CELLULOSE CHEMISTRY AND TECHNOLOGY

ECO-FRIENDLY DYEING AND ANTIBACTERIAL

TREATMENT OF COTTON

AMINODDIN HAJI
Textile Engineering Department, Birjand Branch, Islamic Azad University, Birjand, Iran

Received June 10, 2012

Berberine, a natural cationic dye with excellent antibacterial activity, was extracted from the roots of Berberis vulgaris
and applied on cotton fabric. Naturally, there is no affinity of cationic dyes for cotton fiber. To improve the dyeability
of cotton fiber, plasma treatment and acrylic acid grafting, using plasma technology for pretreatment, were employed.
The grafting of acrylic acid was confirmed using ATR-FTIR. The effect of pretreatments on the dyeability of cotton
was evaluated. The antibacterial activity of the dyed samples was evaluated according to AATCC test method 100-
2004. The samples dyed after acrylic acid grafting showed the highest antibacterial activity.

Keywords: plasma, grafting, cationic dye, dyeability, cotton, antibacterial

INTRODUCTION
As renewable raw materials for textile and enzymes have been used to improve the
industry, natural dyes and fibers, especially dyeability of cotton with natural dyes.4-6,8,12
cotton, are gaining considerable importance due The prevention of microbial attack on textiles
to recent environment conservation regulations.1 has become increasingly important to consumers
Cotton is one of the most important natural fibers, and textile producers.13 Natural dyes are
which is used extensively in textile industry alone considered to give advantages to applications,
or in blends with synthetic fibers.2 This fiber has such as non-toxic functions, specific medical
great characteristics, such as good water and dye actions and environmentally friendly finishes.3
absorbency, comfort and stability. Synthetic dyes, Several natural dyes have been reported to be
such as direct, vat, sulphur, azoic and reactive effective antimicrobial agents. Tannin-rich extract
dyes can be used simply to dye cotton fiber.2-3 from Quercus infectoria was found to have good
Today, due to environmental and health concerns, activity against gram-positive and gram-negative
there is a great tendency to natural dyes.2-8 bacteria. Colorants extracted from onion pulp and
Natural dyes and pigments are found in some onion skins were grafted onto cotton fabrics and
plants, animals, insects, bacteria, fungi and the antimicrobial activity was evaluated. Also,
minerals. For example, alizarin is a very old and curcumin-treated cotton and wool fabrics showed
common red dye found in roots of madder, Rubia good antimicrobial activity to both E. coli and S.
tinctoria. The development of synthetic dyes in aureus.13-14 Berberine, a natural cationic dye was
the last century reduced the use of natural dyes in applied on wool and nylon fabrics and the dyed
modern dyeing.2-3,8-9 samples showed good antibacterial activity.2,15-19
Natural dyes can be used to dye protein fibers Berberis vulgaris is a shrub, which is extensively
easily, but there are several problems in their planted in Southern Khorasan, Iran, and many
usage on cotton fiber, mainly the low affinity and other places all over the world, for its valuable
fastness properties of natural dyes toward cotton fruit, barberry. In the previous studies, the roots of
fiber.8,10 To overcome these drawbacks, several this plant were used as a source of a natural
studies have been carried out. Vankar et al. have colorant to dye wool fibers.18-19 There is a natural
used mineral and bio-mordants, besides cationic yellow dye (natural yellow 18) in these
ultrasound energy, to improve dyeability of cotton roots named Berberine (Figure 1).18 The amount
fiber with an extract of Rubia cardifia.11 of the dye is lower in the wood of the plant. This
Pretreatments of cotton with chitosan, anionic and natural cationic dye was extracted and applied on
cationic active compounds, cross-linking agents cotton fiber.

Cellulose Chem. Technol., 47 (3-4), 303-308 (2013)

AMINODDIN HAJI

Because of the low affinity of cationic dyes to fibers. The grafted samples were dyed with
cotton fiber, the fabric was pretreated with natural cationic dye. The color strength, fastness
oxygen plasma and grafted with acrylic acid to properties and antibacterial activity of the dyed
create acidic groups on the surface of cotton samples were evaluated.

Figure 1: Chemical structure of berberine

EXPERIMENTAL the air trapped inside the reaction mixture. The

Materials reaction flask was heated for different times at
In this work, scoured and bleached cotton fabric different temperatures. Then the fabric sample was
(142 g/m2) was supplied from Mazandaran Textile drained and Soxhlet extracted with distilled water for
Company, Iran. Before being used, the fabric was 60 min to remove any non-reacted acrylic acid and
treated with a solution containing 1 g/L non-ionic homopolymers adhered to the sample surface. The
detergent and 1 g/L sodium hydroxide at 95 C for 30 samples were then dried in an oven at 50 C for 2 h,
min. Then the fabric was thoroughly washed with cooled over a silica-gel desiccator and weighed. The
water and air-dried at room temperature. grafting percent was calculated according to the
Berberis vulgaris roots were first washed and dried following equation:
and then powdered. To prepare the original solution of G%= [(W1-W2)/W1]*100 (1)
the dye, each 100 gram of powder was added to 1 liter where W1 and W2 are the weights of the conditioned
of distilled water and boiled for 2 hours and then cotton fabric (25 C, 60% RH) before and after the
filtered. Before filtration, the volume of the solution grafting process, respectively.
was adjusted to the initial amount by adding distilled
water. The concentration of the resultant solution is FTIR analysis
10% w/v. All chemicals used were analytical grade Fourier transform infrared measurements were
reagents from Merck. carried out using a Nicolet 670 with a resolution of 4
cm-1. An average of 40 scans was recorded in the ATR
Methods mode.
Plasma treatment
The fabric samples were treated using radio Dyeing
frequency (13.56 MHz) low pressure plasma 50 cc of the original dye solution was mixed with
equipment (model: Junior plasma, Europlasma, 50 cc of distilled water for each 2 gram of cotton (L:G
Belgium). In all treatments, oxygen was used as the = 50:1). The dyeing was started at 40 C and the
processing gas. The system was evacuated to 100 temperature was raised to boil at the rate of 2 C per
mTor and oxygen was introduced into the chamber at a min. The samples were allowed to remain in that
flow rate of 20 sccm (standard cubic centimeters per condition for 45 min, and then were rinsed and air-
minute). The chamber pressure was subsequently dried. All dyeing processes were carried out using a
maintained at 100 mTor and plasma was generated at laboratory dyeing machine made by Rissanj Co., Iran.
100 W for a predefined period of time. Subsequently,
air was introduced into the chamber and the sample Color measurements
was removed for the grafting reaction. The time The reflectance of the dyed samples were measured
between the plasma treatment and the beginning of the on a Color-eye 7000A spectrophotometer, using
grafting reaction was 5 min to ensure the formation of illuminant D65 and 10 standard observer. The color
peroxide radicals necessary to initiate the grafting strengths (K/S) of the dyed samples were calculated at
reaction.20 the maximum absorption wavelength, using the
Grafting Kubelka-Munk equation:
The plasma-treated cotton sample was placed into a K/S= (1-R)/2R (2)
reaction flask containing 50 mL of solutions of where R is the observed reflectance, K is the
different acrylic acid (AA) concentrations in distilled absorption coefficient and S is the light scattering
water. Nitrogen was purged into the flask to remove coefficient.

304
 Cotton

Color fastness tests plasma treatment time of 120 s seems to be the

Color fastness to washing, light and rubbing was optimum time for plasma treatment to reach the
measured according to ISO 105-C01: 1989(E), ISO maximum grafting yield.
105-B02: 1994(E) and ISO 105-X12: 1993(E), Plasma treatment can lead to the production of
respectively.
some radical sites. These radical sites will be
Antibacterial test oxidized with oxygen molecules in air and
The antibacterial property of the dyed samples was produce peroxides, and graft reaction will take
quantitatively evaluated according to AATCC 100- place between cellulose and AA monomer. There
2004. The bacterial species used were Klebsiella are already some explanations regarding the
pneumoniae (gram-negative) and Staphylococcus optimal plasma treatment time. Before the optimal
aureus (gram-positive). Before and after incubation on time, plasma treatment mainly produces radical
the agar plate, the colonies of both bacteria were sites; after the time, some existing radicals will
counted by microscope. The percent reduction in the disappear due to chemical degradation and finally
number of bacteria, which was calculated using reach a dynamic equilibrium. Besides, long-time
equation (3), shows the efficacy of the antibacterial
plasma treatment can lead to the cross-linking
treatment.
E%= [(N1-N2)/N1]*100 (3) between some radicals.21 The grafting percent on
where N1 is the number of bacterial colonies at the the blank sample (grey cotton fabric) is
beginning of the test (0 hour), and N2 is the number of approximately zero, which confims the positive
bacterial colonies after 24 hours of contact with the effect of plasma treatment on grafting yield.
dyed samples.
Effect of AA concentration on grafting
RESULTS AND DISCUSSION efficiency
Effect of plasma treatment on grafting Plasma-treated cotton samples (2 min, 100 W)
efficiency were grafted using different concentrations of
Cotton samples were plasma-treated at AA. Figure 2 shows that grafting percent
different times (power = 100 W) and grafted with increased as the AA concentration increased from
a 20% V/V of AA for 1 hour at 60 C. Table 1 10% to 40%, and thereafter decreased with a
shows the effect of plasma treatment time on graft further increase in AA concentration. This
yield of AA on cotton. As can be seen, the graft decrease can be due to more chances for AA
efficiency increases with the increase in plasma monomers to form homopolymer, instead of
treatment time. The reason is the creation of more copolymer, with cellulose at increased
free radicals and active sites as the plasma concentrations.20 So the viscosity of the reaction
treatment time increases. When the plasma medium increases significantly, which causes the
treatment time extends beyond 120 s, the grafting monomer depletion and hence diminishes
degree decreases. This decrease can be due to monomer accessibility to the grafting sites.20
over-etching of the fiber surface and reducing the
accessible free radicals on the surface. So, a

Table 1
Effect of plasma treatment time on grafting percent

Plasma treatment time (s) Grafting, %

0 (blank) 0
30 0.81
60 1.74
90 2.66
120 3.54
150 3.47

305
AMINODDIN HAJI

8 7

7 6

6
5

Graft yield (%)

Graft yield (%)

5
4
4
3
3
2
2

1 1

0 0
0 10 20 30 40 50 60 70 0 30 60 90 120 150
AA Concentration (%) Grafting time (Min)

Figure 2: Effect of AA concentration on graft yield Figure 3: Effect of grafting time on graft yield (plasma
treated, 20% AA, 60 C)

Figure 4: ATR-FTIR spectra of (c) raw, (b) plasma-treated (2 min, 100 W) and (a) acrylic acid grafted cotton fibers (G
% = 3.54)

Effect of grafting time on graft yield validate the grafting (Figure 4). The small peaks
As can be noted from Figure 3, the grafting at 1650 and 1710 cm-1 in the FTIR spectrum of
yield increases with the increase of grafting time the plasma-treated fabric confirm the creation of
from 30 min to 120 min, thereafter any further carbonyl groups after the oxygen plasma
increase in grafting time has no significant effect treatment. The FTIR spectrum of the grafted
on grafting yield. It can be explained by the fabric, when compared to that of the raw fabric,
reduced amount of AA monomer in the solution clearly indicates the peak for the COOH group at
and the free radicals at the fiber surface after 1710 cm-1, which is due to the introduction of
prolonged time. It may be stated that the growing poly(acrylic acid) graft onto the cotton fibers.1
chains are exhausted within 2 h and lead to the
equilibrium degree of grafting.20 Effect of plasma treatment and grafting on
color strength of dyed cotton sample
FTIR Analysis Raw, plasma-treated and AA-grafted cotton
The raw, plasma-treated and acrylic acid samples (with different graft percents) were dyed
grafted fabrics have been characterized in order to by the above-mentioned process. As noted from

306
 Cotton

Table 2, the raw sample absorbed a very low making cellulose anionic and, hence, cationic
amount of the berberine dye, because of the low dyeable, as the carboxyl groups introduced as a
affinity of the dye towards cotton fiber. The result of grafting act as sites for the attachment of
plasma-treated sample showed a little cationic dye molecules.1
improvement in dye absorption due to the creation
of some oxygen-containing chemical groups on Fastness properties
the fibers surfaces due to plasma treatment, as As mentioned in Table 3, the fastness
evidenced by the FTIR analysis. The K/S of the properties of the samples dyed after AA grafting
samples increases as the graft yield increases. were also found to improve. Cationic dyes are
This is due to the creation of more acidic sites known for inferior fastness properties on
after grafting of AA on cotton. Cellulose has no cellulose; hence the improvement in fastness
active site to react with cationic dye, berberine properties of the grafted product may be attributed
(Figure 1). After grafting of AA on cotton, the to the increase in the content of carboxyl groups,
acidic COOH groups will appear on cotton which provides a better attachment of the dye
surface, which will promote more absorption of molecules to the sites, offering resistance against
cationic dye to it. Cationic dyeing of cellulose is removal through washing or rubbing. The
generally done by pre-mordanting it with tannic improvement in light fastness is due to a larger
acid, as cellulose lacks the groups required for the amount of dye being adsorbed onto the fiber, as
attachment of cationic dye molecules. Grafting of compared to the experiment with no grafting.
cellulose with acrylic acid is another technique for

Table 2
Effect of plasma treatment and grafting on color strength of dyed cotton sample

Graft yield (%) K/S

0 (Untreated cotton) 0.577
0 Plasma-treated cotton) 0.765
2.3 2.15
3.54 3.17
4.76 4.56
6.32 5.98

Table 3
Fastness properties of dyed samples

Sample Washing fastness Rubbing fastness Light fastness

Raw 1 1 3-4
Plasma treated 2 1-2 3-4
AA grafted (3.54%) 4 3-4 6

Table 4
Antibacterial activity of different samples (% reduction of bacteria after 24 h incubation)

Bacterium Staphylococcus Klebsiella

Sample aureus pneumoniae
Raw (Undyed) 0% 0%
Raw-Dyed 0% 0%
Plasma treated-Dyed 0% 0%
AA grafted (3.54%)-Dyed 99.2% 99.1%

Antibacterial activity acid grafting showed good antibacterial activity.

Table 4 shows the reduction (%) in number of Berberine colorant is a quaternary ammonium
two bacteria after 24-hour incubation on the compound, containing a positive charge on the N
surface of different samples. Only the cotton atom that could destroy the negatively charged
sample dyed after plasma treatment and acrylic cell membrane of the bacteria by disturbing the

307
AMINODDIN HAJI

4.
charge balances of the cell membrane. Other A. K. Sarkar and C. M. Seal, Clothing Text. Res. J.,
detrimental effects of quaternary ammonium 21, 162 (2003).
5.
compounds on microbes are denaturizing of S. Ali, T. Hussain and R. Nawaz, J. Cleaner Prod.,
proteins and disruption of the cell structure.18 The 17, 61 (2009).
6.
A. V. Popoola, J. Appl. Polym. Sci., 77, 752 (2000).
samples dyed without plasma treatment or only 7.
M. M. Kamel, R. M. El-Shishtawy, B. M. Youssef
after plasma treatment showed no antibacterial and H. Mashaly, Dyes Pigm., 73, 279 (2007).
activity, because the amount of antibacterial dye 8.
M. M. Kamel, M. M. El Zawahry, N. S. E. Ahmed
on the fabric seems to be less than the minimum and F. Abdelghaffar, Ultrason. Sonochem., 16, 243
inhibitory concentration of the compound needed (2009).
9.
to inhibit the growth of bacteria. T.-K. Kim, S.-H. Yoon and Y.-A. Son, Dyes Pigm.,
60, 121 (2004).
10.
CONCLUSION M. M. Kamel, H. M. Helmy and N. S. El Hawary, J.
Oxygen plasma treatment of cotton fabric, as Nat. Fibers, 6, 151 (2009).
11.
described in this study, improves the graft yield of P. S. Vankar, R. Shanker, D. Mahanta and S. C.
Tiwari, Dyes Pigm., 76, 207 (2008).
acrylic acid on the fiber. Grafting of acrylic acid 12.
P. S. Vankar, R. Shanker, S. Dixit, D. Mahanta and
on cotton fiber is affected by time of plasma S. C. Tiwari, Ind. Crop. Prod., 27, 371 (2008).
treatment, AA concentration and grafting time. 13.
N. Reddy, S. Han, Y. Zhao, and Y. Yang, J. Appl.
Grafting of acrylic acid onto cotton fiber Polym. Sci., 127, 2698 (2013).
improves the absorption of berberine natural dye 14.
S. Han and Y. Yang, Dyes Pigm., 64, 157 (2005).
15.
on it, because of ionic interactions between the K. Ravikumar, S.-H. Kim and Y.-A. Son, Dyes
dye and the modified fiber. The dyed fabric Pigm., 75, 401 (2007).
16.
showed good fastness properties, besides M. Doru, Z. Baysal and . Aytekin, Prep. Biochem.
excellent antibacterial activity against both gram- Biotechnol., 36, 215 (2006).
17.
negative and gram-positive bacteria. Y.-A. Son, B.-S. Kim, K. Ravikumar and T.-K. Kim,
J. Appl. Polym. Sci., 103, 1175 (2007).
18.
A. Haji, Iran. J. Chem. Chem. Eng., 29, 55 (2010).
REFERENCES 19.
A. Haji and A. M. Shoushtari, Ind. Text., 62, 244
1.
M. D. Teli and J. Sheikh, Cellulose Chem. Technol., (2011).
46, 53 (2012). 20.
S. Saxena, A. R. Ray and B. Gupta, J. Appl. Polym.
2.
G. Ke, W. Yu and W. Xu, J. Appl. Polym. Sci., 101, Sci., 116, 2884 (2010).
3376 (2006). 21.
C. S. Ren, D. Z. Wang and Y. N. Wang, Surf. Coat.
3.
T.-K. Kim and Y.-A. Son, Dyes Pigm., 64, 85 Technol., 201, 2867 (2006).
(2005).

308