Liquor Volume (Wt) 500L 1000L Dye bath Concn. 2 gpl 1 gpl

Case

Recipe owf 1% 1%

Substrate Amount of Weight dye on fibre* 100 Kgs 100 Kgs 1.0 Kgs 1.0 Kgs

Liquor Ratio 1: 5 1:10

I 2

*Arrow indicates tending towards Only 50% of the dye molecules are available at the interface for adsorption and diffusion in case 2.and therefore the rate of diffusion will be lowered and it would take relatively far longer time to reach the equilibrium state. In case 1 starting from 1:10 going to 1:5, the increased concentration of dye in the bath would increase the rate of diffusion (increased concentration gradient) and take shorter time for exhaustion. The relationship E= K/ (K+L) as discussed under Distribution coefficient (K); any increase in L would diminish the E the degree of exhaustion. Such a situation would entail higher starting concentration of the dye and or increase in concentration of Salt to occupy the available sites in water (as explained earlier under salt concentration) in a larger volume of water to displace the dye anion to shift the distribution coefficient to the fiber phase. But increased salt addition cannot always fully compensate for the adverse exhaustion behaviour but only to a point (as discussed under Role of Electrolyte) Therefore, not only increase in concentration of the dye, but also that of salt will be necessary (barring certain marginal cases) quantitative aspects governed by the substatnivity characteristics of the dyestuff. Such a situation would be more pronounced in the case of low/poor substantive dyes compared to the dyes with better substantivity. There are ready reckoners for recipe correction available for changes in liquor ratios from the dyestuff manufacturers but they are only for guidance. As individual dyes would behave differently, an intelligent understanding and application of the given information only can give meaningful results. The corollary is that a change in liquor ratio would affect the least in dyes with high substantivity and most in those with poor substantivity

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Temperature Temperature of the bath is another factor influencing exhaustion As explained earlier presence of salt increases the substantivity facilitating aggregation of the dye in the fiber phase Increase in temperature in the case of high substantive dyes as in the case of direct cotton dyes help in the migration of the dye within the substrate but in the case of dyes that are less substantive increase in temperatures could be counterproductive Temperature up to 50 deg C contributes to de-aggregation of the molecules of dye, both in fibre and water phases; but relatively less in fiber phase and more in the water phase. Therefore the net effect is that there are more deaggregated monomolecular dye free to move towards the fiber phase than that is desorbed from the fibre and therefore the exhaustion proceeds. There is a maxima in the exhaustion curves of dyes of low substantivity at temperature around 40 to 50 deg C. beyond which increase in temperatures results in decreasing degrees of exhaustion explained by the higher degree of de-aggregation of the dye in the fiber phase and lesser physical forces to resist desorption, unlike in the case of substantive direct cotton dyes; annulling the influence of salt..

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Influence of pH. The pH is relevant to the Reactivity aspect and not considered as a factor in the exhaustion process. Also, the dye bath pH during the exhaustion phase is maintained at 5.5 to 6. As long as the pH of the bath is slightly acidic, no reaction can take place and therefore primary exhaustion and bringing the temperature close to the reaction temperatures can be carried out conveniently. Influence of Substantivity High substantivity facilitates exhaustion process; also requiring less concentration of salt for exhaustion but for the same reason migration of the dye would be restricted resulting in unlevel dyeing. However dyes with medium+ substantivity engineered to provide the balance in the molecular structure to promote migration and good reactivity that matches the exhaustion curve (primary and secondary) would give the best results both in terms of dye yield and washing efficiency. Poor substantive dyes that are also not sensitive to electrolyte additions are poor builders and therefore will give poor yields. High substantivity .dyes with low reactivity (Fixation) falling below the exhaustion levels would result in high levels of unfixed and hydrolyzed dye to be washed off and the dye and its hydrolyzed version also being highly substantive, the washing efforts also will be high requiring more water, energy and mechanical efforts

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Migration phase Since fiber surface area is a factor in diffusion process, the exhaustion would proceed to locations where relatively more surface area is presented like in the amorphous areas and less densely packed crystalline areas in that order in the cellulose and therefore the dye concentration within the cellulose substrate would not be uniform/even. Such a situation would result in uneven build up of the dye both in hue and intensity. In a trichromatic mixture the situation could be worse. The process of Migration of the exhausted dye depends on the molecular size of the dye its spatial profile (Steric) and the solubilizing groups present. The other external factors would relate to temperature, machinery used and the package profiles and densities (in case of package dyeings). Raising the temperature would provide the required thermal energy; but cannot be increased arbitrarily due to limitations discussed under Temperature. Both exhaustion and migrations can be maximized /improved by better mechanical agitations that would facilitate intimate surface area contact of the cellulose with dye liquor and by improved flow designs that facilitate better liquor exchange at the fiber liquor inter-phase. Migration phase should precede the fixation phase as once the reactive dye forms a covalent bond with Cell O- it is anchored strongly and cannot be shifted.

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Secondary Exhaustion The observations and inferences in the above deliberations related to primary exhaustion in a Reactive exhaust dyeing process are incomplete without the final fixation. When Alkali is added, the cellulose ionizes to form Cell-O- and H+ (Cell O Na+) and starts forming covalent bonds with the reactive functional groups of the dye Chromophore. When more and more of dye anions are covalently bond, the distribution coefficient shifts to fiber phase effecting further exhaustion due to deficiency of dye anions in the cellulose phase and dye bath concentration starts depleting further. The degree of alkalinity in terms of pH plays a major role in shifting the fixation of dye to its hydrolysis reacting with water. Any exhaustion during this stage if it is hydrolyzed dye it would be far more undesirable In a reactive dye system therefore, primary exhaustion alone does not govern the efficiency of dyeing. The degree of secondary exhaustion also would influence the efficiency. During the secondary exhaustion when alkalie is added, there is a second reaction that also sets in motion in parallel ( i.e. the hydrolysis of the Reactive dye with water) in competition to the fixation of the dye that is the primary aim. The dye anion is equally facilitated to react with OH of water to form the hydrolyzed dye in which state the dye is

as good as a direct dye with all its undesirable characteristics. It is the reactive group in the dye, pH and temperature that influence the hydrolysis of dye in preference to reacting with cellulose. It becomes critical that the hydrolysis is curbed to maximize efficiency. The relationship between temperature and reactivity is that higher temperatures require lower alkalinity; to optimize on hydrolysis. They can be broadly grouped under High Medium and Low categories requiring 40 C. 60 C and 80.C respectively - levels of pH 12.5 for High (cold dyeing), 11.5 for Medium (Warm) and 10 - 11.0 for Low (Hot Dyeing) for the reaction to proceed more favorably towards the substrate. The term more reactive is used in the sense that it requires lesser levels of alkalinity and lower temperatures (and not the reaction itself. Given the right temperatures, alkalinity and time the reaction proceeds to completion in all cases.)

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Hydrolysis of Reactive dyes The most critical part of the Reactive dyeing is the actual fixation where the covalent bond takes place between the Cellulose O - and the Reactive group of the Dye Chromophore. 1. Cynuryl chloride based dyes

2. Vinyl Sulphones Dye-SO2 CH2-CH2-OSO3H CH=CH2 (MINUS) H2SO4 Dye SO2-

The electron attracting Sulphone group causes electron deficiency on the terminal carbon atom enabling neucleophylic attack to take place. . (Addition reaction) Dye-SO2-CH=CH2 + O-R1H (+) Dye-SO2-CH -- CH2-OR1 Dye-SO2-CH 2- CH2-OR1

Where [-O-R1] is [-O Cellulose] or [-OH] of water, etc. The liberated acid in both the two reactions is continuously neutralized by alkalie for the forward reaction to proceed during the fixation process. . Efficiency of Reactive dyeing (Rate of Fixation /Rate of Hydrolysis) for a given exhaust dyeing process has been expressed in mathematical terms

making use of the competing First order /pseudo first order rate constants of the reaction of the dye with the cellulose and the dye hydrolysis with water , the equilibrium concentration of the dye on fabric and concentration of dye in the aqueous phase (For details please refer Chapter 4 of The Dyeing of Cellulosic Fibres by Maurice R Fox and Harry H Sumner Edited by Clifford Preston 1986 - SDC Publication} It has also been emphasized that the expression is too ideal and relates to certain assumptions and conditions that are not practically achievable in the real situation. However, the broad principles are applicable and the direction of the reactions proceeds towards the ideal. To whatever extent the variables can be controlled and maintained, the results achieved could be optimized and also reproduced maintaining the same conditions and controls every time.

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Typical Examples Reviewing the critical variables that govern the dyeing Efficiency in a Reactive dyeing process, the following few examples will highlight the pros and cons of the factors discussed. 1. Low Primary exhaustion (P) and high Reactivity (R) (incidentally higher secondary exhaustion) Where P is low and Fixation is high Initial exhaustion phase will not be critical as less amount of dye is transported. On addition of alkalie the reaction starts and the secondary exhaustion proceeds as more and more of the dye takes part in the reaction. During this phase the competing reaction - hydrolyzation of the unexhausted dye close to the substrate phase and in the dye bath also starts and it would become critical to control minimize this aspect of the reaction. The direction and rate of reaction towards covalent bonding with substrate have to be controlled by careful manipulation of pH and temperature. That would require precision instruments /plc controls. Secondly since the exhaustion is low and better part of the dye exhaustion takes place in the secondary phase, migration would be affected and the dyeing would be non uniform.

Where P, Substantivity and R are high

Primary exhaustion would be high and whatever exhausted would be fixed. In this

case it would be critical during exhaustion phase as the substantivity is high and migration could be a problem. Higher temperatures need to be resorted to for migration and that would not be in favour with Dyes of the low reaction temperatures in view of its high reactivity. Such a situation would warrant graduated salt additions to avoid initial strike linear or step wise in order to facilitate phased migration. It would require cooling if higher temperatures were to be adopted. Because of the high reactivity pH control to maintain low and constant alkaline pH through out the reaction/fixation phase would be critical. Depending on the hot or cold class of colours the temperature maintenance will be critical. In the above example where the substantivity before salt addition is relatively lower but enhanced by salt addition, migration would be better facilitated. It could be possible to standardize on an isothermal dyeing sequence starting with salt bath The desirable features of the dyestuff would be to posess reasonbly good substantivity and migration capability, a good exhaustion percntage including the seondary exhustion that are achievabe within a paracticable time dimension and reactivity that matches the degree of exhaustion so that all the exhausated dye is fixed. This would mean ideally that the curves S and F should super impose at the concluding stages of the dyeing process. Such a dyeing would require least effort for soaping, However such an ideal system is not practicable but efforts should be to move towards the ideal system Dyes with similar substantivity that are moderate and having good primary exhaustion (assisted by salt addition) and migration potentials and also a relatively lower secondary exhaustion with reactivity reaching close to equilibrium exhaustion would be the most suitable choice where auto dozing and sophisticated control systems are not available.

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Evaluation of Substantivity A very useful and simple practical method to assess substantivity of the Reactive dyestuffs in the lab based on chromatographic principles is given in the article Effects of Dye Substantivity in the Dyeing of Cotton with Reactive Dyes a prize winning article By Canadian Association of Textile Colourists and Chemists in TCC Nov 91). The individual process house labs can conveniently assess substantivity of the dyes and group them for using in their recipe mixtures. The dyestuff manufacturers themselves recommend colours that have similar

substantivity features; however it would be safe to assess in ones own lab unless supplied by propriety manufacturers. Evaluation of Migration Index Ref.material Practical method to evaluate migration Index Reactive Dye Selection and Process Development for Exhaust Dyeing of Cellulose BY M.J. Bradbury, P. S. Collishaw and S. Moorhouse, ZENECA Colours, Blackley, England. August1995, Vol. 27, No. 8

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