Indian Journal of Fibre & Textile Research

Vol. 38, December 2013, pp. 424-426

Studies on kinetic and thermodynamic

parameters of natural dye curcumin on
PLA fibre
Jihong Wua, Hui Guo, Jun Ke & Jiangtao Fan
School of Textile Science and Engineering, Wuhan Textile
University, Wuhan 430200, China
Received 7 May 2012; revised and accepted 26 October 2012
The dyeing kinetics and thermodynamics for PLA fibre dyed
with the natural dye curcumin have been studied. The rate of dye
uptake, half dyeing time, diffusion coefficient, standard affinity,
heat and entropy of dyeing have been determined. Linear
isotherms are obtained, suggesting that the mechanism of dyeing
is similar to that of disperse dyes. The rate of dye uptake and the
total dye uptake increase with the increase in dyeing temperature.
Keywords: Curcumin, Dyeing kinetics, Dyeing thermodynamics,
Dyeing mechanism, PLA fibres

In recent years, the natural dyes have been widely

used to dye textile due to their properties of nontoxicity, harmlessness and non-pollution1, natural and
soft luster, solemn and elegant colour2. Turmeric has
traditionally been an important natural source of
yellow colour for textiles, such as cotton, hemp, silk
and polyester3. As the main component of turmeric,
curcumin has been served as a widely used natural
dye today. As a kind of ecofriendly and biodegradable
synthetic polyester fibre, polylactic acid (PLA) fibre
shows both the properties of synthetic fibres and
natural fibres4,5. Thus, increasing attention has been
shown on this fibre. However, few investigations have
been conducted on the dyeing mechanism of PLA
fibre dyed with natural dyes.
In this study, the dyeing kinetics and
thermodynamics of PLA fibre dyed with natural dye
curcumin have been investigated. It provides the
theoretical analysis of dyeing PLA fibre with natural
dyes, which could benefit the application of natural
dyes and PLA fibre in further research.
The purified curcumin dye was obtained from the
Xian Xiaocao Plants Technology Ltd. Polylactic acid
fibres with 1.1 denier fineness and 5.535 m radius
were supplied by the Changshu Yangtze River

a
Corresponding author.
E-mail: jihong_wu@wtu.edu.cn./ 1404706998@qq.com

Chemical Fiber Co., Ltd. All solvents, reagents

and chemicals were purchased from the Sinopharm
Chemical Reagent Co., Ltd (laboratory reagent
grade). The scouring agent RUCOGEN WBL,
was purchased from the Rudolph Chemical
(Dongguan) Co. Ltd. Glacial acetic acid and sodium
hydroxide were the buffer solution used during
the dyeing process in order to maintain a constant
pH 5.
All dyeing processes were carried out in the HH-4
thermostatic bath dyeing machine. The absorbance of
the dye solutions was measured using a Shimadzu
2550 UVvisible (UVVis) spectrophotometer (Japan).
PLA fibres were scoured in a solution of 2 g/L
non-ionic detergent and 1 g/L sodium carbonate for
0.5 h at 60 C, with a liquor ratio of 1:50, followed by
three cycles of repeated rinsing process in hot and
cold water and air drying at room temperature.
The dyeing solution was a mixture of acetone and
water (1:1, w/v). The wavelength of maximum
absorbance value (max) was detected with the UV-Vis
spectrophotometer. At the max, the absorbance values
of dyeing solution with different concentrations were
measured. The relationship between the absorbance
values and its concentration, namely the calibration
curve was acquired.
For kinetic studies, the dyeing was pursued with a
dye concentration of 0.2 g/L at PH 5 (maintained by
the buffer) for the time period ranging from 5 min
to 240 min at 60 C, 80 C and 100 C, with a
liquor-to-goods ratio of 100:1. The dye uptake
was measured at different time intervals by
evaluating the extinction value at max with UV-Vis
spectrophotometer.
For thermodynamic study, the dyeing process was
carried out with a series of different dye
concentrations at pH 5 (maintained by the buffer), a
liquor-to-goods ratio of 100:1 at 80 C and 100 C for
240 min. The dye in the exhausted dye bath was
estimated by evaluating the extinction value at max
with UV-Vis spectrophotometer.
The wavelength of maximum absorbance (max) is
425 nm. The standard working curve of curcumin dye
is shown in Fig.1. The linear regression calibration
equation was obtained by computer fitting, as shown
below:

INDIAN J. FIBRE TEXT. RES., DECEMBER 2013

A = 10.413C , R 2 = 0.9988
(1)
where A is the absorbance; C, the concentration of
dyeing solution (g/L); and R, the linear relative
coefficient of the equation6. It is found that the
relationship between absorbance and concentration of
dye solution is linear.
The dye uptake curves of PLA fibres dyed with the
curcumin natural dye at 60, 80 and 100 oC are shown
in Fig. 2. It is evident that the rate of dyeing increases
with an increase in temperature, and the equilibrium is
arrived at about 100 min.
At 60 oC, the percentage exhaustion of curcumin
dye on the PLA fibres in dyebath at equilibrium is
about 13%, which is rather low. It is possible due to
the high molecular crystallinity of the PLA fibre7.
It poses a difficult dye penetration into the interior of

Fig.1 Standard working curve of curcumin dye

PLA and subsequently heeps in forming the hydrogen

bonds between dye and fibre. Besides, the high degree
of orientation and packed internal structure of PLA
fibre7 is another factor. The temperature of 60 C is
close to the glass transition temperature of PLA fibre.
The molecular chain segments do not move obviously
at 60 C, resulting in a poor liquidity of the dyebath.
Consequently, at 60 C the curcumin dyeing in textile
is due to the physical adsorption but not due to the
affinity adhesion8.
The temperature of 80 oC is already higher than the
glass transition temperature of PLA fibre. The
movements of PLA fibres molecular chains begin to
speed up, resulting in producing the more free volume
of the fibre, which offers more chances for the
curcumin molecules to integrate with PLA molecules
by hydrogen bonds. Thus, the PLA fibre can adsorb
more curcumin. However, at this moment, the PLA
fibre free volume is not lager enough to adsorb more
curcumin, the percentage exhaustion of dye in the
interior of PLA fibre is still not so high. When the
temperature increases to 100 C, the adsorption of
curcumin reaches the maximum and finally makes a
balance at 90.9%, as shown in Fig. 2.
The half dyeing time (t1/2) for PLA at 60, 80 and
100 C was calculated from the dye uptake curves and
is given in Table 1. From the calculated date we can
see that t1/2 decreases when dyeing temperature
increases, indicating that the rate of dye uptake of
curcumin dye on the PLA fibres at 100 C is faster
than that at 60 C and 80 C.
The approximate apparent diffusion coefficient (D)
in the half dyeing time of curcumin on PLA was also
calculated (Table 1). From the calculated values, it
can be observed that the D at 100 C is higher than
that at 80 C. The D value was calculated using the
following equation:
DT1/2
2.64
= 1.36 +

2
1 Es
R

(2)

where R is the fibre radius; D, the diffusion

coefficient; and Es, the equilibrium rate of dye uptake.
Results obtained from dyeing experiments carried
out to equilibrium at 80 C and 100 C are shown in
Table 1 Values of half dyeing time and diffusion coefficient

Fig.2 Percentage exhaustion of curcumin dye on PLA fibre at

60, 80 and 100 C

Temperature, oC R10-4, cm
60
80
5.54
100

t, min
22.37
7.83
5.03

D10-12 , cm2/s
1.84
9.63
11.20

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Table 2 Thermodynamic parameters for dyeing of PLA fibre

with curcumin dye
Temperature Distribution coefficient -
(K), L/kg
C
80
68.45
12.41
100
276.43
22.12

0.415

159.04

The heat of dyeing (H) and entropy of dyeing

(S) are given by the following equations10:

1T2 2T1
T2 T1
= H TS
H =

Fig.3 Adsorption isotherms for dyeing of PLA fibre with

curcumin dye at 80 oC and 100 C

the form of adsorption isotherms (Fig. 3). Linear

isotherms were obtained at both temperatures, which
indicate that the mechanism of dyeing of PLA with
curcumin corresponds to the Nernst model. The slope
of the isotherms of PLA increases with an increase in
temperature. These observations confirm that the
dyeing mechanism of the natural dye curcumin on PLA
is similar to that of disperse dyes on polyester fibres.
The standard affinity (-) of dyeing was
calculated using the following equation 10:

= RT ln

[D]f
V [D ]s

= RT ln K

(3)

where [D]f is the concentration of dye in the fibre;

[D]s, the concentration of dye in the solution; V, the
amount of water associated with the fibre which is
equal to its moisture regain at 100% humidity; and R,
the gas constant.
The standard affinity values obtained from Eq.(3)
for PLA at 80 C and 100 C are given in Table 2.
The standard affinity. Distribution coefficient of PLA
increases with the increase in temperature.
Distribution coefficient increases greatly at 100 C.
This is likely due to the packed molecular structure of
PLA fibre. The higher the temperature, the faster is
the motion of the molecules. At the same time PLA
fibre chain moves faster, and the expansion of the
fibre also improves, thus it is conducive to the
diffusion of dyes in fibre interior.

(4)
(5)

The calculated values of heat and entropy of dyeing

are given in Table 2. The heat of dyeing and entropy
of dyeing are both positive, i.e. this dyeing process is
endothermic and therefore more dye will be adsorbed
at equilibrium with the increase in temperature.
In this study, kinetic and thermodynamic
investigations of natural curcumin show that the dye
exhibits good affinity for PLA. The percentage
exhaustion of dye is found to increase at a slow speed
when the temperature is between 60 C and 80 C,
while at 100 C the percentage exhaustion of dye
increases sharply and finally makes a balance at
90.9%. Dyeing on PLA fibres with curcumin
corresponds to the Nernst isotherm (linear isotherms),
confirming that the dyeing mechanism is similar to
that of disperse dyes.
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