Intechopen 81774
Intechopen 81774
Intechopen 81774
Abstract
1. Introduction
1. Process optimization (water and time saving in every possible area, use of less
chemical, working in lower temperatures).
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Textile Industry and Environment
3. Reuse of water.
In this chapter, the use of ozone as some ecofriendly production method in wet
processing of textiles is investigated.
2. Ozone
Figure 1.
Cycle of formation and destruction of ozone [8].
Figure 2.
Ozone molecule [6, 11].
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Use of Ozone in the Textile Industry
DOI: http://dx.doi.org/10.5772/intechopen.81774
Ozone must be generated “in situ” because it is very reactive gas and cannot
be stored and transported to anywhere. So, it has to be generated [3]. The basic
methods for generating ozone artificially are below [5–7, 9, 12–15]:
• titrimetry,
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• amperometry,
• chemiluminescence,
• calorimetry,
• thermal conductivity,
The last four methods are not commonly used for analysis. It is necessary to be
aware of its reactivity, instability, volatility, and the potential effect of interfering
substances to measure the amount of ozone in water correctly. Ozone sometimes is
sprinkled in drops by using an inert gas for analysis in the gas phase or on reabsorp-
tion in a clean solution in order to eliminate interferences [14].
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Excess reagent pH pH
Iodometric None 3.5–9 2
Amperometric S2O3 = PAO or As (III) 4.5 4.2–6.8
As (III) back As (III) 6.8 6.8
DPD DPD 6.4 6.4
Table 1.
Iodometric methods for ozone analysis [21].
UV absorbance measurement method is mainly useful for gas analysis. This method
also can be used for measuring aqueous ozone solution. However, interference from
turbidity, dissolved inorganics, and organics is a problem. Ozone is sprinkled into
the gas phase in order to eliminate interference for measurement. If the sample is
liquid, the best sample for this method will be clean water free of UV-absorbing
impurities [14, 19, 23–25].
Several different colorimetric methods are used for measuring ozone residuals.
But most of them are sensitive to significant interference from secondary oxidants
[14].
The first reagents for measuring ozone in air and exhaust gases are indigo and its
water-soluble derivatives, the sulfonated indigo compounds like indigo disulfonate,
indigo carmine, and indigo trisulfonate. Water-soluble derivatives of indigo, indigo
disulfonate, and indigo trisulfonate are pH or redox indicators. Purity and age of
the indigo trisulfonate are very important for the method because they affect the
stoichiometry of the reaction [17, 19].
The indigo molecule contains only one double bond (C═C). It reacts with ozone
in order to produce sulfonated isatin and similar substance (Figure 3). Maximum
absorbance of indigo is at 600 nm [17, 26]. If the pH value is below 4, sensitivity
of the method does not vary with ozone concentration, small changes of tempera-
ture of reaction, or the chemical composition of the water. The advantage of the
method is applicable for lake water, too hard groundwaters, and biologically treated
domestic wastewater. Indigo trisulfonate method is quantitative, selective, fast,
and simple. Classical instrumentation of water work laboratories is enough for
measurement. The method is based on the decolorization of the dye by ozone. The
loss of color is directly proportional to the concentration of ozone, and pH value
of the sample is adjusted to about 2 in order to minimize destruction of the ozone
by hydroxide ions [17, 19, 21]. The concentration is the difference in absorbance
between sample and blank [16]. Mn+2 ion is a problem in this method. Because,
oxidation products from the reaction of Mn+2 ions with ozone can demolish indigo
trisulfonate. So, glycine is added to the sample in order to demolish the ozone
Figure 3.
Ozonation of potassium indigo trisulfonate [26].
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selectively. Then, indigo reagent is added to the sample to measure the seeming
ozone concentration because of the reaction with manganous ion oxidation prod-
ucts. This value is subtracted from the value of the sample without glycine [19].
Indigo method is applied to “AccuVac Ampul” ozone measurement. For the
measurement, all the chemicals are packaged under vacuum into an ampule. The
ampule is like a cuvette, and it is used precisely for the spectrophotometric determi-
nation of the dissolved ozone [25].
• The bare-metal electrodes, which are in direct contact with the water;
In the literature, there are various electrochemical methods using a solid redox
polymer electrolyte-based amperometric sensor, a lignin-modified, glassy carbon
electrode, and multiwalled carbon nanotubes to analyze ozone [16].
General advantages of electrochemical methods are low cost, easy operation,
potential for miniaturizing and automation, simple portable devices for fast screen-
ing purposes, and in-field/onsite monitoring [16]. But every 1 or 2 months, ampero-
metric analyzers have to be calibrated against a reference method such as UV, or the
colorimetric indigo methods [25].
There are two types of ozone application in the textile industry. They are:
For wet processes, aqueous ozone is more practical than gaseous ozone because
working principle of finishing machines is suitable for solution. Use of gaseous
ozone needs special airproof machines because of occupational health and comfort.
Material of leakproof gasket has to resist gaseous ozone.
Gas phase: Half-life of gaseous ozone is more than that of aqueous ozone. So,
it decomposes slowly [13]. Gaseous ozone is easily affected by the catalyst. Light,
trace organic matter, nitrogen oxides, mercury vapor, and peroxides act as catalysts
for homogeneous catalysis. Metals and metal oxides are catalysts for heterogeneous
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catalysis. If there is no any effect of the catalyst on the mixture, it will be stable.
Porous solid substrates can adsorb gaseous ozone [14]. Textiles are the sample of
porous solid substrates.
Aqueous phase: Solubility of ozone in water is better than the oxygen [27].
However, ozone dissolves moderately in water. It follows Henry’s law [13]. The
solubility of ozone depends on pressure, temperature, and ionic strength [14].
Efficient moving of ozone to solution needs dispersion of gaseous ozone into small
bubbles. Positive-pressure ozone contractors, negative-pressure reactors (Venturi),
and injectors achieve it [13]. At room temperature, decomposition of ozone in pure
water is very slow. However, ozone decomposes with the catalysts like hydroxyl ion,
trace metals, H2O2/HO2¯, organic substances, heat, and UV light [14].
The parameters affecting the physical mass-transfer rate of ozone into water are:
• temperature,
• pressure,
• gas dispersion,
• turbulence,
Recently, scientific studies about the use of ozone in textile manufacturing are
very popular. But the use of ozone in textile manufacturing is not common in prac-
tice. It is only commercially common in denim and garment washing. Therefore,
the use of ozone in denim washing is discussed in a special title. The other titles are
based on fiber types.
The denim garments are very popular, and they are preferred by people of all
ages, classes, and genders. Depending on the desired effect, denim garments are
treated with different substances [28, 29]. A lot of dry and wet processing tech-
niques are used for desired effects [30]. Wet processes in denim washing are not
environment friendly. High water and energy consumption, large amount of waste-
water, and solid waste like pumice stones are generally environmental problem in
denim washing [29, 30]. Sodium hypochlorite is a very common bleaching agent
in denim washing. Especially AOXs (adsorbable halogenated organic compounds)
are the most important environmental problem. Therefore, chlorine-free bleaching
technologies are a good solution for AOX. Ozonation is an alternative bleaching
method [28]. Ozonation is a simple and “green” process because it does not require
steam and water. Therefore, it greatly reduces process time, water, chemical and
energy consumption, and amount of wastewater [31, 32]. Ozone decomposes indigo
and other dyes because of high oxidation potential. In addition to denim washing, it
is generally applicable to treatment of other textiles like T-shirts, shirts, chinos, and
casual wear. In ozonation, the ozone generated in the equipment can commercially
provide bleaching effect. It is like washing machine without water for fading of
color [31]. And ozone is generally applied to whole of the garment in this ozonation
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machine. However, local bleached spots on the fabric can also be created by ozone.
Ozone gas is scattered onto the denim fabric at a controlled velocity [32].
Özdemir et al. studied on ozonation parameters of denim fabric. They used
prewashed denim fabric for ozonation. They inform that water content of the
denim fabric is very important for efficiency of ozonation, and 50–60% water pick
up value (W.P.V.) is the best for bleaching efficiency. The higher W.P.V. affects the
bleaching efficiency of ozonation negatively. For ozonation, acidic and neutral pH
values are better than basic pH value. Temperature is one of the most important
parameters because higher temperatures decrease the half-life of ozone. Ozonation
of wet denim is especially for bleaching [28].
Hmida and Ladhari studied the parameters affecting dry and wet ozone bleach-
ing of denim fabric. Their results about the effect of W.P.A. on bleaching efficiency
are also compatible with Özdemir’s results. They claim that water film covers
the surface of the fabric and swelling of the fibers is achieved. Then, ozone can
penetrate into fibers, and bleaching efficiency on wet denim is better than that of
dry denim. On the other hand, backstaining problem is solved by ozonation of dry
denim [31, 33].
In the other study, denim fabric was treated with the combination of ozonated
water, ultrasound, and hydrogen peroxide. According to the results, ozone is more
effective with the aid of ultrasonic energy because the ultrasonic cavitations improve
the penetration of ozone into the fabric, and then, ozone decomposes indigo [5, 32].
Bağıran et al. compared ozone to other bleaching agents in denim washing.
According to results, ozone is one of the strong agents. It follows potassium per-
manganate and benzoyl peroxide. But, the most important advantage of ozone is
environment friendly, and it is a good alternative to the others. Benzoyl peroxide
and ozone are the causes of gray tint in bleached denim fabric. The others are the
reason for blue tint of bleached denim. After ozonation, loss of strength is not too
high because ozone is unstable, and it decomposes indigo primarily [34].
In practice, ozone is applied to garments. However, there are a few studies on
ozonation of yarn [35, 36]. Beşen and Balcı try to fade indigo-dyed yarn before
weaving and garment processes. The indigo-dyed yarn is ozonated in hank form.
Their results about the effect of the ozonation condition on bleaching efficiency are
generally compatible with Özdemir’s results. On the other hand, the origin of the
raw material directly affects the fading degree of the yarn. According to the results,
the count of the yarn is the most important parameter on the decrease in strength
of the yarns depending on the ozonation process. However, strength loss is not so
important. As a conclusion, the ozonation condition can be determined according
to desired effect from the yarns. They claim that different fading effects can be
achieved by ozonation before weaving process [35].
He et al. investigated effect of ozone on three typical denim yarns (cotton,
lyocell, and polyethylene terephthalate (PET)) during the color-fading process.
They claim that ozone only smoothly impacts the crystalline structures of these
yarns. PET is not affected by ozone because of its aggregate structure. This struc-
ture prevents the oxidation and decomposition of PET. They suggest that ozonation
for cotton, lyocell, or other cellulosic yarns should be limited within 10 min at the
pH > 7 with a careful selection of water content [36].
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short time, the whiteness of the fabric is acceptable for dyeing and DP losses are not
so important [5, 10].
Eren and Öztürk also investigated ozonation of cotton fabrics. According to
their results, the starch size removal of the greige cotton samples and the water
absorbency of the greige and desized cotton samples are increased by ozonation.
But ozonation does not remove the motes successfully. Bleaching effect of ozonation
is successful because of high oxidation potential of ozone [37].
Maqsood et al. suggest ozonation of cotton fiber for medical textiles and produc-
tion of nanocrystalline cellulose or nanofibrils of cellulose in their paper [38].
Turhan and Soydaş discussed ozonation of cotton terry fabrics. As the results of
the study, ozone cannot sufficiently remove impurities like sizing agents, natural
waxes, and oils. Therefore, they suggest desizing the terry fabric before ozonation
and rinsing the fabric after ozonation [39].
Perinçek et al. also investigated the effects of new advanced processes on cotton
woven fabric. The new advanced processes contain ozonation, ultrasound, and
ultraviolet. In this study, cotton fabrics are bleached by combining ozone with
ultrasound and ultraviolet. According to results, advanced processes can be used
in pretreatment of cotton fabrics. However, advanced processes at 63–65°C are not
sufficient for desizing the cotton fabrics and need desizing agents. After ultrasonic
treatment followed by ozonation, whiteness and hydrophilicity of the fabric are
sufficient for dyeing. The combination of ozone and ultraviolet processes for high
whiteness of the fabric is recommended. However, breaking strengths and hydro-
philicity values have to be considered carefully [3].
Perinçek recommended a removing method of optical brightener from cotton
fabric in her paper. It is difficult to remove optical brightener efficiently from the
fabric when any problem is seen on the fabric due to high stability of optical bright-
ener. Hazardous chemicals are generally used to remove it. Therefore, ozonation
process has ecological advantage. The results show that ozonation can be used for
decolorizing the optical bleached samples. Increasing ozonation time increases the
efficiency. However, bursting strength loss of fabric should be taken into consid-
eration due to the oxidation of cellulose. Meanwhile, a new patterning method for
optical bleached fabrics is proposed in the paper. It provides fashionable products
(Figure 4) like batik or tie-dyed cloths [40].
Figure 4.
The photographs of fabrics treated by developed method (I: optical bleached fabric is tied in knots, tightly
bound with thread; II: a = optical bleached fabric before ozonation; II: b/c = optical bleached fabric after
ozonation in accordance with developed method [40]). (Thanks to Textile and Apparel for copyright).
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Textile Industry and Environment
Gashti et al. studied on surface oxidation of cellulose by ozone gas. The aim of
the study is to investigate the influence of ozonation on the performance of the fluo-
rocarbon monomer on cotton. As a result of the study, fluorocarbon efficiency on
cotton is remarkably improved by ozonation before fluoromonomer grafting. The
contact angle tests and microscopic appearances show that contact angle increases
because of the higher efficiency of the water repellent polymer on the treated cotton
by ozone [41].
In Bahtiyari and Benli’s study, ozone ultrasound humidifier combines to bleach
the cotton fabric before dyeing with green walnut shells. As a result, treated cotton
with ozone can be dyed with green walnut shells, and the colors of the natural dyed
fabrics are good. Even if no mordanting agent is used in natural dyeing, the fast-
nesses are sufficient [42].
Bahtiyari and Benli proposed a green process line in their paper. In their study,
cotton fabrics are treated by ozone gas and ultrasound before natural dyeing
without mordant (Figure 5). Natural dyes are nutshell, orange tree leaves, and
alkanet roots. Finally, ozone and ultrasound are used for the pretreatment of cotton
before natural dyeing without mordanting agent. At the same time, fastnesses of all
the dyed samples are generally sufficient, except light fastness. But light fastness of
dyed samples with pomegranate peels is only sufficient [43].
Figure 5.
Green process line [43].
Erdem and Bahtiyari combined ultrasound and ozone during the pretreatment
of cotton slivers. Ultrasound is used in scouring process, and as expected, ozone
is for bleaching process. As a result of the study, hydrophilicity of the cotton is
achieved by pectinase enzyme/ultrasound combination. Meanwhile, bioscoured
cotton is dyed by using pomegranate peel and green tea. In the end of the study,
they suggest their process line for production of medical and cosmetic textiles [44].
Benli and Bahtiyari applied ozone to natural dyed cotton fabrics in their study.
Aim of the study is to establish an alternative natural dyeing method without
mordanting agents. Ozonation ways are given below:
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• After the dyeing and washing processes, application of ozone gas to dyed fab-
rics, which are wet.
• Before washing process, application of fresh and cold water through ozone gas
to dyed fabrics.
• After dyeing, application of fresh and cold water through ozone gas to dyed fab-
rics. Then, washing of the treated fabrics.
Different ozone application ways present various shades and effects due to
chemical structure of natural dyes. Different types of fastnesses are examined in
terms of ozone application ways and various mordanting agents. Generally, all dyed
samples have high fastness except for light fastnesses. Direct ozonation of wet dyed
samples improves the rubbing fastness values [45].
Kan et al. examined the effect of plasma-induced ozone treatment on the color
fading of reactive dyed cotton fabric. According to the results, color fading effect
is increased by increasing ozonation time, and air ratio has considerable effect on
color fading. Color levelness of the ozone-treated fabrics is excellent [5, 46].
Eren et al. studied the color stripping of reactive dyed cotton by ozonation. The
parameters are ozonation time and type of reactive dyes. The longest ozonation
time gives the best color stripping result. COD value of effluent from ozonation is
less than that of conventional reductive treatment [47].
Yiğit et al. discussed ozonation for discharge printing of reactive dyed cotton in
their paper. The aim of the study is to use ozone gas instead of reductive agent and
caustic soda in discharge printing. Color discharge increases at higher gas flow rates
and prolonged ozonation times. According to results, ozone gas can be used for
discharge printing. However, contour sharpness of conventional discharge printing
is much better than that of ozonation. It is not as excellent as contour sharpness of
conventional discharge printing [48].
Zhong et al. investigated color-fading process of sulfur-dyed cotton fabric by a
plasma-induced ozone. As the results, the plasma-induced ozone color-fading treat-
ment can be used to remove the color from the dyed fabric and the effect is uniform
and even [49].
Perinçek et al. studied the ozonation of jute. The results indicate that the ozonation
conditions for the best whiteness degree are fabric at pH 7, 60% WPV, and temperature
of 23–25°C. The lignin content and DP values of fabrics are reduced by ozonation [50].
Perinçek et al. also combined ozonation and hydrogen peroxide bleaching in
their paper. Linen fabrics are bleached in two steps. First, the linen fabric is treated
by ozone. Then, it is bleached by hydrogen peroxide. The treatment conditions are
optimized statistically [51].
Kurban et al. examined the ozonation of nettle biofiber in their study. Different
bleaching methods are applied to nettle fiber fabric. They are:
• ozonation,
As a result of the study, ozonation improves the whiteness of nettle fiber fabric.
Among all the bleaching ways, the highest whiteness is obtained from combination
of the hydrogen peroxide bleaching and ozonation process [52].
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One of the early studies is about ozonation of wool garments. The aim of the
study is to obtain shrink-resisted wool garments and fabric. Therefore, a continuous
or batch treater was designed, and wool fabric and garments hung in cabin contain-
ing ozone. It was found out that circulation of the vapor around the garments and
fabric is inevitable for rapid reaction. Fabric construction is very important for
desired degree of shrink resistance. It is claimed that ozone-steam process is a solu-
tion to the felting problem of wool [53].
Rahmatinejad et al. discussed innovative hybrid fluorocarbon coating on wool
treated with UV/ozone. The application of fluorocarbons on the wool fabrics is a
problem because of chemistry and structure of the fiber surface. Therefore, UV/
ozone treatment is proposed as a solution to this problem. Firstly, wool is modified
by UV/ozone treatment. Hydrophilicity of treated wool is remarkably better than
untreated wool. UV/ozone treatment can be applied to one side of the fabric and
hybrid functional fabrics with two different properties on each side of the fabric are
thus obtained [54].
The chlorine/Hercosett process is the most common treatment for the wool dye-
ing. It causes environmental problems because of the pollution of wastewater with
absorbable organic halides (AOX). Therefore, ozonation is an alternative surface
modification method for improving wool dyeability [6].
Micheal and El-Zaher examined the effect of ultraviolet and ozone combination
for different times on wool. As a result of the study, wetting of the wool is improved
by the ultraviolet/ozone process because of surface modification. It means that
there is an increase in amorphous areas of the treated wool. Ultraviolet/ozone
oxidizes cystine bond on the surface of the wool fabrics and generates free radical
species. They support dye uptake [6].
Shao et al. investigated the effect of UV/ozone exposure and peroxide pad-batch
bleaching on the printability of wool. It is found that peroxide pad-batch bleaching
can prevent the yellowness caused by UV/ozone treatment and improved the wet-
tability of the treated wool in a short time. Printability performance of treated wool
is similar to that of chlorinated wool [55].
Sargunamani and Selvakumar investigated the effects of ozonation on raw and
degummed tassar silk fabrics. Ozone treatment is compared with soap degumming
and hydrogen peroxide treatment. Soap treatment of silk is less harsh than ozonation.
Peroxide treatment causes lower yellowing index compared to ozonation [6, 56].
Balcı et al. discussed the effects of plasma and ozone treatments on silk in their
paper. In this study, raw and degummed silk fabrics are treated with low-frequency
oxygen plasma and ozone. The processes are applied to the fabrics individually and
alternately. According to the results, fabrics treated with ozone have more yellowing
index that of plasma treatment. Increasing the treatment time of plasma and ozona-
tion processes causes increase in yellowness and decrease in whiteness [57].
In this study, Perinçek et al. examined role of the fiber moisture, pH, and treat-
ment time during ozonation on the dyeing properties of Angora rabbit. It is observed
that ozonation increases the whiteness degree and dyeability property of the fibers.
Ozone oxidizes cysteine linkage in the surface of fiber to cysteic acid [6, 58].
Perinçek et al. combine ozone and ultrasound in their paper. First, Angora
rabbit fibers are bleached by ozonation. Then, treated fibers are dyed by the aid of
ultrasound. It is indicated that the ozonation and ultrasonic dyeing improves the
dyeability of Angora rabbit fiber considerably [59].
Atav and Yurdakul investigated the ozonation of mohair fibers. The optimum
conditions of ozonation process are W.P.V. 60%, pH 7, and 30 min. Dyeability of the
mohair fibers is improved by ozonation [6].
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Figure 6.
Steps of bleaching process [60] (1: ozonation + reductive bleaching, 2: ozonation + oxidative bleaching,
3: ozonation + oxidative bleaching + reductive bleaching).
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• lower water and chemical consumption and time loss of ozonation process than
conventional wet processes,
Limitations of ozone treatment [4, 5, 13, 14, 32, 74, 76, 77]:
• difficulty in using ozone gas due to suitability of textile finishing machine for
wet processes,
• except for stainless steel, corrosion in metal parts of finishing machine due to
high oxidation potential of ozone,
• needs regular monitoring and alarm system in the mill for any leakages, and
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Textile Industry and Environment
Author details
Ayşegül Körlü
Textile Engineering Department, Faculty of Engineering, Ege University,
Bornova-İzmir, Turkey
© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.
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DOI: http://dx.doi.org/10.5772/intechopen.81774
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