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Journal of Cleaner Production xxx (2014) 1e9

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Journal of Cleaner Production


journal homepage: www.elsevier.com/locate/jclepro

Combination of ozone and ultrasound in pretreatment of cotton


fabrics prior to natural dyeing
_
Hseyin Benli a, *, Muhammed Ibrahim
Bahtiyari b
a
b

lu Vocational School, Erciyes University, Kayseri, Turkey


Mustafa krkog
Department of Textile Engineering, Erciyes University, Kayseri, Turkey

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 9 April 2014
Received in revised form
31 October 2014
Accepted 1 November 2014
Available online xxx

In the study it was aimed to show an alternative nishing process for cotton fabrics. The fabrics were
pretreated with ozone and ultrasound combination instead of conventional energy intensive and
chemical based nishing processes. Moreover the coloration of the pretreated fabrics was conducted by
the use of plant based natural dyes. For this aim the extracts obtained from pomegranate peels, nutshell,
orange tree leaves and alkanet roots were used. By this way it was planned to introduce an environmentally friendly nishing for the cotton fabrics and at the same time the usability plantal wastes in
textile coloration processes were presented. It was observed that with the use of ozone gas and ultrasonic washing, sufcient pretreatment values with limited tensile losses could be obtained. Moreover it
was found that by the use of tested plantal wastes the coloration of cotton fabrics can be managed.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Cotton fabric
Ozone
Ultrasonic energy
Pretreatment
Natural dyes

1. Introduction
Cotton bers grow in the seed hair pod of cotton plants and
cultivated in warm climates (Needles, 1986). Pretreatment of the
cotton bers is required to remove natural and human-induced
impurities (Wakelyn et al., 2007). Conventional pretreatment processes such as desizing, scouring, bleaching and mercerization for
cotton fabrics consume enormous amounts of energy, water and
chemicals (Min and Huang, 1999). In addition, current pretreatment processes, using harsh chemicals and severe conditions, are
also problematic from an environmental point of view because of
the high COD, BOD, pH, and salt content in textile efuents and high
air pollution due to high energy consumption (Ibrahim et al., 2004).
In this respect, instead of conventional pretreatment processes
studies on environmentally friendly methods are of great
importance.
Ozone can be an alternative in terms of ecological demands. It is
a strong oxidizing agent, capable of participating in many chemical
reactions with inorganic and organic substances (Iglesias, 2002).
There is a lot of research papers published about use of ozone in the
textile wet processes. For instance, Both Prabaharan and Rao (2001)

* Corresponding author.
E-mail addresses: hbenli@erciyes.edu.tr, hbenli.2013@gmail.com (H. Benli).

and Perincek et al. (2007) reported the importance of moisture


amount and the pH of moisture during ozone bleaching of greige
cotton fabric and they showed the use of ozone in bleaching of
cotton fabrics. Atav and Yurdakul (2011) used ozone in order to
improve the dyeability of mohair bers. Likewise in another study
the effect of ozone on the whiteness degrees and dyeability of
Angora rabbit ber was investigated and it was found that by
ozonation the dyeability of angora bers has increased signicantly
after dyeing with milling type acid dyestuffs (Perincek et al., 2008).
The other environmentally friendlier alternative can be the use of
ultrasounds. Because ultrasound, and its benecial effects offer the
potential for shorter reaction cycles, cheaper reagents, and less
extreme physical conditions, leading to less expensive and,
perhaps, smaller plants (Vajnhandl and Le Marechal, 2005). Several
researchers have reported the usability of ultrasound in textile
processes. For example, Yachmenev et al. (2004) reported the
positive effect of ultrasonic energy for intensication of the cotton
bio-preparation and Hao et al. (2013) were studied the ultrasonic
effect on the desizing efciency of cotton fabrics. In another study,
the efciency of raw wool scouring process via ultrasound was
searched and the authors were reported benets of the use of ultrasound in wool scouring (Bahtiyari and Duran, 2013). Likewise
the positive effect of ultrasound in bleaching processes of cotton
lu, 2005) and wool (Bahtiyari et al., 2012) has
(Mistik and Ykselog
been reported too.

http://dx.doi.org/10.1016/j.jclepro.2014.11.007
0959-6526/ 2014 Elsevier Ltd. All rights reserved.

_ Combination of ozone and ultrasound in pretreatment of cotton fabrics prior to


Please cite this article in press as: Benli, H., Bahtiyari, M.I.,
natural dyeing, Journal of Cleaner Production (2014), http://dx.doi.org/10.1016/j.jclepro.2014.11.007

_ Bahtiyari / Journal of Cleaner Production xxx (2014) 1e9


H. Benli, M.I.

The dyeing of textiles can also cause environmental problems


too. Up to the end of the 19th century natural dyes were the main
colorants for textiles. But the introduction of synthetic dyes led to
an almost complete replacement of natural dyes due to the several
advantages such as wide range of available colors, higher reproducibility, improved quality and etc. (Bechtold et al., 2006). However almost all the synthetic colorants being synthesized from
petrochemical sources through hazardous chemical processes pose
threat towards its eco-friendliness (Samanta and Konar, 2011).
Generally, large volumes of wastewater, containing signicant
amounts of dyes and chemicals, are discharged from typical cotton
dye warehouse. Therefore, natural dyes are generally environmentally friendlier and have many advantages over synthetic dyes
(Kamel et al., 2009). Additionally different advantages of using
natural dyes sources have been studied recently. For example,
Baliarsingh et al. (2012), examined the solvent extraction of natural
dyes from two plant species called Saraca asoca and Albizia
lebbeck, and they have reported that the dyed silk displayed
excellent antimicrobial activity. Ghaheh et al. (2014) studied ve
different natural dyes obtained from green tea, madder, turmeric,
saffron petals, and henna they showed that all these natural dyes
could provide some antibacterial activity against Staphylococcus
aureus, Escherichia coli, and Pseudomonas aeruginosa bacteria on
wool fabric. In another study ultraviolet protective properties of the
fabrics dyed by Rheum and Lithospermum erythrorhizon were
investigated. This study has showed that some natural dyes have
got solar UV-protective properties (Feng et al., 2007). Hou et al.
(2013) were used orange peel extracts for dyeing of wool fabrics.
They have reported that orange peel extracts have great potential as
a natural textile dyestuff and could impart remarkable UVprotection properties. Besides this, studies on introduction of
different natural dye sources are popular too. For instance, Tutak
and Benli were studied the dyeing properties of the leaves, coat,
shell and dice of the hazelnut in coloration of wool, cotton and
viscose fabrics by using different mordants (Tutak and Benli, 2012).
In another study, the usability of green shell of almond fruit as a
novel natural dye was introduced by Erdem Ismal et al. (2014).
2. Methodology
In the light of the introduction part it is easy to talk about the
serious demand and studies on the environmentally friendly nishing of textile goods. As a result of this, the study was aimed to
develop an environmentally friendly textile nishing process. For
this aim, pretreatment of cotton was managed with the use of both
ozone gas-ultrasonic energy and further dyeing was conducted
with natural dyes obtained from plantal wastes such as; pomegranate peels, nutshell, orange tree leaves and alkanet roots as
schematized in Fig. 1.

the study grinded dried pomegranate peels were used as natural


dye source.
Nutshell: Turkey is the main hazelnut producer in the world,
contributing approximately 70% of the total global production
(Alasalvar et al., 2003). During the study grinded nutshell was used
as natural dye source.
Orange tree leaves: Oranges are grown in tropical and subtropical
climates throughout the world. Brazil and the United States are the
top-producing countries and Turkey is the other principal country
that grows oranges (Shultz, 2005). The dried orange tree leaves
from Turkey has been used as natural dye source.
Alkanet root: Alkanet (Alkanna tinctoria) belongs to the family
Borginaceae. The roots, which are often very large in proportion to
the size of the plant, yield in many of the species a red dye. The
main pigment is alkannin, which was earlier called anchusin
(Rekaby et al., 2009). During the study grinded root of alkanet was
used as natural dye source.
2.1.2. Equipments
During the study ozone generator and ultrasonic bath used to
remove noncellulosics matter on the raw cotton and pretreatment
of it. The capacity of the ozone generator (ProdOzon) is 25 g/h. The
ozone gas ow was maintained at a constant rate of 5 L/min for the
all experiments. An ultrasonic bath (Wiseclean) with a volume of
2 L in 28 KHz frequency was used for ultrasonic treatment. Meanwhile to obtain dyes from the natural dye sources a soxhlet based
system has been equipped.
2.2. Methods
Conventional pretreatment method: Firstly, greige cotton fabrics were pretreated conventionally with the recipes shown in
Table 1.
Instead of the conventional pretreatment processes, the fabrics
were also pretreated with the aid of ozone and ultrasound. These
processes were called as environmentally friendly pretreatment
methods in the study.
Environmentally friendly pretreatment method: The aim of this
study is to show the usability of ozone gas and ultrasound as pretreatment of cotton fabric prior to natural dyeing without mordant.
All samples were dried in room temperature before testing.
Ozone and ultrasound has been applied to the fabrics step by
step. In the rst application step the wetted fabrics were treated
directly with ozone gas for 15 min in a closed system. It is well

2.1. Materials
2.1.1. Fabric and the natural dye sources
In the study 100% woven, starch sized cotton fabric with a
weight of 200 g/m2 was used for experiments.
For the coloration of the fabrics pomegranate peels, nutshell,
orange tree leaves and alkanet roots were used:
Pomegranate peels: Pomegranate is native to Western Asia, most
likely from Iran, Northeastern Turkey and the region of the South
Caspian Sea. It has been cultivated from early antiquity for its
valuable fruit throughout the Mediterranean and North African
regions, including Central Saharan oases (Bruni et al., 2011). The
major coloring component in pomegranate is tannins, ellagic acid,
extracted from the fresh and dried peels (Adeel et al., 2009). During

Fig. 1. The schema of the proposed green process line.

_ Combination of ozone and ultrasound in pretreatment of cotton fabrics prior to


Please cite this article in press as: Benli, H., Bahtiyari, M.I.,
natural dyeing, Journal of Cleaner Production (2014), http://dx.doi.org/10.1016/j.jclepro.2014.11.007

_ Bahtiyari / Journal of Cleaner Production xxx (2014) 1e9


H. Benli, M.I.
Table 1
Conventional pretreatment of cotton fabrics.
Conventional Enzyme/
pretreatment Chemical
Desizing

Scouring

Bleaching

a-amilaze
Nonionic
wetting
agent
NaOH
Na2CO3
Nonionic
wetting
agent
H2O2 (%35)
NaOH
Stabilizator

Table 3
The properties of the fabrics after conventional pretreatment processes.

Quantity Liquor pH
ratio

Temperature Duration
( C)
(min)

5 g/L
1 g/L

1:20

60

60

%2
%2
1 g/L

1:20

10.5e11 95

60

5 mL/L
1.2 g/L
0.8 g/L

1:20

10e11

95

Breaking force (N)


Desizing degree
Hydrophility (mm/90 s)
Whiteness degree (stensby)

60

known in literature that wetting prior to ozonation has a great


importance in terms of ozone efciency (Perincek et al., 2007).
Because of this and in the light of our studies the fabrics were
wetted with fty per cent of water (w/w) at pH7 before ozonation.
After ozonation the same sample were exposed to washing with
ultrasound for 5 min at 40  C and no chemical was used during the
washing. These two stepped based OzoneeUltrasound combination was applied repetitively for the same sample and each repeat
was called as passage in the study. In Table 2 the passage numbers
and application duration of ozone ultrasound has been illustrated.
The pretreatment processes, both conventional and environmentally friendly methods were analyzed in terms of, water absorbencies, desizing and whiteness degrees etc. For this aim, the
desizing degrees of the fabrics were collected by dripping iodine/
potassium iodide solution onto the different areas of the fabric
samples as a starch sizing indicator, and comparing the color iodine
gave as a result of the reaction with starch with the Tegewa scale.
Then hydrophility of the fabrics were analyzed by the vertical
wicking of fabrics in warp direction and determining the rising
height (mm) according to DIN 53924 (1997) and nally the
whiteness degrees of fabrics according to the Stensby formula were
collected in a Minolta 3600 d Model Spectrophotometer. Moreover
for the evaluation of the breaking force of warp yarns during the
pretreatment, the fabrics were tested according to ISO 2062 in
Instron 4411 testing device and some selected fabrics FTIR measurement with Perkin Elmer Spectrum 400 and surfaces with
Scanning electron microscopy with LEO 440 instrument were
analyzed too. Dyeability of the fabrics was investigated, as well. For
environmentally friendly process, the treated samples were dyed
with four different natural dyes without mordant.

Table 2
Application of ozoneeultrasound combination in pretreatment of the cotton fabrics.
Passage no

ATO
ATU
ATO
ATU
ATO
ATU
ATO
ATU
ATO
ATU
ATO
ATU

15
5
e
e
e
e
e
e
e
e
e
e

15
5
15
5
e
e
e
e
e
e
e
e

15
5
15
5
15
5
e
e
e
e
e
e

15
5
15
5
15
5
15
5
e
e
e
e

15
5
15
5
15
5
15
5
15
5
e
e

15
5
15
5
15
5
15
5
15
5
15
5

ATO: Application duration of ozone gas (min).


ATU: Application duration of ultrasonic washing (min).

Untreated
fabric

Desized
fabric

Scoured
fabric

Bleached
fabric

4.9
1
0
52.0

4.30
5
10
56.7

4.03
7
16
58.2

3.80
8
23
77.2

Natural Dyeing procedure: The pretreated fabrics were dyed


with four different natural dyes obtained from pomegranate peels,
nutshell, orange tree leaves and alkanet roots.
5 g of these four different dye sources were taken into extraction
cycle. In the extraction equipment the base of dye was extracted by
water. Afterwards, from the obtained aqueous solutions, 100 mL
concentrate dye solution was prepared by evaporation of water for
each dye extract.
Dyeing was managed by the use of this extract as a dye bath
without addition of any chemical. The liquor ratio (liquor-to-goods
ratio) was arranged to 20:1. During the dyeing, bath containing
fabric has been heated to 100  C and at this temperature the process was carried out for 60 min. After that the bath has been cooled
and the fabrics were rinsed and then hot washed with a washing
agent for 15 min subsequently, warm and cold rinses were
managed too.
The dyed fabrics were then evaluated in terms of color efciencies (K/S) and CIE L*a*b* color space values by using Konica
Minolta 3600 d spectrophotometer (D65/10 ). The washing fastness with ISO 105-C10 standard in test condition of Test A (1) (ISO
105-C10, 2006), light fastness with ISO 105-B02 standard (ISO 105B02, 1994), rubbing fastness with ISO 105-X12 standard (ISO 105X12, 1993) and perspiration fastness with ISO 105-E04 standard
(ISO 105-E04, 1994) of the dyed samples were also tested too.
3. Results and discussion
Evaluation of pretreatment efciencies of different methods
Pretreatment is an essential step for the fabrics prior to use.
Especially before dyeing or printing processes the fabrics should be
ready and have enough hydrophility and whitenesses. Conventionally it has been managed by desizing, scouring and bleaching of
the fabrics. These separate processes are generally combined in
textile miles. But in the study these processes have been managed
separately to show the effect of each step.
As seen from Table 3, the tensile losses are increasing after each
pretreatment process and nally after bleaching, the breaking force
has been found as 3.8 N. Meanwhile the desizing degree was 8
which has been increased especially after desizing process. Scouring process has also increased the desizing degree and signicantly
the hydrophility of the fabric but the whiteness of the fabric was
still not increased remarkably till the bleaching process. Hence,
after bleaching the fabric has reached the highest hydrophility
(23mm/90 s), desizing degree and whiteness degree (77 stensby)
which are acceptable values for pretreatment of greige cotton,
before dyeing. These results obtained from the conventional pretreatment processes were then used for the comparison of the results
obtained
from
the
ozoneeultrasound
combined
environmentally friendly pretreatment process. For this aim the
fabrics were treated as detailed in Table 2. After each ozoneeultrasound cycle which was called as passage the properties of the
fabrics were collected and illustrated in Table 4.
The combination of ozoneeultrasound which is introduced as
an environmentally friendly pretreatment process in the paper has

_ Combination of ozone and ultrasound in pretreatment of cotton fabrics prior to


Please cite this article in press as: Benli, H., Bahtiyari, M.I.,
natural dyeing, Journal of Cleaner Production (2014), http://dx.doi.org/10.1016/j.jclepro.2014.11.007

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H. Benli, M.I.

Table 4
The properties of the fabrics after combined ozoneeultrasound applications.
Untreated
fabric

Ozoneeultrasound combination
based treatment (passage number)
1

Breaking force (N)


Desizing
degree
Hydrophility
(mm/90 s)
Whiteness
degree (stensby)
Weight loss (%)

4.9
1
0
52.0
e

2
4.43
3

3
4.34
4

4
4.30
4

5
4.29
5

6
4.16
5

4.00
6

15

18

20

22

22

23

64.3

67.0

69.8

72.8

72.5

72.4

1.13

1.71

2.37

2.84

3.01

3.11

found as an alternative for the conventional pretreatment processes. Each ozoneeultrasound combination passage lasted 20 min
(15 min ozonation 5 min ultrasonic washing) and after each
passage the obtained pretreatment values increased with the increase in the strength loss. This increase is more dominant in
whiteness degrees. For example after rst passage the whiteness of
the fabric has raised to 64.3 stensby from the 52 stensby and after
4th passage 72.8 stensby degree has been achieved which was not
changed after subsequent passages (5th and 6th passages). Likewise the increase in hydrophility and desizing degrees has optimally obtained after 4th passage. The desizing degree was 5 after
4th passage but applying two more ozoneeultrasound cycle did not
cause a signicant increase in desizing degree. This is valid in
hydrophility values too. For example the hydrophility of the fabric
after 4th passage was 22 mm/90 s and after 6th passage it was
23mm/90 s however the strength losses were signicant and while
the fabric after 4th passage has 4.29 N of breaking force, after 6th
passage it was 4 N and nearly %7 strength loss has been occurred.
Similar trend has been seen in weight loss values too. Hence in
terms of pretreatment efciencies, the four passage of ozoneeultrasound combination was selected as an optimized environmentally friendly pretreatment process. These obtained values
were showed that with this kind of process the cotton fabrics'
pretreatment can be managed but the pretreatment results were
limited when compared with one obtained after the conventional
process. On the other hand the strength losses of the fabrics were

lower if the environmentally friendly pretreatment process used in


stead of conventional one. Additionally the water and energy
consumptions were limited in this kind of environmentally friendly
pretreatment process.
To compare the effects of the conventional and environmentally
friendly pretreatment processes, the surface photographs with SEM
and FTIRs of the samples were investigated too.
The infrared band assignments for untreated and bleached
fabrics were illustrated in Fig. 2. For the evaluation of the effect of
the environmentally friendly pretreatment process, samples after
4th passage have been examined in FTIR analysis. In general, no
signicant differences were observed between the samples. For
example, the peat at 895 cm1 which is related with asymmetric
out-of-phase ring stretch: C1eOeC4; b glucosidic bond (Chung
et al., 2004) did not change after pretreatment processes. In literature some bands related to the chemical structure of cellulose
were listed like this; the hydrogen-bonded OH stretching at
3550e3100 cm1, the CH stretching at 2800e3000 cm1, (Chung
et al., 2004) the asymmetrical COOe stretching at 1617 cm1 and
the CH wagging at 1316 cm1 (Wang et al., 2006). When the spectra
of the samples were examined in the light of this information, it can
be told that after both pretreatment methods the peaks at 3336 and
3280 cm1 corresponding to hydrogen bonded OH stretching,
2899 cm1 corresponding to the CH stretching and 1315 cm1
corresponding to the CH wagging did not change signicantly. On
the other hand, the wide peak at 1602 cm1 was shifted to around
1630 cm1 and the %T of the peak increased after conventional
pretreatment process. This shift in the peaks can be related with the
cleaning of the cotton with pretreatment processes because the
peak at 1600 cm1 was introduced as caused from the impurities
such as waxes and pectins (Chung et al., 2004). Likewise the slight
peak at 1738 cm1 was assumed as related with the presence of the
carboxylic ester in pectins and waxes (Wang et al., 2006). This slight
peak has been completely lost after pretreatment processes too. As
a result, it can be told that after pretreatment processes the fabrics
were cleaned meanwhile no signicant chemical changes were
occurred. The SEM photographs of the samples were also
conrmed this argument. As seen from the Fig. 3, the ber surface
of the untreated fabric become smooth and clean after pretreatment processes. Also in some bers some surface modications
occurred too.

Fig. 2. FTIR analysis of the untreated and pretreated fabrics.

_ Combination of ozone and ultrasound in pretreatment of cotton fabrics prior to


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natural dyeing, Journal of Cleaner Production (2014), http://dx.doi.org/10.1016/j.jclepro.2014.11.007

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H. Benli, M.I.

Fig. 3. SEM photographs of the untreated and pretreated fabrics.


Evaluation of natural dyeing process

In the second part of the study the differently pretreated fabrics


were dyed with natural dye sources. It was planned to show the
usability of the ozoneeultrasound combination as an environmentally friendly pretreatment for the fabrics to be dyed. For this
aim four different natural dye sources were selected as detailed in
experimental part and their extracts were use as natural dyes. Beside to show the applicability of the environmentally friendly
pretreatment process and usability of natural dyes it was also
planned to introduce a process line containing ozone, ultrasound
and natural dyes in which water, chemical and energy consumption
was limited and in which only natural chemicals were used.
The dyeing afnity of textile materials is generally dependent on
the content and type/polarity of functional groups of bers. It is
well known that the number of functional group in wool is larger
than that of silk, and polarity of protein bers is higher than that of
cellulose ber (Lee et al., 2010). As a result bers can present
different opportunities during dyeing with natural dye sources. To
investigate this, rstly the color efciencies of the fabrics dyed with
different natural dye sources were analyzed.
To investigate the environmentally friendly pretreatment conditions on the dyeing of the after dyeing of the fabrics the color
values and efciencies were analyzed. It was observed that all
tested natural dye source can be alternative for the dyeing of the
wool. It was also seen that the color efciencies of the dyed samples
can vary with the use of the different natural dye source even in the
same dye extract concentration too. Independent of the applied
pretreatment process, the color efciencies (K/S) of the samples has
increased in such an order: orange tree leaves < nutshell < alkanet
root < pomegranate peel. However it is easy to change color efciencies by varying colorant concentration used in dyeing process.
The highest color efciency was obtained with the use of
pomegranate peels in dyeing of cotton. When the fabrics, differently pretreated, has examined in terms of color efciencies, It was
found that the color efciencies of the fabrics environmentally
friendly pretreated have higher color efciencies if the passage
number is low than four. In other words after 4th passage the color

efciency was 5.38 while it was 4.55 in conventionally pretreated


fabrics. However the color efciencies after 5th and 6th passages,
was lowered to 3.08, 3.64 respectively. Finally it can be told that
with an environmentally friendly pretreatment process after 4th
passage sufcient hydrophility, desizing degree, whiteness and
limited strength loss can be obtained. Moreover with the use of
pomegranate peels in dyeing higher color efciencies can be obtained when compared with the conventional pretreatment
process.
The obtained color with the use of pomegranate peels was
showed in Table 5. The CIE L*a*b* values were also examined. In CIE
L*a*b* space, L* indicates the lightness; the perfect reecting
diffuser has L* 100 and the perfect black has L* 0. The colors
with a* > 0 represent redness and with a* < 0 greenness; b* > 0
means yellowness and b* < 0 blueness (Smith, 1997). In the light of
this it can be told that light brown colors can be obtained with the
use of pomegranate peels with different shades depending on the
applied pretreatment process. For example, via the equation (1) the
color difference (DE) between the fabrics conventionally pretreated
and environmentally friendly pretreated with ozoneeultrasound
four times was calculated 4.49. It means that this two obtained
color has high color difference and the color conventionally pretreated and dyed one is lighter because of higher L* value and has
lower yellow shade because of the lower b* value (Smith, 1997).

DE

h

DL*

2


2 
2 i1=2
Da* Db*

(1)

DL* L* conventional  L* environmentally friendly; Da* a*


conventional  a* environmentally friendly; Db* b*
conventional  b* environmentally friendly.
The lowest color efciency was seen from the fabrics dyed with
orange tree leaves and in those fabrics also the highest L* values
were obtained too. The color of the dyed fabrics can be dened as
beige as seen from the Table 5. Depending on the applied pretreatment type the obtained colors were also changed in orange

_ Combination of ozone and ultrasound in pretreatment of cotton fabrics prior to


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natural dyeing, Journal of Cleaner Production (2014), http://dx.doi.org/10.1016/j.jclepro.2014.11.007

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Table 5
Color efciencies (K/S) and CIE L*a*b* color space values of samples via photograph.

tree leave based dyeings too. Up to the 5th passage the environmentally friendly pretreated and then dyed fabrics have provided
higher color efciencies than the fabrics conventionally pretreated
and dyed. For instance the fabric conventionally pretreated and
dyed one has 0.55 K/S value. It was 0.65 if the fabric has pretreated
with ozoneeultrasound combination cycle four times. Meanwhile
the color difference between the fabrics was 1.51. The fabric dyed
after 4th passage of environmentally friendly pretreatment redder
and a bit more yellow when compared with the fabric conventionally pretreated and dyed because of the higher a* and b* values.

The highest effect of pretreatment process type was occurred in


dyeings with alkanet root extracts. Because the highest color differences were come across between conventionally and environmentally friendly pretreated fabrics after dyeing with alkanet root
extracts. For example the fabric dyed after 4th passage of ozoneeultrasound combination was darker (L* 55.49) when compared
with the one conventionally pretreated and then dyed sample
(L* 69.41). The color difference between these two samples was
also high too (DE 14.2) but in general the color of the samples was
in khaki shade. On the other hand in terms of color efciencies in all

_ Combination of ozone and ultrasound in pretreatment of cotton fabrics prior to


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natural dyeing, Journal of Cleaner Production (2014), http://dx.doi.org/10.1016/j.jclepro.2014.11.007

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environmentally friendly pretreatment processes the obtained color efciencies after dyeing with alkanet root extracts were higher
than the fabrics conventionally pretreated and dyed.
Nutshell extracts were the other dye source for the dyeing of
cotton. It was observed that rosy brown colors can be obtained by
the use of these extract (Table 5). The color efciency of the sample
conventionally pretreated and then dyed was 0.85. On the other
hand ozoneeultrasound based pretreatment cause different color
efciencies after dyeing with change of passage number. In general
the color efciencies were reduced with the increase in the ozoneeultrasound cycle. For example after 4th passage, which was
found as an optimum application cycle in terms of pretreatment
results, the color efciency was 0.7 after dyeing with nutshell
extract. Meanwhile the color difference between the dyed fabrics
conventionally pretreated and four times treated with ozoneeultrasound cycle was 3.9. Ozoneeultrasound application can be
applied in different number of passages as detailed in Table 2 so
instead of 4th passage, 5th passage ozoneeultrasound treatment
could be an alternative to the conventionally pretreatment. In that
case, closer results between conventional and environmentally
friendly pretreated fabrics could be obtained (DE was 1.3).
In general it can be easily said that no signicant differences
were available between the fabrics differently pretreated. The results indicate fair to good fastness properties of the dyed samples
using both the ozonation and ultrasound methods. Beside the effect
of the different pretreatment processes the different dye sources
have more dominant effect on the obtained fastness results.
Washing fastness of cotton fabrics that dyed after conventional
pretreatment methods had moderate to good staining and alteration rates. The values were between 3 and 5 point. Similarly, the
washing fastness of cotton fabrics dyed after environmentally
friendly methods were also good too. For example 4 to 5 point has
been obtained. Among conventional and environmentally friendly
methods there was not any different in terms of washing fastness
properties.
Dry and wet rubbing fastnesses of cotton fabrics that dyed after
conventional pretreatment methods were good; the rates were

between 4 and 5 point. Similarly, the dry and wet rubbing fastness
of cotton fabrics dyed after environmentally friendly methods were
also good too. Rates were between 4 and 5 point. Hence it can be
easily told that between conventional and environmentally friendly
methods there was not any different in terms of rubbing fastness
properties (Table 6).
Acidic and alkaline perspiration color fastness of cotton fabrics
dyed after conventional pretreatment and environmentally
friendly methods had moderate to good staining and alteration
with rates between 4/5 and 5 point. Among conventional and
environmentally friendly methods there was not any difference in
terms of acidic and alkaline perspiration color fastness values.
Light fastness of many natural dyes, particularly which are
extracted from ower petals are found to be poor to medium
(Samanta and Agarwal, 2009) and nearly all natural dyes fade after
exposure to daylight (Padeld and Landi, 1966). This is the signicant drawback of the natural dyes and usability. Many papers
indicated that some natural dyes had poor light fastness values.
There are also studies to increase the light fastness of the fabrics
dyed with natural dyes. So light fastness of fabrics dyed with
natural dyes is an important parameter too. The light fastnesses of
cotton fabrics that dyed after conventional pretreatment methods
had poor to moderate rates. Fabrics dyed with pomegranate peel,
nutshell, orange tree leaves and alkanet root extracts have showed
light fastness values of 6, 3, 2 and 2 respectively. Among them the
lowest light fastness value was obtained from the alkanet, the
fastness was between 2 and 3 point. The results have not changed
for both conventional and environmentally friendly methods. At
the same time, values of light fastness of cotton fabrics that dyed
with orange tree leaves were 2 point, too. This was valid after
dyeing with nutshell too. The best light fastness value was obtained from the fabrics dyed with pomegranate peel extracts. Results of the all fabrics that dyed with pomegranate bark had 6
point. So in the dyeing with pomegranate peels the obtained
fastnesses were generally good which was showing also the usability of these dye source without need of any mordanting or any
process.

Table 6
Color fastness properties of sample.
Pomegranate fruit peel
Washing

Nutshell

Rubbing

Perspiration
Acidic

Con. pret.
Passage no

1
2
3
4
5
6

Light

Alt.

Wet

Dry

Sta.

Alt.

Sta.

Alt.

5
5
5
5
4/5
5
4/5

3
4
4
4/5
4/5
4
4

5
5
5
5
5
4/5
5

4
4/5
4/5
4/5
4/5
4/5
4

4/5
4/5
4/5
4/5
4/5
4/5
4/5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

4/5
5
5
4/5
4/5
4/5
4/5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

Light
Alkaline

Alt.

Wet

Dry

Sta.

Alt.

Sta.

Alt.

6
6
6
6
6
6
6

5
5
4/5
5
5
5
5

5
5
5
5
4/5
4/5
5

4/5
4/5
4/5
4/5
5
5
4/5

4/5
4/5
4/5
4/5
4
4/5
4/5

5
5
5
5
5
5
4/5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

5
4/5
5
5
5
5
5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

Light

Washing

3
2
2
2
2
2
2

Alkanet root

Rubbing

Perspiration
Acidic

1
2
3
4
5
6

Perspiration

Sta.

Orange tree leaves

Con. pret.
Passage no

Rubbing

Acidic

Sta.

Washing

Washing

Alkaline

Rubbing

Perspiration

Alkaline

Acidic

Sta.

Alt.

Wet

Dry

Sta.

Alt.

Sta.

Alt.

5
5
5
5
5
4/5
5

4
4
4
4/5
5
4
4

5
5
5
5
5
5
5

4/5
4
4/5
4
4/5
4
4/5

5
5
5
5
5
5
5

4/5
4/5
4/5
4/5
4/5
5
4/5

5
5
5
4/5
5
5
5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

2
2
2
2
2
2
2

Light
Alkaline

Sta.

Alt.

Wet

Dry

Sta.

Alt.

Sta.

Alt.

5
4/5
5
5
5
5
4/5

3
4
4
4
4
4
4

4/5
5
5
5
5
5
5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

5
5
4/5
5
5
5
4/5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

4/5
4/5
4/5
5
4/5
4/5
5

4/5
4/5
4/5
4/5
4/5
4/5
4/5

2
3
3
3
3
2/3
2/3

Sta.: Staining on cotton; Alt.: Alteration; Con. pret.: Conventionally pretreated.

_ Combination of ozone and ultrasound in pretreatment of cotton fabrics prior to


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H. Benli, M.I.

4. Conclusions
This study was focused on the applicability of ozone, ultrasound
and natural dyes to introduce an environmentally friendly process
for the cotton fabrics. It is easy to nd studies on the use of ozone,
ultrasound and natural dyes however detailed studies on the
combination of these items were inadequate. As a result, this study
is hoped to be attractive for the textile nishers as well scientists
focused on ecologic methods. Especially the ozoneeultrasound
application by cycles will be a novel approach for the use of these
technologies and it is predicted that these combinations will lead to
alternative ecologic processes in textile nishing.
Conventionally the nishing of textiles needs of chemicals,
water and energy, however in the study the cotton fabrics were
pretreated with ozone gas and subsequently rinsed with only water
via ultrasound. By this way it was planned to minimize use of
chemicals and water meanwhile during this process the ambient
temperature was lowered when compared with the conventional
pretreatment process. So addition to chemical and water savings
heat energy consumption was limited too. The combined ozoneeultrasound application exhibited nearly similar desizing, hydrophility, whiteness degrees with the conventional pretreatment
process. The tensile loss was also found limited if the combined
ozoneeultrasound application was used instead of conventional
pretreatment process.
The coloration of textile materials is also an important textile
nishing process. For this aim today synthetic dyes have been
widely used in comparison to natural dyes, however when
compared with synthetic dyes, natural dyes are mostly ecofriendly, less toxic, and less allergenic (Mirjalili et al., 2011). In
this study, after combined ozoneeultrasound application, cotton
fabrics were dyed with natural dye sources. During the dyeing
process no mordanting was conducted because of environmental
aspects. The natural dyes used were extracted by soxhlet apparatus
from pomegranate peels, nutshell, orange tree leaves and alkanet
roots, which are generally seen as plantal wastes. It was found that
these extracts could be use for the coloration of the cotton fabrics
and different colors and shades can be obtained by changing the
natural dye source. Meanwhile except light fastness, the fastnesses
of the all dyed samples were good and sufcient for the use. The
light fastnesses of the samples dyed with nutshell, orange tree
leaves and alkanet roots were found limited while it was sufcient
in the dyeing with pomegranate peels. As a summary, It was seen
that ozoneeultrasound can be used for the pretreatment of cotton
and natural dye based coloring can be a way for the coloration of
the cotton fabrics. It is estimated that these methods with simple
changes can be applied to the nishing of different bers such as
linen, wool, jute etc. Hence for further studies it is highly recommended to investigate of these methods for different bers maybe
with different natural dye sources.
Acknowledgment
This work was supported by the Research Fund of Erciyes University. Project Number: FDK-2014-5156.
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