Kiran res. paper draft final

POTENTIOSTATIC STUDIES ON INDIRECT

ELECTROCHEMICAL REDUCTION OF VAT DYE

Prof. R. B. Chavan* and Kiran Patil, Department of Textile Technology, Indian Institute

of Technology, Delhi, Hauz Khas, New Delhi – 1100016 (India)

&

M. Anbu Kulandainathan, Scientist, Central Electrochemical Research Institute,

Karaikudi, Tamil nadu –630006 (India)

Abstract

Dispersed vat dyestuffs can be reduced by indirect electrolysis using iron-

triethanolamine complex. The application of indirect electrolysis as a reduction technique

is described along with the mechanism. Electrochemically reduced vat dye is tested in

laboratory scale dyeing experiments, and the results of different reduction conditions are

discussed. The influence of the concentration of the complex-system on the build-up of

colour depth, shade and fastness is discussed and compared with samples of the standard

dyeing procedure using sodium dithionite as reducing agent. The new process offers

environmental benefits and offers the prospects of improved process stability, because the

reduction state in the dyebath can be readily monitored by measuring reduction potential.

Introduction

Vat dye is one of the most important among the dye classes used for colouration

of cotton, particularly, when high fastness standards are required to light, washing and

chlorine bleaching.1 Also, from the commercial point of view, vat dyes (including indigo)

acquires a large share in the dyestuff market for the colouration of cellulosic fibres. The

annual consumption of vat dyes including indigo is around 33,000 metric tons since 1992

and it holds 24% of cellulosic fibre dye market in value terms.2

Vat dyes being water insoluble have to be first converted into water soluble form

by reduction with strong reducing agent like sodium dithionate. The use of sodium

dithionate is being criticized for the formation of non-environment friendly

decomposition products such as sulphite, sulphate, thiosulphate and toxic sulphur. 3,4

Attempts are being made to replace the sodium dithionite by ecologically more

attractive alternatives. α-hydroxyketone which meets requirements in terms of reductive

efficiency and biodegradability had been tried. However such compounds are expensive

and their use is restricted to closed systems due to its strong smelling condensation

products in alkaline solution.5 Some other sulphur containing compounds like

hydroxyalkyl sulphinate, thiourea etc, have also been recommended recently. 6 These

compounds have relatively low amount of sulphur content and also have lower equivalent

mass which leads to lower sulphur based salt load in the waste water. However, in these

cases too, it is not possible to dispense with sulphur based problems totally.

Being Fe(OH)2 as a strong reducing agent in alkaline medium, this possibility has

also been explored for reducing organic dyestuffs. The reducing effect of Fe(OH)2

increases with increase in pH. However, Fe(OH)2 is poorly soluble in alkaline solution

and gets precipitated. It must be complexed in order to hold Fe(OH) 2 in solution7. A stable

complex with reducing power is obtained with weaker ligands, e.g. gluconic acid.

Regarding eco-friendliness, gluconic acid can be eliminated in the sewage tank through

neutralization with alkali; free Fe(OH)2 can be aerated and converted to Fe(OH)3 which

acts as a flocculent and reduces wastewater load. Tartaric acid has also been tried as a

ligand by Chavan and Chakraborty for complexing Fe(OH)2 in presence of NaOH for

reduction and dyeing of cotton with indigo and other vat dyes at room temperature.8

Efforts have been made to complex Fe(OH)2 with single and double ligand systems using

tartaric acid, citric acid and gluconic acid which has shown optimistic results.

Recently electrochemical reduction of vat, indigo and sulphur dyes is suggested.

There are two ways by means which electrochemical reduction is achieved. Direct and

indirect electrochemical reduction. In direct electrochemical reduction the chemical

reducing agents are replaced by electrons from electric current, and effluent

contaminating substances can be dispensed with all together.9,10 Although this technique

is ideal, the stability of reduced dye species is poor affecting the colour yield. In Indirect

electrochemical reduction technique the dye reduction is achieved through a redox

mediator system. Among the various mediator systems suggested in the literature, iron-

triethanolamine complex (iron-TEA) seems to be promising. 11,12

Both the electrochemical reduction techniques are not yet commercialized and

research and development efforts are in progress in this direction.

In the present paper attempts are being made to understand the fundamentals of

indirect electrochemical reduction of selected vat dyes using iron-TEA complex as

mediator. Essential requirements for the design of electrochemical cell are suggested.

Iron-TEA-NaOH molar ratio has been standardized to get the dyeing of cotton by

indirect electrochemical reduction technique. The colour yields are compared with

conventional sodium dithionate method. The repeated use of dye bath after dye

separation is explored.

Experimental

Materials.-The sodium dithionite and sodium hydroxide used for vat dyeing by

conventional method were laboratory grade chemicals. The mediator system necessary

for indirect electrochemical reduction of vat dyes was prepared in alkaline medium from

triethanolamine and ferric sulphate which were analytical grade chemicals. The

potentiometric titrations were carried out to measure the dye reduction potential by using

K2Fe(CN)6 as an oxidizing agent which was too an analytical grade chemical. The dye

systems investigated were commercial products from Atul Ltd: Novatic Yellow 5G (CI

Vat Yellow 2), Novinone Brown RRD (CI Vat Brown 5), Novinone Green FFB (CI Vat

Green 1), Novinone Blue RSN (CI Vat Blue 4), Novinone Blue BO (CI Vat Blue 20),

Novinone Brown BR (CI Vat Brown 1), Novinone Black BB (CI Vat Black 36),

Novinone Brill. Violet RR (CI Vat Violet 1) and Novinone Black CH.

Dyeing procedure and process control

Conventional dyeing.-The conventionally vat dyed samples were prepared in the

laboratory, with a standard procedure using sodium dithionite and sodium hydroxide.8

Electrochemical dyeing

Design of an electrochemical cell.-The electrochemical cell consists of a rectangular

polyvinyl chloride vessel containing 1 l catholyte and 0.1 l anolyte. The anolytes used

were the same solutions which were being used as the catholytes in every case. The

anode used was thin stainless steel rod with the surface area of 6 cm 2. A three-

dimensional copper wire electrode with a surface area of 500 cm2 was served as the

cathode. The cathode compartment was thus providing porous flow through electrode

filling the cathode compartment as coil (depth 10cm, front area cm2). The anolyte was

separated from the catholyte by a diaphragm (cation exchange membrane) to prevent the

two electrolytes from mixing. The catholyte was agitated by an analytical rotator at a

constant speed to guarantee homogeneous and stable conditions in the cathode chamber.

The dyebath of the dyeing apparatus was circulated through the electrochemical reactor

for continuous renewal of the reducing capacity of the dyebath. In accordance with

technical conditions, the electrolysis experiments did not involve an inert atmosphere.

A schematic drawing of the dyebath circulation through the laboratory dyeing unit

and the catholyte circulation through the electrochemical cell is given in Fig. 1.

Analytical rotator

+ -

Anode: SS Cathode: Cu
Peristatic Peristatic
Anolyte: Catholyte: Dyebath
Pump 1 Pump 2
Mediator (Mediator system
175 ml/min 175 ml/min
100 ml + dye) 1200ml
1000 ml

Electrochemical cell

Cu wire to measure solution potential w.r.t. reference electode

Reference electrode (Hg / HgO/OH-)

Fig. 1. Schematic representation of the electrochemical flow cell

Determination of reduction potential of vat dyes.-Here, the reduction potential of the

dye is referred as the potential developed on the bright platinum electrode when dipped in

the dye bath versus the reference electrode at which the dye gets just solubilized. In

order to measure the reduction of the vat dyes, the titration was carried out using bright

platinum electrode with Ag/AgCl/3M KCl as a reference electrode. A solution of 100mg

vat dye was prepared which was reduced with 25ml of 0.1M NaOH and 100mg Na2S2O4.

This solution was then diluted to 50 ml with distilled water and then titrated against

0.05M K2Fe(CN)6. The K2Fe(CN)6 solution added in the steps of 0.5ml and the dye

solution potential measured at every step. The ml of 0.05M K2Fe(CN)6 solution is then

plotted against the dye solution potential in order to find out dye reduction potential.

Dyeing Procedure.-Selected vat dyes were dyed under the standardized conditions of the

mediator system as described in results and discussion section. While following the

electrochemical dyeing technique, the dyebath was circulated through the cathodic

compartment of the electrolytic cell for continuous renewal of the reducing capacity. All

the experiments were performed under potentiostatic conditions (-1050 mV) at room

temperature. The catholyte was called as a mediator solution which was comprised of

triethanolamine, ferric sulphate and sodium hydroxide. The potential prevailing in the

catholyte, while electrolysis, was measured with a copper wire versus a reference

electrode (Hg/HgO/OH-). The catholyte was agitated in the catholyte compartment itself

and was also circulated through the dyebath continuously. When the potential achieved in

the catholyte was equivalent to the reduction potential of the dyestuff, the dyestuff was

introduced into the catholyte compartment. In all the experiments 2% on weight of fabric

dye was used in the dyeing recipe. The fabric sample was introduced into the dyebath

after ten minutes of introduction of dyestuff in order to allow reduction of the dyestuff.

The experiments were carried out at a relatively long liquor ratio i.e. 240:1. The dyeing

was continued in the dyebath for one hour with constant agitation of the fabric sample

with glass rods by hand, while electrolysis and circulation of the catholyte was on going.

After dyeing the sample was withdrawn from the dye bath, air oxidized, cold rinsed,

soaped at boil, cold rinsed and air dried.

Optimization of mediator solution.-In order to make the indirect electrochemical

dyeing technique ecological and economical, the concentration of the mediator system

should be as low as possible. High concentrations of the chemicals in the dyebath bestow

more stable reduction conditions and prevent oxidation of the reduced dyestuff. However,

if we use the mediator solution towards its higher concentration end then there will be

eventual increase of the losses of the chemicals in the recycling loop and also carried

along the fabric at the end of dyeing operation. This makes the process uneconomical.

The indirect electrochemical dyeing was carried out with the selected dyestuffs at

different mediator solution concentrations in three sets of mediator systems as shown in

table I. In the group I, the ferric sulphate to TEA and ferric sulphate to sodium hydroxide

molar ratio was kept constant 1:11.48 and 1:14.3 respectively as followed in the reference

13. In the group II, the ferric sulphate to TEA molar ratio was kept constant at 1:11.48

while the ferric sulphate to sodium hydroxide molar ratio was varied. Whereas in group

III, the ferric sulphate to sodium hydroxide molar ratio was kept constant at 1:14.3 and

the ferric sulphate to TEA molar ratio was varied.

The mediator solution was prepared according to the procedure followed in

reference 14. The caustic soda was dissolved in a small amount of water in which TEA

was added. The ferric sulphate was separately dissolved in a small amount of water and

then added to the TEA/caustic soda mixture with continuous stirring with the magnetic

stirrer. After complete dissolution of the precipitated iron oxide, the solution was diluted

to the full volume. The solution was kept under constant magnetic stirring for 90 minutes.

Table I. Composition of the mediator solutions

Group I

Mediator Ferric pH Mediator solution composition

solution sulphate

index conc. g/l

1.1 10 14 10 g/l Fe2(SO4)3 + 48.811 g/l TEA +14.28 g/l NaOH

1.2 12 14 12 g/l Fe2(SO4)3 + 51.372 g/l TEA + 17.372 g/l NaOH

1.3 14 14 14 g/l Fe2(SO4)3 + 60 g/l TEA + 20 g/l NaOH



Group II


solution sulphate :

index NaOH

molar ratio

2.1 1:6.166 10. 12 g/l Fe2(SO4)3 + 51.372 g/l TEA + 7.411 g/l NaOH

5

2.2 1:7.5 12 12 g/l Fe2(SO4)3 + 51.372 g/l TEA + 9.0 g/l NaOH



2.5 1:12.5 14 12 g/l Fe2(SO4)3 + 51.372 g/l TEA + 15 g/l NaOH


2.7 1:16 14 12 g/l Fe2(SO4)3 + 51.372 g/l TEA + 19.2 g/l NaOH

Group III


soluion sulphate :

index TEA molar

ratio






Material to liquor ratio experiments.- As the electrolysis cell was not optimized with

regard to short liquor ratios, the experiments were carried out at a relatively long material

to liquor ratio i.e. 1:240. To see the effect of the various material to liquor ratios on the

colour dept developed on the fabric samples by indirect electrochemical dyeing,

experiments were also carried out with 1:120, 1:80 and 1:60 material to liquor ratios by

making appropriate modifications in the system.

Recycling of mediator solution experiments.- After the dyeing experiment, the

remaining dye and reduced mediator were oxidized by bubbling air though the solution to

form insoluble dye.

The oxidized dye particles can be segregated out through the vacuum filtration by

using G3 type of porcelain beaker. The clear filtered out mediator solution was recycled

further to carry out dyeing experiments.

Dyed samples evaluation.- The results of the dyeing experiments were characterized by

colour measurement in the form of K/S and CIELab coordinates with the help of

spectrophotometer X4000 (Jaypak) using D65 light source, 10O viewing angle.

The dyed samples were also evaluated for Wash fastness (SOURCES: IS 764;

1979), light fastness (SOURCE: IS 2454; 1985) and rubbing fastness (SOURCE: IS 766;

1988).

Results and discussions

Reduction potential of vat dyes.- The reduction potential of vat dyes gives idea about

the level of difficulty involved in their reduction. Higher the reduction potential of the

dye, higher is the reducing power required in the dyebath for its reduction. Thus, from the

reduction potential values, we can group the dyes under consideration in three groups viz.

easy to reduce, normal to reduce and difficult to reduce.

Table II. Reduction potential of selected vat dyes

Dye Reduction Dye Reduction Dye Reduction

Potential Potential Potential

(-mV) (-mV) (-mV)

Novatic 818 Novinone 880 Novinone 952

Yellow 5G Blue RSN Black BB

Novinone 841 Novinone 903 Novinone 953

Brown RRD Blue BO Brill. Violet

RR

Novinone 850 Novinone 935 Novinone 964

Green FFB Brown RR Black CH

While following the indirect electrochemical dyeing technique, three dyestuffs, Green

FFB as a easy to reduce dye, Blue RSN as a normal to reduce dye and Violet RR as a

hard to reduce dye were selected.

Dyeing results

The rate of potential development while potentiostatic electrolysis in the group I,

II and III dyeing experiments with Violet RR dye only are shown in fig. 2, 3 and 4

respectively. In each dyeing experiment, the dye was introduced in the cathodic chamber

as soon as the reduction potential of Violet RR was reached i.e. -953mV. The final

dyebath potential achieved at the end of dyeing in few cases was lower than that of

achieved during the course of dyeing, especially while dyeing with Green FFB and Blue

RSN.

1000

900

Solution Potential (-mV)
800

Mediator index: 1.1***
700
600

500
-50 0 50 100 150 200 250 300 350
Time (min)

Fig. 2. Dyebath potential development with varying ferric sulphate concentration (Group

I) electrolysis with Violet RR dye.

Mediator index:2.1***
1000 Mediator index:2.2***

800

700

600

500

0 50 100 150 200 250 300 350
Time (min)

Fig. 3. Dyebath potential development with varying sodium hydroxide concentration

(Group II) during electrolysis with Violet RR dye.

1000

900

800

700

500

-20 0 20 40 60 80 100 120 140 160
Time (min)

Fig. 4. Dyebath potential development with varying TEA concentration (Group III)

during electrolysis with Violet RR dye.

From the variation of the CIELab coordinates from the group I experiments as

shown in table III, it becomes clear that the colour depth and shade did not show strong

dependence on the iron salt concentration in the mediator solution. However the depth

appears to be good around 12 to 14 g/l ferric sulphate concentration. The potential

development rate appears to be increasing with increase in ferric sulphate concentration

as can be seen from figure II.

Table III. Comparison of colour yield and colour coordinates of conventional and

electrochemical dyeing

Mediator solution Final dyebath K/S L* a* b*
index potential (-
mV)

With dithionite * 15.462 35.44 -35.20 -0.98
6

1.1* 860 5.1460 55.37 -39.92 -2.67

1.2* 880 4.7258 53.39 -32.58 -6.24

1.3* 870 5.6865 52.95 -38.25 -3.72

1.4* 874 3.3465 58.97 -33.46 -4.71

1.5* 996 4.1874 57.42 -36.84 -3.27

With dithionite ** 9.1666 35.94 6.62 -38.03

1.1** 875 2.6641 52.92 -3.29 -27.93

1.2** 900 3.6045 48.44 0.58 -32.87

1.3** 890 2.2319 55.17 -2.25 -28.24

1.4** 905 2.5897 52.71 0.23 -31.25

1.5** 983 1.9702 56.10 -1.10 -27.58

With dithionite 15.73 23.10 16.93 -23.13
***

1.1*** 922 0.2810 77.92 10.16 -9.76

This kind of
symbols does not
indicate any thing.
Modify suitably all

1.2*** 996 3.0499 47.82 22.82 -28.25

1.3*** 994 3.2752 47.87 26.70 -30.07

1.4*** 979 2.4236 52.75 26.42 -27.63

1.5*** 1001 2.9228 49.78 26.78 -29.23

2.1*** 539 Dyeing not possible



2.4*** 987 2.0706 54.97 25.45 -26.87

2.5*** 993 2.2632 53.53 25.15 -26.66

2.6*** 1001 3.1007 48.72 26.54 -30.03

2.7*** 1001 4.4808 43.71 28.11 -30.84

3.1*** 1002 2.8823 49.71 26.59 -30.50

3.2*** 992 3.5124 47.04 27.51 -30.79

3.3*** 997 3.9246 45.32 27.49 -31.02

3.4*** 1001 3.0499 47.82 22.68 -28.25

3.5*** 995 3.1660 48.79 26.99 -28.83

Foot Note: * with Green FFB ** with Blue RSN *** with Violet RR
Initial dyebath potential before electrolysis in each case was around -350 mV.

In case of group II experiments, the solution potential could not be developed

above -953 mV while working up to pH 13. Therefore dyeing was not possible during

working with NaOH concentration below 11 g/l in the mediator solution. While

electrolysis with pH below 13, the complex was found to be unstable and caused

additional problems in the proper functioning of the electrochemical cell due to a

blackish material deposition in the form of a hard layer on the cathode. As can be seen

from the corresponding K/S values in table III, the colour depth appears to be increasing

with NaOH concentration above pH 13.

There has not been any effect of the TEA concentration variation in the mediator

solution in the given range of the group III experiments on the colour depth and shade.

Also the solution potential development rate found to be unaffected (fig.4). However at

44.75 g/l TEA, the iron complex became instable and ferric hydroxide was found to be

precipitating.

Influence of MLR on colour yield. - All the dyeing experiments for mediator solution

optimization were carried out at 1:240 material to liquor ratio. The depth of the dyed

samples was very low as compared to the conventionally dyed samples which were dyed

at 1:30 material to liquor ratio. In order to investigate the possibilities to improve the

colour depth, dyeing experiments were carried out with Blue RSN dye at 1:240, 1:120,

1:80 and 1:60 material to liquor ratio using 1.2 mediator index solution.

Table IV. Effect of ML Ratios on colour yield and CIELab coordinates

MLR Final dyebath K/S L* a* b*

potential (-mV)

1:240 900 3.6045 48.44 0.58 -32.87

1:120 958 2.9914 50.85 -0.72 -30.43

1:80 950 3.0879 50.49 -1.65 -29.25

1:60 965 4.0401 46.55 -1.01 -29.91

The K/S and CIELab coordinates of the dyeing experiments are given in table IV which

shows marginal improvement in colour depth of the dyed samples with shorter material

to liquor ratios.

Recycling of mediator solution.-Dyeing without effluent i.e. dyebath recycling seems

to be very attractive in today’s environment conscious era. In order to reuse to the

mediator solution with different dyes, the residual dye has to be removed from the dye

liquor. However, this is very straightforward especially in case of vat dyes which become

insoluble in the dyebath on oxidation. In the laboratory dyeing experiments, this can be

achieved with air bubbling through the dye bath. The insoluble oxidized dye particles

were removed by vacuum filtration with G3 porcelain filter.

The mediator solution used for the recycling experiments was composed of 12 g/l

Fe2(SO4)3 + 51.372 g/l TEA + 17.372 g/l NaOH (1.2 index mediator solution). Table V

shows the absorbance of the dyebath before oxidation and filtered out oxidized dye bath

at 620 nm. The difference in the absorbances shows a high degree of dye removal. The

filtered mediator solution was again used for the next dyeing experiment. However, there

was a loss of 4-5% of the mediator solution throughout the process which was required to

be replenished with fresh mediator solution which is also given in table V. Thus the

dyebath was recycled four times. Blue RSN dye was used during each dyeing

experiment.

Table V. Regeneration of mediator solution
Recycling Fresh Solution Absorbance
step Added
Before Oxidation & After
(ml)
filtration Filtration
Original 0 1.384 0.072
1 30 1.533 0.027
2 41 1.403 0.050
3 28 1.417 0.079

4 42

The CIElab coordinates of the dyed samples (table VI) for four recycling dyeing

experiments, carried out under the similar experimental conditions shows no effect on the

colour depth and shade. There was also no effect on the rate of development of the

solution potential since the curves in the fig. 5. Thus, reproducibility of the dyeing results

were confirmed along with the electrochemical regeneration of the reducing agent.

Table VI. Colour yield and CIELab coordinates for repeated dyeing with regenerated
mediator solution

Recycling Final dyebath K/S L* a* b*

step potential (-mV)

Original 995 2.4954 52.95 0.62 -31.06

1 965 2.3803 53.82 -0.97 -29.35

2 950 2.8766 51.25 -0.55 -30.31

3 958 2.6414 52.39 -0.39 -29.67

4 953 3.0783 50.65 -1.09 -30.50

1000

900

800

Mediator Index: 1.2**
700
Original
First Recycle
Second Recycle
600
Third Recycle
Fourth Recycle
500

0 20 40 60 80 100 120
Time (min)

Fig. 5. Effect of mediator recycling on the dyebath potential development

Fastness results.- The few selected dyed samples with indirect electrochemical dyeing

technique were tested for washing fastness, light fastness, wet and dry rubbing fastness.

The results are shown in table VII. All the fastness properties appear to be equivalent

with the conventionally dyed samples using sodium dithionite as a reducing agent.

Table VII. Comparison of fastness properties of electrochemical and conventional

dyeing

Reduction/Mediator Washing Light Rubbing fastness

system fastness fastness Wet Dry

With dithionite * 4-5 5 4 5

With dithionite ** 4-5 5 4 5

With dithionite *** 4-5 5 4 4-5

12 g/l Fe2(SO4)3 +
51.372 g/l TEA +
4-5 4-5 4-5 5
17.372 g/l NaOH (MLR
1:240) *

12 g/l Fe2(SO4)3 +
51.372 g/l TEA +
4 4-5 4 4-5
1:240) **

12 g/l Fe2(SO4)3 +
51.372 g/l TEA +
4-5 5 4 4-5
1:240) ***

12 g/l Fe2(SO4)3 +
51.372 g/l TEA +
4 4-5 4-5 5
1:60)**

12 g/l Fe2(SO4)3 +

51.372 g/l TEA + 19.2 4 4-5 4-5 5
g/l NaOH ***

* with Green FFB ** with Blue RSN *** with Violet RR

Conclusions

Potentiostatic experiments revealed that iron-TEA complexes show a sufficiently

negative redox potential in alkaline solution which is sufficient for indirect

electrochemical reduction of vat dyes. The continuous regeneration of the reducing agent

is possible by cathodic reduction. However, colour depth appears to be poor with the

implemented electrochemical system as compared to the conventional vatting technique

using sodium dithionite as a reducing agent. Better results may be possible with

sophisticated electrochemical systems and optimization of the mediator system.

Experiments with shorter material to liquor ratios have shown better colour depths.

Fastness properties appear to be equivalent with the conventional dyeing technique with

good light, washing and rubbing fastnesses.

Iron-TEA complex regenerable reducing system allows reuse of the dyebath

chemicals after replenishing it with the lost amount of chemicals during the oxidation and

filtration stage of indirect electrochemical dyeing. Thus the system offers enormous

ecological advantages. Recycling experiments also shows the capability of reproducing

the same depth and shade while working with the same dye.

1. design of suitable electrochemical cell for electrochemical dyeing of cotton

with dyes on laboratory scale is suggested.

2. molar concentrations of mediator system were optimized for development of

reduction potential suitable for reduction of vat dyes

3. It was possible to get the electrochemical dyeing of cotton with selected vat

dyes under optimized conditions. However the depth of dyeing is much

weaker compared to conventional dyeing with sodium dithionate as reducing

agent.

4. It was possible to regenerate the mediator system and its repeated use for

dyeing.

5. Further work is essential to improve the dye uptake and establish the

economic and environment benefits of the electrochemical dyeing system.

Acknowledgements

We are obliged to Prof. A. K. Shukla, Director, Central Electrochemical Research

Institute for providing their laboratory facilities to carry out this research work.

REFERENCES

1. D. Phillips, JSDC, 12, 183 (1996).

2. Albert Roessler & Xiunan Jin, Dyes and pigments, 59, 223 (2003).

3. JR. Aspland, Textile Chem Coor, 22, 24 (1992).

4. Jose Cegarra, Publio Puente, Jose valldeperas, ‘The dyeing of textile Material’,

Texilia, Italy, 355 (1992).

5. E.Marte, Textile Praxis Int, 44, 7, 737 (1989).

6. U. Baimgartev, Rev Prog Coloration, 17, 29 (1987).

7. B. Somet, Melliand Textilberichte, Vol. 76 (1995), p161

8. R. B. Chavan and J. N. Chakraborty, J.N. Chakraborty PhD thesis, Indian

Institute of Technology, 2002

9. Dr. Wolfgang Schrott, ITB International textile Bulletin, May (2000).

10. T. Bechtold, US patent No. US5244549, 1993-09-14

11. T. Betchtold, E. Burtscher, G Kuhnel & Bobleter, JSDC, 113, 135, (April 1997).

12. Thomas Bechtold, Eduard Burtscher, Angelika Amann & Ortwin Bobleter, J.

Chem. Soc. Farady Trans., 89, 2451 (1993).

13. T. Bechtold, et al., JSDC, 110, 14 (January 1994).

14. T. Bechtold, et al., JSDC, Vol. 110, January (1994), p14-19

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