Indian Journal of Fibre & Textile Research

Vol 39, March 2014, pp. 102-106

Dyeing properties of natural dye extracted
from Rhizoma coptidis on acrylic fibres
Guizhen Ke
a

School of Textile Science and Engineering, Wuhan Textile
University, Wuhan 430200, P R China
Received 13 November 2012; revised received and
21 February 2013
Acrylic fibre has been dyed with Rhizoma coptidis aqueous
solution and its dyeability is studied in terms of the
thermodynamic and kinetic properties and dyeing conditions. The
results show the Langmuir type adsorption isotherm for dyed
acrylic fibre. The dye uptake and dyeing diffusion coefficient of
acrylic fibres increase with the increase in dyeing temperature.
The effects of dyeing conditions such as dye concentration,
dyeing temperature, dyeing time, pH value of dyebath and
mordant dyeing on color characteristics of the dyed fibres have
been studied, and the optimal dyeing process is selected by
orthogonal experimental. The results show that the dyeing
temperature and mordant content are the most important
influencing factors. Wash fastness and rub fastness of the dyed
acrylic show above 4 grade.
Keywords: Acrylic fibre, Dyeing, Natural dye, Rhizoma coptidis
Currently, there is a move to use natural dyes, and
considerable research work on natural dyes has been
reported
1-5
. This is due to the stringent environmental
standards imposed on the toxic and allergic reactions
associated with synthetic dyes
6
. Natural dyes
generally are more friendly to the environment and
thus interests in the use of natural dyes revive. At
present, natural dyes are mostly used in the dyeing of
natural fibres such as wool, silk and cotton
1,2,7,8
, and
occasionally there are some reports about the use of
natural dyes on synthetic fibres
9,10
.
Natural dyes are obtained from plants, minerals and
animals; most of them are extracted from plants
which are herbs themselves. According to the
chemical structure, the natural plant dye can be
divided into indigo type, anthraquinone type, flavone
type, alkaloids type, poly-hydroxybenzene type,
diketone type, benzopyran type, and carotenoid
type
11,12
. Dye extracted from Rhizoma coptidis is
mainly berberine, a widely distributed berberidaceaen
alkaloid that has been employed in traditional
medicine as an antiprotozoal and antidiarrheal agent
13
.
It is found mostly in roots of Rhizoma coptidis and
stems of phellodendron. Another name of Rhizoma
coptidis is Coptis chinensis. Coptis chinensis is the
perennial herbaceous plants, belonging to the
buttercup, which spreads all over the mountain of
west, east to central China. In addition to the wild
resources, at present Coptis chinensis mostly comes
from artificial cultivation.
As a yellow natural cationic dye, Rhizoma coptidis
extraction is usually used for dyeing natural protein
fibre such as silk and wool
14,15
. In this study, Rhizoma
coptidis dye has been used to dye acrylic fibre and its
dyeability is studied in terms of the thermodynamic
and kinetic properties and dyeing conditions.

Experimental
Mid-length type acrylic fibre(51~76mm, about
1.1dtex) was procured commercially. The fibre was
prepared by copolymerization of acrylic (the first
monomer, >85%), methyl acrylate (the second
monomer, 3~12%) and sodium allylsulfonate (the
third monomer, 1~3%). Rhizoma coptidis was
obtained from medicine market. All other reagents
were of analytical grade. To remove grease and other
impurities in the fibre surface, acrylic fibre was
pretreated in 7.5g/L acetone solution with bath ratio
1:80. After that, all the fibres were washed and dried
for further use.

Rhizoma coptidis (5 g) was minced and dipped in
500mL distilled water for 60 min, and then boiled in
distilled water for 50min. The content was cooled at
room temperature and filtrated. The Rhizoma coptidis
residue was again boiled for 50min in distilled water
and filtrated. Finally, the filtrate from the two
extractions was mixed and the mixed filtrate was
concentrated to 100mL. The extraction rate was 50.2%,
and R.S.D value was 1.086%. The concentrated
solution was frozen at -80C for 2h and then freeze-
dried for 15h in lyophilizer. Rhizoma coptidis
extraction powder thus obtained was used for dyeing.
The dyeing solutions of different concentrations
were prepared with Rhizoma coptidis extraction
powder, and acrylic fibre was dyed at 60C and 95C
for 5h, keeping liquor-to-material ratio at 200:1. The
initial pH of the dyeing solution was adjusted at 6.5.

a
E-mail: kgz66@126.com
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103
The absorbency of residual dyeing solution was
measured with UV-vis spectrophotometer and the dye
concentrations of final bath ([D]
s
, g L
-1
) was
calculated using calibration curve [Eq.(1)] according
to Lambert-Beer law. The dye concentration in the
fibre at equilibrium ([D]
f
, g/kg) was obtained with
subtraction. Then absorption isotherm of Rhizoma
coptidis on acrylic fibre was drawn.
For the study of dyeing rate, 0.25g fibre was dyed
with 0.08g/L dye concentration at 60C and 95C,
keeping the liquor-to-material ratio at 200:1. The
extent of dye uptake (%) was determined using the
following equation by the absorbance spectroscopic
analysis of the dyebath at different time intervals, and
the exhaustion curves were obtained:
0 1
0
Dye uptake(%)= 100(%)
A A
A

(1)
where A
0
is the absorbance of the dyebath before
dyeing; and A
1
, the absorbance of the dyebath after
dyeing. Dyeing diffusion coefficient and the related
other parameters were calculated accordingly.
Acrylic fibre was dyed with Rhizoma coptidis dye
under different conditions and color difference(E) of
the dyed fibre was measured with UV/Vis
spectrophotometer plus an integrating sphere
attachment and color measuring software, using
illuminant D65 and 10 standard observer. The effects
of dyeing conditions such as dye concentration,
dyeing temperature, dyeing time, pH value of dyebath
and mordant dyeing on color difference of the dyed
were discussed, and optimal dyeing process was
selected by orthogonal experimental.
The following experiments were carried out
according to L
9
(3
4
) orthogonal experiment with bath
ratio 1:100 and each factor adopted three levels.
Firstly, acrylic fibre was dyed directly with
solution of Rhizoma coptidis extraction powder,
which was called direct dyeing. The four factors used
in this orthogonal experiment were temperature,
pH value, dyeing concentration and dyeing time.
Acrylic fibre was pretreated with mordant solution
and the pretreated fibre was dyed with Rhizoma
coptidis dye, which was called pre-mordant dyeing.
The used mordants were ferrous sulfate (iron salt) and
cupric sulfate (copper salt). The factors used in this
orthogonal experiment were temperature, pre-treating
time and mordant content.
Acrylic fibre was dyed with the mixed solution of
Rhizoma coptidis extraction powder and mordant,
which was called simultaneous mordant dyeing.
The four factors used in this orthogonal experiment
were temperature, dyeing time, pH value and
mordant content.
Wash fastness and rub fastness tests were carried
according to GB/T3921.1-1997 (eqv ISO105-
CO1:1989) and GB/T3920-1997(eqv ISO 105-
X12:1993) respectively.
Absorption isotherms of acrylic fibre dyeing with
Rhizoma coptidis are shown in Fig.1. For the
absorption isotherm, the dye concentration in the
fibre at equilibrium ([D]
f
), the dye concentration of
dyeing solution ([D]
s
), their reciprocal 1/[D]
f
and
1/[D]
s
and their logarithm ln[D]
f
and ln[D]
s
were
treated with linear fitting respectively, and their
results are shown in Table 1.

Results and Discussion
As can be seen from Table 1, for the acrylic fibre
dyeing at 60 C and 95 C, 1/[D]
f
and 1/[D]
s
show the
highest fitting degree respectively 0.9905 and 0.9826,
which indicates that the absorption isotherms of
acrylic fibre dyeing with Rhizoma coptidis extraction
follow Langmuir type. Since the dye contains cationic
quaternary ammonium salt, it would interact ionically
with the sulfonic acid groups of acrylic fibres. Dye
adsorption ([D]
f
) increases with the increase in dye
concentration until it reaches saturation. It is observed
that the slope at the initial segment of the adsorption


Fig. 1Absorption isotherm of acrylic fibre dyeing with Rhizoma
coptidis

Table 1Fitting degree of absorption isotherm for acrylic fibre
Temperature, C Directness Reciprocal Logarithm
60 0.9341 0.9905 0.9733
95 0.8972 0.9826 0.9525
INDIAN J FIBRE TEXT RES , MARCH 2014


104
isotherm and the equilibrium adsorption amount
increase with the increase in dye temperature.
Especially when dyeing at 95C, the increase in [D]
f

is more obvious, which is related to the glass
transition temperature of acrylic fibre. When the
acrylic fibre is dyed above the glass transition
temperature, dye adsorption happens quickly due to
the intense movement of fibre macromolecular chain.
Dyeing rate curve is an important means to study
dyeing kinetics. The dyeing rate curves of Rhizoma
coptidis on acrylic fibres are presented in Fig.2, which
provides complete description of dye adsorption rate
under different dyeing conditions.
Figure 2 shows that the adsorption of Rhizoma
coptidis dye on acrylic fibre is rapid in the initial
dyeing phase, i.e. initial dyeing rate is higher. And the
equilibrium dye uptake amount increases with the
increase in dyeing temperature, which is consistent
with the thermodynamic results. When dyeing is done
at 95 C, dyeing rate reaches as high as 90%, and the
adsorption of Rhizoma coptidis dye is higher by far
than that at 60C.
Dye uptake rate depends on the dye diffusion rate
in the fibre. The dye diffusion performances in the
fibre are affected by the characteristics of dyes and
fibres and dyeing conditions such as dyeing
concentration, temperature, pH, etc. According to Hill
formula, the average diffusion coefficient of acrylic
fibre is bound to be 1.8910
-8
cm
2
min
-1
at 60C and
3.5910
-8
cm
2
min
-1
at 95C, which indicates that at
higher temperature, the diffusion coefficient improves
obviously. When acrylic fibre is dyed at near glass
transition temperature, molecular chain segment
movement becomes quite fierce, and the gap between
macromolecular is broadened. Hence, more Rhizoma
coptidis dye is absorbed and the time towards
adsorption equilibrium is shortened. The results of
orthogonal experiment for direct dyeing and simple
analysis are shown in Table 2.
The results indicate that the dyeing temperature is
the most important factor in direct dyeing of acrylic
fibre with Rhizoma coptidis dye, followed by dyeing
concentration and dyeing time in sequence.
As shown in Table 2, the higher the dyeing
temperature and dyeing concentration, the greater is
the color difference (E), which corresponds with the
results of thermodynamics and kinetics test. The
effect of dyeing time and pH value on color difference
is relatively less. Higher E can be obtained for
dyeing in weak acid to neutral environment.
According to E, the optimum dyeing conditions for
direct dyeing are selected as dyeing temperature 90C,
pH value 6, dyeing concentration Y, dyeing time
60min and bath ratio 1:100. The combination is the
eighth set of experiments, in which color difference
value is turned out to be 38.74, the highest value
among all, and verified the rationality of the
combination process further.
Acrylic fibre is pretreated with iron salt and
copper salt mordant according to the designed
orthogonal experiment with bath ratio 1:100 and
then dyed with above optimum direct dyeing
conditions. The color difference of the dyed fibre is
measured and the results and simple analysis are
shown in Table 3.


Fig. 2Dyeing rate curves of Rhizoma coptidis on acrylic fibre at
different temperature
Table 2Orthogonal trial results for direct dyeing of acrylic fibre
Number Temperature
C
pH
value
Dyeing
concentration
g/L
Dyeing
time, min
E
1 70 4 Y 30 20.28
2 70 6 (1/2Y) 45 16.61
3 70 8 (1/4)Y 60 15.51
4 80 4 (1/2Y) 60 27.80
5 80 6 (1/4)Y 30 25.61
6 80 8 Y 45 31.66
7 90 4 (1/4)Y 45 25.09
8 90 6 Y 60 38.74
9 90 8 (1/2Y) 30 32.10
1
K
17.47 24.39 30.23 26.00
2
K

28.36 26.99 25.50 24.45
3
K

31.98 26.42 22.07 27.35
R 14.51 2.60 8.16 2.9
Y represents initial dyeing concentration 0.05g/L.
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Table 3 shows that the mordant pretreatment has
obvious effects on improving color values. The
direct analysis shows that for iron salt treatment,
mordant content is the most important factor on
color value, followed by treating temperature and
time in sequence. The optimum treating conditions
for iron salt mordant are selected as treating
temperature 60 C, treating time 45min and mordant
content 3%. To verify the findings, acrylic fibre is
treated under the selected optimum conditions and
dyed with above optimum direct dyeing conditions.
The color difference of the treated acrylic fibre is
turned out to be about 44.28. For copper salt
treatment, treating temperature is found to be the
most important factor, followed by treating time and
mordant content in sequence. The optimum treating
conditions for copper salt mordant are selected as
treating temperature 80 C, treating time 45min and
mordant content 3%. The combination is the eighth
set of orthogonal experiments, wherein color
difference value is turned out to be the highest value,
and verified the rationality of the combination
process further. The results of orthogonal experiment
for simultaneous mordant dyeing and simple analysis
are shown in Table 4.
Dyeing temperature is the most significant factor
on color difference both for iron salt and copper salt
mordant dyeing. Both color values increase with the
increase in dyeing temperature. According to the
direct analysis, the optimum dyeing conditions for
two salts are: for iron salt, dyeing temperature 90C,
dyeing time 60min, pH value 8, mordant content 6%
and bath ratio 1:100; and for copper salt, dyeing
temperature 90C, dyeing time 60min, pH value 8,
mordant content 3% and bath ratio 1:100. To verify
the findings, acrylic fibre is dyed under the selected
optimum conditions. The color difference is turned
out to be 41.83 and 44.40 respectively for iron and
copper salt simultaneous mordant dyeing.
Wash fastness and rub fastness test results show
that both direct dyeing and mordant dyeing give good
wash fastness (4~5 grade) and rub fastness (wet rub
fastness 4~5 grade, dry rub fastness 5 grade), which
indicate that natural plant dye extracted from Rhizoma
coptidis is suitable for acrylic fibre.
Natural plant dye was extracted from Rhizoma
coptids with water and freeze-dried with lyophilizer.
The adsorption isotherm of dye on acrylic fibres
belongs to Langmuir type. When dyeing temperature
is reached 95C, the equilibrium dye uptake is much
higher than that at 60C. Dye uptake rate curves
shows that the dyeing rate at the early stage and the
diffusion coefficient increase with the increase in
dyeing temperature. Dyeing temperature is the most
important influencing factor during direct dyeing,
simultaneous mordant dyeing and copper salt

Table 3Orthogonal trial results and straight analysis for acrylic fibre pre-mordant dyeing
E
Level Temperature, C Pre-treating time, min Mordant content,
(o.w.f)
Iron salt Copper salt
1 40 30 3 42.08 40.55
2 40 45 6 40.12 40.54
3 40 60 9 40.65 37.22
4 60 30 6 39.00 37.84
5 60 45 9 43.56 39.58
6 60 60 3 41.42 39.59
7 80 30 9 39.9 42.07
8 80 45 3 44.37 40.45
9 80 60 6 35.80 41.70

1
K
40.95 40.33 42.62
2
K

41.33 42.68 38.31
3
K

40.02 39.29 41.37
Iron salt
R 1.30 3.39 4.32
1
K
39.44 40.15 40.20
2
K

39.00 40.19 40.03
3
K

41.41 39.50 39.62
Copper salt
R 2.40 0.69 0.57
INDIAN J FIBRE TEXT RES , MARCH 2014


106


pre-mordant dyeing, and color difference value
increases clearly with the increase in dyeing
temperature; the most important influencing factor is
mordant content during iron salt pre-mordant dyeing;
and mordant deepens the color clearly. The color
fastness test shows that the dyed acrylic fibre has
good wash fastness and rub fastness.

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Table 4Orthogonal trial results and straight analysis for mordant dyeing of acrylic fibre
E
Level Temperature, C Dyeing time, min pH value Mordant content
(o.w.f)
Iron salt Copper salt
1 70 30 4 3 18.42 15.47
2 70 45 6 6 20.25 7.50
3 70 60 8 9 21.58 18.22
4 80 30 6 9 29.61 10.70
5 80 45 8 3 34.29 30.60
6 80 60 4 6 35.09 21.35
7 90 30 8 6 44.29 31.98
8 90 45 4 9 35.99 30.86
9 90 60 6 3 46.84 30.19

1
K
20.08 30.77 29.83 33.18
2
K

33.00 30.18 32.23 33.21
3
K

42.37 34.50 33.39 29.06
Iron salt
R 22.29 4.33 3.55 4.15
1
K
13.73 19.38 22.56 25.42
2
K

20.88 22.99 16.13 20.28
3
K

31.01 23.25 26.93 19.93
Copper salt
R 17.28 3.87 10.80 5.49