RFT PRINCIPLES

Right first time dyeing

R.Monica,' G.Myvizhirajeswari^ & M.Senthil Kumar* Department of Textile Technology PSG College of Technology, Coimbatote - 4

ABSTRACT In dyehouses "Right First Time Dyeing" had been a proven boon to Textile chemical processing industry. It helps lo eliminate extra expense on re-dyeing, re-shading and reproducing the color. This paper deals with dye selection criteria, process involved while dyeing, assigning dye uptake, machineries developed, type and principles of reactive dyeing and benefits involved in right first time dyeing. In dyehouses processing, cellulosic fibers with reactive dyes, much progress has been made in the quest for zero defect production by the innovative introduction of controlled coloration technique that has supported the dyeing performance. Exhaust dyeing using reactive dyes quantify dye migration properties, the degree of process control to achieve shade reproducibility and level dyeing performance. The concept of Reactive Dye compatibility Matrix (RCM) will allow to identify dyes with similar properties and used in combination to support right first time production. It can also be used as a diagnostic tool when optimizing application techniques. Hence this becomes an important factor for industries to produce a value added product at a higher profit so that both the manufacturers and consumers are satisfied.

Introduction
TO improve the financial performance i.e. to increase profit margin by decreasing the working capital and to withstand intemadonal competitiveness one has to focuss attention on the need for right first time production. This demands the elimination of wastes at all stages of the textile production chain. The trends thus are towards lower ratios to increase productivity throi^gh reduced fillings draining, heating and cooling fibres and to reduce chemicals. The Reactive dye compatibility (RCM) can be used to achieve this. Understanding RCM will allow dyes with similar properties to be identified and used in combination to support tight first time production. Dye selection criteria are based on accurate and consistent standardisation of dyes is the principal requirement for optimized dye house efficiency &c right first time production. , Exhaust dyeing of cellulose with reactive dyes is a complex process. It involves the exhaustion of dye onto the
* Part of B.Tech Textile Technology Under the Guidance of Mr. M.Senthil Kumar (Lecturer) ' B.Tech final student (E-mail id: myvizhL1987@yahoo.co.in) ^ B.Tech final student ' Lecturer, Dept of Textile Technology COLOURAGE O DECEMBER 2009

fibre in the presence of electrolyte and then the addition of alkali to promote the chemical reaction between dye & cellulose. During the "Right First Time" production in the exhaust application of reactive dyes to cellulose the following will affect the dye regularity. Hardness in the dye bath ' i M Bicarbonate in the dye bath

Dye selection criteria

Accurate and consistent standardization of dyes is the principal requirement for optimized dye house efficiency and right-first-time production. A Statistical analysis which assesses the effect of dye standardization liniits on rightfirst-time production is shown in Fig. 1 <& 2. The external factors which influence the process have been identified and segregated into two variables. The Assignable variables - e.g. internal fabric pH at the start'of the dyeing cfdt, the liquor ratio, the temperature gradient, the fixation temperature, the electrolyte concentration, the addition profiles of dye, electrolyte and fixation alkali, the fixation pH and time. The random variables - e.g. the impurities in cotton, water supply, chemicals, and the dyes selected to reproduce the target shade.

RFT PRINCIPLES

the dye bath to reach equilibrium between additions. woThe dyeing process is completed by the dye fixation stage. The process is long, OT complex, labor-intensive, extremely difficult to control and reproduce, and therefore requires a highly skilled and reliable workforce. The complexity of the process is the source of many of the I 1 -T r 2\ *hi.Qy- /-TAX tl-1t> level dyeing and shade reSTAMDAROISING UMfTS producibility problems assoV K (in) ZK ciated with reactive dyes. Fig. 1: Effect of dye standardization on Fig. 2: S.E.F. profile. Furthermore, the process Probability of right-first-timc production. does not exploit the properties of more recently developed reactive dyes especially Process involved in "Right first time dyeing*' when applied on more modem jet or overflow machines. Table V shows the RCM for dyes applied by the portion Right first dyeing involves exhaust dyeing using reactive wise salt process. dyes. Exhaust dyeing of cellulose with reactive dyes is a complex process. It involves the exhaustion of the dye onto the Portion wise Salt vs. Standard process fiber in the presence of electrolyte and then the addition of Comparison of Tables N and V shows that the MJ and alkali to promote the chetnical reaction between the dye and LDF values of dyes when applied in a portion wise salt cellulose. process are not optimized and therefore the process reThe controlled coloration approach has proven to be the quires precise control to support level dyeing performance basis of a systematic, structured and successful approach to and shade reproducibility. The standard is a short, simpleimprove the right-first time production rate. The level process based on a salt-at- start profile and linear addition dyeing performance of reactive dyes has benefited from the of fixation alkali. introduction of controlled coloration and it is now perThis process is suitable for medium to heavy shades dyed ceived that shade reprodudbity is the major obstacle on unmercerized cotton and does not require exponential preventing zero defect production. microprocessor control of the addition of dyes or chemicals. However, if total automation of machine is available then Portion wise salt process the isothermal method can be used for these shades and The established application profile for reactive dyes is substrates. ' based on the portion wise addition of electrolyte and fixation alkali. It was developed for application at long Isothermal Process ' liquor ratios and for dyeing equipment such as winches and The isodiermal process offers further improvements in side paddle machines which have low liquor to fiber interproductivity but because the MI and LDF values in this change. The low liquor to fiber interchange on these types process are lower than in the standard process more precise of machines demands controlled rates of dye exhaustion control of the dye addition is required. and fixation to achieve level dyeing performance. In an
100

PROCIOH K-XZX.

attempt to control the rate of dye exhaustion, the electrolyte is added in discrete portions, allowing time for the dye bath to reach equilibrium between the additions. The addition profiles used to retard the exhaustion of the dye range from two or three equal portions made at the starting temperature to complex pyramid addition profiles often made at different temperatures on the temperature gradient. On reaching the fixation temperature a period for dye migration is followed by the addition of fixation alkali. This is generally made in two or three portions, again allowing time for

Assigning the dye uptake

The performance of a reactive dye is defined by the S.E.F. profile. The substantivity equilibrium S. represents the primary exhaustion of the dye in the presence of neutral electrolyte. The exhaustion equilibrium, E. represents the final exhaustion of the dye which takes place after the addition of the fixation alkali. The fixation value, F, represents the fixation level for the dye. The secondary exhausc a i - o u R A G E O DECEMBER 2009

RFT PRINCIPLES

don, represented by E-S, takes place simultaneously with dye fixation after the addition of the fixation alkali. Dyes with a wide range of S.E.F. profiles can be ohi;iined. Dyes with S values as high as 96% and as low as /7% are commercially available. Dyes with such wjde differences in substantivity will exhibit different levels of performance and sensitivity to external influences. Dyes with low substantivity will generally be n:iore sensitive to variations in litjuor ratio and electrolyte concentration. In contrast, dyes with high substantivity will be robust and provide shade stability to these variations in processing conditions. During the initial phase of the process, the neutral primary exhaustion of the dye in the presence of electrolyte, migration and diffusion can take place. Dye which has exhausted onto the fiber is available for migration, and leveling will take place by the classical mechanism. The actual migration which takes place during primary exhaustion will depend on the cheaiistry of dye - its molecular structure, physical chemistry and stereochemistry, and on external factors-concentration of the dye added to the dye bath, time, temperature, liquor ratio, rate of liquor circulation and fabric construction, or in the case of yam dyeing, package format. From practical considerations it is the chemistry of the dye which has the dominant influence on migration properties and therefore on its level dyeing performance. The migration properties of dyes are easily measured using a simple laboratory test. Using color measurement techniques to measure the depth of shade of the test samples D2 and B2 it is possible to calculate a migration index, MI. as in Equation 1. Migration Index (MI) = Strength B2*100 / Strength D2 The migration index defines the migration properties of an individual dye applied by a defined process. A dye with itieal migration properties in a defined process will possess a M7 of 100. Probably the most critical stage of the reactive dyeing process is the addition of the fixation alkali. It is especially critical for dyes with a h i ^ ES value. For these dyes, the addition of alkali increases the substantivity of the dye and exhaustion and rapid fixation take place simultaneously. The rate of fixation must be controlled by the use of complex and time-consuming addition profiles. This requires the use of metering systems to achieve linear fixation of the dye which is necessary to secure level dyeing performance. The migration which can take place dxiring the secondary exhaustion phase of the process is severely restricted due to the rapid fixation of the dye and will not significantly contribute to level dyeing performance. Thus for a dye with a high secondary exhaustion the only control option available to obtain level dyeing is the precise control of the rate of fixation of the dye.
CDLOURAGE O DECEMBER 2009

The level dyeing performance of reactive dyes and the degree of control required to achieve level dyeing are governed by the substantivity equilibrium value, the migration which takes place during the primary exhaustion and the secondary exhaustion which takes place after the addition of the fixation alkali. It is possible to quantify the relationship between these parameters, assign a measure of dye performance, and define the degree of control required to achieve reproducible level dyeing, and robust to small expected variations in processing conditions by calculating an empirical value, the Level Dyeing Factor, LDF, which is defined in Equation. Level Dyeing Factor, IJ3F=S/E*MI% While LDF values are derived from an empirical equation, the values are consistent with expetience and expectations of the performance of dyes which are commercially available. As with the migration indices, WF values reflect the performance of individual dyes applied by a defined process. TabU shows the S, E, MI and WF values for the series of blue dyes previously discussed. Generally, the LDF value will define the most suitable

Table II: Level Dyeing Factor

Dyebaths Based on C.I. Reactive Blue 171 Prodon Navy H-EXL Blue 184 Blue 222 Blue 225 Blue 238
%S 87 73 66 VoE 95 90 90 88 96 97

%MI%
60 90 81 74 91 89

%LDF
55 73 67 37 40 36

45 42 39

application technique for the dye which will minimize the risk of unlevel dyeing and optimize shade reproducibility. Dyes with high substantivity, low secondary exhaustion, low MI values and therefore modest LDF values will require controlled addition of the electrolyte after the addition of the dyes. In contrast, dyes with low substantivity, high secondary exhaustion, and medium to high MI values will possess low LDF values. These dyes will require precise control of the liquor ratio, the concentration of electrolyte, and the addition profile of the fixation ikaD. S, Ml and LDF values provide data on the sensitivity of the dye to external factors such as variations in liquor ratio and chemical concentrations, but to assess the sensitivity of the dye to variations in fixation time and temperature it is necessary to study the reactivity of the dye. A convenient method of assessing the reactivity of the dye is to measure the time taken for half of the dye to teact, TSO. Table UI shows the variation in T50 values for a range of blue dyes applied by the manufacturers' standard recommendations.

"1

RFT PRINCIPLES

Table III: Time of Half Fixation, T50 Minutes

Dyebathg Based on C.I. Reactive Blue 171 Procion Navy H-EXL Blue 184 Blue 221 Blue 225 Blue 238 Alkali Addition profile

Machinery Developments
Machine Volume and Liquor Ratio Tlie volume of an exhaust dyeing machine (Jet, Winch, Circulating >X%ich, Package, and Hank) is a vitally important parameter of any exhaust dyeing process. It determines the liquor - to - goods ratio of the dyeing. Let us think for a moment about the volume of

T50 (min)
6.0 11.0 10.0

Na^CO, NaOH Na^CO, Na^CO, Na^CO,

linear over 10 min. Linear over 10 min. 70% progression over 30 min. 3 equal adds over 20 min 70% progression over 30 min. 70% progression over 45 min.

3.0 3.5
14.0

For this series of dyes the T50 values vary from 3-14 minutes. For dyes with T5Q values of three minutes the initial rate of fixation is rapid and the addition profile used becomes the critical step to effect level dyeing performance.

Calibrated In piece dyeing the target rope CulibruU-d circulation time for cotton knits is Viilumr normally two to three minutes. Under these circumstances and in extreme cases, 50% of dye fixation takes place before two rope revoluWalcr Supjih tions and the addition of fixation alkali is completed. In package dyeFig: Exhaust Dyeing Machine before Fig: Exhaust Dyeing Machine with ing, the in-outlet-in directional flow Loading with Fabric. Prepared (absorbent) Cellulose. qrde is generally set at 10 minutes; e.g., 3-4 minutes in-out and 6-7 minutes out-in. Again, in extreme cases, SOVo of dye fixadon an exhaust dyeing machine a litde more closely. takes place before the in-out cycle and the addition of The machine has a calibrated levelling device (usually at fixadon alkali is completed. Such rapid fixation can only put the side of the machine). level dyeing performance at risk and therefore precise conThe machine is calibrated by the machinery manufacturer trol is required at this stage of the process. T50 values will before delivery. depend on the reactivity of the dye, fixation temperature, Known volumes of water are pumped through a meaand the fixation alkali addidon profile. To support level suring meter (Electro Magnetic Flow meter) which tells us dyeing performance the target TSO value should be set at a exacdy how much water has been delivered to the maminimum of ten minutes, or, in piece dyeing five rope chine. revolutions, or in package dyeing one complete in-out/outEach water fill level registers on the levelling device, and in cycle. is therefore calibrated against the known delivered volume. The criteria for the selection of reactive dyes, which will, In this sense, the machine volume before addition of when applied using the principles of controlled coloration, substrate is known, and known quite precisely what is not maxim2e right-first-time production are based on S, MI, quite so certain is the "Working Volume" of the machine in LDF, and T5Q values.' These parameters are the key meathe presence of an absorbent substrate. sures of performance for a reactive dye and represent the Cellulose, and especially knitted cotton, absorbs water, RCM. Right-fixst-time production will be maximized within Therefore, the working volume cannot possibly be equal the RCM set at: to the calibrated volume. Furthermore, the amount of water absorbed (and therefore the difference between Substantivity in neutral electrolyte 70-80% working and calibrated volumes) is extremely difficult to >go% Migration Index predict. It is even difficult to predict for a vertical >70% LDF organisation. It is well nigh impossible for the commission dye house. 10 minutes minimum T50

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CO LOU RASE O DECEMBER 2009

RFT PRINCIPLES

Basic principles of reactive dyeing

Reactive Dyes
Reactive dyes receive their name because they contain reactive groups that can react with the fiber being dyed to produce a permanent chemical bond between the dye and the fiber. There are many different reactive systems, but the two major reactive groups, which give their name to the dye type> a.re "monochlorotriazine" (MCT) dyes and "vinyl sulphone" (VS) dyes. These dyes "react" in different ways and they require different dyeing conditions, particularly in terms of pH, and temperature and time profiles. Dyes can contain more than one of these reactive groups. If they contain two of the same group they are called "homo bifunctional" reactive dyes (e.g. MCT-MCT or VSVS). With these, each dye molecule provides twice as many chances for the dye to react with the fiber. If a reactive dye contains a mixture of two reactive groups it is called a "mixed bifunctional" or a "hetero bifunctional" dye (e.g. MCT-VS). Hetero bifunctional dyes can normally react under a wider range of dyeing conditions. Reactive dyes must be used under the correct conditions to ensure high fixation levels and better "right first time" dyeing.

Fig: winch Dyeing Machine Dye for 30-60 mins after the addition of alkali depending on the depth of shade.

Mixed bifunctional dyes: Monochlorotriazine

Typical dyeing conditions:

Sulphone &

Monochlorotriazine dyes
Typical dyeing conditions: Dye at 80C In the presence of an electrolyte (e.g. NaQ) pH 10.5 after addition of a suitable alkali Dye for 30-60 mins after the addition of alkali depending on the depth of fabdc shade

Dye at 60C and raise to 80C to ensure both reactive groups are used In the presence of an electrolyte (e.g. NaCl) pH 11.5 after addition of suitable alkali Dye for 30-45 mins at 6O'*C after the addition of alkali and then ramp to 80C and hold for 30-60 mins depending on the depth of shade The commercial names of many dyes provide information on which reactive group they contain.

Vinyl sulphone dyes

Typical dyeing conditions:
. Dye at 6O'*C In the presence of an electrolyte (e.g. NaQ) pH 11.5 after addition of suitable alkali
COLOURACiE O DECEMBER 2009

Electrolyte
This has long been known as a significant source of temporary hardness, which can exceed even that of the hardest of incoming water suppUes (see Tabie). Common salt (NaCl) is sourced from underground deposits or by evaporation of sea water. In the latter case,

RFT PRINCIPLES

Table: Total Metal Content by Source of Common Salt Source

UnpuriGed Rock Salt Source 1 Unpurified Rock S^t Source 2 Unpurified Sea Salt Purified Sea Salt Pure Vacuum Dried AUfiguresare in ppm

Ca** 1600 2200

1300

Fe *** 920 1800

260 50 2

25 100 45 2 2

100
23

which should be of prime concern. Fortunately, it is relatively easy to ensure that it is the interior of the fibre which is tested, and not simply the surface condition. This can be achieved by extraction of the prepared cotton in boiling distilled water (at the same liquor to goods ratio as that used in dyeing). The extract can be cooled to room temperature, and then measured for . pH peroxide Hardness.

calcium and magnesium impurity from discarded sea shells and mineral salts is highly likely.

RFT dyeing: Varioud technologies

Luft-roto plus: Economical exhaust dyeing technology
The Luft-roto plus and selected Levafix, Remazol and Prodon reactive dyes can reduce exhaust dyeing cycles for cdlulosics by up to 30% and virtually reduce water and chemical requirements to one-half. This technology was developed in cooperation with Thies.

Testing prepared cotton for residual chemicals

For any cotton in an aqueous medium there are three phases which we need to concern ourselves with: The aqueous bath The surface layer The internal BATH. Most testing regimes which screen for the efficiency of preparation focus upon the concentration of chemicals in last aqueous rinse before dyeing. There are three chemicals which can interfere with successful dyeing with reactive dyes if carried forward from preparation into the dye bath: peroxide (some dyestuff chromophores are extremely sensitive to peroxide) Hardness {all dyes susceptible to one degree or another) Alkali (which will cause premature fixation before migration and premature hydrolysis before exhaustion and fixation). Once a prepared substrate is placed in an aqueous dye bath, the temperature will be raised to a minimum of 60 'C. Therefore, anything which is in the interior of the prepared cotton can desorb into the bath. So - it is the Internal condition of the prepared cotton

Innodye/InnoVat: New jet dyeing concept

Innodye/InnoVat is a fiexible and economical new jet dyeing technology. Developed in conjunction with Brazzoli, this economical system allows rapid and efficient dyeing with Levafix, Prodon and Remazol reactive dyes and Indanthren vat dyes. This technology, therefore, meets demands for increased fiexibity and improved color fastness. The concept comprises the Innodye dyeing unit and the InnoVat dyeing process developed spedfically for this unit. The Innodye unit uses unique vacuum tedmology that opens up completely new process options. It indudes a patented traversing mechanism with a movable material basket. Innodye/InnoVat therefore ensures level dyeing even on problematic substrates.

Econtrol: Economical new continuous dyeing process

Econtrol is a rapid and reliable method of dyeing a wide range of substrates. It does not require steaming or curing and ensures high reproducibility and excellent fixation. Econtrol is a registered trademark of DyStar. It was developed in conjunction with Minford's and is based on the Thermo hot flue technology. Econtrol is environmentfriendly and dyeing can be carried out without silicate, urea and salt, thus reducing redpe costs and effiuent load. Econtrol is easy to use in the lab and lab-to-bulk reproducibility is very good. Excellent reprodudbility and high fastness levels can be obtained on both lightweight and heavyc a t - a u R A B E o DECEMBER 2009

Test the prepared fibre here Fig: Internal Bath of Cotton.

RFT PRINCIPLES

weight cotton, viscose and Lyocell qualities with selected Levafix and Remazol reactive dyes. Fluidyer Reliable dyeing of carpets & pile Fluidyer technology from Ksters and quality dyes frotn DyStar help dye houses achieve their aims faster, more economically and more reliably. Unlike conventional technology, the Fluidyer applies the liquor direcdy to the fabric through rows of holes, giving liquor pick-ups of 80-350%. A joint development project by DyStar and Ksters has developed this technology for dyeing pile fabrics. The world's only Fluidyer pilot plant, located in the service laboratory at DyStar's new headquarters in Frankfurt am Main, Germany, is available for test dyeing for customers. Electrochemical decolonization of textile effluent The decolonization of effluent is a new technology, which does not require chemicals or the disposal of residues. Electrochemical decolon2ation is based on the principle that electrons in an electric current split textile dyes into smaller, colorless parts that are more readily biodegradable. A cooperation agreement has been concluded with Bentiinger on the marketing of this environment-fdendly technology. Pilot trials show that this technology can remove over 80% of color from dye house effluent, especially effluent contaminated with reactive dyes. It is particularly effective for treating effluent from continuous dyeing which contains high dye concentrations.
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: to fill iln ob

decrease the production cost and give more quality products so that the profit margin is increased. Also this type of dyeing is ecofriendly.

References
www.dyehouses.com www.alternative.pdf CoUishaw, P. S.B. Glover and M. J. Bradbury, Joumai of die Sodety of Dyers and Colorts. Vol. 108, No. 1. January 1992. pi 3. Farrington, D.W. Journal of the Sodety of Diversion
ColorisU. VaL 105.

Conclusion
So it is dear that using "Rigjit First Time Dyeing" conceptsprovides broad scope of increasing the profit by reducing the after treatments. This is clear by the following flow chart In this competitive world "Only the fittest will survive". The Indian textile industry must improve its Productivity, and particularly in the Dyeing & Finishing sector; and must target the Value-Added sectors. This can be achieved mainly by introducing innovative ideas and applying chemistry to

. No. 9 September 1989, p301. Diggle. P., Textile Institute Conference Proceedings, Ghent, Belgium. 1991. Glover, B., journal of the Sodety of Dyers and Cokrisis, Val. 107, No. 5/6. May/June 1991, pi 84. Carbonell. J., American Dyestuff Reporter, Vol. 76 N0.3. March 1987, p34. . Bradbury, M. J. P. S. CoUishaw and D. A. S.Phillips, 16th IFATCC Congress. 1993. . CoUishaw. P. S. D. T. Parkes. I5th IFATCC Congress. 1990. Lidyard. A. M.. A. Woodcock and P. Noone. journal of the Sodety of Dyers and Colorists. Vol. 108, No. U . November 1992. p501.

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