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Study of Parameters Affecting Dry and Wet Ozone Bleaching of Denim Fabric

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DOI: 10.1080/01919512.2015.1113380

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 Ozone: Science & Engineering
The Journal of the International Ozone Association

ISSN: 0191-9512 (Print) 1547-6545 (Online) Journal homepage: http://www.tandfonline.com/loi/bose20

Study of Parameters Affecting Dry and Wet Ozone

Bleaching of Denim Fabric

Sarra Ben Hmida & Neji Ladhari

To cite this article: Sarra Ben Hmida & Neji Ladhari (2015): Study of Parameters Affecting
Dry and Wet Ozone Bleaching of Denim Fabric, Ozone: Science & Engineering, DOI:
10.1080/01919512.2015.1113380

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 OZONE: SCIENCE & ENGINEERING
http://dx.doi.org/10.1080/01919512.2015.1113380

Study of Parameters Affecting Dry and Wet Ozone Bleaching of Denim Fabric
Sarra Ben Hmidaa,b and Neji Ladharic
a
Textile Engineering Laboratory of the Higher Institute of Technological Studies of Ksar Hellal, National Engineering School of Monastir,
Monastir University, Monastir 5016, Tunisia; bDenim Laundry Department, Company of Textile Arts Sartex, Ksar Hellal 5016, Tunisia; cHigher
Institute of the Fashion Trades of Monastir, Textile Engineering Laboratory of the Higher Institute of Technological Studies of Ksar Hellal,
Monastir University, Monastir 5070, Tunisia

ABSTRACT ARTICLE HISTORY

The present research is related to a recent eco-friendly technology in a denim laundry that relies Received 8 July 2015
on ozone oxidation of indigo. In this work, denim fabric was treated with ozone at different values Accepted 18 September
of ozone concentration, moisture content and time of exposure to ozone. The fading increased 2015
with the increase of the various mentioned factors. Residual products of the indigo oxidation by KEYWORDS
ozone, the cause of the yellowing observed on the surface of the fabric were identified through Ozone; Denim; Fading;
spectrophotometric measurements, pH variation and FTIR analysis. Ozone effect on mechanical Mechanical Properties;
properties of the fabric was studied through the measurement of ultimate tensile strength. Moisture; Oxidation;
Downloaded by [Gazi University] at 02:32 11 January 2016

Yellowing

Introduction Ozone is a gas that is generally present in our atmo-

sphere and is formed naturally by photochemical reac-
The present research is related to the decolorization
tion with solar UV radiation (Hegglin et al. 2014). It
of clothing dyed in indigo using ozone. Denim has
can be generated artificially by several ways such as
survived the decades and even centuries; it is desired
corona discharge. Ozone is a triatomic molecule con-
and necessary in every trend, yet denim/jeans
sisting of three oxygen atoms. Ozone has a strong
remain the most polluting textile products of the
tendency to react with almost any organic substance.
world, not only because of its indigo dyeing but
The use of ozone in water and wastewater treatment
also the chemicals and the amount of water that it
currently remains the most prevalent industrial appli-
requires to obtain the best washes. Textile indus-
cation. Ozone is a powerful oxidant and disinfectant
tries, conscious about levels of performance and
capable of destroying the cellular structure of viruses,
productivity, wash out their jeans with lowest costs
parasites and bacteria (Sacco 2009). It has some advan-
without regard for the consequences on the envir-
tages over other oxidants commonly used in the textile
onment and on humans. The ozone fading of textile
industry, particularly in chlorine. The main advantage
dyed fabric is a revolution in the entire textile sec-
is the lack of persistence: ozone is chemically unstable;
tor. The ozone wash is based on a natural process
it leaves no secondary derivative products on treated
that ensures enrichment of oxygen. It fades clothing
products.
and provides a significant gain in water and chemi-
Among the most common oxidizing agents used in a
cals unlike the usual processes of bleaching based on
denim laundry, ozone remains the most efficient. In
pumice stone, bleach and enzymes that cause
fact, this gas fades dyed textile materials by the rupture
mechanical and chemical damage of the fabric, and
of the chromophores in dyes of synthetic or natural
a loss of tensile strength and a risk of tearing the
fibers. Because of its high oxidation potential
article in thickness zones, critical areas (from hem)
(E = 2.07 eV), ozone can effectively break down com-
and presence of stone spots. An antiredepositing
plex aromatic rings of the dyes, resulting in decoloriza-
agent must be put in the bath in order to avoid
tion. Color is removed when certain bonds are broken
redeposition of indigo after removing it from the
by the ozone, such as the bond -C = C- and hetero-
surface of the fabric. That is not the case for ozone
cyclic and aromatic rings (Wasinger 1998). Indeed,
because it degrades the dyeing without generation of
indigo ozonolysis leads to the formation of isatin
annoying or harmful waste products.

CONTACT Sarra Ben Hmida benhmida.sarra87@gmail.com Textile Engineering Laboratory of the Higher Institute of Technological Studies of Ksar
Hellal, National Engineering School of Monastir, Monastir University, Monastir 5016, Tunisia.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/BOSE.
© 2016 International Ozone Association
 2 S. BEN HMIDA AND N. LADHARI

Figure 1. Reaction of indigo oxidation by dry ozone.

(Figure 1). The isatin molecule presents a yellowish The ozone machine
color. Thus, the material passes from blue (indigo) to
The bleach testing of denim was performed by means
the yellow (isatin) during the reaction.
of an ozone machine G2 Plus from Jeanologia
The process allows replacing carbon-carbon double
(Valencia, Spain) (Figure 2).
bonds by carbon-oxygen double bonds. Indeed, in an
This finishing machine is equipped with an ozone
anhydrous medium, ozonolysis of indigo results in two
generator using electric power to charge the oxygen
reaction products: isatin and isatoic anhydride
molecules in the incoming air and generate ozone for
(Ledakowicz, Solecka, and Zylla 2001).
denim. The oxygen is compressed and gathered in a
We chose to study various parameters influencing
Downloaded by [Gazi University] at 02:32 11 January 2016

tank that will supply the ozone generator. Oxygen

denim ozonation, which are moisture content of the
fabric, power of the ozone gas, and the treatment time.
The ozonation treatment does not require vapor or hot
water, because temperature has an important effect on
the half-life of ozone. As the temperature increases, the
half-life of ozone decreases due to its rapid decomposi-
tion and low stability.
Materials and methods
Fabric
The fabric used in the tests has the following character-
istics: composition: 100% cotton (cellulosic fiber),
weave: 4 twill, weight: 456 (g/m2), dye: blue indigo,
and it contains starch.
should be dry and not moistened so it does not inter-
fere with the dielectric generator. Because ozone is an
unstable molecule, it must be generated at the moment
of use. Oxygen (O2) is purified and enriched, then an
O2 molecule is converted into O3 by the corona dis-
charge generator. The resulting ozone is injected into
the drum containing the fabrics. Ozone naturally ages
the denim, similar to the effect of sunlight on the
textile. At the end of the fading cycle, the ozone is
sucked from the drum to a burner and then destroyed
with a temperature of 300 °C to become oxygen before
being discharged to the atmosphere. This operation
takes several cycles to reach a sufficient concentration
of ozone in the machine. The ozone generator is
equipped with a cooler to prevent the increase of tem-
perature in the discharge space. The temperature of the
cooler should not exceed 25 °C.

Desizing and spinning

Spectroscopy and FTIR analysis
Before proceeding with the ozonation process, the fab-
rics must undergo desizing treatment in order to guar-
antee the diffusion of ozone and water into the fiber.
The amount of moisture was set after some spin testing
by varying the spinning time. The designing recipe is
presented in Table 1.

Table 1. Desizing recipe.

Treatment time Temperature
Treatment Additives (min) (°C)
Preparation Detergent + acetic Until the temperature reaches 70 °C
acid
Desizing Enzyme 20 70
Rinses (×2) _ 3 30 Figure 2. Ozone machine Jeanologia G2 Plus.
 OZONE: SCIENCE & ENGINEERING 3

A Datacolor 400-Top spectrophotometer (USA) was
used to measure the lightness DL* and the yellowing
degree Db* of the ozonated samples compared to the
untreated ones.
The presence of isatin was confirmed by the wavelength
value given by the photoLab® 6000 spectrophotometer
(Xylem-Germany) after its dissolution in toluene while
anthranilic acid was identified (using a Perkin Elmer
Spectrum Two ATR-FTIR in the science department of
Monastir in Tunisia) by the measurement of the pH of
aqueous extracts of treated and untreated samples.
Mechanical characterization
Ultimate tensile strengths of the fabrics were measured
using a Sodimat dynamometer HJKS 1304 in Sartex,
Ksar Hellal, Tunisia.
Downloaded by [Gazi University] at 02:32 11 January 2016
The variation of the moisture content of the fabric
enormously influences response DL*. The degradation
of the color from the surface of the fabric becomes more
intense over the course of time. We observe, according to
these graphs, that the increase of lightness is not signifi-
cant for moisture values of 10 and 20%. However the
decolorization of fabric for these values slightly increases
with values of ozone concentration of 60 and 84 g/Nm3.
The value of DL* increases considerably for 40% and 60%
of water pickup. In fact, high moisture gives place to a film
of water on the surface of the fabric and generates a
swelling of the fiber, which ensures the diffusion of gas
and consequently increases the specific surface attacked
by ozone, where the decolorization of fabric is better.
When the fiber inflates after the absorption of
water, it becomes more receptive. The uncolored
weft of the denim fabric is also bleached when
ozone gets access into the fiber; the hydration of

cellulose accelerates the oxidation. However, the

Rubbing fastness test
The purpose of this test is to determine the dyes
strength to dry and wet rubbing (NF G 07-016). The
apparatus used is a Crockmaster (James H. Heal & Co.
Ltd, Halifax, England), gray scale and a cotton cloth cut
into a square size equal to 5 * 5 cm.
Study of ozonation parameters
To have a complete study of the effect of each ozonation
parameter, we carried out a series of tests with we studied
various levels of each parameter to study their effects more
closely.
Results and discussion
Effect of ozonation parameters on denim shade
Table 2 illustrates the variation of lightness degree
DL* after the treatment was carried out under the
various conditions:
excess of water that enters the intermicellar and
interfibrillar space of cellulose retards the bleaching.
This way, the fabric requires an important value of
ozone concentration to be bleached. According to
these results, the effect of the power does not have
the same importance as the other parameters on the
ozone treatment. For example, we notice that DL*
increased slowly over the course of time, until 84 g/
Nm3 of ozone concentration, where the decoloriza-
tion of the fabric becomes significant. Beyond this
value, we observe a slight reduction, as shown in
Figure 3.
This suggests that the temperature inside the drum
increases considerably when the value of the ozone
concentration is very high, especially when the load of
the machine is not significant. This decreases the
moisture content of the samples and consequently the
latter will not have a significant effect any more.
Indeed, we noticed that the temperature of the cooler
increased from 21 to 37 °C for 108 g/Nm3 of ozone
concentration, which resulted in a reduction in the

Table 2. Lightness measurement of treated samples after neutralization.

Ozone concentration (g/Nm3) 12 60
Moisture content (%) 10 20 40 60 10 20 40 60
Treatment time (min) 3 0.24 0.84 0.78 1.25 0.36 1.51 2.03 3.87
8 0.38 1.26 1.62 2.88 0.51 1.58 3.86 5.76
13 0.43 1.59 2.44 3.17 0.65 1.61 4.28 7.05 DL*
18 0.55 1.68 2.67 3.24 0.82 1.69 4.52 7.67
23 0.79 1.76 3.34 3.45 1.31 2.93 4.63 9.72
Ozone concentration (g/Nm3) 84 108
Moisture content (%) 10 20 40 60 10 20 40 60
Treatment time (min) 3 0.44 1.97 3.27 3.73 0.1 1.72 3.52 3.65
8 0.64 2.43 4.44 7.06 0.36 3.2 4.43 6.75
13 0.77 2.97 4.92 14.36 0.69 3.57 6.14 9.9 DL*
18 1.27 3.21 5.21 22.1 0.39 3.96 6.69 14.31
23 1.7 3.25 8.67 33.12 0.69 4.14 7.24 19.20
 4 S. BEN HMIDA AND N. LADHARI

35
the indigo dye. It certainly cannot be the indigo dye in
its leuco form because ozone breaks the -C = C- double
30 bond entirely. We estimated that this yellowing might
25
be due to a derivative of isatin. The yellowing becomes
more significant when moisture increases as shown in
20 Figure 4. The yellowing as it is directly related to the
DL*

amount and position of the dyestuff in the fiber may be

15
increased by redeposited indigo released from a pre-
10 vious washing process, especially stone wash treatment.
Indeed, the spectrum of absorbance in the visible UV of
5
isatin (in toluene) comprises a peak at λ = 405 nm.
0 According to Table 3, we can affirm that the value found
0 24 48 72 96 108 120
for maximum wavelength is an undeniable proof of the
Ozone concentration (g/Nm3)
isatin formation (Khalil and Al-Seif 2008). Because the
Figure 3. Effect of the ozone concentration on denim fading at yellowish product is soluble in water, it certainly cannot
H = 60% and treatment time = 23 min. be the isatin in its rough form, because this one is not
soluble in cold water (Crookes 1874). To better identify the
residual products deposed on the surface of the fabric after
Downloaded by [Gazi University] at 02:32 11 January 2016

output of the ozone generator and promotes the rever-
sibility of the ozone generation reaction. The effect of
the moisture content is higher than that of the ozone
concentration, but the treatment time remains the most
effective parameter. According to these results, having
better bleaching of the denim fabric would always be
better with the increase of the treatment time at mod-
erated ozone concentrations to keep the efficiency of
the ozone generator and guarantee an even fading.
Study of the yellowing observed on the surface of
the fabric after ozonation
We noticed after ozonation that the fabric has a yellow-
ish aspect, sometimes greenish. This yellowing is due to
the formation of new products from ozone oxidation of
ozonation, the pH of the aqueous extract of treated samples
has been measured as shown in Figure 5. The different
values of measured pH showed that after ozonation the
more the fabric becomes yellow, the more the pH becomes,
acidic which can be explained by the formation of anthra-
nilic acid (Reidies, Jensen, and Guisti 1992). FTIR spectrum
shown in Figure 6, proves the formation of C = O groups at
1730 cm−1 in the treated sample, which does not appear in
the untreated one (Spinelle 2012). This might confirm the
formation of anthranilic acid (Mock and Rucker 1991).
The elimination of the yellowing was studied through
Table 3. Spectrophotometric analysis of yellowish residue.
Solvent λmax (nm) Absorbance
Sample Toluene 403 0.475
Isatin 405 0.473

8 Yellowing of treated samples

pH of treated samples

7
10

6 6
8
5
Db*

4 6
Db*

4
pH

3
4
2

1 2
2

0
10 20 30 40 50 60
0
0 12 24 36 48 60 72 84 96 108
Moisture content (%)
Ozone concentration (g/Nm3)
Figure 4. Effect of moisture on yellowness index of samples
treated for 23 min. Figure 5. Variation of aqueous extract pH of ozonated samples.
 OZONE: SCIENCE & ENGINEERING 5

108
12 g/Nm3 of ozone
106
Untreated sample 48 g/Nm3 of ozone
1120 96 g/Nm3 of ozone
104
1100

Ultimate tensile strength (%)

Transmittance,%

102

C=O, 1730 cm–1

Treated sample 1080
100 1060
98 1040

96
1020
1000
94
980
92
4000 3500 3000 2500 2000 1500 1000 500 0
960
Wave number, cm–1 940
920
Figure 6. ATR-FTIR spectrum of treated and untreated sample. 900
0 5 10 15 20 25
Treatment time (min)
Table 4. Evaluation of the efficiency of different neutralizing
agents. Figure 7. Variation of ultimate tensile strength of treated sam-
Hydroxylammonium Sodium ples in the warp direction.
sulfate metabisulfite Oxalic acid
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Δb* of ozonated sample Δb* of neutralized samples

5.88 −6.95 −6.9 −7.11 −7.28 −9.38 −9.43 12 g/Nm3 of ozone
pH of untreated samples pH of neutralized sample 48 g/Nm3 of ozone
7.21% 7.15 7.11 7.1 7.06 7.04 500 96 g/Nm3 of ozone

490
Ultimate tensile strength (%)

480
several rinses at high temperature (50 °C to 70 °C) and a
470
neutralization step.
The efficiency of different neutralizing agents was 460

tested as shown in Table 4. Hydroxyl ammonium sul- 450

fate did not really change the yellowish shade of the 440
ozonated sample. With sodium metabisulfite we
430
reached acceptable results; the neutralized sample was
420
bluer and less yellowish compared to the untreated one.
The oxalic acid gave the best results, the samples are 0 5 10 15 20 25
cleaner, bluer, and the yellowing was totally eliminated. Treatment time (min)
Note that ozone does not reproduce aspects obtained Figure 8. Variation of ultimate tensile strength of treated sam-
by the usual bleach, but it offers a different and rich ples in the weft direction.
range of washed fabrics with a greyish appearance. The
pilling intensity of samples treated with ozone is very
important. An anti-pilling step helps decreasing it while fiber is then surrounded with ozone more molecules,
giving a bluer appearance. which explains the important degradation of cellulose.
Katai and Schuerch (1966) proposed a mechanism of
ozone attack on cellulose (Lemeune et al. 2004) that
Evaluation of the mechanical properties of ozone
explained the damage induced by this oxidative gas by
treated samples
hydrolysis of the glycosidic bonds (Perincek et al.
As shown in Figures 7 and 8, ozone slightly damaged 2007). Then, zone-induced damage affected mechanical
the fabrics by reducing their tensile strength. Ultimate properties of the fabric, but this can be resolved by
tensile strengths decreased when the ozonation time controlling the ozone dose that bleaches the fabric
and the ozone concentration increased. The weft without causing important damage. Desizing should
yarns were more affected by ozone than the warp not be overdone in order to maintain a certain amount
yarns, which contain a minimum of sizing agent that of sizing that protects the fabric. Factors such as sun-
offers a better strength. The presence of water in the light, heat, humidity and the presence of microorgan-
interfibrillar space facilitates the access of ozone mole- isms reduce the tensile strength of a much greater
cules into the fiber and increases the contact area. The extent than the exposure to ozone.
 6 S. BEN HMIDA AND N. LADHARI
Table 5. Color fastness to rubbing.
Wet ozone (Treatment time = 23 min; Moisture content = 40 %)
Ozone concentration (g/Nm3) Dry rubbing
12 5 3/4
60 4/5
84 4/5
96 4/5
108 4/5
Dry ozone (Treatment time = 23 min; Moisture content = 10 %)
Ozone concentration (g/Nm3) Dry rubbing
12 5 4/5
60 5 4/5
84 4/5
96 4/5
108 4/5
Evaluation of rubbing fastness of the treated
samples
Denim is a twill cotton fabric in which the dye is
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oxidized on the surface of the fabric, which is why
after evaluation of the results using the gray scale as
shown in Table 5, a certain amount of color rubs off the
fabric, especially at wet test. Such a result does not
mean the rejection of the process, as it is still acceptable
compared to the results given by the conventional
denim washing process. The cotton test cloth does not
show any yellowing stains in the wet or dry rubbing,
which confirms the efficiency of the neutralization
done after ozonation.
Conclusion
The process of ozone bleaching is integrated in the
portfolio of clean technologies used in the industry to
allow the significant reduction of the level of environ-
mental impact. Such a treatment makes it possible to
minimize the consumption of hot water and the harm-
ful products of denim wash to the environment. It also
allows us to get rid of the problem of redeposition of
indigo, especially in pocket bags and the extended time
of treatment. This technology proves to be interesting
not only in economic dimensions but also because it
offers a better image of the textile industries. Wet ozone
treatment is more profitable and gives a richer range of
washed jeans than dry ozone; however, the moisture
content of the fabric remains a difficult factor to con-
trol at the textile industry work conditions and depends
on the spin and the time where the jeans remain in
carriages between the different finishing treatments.
The denim bleaching by the action of ozone dissolved
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in water may offer better results by maintaining the
same wetting conditions and an even bleaching.
Wet rubbing
2/3 Funding
2/3
2/3 This project is carried out within the framework of a
2/3
thesis of doctorate MOBIDOC of PASRI program
Wet rubbing financed by the UE and managed by the ANPR.
2/3 References
2/3
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