Journal of Cleaner Production 143 (2017) 269e277

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

An ecofriendly dyeing of wool with supercritical carbon dioxide fluid

Huanda Zheng, Yanyan Xu, Juan Zhang, Xiaoqing Xiong, Jun Yan, Laijiu Zheng*
Liaoning Provincial Key Laboratory of Ecological Textile, Dalian Polytechnic University, Dalian, Liaoning 116034, China

a r t i c l e i n f o a b s t r a c t

Article history: Dyeing feasibility of wool was investigated with Disperse Red 54, Disperse Blue 183, Disperse Red 153,
Received 13 August 2016 Disperse Blue 148, Disperse Red 92, and Disperse Yellow 82 in supercritical carbon dioxide. The effects of
Received in revised form dyeing temperature, pressure, time, dye mesh number, as well as CO2 flow on the K/S values and fixation
27 September 2016
rates of the wool samples were discussed. The results showed that the higher K/S values and fixation
Accepted 21 December 2016
rates were obtained with Disperse Red 153 and Disperse Blue 148 in comparison with other disperse
Available online 22 December 2016
dyes. Simultaneously, the K/S values and the fixation rates were improved gradually from 70
C to 110
C,
15 MPa to 25 MPa, 60 min to 120 min, as well as 40 mesh number to 100 mesh number for Disperse Red
Keywords:
Ecofriendly dyeing
153, and from 80
C to 120
C, 15 MPa to 25 MPa, 60 min to 120 min, as well as 40 mesh number to 100
Wool mesh number for Disperse Blue 148 during supercritical carbon dioxide dyeing procedure. Moreover,
Supercritical carbon dioxide excellent permeability and color fastness were obtained whereas the breaking force and tensile strength
Disperse dye of the dyed wool fibers were reduced slightly after supercritical carbon dioxide dyeing.
Performance © 2016 Elsevier Ltd. All rights reserved.

1. Introduction dyeing procedure for wool to conserve the scarce water resources,
reduce the negative environmental impacts and improve the eco-
As an important protein fiber, wool which exhibits the charac- nomic sustainability (Xu et al., 2016).
teristics of excellent flexibility, good warmth retention, high In order to solve the problem of severe water pollution,
hygroscopy, satisfactory static and stain resistance, tender luster, numerous researches have been conducted over the last two de-
soft handle, as well as higher igniting temperature than most of cades to investigate the ecofriendly dyeing procedure for wool fi-
conventional fibers, is amongst the earliest natural fibers for ber, including solvent dyeing (Shukla and Mathur, 1997), foam
clothing and very important for human being to live in the eco- dyeing (Yu et al., 2014), and other cleaner dyeing methods. Of
friendly world (Shen et al., 2014; Long et al., 2013). At present, wool which, supercritical carbon dioxide dyeing established by Professor
fiber has been widely used in textile, automotive, medical, deco- E. Schollmeyer from Deutsches Textilforschungszentrum Nord-
ration, aerospace and other technical fields (Benisek et al., 1991; West e.V. (DTNW) in 1980s, shows the potential of replacing the
Jeon et al., 2015). In the industrial production, dyeing is a key far more environmentally damaging aqueous dyeing procedure due
procedure to add the commodity value for wool. However, tradi- to its low energy consumption, high uptake rate, recycling of dyes
tional dyeing process requires a large amount of water, averagely and carbon dioxide, as well as zero waste water emission (Zhang
100e150 L of water per 1 kg of fiber (Cid et al., 2005). Corre- et al., 2015; Zheng et al., 2016). Moreover, carbon dioxide is an
spondingly, considerable levels of dyes, salts and acetic acid are attractive dyeing medium alternative for a wide variety of chemical
added in the wool dyeing process, producing huge quantities of solvents because of its low cost, wide availability, as well as envi-
effluent which is difficult to treat with conventional biochemistry ronmentally friendly and chemically benign nature (Zheng et al.,
methods (Zheng and Zheng, 2014; Zheng et al., 2015). Given the 2015a,b).
extremely huge quantities of effluent, aqueous dyeing procedure Generally, reactive dyes and/or acid dyes are mainly used in the
not only leaves large water footprint on the planet but also suffers conventional wool dyeing procedure since wool is a hydrophilic
from the increasing costs of wastewater treatment (Chico et al., fiber containing polar groups of amino. Reactive dyes and/or acid
2013). Thus, it is highly desirable to develop an ecofriendly dyes having water-soluble groups are chemically bonded with the
amino, hydroxy and/or mercapto groups on macromolecular chains
of wool fiber, thereby improving the fixation rate and colorfastness
* Corresponding author. (Broadbent, 2001). However, supercritical carbon dioxide, a non-
E-mail address: [email protected] (L. Zheng). polar dyeing medium, can only dissolve hydrophobic dyes, such

http://dx.doi.org/10.1016/j.jclepro.2016.12.115
0959-6526/© 2016 Elsevier Ltd. All rights reserved.
270 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277

as disperse dyes, which have similar molecular structure with acid 2.2. Preparation for dyes and wool
dyes except for the content of sulfonic groups. Wool molecules also
contain a lot of hydrophobic components, non-ionic polar groups, Before dyeing, all the disperse dyes were dried to a constant
and a small amount of lipid-based compounds, so that it is possible weight at 60
C by employing a dry oven. After drying, the dyes
for the dye molecule to reduce its potential energy by being were grinded and sieved with grading sieves to obtain the dyes
adsorbed with its hydrophobic parts on the hydrophobic portions with mesh number ranging from 40 to 100. These dyes were then
of the wool (Chao and Lin, 2000). Hence, the potentially high af- placed into a drying basin and used for dyeing. Wool fibers were
finity of the hydrophobic sites on wool for disperse dyes can then be also dried to a constant weight at 60
C, and then stored in the
exploited (Shen, 2003), and it is feasible for wool to be dyed using drying basin for the dyeing use.
some disperse dyes with special structures. Several reports had
been documented that disperse dyes with suitable groups could 2.3. Dyeing of wool in supercritical carbon dioxide
dye wool in water. Turner discussed the distribution of disperse dye
between triacetate and polyester, and found that the inclusion of a A self-built supercritical carbon dioxide dyeing apparatus
hydrophilic group in the disperse dye molecule increases the dis- making up of a pressure and heating system, a dyeing system, a
tribution ratio in favour of the polar fiber (Chao and Lin, 2000). Lee recycle system, as well as a control system, is adopted in the ex-
and his cooperators applied some temporarily solubilised disperse periments, as shown in Fig. 1. In the supercritical carbon dioxide
dyes derived from aminophenyl-4-(b-sulphatoethylsulphone) to dyeing apparatus, the recycle system was mainly composed with a
wool in aqueous bath without the use of a levelling agent, and compressor, a refrigerator, a carbon dioxide cylinder, and a sepa-
observed excellent levelling properties, exhaustion, fixation and rator. Before dyeing, carbon dioxide in the gas cylinder was firstly
fastness (Lee et al., 2001). Nevertheless, to the best of our knowl- cooled to liquid by employing the refrigerator connected with the
edge, supercritical carbon dioxide dyeing for wool with suitable compressor. The liquid carbon dioxide cooled with a pre-cooler was
dyes has not been reported up to date. then pressurized to above the critical pressure (7.38 MPa) using a
In addition, in order to acquire good dyeing performance of high-pressure pump, and heated to above the critical temperature
wool fiber, disperse dyes modified with reactive groups of bro- (31.10
C) with a heat exchanger attached to a conduction oil unit,
moacrylic acid (Schmidt et al., 2003), triazine (Cid et al., 2005; Patel thereby tuning carbon dioxide into the supercritical state. In this
and Patel, 2011), as well as vinylsulphone (Kraan et al., 2007), process, the pressure and heating system was composed of the pre-
named disperse reactive dyes, have been synthesized to achieve the cooler, the high-pressure pump, the heat exchanger and the con-
coloration of wool in supercritical carbon dioxide (Zhang et al., duction oil unit. Using the pressure and heating system, the su-
2016). But unfortunately, to date, there are few successful practice percritical carbon dioxide fluid was introduced into the dyeing
application reports about these disperse reactive dyes in super- system where solid disperse dyes and wool fibers were placed into
critical carbon dioxide as the properties of disperse reactive dyes a dye vessel and a dyeing vessel, respectively. The dissolution of
are related with the structures of both disperse dyes and reactive dyes and the dyeing for fibers were conducted continuously with
groups. Therefore, selection of suitable disperse dyes not only can the action of a magnetic drive circulating pump between the dye
meet the needs of the exploration for wool dyeing in supercritical vessel and the dyeing vessel.
carbon dioxide, but also provide appropriate dye structures for the When the dyeing process was finished, the dye residues were
modification process of disperse reactive dyes, which plays a sig- precipitated out in the separator. The carbon dioxide was recycled
nificant role in the ecofriendly dyeing procedure of wool. at pressures and temperatures ranging from 3 MPa to 4 MPa and
The objective of this work is to investigate the ecofriendly from 25
C to 40
C, and flowed into the carbon dioxide cylinder for
dyeing of wool with disperse dyes in supercritical carbon dioxide. next experimental use. During the dyeing, parameter regulation
Wool dyeing was conducted with six disperse dyes which are and device switch were all controlled by a computer terminal to
affiliated with azo dyes (Disperse Red 54 and Disperse Blue 183), achieve the convenient and safe dyeing operation.
thiazole dyes (Disperse Red 153 and Disperse Blue 148), anthra-
quinone/amide dyes (Disperse Red 92), as well as fluorescence dyes
(Disperse Yellow 82). The effects of dyeing temperature, pressure, 2.4. Color strength and fixation rate assessment
time, dye mesh number, as well as CO2 flow on the K/S values and
fixation rates of the dyed wool samples were discussed systemat- The color strength (K/S value) of the dyed wool fibers was
ically. Furthermore, the permeability, color fastness and mechanical measured by the light reflectance technique using the Kubelka-
properties of the dyed wool fibers in supercritical carbon dioxide Munk equation, as shown in Equation (1) (Zheng and Zheng,
were also evaluated. This study can provide the beneficial refer- 2014). K/S values were measured with a Color-Eye 7000A spec-
ences for the ecofriendly dyeing procedure of wool. trophotometer (X-rite, America). D65 light source was adopted and
the observation angle was 10
.
.
2. Experimental K=S ¼ ð1  RÞ2 2R ¼ aq (1)

2.1. Materials where K is the absorbance coefficient of the fiber to be tested; S is

the scattering coefficient of the fiber to be tested; R is the reflec-
Fully pretreated wool fibers (14.29 tex) were kindly supplied by tance of the fiber at each wavelength; a is a constant and q is the
Liaoning Chaoyi Co., Ltd. (China) in this study. Disperse Red 54, adsorbed dye concentration on the fiber.
Disperse Blue 183, Disperse Red 153, Disperse Blue 148, Disperse In order to assess the dye fixation on the wool substrate, the
Red 92, and Disperse Yellow 82 without any addition of surfactants colored wool samples were extracted by a Soxhlet extraction method
and salts were supplied by Zhejiang Jihua Group Co., Ltd. (China) with a 50 wt% solution of acetone in water for 30 min to remove the
and used without further purification. The chemical structures of excess dye molecules which were unfixed at the substrate during the
these dyes are shown in Table 1. Carbon dioxide gas (99.9 vol %) dyeing procedure. The K/S values of the extracted fibers (K/S)extr
obtained from China Haohua (Dalian) Research & Design Institute were determined and used to calculate the percentage of dye mol-
of Chemical Industry Co., Ltd. was used for supercritical dyeing. ecules that was fixed to the fibers (F) (Kraan et al., 2007):
 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277 271

Table 1
Disperse dyes for supercritical carbon dioxide dyeing.

Type of Dyes Molecular formula Molecular weight Chemical structure

Disperse Red 153 C18H14Cl3N5S 438.76 Cl S CH2CH3

N N
N CH2CH2CN
Disperse Blue 148 C19H19N5O4S 413.45 S CH2CH3
N N N
N CH2CH2COOCH3
Disperse Red 54 C19H18ClN5O4 415.83 CH2CH2COOCH3
O2N N N N
CH2CH2CN
Cl
Disperse Blue 183 C20H21BrN6O3 473.32 NHCOCH3
Br
CH2CH3
O2N N N N
CH2CH3
CN
Disperse Red 92 C24H22N2O7S 482.51 O OH

O
O S NH(CH2)3OCH2CH3
O
O NH2
Disperse Yellow 82 C20H19N3O2 333.38
H
N
H3CH2C N
N
O O
H3CH2C

Fig. 1. Schematic diagram of the supercritical carbon dioxide dyeing apparatus equipped with (1) Control terminal; (2) Refrigerator; (3) Compressor; (4) Carbon dioxide cylinder; (5)
Pre-cooler; (6) High-pressure pump; (7) Conduction oil unit; (8) Heat exchanger; (9) Dye vessel; (10) Dyeing vessel; (11) Circulating pump; (12) Separator.

2.5. Fastness assessment

.
F ¼ ðK=SÞextr ðK=SÞdyed  100% (2) Color fastness to washing and rubbing of the dyed wool samples
were estimated according to ISO 105-C10-2006 Color fastness to
where F is the ratio of the K/S values of wool samples (fixation rate) washing with soap or soap and soda, as well as ISO 105-X12-2001
after (K/S)extr and before (K/S)dyed a Soxhlet extraction. In theory, Color fastness to rubbing.
the higher the value of a fixation rate, the more dye molecules were
observed to be fixed on a wool sample.
272 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277

2.6. Mechanical properties assessment and Lin, 2000). The above characteristics make Disperse Red 153
and Disperse Blue 148 show better dyeing properties to wool.
The tensile strength of the wool samples was carried out on a During dyeing, the diffusion of disperse dyes into wool fibers
universal material testing machine with the gauge length 10 mm, conforms to the intercellular diffusion model (Rippon, 1992). Wool
test speed 20 mm/min. The strength value (sb/cN) was calculated fibers were swelled in supercritical carbon dioxide. Dye molecules
according to Equation (3) (Zheng and Zheng, 2014): diffused firstly from the intercellular cement on the edge of
. covering scales, proliferated into fibers through the cell membrane
sb ¼ 4Fp pD2 (3) complex, and then entered into the micro-fibrils of cortex cells,
thereby achieving the wool dyeing with Van der Waals’ force and
where Fp is the maximal tensile fracture force; D is the mean hydrogen bonding. Moreover, disperse dyes can also diffused into
diameter of the wool fiber. The data shown for each sample were the hydrophobic components of wool. These dyes will be entrapped
averages of 200 single measurements. in the fiber after the temperature was reduced due to the closure of
the covering scales. Thus, the better dyeing effect of wool was ob-
3. Results and discussion tained in supercritical carbon dioxide, and Disperse Red 153 and
Disperse Blue 148 were selected to carry on the systematic dyeing
3.1. Selection of suitable dyes for wool fibers optimization of wool.

Parameters in supercritical carbon dioxide dyeing procedure 3.2. Effect of dyeing temperature on the dyeing performance of wool
have the direct influence on the solubility and diffusion rate of dyes, fibers
thereby affecting the color strength, colorfastness, permeability
and other dyeing performance. In the dyeing process, K/S value and Temperature variation can result in the change of dye subli-
fixation rate are the most important indicators for evaluating mation pressure and fluid density, and will also affect the move-
dyeing performance of fibers and dyes. Therefore, effects of dyeing ment of dyes and fiber macromolecules. Therefore, effects of
temperature, pressure, time, dye mesh number, and CO2 flow on temperature on the dyeing performance of wool fibers with
the dyeing performance of wool fibers were analyzed. Wool fibers Disperse Red 153 and Disperse Blue 148 were investigated at
were dyed with Disperse Red 54, Disperse Blue 183, Disperse Red temperatures ranging from 70
C to 120
C, with a pressure 25 MPa,
153, Disperse Blue 148, Disperse Red 92, and Disperse Yellow 82 at a dyeing time 120 min, a dye mesh number 100, as well as a CO2
100
C with a pressure 28 MPa, a dyeing time 60 min, a CO2 flow flow 20 g/min, and at temperatures ranging from 80
C to 130
C,
20 g/min, and a dye mesh number 80 to select the suitable dyes for with a pressure 25 MPa, a dyeing time 120 min, a dye mesh number
wool dyeing in supercritical carbon dioxide. It can be seen from 80, as well as a CO2 flow 30 g/min, respectively.
Table 2 that it is technically feasible to dye wool fibers in super- As depicted in Fig. 2, the K/S values of the wool fibers dyed with
critical carbon dioxide using these disperse dyes, and the fixation Disperse Red 153 were increased gradually as dyeing temperature
rates for all kinds of dyes can be reached more than 58.79. Of which, increased from 70
C to 110
C, and did not increase further at
the maximum values of the fixation rates obtained were 80.87 for 120
C. Moreover, the fixation rates of Disperse Red 153 on wool
Disperse Red 153, and 81.94 for Disperse Blue 148. Moreover, the K/ fibers were enhanced significantly with dyeing temperature
S values of the wool samples dyed with these two dyes were 2.51 increasing, and arrived at the maximum value at 110
C, which
and 2.27, respectively. indicated that the equilibrium of fixation rates was obtained after
Compared with other dyes, the better dyeing effect for Disperse dyeing temperature was increased to 110
C. The same increase
Red 153 and Disperse Blue 148 is depending on their detailed trends were also observed for wool fibers dyed with Disperse Blue
molecular structures. The affinity is attributed to the attraction 148 in supercritical carbon dioxide. Nevertheless, the equilibrium
between the fiber and disperse dye molecules, where the primary of fixation rates for Disperse Blue 148 was initially obtained at
force in this attraction is believed to be hydrogen bonding between 120
C whereas the K/S values of the dyed wool were still increased
the fiber and polar groups in the dye molecule (Afifi and Sayed, after 120
C in comparison with that of Disperse Red 153, which
1997). On the one hand, the incorporation of thiazole ring is indicated that higher dyeing temperature was required for super-
highly desirable and increases significantly the forces of interaction critical carbon dioxide dyeing procedure with Disperse Blue 148.
between protein chains and disperse dyes, enhancing the affinity Theoretically, there represent three aspects for the effect of
with wool fibers (Broadbent et al., 2007). Simultaneously, Cl, eCN temperature on the dyeing performance of wool fibers. First of all,
and eCOOCH3 groups in disperse dyes increase the chemical po- the density of supercritical carbon dioxide was increased with the
larity of dye molecule, improving the dye fixation and colorfastness dyeing temperature rising, improving the solubility of dyes and
of wool. On the other hand, the thiazole ring and the ethyl at the increasing the dye concentration distributed at the interior and
end of dye molecules make the dyes exhibit good hydrophobicity, exterior of fiber. In the dyeing procedure, dye molecules continu-
and present better solubility in supercritical carbon dioxide, which ously adsorbed on the fiber surface, and then diffused and fixed into
can further improve the dyeing performance of wool. The molec- the interior of wool. The next, free motion of dye molecules was
ular weight of disperse dye is also an important factor in deter- intensified with the rising of dyeing temperature, thus accelerating
mining the affinity for wool. In general, the higher molecular the diffusion and absorption of dye molecules. Eventually, the
weight of disperse dye, the higher affinity will be obtained (Chao motion of macromolecule chain segments in wool fibers was also

Table 2
The K/S values and the dye fixation of the dyed wool fibers in supercritical carbon dioxide.

Parameters Disperse Red 153 Disperse Blue 148 Disperse Red 54 Disperse Blue 183 Disperse Red 92 Disperse Yellow 82

(K/S)dyed 2.51 2.27 1.16 1.49 1.38 1.22

(K/S)extr 2.03 1.86 0.86 0.88 0.83 0.94
Fixation rate (%) 80.87 81.94 74.14 58.79 60.14 77.05
 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277 273

Fig. 2. Effect of dyeing temperature on the K/S values and the fixation rates in supercritical carbon dioxide: (a) Disperse Red 153, (b) Disperse Blue 148.

promoted as dyeing temperature increased, making the dissolved the minor changes were obtained for the K/S values, but the fixa-
dye molecules enter into fiber macromolecule more easily. How- tion rates of Disperse Red 153 were increased dramatically. This is
ever, the acceleration of dyeing temperature for the dyeing cannot maybe because the dye concentration at interior and exterior of the
be increased endlessly because the density of supercritical carbon fiber was increased due to the rising of dyeing pressure, thus
dioxide fluid depends on the temperature and pressure (Liao et al., facilitating the diffusion and absorption of dye molecules towards
2000), which also revealed in Fig. 2. Taking account of the effects of wool fibers. The increase for the K/S values and the reduction for
dyeing temperature on the K/S values and the fixation rates in the fixation rates over 30 MPa may be because the further increase
supercritical carbon dioxide, a temperature of 110
C for Disperse of the dyeing pressure can continuously improve the solubility of
Red 153 and 120
C for Disperse Blue 148 were employed for disperse dyes; meanwhile, they also leads to the desorption of the
further dyeing experiments. dye molecules in the fibers, thereby decreasing the fixation rates.
Fig. 3(b) shows the similar increase trend for the wool fibers
3.3. Effect of dyeing pressure on the dyeing performance of wool dyed with Disperse Blue 148. The K/S values and the fixation rates
fibers were increased with the rising of the dyeing pressure. The optimal
K/S values was obtained at 20 MPa while the maximum of the
In supercritical carbon dioxide, pressure change especially the fixation rates was obtained at 25 MPa, which revealed that the
fluctuation near its critical point, greatly affects the solubility of stronger driving force of the fluid, the more dye molecules will
carbon dioxide fluid. Therefore, effects of dyeing pressure on the diffuse into the interior of the fibers (Zheng et al., 2015a,b; Pitzer,
dyeing performance of wool fibers with Disperse Red 153 and 1955). Hence, a dyeing pressure of 25 MPa was recommended in
Disperse Blue 148 were investigated at pressures ranging from further experiments for wool dyeing in supercritical carbon
15 MPa to 35 MPa, with a temperature 110
C, a dyeing time dioxide.
120 min, a dye mesh number 100, as well as a CO2 flow 20 g/min,
and at pressures ranging from 15 MPa to 35 MPa, with a temper- 3.4. Effect of dyeing time on the dyeing performance of wool fibers
ature 120
C, a dyeing time 120 min, a dye mesh number 80, as well
as a CO2 flow 30 g/min, respectively. Effects of dyeing time on the dyeing performance of wool fibers
As shown in Fig. 3(a), the K/S values of the wool fibers dyed with with Disperse Red 153 and Disperse Blue 148 were investigated at
Disperse Red 153 were increased slowly with the dyeing pressure dyeing time ranging from 30 min to 180 min, with a temperature
raising from 15 MPa to 30 MPa, and a noticeable increase was 110
C, a pressure 25 MPa, a dye mesh number 100, as well as a CO2
observed at 35 MPa. The fixation rates of Disperse Red 153 were flow 20 g/min, and at dyeing time ranging from 30 min to 150 min,
increased from 15 MPa, and then reached a peak at 30 MPa while a with a temperature 120
C, a pressure 25 MPa, a dye mesh number
remarkable decrease appeared with the further increasing of 80, as well as a CO2 flow 30 g/min, respectively.
pressure. Furthermore, as depicted in Fig. 3(b), an increase ten- Fig. 4(a) shows that a reduction of K/S values was achieved from
dency of the K/S values and the fixation rates was presented from 30 min to 60 min, and then a notable improvement was obtained
15 MPa to 25 MPa for the wool fibers dyed with Disperse Blue 148 till the dyeing time was increased to 120 min. Simultaneously, the
in supercritical carbon dioxide. fixation rates of Disperse Red 153 were increased moderately with
Generally, effects of dyeing pressure on the K/S values and the the dyeing time rising from 30 min to 150 min. This is maybe
fixation rates in supercritical carbon dioxide can be also divided because it took comparatively long time to finish the dye transfer
into three steps. When the dyeing pressure was lower than 20 MPa, from the surface to the interior of the fiber. Most of the dye mol-
the K/S values of the wool fibers were enhanced with the dyeing ecules absorbed on the surface of the fiber at initial dyeing stage,
pressure increasing while there was no significant change for the resulting in a higher K/S values and lower fixation rates. With the
fixation rates, which demonstrated that increase of dyeing pressure dyeing lasting, the dye molecules absorbed on the fiber’s surface
at this stage resulted in the increase of the dyes’ solubility, but the began to diffuse into the fiber, thereby decreasing the K/S values
dye diffusion into the interior of wool fiber cannot be finished at and increasing the fixation rate. Until the dyeing time reached
20 MPa. After the dyeing pressure was increased further to 30 MPa, 90 min, the fixation rate rose rapidly to more than 80%, which
274 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277

Fig. 3. Effect of dyeing pressure on the K/S values and the fixation rates in supercritical carbon dioxide: (a) Disperse Red 153, (b) Disperse Blue 148.

Fig. 4. Effect of dyeing time on the K/S values and the fixation rates in supercritical carbon dioxide: (a) Disperse Red 153, (b) Disperse Blue 148.

meant most dyes dissolved could transfer, and fix into wool fibers. the contact area of dyes with supercritical carbon dioxide, causing
In addition, Fig. 4(b) displayed that with the increase of the the change of their solubility and dyeing effect. Furthermore, par-
dyeing time, the K/S values of the wool fibers dyed with Disperse ticle size of dye is also directly related to dye production cost. Thus,
Blue 148 were decreased at the earlier and then increased. In this effects of dye mesh number on the dyeing performance of wool
process, the fixation rates were increased gradually. Unlike the fibers with Disperse Red 153 and Disperse Blue 148 were investi-
fixation rates of Disperse Red 153, dye equilibrium at the interior gated at dye mesh number ranging from 40 to 100, with a tem-
and exterior of the wool fibers with Disperse Blue 148 was obtained perature 110
C, a pressure 25 MPa, a time 120 min, as well as a CO2
at 120 min, which was faster than that of Disperse Red 153. In brief, flow 20 g/min, and with a temperature 120
C, a pressure 25 MPa, a
by consideration of the all effects of dyeing time on the dyeing time 120 min, as well as a CO2 flow 30 g/min, respectively.
performance of wool fibers, a time of 120 min was recommended in Fig. 5 depicts that the K/S values and the fixation rates of the
further dyeing experiments for wool in supercritical carbon wool fibers were increased as dye mesh number rose from 40 to
dioxide. 100 for Disperse Red 153 and Disperse Blue 148, which indicated
that the increase of the dye mesh number led to the increase of dye
3.5. Effect of dye mesh number on the dyeing performance of wool solubility, and contributed to the diffusion process. However, the
fibers increasing of solubility and dye adsorption quantity in fibers were
very limited, thereby slowing down the increase of the fixation rate.
Particle size is an indicator for the size of dye, its elementary It is also interesting to observe that the climbing speed of fixation
unit is mesh number. In the dye filtration process, mesh number rates for Disperse Blue 148 was increased significantly when the
refers to the number of meshes on the same area of the filter. In dye mesh number was raised from 80 to 100 whereas the climbing
general, the higher the value of a mesh number, the smaller size of speed of fixation rates for Disperse Red 153 was reduced accord-
dye molecules was filtrated. During dyeing, dye particle size affects ingly, which disclosed that the decrease of dye particle size was
 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277 275

Fig. 5. Effect of dye mesh number on the K/S values and the fixation rates in supercritical carbon dioxide: (a) Disperse Red 153, (b) Disperse Blue 148.

Fig. 6. Effect of CO2 flow on the K/S values and the fixation rates in supercritical carbon dioxide: (a) Disperse Red 153, (b) Disperse Blue 148.

Fig. 7. Optical microscope analysis of the wool dyed in supercritical carbon dioxide: (a) Disperse Red 153, (b) Disperse Blue 148.

beneficial to the motion of dye molecules into the fibers, causing 3.6. Effect of CO2 flow on the dyeing performance of wool fibers
the improvement of the fixation rates. Thus, a dye mesh number of
100 for Disperse Red 153 and 80 for Disperse Blue 148 were rec- CO2 flow refers to the weight of flowing CO2 per minute, and is
ommended for further dyeing experiments in supercritical carbon related with the solubility of dyes in supercritical carbon dioxide.
dioxide. Therefore, effects of CO2 flow on the dyeing performance of wool
fibers with Disperse Red 153 and Disperse Blue 148 were
276 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277

Table 3 To investigate color fastness properties of the dyed wool fibers,

Colorfastness of the dyed wool fibers to washing and rubbing. color fastness to washing and rubbing were measured after su-
Dyes Washing fastness Rubbing percritical carbon dioxide dyeing. It can be seen from Table 3 that
fastness the wool fibers dyed with Disperse Red 153 showed excellent color
Shade Stain Dry Wet fastness to washing and rubbing, which were rated above 4.
Moreover, the wool fibers dyed with Disperse Blue 148 also pre-
Wool Nylon Cotton
sented excellent rubbing colorfastness while the washing color-
Disperse Red 153 4 4e5 4e5 4e5 4e5 4e5
fastness was little lower than that of Disperse Red 153.
Disperse Blue 148 4 3e4 3e4 4e5 4e5 4e5

Table 4
Tensile performances of the dyed wool fibers in supercritical carbon dioxide.

Samples Breaking force (cN) Tensile strength (cN/dtex) Elongation at break (mm) Initial modulus (cN/dtex)

Control sample 3.1512 ± 0.30 1.211 ± 0.11 1.724 ± 0.15 1.801 ± 0.18
Disperse Red 1531 2.9818 ± 0.26 1.209 ± 0.13 0.517 ± 0.02 1.973 ± 0.15
Disperse Blue 1482 2.8944 ± 0.24 1.198 ± 0.10 0.514 ± 0.02 1.976 ± 0.17

Note:
1
Disperse Red 153 with a temperature 110
C, a pressure 25 MPa, a time 120 min, a dye mesh number 100, as well as a CO2 flow 20 g/min.
2
Disperse Blue 148 with a temperature 120
C, a pressure 25 MPa, a time 120 min, a dye mesh number 80, as well as a CO2 flow 30 g/min.

investigated at CO2 flow ranging from 10 g/min to 40 g/min, with a 3.8. Mechanical performances of wool fibers
temperature 110
C, a pressure 25 MPa, a time 120 min, as well as a
dye mesh number 100, and with a temperature 120
C, a pressure In order to investigate the mechanical performances of wool
25 MPa, a time 120 min, as well as a dye mesh number 80, fibers before and after supercritical carbon dioxide dyeing, the
respectively. tensile performances of the dyed fibers were measured, as sum-
As shown in Fig. 6(a), a higher K/S value was obtained at 10 g/ marized in Table 4. It can be seen from Table 4 that after super-
min for the wool fibers dyed with Disperse Red 153 while the critical carbon dioxide dyeing, the breaking force and tensile
lowest fixation rate was achieved since most of the dyes absorbed strength of the dyed wool fibers were reduced slightly. This may be
on the surface of the fiber with the smaller CO2 flow. With the because the excellent mass transfer and penetration effect of su-
increase of the CO2 flow, more dyes diffused into the interior of the percritical carbon dioxide could result in the change of the micro-
fibers, which led to the improvement of the fixation rates. How- structure of wool fibers (Zheng et al., 2015a,b). Furthermore, the
ever, the K/S values were increased with the further increase of breaking force and tensile strength of the wool samples dyed with
CO2 flow while the fixation rates were decreased slightly, which Disperse Blue 148 were lower than that of Disperse Red 153 due to
indicated that higher CO2 fluid flow can not only improved the the higher dyeing temperature and CO2 flow.
penetration and diffusion of dyes, but also accelerate the desorp-
tion of dyes from the fibers in supercritical carbon dioxide (Park 4. Conclusions
and Bae, 2002).
Furthermore, Fig. 6(b) displayed that the minimum of K/S values In this work, dyeing of wool was successfully carried out with
for wool fibers and fixation rates for Disperse Blue 148 were ob- Disperse Red 54, Disperse Blue 183, Disperse Red 153, Disperse Blue
tained at 10 g/min. Then, the K/S values of the wool fibers dyed with 148, Disperse Red 92, and Disperse Yellow 82 in supercritical car-
Disperse Blue 148 were increased gradually with the CO2 flow bon dioxide. Effects of dyeing temperature, pressure, time, dye
rising. Most of the dyes diffused into the interior of the wool fibers mesh number, as well as CO2 flow on the K/S values and fixation
at 30 g/min, thus acquiring the optimal K/S value and the fixation rates were analyzed. The results revealed that the higher K/S values
rate. Taking account of the effects of CO2 flow on the K/S values and and fixation rates of wool fibers was obtained with Disperse Red
the fixation rates in supercritical carbon dioxide, a CO2 flow of 20 g/ 153 and Disperse Blue 148 in supercritical carbon dioxide.
min for Disperse Red 153 and 30 g/min for Disperse Blue 148 were Furthermore, an optimized ecofriendly dyeing procedure for wool
employed for further dyeing experiments. fibers was recommended in supercritical carbon dioxide at a tem-
perature of 110
C, a pressure 25 MPa, a time 120 min, a dye mesh
3.7. Permeability and color fastness of wool fibers number 100, as well as CO2 flow 20 g/min for Disperse Red 153, and
with a temperature 120
C, a pressure 25 MPa, a time 120 min, a dye
The permeability of the wool fibers dyed with Disperse Red 153 mesh number 80, as well as CO2 flow 20 g/min for Disperse Blue
and Disperse Blue 148 was investigated by fiber cross sections with 148. Simultaneously, the excellent permeability, and acceptable
a temperature 110
C, a pressure 25 MPa, a time 120 min, a dye color fastness and mechanical properties of the dyed wool samples
mesh number 100, as well as a CO2 flow 20 g/min, and with a were obtained after supercritical carbon dioxide dyeing with
temperature 120
C, a pressure 25 MPa, a time 120 min, a dye mesh Disperse Red 153 and Disperse Blue 148, which can provide the
number 80, as well as a CO2 flow 30 g/min, respectively. As shown beneficial references for the ecofriendly dyeing procedure of wool
in Fig. 7, there were no white dots in the slices of the dyed wool and the appropriate dye structures for design of disperse reactive
samples, and the uniform red and blue color were presented after dyes.
supercritical carbon dioxide dyeing, which indicated that the dye
particles diffused throughly into the wool fibers, and good Acknowledgments
permeability was obtained for the fibers dyed with Disperse Red
153 and Disperse Blue 148. We gratefully acknowledge the financial support from Program
 H. Zheng et al. / Journal of Cleaner Production 143 (2017) 269e277 277

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