Bleaching of indigo-dyed denim fabric

Coloration
by electrochemical formation of
Technology
hypohalogenites in situ
Thomas Bechtold,a Peter Maierb and Wolfgang Schrottc
aInstitutefor Textile Chemistry and Textile Physics of the University of Innsbruck,
Hoechsterstrasse 73, A-6850 Dornbirn, Austria
Email: textilchemie@uibk.ac.at
bLilienweiss GmbH Textile Services, D-73639 Remshalden, Germany
Society of Dyers and Colourists
cDyStar Textilfarben GmbH, D-65926 Frankfurt am Main, Germany
Received: 27 September 2004; Accepted: 7 December 2004

The use of hypochlorite, formed in situ by anodic oxidation of sodium chloride solution, for bleaching
indigo-dyed denim has been studied at room temperature and at 50 °C. A direct relationship between
the charge fl ow applied and the bleaching effect was observed. This enables consistent oxidative
bleaching to be achieved by controlling the electrochemical process. The use of mixed anolytes
containing small concentrations of bromide ions enhanced the bleaching effect considerably, even after
lowering the temperature to room temperature. The molar concentration of bromide ions required was
much lower than that of chloride in the anolyte.

Introduction
The production of indigo-dyed textiles for denim jeans
occupies a virtually unique position in the worldwide
textile market. Annual production is of the order of five
billion square metres of fabric, for which the indigo
dyestuff requirement is estimated at 30 000 tonnes.
An important step in the processing of indigo-dyed
textiles is the finishing of the garment to obtain the
required visual effect. The removal or destruction of a
proportion of the indigo on the ring-dyed yarn requires a
combination of mechanical agitation and chemical attack,
either to oxidise or reduce the dyestuff. Table 1 gives a
summary of suitable bleach chemicals for this purpose
[1]. It can be seen that the majority of these chemicals are
oxidising agents, and that sodium hypochlorite accounts
for over 85% of the total. Hypochlorite offers a range of
bleach effects, and it is easy to use and is inexpensive.
Reproducibility of the bleaching process may, however,
be affected by its lack of stability on storage, particularly
under warm conditions. There are also safety issues in the
handling of hypochlorite.
Processes for the electrochemical formation of bleach
chemicals have been reported in the literature for the
delignification of wood pulp and for bleaching textiles [1–11].
The use of electrochemical processes for in situ production
of oxidants, such as hypochlorite, is also an interesting
possibility for bleaching denim, since it allows improved
process control and consistency. In addition, process costs
would be lower due to reduced handling with the production
of more regular shades, along with the fact that the used
bleaching bath could be regenerated, reducing the quantity
of effluent generated [12].
The in situ preparation of sodium hypochlorite has been
described in the literature [1,6–12]. The efficiency of the
electrolysis and bleaching processes has been described as
low [13], but the addition of bromine-containing oxidising
agents, such as bromate and hypobromite, is reported to
assist the bleaching of indigo significantly [14–16].

Table 1 Processes and chemicals used in denim wash-down processes

Chemical Formula Form of application Reaction Market share (%)

Hypochlorite NaOCl Solution (10–15% w/w) Oxidative > 85

Persulphate K2/Na2S2O8 Salt/powder Oxidative <5
Permanganate K/NaMnO4 Solution Oxidative <2
Enzymes Oxidoreductases Granules Oxidative <2
Ozone O3 Gaseous or in solution Oxidative No relevance
Peroxo compounds –O–O– Commercial products/salt Oxidative No relevance
Glucose C6H12O6 Powder/solution Reductive <5
Sulphinic acids R–S(O)OH Salt/solution Reductive <1

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 Only a limited amount of information has been
published about the application of hypohalogenite formed
in situ to textile bleaching. In the present study the cathodic
oxidation of chloride to hypochlorite for the bleaching of
denim fabric has been investigated on a laboratory scale.
Particular attention has been given to the improvement
in bleaching efficiency resulting from small additions of
bromide ion.
Experimental
Materials
Sodium ca rbonate (Na 2 CO 3 ), sodium bica rbonate
(NaH 2CO3), sodium chloride (NaCl) and sodium hypo-
chlorite (NaOCl) solution were obtained in technical grade
from Salinen (Austria) and Solvay (Germany). Analytical
grade potassium bromide (KBr) was supplied by Merck.
Desized indigo-dyed denim fabric (warp, dyed with
indigo; weft, raw cotton yarn) was used for the bleach
experiments and supplied by DyStar (Germany).
Bleaching
Laboratory bleaching
In the laboratory bleach experiments, samples (5 g) were
treated for 20 min with sodium hypochlorite (5 and 20
ml/l) and potassium bromide (0.0, 0.1, 1.0 and 2.35 g/l) at
a liquor-to-goods ratio of 50:1 and at various pH (7.0–11.3)
and temperature (23 and 50 °C). The samples were then
dechlorinated for 10 min at 50 °C using a solution of 2 ml/l
hydrogen peroxide (35% w/w) and rinsed with cold water.
The pH was adjusted using sodium carbonate and sodium
dihydrogen phosphate.
Electrochemical bleaching
For electrochemical bleaching, a divided cell with a Nafion
stainless steel cation exchange membrane (100 cm2) was
used (Haver und Boecker, Germany). This had a catholyte
volume of 350 ml. The anode was a Pt-mixed oxide-coated
titanium electrode (area, 60 cm2; anolyte volume, 800–
1500 ml; anolyte flow, 150 ml/min) and was obtained from
De Nora (Germany). The total cell current (I) was 0–500
mA and the anodic current density was 0–8.3 mA/cm2.
Alternatively, diamond electrodes could have been used
[17]. A schematic representation of the electrolyser is given
in Figure 1.
Catholyte and anolyte solutions of similar composition
were used. The potential of the anolyte was measured with
a Pt-electrode vs Ag/AgCl (3 M KCl) reference electrode.
The bleaching bath, containing sodium chloride (0.171
mol/l) and potassium bromide (0 or 8.4 × 10 –4 mol/l), was
circulated through the reaction vessel containing the fabric
samples (10 g) using a tube pump. Catholyte flow was
adjusted to 150 ml/min and the system had a liquor-to-
goods ratio (volume of anolyte to mass of fabric) in the
range 70:1 to 80:1. During electrolysis the pH of the anolyte
was maintained in the range 7.1–10.6 by addition of small
quantities of sodium hydroxide (5% w/w) solution. Once
the chosen redox potential (P L) had been achieved after ca.
18 min, bleaching was continued and samples were taken
after a further 10 and 30 min at different charge flow (Q).
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20050202_j115-04.indd 2
A
H
C
G
B
E F
D
A Power supply E Anolyte
B Anode F Membrane
C Cathode G Denim fabric
D Catholyte H Redox measurement
Figure 1 Schematic representation of the electrochemical
apparatus used
After bleaching, the fabric specimens were rinsed with
water and dried. The current efficiency of the electrolyser
could not be determined during the bleaching experiments
due to the presence of oxidisable matter (denim fabric)
in the anolyte, as this progressively decreased the
concentration of oxidant formed.
CIELAB colour space
The bleaching of denim (i.e. the oxidation of indigo) was
monitored measuring the CIELAB colorimetric coordinates
(L*a*b*). These were determined using a tristimulus
colorimeter (Minolta Chroma Meter CR 210). In the case
of electrochemical bleaching, readings were taken at three
different locations. Average values and standard deviations
were calculated.
Results and Discussion
Catalytic effect of bromide
To characterise the bleaching process and to demonstrate
the effect of bromide addition, a series of bleach
experiments was conducted using NaOCl and NaOCl/
KBr mixtures. The results are shown in Table 2 and the
catalytic effect of bromide ions is clear, with intensive
bleach effects observed [increase in the lightness value
(L) due to oxidation of the indigo dye]. Even at room
temperature (23 °C) and with ca. pH 7, the bleaching effect
was enhanced (experiments 13–17).
The data in Table 2 indicate that the main parameters
– concentration of bleach reagent, concentration of bromide
ion, bath temperature and pH of the bath – each had an
impact on the bleaching effect to differing extents. These
results formed the basis for choosing the conditions
which were then used in the electrochemical bleach
experiments.
© Color. Technol., 121 (2005) 65
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 Table 2 Colorimetric coordinates (Lab) of the denim samplesa treated in the laboratory bleach experiments

Expt. KBr (g/l) NaOCl (ml/l) pH Temp. (°C) L a b

1 0.0 5 9.8–9.6 50 23.09 +1.68 –13.52

2 0.0 20 10.7–10.4 50 25.08 +1.53 –15.91
3 0.1 5 10.0–10.6 50 28.14 –0.32 –13.70
4 2.35 5 10.3–10.1 50 27.39 –0.28 –13.62
5 0.1 20 10.8–10.5 50 35.44 –1.43 –15.16
6 0.1 20 10.9–10.4 50 34.69 –1.50 –15.64
7 1.0 20 10.8–10.4 50 63.26 –5.92 +2.51
8 2.35 20 10.8–10.4 50 62.43 –6.15 +2.24
9 0.0 5 10.5–10.4 23 22.21 +1.44 –12.24
10 0.0 5 10.1–10.0 23 21.85 +1.51 –12.21
11 0.0 20 11.3–11.1 23 22.46 +1.71 –13.39
12 0.0 20 11.3–11.1 23 22.50 +1.60 –13.33
13 0.1 5 10.5–10.4 23 22.92 +1.36 –12.92
14 1.0 5 10.4–10.3 23 25.28 +0.26 –13.05
15 1.0 20 7.5–7.3 23 41.02 –6.71 –6.01
16 1.0 20 7.0–7.0 23 42.83 –7.00 –5.96
17 1.0 20 6.0–6.0 23 40.46 –6.42 –2.79

a Untreated sample: L 20.84, a +1.70, b –11.03

Electrochemical oxidation anolyte was then controlled by cell current within a defined
The bleaching effect of the in situ generation of sodium range of P L. Samples were taken after bleaching for 10 and
hypochlorite was studied at room temperature and at 50 30 min, and values are given in Table 3. The oxidation of
°C. The initial pH was adjusted by the addition of sodium indigo to yellow or colourless materials, such as isatin (2,3-
bicarbonate. The reaction involved in the bleaching process indolinedione) and anthranilic acid [18,19], was monitored
can be represented by Eqns 1 and 2. by determining the CIELAB coordinates and the results are
given in Table 3.
In compliance with the normal bleaching practice, the
Cl + H2O OCl + 2H + 2e (Anode reaction) (1)
temperature was adjusted to 50 °C. Depending on the pH
of the bleaching bath, P L varied between +500 mV at pH 10
OCl + indigo Cl + 2,3-indoline dione (Bleach process) (2) (50 °C) and +750 mV at pH 7 (23 °C). For experiment E1 (50
°C) at cell currents of 100, 300 and 500 mV, the cell voltage
(UZ) was 2.5, 3.5 and 4.2 V, respectively. In experiments
Figure 2 shows the key experimental data as a function E7–E9 (23 °C) at cell currents 100, 200 and 500 mV, UZ was
of time for a representative electrochemical bleaching 2.9, 3.4 and 4.9 V.
experiment. The cost of bromine-containing oxidants such as
In the fi rst phase of the experiment, the redox potential sodium bromate (NaBrO3) places a limit on their use as
was raised to the selected level by application of maximum primary bleaching agents for denim. On the other hand
cell current (500 mA). The redox potential (P L) in the this drawback might be avoided if catalytic amounts of
hypobromite could be generated in the bleaching bath.
To study the practicability of using hypobromite, this
800 was generated in the anolyte by the reaction of bromide ions
with anodically-formed hypochlorite. A set of electrolytic
50 experiments was performed by adding a low concentration
600 of potassium bromide (KBr) to the anolyte containing
I, mA

Cell current (mA) 40

Redox potential (mV) sodium chloride (experiments E4–E9). Due to the lower
T, °C

Temperature (°C) redox potential of the hypobromite, anodically-formed

400 Cell voltage (V) 30 hypochlorite continuously regenerates hypobromite, which
PL, mV

then reacts with the indigo more rapidly than hypochlorite.

20
In the literature the redox potential of OBr – /Br – at alkaline
Uz, V

200
pH is quoted as 0.766 V (vs standard hydrogen electrode)
10
and the corresponding value for OCl– /Cl– is 0.890 V (vs ref)
[20]. In acid solution the Br2/Br– couple produces a potential
0 0
0 10 20 30 40 50 of 1.065 V, compared with 1.358 V for the Cl2/Cl– couple.
Sample 1 Sample 2 Due to the higher reaction rate of hypobromite and
t, min indigo, the addition of bromide ions results in a significant
improvement in the bleaching effect. This is confi rmed
Figure 2 Relevant experimental parameters (cell current, I;
redox potential in the anolyte, P L; temperature, T; cell voltage, by the higher L values of the bleached samples. Even
UZ) for experiment E4 as function of electrolysis time at room temperature, a much higher proportion of the

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 Table 3 Redox potential (P L), charge flow (Q) and colorimetric coordinates (Lab) a of the denim samplesb treated in the electrochemical
bleach experiments

KBr NaCl NaHCO3 Na2CO3 Temp. PL Q

Expt. (mol/l) (mol/l) (mol/l) (mol/l) (°C) pH (mV) (A min) L a b

E1 0.171 0.0 0.0094 50 10.1–10.5 440–475 6.5 26.20 (±0.22) +0.90 (±0.03) –13.95 (±0.09)
13.1 27.60 (±0.41) +0.72 (±0.09) –13.80 (±0.16)
E2 0.171 0.0059 0.0047 50 7.8–8.5 670–780 7.7 26.65 (±0.24) +0.94 (±0.07) –13.97 (±0.16)
16.3 27.73 (±0.23) +0.88 (±0.12) –14.30 (±0.08)
E3 0.171 0.0012 0.0094 50 10.4–10.6 460–550 5.62 26.64 (±0.17) +0.72 (±0.01) –14.18 (±0.21)
9.17 26.70 (±0.48) +0.67 (±0.04) –14.22 (±0.16)
E4 0.00084 0.171 0.0059 0.0047 50 8.0–8.6 700–760 5.2 48.53 (±0.31) –5.72 (±0.07) –2.52 (±0.05)
10.6 54.01 (±0.55) –6.00 (±0.05) +0.47 (±0.16)
E5 0.00084 0.171 0.0059 0.0047 23 8.9–9.5 710–745 2.45 27.60 (±0.58) +0.51 (±0.14) –14.77 (±0.22)
3.15 29.78 (±1.21) –0.45 (±0.53) –14.99 (±0.43)
E6 0.00084 0.171 0.0119 23 7.5–7.7 710–815 1.89 28.96 (±0.92) +0.11 (±0.16) –15.25 (±0.12)
2.05 29.19 (±2.03) +0.02 (±0.44) –15.02 (±0.29)
E7 0.00084 0.171 0.0119 23 7.1–7.7 600–640 10.0 41.32 (±0.20) –4.72 (±0.06) –6.13 (±0.32)
20.0 46.82 (±0.25) –5.52 (±0.07) –2.34 (±0.52)
E8 0.00084 0.171 0.0119 23 8.0–8.5 730–780 1.74 26.01 (±0.02) +1.08 (±0.08) –13.44 (±0.15)
2.98 25.71 (±0.66) +0.49 (±0.20) –13.19 (±0.25)
E9 0.00084 0.171 0.0119 23 7.8–8.3 760–825 6.5 35.27 (±1.64) –2.97 (±0.53) –11.56 (±0.76)
16.5 43.26 (±1.19) –5.65 (±0.26) –3.94 (±0.81)

a Values in parentheses = standard deviation from the mean

b Untreated sample: L 24.02 (0.24), a +1.09 (0.12), b –13.24 (0.17)

indigo was oxidised than at 50 °C in the absence of Br –.
If the temperature was increased to 50 °C, the presence of
Br– improved the bleaching effect still further.
In case of hypochlorite bleaching, L values of samples
increased after 30 min from ca. 24 to 26–27 at 50 °C, whereas
the addition of potassium bromide gave final L values in the
range 30–54 at room temperature (23 °C) (Table 3).
The increase in bleach activity caused by the presence of
potassium bromide also gave rise to a difference in the shade
of the bleached material. It can be seen from the CIELAB
coordinates that the colour of the bleached denim tended
towards a more yellow or greenish hue when bromide was
present. The bleaching formulation must therefore make
allowance for the final shade required.
The reactions occurring can be summarised in Eqns 3,
4 and 5.
Cl + H2O OCl + 2H + 2e (Anode reaction)
OCl + Br Cl + OBr (Homog. reaction)
OCl + indigo Br + isatin (Heterog. bleach)
The concentration of bromide in the anolyte is too low for
it to make a significant contribution to the anodic current.
The current density of the anodic process is determined
by the concentration of chloride ion, and the addition of
bromide merely intensifies its effect. The acceleration in
the decolorisation of indigo by hypobromite occurs despite
the fact that the molar concentration of bromide ions in the
electrolyte (8.4 × 10 –4 mol/l) is less than 0.5% of the molar
concentration of chloride ions (0.171 mol/l).
The current efficiency of the anodic process is defi ned
by the heterogeneous charge transfer reaction between the
anode and chloride ions (Eqn 3). However, the formation
of the more active hypobromite subsequently takes place
in solution (Eqn 4). Due to the homogeneous conditions,
catalytic concentrations of bromide are sufficient for
amplifying the bleaching effect, and the Br – /OBr – system
is continuously regenerated according to Eqns 4 and 5.
Influence of charge flow
Experiments without the addition of bromide (E1–E3 in
Table 3) conducted at 50 °C and pH between ca. 8.0 and
10.5 showed similar L values even at various charge flow
(Q). Despite changes in pH and charge, the bleaching
effect remained limited. In practice the low reactivity of
hypochlorite is normally compensated for by increasing
its concentration, for example it is usual to add up to 35
ml/l of commercial 2 M sodium hypochlorite solution to
the bleaching bath.
The results of this study show that when as little as 8.4
(3) × 10 –4 mol/l potassium bromide was added, a significant
acceleration in the bleaching process was produced. As a
(4) result, a direct relationship between charge flow and bleach
effect could be observed. Higher temperatures intensified
the bleaching effect, as can be seen if the results of E4
(5)
and E5 are compared. Experiments E5–E9 confi rmed that
higher concentrations of bleach chemicals gave greater
destruction of dyestuff, even at room temperature. The L
value (54.01) in experiment E4 is higher than that in E7
(46.82) despite the fact that in the latter almost double
the amount of oxidant was produced in the bath in the
presence of bromide (20.0 compared to 10.6 A min in E4).
In Figure 3 the bleaching effect (L value) is shown as a
function of charge flow. At similar concentration, pH and
temperature, the experimental results for the bleaching
process followed a similar curve, indicating a direct
relationship between applied charge flow and bleaching
effect.

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50
40
L-value
OCl–, 50 °C (E1–E3)
Br –, 50 °C (E4)
Br –, RT (E5–E9)
30
0 temperature was lowered from 50 °C to room temperature.
0 4 8 12 16 20
Q, A min
Figure 3 Bleach effect (given by L values) as function of charge
flow (Q)
Energy consumption
An important advantage of the electrochemical process
is revealed by comparing the applied charge flow with
the conventional use of bleaches giving an equivalent
result. From the results given in Table 3, a charge flow
of ca. 5–20 A min was sufficient to bleach 10 g denim
fabric. At a cell voltage of 5 V this corresponded to an
energy consumption of 0.083–0.17 kWh/kg of bleached
denim. Assuming a theoretical current yield of 100%,
the equivalent consumption of 2 M sodium hypochlorite
amounts to 80–320 ml (or at 50%, 40–160 ml).
In a commercial washing machine, a liquor-to-goods
ratio of 5:1 to 10:1 is usual and a concentration of 10–
30 ml/l 2 M sodium hypochlorite is used for bleaching.
Each kilogram of denim thus requires ca. 50–300 ml of
2 M sodium hypochlorite solution. Even under the non-
optimised conditions in the laboratory experiments, the
consumption of the electrochemically formed bleach was
comparable to that in conventional bleaching, indicating
potential for future optimisation.
Conclusions
It has been shown possible to replace the use of sodium
hypochlorite solution by the electrochemical formation of
hypochlorite in situ for the bleaching of indigo-dyed denim.
The formation of hypohalogenites by anodic oxidation
of halogenides has considerable potential. It avoids the
reduction in active chlorine content in hypochlorite
solutions during storage as well as safety issues associated
68 © Color. Technol., 121 (2005)
20050202_j115-04.indd 5
with storage and handling. It also offers better process
control and reproducibility, and in consequence lower
processing costs.
The bleach effect on indigo-dyed material can be
adjusted by the concentration of oxidant formed in the
cell. According to Faraday's law, measurement of cell
current and time permits formation of a defined amount by
adjustment of a certain transported charge.
The addition of small quantities of bromide ions to the
hypochlorite bleaching bath gave a significant acceleration
in the bleaching process. This was true even if the
The addition of bromide was found to affect the shade of
the bleached goods and this must be taken into account
when selecting bleaching formulations and conditions.
Acknowledgements
The authors wish to thank DyStar Textilfarben GmbH,
Frankfurt, and Lilienweiss GmbH for their help in
supplying materials and providing technical assistance.
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