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 knitware, 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. Top
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. Top
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.

D Diffusion coefficient

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.

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. Top
Substantivity

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 deaggregation 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. Top
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. Top
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.

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 Top

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

Case

Amount of Recipe Substrate Liquor dye on owf Weight Ratio fibre* 1% 1% 100 Kgs 100 Kgs 1.0 Kgs 1.0 Kgs 1: 5 1:10

Liquor Dye Volume bath (Wt) Concn. 500L 1000L 2 gpl 1 gpl

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 Top
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 de-aggregated 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 deaggregation 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..

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

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. Top
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-Oand 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.)

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. Top
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