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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

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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.

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