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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch
a r t i c l e
i n f o
Article history:
Received 25 March 2008
Received in revised form 22 July 2008
Accepted 7 August 2008
Available online 15 August 2008
Keywords:
Cationization
Cotton
Ultrasound
Sonochemistry
Cochineal dye
Dyeing
a b s t r a c t
The dyeing of cationized cotton fabric with Solx E using colouring matter extracted from Cochineal dye
has been studied using both conventional and ultrasonic techniques. Factors affecting dye extraction such
as ultrasound power, particle size, extraction temperature and time were studied. The results indicated
that the extraction by ultrasound at 300 W was more effective at lower temperature and time than conventional extraction. The effect of various factors of dye bath such as pH, salt concentration, ultrasound
power, dyeing time and temperature were investigated. The colour strength values obtained were found
to be higher with ultrasound than with conventional techniques. The results of fastness properties of the
dyed fabrics were fair to good. The scanning electron microscope (SEM) images of the morphological and
X-ray analyzes were measured for cationized cotton fabrics dyed with both conventional and ultrasound
methods, thus showing the sonicator efciency.
2008 Published by Elsevier B.V.
1. Introduction
The dyeing of cotton fabrics with anionic dyes such as direct
and reactive dyes requires the presence of large quantities of electrolyte to increase dye uptake, resulting in serious environmental
problems. As a result of this process, large volumes of wastewater,
containing signicant amounts of dyes and chemicals, are discharged from a typical cotton dye house [1]. One method of avoiding this problem is to cationize the cotton bre by cationic agents
that increase the colour strength of the dyeing process and improved wash fastness [2].
Natural dyes are generally environmentally friendly and have
many advantages over synthetic dyes [3]. In recent years, there
has been an interest in the application of these dyes due to their
bio-degradability and higher compatibility with the environment
[47]. Cochineal dye which is isolated from the dried bodies of
the female scale insects was the main red dye used in Central
America before the Spanish conquest. During the 16th century, it
was imported into Europe and began to replace the domestic kermes as an artists pigment and for dyeing [8]. These insects are still
collected in Peru and India to furnish the permanent brilliant carmine for the food, drink and cosmetic industries and artists colours [8,9]. The compound responsible for the purple colour of
this dye is carminic acid [1012].
The use of ultrasound energy for dyeing textiles as a cleaner
production is very well known in the literature [1315], Although,
* Corresponding author. Tel.: +20 2 33371718; fax: +20 2 33370931.
E-mail address: mona_kamel_nrc@yahoo.com (M.M. Kamel).
1350-4177/$ - see front matter 2008 Published by Elsevier B.V.
doi:10.1016/j.ultsonch.2008.08.001
it has not been applied in the area of dyeing with natural dyes as
much as it is being used for direct and reactive dyes. Ultrasound
can enhance a wide variety of chemical and physical processes,
mainly due to the cavitation effect in liquid mediums (that is the
growth and explosive collapse of microscopic bubbles, which
causes a large increase in the pressure and temperature) that enhances the rate of dyeing process.
The aim of this work was to focus on the use of ultrasound (US)
for enhancing the dyeing efciency and fastness properties of
cationized cotton fabrics with Solx E using Cochineal as a natural
dye. Although it was previously reported that the exhaustion
method was the applicable method for cationization of cotton fabrics with Solx E [16], our present study was the rst work to
investigate using the pad dry cure cationized method for cotton
fabrics. Different factors affecting dyeability and fastness properties were thoroughly investigated. Comparative results of the dyeing efciency of cationized cotton fabrics using both the US and
conventional (CH) dyeing methods are also presented. The microscopic images obtained by SEM and X-ray diffraction techniques
were also investigated to provide visual evidence of the existence
of ultrasonic effects.
2. Materials and methods
2.1. Dyes
The whole insect part of Cochineal was used and it was supplied
from local marketing in Egypt as a powder form, which was
244
imported from India. The characteristics of this commercial material were as follows: the botanical name of the Cochineal dye is
Dactylopius coccus, the C.I. name is Natural Red 4, the class is
Anthraquinone, and kmax in water is 532 nm.
2.2. Fabrics
In this work scoured and bleached cotton fabric (142 g/m2) was
supplied from Miser Spinning and Weaving Company, Mahalla
El-Kobra., Egypt. Before being used, the fabric was treated with a
solution containing 5 g/L non-ionic detergent (Hostapal CV,
Clariant), at 95 C for 4 h. Then the fabric was thoroughly washed
with water and air dried at room temperature.
Solx E was supplied by Ciba GeigyCo., Germany as an aqueous solution of approximately 40% solid content. It is a polyaminochlorohydrin quaternary ammonium polymer with epoxide
functionality that can react with cellulose via ether formation in
the presence of alkalis [16].
K=S
1 R2
2R
Table 1
Effect of different concentrations of Solx E
Concentration. of Solx E (g/L)
0
25
50
75
100
125
150
0.00
0.169
0.337
0.680
0.712
0.740
0.760
K/S
CH
US
0.0998
5.37
6.18
6.39
6.50
6.61
6.61
0.325
5.72
6.62
6.84
6.90
6.98
7.02
245
Table 2
Effect of ultrasound dye extraction power level on the colour strength
Power level (W)
Standard deviationa
100
200
300
400
500
1.5025
1.2375
1.190
1.1475
1.2103
1.229
0.31
0.35
0.37
0.33
0.31
0.32
K/S
CH
US
4.42
6.18
6.50
6.73
6.61
6.39
5.37
6.73
7.23
7.50
7.10
6.81
sity within 3346 and 1033 cm1 with increasing nitrogen content
of the cationized fabric.
These distinct narrow, high intensity bands (OH/N+ R3) conrm
presence of the quaternary ammonium salts. In addition, a two
splitting distinct bands can be observed in the spectrum (B) with
in 2922 and 2853 cm1, 1430 and 1373 cm1 corresponding to aliphatic CH stretching, bending deformations and rocking vibrations of the methylene groups (CH2).
FTIR spectra were obtained for the untreated (A) and treated (B)
cotton fabric with cationizing agent Solx E (nitrogen content of 0%
and 0.68%, respectively), as shown in Fig. 1. In the treated fabric
certain absorption bands can be observed in the 1116 cm1 range
(CN stretching vibration) as well as an intensive distinct band at
1059 cm1 which are characteristic of primary-COH stretching
deformation, which are not present in the untreated fabric in spectrum (A). The spectrum of the cationized cotton fabrics with Solx
E is markedly different from the uncationized fabric.
In addition, the broad absorption band within 3352 and
1032.71 cm1 for the unmodied cotton fabric revealed the presence of numerous hydroxyl groups. However, the (primary-OH)
band of the cationized cotton become narrow with a higher inten-
Fig. 1. FTIR spectra of (A) untreated cotton fabric and (B) treated cotton fabric.
during the cavitation phenomenon which might reduce the efciency of the ultrasound energy transmitted into the medium
[19,20]. These results emphasize the enhancement effect of US,
which increases the rate of dye extraction from Cochineal insects
by virtue of its dispersion, degassing and diffusion capabilities
(accelerating the rate of dye desorption from the insect body). On
the other hand, it can be observed from Table 2 that US in comparison with CH extractability will enhance the dyeability as the colour strength values associated with pronounced increase using US
than CH dyeing method and this point will be discussed in detail
later.
Consequently, a power level of 300 W was chosen as an optimum power level for the dye extraction method. Some dyes extracted via US are more susceptible than others to the effect of
US with different power levels. This observation means that, for
each dye there is an optimum US power level [21].
8
7
K/S
246
CH
US
4
3
0.1
0.2
0.3
0.5
0.7
7.8
7.4
7
K/S
6.6
6.2
5.8
CH
5.4
US
5
15
30
45
60
90
120
7.6
7.4
CH
7.2
US
K/S
6.8
6.6
6.4
6.2
6
5.8
5.6
50
60
70
80
Temperature (C)
Fig. 2. Effect of dye extraction temperature on the colour strength (extraction
conditions: concentration of dye 0.5 g/100 mL, 300 W, for 60 min, dyeing conditions: L.R. 1: 30, pH 4, 500 W, at 80 C for 60 min).
247
methods. It is clearly indicated that, in the absence of salt, the colour strength in case of the US dyeing method was higher than the
CH dyeing method. Moreover, as the salt concentration increased
from (015 g/L) the colour strength also decreased in both dyeing
methods, which is good for the environment.
K/S
6
5
CH
US
4
3
5
pH value
10
Fig. 5. Effect of dye bath pH on the colour strength of dyed cationized cotton fabrics
(extraction conditions: concentration of dye 0.5 g/100 mL, 300 W, at 80 C for
60 min, dyeing conditions: L.R. 1: 30, 500 W, at 80 C for 60 min).
K/S
CH
US
4
0
2.5
7.5
10
15
Fig. 7. Effect of salt addition on the colour strength of dyed cationized cotton
fabrics (extraction conditions: concentration of dye 0.5 g/100 mL, 300 W, at 80 C
for 60 min, dyeing conditions: L.R. 1: 30, pH 4, 300 W, at 80 C for 60 min).
7.4
6.8
K/S
K/S
7.2
6.6
6.4
CH
US
6
5
4
3
6.2
0
100
200
300
400
500
30
40
50
60
70
80
Temperature (C)
Fig. 8. Effect of dyeing temperature on the colour strength of dyed cationized
cotton fabrics (extraction conditions: concentration of dye 0.5 g/100 mL, 300 W, at
80 C for 60 min, dyeing conditions: L.R. 1: 30, pH 4, 300 W, no salt, for 60 min).
248
increasing more possibility for the penetration of the dye molecules into the bres. On the other hand, the US dyeing method is
associated with cavitation effects, which would lead to [11,21]:
dispersion, degassing and diffusion (accelerating the rate of dye
diffusion inside the bre by piercing the insulating layer covering
the bre and accelerating the chemical reaction between dye and
bre).
8
7.5
K/S
7
6.5
CH
US
5.5
5
15
30
45
60
90
120
Dyeing time (min)
180
240
Fig. 9. Effect of dyeing time on the colour strength of dyed cationized cotton fabrics
(extraction conditions: concentration of dye 0.5 g/100 mL, 300 W, at 80 C for
60 min, dyeing conditions: L.R. 1: 30, pH 4, 300 W, no salt, at 80 C).
Table 3
Effect of CH and US dyeing method on crystallinity, crystallite size, 2h angle and dspacing of cationized cotton fabric
Dyeing
method
Crystallinity
(%)
2h ()
d-Spacing
()
Crystallite size
()
CH
51.35
3.87467
38.44
US
44.00
3.90248
20.76
Fig. 10. SEM photographs of cationized cotton fabrics (a) dyed with CH method and (b) dyed with US method.
Fig. 11. X-ray diffraction patterns of cationized cotton fabric dyeing with (1) CH dyeing method and (2) US dyeing method.
249
Washing
Perspiration
Rubbing fastness
Acid
CH
US
Light
Alkali
Alt.
Alt.
Alt.
Dry
Wet
4
34
4
45
4
45
4
34
34
4
34
34
45
4
3
3
4
34
34
34
12
23
2
2
IC
Cx%
100
I C Ia
where Cx% is the crystallinity percentage and Ic and Ia are the intensities of the X-ray diffraction pattern of the crystalline and amorphous components, respectively. It is clear from Table 3 that the
US dyeing method decreased the crystallinity as well as the crystallite size than the CH dyeing method, which indicates that the amorphous region increases. An increase in the d-spacing values of the
US dyeing method as compared to CH dyeing method occurred in
the indicated region. It can be concluded that the dye uptake increased via dyeing with the US method [24].
4. Fastness properties
The fastness tests involving washing, rubbing, perspiration
(acidalkali) and light of dyed cationized cotton fabric using the
US and CH methods are shown in Table 4. The results indicate fair
to good fastness properties of the dyed samples using both the US
and CH methods. Generally in the case of washing and perspiration
fastness properties did not alter where a decrease in rubbing fastness was observed in both CH and US methods.
5. Conclusions
Ultrasound appears to be an effective technique for the extraction of Cochineal dye and gave maximum extraction value at
300 W which was associated with decreasing the average particle
size. Better K/S values were observed for dyed cationized cotton
fabrics using ultrasound compared to the results obtained via the
conventional method. The results of X-ray diffraction studies and
SEM images provided visual evidence that the ultrasound technique is useful in enhancing the dyeability as measured by K/S values, than the conventional dyeing method. Comparing the fastness
Appendix
Ultrasound US
Conventional CH
Fourier transform infrared FTIR
Nitrogen content percent N%
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