International Conference of Applied Research in Textile

Monastir, Tunisia

CIRAT-5, 2013

Dyeing study of Cationic cotton with Isosalipurposide natural dye

Guesmi A. , Ladhari N. and Sakli F.
Textile Engineering Laboratory, Higher institute of Technological Studies of Ksar Hellal, Tunisia
Abstract :
Modified cotton fabric was subsequently dyed in both conventional and ultrasonic techniques with Isosalipurposide dye
isolated from Acacia cyanophylla yellow flowers. The effect of dye bath pH, ultrasonic power and frequency, dyeing
time and temperature were studied and the order of K/S values indicates Ultrasound, 25 kHz > Ultrasound, 40 kHz > CH.
Ultrasound was also found to enhance the dye uptake and the overall fastness properties.
Key Words: Cationic cotton; Ultrasound; Isosalipurposide dye; Dyeing.

added for extraction. This unit was immersed

in a water bath and sonicated for 15 min
(power 100W). After complete extraction, the
extract was filtered through a filter paper
(ashless filter paper, 12.5 cm) and evaporated
to dryness using a rotary evaporator and a
water bath at 60 C. The residue was dissolved
in 5 mL of water and extracted with ethyl
acetate. The extract was filtered through a
0.45m filter that was compatible with
organic solvents and was subjected to silica
gel column chromatography eluting with
(CH3)2O / CH3OH (9:1) to afford 3.95 g of
Isosalipurposide (extraction yield = 0.79%).

1. INTRODUCTION
In order to evaluate the effectiveness of the
treatment of cationization, ultrasonic dyeability of
modified cotton fabric with Acacia has been
studied. Indeed, it has been made clear that
proteinic fibres (silk and wool) have great affinity
to dyes extracted from Acacia and that cellulosic
fibre (cotton, rayon, and acetate), on the contrary
have very little affinity to those colorants (Itoh,
Ohara, 1999). For reasons of reproducibility of
dyeing, the present study investigates the dyeing
and fastness properties of modified cotton fabric
using Isosalipurposide dye; a purified chalcone
isolated from Acacia cyanophylla yellow flowers.
The modification conditions such as sonication,
triethylamine concentration, the modification
temperature and time were investigated. Also the
dyeing conditions in both conventional and
ultrasonic techniques, the fastness properties, the
kinetics and the isotherms of dyeing of modified
cotton
using
Isosalipurposide
dye
were
investigated.

Pre-treatment of cotton: Following a

previously published method (Ahlem,
ultrasonic), the sonicator preparation of
cationic cotton was provided by the reaction
of cellulose with bromoacetyl bromide,
followed by the substitution of the terminal
bromo groups by triethylamine.
Cotton fabric was firstly acylated in a DMF
solution containing 0.4 mL of bromoacetyl
bromide at a liquor to goods ratio of 20:l; the
treatment was carried out with ultrasound. The
fabric was exposed to ultrasonic frequency of
25 kHz at a power level of 350 W for 30
minutes. After acylation of cotton, the fabric
was treated in an aqueous solution with a large
excess of triethylamine (5mL) at liquor to
good ratio of 20:1. The treatment was carried
out with ultrasound. The fabric was exposed to
ultrasonic frequency of 25 kHz at a power
level of 500 W for 30 minutes.

2. MATERIALS, METHODS AND

MEASUREMENTS
2.1. Materials
Textile materials: Scoured and bleached cotton
fabric (150 g/m2) was used.
Plant material: Yellow flowers of Acacia
cyanophylla) were collected in March 2010. The
pigment obtained from Acacia has good colouring
capacity.
Chemicals: Thin layer chromatography was
performed on silica gel 254 plates (Merck) with
UV
(254
nm)
visualisation
whereas
chromatographic separations were conducted on
silica gel Si-60-7734 Merck using water-Jacketed
columns.

Dyeing procedure: In a dye bath containing

30 mg/L of dye with liquor ratio 40:1,
modified cotton fabric was dyed using
conventional heating at different pH values (510.5) for different durations (1560 min) and
at different temperatures (4080 C). For
comparison, the same condition of dyeing was
made using ultrasonic dyeing. The fabric was

2.2. Methods
Extraction and isolation of colorants: 500 g of
dried and powdered flowers A. cyanophylla were
placed in a glass and 500 mL of methanol were

CIRAT-5

exchange reaction.. This ionic attraction

would increase the dyeability of the fabric. At
pH 9, all the protonated terminal amino groups
fixed on cotton fabric interact with the dye, no
additional dye is adsorbed, and the maximum
colour strength was obtained at this value. The
effect of temperature on the dyeability of
modified cotton fabrics with isosalipurposide
dye was conducted under (US) and (Heat)
conditions at different temperatures (40, 50,
60, 70, and 80C). As shown in Fig.1B, it is
clear that the colour strength increases with
the dyeing temperature up 40 C for (US)
method and up 60C for (Heat) method, with a
much higher colour strength in the (US) case
especially at a frequency of 25 kHz. Beyond
60C, the K/S values decrease slowly in case
of (Heat) and it decrease with a pronounced
manner in case of (US) method. These data
are probably due to the dye desorption from
the fibre which is more pronounced with US.
From Fig.1C, it was observed that in case of
ultrasonic method the colour strength
increases slowly with increasing the dyeing
time, till 20 min, then a plateau value was
observed. In case of CH method, the K/S
value increases as the time increases.
Globally, it was shown that the K/S values
reported to (Heat) are lower than the K/S
values reported to (US). The order of K/S
values for various processes indicates,
Ultrasound, 25 kHz > Ultrasound, 40 kHz >
Conventional heating. These data reveal that
the extra shear attributed on the dyeing system
by ultrasound would lead to dispersion
(breaking up of micelles and high molecular
weight aggregates into uniform dispersions in
the dye bath), degassing (expulsion of
dissolved or entrapped gas or air molecules
from modified cotton fibre into liquid and
removal by cavitations, thus facilitating dyefibre contact) (Ghorpade et al., 2000), and also
that the better cavitations are produced at
lower ultrasonic frequency (Khatri et al.,
2011). Also, the effect of ultrasonic power on
the dyeability of modified cotton fabrics with
Isosalipurposide dye was conducted at
different power levels (100, 200, 300, 400,
500 W). As shown in Fig.1D, the colour
strength increases with increase in power
level, with a sudden increase observed beyond
300W. Indeed, at a given frequency, the power
defines the cavitation threshold, above a
certain power; cavitation happens, underneath,
there is only the spreading of the waves. Thus,
optimal dyeing conditions were fixed to pH 9,
60C, 30 min, 25 kHz and 500 W. The overall
fastness properties of the dyed samples using

exposed to ultrasonic frequencies of 25 or 40 kHz

at different power levels (100500 W). Finally, the
dyed samples were rinsed with cold water and
finally dried at ambient temperature. Throughout
the manuscript, conventional heating is abbreviated
to Heat and ultrasonic treatment is abbreviated to
US.
Dyeing rate: Modified cotton fabric samples were
cut into pieces approximately 2 cm2 and dyed at pH
9 with aqueous solution composed of 30 mg/L of
Isosalipurposide dye, with liquor ratio 50:1 at 60
C. Dyeing was conducted using both ultrasonic
power at
500 W and conventional heating
conditions. After selected time intervals, 0.5 mL of
the dye bath was pipetted into test tubes and diluted
with water to 5 mL to measure its absorbance at
230 nm.
2.3. Measurements
Photometric quantification: Visible absorption
spectra were recorded using a Philips model PU
UV/visible spectrophotometer.
Colour measurements: The colour yield of
samples was evaluated by light reflectance
measurements using SF 300 spectrophotometer.
Relative colour strengths (K/S values) were
determined using the Kubelka-Munk equation
(Judd, Wysezcki, 2000).
Colour fastness testing: The dyed samples were
tested for fastness properties according to standard
methods, the specific tests were for colour fastness
to washing ISO 105-C02:1989, colour fastness to
rubbing ISO 105-X12:1987, colour fastness to
water ISO 105-E01:1989 and colour fastness to
light ISO 105-B02:1988 ( carbon arc).
3. RESULTS AND DISCUSSIONS
3.1. Dyeing
In order to optimize the dyeing process, the overall
dyeing parameters were studied (Fig.1).
As shown in Fig.1A, the pH values of the dye bath
have considerable effect on the dyeability of
modified cotton fabric with natural dyes. At acidic
pH, the K/S values are so low as to make the
'dyeing' just pale stains. From pH 7, the colour
strength obtained was increased as the pH increases
up to 9, and then a plateau value of K/S was
observed. At pH < 7, no interaction is susceptible
to occur between dye structure and modified cotton
fabric. At pH 7, the hydroxyl groups of the dye
begins to convert to alkoxide ion which would
interact ionically with the protonated terminal
amino groups of modified cotton fibres via an ion

CIRAT-5

power level (Fig.1B; dyeing conditions: pH 9, Cdye

30 mg/L, 50 C, 20 min, 25 kHz).

both ultrasonic and conventional techniques were

about 5, only washing and water fastness were
about 4-5.

Kinetics of dyeing
The rate of any process means the change in
reactant concentration with time. Applying
this definition in the dyeing process can be
considered as the change in the dye-uptake per
unit time. Time-dye-uptake isotherms of
modified cotton fabric under US and CH
dyeing conditions dyed with isosalipurposide
dye, isolated from yellow flowers of Acacia
cyanophylla, are shown in Fig. 2. The
concentration of the dye in the fibre was
estimated using Eq 1:

Heat
US (25 kHz)
US (40 kHz)

25
20

K/S

15
10
5
0
5

10

11

pH

Fig.1A
25

Qt = (C0-Ct) * V/W

Heat
US (25kHz)
US (40 kHz)

20

Were Qt is the concentration of dye in the fibre

(mg/g), C0 and Ct are the initial and the
equilibrium of dye in the dye bath,
respectively, V is the volume of the dye bath
(L), W is the weight of the fibre (g).

K/S

15
10
5
0
40

50

60

70

(1)

80

T (C)

1,2
Dye-uptake (mg/g)

Fig.1B
25

20

K/S

15
10

Heat
US (25 kHz)
US (40 kHz)

US

Heat

0,8
0,6
0,4
0,2
0
-0,2 0

50

100

Time (min)

0
15

30

45

Fig.2. Ultrasonic and conventional dyeing rate of

modified cotton fabric using Isosalipurposide dye.
Dyeing conditions: cotton fabric 0.5 g, L.R. 1:50,
Cdye 30 mg/L, pH 9, 50C, 500 W, 25 kHz.

Time (min)

Fig.1C

Firstly the figure shows that the dye-uptake

values of ultrasonically dyed samples are
higher than those obtained from a
conventional heating method. Improvements
observed in ultrasound-assisted dyeing
processes are generally attributed to cavitation
phenomena and, as a consequence, other
mechanical effects are produced such as
dispersion (breaking up of aggregates with
high relative molecular mass), diffusion
(accelerating the rate of diffusion of dye inside
the fibre) and intense agitation of the liquid.
The acceleration in dyeing rates observed
might be the cumulative effects of the above.
The data in Fig.2. can be analyzed by using
the derivable general form of the first order
rate Eq. (2) :

25

K /S

20
15
10
5
0
0

100

200

300

400

500

600

ultrasonic power (W)

Fig.1D
Fig.1. The colour strength of dyed modified cotton
fabrics as a function of dye bath pH (Fig.1A; dyeing
conditions: Cdye 30 mg/L, 30 min, 50C, and LR 40:1,
500 W), of dyeing temperature ( Fig.1B; dyeing
conditions: Cdye 30 mg/L, 30 min, pH 9, and LR 40:1,
500 W), of dyeing time ( Fig.1C; dyeing conditions: Cdye
30 mg/L, 60 C, pH 9, and LR 40:1, 500 W), and of

CIRAT-5

(At - Af) / (A0 - Af) = e -kt

(2)

ultrasonic in comparison with those dyed

conventionally.

where At is the absorbance at time t, A0 is the

initial absorbance, Af is the final absorbance, t is
the reaction time and k is the reaction rate. Since
the absorbance of solution is directly related to the
concentration by Lambert Beer law, Eq. (2) can be
rewritten in terms of dye-uptake to give Eq. (3):
(Qt - Qf)/ (Q0 - Qf) = e-kt

Table 1. Dyeing rate constant k, efficiency of

ultrasonic k, times of half dyeing t1/2, standard
affinity - and amount of final dye-uptake by
modified acrylic fabrics using Isosalipurposide dye.
k*100(min-1)

(3)

where Qt is the dye-uptake at time t, Q0 is the dyeuptake at zero time, Qf is the final dye-uptake, t is
the dyeing time and k is the dyeing rate. Taking the
logarithm of Eq. (3) would lead to Eq. (4), and
since Qf is known, Qt - Qf can be calculated as
follows:
ln | Qt - Qf |= ln | Q0 - Qf | - kt

ln( Qt-Qf) (mg/g)

20

40

(4)

8.04

CH

16

19

Qf (mg/g)
US

CH

0.964

0,65

Itoh. S, Ohara. S, (1999). Fiber Processing

Characteristics with Bark Extractives of
Acacia mearnsii De Wild, JWRS. 45, 157
163,
Judd, D. B. Wysezcki, G. (2000). Color in
Business, Science and Industry, third Ed., John
Wiley & Sons , New York.
Ghorpade, B. Darvekar, M. Vankar, P.S.
(2000). Ecofriendly cotton dyeing with
Sappan wood dye using ultrasound energy,
Colourage. 47, 2730.
Khatri,Z. Memon, M.H. Khatri, A. Tanwar
i, A. (2011). Cold Pad-Batch dyeing method
for cotton fabric dyeing with reactive dyes
using
ultrasonic
energy,
Ultrasonics
Sonochemistry. 18, 13011307.

60

y = -0,0547x + 0,0804
R 2 = 0,981

-2
-3

5.03

t1/2 (min)
US

REFERENCES

-1,5
-2,5

5.47

k%

The application of ultrasound in the dyeing of

cationic cotton fabric shows better results, a
marked enhancement was registered in the
colour depth shade and in the dye-uptake of
cationized
cotton
fabric
dyed
with
Isosalipurposide dye; the enhanced of K/S was
about 16.4% more than conventional heating.

0,5

-1

CH

4. CONCLUSION

A plot of ln | Qt - Qf | versus time is expected to be

linear with a slope of -k and an intercept of ln | Q0
- Qf | if the reaction is first order. Fig.3 shows the
plot of ln | Qt - Qf | as a function of time for dyeing
of modified cotton fabrics with Isosalipurposide
dye using both ultrasonic and conventional heating
methods.

0
-0,5 0

US

y = -0,0503x - 0,3023
R 2 = 0,9842

Time (min)

Fig.3. Plots of ln | Qt - Qf |versus time of dyed modified

cotton fabrics under conventional and ultrasonic
methods. For legend see Fig 2.

As can be seen in this figure, the linear fitting of

Eq. (4) holds indeed and the values of dyeing rate
constants could be obtained as listed in Table 1.
The time of half dyeing t1/2, which is the time
required for the fabric to take up half of the amount
of dye taken at equilibrium, is estimated from each
isotherm directly (Fig. 2).
The values of half dyeing t1/2 are given in Table 1.
The rate constant of dyeing modified cotton fabrics
with Isosalipurposide dye is clearly increased with
ultrasonic treatment in comparison with
conventional heating. Also, the values of t1/2 of
dyeing are clearly less for those samples dyed with