Dyeing natural fibres in supercritical carbon

Coloration
dioxide using a nonionic surfactant reverse
Technology
micellar system
K Sawada,a T Takagi,a J H Jun,a M Uedab and D M Lewisc
aDepartment of Chemistry and Material Technology, Kyoto Institute of Technology,
Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
Email: sawada@kk.chem.kit.ac.jp
bDepartment of Design Engineering and Management, Kyoto Institute of Technology,
Society of Dyers and Colourists
Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
cDepartment of Colour Chemistry, University of Leeds, Leeds LS2 9JT, UK

A reverse micellar system in supercritical carbon dioxide has been developed as a dyeing medium.
Water-soluble dyes such as reactive dyes and acid dyes could be sufficiently solubilised in the interior of
a specially constituted reverse micelle. Protein fabrics, silk and wool, were satisfactorily dyed even in
deep shades with conventional acid dyes without any special pretreatment. Cotton cellulose fabric was
also dyed with conventional reactive dyes when the electrostatic force of repulsion between dye and
cotton was eliminated. Compared to previously proposed supercritical dyeing methods, dyeing of
fabrics with this system could be performed at low temperatures and pressures in a short time.

Introduction et al. have thus synthesised a disperse-reactive dye and

investigated the dyeing of cotton with this dye [5,6].
Conventional dyeing and subsequent washing processes
Although natural fibrous materials can be dyed using these
are generally performed in water-based dyebaths. However,
techniques, poor handle, prolonged dyeing times, high
waste aqueous effluent containing coloured compounds
energy consumption and low colour fastness seem to be
and concentrated electrolytes cause serious environmental
major problems making the system unsuitable for
problems. In order to overcome this problem, new concepts
industrial requirements.
that avoid the use of water are being evaluated. In 1991,
In this study, we have investigated the dyeing of
Schollmeyer and co-workers, demonstrated a new dyeing
unmodified natural fibrous materials in SC-CO2 using
method using supercritical carbon dioxide (SC-CO2) as the
conventional water-soluble dyes. Unlike SC-CO2-soluble
dyebath medium [1]. The viscosity (10–5–10–4 Pa s) and
disperse dyes, water-soluble dyes such as reactive dyes and
diffusion coefficient (10 –8–10–7 m2 s) values of this
acid dyes do not dissolve in SC-CO2. The most current
supercritical fluid are similar to those of water, making it
technique to dissolve polar substances in SC-CO2 is to
suitable for use as a dyeing medium. In addition, SC-CO2
make an addition of a small amount of entrainer to increase
is an attractive alternative to both water and organic
the polarity and therefore the solvent power. However,
solvents because it is inexpensive, essentially nontoxic,
water-soluble dyes are insufficiently soluble in this SC-
nonflammable, requires relatively gentle critical conditions
CO2/entrainer medium for it to function in a dyeing process
(critical temperature, TC = 31.1 °C and critical pressure,
[7]. Our strategy is to dissolve the water-soluble dye in a
PC = 7.38 MPa) and can easily be recovered and recycled
SC-CO2/reverse micellar system that involves dispersing a
after use. Unfortunately, SC-CO2 is a poor solvent for a
small amount of water in the SC-CO 2. A schematic
wide range of hydrophiles because of its low permittivity
representation of the reverse micelle system in either an
[2]. Dyeing of textile fibres in SC-CO2, therefore, has been
SC-CO2 or organic medium is shown in Scheme 1. Reverse
limited to synthetic fibres using SC-CO2-soluble disperse
micelles provide a stable aqueous micro-environment,
dyes but the dyeing of natural fibres in this medium is still
consisting of a water pool in a non-aqueous medium.
under development. Considering the large market share of
cotton and wool fabrics, an investigation to establish a
dyeing method for these fibres in SC-CO2 has been Water pool
undertaken. Chemical modification of natural fabrics Dye
before dyeing is one of the possible techniques. Gebert et
al. [3] and Ozcan et al. [4] have examined the hydrophobic Dy
e

finishing of cotton cellulose in order to dye it with

Fabric Fabric
conventional disperse dyes. On the other hand, modific-
ation of the dye to render it suitable for SC-CO2 application
has also been evaluated; Mishima et al. and Schollmeyer Scheme 1

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20020505_j1802.pmd 233 01/10/02, 10:31

 In a previous study [8], we investigated the dyeing of O NH2
fibrous materials from a reverse micellar system in an SO3Na
organic solvent. Cotton, silk, wool and polyester fabrics SO3Na
could be satisfactorily dyed in deep shades from such a CH3
reverse micellar/organic solvent medium. If a water-soluble O N SO3Na
dye can be dissolved in a SC-CO2/reverse micellar system, H
this system may be suitable for use in dyeing processes. N
H3C CH3 N H
In general, the solubility and aggregation properties of
N N OC2H5 O
surfactants in SC-CO2 are quite different from those in H
conventional organic solvent media and supercritical fluid N N
alkane solvents [9–11]. According to the report by Consani
2 Cl 3
and Smith, over 130 commercially available surfactants are
insoluble or only slightly soluble in SC-CO2 and neither
do they attract and retain significant amounts of water [12].
Goether et al. [13] have reported on the structural
requirements of a surfactant molecule which would form
NaO3S SO3Na
a reverse micelle in SC-CO 2. At present, fluorinated
N N
surfactants synthesised by Johnston and co-workers [14– H5C2 C2H5
18] and DeSimone and co-workers [19–21] seem to have +
the highest solubility in SC-CO2. In practice, fluorinated –
SO3
surfactants form thermodynamically stable reverse
micelles, but on the other hand some disadvantages
remain. For example, these surfactants are not
commercially available, expensive and may have an 4
undesirable environmental impact. In this study, we have
chosen to use pentaethylene glycol n-octyl ether (C8E5) as (H5C2)2N O N(C2H5)2
the surfactant, since it is highly soluble in SC-CO2 and has
great potential to solubilise a significant amount of water +
[22,23]. SO3
–

Experimental
Materials SO3Na
The surfactant used in this study was pentaethylene glycol
5
n-octyl ether (C 8E5). C 8E5 was purchased from Nikko
Chemicals Co. Ltd and was used without further purific-
ation. The initial water content of C8E5 was found using NaO3S CH3
the Karl Fisher titration method to be 0.3% w/w. H
1-Pentanol, co-surfactant, was purchased from Nacalai O N
Tesque Co. Ltd and was used after drying with a 3A
molecular sieve. Pure carbon dioxide (> 99.9%) was
purchased from Sumitomo Seika Chemicals Co. Ltd.
Fabrics used in this study were cotton broad cloth, silk O N
H
habutae cloth and wool muslin cloth, which had been
properly desized and scoured with conventional methods. NaO3S CH3
These were purchased from Shikisen-sha Co. Ltd, and were
further pretreated in boiling water for 1 h before use. The 6
dyes used in this study were CI Reactive Red 2 (1), CI
Reactive Blue 74 (2), CI Acid Orange 7 (3), CI Acid Blue 9
(4), CI Acid Red 52 (5) and CI Acid Green 25 (6). All other
Procedures
chemicals used were of reagent grade and were obtained
The high-pressure reaction apparatus was newly
from Kanto Chemical Co. Inc.
constructed in our laboratory. The main component of the
apparatus was a stainless steel viewing cell (4.6 cm3 total
Cl volume) containing a 3 cm diameter optical window, which
was 1.5 cm thick. In all experiments, the prescribed
N N amounts of C8E5 surfactant, co-surfactant, water and dye
H H were loaded into the bottom of the cell before commencing.
N O N N Cl
Liquid carbon dioxide from a cylinder was compressed via
N
a pressurising pump and caused to flow to the reaction cell
until the pressure reached the desired value. The contents
NaO3S SO3Na
of the cell were stirred using a Teflon-coated bar driven
1
by an exterior magnet. Based on the detailed phase diagram

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 obtained in our previous study [23], most of the experi-
mental conditions were adjusted to produce a clear one-
phase fluid. In this study, 1-pentanol was also added as a
co-surfactant in order to form stable reverse micelles. In
this paper, the amount of solubilised water, w, in a reverse
micellar system is expressed as molar ratio of water ([H2O])
to surfactant ([C8E5]), as shown in Eqn 1:
system was also observed at ca. 0.7 g cm–3 as reported
previously [23]. The agreement of these results suggests
that solubilisation of the dye in the system begins at the
same time as the formation of reverse micelles. After the
formation of reverse micelles, the water pool is saturated
with dye immediately and maintains a constant dye
concentration regardless of an increase of pressure.

w = [H2O] /[C8E5 ] (1) Dyeing of natural fabrics

Protein fibres
The absorbance of the dye in the SC-CO2 was measured In every experiment, complete solubilisation of the dye in
using a multichannel spectrophotometer MCPD-100 the system was visually confirmed. Figure 3 shows the K/
(Otsuka Electronics Co. Ltd) and a similar stainless steel S values obtained after dyeing silk and wool with CI Acid
viewing cell. Before recording the spectrum, the contents Red 52 as a function of time.
were stirred and equilibrated for 15 min each.
The reflectance of the dyed fibre mass was measured
with a Minolta CM-1000 spectrophotometer and from this 1.2
the colour depth, K/S, of the dyed fabrics was calculated (a)
using the Kubelka–Munk equation.
In the dyeing of fabrics with this system, fabrics were (b)
fixed at the upper side of the cell. In order to prevent
Absorbance

0.8
advance staining of the fabrics due to direct contact with
dye, stirring was not conducted until the temperature and
(c)
pressure reached the chosen operating conditions.
0.4 (d)

Results and Discussion (e)

Solubility of dyes 0
Figure 1 shows the absorption spectra from the C 8E5 480 500 520 540 560
reverse micellar system in SC-CO2 containing different Wavelength, nm
concentrations of CI Acid Red 52. For comparison, the
(a) [C8E5] = 62 mM, [Dye] = 4.3 mg/l
absorption spectrum from a similar system without C8E5
(b) [C8E5] = 62 mM, [Dye] = 3.3 mg/l
is also presented. The spectrum obtained from the system (c) [C8E5] = 62 mM, [Dye] = 2.2 mg/l
without C8E5 shows zero dye absorbance, indicating that (d) [C8E5] = 62 mM, [Dye] = 1.1 mg/l
(e) [C8E5] = 0 mM, [Dye] = 3.3 mg/l
the acid dye is not solubilised in the system. In the systems
containing C 8E5 surfactant, an increase in dye concen-
tration produced an increase in absorbance. Similar results
Figure 1 Absorption spectra from microemulsion system for
were obtained when other water-soluble dyes were used. dyeings with CI Acid Red 52 in SC-CO2 (temp., 40 °C; pressure,
From these results water-soluble dyes seem to be 14 MPa; w, 3; [1-pentanol], 0.74 M)
solubilised in the SC-CO2 media.
Figure 2 shows the effect of pressure, i.e. the SC-CO2
density, on the absorbance of CI Acid Red 52 in the reverse
micellar system. The absorbance of the acid dye increases
markedly as the pressure increases up to ca. 10 MPa and
1.2
then a plateau is observed and the absorbance does not
increase further.
These results are quite different from those obtained
from SC-CO 2-soluble dyes such as a disperse dye or a 0.8
Absorbance

disperse-reactive dye in pure SC-CO2 [24–27]. As reported

by Hori and Tabata, the solubility levels of disperse dyes
in SC-CO 2 are greatly dependent on temperature and
pressure [28]. At constant temperature, the solubility of 0.4
these dyes increases linearly with increasing pressure. An
abrupt increase in the absorbance observed in this study
may be related to the formation of reverse micelles. In
0
contrast to a SC-CO2-soluble dye, the acid dye in the SC- 8 12 16 20
CO2/reverse micelle system would not be solubilised in the Pressure, MPa
bulk carbon dioxide but solubilised in the water pool of
the micelles. In Figure 2, just after the abrupt increase of
Figure 2 Effect of pressure on the absorbance of CI Acid Red 52
absorbance, the SC-CO2 density can be estimated to be ca. in C8E5 reverse micellar system (temp., 40 °C; w, 2.2; [C8E5], 62
0.7 g cm–3. In contrast, the phase transition of the same mM; [1-pentanol], 0.74 M; [Dye], 4 mg/l)

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20020505_j1802.pmd 235 01/10/02, 10:31

 30
20
K/S
10
Silk
Wool
0 tained. This uneven, pale shade dyeing was not improved
0 4 8 12 16
Dyeing time, h
Figure 3 Variation of K/S values with time of silk and wool
fabrics dye with CI Acid Red 52 from C 8E 5 reverse micellar
system (temp., 40 °C; pressure, 16 MPa; w, 5; [C8E5], 62 mM; [1-
pentanol], 0.74 M; [Dye], 2% owf)
It can be seen that both silk and wool fabrics are
satisfactorily dyed in deep shades without auxiliaries. In
particular, equilibrium dyeing is completed for silk fabrics
within 15 min even at the moderate temperature used
(40 °C). Acid dye solubilised in the water pool would
effectively migrate into the fibre due to the high dis-
persibility and mass transfer rate of SC-CO2. On the other
hand, the dyeing rate of the wool fabric dyed under the
same conditions is lower than that of silk, although the
final colour depths of the dyed wool and silk fabrics are
similar. These differences in dyeing rate may be attribu-
table to the characteristic structure of the wool fibre. In
contrast to the silk fibre, the surface of the wool fibre is
covered with highly hydrophobic cuticle cells. In the
conventional water-based dyeing process, the dyeing of
wool is performed at a high temperature (98 °C). Under
these conditions the hot water swells the non-keratinous
proteins of the cell membrane complex between the cuticle
and cortical cells and also the non-keratinous endocuticle,
moving them apart and allowing access for the aqueous dye
solution into the bulk of the fibre. Dyeing at low
temperatures (e.g. 40 °C) with a small amount of water may
not have sufficient effect on the cuticle cells to achieve
access to the fibre. Consequently, migration of dye into the
fibres would be restricted to the surfaces of the wool fibre.
Figure 4 shows the dyeability of silk fabrics as a
function of working pressure. Similar results were also
obtained for wool fabrics when dyeings were performed
for more than 1 h.
In this experiment, we have previously confirmed that
variation of the molar concentrations of C8E5 surfactant and
water due to an increase in pressure has negligible
influence on the experimental data, since these
concentrations are lower than that of the carbon dioxide.
As shown in Figure 4, the dyeability of silk fabrics in the
reverse micellar system is not affected by the working
pressure. Although these phenomena are quite different
from the SC-CO2 dyeing of synthetic fabrics with disperse
dyes, these results do not contradict the solubility
properties of acid dyes shown in Figure 2. The dyeing of
236 © Color. Technol., 118 (2002)
20020505_j1802.pmd 236
protein fabrics with an acid dye seems to be achieved even
in low-pressure ranges provided the dye is satisfactorily
solubilised in the water pool of the micelles. Dyeings
confirmed that both silk and wool fabrics are satisfactorily
dyed in deep shades, with conventional acid dyes, in this
SC-CO2/reverse micelle medium.
Cellulose fibres
A similar dyeing process using conventional reactive dyes
and the SC-CO2/reverse micelle medium was applied to
cotton fabrics. Unfortunately the dyed cotton fabrics
showed unevenness and only pale shades could be ob-
even under high-pressure or high-temperature conditions
or for prolonged dyeing times. The poor cotton dyeability
obtained in this study may be explained either in terms
of low fibre swelling, low concentration of available dye
or lack of affinity between the dye and the fabric.
Dealing with the first issue of insufficient swelling of
fabrics, in contrast to synthetic fibres like polyester, natural
fibres are hardly swollen with SC-CO2. Mishima et al.
emphasised that pretreatment with a swelling agent is
indispensable for the dyeing of cotton in SC-CO2 [5]. How-
ever considering the successful dyeing of protein fabrics
described above, natural fibres appeared to be sufficiently
swollen by the water phase in the reverse micelle system
for adequate dye penetration to occur.
The second factor to be considered is an insufficient
concentration of dye in the system. As reported previously,
we have found that cotton fabrics are satisfactorily dyed
in deep shades with direct dyes and reactive dyes from
ionic reverse micellar systems in organic solvent [8].
Because of the success of the previous study, the dyeing
conditions (such as the concentration of dye, liquor ratio
and water content) in this study were adjusted to be almost
the same as the previous work, with the exception that the
hydrophobic component of the reverse micelle system was
SC-CO2. Since complete solubilisation of the dye in the
system occurred, we can conclude that the solubility of the
dye is not the cause of the uneven dyeing.
The third suggestion was that the poor quality dyeings
were the result of a reduction in the affinity between the
dye and the fabric in the SC-CO2/reverse micelle medium.
30
20
K/S
10
0
12 16 20 24
Pressure, MPA
Figure 4 Effect of working pressure on colour depth of silk
fabric dyed with CI Acid Red 52 (temp., 40 °C; w, 5; [C8E5], 62
mM; [1-pentanol], 0.74 M; [Dye], 2% owf; dyeing time, 2 h)
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 In the dyeing of cellulose fibres by the conventional water-
based method, a large amount of electrolyte is added to the
dyebath in order to overcome the electrostatic repulsion
between the dye and the surface of the cellulose. The
reverse micellar system without auxiliaries may not be able
to overcome this repulsion between the negative charges
on the dye and on the fibre. Thus chemical pretreatment
to cationise the cotton fabrics was performed according to
the method of Shirai [29] in order to investigate the role
of electrostatic repulsion effects. After dyeing, any unfixed
dye on the cotton fabric was completely removed by the
conventional soaping process.
The pretreated cotton fabrics exhibited high dyeabilities
compared to those of the untreated cotton fabrics. These
results obviously suggest that the adsorption of anionic dye
to the fabric is prevented by the negative charge on the
surface of the cotton. In order to dye unmodified cotton
with conventional reactive dyes in this system, it is
necessary to reduce the electrostatic repulsion. The type
of surfactant molecule used to form the reverse micelle
may solve this problem. Our previous study described the
satisfactory dyeing of cotton from a reverse micellar system
based on an organic solvent and an ionic surfactant;
unmodified cotton fabrics were satisfactorily dyed with
conventional reactive dye without auxiliaries [8]. The
surfactant’s ionic head-group might play the role of a
dyeing auxiliary. If an ionic surfactant, which can form
stable reverse micelles in supercritical carbon dioxide, can
be applied to this system, the potential to dye natural
fibrous materials in supercritical fluids would be
increased.
Conclusions
Dyeing of natural fabrics was investigated utilising a
nonionic reverse micellar system in supercritical carbon
dioxide. Unmodified silk and wool fabrics were success-
fully dyed with conventional acid dyes. On the other hand,
cotton fabrics dyed with conventional reactive dyes did not
produce deep shades because of the electrostatic repulsion
between the dye and the surface of the fabric. However, it
was found that a pretreatment to cationise the cotton
produced a significant improvement in the dyeability. The
dyeing temperature, working pressure and dyeing time
were remarkably reduced with this technique compared to
either the conventional dyeing process or previously
proposed supercritical dyeing techniques.
Supercritical dyeing can reduce waste fluid and recover
surplus dye from the system. In order to apply reverse
micellar systems to a practical supercritical dyeing process,
more detailed knowledge would be necessary of the dyeing
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20020505_j1802.pmd 237
mechanism, the recovery of all the substances except
fabrics, as well as the fastness properties of the dyed fibres.
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