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Exhaust Dyeing with Reactive Dyes

Dr. Tanveer Hussain Dean Faculty of Engineering & Technology National Textile University Faisalabad.
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Variables in Reactive Dyeing

Dye variables System/process variables

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Dye variables in Reactive Dyeing

Dye chemistry Substantivity Reactivity Diffusion coefficient Solubility

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Reactive Dye Chemistry

Chromophore
Affects colour gamut, light fastness, chlorine/ bleach fastness, solubility, affinity, and diffusion Azo dyes are dischargeable. Disazo dyes have the disadvantage of being much more sensitive to reduction and many of them are difficult to wash-off. Anthraquinone dyes exhibit relatively low substantivity and are easier to wash-off. Most of them possess excellent fastness to light and to creaseresistant finishes, but they are not dischargeable. Phthalocyanine dyes diffuse slowly and are difficult to wash-off
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Reactive Dye Chemistry

Reactive Group
Affects
affinity efficiency of reaction with the fibre, dyefibre bond stability,

Determines
Sat requirement Alkali requirement Temperature requirement

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Reactive Dye Chemistry

S-triazine dyes
Do not have good wet fastness properties in acidic media Due to their high substantivity, have poor wash-off properties. Monochlorotriazines have good fastness to light, perspiration and chlorine. The fluorotriazine groups form linkages with cellulose that are stable to alkaline media
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Reactive Dye Chemistry

Reactive dyes of dichloroquinoxaline, monochlorotriazine and monofluorotriazine types show a tendency for lower resistance to peroxide washing and dyefibre bond stability A lower sensitivity to changes in dyeing conditions (particularly temperature) is the most important characteristic feature of the monochlorotriazine-vinyl sulphone heterobifunctional dyes
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Reactive Dye Chemistry

Vinyl sulphone reactive system
have poor alkaline fastness. chemical bond between the vinyl sulphone and the cellulosic fibre is very stable to acid hydrolysis. The substantivity of hydrolysed byproducts of vinyl sulphone is low, so washing off is easy

The turquoise reactive dye shows an optimum dyeing temperature that is generally about 20 C higher than that of other dyes with the same reactive group
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Dye Substantivity
Substantivity is more dependent on the chromophore as compared to the reactive system. A higher dye substantivity may result in:

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a lower dye solubility a higher primary exhaustion a higher reaction rate for a given reactivity less diffusion, migration and levelness a higher risk of unlevel dyeing, more difficult removal of unfixed dye
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Dye Substantivity
An increase in the dye substantivity may be affected by:
higher concentration of electrolyte, lower temperature, higher pH (up to 11) lower liquor to goods ratio

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Half dyeing time

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Dye Reactivity

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Dye Reactivity
A high dye reactivity entails a lower dyeing time and a lower efficiency of fixation. Reactivity of a dye can be modified by altering the pH or temperature, or both.

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Diffusion Coefficient
Dyes with higher diffusion-coefficients usually result in better levelling and more rapid dyeing. Diffusion is hindered by the dye that has reacted with the fibre and the absorption of active dye is restrained by the presence of hydrolysed dye. Different types of dyes have different diffusion characteristics. For example, the order of decreasing diffusion is: unmetallised dyes, 1:1 metal-complex dyes, 1:2 metal complex dyes; phthalocyanine dyes. An increase in the diffusion is affected by:
increasing temperature, decreasing electrolyte concentration, adding urea in the bath using dyes of low substantivity.

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Dye Solubility
Dyes of better solubility can diffuse easily and rapidly into the fibres, resulting in better migration and levelling. An increase in dye solubility may be affected by:
increasing the temperature, adding urea decreasing the use of electrolytes.

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System Variables in Reactive Dyeing

Temperature pH Electrolyte Liquor ratio Surfactants & other auxiliaries

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Effect of Temperature
A higher temperature in dyeing with reactive dyes results in:
a higher rate of dyeing lower colour yield better dye penetration rapid diffusion better leveling a higher risk of dye hydrolysis lower substantivity
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Effect of pH
pH influences primarily the concentration of the cellusate sites on the fibre. Raising the pH value by 1 unit corresponds to a temperature rise of 20 C. The dyeing rate is best improved by raising the dyeing temperature once a pH of 1112 is reached. Further increase in pH will reduce the reaction rate as well as the efficiency of fixation
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Type of Alkali
Different types of alkalis, such as caustic soda, soda ash, sodium silicate or a combination of these alkalis, are used in order to attain the required dyeing pH. The choice of alkali usually depends upon the dye used, the dyeing method as well as other economic and technical factors

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Effect of Electrolyte
The addition of electrolyte results in:
increase in the rate and extent of exhaustion, increase in dye aggregation decrease in diffusion.

The electrolyte efficiency increases in the order: KCl < Na2SO4 < NaCl There may be impurities present in the salt to be used, such as calcium sulphate, magnesium sulphate, iron, copper and alkalinity, that can be a source of many dyeing problems
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Effect of Liquor Ratio

At lower liquor ratios, there is:
Higher exhaustion, and Higher colour strength

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Effect of surfactants & auxiliaries

Some anionics may enhance colour yield Some non-ionics may decrease exhaustion and colour yield Some non-ionics may slow down dye hydrolysis Triethanolamine (TEA) is known to enhance colour strength by enhancing the swellability and accessibility of the cellulose structure
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Reactive Dye Exhaustion

Primary exhaustion
Occurs before addition of alkali

Secondary exhaustion
Occurs after addition of alkali

Rate of exhaustion can be increased by selecting dyes of high substantivity, increasing the temperature and increasing the electrolyte concentration. Degree of exhaustion can be increased by selecting dyes of high substantivity, lowering a bit the equilibrium temperature and increasing the electrolyte concentration and dyeing time.
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Reactive Dye Migration

The intrinsic properties of a reactive dye that affect migration are:
substantivity, molecular structure, physical chemistry and stereochemistry.

The higher the dye substantivity, the lower is the migration. The external factors that affect migration are:
concentration of the dye, temperature, time, liquor ratio, liquor circulation the form of the textile material

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Reactive Dye Levelness

Levelness of dyeing may be inhibited by:

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high substantivity, lower dye migration too much salt in the dyebath too high rate of exhaustion too high concentration of alkali a rapid shift of dyebath pH, too high rate of fixation too high rate of rise of temperature poor liquor agitation.
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Approaches to Obtain Level Dyeing

Controlled absorption can be obtained by salt dosing, alkali dosing, and/or controlling the rate of heating.
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Obtaining Level Dyeing in Light Shades

During the primary exhaustion, the dye is free to migrate. During the secondary exhaustion stage, dye migration is poor. For light dyeing shades (less than 1 % o.w.f.) the degree of primary exhaustion is over 80% and the degree of secondary exhaustion is very small. Therefore control of the primary exhaustion stage is very important if level dyeing is to be obtained. The rate of primary exhaustion is dependent on the amount of electrolyte used. Dosing or split addition of salt is recommended to obtain level dyeing.

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Obtaining Level Dyeing in Medium & Dark Shades

For medium shades, both primary and secondary exhaustion steps are important for obtaining level dyeing. Both controlled salt and alkali addition are important in this case. In the case of deep shades, the all-in salt addition may be possible, but during the secondary exhaustion, alkali dosing is important
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Obtaining level dyeing in general

Dyes with high substantivity, low secondary exhaustion, and low MI (Migration Index) values require controlled addition of electrolyte after the addition of the dye. In contrast, dyes with low substantivity, high secondary exhaustion, and medium to high migration index values require precise control of liquor ratio, concentration of electrolyte, and addition profile of the fixation alkali
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Ways to Enhance Dye Fixation & Colour Yield

Use of fixation accelerators Use of shorter liquor ratio Dyeing at low temperature (with decreasing temperature the substantivity for fibre increases, causing increased exhaustion) Modification of chromophore and reactive group Use of dyes with high substantivity and high reactivity Treating cellulosic fibres with swelling agents Modification in appearance techniques Changing the morphology of fibre by chemical modification.
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Approaches for Uniform Rise in Rate of Fixation

Controlling the temperature of the dyeing process suitably (possible for hot dyeing dyes only); Adding alkali in stages (it is virtually impossible, however, to prevent a sharp rise in fixation rate whenever alkali is added); Starting with a weaker alkali such as soda ash, and following this with a stronger alkali, but only after a higher degree of fixation has been achieved; Progressive metering of alkali (such as the Remazol automet process);

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Exhaust dyeing method example 1

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Exhaust dyeing method example 2

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Washing-off of Hydrolyzed Dye

Phases
dilution of dye and chemicals (salt, alkali) in solution and on the surface of the cellulose; diffusion of the deeply-penetrated, unfixed, hydrolysed dye to the fibre surface; and dilution and removal of the diffused-out dye

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Washing-off of Hydrolyzed Dye

Goods are rinsed cold twice to remove electrolyte & alkali then rinsed hot to desorb some hydrolysed dye from the fibre, prior to a soaping process at or near the boil. A subsequent cold rinse completes the task of removing un-reacted and hydrolysed dye

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Washing-off Factors
Dye substantivity Diffusion behaviour Liquor ratio Washing temperature Electrolyte concentration pH Presence of calcium and magnesium ions in the boiling soap/hardness of water Amount of unfixed dye Washing time Number of washing cycles/washing baths/Filling and draining Washing auxiliary employed Mechanical action

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Dye-fiber Bond Stability

Dyes that react by a nuceophilic displacement mechanism show good stability to alkali and, to different degrees, less stability to acid. Dyes that react by nucleophilic addition give dye fibre bonds with good stability to acid, but are less stable to alkali. The triazinecellulose bond is generally resistant to oxidative breakdown in the presence of perborate, whereas this is a serious defect of some of the pyrimidine based systems
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Fastness of Reactive Dyes

Factors
The chromophoric group, the stability of the dyefibre bond the completeness of the removal of the unfixed dye.

To maximise wet fastness, particularly in deep shades, it is advisable to apply cationic aftertreatments.
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Sustainable Reactive Dyeing

Shorter/more robust dyeing procedures Reduced water consumption Reduced energy consumption Reduced effluent discharge Improved ecological image

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BASF has developed a new polymer which combines with a reactive dye hydrolysate to eliminate its substantivity for the substrate in the presence of salt.

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