ORIGINAL PAPER
Use of ultrasound in biopreparation and natural dyeingof cotton fabric in a single bath
Huseyin Benli • Muhammed Ibrahim Bahtiyari
Received: 11 July 2014 / Accepted: 30 October 2014 / Published online: 21 November 2014
� Springer Science+Business Media Dordrecht 2014
Abstract Use of enzymes in different parts of textile
finishing processes has become popular, and several
enzymes have been introduced into the textile indus-
try. This study aimed to carry out the whole fabric
pretreatment process in a single bath containing
different enzymes. Ultrasonic cavitation was also
tested to show its effect on enzyme-based finishing of
cotton fabric. After optimization of the enzyme-based
ultrasound-aided finishing, the fabrics were also
colored in the same bath using natural dyes of
pomegranate peel, nutshell, orange tree leaf, and
alkanet root. Finally, it was observed that ultrasound-
aided biopreparation of cotton fabric could provide
sufficient pretreatment results. Coloration of these
fabrics could be achieved with the use of natural dyes
in the same bath as biopreparation.
Keywords Cotton fabric � Ultrasonic energy �Pretreatment � Enzyme � Biopreparation �Natural dyes
Introduction
The textile industry is the second largest in the world,
consuming at least 10 % of the world’s productive
energy. In addition to this energy consumption, water
has been used during the relevant production processes
since ancient times for several aims such as cleaning,
dyeing, rinsing, etc. (Moore and Ausley 2004). Today,
environmentally friendly processes are becoming
increasingly popular. Thus, application of biotechnol-
ogy to textile finishing is an example of the develop-
ment of more environmentally compatible processes
(Aly et al. 2004).
Use of amylase enzymes is one of the oldest
enzyme applications in the textile industry, being
applied for removal of starch sizes (Anis et al. 2008).
In addition to amylase enzymes, other enzymes have
also been introduced into textile finishing; for exam-
ple, b-D-glucose:oxygen 1-oxidoreductase enzyme
catalyzes oxidation of b-D-glucose to gluconic acid
by utilizing molecular oxygen as an electron acceptor
with simultaneous production of hydrogen peroxide
(Bankar et al. 2009). Saravanan et al. (2010) used this
enzyme to convert glucose to hydrogen peroxide and
showed the importance of agitation and oxygen supply
for fabric whiteness (Saravanan et al. 2010). In
another study, they also reported that the conversion
of glucose to hydrogen peroxide was influenced by the
aeration of the reaction bath and the concentration of
the glucose oxidase enzyme (Saravanan et al. 2012).
Another important enzyme studied for application in
H. Benli (&)
Mustafa Cıkrıkcıoglu Vocational School,
Erciyes University, Kayseri, Turkey
e-mail: [email protected]
M. I. Bahtiyari
Department of Textile Engineering, Erciyes University,
Kayseri, Turkey
123
Cellulose (2015) 22:867–877
DOI 10.1007/s10570-014-0494-x
textile finishing is pectinase. Alkaline pectinase
enzymes are the most important industrial enzymes,
having wide-ranging applications. They can be used in
textile processing, degumming of plant bast fibers,
treatment of pectic wastewater, paper-making, and
coffee and tea fermentation (Hoondal et al. 2002).
Pectinase enzymes have been used in scouring of
cotton to promote absorbency (Etters et al. 1999)
without any negative side-effects in terms of cellulose
degradation (Jayani et al. 2005).
Beyond the application of enzymes, the combina-
tion with ultrasound energy has also been tested, and
the advantages of the use of ultrasound during
enzymatic finishing processes have been reported
before; for example, Karaboga et al. (2007) deter-
mined that ultrasound-based desizing with amylase
and scouring with pectinase ensured distinctively
improved pretreatment results compared with pro-
cessing without ultrasound. Ultrasound produces
chemical effects through several different physical
mechanisms, with the most important nonlinear
acoustic process in such sonochemistry being cavita-
tion (Vajnhandl and Le Marechal 2005). The cavita-
tion phenomenon of bubble formation and collapse is
generated by ultrasonic waves. It is generally consid-
ered as being responsible for most of the effects of
ultrasound observed in solid–liquid or liquid–liquid
systems (Vouters et al. 2004).
In this work, fabric treated enzymatically with or
without ultrasound was colored using natural dyes. It
is known that there is growing interest in application of
natural dyes for natural fibers due to worldwide
environmental awareness (Samanta and Agarwal
2009). Natural dyes have mainly been used for
coloring of food substrates, leather, wool, silk, and
cotton since prehistoric times (Samanta and Agarwal
2009). They are derived from naturally occurring
sources such as plant, insect, and mineral extracts.
Moreover, these sources are believed to be safe
because of their nontoxic, noncarcinogenic, and
biodegradable nature. So, natural dyes do not cause
pollution or wastewater problems (Ali et al. 2009). In
this study, pomegranate peel, nutshell, orange tree
leaf, and alkanet root were used as natural dyes.
Pomegranate is native to Western Asia, most likely
from Iran, northeastern Turkey, and the region of the
south Caspian Sea (Bruni et al. 2011). The major
coloring components in pomegranate are tannins and
ellagic acid, extracted from fresh and dried peel
(Adeel et al. 2009). Turkey is the main hazelnut
producer in the world, contributing approximately
70 % of total global production (Alasalvar et al.
2003). The leaf, coat, shell, and dice of the hazelnut
have been tested previously for coloration of wool,
cotton, and viscose fabrics (Tutak and Benli 2012).
Alkanet (Alkanna tinctoria) belongs to the family
Boraginaceae. The roots of many species, which are
often very large in proportion to the size of the plant,
yield red dye. The main pigment is alkannin, previ-
ously called anchusin (Rekaby et al. 2009). The other
tested natural dye was orange tree leaf. Bahtiyari and
Benli (2012) declared the usability of orange tree leaf
for coloration of viscose fabrics.
Materials and methods
The aim of this study is to show the usability of the
enzyme–ultrasound combination for pretreatment of
cotton fabric prior to natural dyeing without mordant.
Accordingly, enzymes were used in an ultrasonic bath
to remove noncellulosic matter from raw cotton. The
aim was to achieve the whole finishing process of
cotton in the same bath.
Materials
Fabric, enzymes, and natural dyes
Starch-sized cotton fabric (100 % woven) with weight
of 200 g/m2 was used for the experiments. The
enzymes used for biopreparation of the cotton fabric
were glucoamylase enzyme (Novozyme), alkali pec-
tinase enzyme (Rudolf Duraner), and glucose oxidase
enzyme (Muhlenchemie).
Powders from dried and milled pomegranate peel,
nutshell, orange tree leaf, and alkanet root were
directly added to the dyeing bath as a kind of natural
dyestuff for coloration of the fabrics. They were
cultivated in Anatolian region and obtained from local
markets in Turkey.
Equipment
An ultrasonic bath (Elmasonic S15H) with volume of
1 L and frequency of 37 kHz was used for finishing of
cotton fabric for the processes both with and without
ultrasound assistance.
868 Cellulose (2015) 22:867–877
123
Throughout the study, the fabrics were submerged in
the bath as shown in Fig. 1, moving semicontinuously
like an endless conveyor with velocity of 1 cm/min.
This movement was achieved manually. So, the
submerged fabric stood still for a while and was then
moved by hand to change the position of the fabric in
the bath. This motion was conducted repetitively, with a
final velocity of 1 cm/min being ensured.
Methods
The study was conducted in two steps. First, optimi-
zation of the enzyme-based pretreatment was carried
out using processes both with and without ultrasound
assistance. In the second step, dyeing with the four
different natural dyes was carried out in the same bath
as the optimized bioscouring process.
Optimization of cotton biopreparation
During these studies, the enzyme concentrations were
adjusted to 1 % glucoamylase, 5 % pectinase, and 5 %
glucose oxidase in the same bath containing 1 mL/L
nonionic wetting agent. The pH and temperature for
enzyme application were 7 and 50 �C, respectively.
The liquor ratio (goods-to-liquor ratio) was fixed at
1:100.
The duration of the enzymatic processes was varied
from 15 to 120 min as shown in Fig. 2. In this way, it
was planned to optimize the biopreparation period
before combination with dyeing. After the enzymatic
process at 50 �C, the temperature of the bath was
increased to 80 �C and the pH was adjusted to 7 or 12
for decomposition of the generated hydrogen peroxide
(Fig. 2). These different enzyme applications were
carried out in systems both with and without ultra-
sound assistance, as shown in Fig. 1.
The differently pretreated fabrics were then ana-
lyzed in terms of tensile strength, water absorbency,
desizing, and whiteness degree. The desizing degree
of the fabrics was obtained using the Tegewa scale
after dripping iodine/potassium iodide solution onto
different areas of the fabric. On the Tegewa scale, 1
is the lowest rating, indicating the presence of starch
size on fabric, whereas 9 is the highest rating,
indicating perfect desizing (Eren and Ozturk 2011).
The hydrophilicity of the fabrics was analyzed
according to DIN 53924 (1997), and the vertical
wicking in the warp direction after 90 s was
collected. The whiteness degree of fabrics was
measured using a Minolta model 3600d spectropho-
tometer according to the Stensby formula. Breaking
force of warp yarns was measured using an In-
stron 4411 testing device according to ISO 2062
(2009). Fourier-transform infrared (FTIR) spectros-
copy (Spectrum 400; PerkinElmer) and scanning
electron microscopy (LEO 440) results were ana-
lyzed for some selected fabrics.
Natural dyeing of cotton fabric
The bio-pretreated fabrics were dyed with four
different natural dyes obtained from pomegranate
peel, nutshell, orange tree leaf, and alkanet root.
Dyeing was carried out in the same bath after
biopreparation of cotton fabric, as shown in Fig. 3.
All applications were performed in a single bath in
which the pH was 7. In the biopreparation step, fabrics
were first treated enzymatically at 50 �C for 60 min,
then the bath was heated to 80 �C and the fabrics were
treated for 30 min at this temperature. Subsequently,
dye powder was added to the same bath and dyeing of
the fabrics was conducted at 80 �C for 60 min (natural
dyeing step).
Four grams of dried milled pomegranate peel,
nutshell, orange tree leaf, or alkanet root was added
directly to the bath with volume of 400 mL. Dyeing
was carried out with and without ultrasonic energy in
the same bath after pretreatment without use of any
Ultrasonic tank
Fabric
Bath
MeshBasket
Fig. 1 Ultrasonic bath and fabric circulation
15 – 30- 60 - 120 min
30 min80 0C/pH 7 or 12
50 ˚CEnzymes
Fig. 2 Application graph for enzymatic pretreatment of cotton
fabric
Cellulose (2015) 22:867–877 869
123
mordanting process. The liquor ratio (liquor-to-goods
ratio) was fixed at 100:1.
In the dyeing step, the natural dyes obtained from
natural sources after drying and milling were added to
the bath at the end of the biopreparation step, as shown
in Fig. 3. Dyeing was carried out for 60 min. After the
dyeing process, the fabrics were rinsed and then
subsequently hot washed with a washing agent for
15 min; warm and cold rinses were carried out. All
samples were dried at room temperature before
testing. Color efficiencies (K/S) and CIE L*a*b* color
space values of the dyed fabrics were obtained using a
Konica Minolta 3600d spectrophotometer (D65/10�).
Meanwhile, fastnesses to washing [ISO 105-C10 2006
in test condition of Test A (1)], light (ISO 105-B02
1994), rubbing (ISO 105-X12 1993), and perspiration
(ISO 105-E04 1994) were also analyzed.
Results and discussion
Optimization of cotton biopreparation
In the first part of the study, enzymatic biopreparation
of the fabrics was carried out with the help of
ultrasound as well as using the same processes in the
same conditions but without use of ultrasound. During
the processes, the fabrics were pretreated semicontin-
uously with the help of the enzymes, ensuring a
velocity of 1 cm/min. It was planned to obtain
desizing, scouring, and bleaching effects, so the
fabrics were analyzed after the enzymatic treatment
in terms of desizing effect, hydrophilicity, and white-
ness degree.
Enzymatic processes were carried out with the use
of three different enzymes in the same bath. In all
experiments, the initial pH was 7. Biopreparation was
started at 50 �C and applied for different durations (15,
30, 60, and 120 min). In this way, it was planned to
obtain desizing and bioscouring effects with genera-
tion of hydrogen peroxide. After treatment at 50 �C,
the bath was heated to 80 �C and the pH was adjusted
to 7 or 12. The fabrics were treated at 80 �C for
30 min. This increase in temperature and pH provided
a complete bleaching effect by decomposition of
hydrogen peroxide to superoxide.
This study investigated the effects of ultrasound
application, the enzyme application time at 50 �C, and
the bath pH at 80 �C. The most important result
obtained from Table 1 is that the enzymatic pretreat-
ment ensured better results when compared with
untreated fabric in all tested conditions. The desizing
degree of the raw cotton fabric was found to be 1. After
the enzymatic pretreatment processes, it was increased
enormously. It was found that an increase in the
desizing degree arose from the ultrasound treatment.
In all cases with ultrasound assistance, the desizing
efficiency of the enzymes was increased, achieving an
increase of the desizing degree of nearly 1 on the
Tegewa scale. The other parameter tested in the study
was the enzyme application time. In this regard,
durations of 15, 30, 60, and 120 min were investi-
gated. It was found that a duration of 15 min gave the
lowest desizing degree, indicating insufficient desiz-
ing. On increasing the enzyme application time to 30
or 60 min, the desizing degree increased in all
conditions, but no significant differences were found
between the fabrics treated for 60 or 120 min. The
other parameter tested was the bath pH at 80 �C. It was
found that the increase of the pH from 7 to 12 did not
have any positive effect on the desizing degree. In fact,
the desizing effect of the enzymes was decreased
somewhat in this case. As a result, the enzyme
application time at 50 �C should be 60 min and the
bath pH at 80 �C should be 7, in terms of the desizing
degree.
The other important parameter in terms of the
pretreatment efficiency is the hydrophilicity of the
fabric. In this regard, the vertical wicking after 90 s
was obtained. It was observed that the hydrophilicity
of the fabric was significantly changed after the
biopreparation processes (Table 1) in all cases. Ultra-
sound was found to be an important parameter during
Fig. 3 Application graph of enzymatic pretreatment and
natural dyeing of cotton fabric
870 Cellulose (2015) 22:867–877
123
the enzymatic processes in terms of hydrophilicity. It
was observed that the enzyme efficiency was
increased by the use of ultrasound, as detailed in the
‘‘Introduction’’ section. The heights after wicking for
90 s were nearly doubled in all cases; For example,
choosing the parameter values for which the desizing
efficiency was highest, i.e., enzyme application time
of 60 min and pH at 80 �C of 7, the hydrophilicity
achieved with enzymes alone was 27 mm/90 s; how-
ever, the hydrophilicity was found to be 54 mm/90 s
with the addition of ultrasound to the system. So, it is
easy to say that the most important parameter during
the enzymatic processes in terms of hydrophilicity was
the application of ultrasound. Meanwhile, the enzyme
application time and the bath pH at 80 �C were also
analyzed. It was observed that, with increasing
enzyme application time, the hydrophilicity of the
fabric was increased, albeit slightly. In particular, the
applications for between 30 and 60 min produced
nearly the same results, whereas after application of
the enzymes for 120 min, the results obtained were
significantly higher. Especially in the ultrasound-
aided case, an application time of 120 min instead of
60 min ensured a significantly higher hydrophilicity
result; For example, the hydrophilicity of fabric with
enzyme application time of 60 min and bath pH at
80 �C of 7 was 54 mm/90 s for the ultrasound-aided
process compared with 27 mm/90 s without applica-
tion of ultrasound. These values were increased to
62 mm/90 s in the ultrasound-aided process and
28 mm/90 s without application of ultrasound for the
enzyme application time of 120 min. The other
parameter investigated during this study was the bath
pH at 80 �C. It was found that the bath pH at 80 �C did
not have a significant effect on the hydrophilicity
values of the fabric.
Fabric whiteness is also an important parameter that
should be investigated to determine the efficiency of a
pretreatment process. In this study, glucoamylase
enzyme was used to convert the starch, which is
available in the fabric as a sizing agent, to glucose.
Then, it was planned to convert glucose to hydrogen
peroxide via glucose oxidase. Finally, the hydrogen
peroxide generated during the biopreparation was used
for bleaching of the cotton fabric. It was observed that,
in all cases, the whiteness degree of the fabric was
significantly higher than for untreated fabric. The
fabric whiteness degree was increased from 52
Stensby to 57–61 Stensby depending on the process
conditions. It is well known that, for the bleaching
Table 1 Pretreatment results of bioprepared fabric
Bath pH
at 80 �C
Enzyme application
time (min)
Tensile
force (N)
Desizing degree
(Tegewa scale)
Hydrophilicity
(mm/90 s)
Whiteness
(Stensby)
Raw cotton – 4.90 1 0 52.00
No ultrasound 7 15 4.31 7 22 58.89
30 4.01 8 24 58.8
60 3.96 8 27 58.8
120 3.92 8–9 28 58.91
12 15 4.22 7 21 57.19
30 3.97 7–8 20 58.92
60 3.88 8 28 58.91
120 3.79 8 31 58.97
Ultrasound 7 15 4.42 8–9 53 59.98
30 4.16 8–9 54 60.12
60 4.01 9 54 60.68
120 3.97 9 62 61.01
12 15 4.30 7 40 57.92
30 3.98 8–9 50 58.76
60 3.86 9 49 58.94
120 3.75 9 60 59.75
Cellulose (2015) 22:867–877 871
123
effect of hydrogen peroxide, decomposition of the
peroxide should be achieved. This is generally done by
the use of high temperature and pH. For this aim, in
this study, the bath was heated to 80 �C and the pH
was adjusted to 12. It was found that the bath pH at
80 �C did not have a significant effect in terms of the
whiteness degree. So, after generation of hydrogen
peroxide, increasing the bath pH to 12 was found to be
unnecessary. It is thought that this could be related to
the limited amount of hydrogen peroxide generation
during the enzymatic processes. So, continuing at the
same pH even at 80 �C was found to be more logical.
The other parameter tested was the enzyme applica-
tion time. It was observed that, in nearly all cases, with
increasing enzyme application time there was an
increase in whiteness degree. However, this increase
was limited; For example, for application time of
15 min, the whiteness achieved was 58.89 Stensby
without use of ultrasound and 59.98 Stensby with use
of ultrasound. These values were increased to 58.91
and 61.01 Stensby, respectively, for enzyme applica-
tion time of 120 min. The effect of ultrasound during
enzyme application in terms of whiteness degree was
also tested. It was found that ultrasound had a
significant effect if the bath pH at 80 �C was 7.
The tensile strength losses during the processes
were also tested. As expected with the enzymatic
pretreatment processes, depending on the procedure
parameters, strength losses were observed. Increase in
the enzyme application time caused greater strength
losses, and generally use of bath pH of 12 at 80 �C
presented higher strength losses. Interestingly, the
tensile losses in warp yarns were found to be limited
when the enzymatic processes were conducted with
ultrasound assistance. Finally, based on these findings,
it was found that application of enzymes at 50 �C
should be for 60 min and the pH at 80 �C should not be
changed.
Moreover, the fabrics enzymatically pretreated
using these application conditions with or without
ultrasound were also examined based on scanning
electron microscopy (SEM) images, FTIR spectros-
copy, and dyeability with natural dyes.
Figure 4 shows SEM images of untreated and
differently pretreated fabrics at magnification of
10,0009. These images show that there were no
significant differences in the fiber surface with the use
of the different pretreatment processes. However, it is
thought that the smooth surface of the untreated fibers
was changed and the fiber surface became uneven as a
result of decomposition of sizing agents and pectin.
The infrared band assignments for the untreated and
enzymatically treated fabrics were also collected to
determine the effect of the enzymes and ultrasound. In
the literature, some bands related to the chemical
structure of cellulose are listed such as hydrogen-
bonded OH stretching at 3,550–3,100 cm-1, CH
stretching at 2,800–3,000 cm-1 (Chung et al. 2004),
asymmetrical COO- stretching at 1,617 cm-1, and
CH wagging at 1,316 cm-1 (Wang et al. 2006).
However, it was observed that use of ultrasound
during biopreparation of cotton fabric did not cause
significant changes to the FTIR bands (Fig. 5).
Natural dyeing of cotton fabric
Following the optimization of the cotton bioprepara-
tion, the fabrics were dyed with natural dyes. In the
dyeing of the fabric, pomegranate peel, nutshell,
orange tree leaf, and alkanet root were used. They
were added directly without use of any mordants and
without any prior extraction. The fabrics were dyed in
the system shown in Fig. 1 after the enzymatic
pretreatment in the same bath, as detailed in Fig. 3.
The dyeing was also carried out with and without
ultrasound to determine the effects of ultrasound on
the dyeing of the cotton fabric too.
In this part of the study, first the color efficiency of
the dyed fabrics was analyzed and the effect of
ultrasound was investigated.
Figure 6 shows the color efficiencies for the
samples pretreated with only enzymes and using
enzymes plus ultrasound prior to dyeing. It was found
that all the applied natural dyes demonstrated capacity
to color the cotton fabric. Interestingly, the fabrics
pretreated with the enzyme ? ultrasound system and
dyed with the use of ultrasound showed significantly
higher color efficiencies when compared with the
sample enzymatically pretreated and dyed without use
of ultrasound. The significant effect of use of
ultrasound in dyeing of the fabric was especially
found to be dominant when coloring with pomegran-
ate peel; For example, if the fabric was enzymatically
pretreated and then dyed in the same bath with
pomegranate peel, the color efficiency was 1.01;
however, the color efficiency was 2.08 in the case of
using ultrasound during both the enzymatic pretreat-
ment and dyeing processes. During the dyeing process,
872 Cellulose (2015) 22:867–877
123
the natural dyes were directly added to the bath in
milled form. In this case, the dyeing was completed in
two steps. The first step is the extraction of the dye
from the milled plant waste, whereas the second step is
fixation of these extracts to the fiber. It is not easy to
separate these two steps in a certain way, but it is easy
to say that, with the use of ultrasound, both the dye
extraction and fixation were accelerated. It is thought
that this was achieved due to the occurrence of two
related phenomena, i.e., cavitation and advanced mass
transfer. Due to cavitation, locally high temperatures
and pressures occur, triggering acceleration of the
extraction of the dyestuff from the natural dye source.
In addition, with the developed mass transfer caused
by ultrasonic waves, transportation of the dyestuffs to
the fiber was also increased. As a result of these
effects, better color efficiencies were obtained when
using ultrasound, depending on the natural dye
applied. Among the tested natural dyes, the smallest
effect was obtained when dyeing with alkanet root. In
this dyeing, the color efficiency increased from 0.75 to
0.92 with the use of ultrasound throughout the whole
finishing process.
The obtained colors were investigated by scanning
the colored fabrics and measuring the Commission
Internationale de l’Eclairage (CIE) L*a*b* values. The
scanned fabrics and CIE L*a*b* values of the fabrics
are illustrated in Table 2. In CIE L*a*b* space, L*
indicates the lightness; a perfectly reflecting diffuser
has L* = 100, and perfect black has L* = 0. Values of
Untreated fabric
Enzymatically Pretreated FabricsWithout ultrasound
Enzymatically Pretreated FabricsWith Ultrasound
Fig. 4 SEM images of samples
Cellulose (2015) 22:867–877 873
123
a* [ 0 represent redness, while a* \ 0 represents
greenness; b* [ 0 means yellowness, while b* \ 0
indicates blueness (Smith 1997).
It was found that, with the use of the different
natural dyes, different colors were obtained. As
presented in Table 2, pomegranate peel resulted in
slightly desaturated orange shades. Use of nutshell for
coloration of cotton fabric resulted in grayish-orange
shades. Orange tree leaf was tested as another natural
dye, representing an alternative for coloration of
cotton that achieved slightly desaturated yellow or
cream shades. Finally, it was observed that use of
alkanet root resulted in dark grayish blue, as seen in
Table 2. In the light of these data, it is easy to say that
all the tested natural dyes could represent alternatives
for coloration of the fabric, and different colors could
be obtained from them. In addition, the effect of
ultrasound application during both the enzymatic
process and the dyeing of the fabric resulted in darker
shades of all the colors; For example, addition of
ultrasound to the finishing system in dyeing with
pomegranate peel caused a decrease in the L* value
from 73.13 to 69.32. This tendency was valid for all
the fabrics dyed with the different tested natural dyes;
For example, when dyeing with orange tree leaf, the L*
value of the dyed samples decreased from 76.79 to
73.97 on addition of ultrasound to the system.
The other important parameter for the dyed samples
is the fastness of the fabric. This is especially
important when testing new dyes or methods. In this
regard, dyed samples which had been enzymatically
pretreated and dyed with and without ultrasound were
analyzed in terms of washing, rubbing, perspiration,
and light fastness (Table 3). It was observed that, for
all the tested natural dyes, the washing fastness of the
fabrics was very good. In all cases, staining on cotton
was 5 points, and the alteration was in the range
between 4/5 and 5 points.
Dry- and wet-rubbing fastness values were also
good, being between 4/5 and 5 points. For dyeing
using nutshell and orange tree leaf, both the dry and
wet rubbing fastness were found to be 5 points.
Moreover, the acidic and alkaline perspiration color
fastness of the dyed samples were also found to be
good. In nearly all cases, the staining on cotton was 5
points and the alteration lay in the range between 4 and
5 points.
Despite the good results obtained for washing,
rubbing, and perspiration fastness, the light fastness of
the dyed samples was found to be limited. The light
fastness of many natural dyes, particularly those
extracted from flower petals, is found to be poor to
Enzy
me+
Ultr
asou
nd
%T
560,4
662,7
980,61024,9
1049,81105,1
1157,6
1204,6
1315,2
1428,61774,2
2888,5
3270,03339,2
60
70
80
90
50
60
70
80
90
600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 Wavenumbers (cm-1)
Enzy
me
Fig. 5 FTIR results of samples
0
0,5
1
1,5
2
2,5
PomegranatePeels
Nutshell Orange TreeLeaves
Alkanet Root
Col
or E
ffici
ency
(K/S
)
Enzyme Enzyme + Ultrasound
Fig. 6 Color efficiencies of dyed samples
874 Cellulose (2015) 22:867–877
123
medium (Samanta and Agarwal 2009), and nearly all
natural dyes fade after exposure to daylight (Padfield
and Landi 1966). This well-known drawback mostly
depends on the particular natural dye; For example,
when dyeing with orange tree leaf, the light fastness of
the dyed samples was very poor, being 1 point.
Likewise, for alkanet root dyeing, the light fastness
was also poor (2 points). Moreover, it was found that
the pretreatment conditions and use of ultrasound did
not have a significant effect on the light fastness
obtained when alkanet root or orange tree leaf was
used. However, in the cases of nutshell and pome-
granate peel, use of ultrasound during the finishing
processes resulted in better light fastness values; For
example, when dyeing with pomegranate peel, the
fabrics finished using ultrasound showed light fastness
of 4/5 points, which is moderate and higher than the
value for the fabric finished without ultrasound. This
Table 2 CIE L*a*b* color space values of dyed cotton samples and scanned views
Pomegranate Peels Nutshell Orange Tree Leaves Alkanet Root
Enzyme
L* a* b* L* a* b* L* a* b* L* a* b*73.43 2.68 17.68 76.17 2.23 14.35 77.57 1.82 13.54 63.01 -0.59 -3.38
Enzyme +Ultrasound
L* a* b* L* a* b* L* a* b* L* a* b*70.08 4.04 23.33 71.47 3.55 15.18 70.04 2.0 9.76 61.29 0.02 -2.65
Table 3 Colorfastness properties of samples
Washing Rubbing Perspiration Light Washing Rubbing Perspiration Light
Acidic Alkaline Acidic Alkaline
Sta. Alt. Dry Wet Sta. Alt. Sta. Alt. Sta. Alt. Dry Wet Sta. Alt. Sta. Alt.
Pomegranate peel Nutshell
Enzymes 5 4/5 4/5 4/5 5 4 5 4/5 4 5 4/5 5 5 5 4/5 5 5 2–3
Enzymes ?
ultrasound
5 5 5 4/5 5 4/5 5 5 4–5 5 5 5 5 5 4/5 5 4/5 3
Orange tree leaf Alkanet root
Enzymes 5 5 5 5 5 4/5 5 4/5 1 5 4/5 4/5 4/5 5 4/5 5 4/5 2
Enzymes ?
ultrasound
5 5 5 5 5 5 5 5 1 5 5 5 4/5 4/5 4/5 5 4/5 2
Sta, staining on cotton; Alt., alteration
Cellulose (2015) 22:867–877 875
123
tendency also applied after dyeing with nutshell too.
This drawback can be related to the interaction of the
UV irradiation with the natural dyes, so subsequent
processes such as UV-absorber treatment may also
solve this drawback. However, this should be studied
more deeply in further studies.
In general, it can be easily said that, except for the
light fastness, all the fastness values of the tested
samples were good. In terms of light fastness,
especially use of pomegranate peel as a natural dye
resulted in better values compared with the other
natural dyes. It was observed that use of ultrasound
had a significant effect only in term of the light
fastnesses when using some natural dyes.
Conclusions
This study aimed to show the utility of ultrasound
application during biopreparation and natural dyeing
of cotton fabric without metal salts in a single bath.
Thereby, it was planned to reduce use of hazardous
chemicals, and water and energy consumption when
compared with conventional pretreatment and dyeing
processes. To this end, instead of the whole pretreat-
ment processes, enzymatic pretreatment in the same
bath was achieved and the usability of different
enzymes in the same bath was tested. Subsequently,
the fabrics were dyed in the same bath as used for the
enzymatic pretreatment process by using four differ-
ent natural dyes. In all the processes, addition of
ultrasound was also investigated. Finally, it was found
that cotton fabric could be treated with only enzymes
and that the color could be adjusted using the same
bath by application of pomegranate peel, nutshell,
orange tree leaf, and alkanet root. It was also observed
that addition of ultrasonic energy to the system
provided several advantages. The benefits obtained
with the use of ultrasound can be summarized as
follows: better desizing and hydrophilicity effect, and
whiteness effect with lower strength loss, higher color
efficiency, and darker shades.
In summary, this study focused on the application
of enzymes, ultrasound, and natural dyes in a single
bath to develop an environmentally friendly process
for cotton fabric. For this aim, experiments were
carried out in a single bath at a maximum temperature
of 80 �C, resulting in lower water consumption and
lower energy cost. Enzymes that do not damage the
environment are used, so the environment is protected.
Also, separate dye extraction from substances that
may be considered as waste was not required, because
extraction was achieved simultaneously with dyeing.
Acknowledgments This work was supported by Research
Fund of the Erciyes University. Project Number: FDK-2014-
5156.
References
Adeel S, Ali S, Bhatti IA, Zsila F (2009) Dyeing of cotton fabric
using pomegranate (Punica granatum) aqueous extract.
Asian J Chem 21:3493–3499
Alasalvar C, Shahidi F, Ohshima T, Wanasundara U, Yurttas
HC, Liyanapathirana CM, Rodrigues FB (2003) Turkish
Tombul hazelnut (Corylus avellana L.) 2. Lipid charac-
teristics and oxidative stability. J Agric Food Chem
51:3797–3805
Ali S, Hussain T, Nawaz R (2009) Optimization of alkaline
extraction of natural dye from Henna leaves and its dyeing
on cotton by exhaust method. J Clean Prod 17:61–66
Aly AS, Moustafa AB, Hebeish A (2004) Bio-technological
treatment of cellulosic textiles. J Clean Prod 12:697–705
Anis P, Davulcu A, Eren H.A (2008) Enzymatic pre-treatment
of cotton. Part 1. Desizing and glucose generation in de-
sizing liquor. Fibres Text East Eur 16 4(69):100–103
Bahtiyari MI, Benli H (2012) Use of orange tree leaves in dyeing
of viscose fabrics. International Antalya Fashion and
Textile Design Biennial, Antalya
Bankar SB, Mahesh VB, Singhal RS, Ananthanarayan L (2009)
Glucose oxidase—an overview. Biotechnol Adv
27:489–501
Bruni S, Guglielmi V, Pozzia F, Mercurib AM (2011) Surface-
enhanced Raman spectroscopy (SERS) on silver colloids
for the identification of ancient textile dyes. Part II:
pomegranate and sumac. J Raman Spectrosc 42:465–473
Chung C, Lee M, Choe EK (2004) Characterization of cotton
fabric scouring by FT-IR ATR spectroscopy. Carbohydr
Polym 58:417–420
DIN 53924:1997 Testing of textiles—velocity of soaking water
of textile fabrics (method by determining the wicking
height). Berlin, Deutsches Institut fur Normung E.V.
Eren HA, Ozturk D (2011) The evaluation of ozonation as an
environmentally friendly alternative for cotton preparation.
Text Res J 81:512–519
Etters JN, Condon BD, Husain PA, Lange NK (1999) Alkaline
pectinase: key to cost-effective, environmentally friendly
preparation. Am Dyest Rep 19–23
Hoondal GS, Tiwari RP, Tewari R, Dahiya N, Beg QK (2002)
Microbial alkaline pectinases and their industrial applica-
tions:a review. Appl Microbiol Biotechnol 59:409–418
ISO 105-X12:1993 Textiles–tests for color fastness, Part X12:
color fastness to rubbing. Geneva, International Organi-
zation for Standardization
ISO 105-B02:1994 Textiles–tests for color fastness, Part B02:
color fastness to artificial light. Geneva, International
Organization for Standardization
876 Cellulose (2015) 22:867–877
123
ISO 105-E04:1994 Textiles–tests for color fastness, Part E04:
color fastness to perspiration. Geneva, International
Organization for Standardization
ISO 105-C10:2006 Textiles–tests for color fastness—Part C10:
color fastness to washing with soap or soap and soda, test
condition: test A (1). Geneva, International Organization
for Standardization
ISO 2062:2009 Textiles-yarns form packages-determination of
single-end breaking force and elongation at break
Jayani RS, Saxena S, Gupta R (2005) Microbial pectinolytic
enzymes: a review. Process Biochem 40:2931–2944
Karaboga C, Korlu AE, Duran K, Bahtiyari MI (2007) Use of
ultrasonic technology in enzymatic pretreatment processes
of cotton fabrics. Fibres Text East Eur 15(4):97–100
Moore SB, Ausley LA (2004) Systems thinking and green
chemistry in the textile industry: concepts, technologies
and benefits. J Clean Prod 12:585–601
Padfield T, Landi S (1966) The light-fastness of the natural dyes.
Stud Conserv 11:181–196
Rekaby M, Salem AA, Nassar SH (2009) Eco-friendly printing
of natural fabrics using natural dyes from alkanet and
rhubarb. J Text Inst 100:486–495
Samanta AK, Agarwal P (2009) Application of natural dyes on
textiles. Indian J Fibre Text Res 34:384–399
Saravanan D, Vasanthi NS, Raja KS, Das A, Ramachandran T
(2010) Bleaching of cotton fabrics using hydrogen
peroxide produced by glucose oxidase. Indian J Fibre Text
Res 35:281–283
Saravanan D, Sivasaravanan S, Prabhu MS, Vasanthi NS, Raja
KS, Das A, Ramachandran T (2012) One-step process for
desizing and bleaching of cotton fabrics using the combi-
nation of amylase and glucose oxidase enzymes. J Appl
Polym Sci 123:2445–2450
Smith KJ (1997) Colour order systems, colour spaces, colour
difference and colour scales. In: McDonald R (Ed) Colour
physics for industry, 2nd edn. JSDC, Bradford, England.
pp. 121–208 (ISBN 0 901956 70 8)
Tutak M, Benli H (2012) Dyeing properties of textiles by
Turkish hazelnut (Corylus colurna): leaves, coat, shell and
dice. Color Technol 128:454–458
Vajnhandl S, Le Marechal AM (2005) Ultrasound in textile
dyeing and decolouration/mineralization of textile dyes.
Dyes Pigment 65:89–101
Vouters M, Rumeau P, Tierce P, Costes S (2004) Ultrasounds:
an industrial solution to optimise costs, environmental
requests and quality for textile finishing. Ultrason Sono-
chem 11:33–38
Wang Q, Fan X, Gao W, Chen J (2006) Characterization of bi-
oscoured cotton fabrics using FT-IR ATR spectroscopy and
microscopy techniques. Carbohydr Res 341:2170–2175
Cellulose (2015) 22:867–877 877
123