Textile Research Journal
Study of Dyeing Behavior of Polyester Fibers
with Disperse Dyes
Abstract Sorption isotherms of disperse dyes
from water with small and big molecules on vari-
ous polyester fibers were obtained at 130, 115, and
105°C. Isotherms were plotted using a large range
of initial dye concentration. A remarkable devia-
tion from Nernst behavior was observed for all
plotted isotherms. Langmuir fitting was tested and
appeared to be in good agreement with experimen-
tal curves. Distribution of disperse dyes between
polyester substrate and water and the saturation
solubility of these dyes in polyester fibers was com-
pared by considering the crystallinity and surface
area of the fibers.
Key words polyester, microfiber, dyeing, dis-
perse dyes, sorption isotherms, Langmuir fitting,
Nernst fitting, aggregation, crystallinity, surface area
The dyeing of polyester fibers has been widely studied.
However, the modeling of the sorption isotherms of dis-
perse dyes on polyester fibers is still the subject of discussion.
In the present study the influence of fiber characteristics
and dye size on sorption isotherms of disperse dyes on pol-
yester fibers at high temperature was investigated.
A survey of the literature showed that until the 1990s a
linear distribution of Nernst type has always been used as a
reference for sorption isotherms of disperse dyes on poly-
ester fibers [1–4]. In 1995, Nakumara et al. [5] proposed a
dual-mode model in which they combined a Langmuir
component with the Nernst classical model for the sorption
isotherms of two purified disperse dyes on polyester fibers.
During the last few years, some other research has led to
sorption isotherms of commercial disperse dyes on polyes-
ter fibers obeying the Langmuir law, but without a convinc-
ing explanation [6, 7]. The present study was performed to
try to find a theoretical foundation to explain such a result.
Experimental
The polyester filament yarns, 72dtex/88fil (partially ori-
ented yarn, fineness of monofilament 1.95 dtex), 50 dtex/
Textile Research Journal Vol 76(4): 271–280 DOI: 10.1177/0040517506061243
Article
Soufien Dhouib1 and Abdelaziz Lallam
Laboratoire de Physique et Mécaniques Textiles de
Mulhouse, ENSITM, 11 rue Alfred Werner, 68093,
Mulhouse, Cedex, France
Faouzi Sakli
Unité de Recherches Textiles de Ksar Hellal, Institut
Supérieur des Etudes Technologiques de Ksar Hellal,
Avenue Hadj Ali Soua, 5070, Ksar Hellal, Tunisia
22 fil (fully oriented yarn, 2.27 dtex), 40 dtex/44 fil (fully ori-
ented yarn, 0.9 dtex) were manufactured by SETILA S.A.
All yarns were transformed into knitted fabrics then treated
in alkaline solution of 1 g/L non-ionic detergent and 2 g/L
Na2CO3 at 80°C for 30 minutes with a 30 : 1 liquor ratio.
Later, the fabrics were heat-set at 180°C for 30 seconds
without any tension. The crystallinity, the diameter and sur-
face area were determined for all fibers before any treat-
ment (1) and after heat-setting (2). The crystallinity was
obtained by measuring the densities with a density gradient
column of carbon tetrachloride and petroleum ether. Equa-
tion (1) [8] shows the relation between the crystallinity
rate (χ%) and the density (ρ) of polyester fibers. The sur-
face area was estimated by the use of the BET equation of
krypton gas adsorption on polyester samples [9] (Table 1).1
1.455 ( ρ – 1.335 )
χ ( % ) = 100 × ----------------------------------------- (1)
0.120 × ρ
1
Corresponding author: Tel.: (00216) 73475900; fax: (00216)
73475163; e-mail: dhouib.soufien@laposte. net/soufien.dhouib@
isetkh.rnu.tn Also at: Unité de Recherches Textiles de Ksar Hellal,
Institut Supérieur des Etudes Technologiques de Ksar Hellal, Ave-
nue Hadj Ali Soua, 5070, Ksar Hellal, Tunisia
www.trj.sagepub.com © 2006 SAGE Publications
TRJ 272 Textile Research Journal 76(4)

Table 1 Fiber characteristics.

Fineness Shrinkage after Surface area

Diameter (µm) Crystallinity (%)
(dtex) heat-setting (%) (m2/g)

Treatment
(1) (1) (2) (2) (1) (2) (2)
Fiber
FOY 0.9 0.9 dtex 9.3 9.3 1.9 38 51 0.33
POY 1.95 1.95 dtex 13.8 21.3 58.7 10 39 0.14
FOY 2.27 2.27 dtex 14.7 14.8 3.21 35 51 0.18

It was not possible to measure the surface area at the
dyeing temperature with the laboratory equipment availa-
ble. The estimated values obtained allowed us to compare
the surface area of the different fibers.
All dyeings were carried out with a well-stirred dyebath
using a Mathis laboratory-scale dyeing machine at a liquor
ratio of 20 : 1 and pH 5. Two dyes were selected (Figure 1)
according to their molecular weights, which were obtained
from Ciba, and used in the dyeing process without fur-
ther purification: dye 1, CI Disperse Yellow 42 (molecular
weight = 369 g) and dye 2, CI Disperse orange 3 (molecu-
lar weight = 242 g).
No dispersing agent was added to the dyebath during
dyeing. After dyeing, the samples were soaked twice in boil-
ing water for 5 minutes then transferred to a fresh pot of
cool water. Finally, surface dye was removed by rinsing the
specimens in a cold acetone bath for 30 s and then blotted
and dried.
Dye on the polyester substrate was measured by colori-
metric analysis after its extraction with dimethylformamide
(DMF) using a Kumagawa extractor. The disperse dyes
were purified by Soxhlet extraction with benzene for 10 h
as described in the previous paper [10]. Calibration curves
were prepared using solutions of the pure dyes.
Experimental isotherm curves were plotted using a
large range of initial dye concentrations. The quantity of
commercial dye added to the dyebath was varied between
0.1 and 20% in order to be able to determine the isotherm
curves with great precision. The quantity of pure dye on
the commercial powders was about 49.5% for dye 1 and
31.8% for dye 2.

Results and Discussion

Figure 1 Chemical formula of dye 1 and dye 2.
It was clear that all the sorption isotherms of disperse dyes
on all polyester fibers at dyeing temperatures 130, 115, and
105°C obeyed the Langmuir law with a correlation coeffi-
cient R > 0.99 as presented in Table 2.
As shown in Table 2 and Figures 2–7, the greatest satura-
tion concentration (Cs) was always obtained with the fiber
POY 1.95 for both dyes and at all temperatures in spite of it
having the lowest surface area after heat-setting. This result
can be explained by its low crystallinity, which gave it more
amorphous zones that were able to receive more dye mole-
cules in comparison with the other fibers. Indeed, Table 1
shows that despite its very high shrinkage, the fiber POY
1.95 was still the most amorphous after heat-setting. How-
ever, its diameter became greater than that of the fiber
FOY 2.27 and its specific area became the lowest of all. More-
over, it was noted that at all dyeing temperatures when
sorption isotherms of dye 1 on FOY 2.27 and FOY 0.9 fibers
reached the saturation concentration Cs, the dye concentra-
tion on the fiber POY 1.95 continued to increase with increas-
ing dye concentration in the bath at equilibrium (Figures 2,
4 and 6). This fact indicates that the measured sorption iso-
therms cannot be adjusted to the Nernst model in which the
fibers saturate with dyebath saturation [1, 2, 4, 11], as oth-
erwise, we would need to accept that dye solubility in the
 Study of Dyeing Behavior of Polyester Fibers With Disperse Dyes S. Dhouib et al. 273 TRJ

Table 2 Values of Langmuir fitting parameters of dye sorption isotherms.

Parameters of Disperse Yellow 42 Disperse Orange 3

T (°C)
Langmuir fitting FOY 0.9 POY 1.95 FOY 2.27 FOY 0.9 POY 1.95 FOY 2.27
130°C KL (L/g) 7.2 3.3 2.6 3.7 3.8 2.5
Cs (g/kg) 49.7 92.7 64.0 50.6 62.8 56.9
Cs (mol/kg) 13.5 25.1 17.3 20.6 25.5 23.1
KLCs (L/kg) 357 304 168 188 238 139
R 1.00 0.99 1.00 1.00 1.00 0.99
115°C KL (L/g) 12.7 3.0 15.7 9.2 8.2
Cs (g/kg) 36.8 92.7 28.2 33.0 31.6
Cs (mol/kg) 9.9 25.1 7.6 13.4 12.9
KLCs (L/kg) 463 277 443 303 259
R 0.99 1.00 0.99 0.99 1.00
105°C KL (L/g) 28.1 8.24 27.1 12.7 14.7
Cs (g/kg) 24.3 60.1 11.8 26.1 24.2
Cs (mol/kg) 6.6 16.3 3.2 10.6 9.8
KLCs (L/kg) 682 495 320 333 355
R 0.99 0.99 0.99 0.99 0.99
Langmuir equation: Cf = KLCsCb/(1 + KLCb), where Cf = dye concentration on the fibre; Cb = dye concentration in the bath; Cs = saturation
value for Langmuir sorption; KL = Langmuir constant; R = correlation coefficient between experimental results and Langmuir sorption curve.

dyebath can take different concentration values, which is
impossible. These results are very important because they
confirm that the saturation of polyester fibers was not
obtained after saturation of the dyebath but after satura-
tion of fiber sites that are able to receive dye molecules.
Such sites can be assimilated to porous regions or disloca-
tions within amorphous zones in which the dye can be bound
to the fiber with hydrogen bonding and Van Der Waals
forces. This hypothesis agrees very closely with the theory of
Langmuir isotherms as found in our experiments.
Thus, we can say that the real deviations from the ideal
Nernst behavior that occur in the distribution of disperse
dyes between polyester substrate and water seems to be
due to two phenomena bound to the characteristics of the
fiber and the dye behavior within the fiber. The first one is
the reduction of the volume able to fix dye molecules when

Figure 2 Sorption isotherms of

dye 1 on polyester fibers at 130°C:
◦ = FOY 0.9,
= POY 1.95,  = FOY
2.27.
TRJ 274 Textile Research Journal 76(4)
the dye concentration on the fiber increases. The second
one may be the aggregation of the dye inside the fiber that
can obstruct some pores which were able to accept dye in
the molecular state. This tendency to aggregation should
be higher when dye size increases. Figure 8 represents a
Figure 3 Sorption isotherms of
dye 2 on polyester fibers at 130°C:
◦ = FOY 0.9,
= POY 1.95,  = FOY
2.27.
Figure 4 Sorption isotherms of
dye 1 on polyester fibers at 115°C:
◦ = FOY 0.9,
= POY 1.95,  = FOY
2.27.
dyeing model that we have established to explain such a
phenomenon.
In addition, we observed that sorption isotherms of
dye 1 at 115°C on FOY 0.9 and FOY 2.27 fibers (Figure 4)
present a point that approximates to the general form of
 Study of Dyeing Behavior of Polyester Fibers With Disperse Dyes S. Dhouib et al. 275 TRJ

Figure 5 Sorption isotherms of

dye 2 on polyester fibers at 115°C:
◦ = FOY 0.9,
= POY 1.95,  = FOY
2.27.

Figure 6 Sorption isotherms of

dye 1 on polyester fibers at 105°C:
◦ = FOY 0.9,
= POY 1.95,  = FOY
2.27.

the Langmuir adjustment curve when it approaches the
dye saturation concentration; something that we did not
detect with dye 2. In fact, we found that at 115 and 105°C
the experimental curves fitted better to curves composed
of two parts. The first one ranged from zero to this point
and obeyed (as shown in Figures 9 and 10) the Langmuir
law or a dual-mode sorption model composed of both
Nernst and Langmuir models, whereas the second one cor-
responded to a straight line of equation Cf = Cs. Such a
phenomenon is related to the fact that at 115 and 105°C,
the fiber is not sufficiently swollen and its pores are still
tight. Thus, when the dye concentration Cf on the high crys-
TRJ 276 Textile Research Journal 76(4)
Figure 8 Dyeing model of polyester fiber dyed with high concentration of big (on the left) and small (on the right) dye
size.
talline fibers (such as FOY 0.9 and FOY 2.27) approaches
the saturation value, the large amount of dye adsorbed on
the fiber accelerates the aggregation of dye molecules inside
the fiber. So a multilayer adsorption is produced and the
pores of the fiber are quickly plugged, the thing that prevents
the dye from reaching the accessible interior regions (Fig-
ure 8) and so adsorption of the dye is abruptly stopped.
The behavior of the fiber POY 1.95 did not appear to be
affected by the reduction of the dyeing temperature to
115 or 105°C because of its development of amorphous
zones.
Figure 7 Sorption isotherms of
dye 2 on polyester fibers at 105°C:
◦ = FOY 0.9,  = FOY 2.27.
With reference to earlier studies that have led to sorp-
tion isotherms for disperse dyes with Nernst behavior, we
suggest that such a result may be due to the fact that most
plotted isotherms have been measured at low dyeing tem-
peratures, generally less than 100°C and very rarely up to
110°C. At such low dyeing temperatures, most previous stud-
ies have been made with small dye sizes (as for dye 2 herein)
that can diffuse through the polyester substrate much more
easily under such conditions.
In this case, the decrease of the dyeing temperature dis-
places the dyeing equilibrium towards the fiber. Furthermore,
 Study of Dyeing Behavior of Polyester Fibers With Disperse Dyes S. Dhouib et al. 277 TRJ

Figure 9 Sorption isotherms of

dye 1 on FOY0.9 (top) and FOY2.27
(bottom) fibers fitted to curves
composed of two parts: the first
part obeys the Langmuir law and
the second one corresponds to a
straight line of equation Cf = Cs:

= 105°C, ◦ = 115°C,  = 130°C.

dye saturation in the bath and the fiber become lower and,
in addition the use of low dyeing temperatures leads to an
earlier saturation of the fiber, thereby limiting the first part
of the sorption isotherms to the weak concentrations that are
close to the origin of the curve. At this point it should be
noted that for low dye bath concentrations, the Langmuir
curve can be easily assimilated to the ideal Henry behavior
with a slope equal to KLCs. As the dye concentration of
sorption isotherms with disperse dyes at low temperatures
are limited to low or middle concentrations, it was easy to fit
such experimental curves to Nernst-type isotherms. On the
other hand, if the dye molecule size was large, the use of low
dyeing temperature would cause an early aggregation of the
dye in the fibers that were slightly swollen and, as a result,
the isotherms obtained seem to resemble those shown in
Figures 9 and 10. Thus, the first part of the isotherm can
TRJ 278 Textile Research Journal 76(4)
also be fitted to the Nernst model with low error. The devi-
ation from linearity for the highest concentrations that
occurs with pure and commercial dyes is explained by vari-
ous events such as the increasing amounts of dispersing
agent included in the increasing amounts of commercial
dye in the bath, errors in measured dye concentration, and
the presence of certain associated disperse dyes on the
aqueous solution [3].
Figure 10 Sorption isotherms of
dye 1 on FOY0.9 and FOY2.27 fibers
fitted to curves composed of two
parts: the first part obeys a dual-
mode sorption model composed of
both Nernst and Langmuir models
and the second one corresponds to
a straight line of equation Cf = Cs:

= 105°C, ◦ = 115°C,  = 130°C.
Furthermore, it is easily seen in Figures 2 and 3 that at
130°C the microfiber FOY 0.9 was able to fix less dye than
the classical fiber FOY 2.27, in spite of its greater surface
area. Hence, the surface area is not well correlated to the
dye adsorption ability of the fiber at this temperature; how-
ever, other parameters have a real influence on fiber acces-
sibility such as the crystallinity and probably the geometry
and the pore size of the fiber. As FOY 0.9 and FOY2.27 fib-
 Study of Dyeing Behavior of Polyester Fibers With Disperse Dyes S. Dhouib et al. 279 TRJ

ers have close crystallinity after heat setting, this result can
be explained by supposing that even though the total vol-
ume of pores of the classical fiber is lower than that of the
microfiber sample, the pores of the classical fiber are larger.
At high dye concentration, when the dye began to aggre-
gate within the fibers, the classical fiber FOY 2.27 would fix
a greater quantity of dye. Indeed, the dye aggregation could
block the passage of other dye molecules to deeper sites if
the pore diameters were small (Figure 8). This hypothesis is
further justified when observing the values of Langmuir
constants KL and KLCs that correlate with the slopes of the
first parts of the isotherm curves. These constant values
show that for low dye concentrations (when the aggregation
phenomenon had not still occurred) the dye quantity
adsorbed by the microfiber FOY 0.9 was greater than the
classical fiber FOY 2.27 due to the greater surface area of
Figure 11 Different types of fiber’s pores able or not to
the microfiber.
receive dye molecules: = dye 1, = dye 2.
At low temperatures (115 and 105°C), swelling of the
microfibres (as FOY 0.9) is easier than that of the classical
fibers (as FOY 2.27) due to the larger surface areas of the
microfibers, and this gives them a greater adsorption area
to the dye [12]. This explains why, at these temperatures, mass of dye 1 was 1.53 times that of dye2, obviously a lower
the ability of fiber FOY 0.9 to fix dye molecules became mass concentration would be obtained with dye 2.
better in comparison with fiber FOY 2.27 and consequently Finally, as shown in Table 2, for all the dyes and fibers,
the Cs values of fiber FOY 2.27 became the slowest when when the dyeing temperature decreased, the KL values
dyeing at 115 or 105°C whatever the dye used (Table 2). increase distinctly whereas the Cs values decrease. This was
The fiber POY1.95 always preserved the highest saturation due to two phenomena related to the reduction of dyeing
values due to its very large amorphous domain and this temperature: first, there is a decrease of the solubility of
facilitated its swelling and increased the number of sites disperse dyes in the bath that displaces the dyeing equilib-
which were able to fix dye molecules. rium to the fiber; second a reduction of the fiber accessibility
On the other hand, in comparison with those achieved has occurred due to the decrease of fiber swelling. There-
with dye 1, the sorption isotherms of dye 2 on polyester fib- fore, the fiber is saturated with lower dye concentrations.
ers show some differences not in the form of curves but
rather in the proportionality of values of Langmuir fitting
constants. Indeed, with dye 2, the values of KL and KLCs Conclusion
became smaller. This indicates that the affinity of dye 1 to
polyester fibers was better than that of dye 2. Furthermore, The sorption isotherms of disperse dyes on polyester fibers
as shown in Table 2, at 105°C the mass and molar concen- from water are well correlated to Langmuir law. The most
trations of Cs were higher when using dye 2. This means important parameters for dye saturation on the fiber are
that, in this case, the fibers were slightly swollen and their temperature, dye size and volume of accessible domains
pores were not dilated enough. Then, the small dye mole- able to receive dye molecules. This volume is very depend-
cules (as dye 2) were fixed inside the fibers more easily and ent on fiber crystallinity. Both fiber surface area, and dyeing
in a much more significant number. temperature have a second-order effect. The temperature
At 130°C, in a saturation state, the molar concentration will have more influence when fiber accessibilty is poor.
[Cs (mol/kg)] of dye 2 remained the highest; but, the mass
concentration [Cs (g/kg)] became slightly lower than those
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