Review Article Electrochemical dyeing : A noval dyeing Approach

Mr. Amit kumar & Sahil Sharma(Managenent Trainee) amittc2@gmail.com AADTT (Advanced Academy for Development of Textile Technologist)

Abstract

There is a continuing need for improving the eco-efficiency of critical textile wet processes specially in dyeing. For example, dyestuffs such as sulphur and vat dyes, especially indigo, play an important role in today's dyeing industry. The present use of this dye category is based on the application of sodium to attain a water soluble form of the dye (= leuco dye) by reduction but the disposal of dyeing baths causing various problems, because the reducing agents necessary will finally be oxidized into species that can hardly be regenerated. These sulphite, sulphate, thiosulphate and toxic sulphide heavily contaminate waste water from dyeing plants. Therefore, many attempts are being made to replace the environmentally unfavourable sodium dithionite by ecologically more attractive alternative. In this reference, electrochemistry presents a very effective technique. The process uses an electric current instead of chemical reducing agents, giving it a number of technical, economic and ecological benefits. Electrochemical dyeing process results in, product savings, less chemicals with special safety requirements, unsurpassed environmental compatibility. Moreover new process also facilitates dye bath monitoring in real time, the high quality of the dyed fabric is ensured. The dye liquor used in electrochemical dyeing can be reused several times without altering the dyeing effect and contamination of dye house effluent is negligible. Keywords Leuco Vat dyes, reducing agents, reduction, electrochemical, environmental friendly, effluent Introduction The major dye classes used for colouration of cotton/cellulosics include reactive, vat, sulphur, azoic, direct and solublised vat. The worldwide consumption of different dye classes is given as:

DYES Sulphur Direct Vat Indigo Azoic Reactive TOTAL

1988 90000 74000 36000 12000 28000 60000 300000

1992 70000 60000 21000 12000 18000 109000 290000

2004 70000 68000 22000 12000 13000 178000 354000

Table shows that reactive dye consumption increases, and next important dye class are vat and sulphur.These dyes are insoluble in water; before application they are solublised using suitable reducing agent and alkali. But due to their non ecofriendly and polluting nature, an alternative reducing method using instead of conventional reducing agent called electrochemical dyeing getting emphasis these days. REDUCING AGENT FOR VAT DYE Sodium dithionite(sodium hydrosulphite)is commercially reducing agent.And other reducing agents are thiourea dioxide,sodium borohydride.But due to commercial problem,they are no used.

SODIUM DITHIONITE Its Chemical formula is Na2S2O4.It reduces all vat dyes at a temperature range from 30C to 60C and above. The reducing property of sodium dithionite is due to libration of hydrogen as follows: Na2S2O4 + 4H2O Na2S2O4 + 2NaO 2NaHSO4 +6H2Na2SO3 + 2H-

The amount of reducing agent and NaOH required for a specific vat dye to reduce and bring it to soluble depends on number of C=O groups and how compact the structure is. Sodium dithionite is unstable,gets decomposed oxidatively and thermally to several byproducts. Some byproducts are acidic in nature, and need overdosing of alkali over stoichiometric requirement. The stability of solution decreases with increased temperature, increased surface exposed to air and decrease agitation of bath. And Salts of sulphur also in form of sulphates and sulphites contaminate sewage, lower its pH and corrosive action in pipes. REDUCING AGENT FOR SULPHUR DYES The sulphide reducing agents are sodium sulphide(Na2S),sodium hydrosulphide(Na2H2S4),and sodium poly sulphide(Na2Sx where x can be from one to six).But problems associated with sulphide based reducing agents are Contamination of effluent with sulphur and Libration of H2S which gives foul smell of rotten eggs and is toxic when healed. Some ecofriendly reducing agents are also there like hydroxyacetone,ironcomplexes,glucose, mercaptethanol but there are problem of using these related to stability,reduction time and cost.

But now-a days we try to establish the newer method due to some disadvantages of older methds and wealthy procedure of newer one.(like electrochemical dyeing). Electrochemical method fulfill the entire requirement for dyeing, it provides sufficient negative reduction potential in the range of 450m V to -1000m V to reduce the dyes. It is a reproducible process and gives similar or improved dyeing result compared with the technique already in use.It requires low concentration of chemicals and nontoxic chemicals and economic technique for recycling of chemicals and washing water. The main key point is it is adaptable to equipment and apparatus in use at present time. ELECTROCHEMICAL DYEING In this,chemical reducing agents are replaced by electrons from electric current, and effluent contaminating substances can be dispensed with altogether. In conventional method, reducing power of chemicals can not be regained ,so recycling of bath is not possible. So due to residual chemicals and unused dye in disposable liquor. problems will generate due to non eco friendliness.Then electrochemical dyeing introduced as a big boon for textile dyeing.This process was developed by BASF. The first attempt was made in this context by reducing the amount of sodium dithionite by application of direct voltage.This results powerful reducing agent species due to the decomposition of hydrosulphite and production of free radical ion,SO2. S2O4 2SO2-

In this case also recycling is not possible.Then its one step ahead is electrochemical dyeing. THE CLASSIFICATION OF ELECTROCHEMICAL DYEING CAN BEEN SHOWN AS: DIRECT ELECTROCHEMICAL DYEING In this technique,the dyes have been reduced by direct contact of electrode and dye.But,the partial reduction of dye should be carried out by conventional method,then complete reduction is done by electrochemical process which facilitates improved stability of reduced dye. In order to start the process,an initial amount of leuco dye has to be generated by a conventional reduction i.e.by adding a small amount of reducing agent.Once the reactions have set in,it is not needed anymore and the further process is self sustaining.This system is sucessful in the case of sulphur dye. MECHANISM OF REDUCTION OF DYE MOLEULE BY DIRECT METHOD

The

basic

reduction

of

indigo

molecule

by

any

method.

Direct electrochemical reduction of indigo molecule

DIRECT ELECTROCHEMICAL REDUCTION OF SULPHUR MOLECULE

PROBLEM IN DIRECT ELECTROCHEMICAL METHOD: 1) The concentration of dye required to get a specific shade is higher than the conventional
reducing process.

2) The dyestuff particles must come in contact with the electrode surface to get reduced.But
atmospheric oxygen present in the dye solution reoxidises the dyestuff molecules.

3)The surface area of the cathodic is constraint.

DIRECT ELECTROCHEMICAL REDUCTION OF INDIGO ON GRAPHITE ELECTRODES It has been found that graphite granules can act as electrode material for the direct electrochemical reduction of indigo in aqueous suspension.Optimised conditions of 10gpl was achieved for indigo. Results are favourable since very cheap and stable material.In addition,an electrochemical fixed or fluidized bed reactor is a reasonable economic reactor design for this task.Due to the high hydrogen over voltage on graphite under the applied conditions,no chemisorptions or only very weak,chemisorption of hydrogen is possible. Therefore a normal electron transfer seems to be the relevant process for the reduction of indigo.Unfortunately the reduction rate is very low.It should be possible to accelerate the relevant process i.e.electron transfer kinetics and probably also the absorption rate 1)by the selective generation of quinine like functionalities on the surface of the used graphite electrode. 2)Oxidative pre treatment can increase the content of oxygen-containing groups on the surface of carbon.e.g.soaking with hydrogen peroxide. 3)By covalent bonding of quinoid molecules onto the graphite surface.Thus,electron transfer mediators,which can undergo fast electron transfer with the electrode and also with the substrate(indigo),are immobilized on the carbon electrode.In the particular case of indigo reduction,anthraquinone have been used as redox active molecules. INDIRECT ELECTROCHEMICAL DYEING It was first patented by THOMAS BECHTOLD in 1993.Here the dye is not directly reduced at electrode; rather a reducing agent is added that reduces the dye in conventional manner which in turn gets oxidized after dye reduction. The oxidized reducing agent is reduced subsequently at the cathode surface which is then further available for the dye reduction. This cycle is continuous for dyeing operation. In electrochemistry, the agent which undergoes reduction and oxidation cycles is known as reversible redox system and is called a mediator. The primary object of redox system is to generate a continuous regenerable reduction potential in the dye liquor. Therefore, addition of conventional reducing agent is

not needed. After the dyeing cycle, the unexhausted dye gets precipitated by air oxidation and can be removed by filteration. then the liquor containing the mediator can be recycled for subsequent dyeing operation.This is the biggest advantage in terms of eco nature and cost of process.

A suitable redox catalyst for indirect electrochemical dyestuff reduction has to fulfill various requirements:
1) No reaction with solvent 2) No affinity for the fibre material 3) Rapid conversion at the electrode surface 4) No catalysis of side reactions(change in colour) 5) No problems in effluent 6) Non toxic 7) Only a small loss,if any,in activity during the useful life;therefore the maximum possible number of reaction cycle. 8) Inexpensive 9) Adequate solubility THIS CAN BE ONLY USED IN DISCONTINUOUS EXHAUST DYEING PROCESSES AND IN CONTINUOUS DYEING PROCESS,IT CAN BE USED TO STABLISE THE DYE BATH BY DIMINISHING THE AMOUNT OF LEUCO INDIGO OXIDISED DURING DYEING DUE TO CONTACT WITH AIR. (Reason is that the huge electrode surface of 500m2 is necessary to achieve a feasible rate of dye reduction at an industrial scale.)

PICTORICAL REPRESENTATION OF MECHANISM OF REDUCTION OF THE DYE BY INDIRECT ELECTROCHEMICAL METHOD

A general reaction for indirect electrochemical dyeing process using Fe(ll)-TEA complex is established as follows: In the first reduction step,the iron complex is cathodically reduced in a reversible electrochemical process.The reduced complexes diffuse from the electrode towards the dyestuff particles.At the surface of the dispersed particle oneelectron charge transfer charge occurs and a dye radical anion gets formed which is an intermediate step to form completely reduced dye dianion. The completely reduced dye dianion can be formed by two routes,Since most of the dye require two electrons for the reduction of each molecules,two dye radical anions are assumed to give one fully reduced dye dianion molecule and to regenerate one dye molecule in its oxidized form.The other possible mechanism for the formation of reduced is such that one electron transfer may takes place from a reduced mediator to a dye radical anion and forms a fully reduced dye anion molecule as a reaction product.In an additional reaction,the equilibrium between the fully reduced dianion molecules and the insoluble oxidized form of dye is built up. A GENERAL REACTION FOR SUCH AN ELECTROCHEMICAL PROCESS IS SHOWN AS: Fe3+L +eFe2+L +dye 2dye Dye.- + Fe2+L Dye2Fe2+ + L Fe3+L +dye.dye2- + dye 3 1 2 cathodic process one-electron transfe

disproportionation 4 secondary reduction

dye2- + Fe3+ L dye + 2e5

oxidation

Where L denotes the associated TEA/Ligand

MEDIATOR SYSTEMS
The great advantages of this technique is the direct information about the state of reduction in the dye bath,which is available by redox potential measurement,and that control by the adjustment of the cell current is possible.
REDUCTION CAPACITY OF THE MEDIATOR SYSTEM

In this theory as per Nernst equation,any desired reduction/oxidation potential (upto the liberation of hydrogen gas)can be achieved in solution by combining an appropriate proportion of reduced and oxidized species.At any given time in an electrochemical system,both the oxidized and reduced pair is available in the solution.By varying the voltage provided,the concentration of these oxidized and reduced species can be adjusted and ultimately the potential prevailing in the solution Nernst equation:

E = Eo +RT/nF . lnCox/Cred
Where, Eo=Standard potential of the redox pair(under the experimental conditions)in Mv,E=Potential prevailing in the solution(mV), R=Gas constant(8.314j/Kmol), F=Faraday constant(96500C), T=Temperature(K), n=Electrochemical valency, Cox=Concentration of the oxidized form of redox pair(mol/l), Cred=Concentration of the reduced form of the redox pair(mol/l) The reduction potential which can be realized industrially in solution is always close to the normal potential of the redox pair used at the electrode and the mediator capacity is expressed in terms of cathodic peak potential. DIFFERENT MEDIATOR SYSTEMS: Some of the mediator systems which can be used as reversible redox systems for the electrochemical dyeing are given as:-

ORGANIC REDOX SYSTEM Organic compounds with anthraquinonoid basic structure are used as a mediator for indirect electrochemical dyeing.They enabled the reduction of sulphur dyes and vat dyes with leuco potentials below the cathodic peak potential of the mediator system. The anthraquinonoid systems have cathodic peak potentials upto a level of -850mV
DISADVANTAGES:

In these redox system,the relatively low rate of conversion at the electrodes.

Indirect redox system

Inorganic compounds used are metal complex salts.The reducing action of metal salts of low valency levels were used earlier for vat dyes.These have several disadvantages such as precipitation of dye bath and,heavy metal content of the effluent due to large quantities employed.The most suitable iron complex system is iron salt/TEA which allows potentials of up to -1050mV to be achieved under dyeing conditios in homogeneous solution.The iron complex can be prepared either from Fe(ll)salts or from Fe(lll)salts.The potential which can be achieved allows a reduction of all the usual vat dyes without use of additional use of reducing agent.

CATHODIC PEAK POTENTIAL OF DIFFERENT ANTHRA QUINONE SYSTEM

ORGANIC COMPOUNDS

CATHODE POTENTIAL(mV) -880

PEAK

ORGANIC COMPOUND

CATHODE POTENTIAL(mV) -885

PEAK

1,2 dihydroxy anthra quinone

1,2,5,8 tetra hydroxyl anthra quinone 1 amino 2 carboxy anthra quinone 1 amino anthra quinone 2 sulphonic acid Anthra quinone 2,6 sulphonic acid 1,2 dihydoxy anthra quinone3 sulphonic acid

1,4 dihydoxy anthra quinone

-760

-750

1,8 dihydoxy anthra quinone

-770

-720

Anthraquinone acid

sulphonic

-750

-560

Anthra quinone 1,5 sulphonic acid

-750

-760

WITH 4GPL NaOH w.r.t. Ag/Agcl/3 M Kcl REFERENCE

Dyeing procedure
The electrolysis was carried out under galvanostaticconditionby maintaining the constant current and optimizing the time required for achieving maximum current efficiency.During the electrolysis, the conversion of ferric ions was estimated by iodometric titration at different intervals of time. After achieving maximum conversion of ferric ions (no further increase in FeII concentration with time), the required quantity of selected dye was added into thecatholyte. The electrolysis was continued for another 30 min for solubilization of the dye molecules. Then, the pretreated fabric sample was introduced into the dye bath. Both electrolysis and electrochemical dyeing were carried out at 300 2 K. Experiments were carried out at relatively large liquor ratio value, such as 1:330, 1:80, and1:60. In all the experiments, 0.8 wt% of the fabric on the dye was used in the dyeing recipe. The dyeing was carried out by exhaustion method for 30 min with constant stirring.After completion of dyeing,the fabric sample was washed with cold water and exposed to air, for oxidation/fixation of dye molecules. Then the fabric was soaped at boil, rinsed with cold water, and air dried. DIFFICULTIES TO ESTABLISH INDIRECT ELECTROCHEMICAL DYEING PROCESS: The actual reduction of dye should be carried separately into electrochemical cell and the reduced dye is then circulated separately into a conventional dyeing unit,e.g.jigger

To keep the dye in reduced form,it is necessary to reduced the oxidized mediator at the cathode.This is possible only through continuous circulation of the dye liquor from the dyeing equipment to the electrochemical cell. The design of the cathode should have maximum enough surface area to reduce the mediator. A three dimensional electrode with large surface area occupying small space in the electrochemical cell should be designed.The kind of cell will have the advantages of carrying out the dye reduction with minimum volume of mediator. A cell with minimum area of separator(semi permeable membrane,separatinganolyte from catholyte)is necessary.It will ensure minimum cost of separator and will not allow the reoxidation processes to takes place due to bleeding of the separator,diffusion of oxygen.Thereoxidation at the separator may cause a chemical short circuit,thus requiring further enlargement of cathode area. ADVANTAGES:

The indirect electrochemical reduction technique using mediators permits direct control of the dye bath potential without the undesirable connection between temperature and reduction potential.

ELECTROCHEMICAL DYEING WITH INDANTHREN DYES The system contains a vessel which contains a reduction system made.Stirring is done by magnetic stirrer.At the bottom of the dyeing vessel a copper cathode is there.The cathode provide electrons as the power supply switch ON.

Factors governing electrochemical dyeing process Effect of dye concentration and material to liquor ratio
Even dyeing was noticed for all MLR values, but depth of the dyeing varied with increasing MLR. When compared the better shade was obtained with MLR value of 1:60. Thus, the liquor amount can be reduced from 240 to 60 litters. The low MLR value saves the consumption of chemicals, water, and cost of the dyeing process.

Effect of electrode material

Both the conversion efficiency and the current efficiency values obtained for the electrogeneration of FeII-oxalate-gluconate system employing different cathode and anode materials. Both platinum and stainless steel may be employed as anode material. Stainless steel is the material of choice as anode due to cost consideration. Copper plate as well as wounded copper coil could be employed as the cathode material with reasonable efficiency.

Effect of electrolyte composition

Studies were carried out to determine the optimum concentration of ferric sulfate, oxalic acid, and Ca-gluconate. The conversion efficiency increases when the ligand concentrations are significantly higher than the Fe(III) concentrations. When the ferric sulfate concentration increased beyond 25 mM by retaining the oxalic acid concentration at 100 mM and calcium gluconate concentration at 50 mM, the conversion

efficiency decreases probably due to the insufficiency of ligands for complete complex formation.

Effect of Complexing agents

The mediator system used in electrochemical dyeing is not stable under highly alkaline condition. Industrial vat dyeing is preferably carried out above pH 12 and very few Fe(III) complexes are stable in such alkaline conditions. The mediator system get precipitate out so not works properly. In presence of excess gluconate, the Fe(III)-oxalate complex does not lead to any hydrolysis or precipitation. The pH of ferric-oxalategluconate system could be raised beyond 13.

Effect of the current intensity

We can achieve fast and more dye reduction by utilizing higher current values but heating effect and limited freedom for reaction. When operating with a galvanostatic mode, the current intensity is a crucial factor. Indeed, low current values will result in high selectivity of the electrochemical reaction but long lasting electrolyses. High current values will produce short experiments but a bad selectivity and a temperature increase due to joule effect.

Requirement satisfied by the electrochemical dyeing process

High number of dyeing cycle of the mediator without cleavage or losses in the activity. High current efficiency and high current density of reversible redox system. High reaction rate between reduced mediator and oxidized dyestuff. Sufficient conductivity of catholyte without change in the dyeing results.

Cheap electrode material for cathode and anode. Simply constructed cell and easy maintenance. Minimum side reactions e.g. dyestuff destruction due to formation of radicals.

ELECTRO CATALYTIC HYDROGENATION

Electro catalytic hydrogenation is a recently introduced reduction method for vat and sulphur dyes and it proves to be a promising and attractive alternative in terms of economic and ecological aspects. The process consists of a sequence of reduction steps which differ principally from those of the previously described indirect and direct electrochemical vatting processes via the dye radical.These involve electron-transfer from the cathode to either a mediator or the leuco radical anion of vat dye.In contrast to this mechanism,electrochemical hydrogenation is a process in which adsorbed hydrogen,produced in situ by electrolysis of water,reacts with adsorbed organic substrates(i.e. vat dye)at the electrode surface.

Exclusive benefits we get from electrochemical dyeing Liquor Recycling possible

In electrochemical dyeing experiment the dye liquor recycling loop is repeated at least 9 to 10 times. The same catholyte solution after dyeing was air oxidized and filtered to remove the insoluble dye molecule (1015% fresh electrolyte).The conversion as well as current efficiencies remain reasonably same during each of this recycling experiment. The dye intensity measured as K/S values were also found to be reasonably stable in all the 10 dyeing recycles.

Stability of electrolyses

The pH is an important parameter influencing the performance of vat dyes reduction. The Vat dyes are found in different form depending on the dye bath pH. In conventional reduction, this parameter must be constantly controlled because the decomposition of dithionite generates a decrease of the pH values which can cause some disturbances.DyebathpH is more stable in the electrochemical process than in the conventional one. Hence, there is no need for the addition of alkali during electrolyses.

Saving

An estimation of chemical savings can be made on basis of the charge flow required to reduce a certain amount of dyestuff. For sulphure dye the chemical saving calculated as 0.644 kg dry SB1 (Sulphur Black 1) was reduced by a charge flow of 57.5 Ah at a voltage of maximum 7.5 V. This corresponds to an amount of 3.33 mol reducing equivalents per 1 kg dry SB1 and to an energy consumption of 0.67 kWh/kg dry SB1 filter cake. When sulphide

reducing agents are used instead of cathodic reduction the amount of Na2S can be calculated from Eq. According to Faradays law 3.33 moles equal an amount of 129 g Na2S, which will be required to reduce 1 kg of dry SB1 filter cake.

Online dye bath Analysis

Controlling the bath composition is of great interest. ECD allows us to avoid a useless prolongation of the reduction time and to prevent the phenomena of over or partial reduction which are frequent and difficult to control when reduction is carried out by dithionite.And the final dyed fabric is of better quality because full control over dyeing parameters is possible.

Economy

The entire textile industry get affected because savings in the chemical costs as chemical wastes reduced by 80% and reduction of waste water recycling cost at the same time water savings around 85% so economical.

Health

Several times bath recycling is possible with this dyeing method so it is an environmentally sound Process. Also the toxic nature sulphates and sulphites are not there in effluent so no adverse effect to aquatic life.

Dyeing Process

Fully controlled dyeing parameters, maximum Process reliability through control of reducing potential as needed ranging from 0 to 1200 mV just by varying the current. Dye Reduction Rate is Very good (10mg dye/min) and dye pick up may go up to 85-90%.

Quality of Products

Better overall fastness property is observed so comparatively more consumer satisfaction.

LIQUOR RECYCLING IN ELECTROCHEMICAL DYEING

The possibility of restoring the reducing power of a used dye bath is an attractive one in these days of heightened concerns over dyehouse effluents. Naturally ,if reuse of the mediator system with different days of intended, the residual dye has to be removed from the dye liquor. This is a more straightforward proposition with vat dyes, because of the insolubility of their oxidised form in aqueous solutions,and their ability to form suspensions, which can be removed by a filtration process from the oxidized dye liquor.After completing the dyeing procedure,the remaining dye and reduced mediator can be oxidized by bubbling air through the solution to form, the insoluble form of dye.

Recycling of dyeing liquor is then achieved by pressure filtration through a PTFE membrane with a pore size of 0.45 or 1.2m at a pressure of 1-2 MPa(10-20 bar).However the dye bath has to be circulated through the electrochemical cell at a rate that must follow the threshold conversion rate in the cell.The complete filtration should be ensured to avoid contamination of cell by impurities released from the goods.In an electrochemical dyeing,the liquor recycling loop was repeated nine times.The dyeing experiments showed good reproducibility in the colour of dyed goods,confirming that electrochemical regeneration of reducing agent can be achieved for many cylces without a measurable loss in electrochemical activity. Two process engineering concepts for continuous electrochemical dyeing which makes liquor recycling liable: a)Closed circuit b)Mediator concentrate technique

CLOSED CIRCUIT TECHNIQUE:

This technique is called as a closed circuit technique because the content of dye bath are circulated through the electrochemical cell in this technique,With this technique,the mediator and vat dyes like indigo can be recovered from wash water.The washing water is passed through an ultra filtration is unit to remove the insoluble dye.The filtrate of the ultra filtration subjected to nano filtration where the concentration of mediator is increased to a final value of 0.6 mol/l of Fe(lll) complex.The Fe(ll)/Fe(lll) ratio in the dye bathis maintained and the prevailing solution dye liquor potential is maintained.The advantages of this system is that it allows almost any desired amount of reduction equivalents to be admitted into the dye bath at constant concentration ratios.

MEDIATOR CONCENTRATE TECHNIQUE

In this mechanism, the content of dye bath are not circulated through the electrochemical cell, nor does a dyes solution flow through it. The technique is analogous to the metering of dithionite solutions in indigo, vat and sulphur dyeing. As far as the dye bath potential is concerned, metering is similar to that of closed circuit technique. The quantity of mediator required in the dye bath is correlated with the composition of dye bath liquor as in case with conventional reducing agent. The great advantages of this technique is that the reduced mediator is stored in tank.The mediator from this tank can be supplied to several installations with different colouristic settings. By doing comparison between two,it reveals that the closed circuit technique offer great advantages.With the closed circuit technique, we can utilize rapid process control by measuring the potential and controlling the cell current.

The composition of the dye bath is independent of dye consumption,so that the risk of tailing is reduced.

Effect of recycling of electrolyte dye bath

The same catholyte solution after dyeing was air oxidized and filtered to remove the insoluble dye molecule. This electrolyte, after addition of 1015% fresh electrolyte, could be recycled at least 10 times.The conversion as well as current efficiencies main reasonably same during each of this recycling experiment. The dye intensity measured as K/S values were also found to be reasonably stable in all the 10 dyeing recycles. In all experiments discussed, so far, the electrochemical reduction was allowed to continue during the dyeing experiment. The dyeing process as well as recycling experiments was also carried out to study the dyeing efficiency without applying any electric current. Such a procedure is, indeed, necessary for continuous process development, where the dyeing unit should be separated from electrolyzer unit.

ADVANTAGES OF ELECTROCHEMICAL DYEING PROCESS

Product saving Less chemicals with special safety requirements Better fastness properties Waste water limits easily achieved. Maximum process reliability through control of the redox potential Existing dyeing machine can be retrofitted. Unsurpassed environmental compatibility. Reduction of water and waste water cost through recycling. Shorter and more reliable dyeing processes.

Literature Cited Textile Chem. Colorist 5 (1973) Textile Chem. Colorist 21, 25 (1989) Textile Research Journal 61 (1991) 773 J.S.D.C. 109 ( July-Aug. 1993) Colourage 17 (1970) 21 Textile Chem. Colorist 21 (1970) Colourage 21 (1976) Textile Chem. Colorist 24(1), 22(2) (1992) Asian Dyers (May-June 2004) US patent Application 5,244,549 Coloration Technology ( June 2007) Asian dyers (April 2007). Textile Chem. Colorist 22 (1990) 13 J.S.D.C. 110 (1994) 14 J.S.D.C. 113 (1997) 135 Coloration Technology (117) 2001 Coloration Technology (121) 2005 Journal of applied electrochemistry (Dec. 2008) Journal of applied electrochemistry (June 2009) Coloration Technology (August 2008) Journal of applied electrochemistry (May 2009) US Patent Application 4609439(September 1986) US Patent Application 6790241B2(September 2004) US Patent Application 20030098246(May 2003) http://www.books.google.co.in/books?isbn=1594545448 (on Dec.25, 2010).

Swiss Federal Institute of Technology (ETH), CH-8093 Zurich, Switzerland (Feb. 2003) US Patent Application 20040069653