Electrochemical dyeing of cellulosics: A novel method

A novel electrochemical dyeing process results in product savings, less chemicals with special safety requirements,
and unsurpassed environmental compatibility. Besides, the new process also facilitates dye bath monitoring in real
time, ensuring high quality of the dyed fabric, affirm Dipankar Das, K N
Chatterjee and Sunil Arora.

Indigo, vat dyes and sulphur dyes are an important class of dyestuffs for dyeing
cellulosic fibres [1]. These dyes are applied to different varieties of products but the
application procedure contains a common reduction step with strong reducing agents
to attain the reduced form of dyestuff. According to the dyeing procedure and nature
of dye, different reducing agents are used. These chemicals produce toxic nature by-
products, which are acidic in nature, necessitating overdosing with NaOH of a
quantity over the stoichiometric requirement. Nearly three times more NaOH and
thionite than the theoretical requirements are applied for efficient dyeing [2-3].

Moreover, only a portion of these agents is used in dye reduction and the excess chemicals find their way into the
waste water. By-products formed in the decomposition of hydrosulfite are suphur compounds (eg, Na2S, NaHS, etc),
which pollute the atmosphere through the formation of H2S. At the same time, salts of sulphur in form of sulfates
and sulfites (Na2SO3, NaHSO4, Na2SO4, Na2S2O3, etc.) contaminate sewage, lowering its pH and causing the
concrete pipes, which carry the sewage to become corroded. To overcome these problems attempts have been made
by several researchers to develop alternative eco-friendly reducing systems.

This article deals with the important characteristics of electrolysis stage in vat and
sulphur dyeing. For cathodic dye reduction, soluble reducing systems are applied,
which can undergo cathodic reduction and thus are electrochemically regenerated.
Electrochemical dyeing process results in product saving, less chemicals with
special safety requirements, unsurpassed environmental compatibility and better
fastness properties. Electrochemical dyeing experiments have established good
reproducibility and almost same/similar results as that of conventional chemical
reduction [4,5,6].

Advantages of electrochemical dyeing process

Economy

The entire textile industry gets affected because savings in the chemical costs as chemical wastes are reduced by
80% and reduction of waste water recycling cost at the same time water savings around 85%, electrode material for
cathode and anode is cheap and simply constructed cell and easy maintenance, so economical process [7,8,9].

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 on aquatic life. Low concentration
of chemicals and non-toxic chemicals. Economic technique for recycling of chemicals and water used for
washing [6,7,8,9].

Dyeing process
Fully controlled dyeing parameters, maximum process reliability through control of reducing potential as needed
ranging from 0 to 1,200 mV just by varying the current, dye reduction rate is very good (10 mg dye/min) and dye
pick up may go up to 85 - 90%. 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. Minimum side reactions, eg,
dyestuff destruction due to formation of radicals [10,11,12].

Quality of products

Better overall fastness property compared with the technique already in use, reproducible process condition and
dyeing results was observed, so better quality product [13, 14].

Electrochemical dyeing:

Condition required for different dyes:

Sufficient ve reduction potential [12]

450 mV to - 700 mV (for Sulphur and sulphur vat dyes)

700 mV to - 800 mV (for Indigo dye)
750 mV to - 1000 mV (for all Vat dye)

Stable reduction condition in the dye bath [14].

The technique relates to a process for electrochemical reduction of reducible dyes.

Electrochemical reduction of organic compounds in the presence of a cathode
comprising a support of an electrically conductive material and an electrically
conductive, cathodically polarized layer formed there on formed in-situ. Useful
metals include preferably all classic hydrogenation metals, especially the metals of
the Ist, IInd and VIIIth transition group of the Periodic Table. Elements, especially
Co, Ni, Fe, Ru, Rh, Re, Pd, Pt, Os, Ir, Ag, Cu, Zn, Pb and Cd, Ni, Co, Ag, Fe and Cu
are preferably. There are two methods by means of which electrochemical dyeing
can be carried out, direct electrochemical dyeing and indirect electrochemical
dyeing [8, 15,16].

Direct electrochemical dyeing:

In case of direct electrochemical dyeing technique, organic dyestuff has been directly reduced by contact between
dye and electrode. In order to start the process, an initial amount of the leuco dye has to be generated by a
conventional reaction, ie, by adding a small amount of a soluble reducing agent. Once the reaction has set in, it is not
needed anymore and further process is self sustaining. In such a system, a dyestuff particle must come into contact
with the electrode surface in order to get reduced [10, 17,18,19].

Indirect electrochemical dyeing

In this system, the dye reduction does not take place due to direct contact of dyestuff with the cathode, like in direct
electrochemical reduction. The dye is not directly reduced at the electrode rather, a reducing agent is added that
reduces the dye in the conventional manner, which in turn gets oxidized after dye reduction. The oxidized reducing
agent is subsequently reduced at the cathode surface, which is then further available for dye reduction. This cycle is
continuously repeated during the dyeing operation. The agent, which undergoes reduction and oxidation cycles, is
known as a mediator [20,21].

A suitable redox catalyst for indirect electrochemical dyestuff reduction has to fulfill various requirements [7, 22]
1) Rapid conversion at the electrode surface.
2) No affinity for the fibre material.
3) No reaction with solvent.
4) No catalysis of side reactions (change in colour).
5) Adequate solubility.
6) Non toxic.
7) No problems in effluent.
8) Inexpensive.
9) Only a small loss, if any, in activity during the useful life; therefore the maximum possible number of reaction
cycle.

Dyeing procedure

The electrolysis is carried out under galvanostatic condition by maintaining the constant current. The pretreated
fabric sample is introduced into the dye bath. The dyeing is carried out by exhaustion method for 30 minutes with
constant stirring. Both electrolysis and electrochemical dyeing are carried out at 300 2 K. 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 [18, 23,24].

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 [19,27].

Table 1: electrochemical dyeing process by using different ML

Exp. Concentration of Dye( %age MLR K/S L* a* b*

No. mg) shade value
1. 100 0.8 1:80 2.27 34.13 - 1.87
43.10
2. 100 0.8 1:60 2.42 32.24 - 1.64
41.54
3. 100 0.8 1:30 2.65 30.15 - 1.75
40.25
4. 200 1.6 1:80 3.80 23.72 - 0.43
28.56
5. 300 2.5 1:80 6.39 19.52 - -
16.95 0.44
6. 400 3.3 1:80 6.91 18.70 - -
16.45 0.64
7. 500 4.2 1:80 6.42 19.15 - 0.77
17.78

Effect of electrode material

Both the conversion efficiency and the current efficiency values obtained for the electro-generation of Fe(II)-
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 [19, 21].

Table 2: electrochemical dyeing process by using different electrode

Experiment No. Anode Material Cathode Material Conversion Efficiency (%) Current Efficiency (%)
1. Platinum Copper Plate 67.74 47.15
2. Stainless Steel Copper Plate 73.23 56.23
3. Stainless Steel Copper Wounded 68.75 56.27
4. Stainless Steel Stainless Steel 46.76 34.41
5. Stainless Steel Mild steel 20.00 20.69
6. Stainless Steel Copper plate 33.33 25.85

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 [15,19,29].

Table 3: electrochemical dyeing process by using different electrolyte

Exp. Concentration of Conversion Current K/S value

No. mediator composition Efficiency (%) Efficiency (%)

-1
Fe2(SO4)3 (mol L ) Oxalic acid Ca-gluconate

(mol L-1) (mol L-1)

1 0.015 0.100 0.050 61.05 35.46 2.08
2 0.020 0.100 0.050 73.23 56.23 2.27
3 0.025 0.100 0.050 58.07 46.22 1.35
4 0.075 0.100 0.050 55.50 30.66 1.13
5 0.020 0.0 0.050 30.54 26.74 1.52
6 0.020 0.025 0.050 47.31 29.06 1.57
7 0.020 0.075 0.050 50.25 37.66 2.05
8 0.020 0.150 0.050 54.70 34.38 2.02
9 0.020 0.100 0.005 38.10 13.71 1.37
10 0.020 0.100 0.025 46.66 24.55 1.49
11 0.020 0.100 0.075 58.55 37.99 1.47

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 gets precipitated 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-oxalate-gluconate system could be
raised beyond 13 [19, 32,33,34].

Effect of the current intensity

More dye reduction can be achived at a faster rate by utilising 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 [30,31].

Effect of pH

The reaction rate is enhanced with increasing pH. This effect is mainly based on higher radical concentration,
because it has been observed that the equilibrium between radical, indigo and luceo indigo is shifted to radical side
higher pH. The non-ionic forms of indigo are poorly water-soluble substances [4,5,14].

Additional benefits of 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 is air oxidized and filtered to remove the insoluble dye molecule (10 - 15% 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 [18,19,20,21].

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. Dyebath pH is more stable in the electrochemical process than in the conventional one. Hence, there is
no need for the addition of alkali during electrolyses [14, 28, 35].

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 Equation:

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 [34,35].

An estimation of water and chemical saving in dyeing cotton with Vat dye is made and the results are given in the
table. It was found discharge in this technique was approximately 15% of the liquor volume [36].

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 [15,21,27].

Electrochemical dyeing parameters

Determination of conversion efficiency and current efficiency

Conversion efficiency was calculated using initial and final concentration of Fe(III) ion, which is determined by
iodometric titration.

The current efficiency (f) was calculated using the following equation [34,37] (Equation 1):

(1)

Where, Z is the number of electrons involved the reaction, F is Faraday constant (C mol-1), V R is the volume of
solution (L), C is the concentration of molecule (g L-1), M is molecular weight (g mol -1), I is cell current (A), and t
is time (s).

Calculation of critical thickness of cathodes in a multi-cathode electrolyser

The cathode stack is built up as combination of isolated three-dimensional cathode units supplied by individual
current sources, connected to a common counter electrode (anode). In the three-dimensional cathode nearest to the
anode, an ohmic drop of considerable magnitude is caused by the current flow in the electrolyte due to charge
transport from other cathodes to the rear of first cathode. This potential difference in the electrolyte limits thickness
of electrodes to avoid bipolar reaction [30,34].

Reduction capacity of the mediators systems

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 [10,23].

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 (8.314 J/Kmol)

F = Faraday constant (96,500C)

T = Temperature (K)

n = Electrochemical valiancy

Cox = Concentration of the oxidized form of redox pair (mol/l)

Cred = Concentration of the reduced form of the redox pair (mol/l)

Conclusion

The results obtained convey the conclusion that reducing agents required in the dyeing process for vat and sulphur
dyes cannot be recycled, and lead to problematic waste products. Therefore, modern economical and ecological
requirements are not fulfilled. The industrial feasibility of the direct electrochemical reduction of indigo as a novel
method has been determined. The final results are similar to those obtained in dyeing with chemical reducing agents.
Improvements in control of the dyeing process can be anticipated, as well as environmental benefits and saving in
process chemical. This is a promising field, which needs to be explored extensively.

References

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Note: For detailed version of this article please refer the print version of The Indian Textile Journal January
2012 issue.

Dipankar Das
Department of Textile Chemistry,
The Technological Institute of Textile & Sciences,
Bhiwani, Haryana 127 021.

K N Chatterjee
Department of Textile Chemistry,
The Technological Institute of Textile & Sciences,
Bhiwani, Haryana 127 021.
 Sunil Arora
Department of Textile Chemistry,
The Technological Institute of Textile & Sciences,
Bhiwani, Haryana 127 021.
published January , 2012

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