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Textile Research Journal Article

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

1
Corresponding author: Tel.: (00216) 73475900; fax: (00216)
Experimental 73475163; e-mail: dhouib.soufien@laposte. net/soufien.dhouib@
isetkh.rnu.tn Also at: Unité de Recherches Textiles de Ksar Hellal,
The polyester filament yarns, 72dtex/88fil (partially ori- Institut Supérieur des Etudes Technologiques de Ksar Hellal, Ave-
ented yarn, fineness of monofilament 1.95 dtex), 50 dtex/ nue Hadj Ali Soua, 5070, Ksar Hellal, Tunisia

Textile Research Journal Vol 76(4): 271–280 DOI: 10.1177/0040517506061243 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 specimens in a cold acetone bath for 30 s and then blotted
dyeing temperature with the laboratory equipment availa- and dried.
ble. The estimated values obtained allowed us to compare Dye on the polyester substrate was measured by colori-
the surface area of the different fibers. metric analysis after its extraction with dimethylformamide
All dyeings were carried out with a well-stirred dyebath (DMF) using a Kumagawa extractor. The disperse dyes
using a Mathis laboratory-scale dyeing machine at a liquor were purified by Soxhlet extraction with benzene for 10 h
ratio of 20 : 1 and pH 5. Two dyes were selected (Figure 1) as described in the previous paper [10]. Calibration curves
according to their molecular weights, which were obtained were prepared using solutions of the pure dyes.
from Ciba, and used in the dyeing process without fur- Experimental isotherm curves were plotted using a
ther purification: dye 1, CI Disperse Yellow 42 (molecular large range of initial dye concentrations. The quantity of
weight = 369 g) and dye 2, CI Disperse orange 3 (molecu- commercial dye added to the dyebath was varied between
lar weight = 242 g). 0.1 and 20% in order to be able to determine the isotherm
No dispersing agent was added to the dyebath during curves with great precision. The quantity of pure dye on
dyeing. After dyeing, the samples were soaked twice in boil- the commercial powders was about 49.5% for dye 1 and
ing water for 5 minutes then transferred to a fresh pot of 31.8% for dye 2.
cool water. Finally, surface dye was removed by rinsing the

Results and Discussion
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
Figure 1 Chemical formula of dye 1 and dye 2. 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 forces. This hypothesis agrees very closely with the theory of
impossible. These results are very important because they Langmuir isotherms as found in our experiments.
confirm that the saturation of polyester fibers was not Thus, we can say that the real deviations from the ideal
obtained after saturation of the dyebath but after satura- Nernst behavior that occur in the distribution of disperse
tion of fiber sites that are able to receive dye molecules. dyes between polyester substrate and water seems to be
Such sites can be assimilated to porous regions or disloca- due to two phenomena bound to the characteristics of the
tions within amorphous zones in which the dye can be bound fiber and the dye behavior within the fiber. The first one is
to the fiber with hydrogen bonding and Van Der Waals 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)

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.

the dye concentration on the fiber increases. The second dyeing model that we have established to explain such a
one may be the aggregation of the dye inside the fiber that phenomenon.
can obstruct some pores which were able to accept dye in In addition, we observed that sorption isotherms of
the molecular state. This tendency to aggregation should dye 1 at 115°C on FOY 0.9 and FOY 2.27 fibers (Figure 4)
be higher when dye size increases. Figure 8 represents a 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 law or a dual-mode sorption model composed of both
dye saturation concentration; something that we did not Nernst and Langmuir models, whereas the second one cor-
detect with dye 2. In fact, we found that at 115 and 105°C responded to a straight line of equation Cf = Cs. Such a
the experimental curves fitted better to curves composed phenomenon is related to the fact that at 115 and 105°C,
of two parts. The first one ranged from zero to this point the fiber is not sufficiently swollen and its pores are still
and obeyed (as shown in Figures 9 and 10) the Langmuir tight. Thus, when the dye concentration Cf on the high crys-
TRJ 276 Textile Research Journal 76(4)

Figure 7 Sorption isotherms of
dye 2 on polyester fibers at 105°C:
◦ = FOY 0.9,  = FOY 2.27.

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 With reference to earlier studies that have led to sorp-
the saturation value, the large amount of dye adsorbed on tion isotherms for disperse dyes with Nernst behavior, we
the fiber accelerates the aggregation of dye molecules inside suggest that such a result may be due to the fact that most
the fiber. So a multilayer adsorption is produced and the plotted isotherms have been measured at low dyeing tem-
pores of the fiber are quickly plugged, the thing that prevents peratures, generally less than 100°C and very rarely up to
the dye from reaching the accessible interior regions (Fig- 110°C. At such low dyeing temperatures, most previous stud-
ure 8) and so adsorption of the dye is abruptly stopped. ies have been made with small dye sizes (as for dye 2 herein)
The behavior of the fiber POY 1.95 did not appear to be that can diffuse through the polyester substrate much more
affected by the reduction of the dyeing temperature to easily under such conditions.
115 or 105°C because of its development of amorphous In this case, the decrease of the dyeing temperature dis-
zones. 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, sorption isotherms with disperse dyes at low temperatures
in addition the use of low dyeing temperatures leads to an are limited to low or middle concentrations, it was easy to fit
earlier saturation of the fiber, thereby limiting the first part such experimental curves to Nernst-type isotherms. On the
of the sorption isotherms to the weak concentrations that are other hand, if the dye molecule size was large, the use of low
close to the origin of the curve. At this point it should be dyeing temperature would cause an early aggregation of the
noted that for low dye bath concentrations, the Langmuir dye in the fibers that were slightly swollen and, as a result,
curve can be easily assimilated to the ideal Henry behavior the isotherms obtained seem to resemble those shown in
with a slope equal to KLCs. As the dye concentration of Figures 9 and 10. Thus, the first part of the isotherm can
TRJ 278 Textile Research Journal 76(4)

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.

also be fitted to the Nernst model with low error. The devi- Furthermore, it is easily seen in Figures 2 and 3 that at
ation from linearity for the highest concentrations that 130°C the microfiber FOY 0.9 was able to fix less dye than
occurs with pure and commercial dyes is explained by vari- the classical fiber FOY 2.27, in spite of its greater surface
ous events such as the increasing amounts of dispersing area. Hence, the surface area is not well correlated to the
agent included in the increasing amounts of commercial dye adsorption ability of the fiber at this temperature; how-
dye in the bath, errors in measured dye concentration, and ever, other parameters have a real influence on fiber acces-
the presence of certain associated disperse dyes on the sibility such as the crystallinity and probably the geometry
aqueous solution [3]. 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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