RJTA Vol. 15 No.

4 2011

Dyeing of Polyester Fabrics with Indigo

Gulzar Ahmad Baig*
College of Textile Engineering and Technology, B.Z.U 60800– Multan, Punjab, Pakistan
gabaig@bzu.edu.pk

ABSTRACT

Polyester fabric was dyed with indigo through the exhaust technique by controlling the
ratios of sodium dithionite and sodium hydroxide concentrations in the dyebath solution. At
different ratios different forms of the indigo existed and each one had different degrees of
substantivity for the polyester. The non-ionic form such as disperse dyes, had substantivity
for polyester. Polyester could best be dyed in the acidic to slightly neutral pH range. The
reflection spectra showed that the absorption maximum for polyester was at 610 nm.
Rubbing and washing fastness were better while light and sublimation fastness were poor.

Keywords: Indigo, Synthetic Fibre, Polyester, pH, Colour Strength, Fastness Properties

1. Introduction difficulty in dyeing the latter with indigo (Hongyo

et al., 1990, 1999, 2000, 2001).
Indigo is a natural dye whose history could be
dated back to 55 BC (Druding, 2008). Chevli and Lewis have proposed dyeing synthetic
fibres with the leuco vat acid method in which pH
Indigo is native to South Asia, although it is also is maintained in the acidic side by using organic
grown in Central America, South & Central Africa, acids such as citric acid (Chevli & Lewis; 1999).
Java and Philippines. The main application of
indigo is for denims. During the Middle Ages By using this method, polyester fibre can be dyed,
fishermen of the Adriatic, Aegean and and the chemicals and waste treatment cost
Mediterranean wore garments that were dyed with increased. Katsushi has dyed polyester with indigo
indigo (Pierce, 1985). by controlling the concentration of sodium
dithionite and sodium hydroxide in the dyebath;
Although indigo is now exclusively applied on the dye was first reduced and then applied on
cotton, historical records show that about 4000 polyester (Kunttou et al., 2005).
years ago it was wool that was first been dyed
with indigo and it was around 1500 AD, when Polyester is a class of synthetic fibres
cotton was dyed with it (Greer & Turner, 1983). characterized by the presence of ester groups in
the backbone of their polymers. Different
Other natural fibres like silk can also be dyed with polyester fibres are being used in the textile
indigo (Koshida & Nakayama, 1987). industry but Polyethylene terephthalate (PET) is
one of the most widely processed. In addition,
Although indigo is a kind of vat dye, it lacks Polylactic acid (PLA), which is a biodegradable
substantivity; it has poor crocking fastness and and renewable fibre, is getting share in the market
washes away easily. Indigo lacks substantivity for steadily. Disperse dyes are used in the dyeing of
synthetic fibres like polyester, nylon, acrylic and polyesters though acid and basic dyeable
spandex because it had been applied by the cotton polyesters also exist on the market. In this work
method. Studies in the literature only describe a vat dye has been reduced in situ and applied onto
few methods about the application of indigo on polyester fabric. Most of the parameters including
synthetic fibres. Hongyo has dyed cotton as well the reducing agent and alkali concentrations,
as synthetic fabrics with indigo and found temperature, and time as well as liquor ratio are
studied. Reflectance spectra and fastness
* Corresponding author. Tel.: 0092-61-9210071-74; Fax: 0092-61-9210075
properties including washing, rubbing, light and
E-mail address: gabaig@bzu.edu.pk (Gulzar Ahmad Baig)
19
RJTA Vol. 15 No. 4 2011

sublimation have been measured and presented. structure, the dye was oxidized in hot air at 120 oC
for 5 minutes. All samples were soaped with
The findings of the present work have been Sandopan DTC 5 gm/l at 80 oC for 10 minutes,
applied to other synthetic fibres as well, and are air-dried and then tested for colour values and
proved very advantageous in dyeing PC blends fastness properties.
with indigo in a single bath. Since a single dye
can be used in the coloration of polyester and 2.3 Measurements
cotton fibres, the process can also save cost. Both
fibres can be dyed to deep shades with a variety of pH of the fresh and spent dyebaths was measured;
effects merely by controlling the pH and Colour Strength (K/S) (AATCC, 2006) was
temperature, in a single bath (Baig, 2008). measured by SWL method at a specified
wavelength (λ) using the following equation:
Single-bath dyeing of polyester-wool has been
carried out with a series of modifed disperse dyes K/S= [(1.0-Rλ)2]/2.0 Rλ
(Chao & Lin, 2000).
where K and S stand for coefficients of absorption
The poor sublimation and light fastnesses suggest and scattering of the dye at λmax respectively. Rλ is
that light and heat can be used in achieving the absorption coefficient of the specimen.
different colour fading effects on 100% polyester Reflectance spectra were measured at 10 nm
or pc blended fabrics to simulate conventional intervals. Fastness properties including rubbing,
jeans look. washing and light were measured according to the
ISO standards while sublimation fastness was
2. Experimental measured according to a Lab-developed method
(ISO, 1989, 1994, 2001).
2.1 Material & Machinery
3. Results and Discussion
HT dyeing machine 75231-1992 was used to dye
polyester samples and the pH was measured 3.1 Effect of NaOH
before and after dyeing using Digital pH Meter
PH-210. Reflectance and colour strength were Figure 1 shows the pH values of the fresh and
measured on GretagMacbeth ColorEye – 7000A spent dyebath solutions. The graph shows that in
Spectrophotometer with D65/10o and UV/specular the fresh dyebath pH changes slowly initially and
excluded. 100% Polyester filament yarn (Warp then rapidly from 0.8 to 1.6 gm/l and finally levels
count: 88 denier & Weft count: 177 denier), off. It is known that as the temperature increases,
plain woven fabric (Warp density: 124 & Weft the reaction rate will also increase. Sodium
density: 78) having 109 gsm was purchased from dithionite is very unstable in the solution, in the
the market and dyed without any prior presence of air and alkalies. At room temperature,
pre-treatment because alkaline-reductive treatment sodium dithionite decomposes slowly and
followed by soaping was considered sufficient to therefore the pH varies slowly and then rises up
remove the impurities. Indigo dye (85%), granular rapidly upto 0.4 gm/l. The acidic products
form, was provided by DyStar Pakistan. All other produced during sodium dithionite decomposition
chemicals were of laboratory grade. tend to consume the existing alkali. At and beyond
1.2 gm/l of alkali concentration, the pH remains
2.2 Dyeing almost the same.

Polyester samples were dyed with indigo to 0.1 to However, when pH of the spent dyebath is
3% o.w.f shade depth. Sodium dithionite and measured, a noticeable difference can be seen
sodium hydroxide concentrations varied from from 0 to 4.6 gm/l alkali concentrations. Starting
0–10 gm/l and 0–4.6 gm/l respectively. Dyeing from 0 to 0.3 gm/l alkali concentrations, there is
temperatures were studied from 80–130 oC for very little change in pH. It is known that sodium
time intervals of 15 minutes each, from 15 - 90 dithionite generates acidic products on
minutes. All dyed samples were subjected to cold decompositions. In this range the amount of these
water rinsing. Since polyester had a very compact acidic products is high enough to consume whole

20
RJTA Vol. 15 No. 4 2011

of the alkali present. This is why pH remains the of about 11. Here the alkali is consumed to
same. From 0.4 to 0.8 gm/l region, pH changes convert vat acid to mono-sodium phenolate. It is
from 3 to 6, deriving the reaction to the forward expected from these results that if pH is studied
direction so that more and more vat acid could be upto 14, there will be another change in the pH
generated. curve that would be corresponding to di-sodium
phenolate.
pH of the Dyebath start
end Figure 4 shows the colour strength of polyester at
14 different alkali concentrations. The shade depth
12 decreases on either side of 0.8-gm/l sodium
10 hydroxide concentration. Below this concentration,
8 the pH value of the dyebath is very low. When
6 indigo is reduced with sodium dithionite, acidic
4 products are generated. If these acidic products are
2 not consumed, then according to the Le Chatlier’s
0 principle the reaction should not proceed further.
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4 4.4 4.8 5.2

NaOH (gm/ l)
Fraction II = 1/ (1+10a+10b) (1)
Where a = (pH – pK1) and b = (2pH – pK1 – pK2)
Fig. 1. pH measured at the start and end of the
dyeing (1% o.w.f, 10 gm/l Na2S2O4, 120oC, Fraction III = 1/ (1+10c+10d) (2)
40:1, 30 minutes) Where c = (pK1 - pH) and d = (pH – pK2)

In this region alkali present is in surplus amount.

Some of this amount is consumed by the acidic Fraction IV = 1/ (1+10e+10f) (3)
products while the leftover causes a steep change Where e = (pK1 +pK2 – 2pH) and f = (pK2 - pH)
in pH. From 0.8 to 2.6 gm/l region, pH change is
again very slow which clues to something that
consumes the alkali. There are different reagents
Oxidized Indigo
that consume the alkali, including the acidic
products generated by sodium dithionite and the
vat acid. It is supposed to be the vat acid that starts
consuming the alkali in this region. As the alkali
concentration increases the ratio of vat acid to Fraction II
mono-sodium phenolate form decreases.

It is possible to calculate the fraction of different

forms, as shown in Figure 2, which could be Fraction III
present at a particular pH by using the equations 1
– 3 (Etters et al., 1989).

It can be seen from Figure 3 that vat acid remains

as the major moiety upto 2.6 gm/l, after which its Fraction IV
concentration drops steeply, which is in line with
our results. Upto 2.6 gm/l of alkali concentration
alkali is consumed by vat acid after which pH Fig. 2. Various forms of Indigo
changes rapidly from 2.6 to 3.8 gm/l. After 3.8
gm/l the pH once again remain the same at a value

21
RJTA Vol. 15 No. 4 2011

-800 mV while that required for indigo reduction

Fraction of Vat acids vs. NaOH concentration is -765 mV.
1
0.9
0.8
0.7
K/S vs. NaOH
Fraction

0.6
120
0.5
0.4 105
0.3
90
0.2

relative K/S
0.1 75

0 60
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4 4.4 4.8 5.2
45
NaOH (gm /l)
30
FormII Form III Form IV
15

0
Fig. 3. Fraction of each of the indigo species 0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4 4.4 4.8 5.2

NaOH (gm/ l)
calculated at sodium hydroxide
concentrations (1% o.w.f, 10 gm/l
Na2S2O4, 120 oC, 40:1, 30 minutes) Fig. 4. Relative K/S versus sodium hydroxide
concentrations (1% o.w.f, 10 gm/l
It is suggested that below 0.4 gm/l concentration, Na2S2O4, 120 oC, 40:1, 30 minutes)
the acidity is so high that most of the vat acid
generated during reduction of indigo is K/S vs. Sodium dithionite
precipitated because of its poor solubility in water.
120
Therefore, only a tint is produced during dyeing. 105
As alkali concentration increases from 0.4 to 0.8 90
gm/l, there is a rapid change in pH. pH jumps
relative K/S

75
from 3 to 6 that derive the solubilisation reaction 60
to the forward direction so that vat acid could stay 45

in the liquor and thereby be picked up by the fibre. 30

At 0.8 gm/l, vat acid is the sole product, as can be 15

seen from Figure 3, and therefore maximum shade 0

0 1 2 3 4 5 6 7 8
depth is produced. As the alkali concentration Sodium dithionite (gm/ l)
increases, the mono-sodium phenolate form also
starts appearing that leads to less dye build-up
Fig. 5. Relative K/S versus sodium dithionite
being produced on polyester. This decrease in
concentrations (1% o.m.f, 0.6 gm/l
shade build-up continues to decrease until alkali
NaOH, 120 oC, 40:1, 30 min)
concentration reaches 3.0 gm/l where there is
sudden decrease in vat acid. Beyond this pH range,
The effect of reducing agent on colour yield was
the mono-sodium phenolate form predominates
been studied and the results are presented
while the vat acid is of very minor quantities. This
graphically in Figure 5. It can be seen that upto a
minor quantity of vat acid continues to tint the
concentration of 4 gm/l, there is very little
polyester fibre. There is a resemblance in curves
substantivity of indigo for the polyester. It reaches
of form II and K/S as shown in Figures 2 and 3
to a maximum at 6 gm/l and then decreases. There
respectively from 0.8 gm/l sodium hydroxide
are two factors, namely sodium dithionite
concentration onward.
concentration as well as dyebath pH. At lower
concentrations, the quantity of sodium dithionite is
3.2 Effect of Reducing Agents not sufficient enough to reduce the whole indigo
to vat acid which is the main colouring matter.
Reducing agents reduce the dye into vat acid When we further increase the dithionite
during reduction reaction. For the dye to be concentration, indigo is reduced and polyester is
reduced properly, a reducing agent should have an dyed to a dark shade, but a further increase
ORP potential sufficiently negative to the dye reduces the colour yield, because beyond 6 gm/l,
itself. Sodium dithionite can produce an ORP of sodium dithionite reduces the dye but after an
22
RJTA Vol. 15 No. 4 2011

optimum concentration, the acidity of the dyebath some unevenness is likely to be resulted. Unlike
also increases, that leads to poor dye uptake. There most other disperse dyes, indigo is smaller and
should be calculated amount of sodium dithionite more compact in structure, which make it easy for
and it should bear an appropriate ratio with its penetration into the fibre structure. On further
sodium hydroxide so that pH lies within the increase in time, shade depth decreases and then
required region. It is not only the dithionite stays constant. Fibre samples have been subjected
concentration but a specific amount of alkali to microscopic studies to investigate the dye
concentration that help in the indigo dyeing of penetration into the fibre matrix. It has been found
polyester. that initial increase in shade depth is due to dye
being accumulated onto the fibre surface. As the
3.3 Effect of Temperature time passes, dye molecules start penetrating into
the fibre structure. After a certain time period, in
Dyeing requires heating so that the dye molecules this case 30 minutes, the shade comes into
have enough kinetic energy to penetrate into the equilibrium and does not change any further.
fibre structure. As an approximation, diffusion Therefore, a time interval of 30 minutes is
coefficient is inversely proportional to the 0.6th sufficient for full shade depth to obtain. A
power of the molecular volume (Brennan & decrease in full dye absorption into the core of the
Bullock, 1996). fibre will lead to poor sublimation as well as light
fastness.
Since indigo molecules are very small as
compared to most of the disperse dyes, the former
can penetrate into the fibrous matrix at a little bit K/S VS. Temperature
lower temperatures. At the same time temperature 120
increases the segmental mobility of the polymeric
100
chains of which the fibre is made. Figure 6 shows
the effect of temperature on the colour yield of 80
relative K/S

polyester. It can be seen that fibre has a tint at 60

lower temperatures; as we increase the 40

temperature upto 110 oC there is a steep increase
20
in the shade depth but on further increase in
temperature shade depth decreases. Polyester is a 0
70 80 90 100 110 120 130 140 150
crystalline material and at lower temperatures the
Temp (C)
polymeric chains do not oscillate at high enough
amplitude to let the dye molecules penetrate into
the structure. As we increase the temperature upto Fig. 6. Relative K/S versus Temperature (1% o.w.f,
the Tg and beyond, the segmental mobility is of 10 gm/l Na2S2O4, 1 gm/l NaOH, 40:1, 30
such a high degree that the transportation of dye minutes)
molecules from the solution becomes possible.
Upon further increase in temperature, this
K/S VS. Time
oscillation is so high that dye molecules can as
easily rush away from the polyester structure as 120

easily as they can penetrate, that leads to less 100

colour yield being produced. There is an optimum

relative K/S

80
temperature of 110 oC at which best colour yield
60
can be obtained.
40

20
3.4 Effect of Time
0
0 20 40 60 80 100
Effect of time on the shade depth of polyester is Time (min)

been shown in the Figure 7. It can be seen that

colour yield increases to the highest point only Fig. 7. Relative K/S versus Time (1% o.w.f, 10
after 15 min. This shows that indigo strikes on gm/l Na2S2O4, 1 gm/l NaOH, 120 oC,
polyester very fast and if not properly controlled 40:1)
23
RJTA Vol. 15 No. 4 2011

3.5 Effect of Liquor Ratio form a solid solution in the polyester fibre that
supports the solid solution theory of dyeing
The effect of liquor-to-material ratio is shown in mechanism. The presence of dye molecules in
the Figure 8. Generally at lower liquor ratios, mono-molecular form may be one of the reasons
shade depth is high but in the present case it is low. of having poor light fastness properties because
It is suggested that at lower liquor ratios, although the dye molecules will be more exposed to light
the concentration remains the same, the total energy than in the aggregated form, as in cotton
amount of sodium dithionite is not sufficient (Ahmad, 2008).
enough to completely reduce the dye, since it is
the reduced dye that has substantivity for the Reflection spectra
material. However, as the liquor ratio increases, 70
the amount of sodium dithionite also increases that 60
leads to the formation of vat acid which is taken
50
up by the material. On further increase of liquor
40
ratio shade depth decreases because the solution
30
starts becoming dilute, leading to lower dye being
20
taken up by the material. There is an optimum
10
liquor ratio of 40 at which maximum colour yield
0
is obtained. 400 450 500 550 600 650 700 750

Wavelength (nm)

0.10% 2%
K/S vs. Liquor ratio
120
Fig. 9. Reflection spectra of indigo
100

80 3.7 Fastness Properties

relative K/S

60

40
Some of the main fastness properties for polyester
2% o.w.f were measured and are presented in the
20
table 1 - 3. The results show that washing and
0
0 20 40 60 80 100 120 140 rubbing are good while the light and sublimation
Liquor ratio
fastness are poor. Washing and rubbing fastness
data are poor on cotton because of the more open
Fig. 8. Relative K/S versus Time (1% o.w.f, 10 and hygroscopic nature of the fiber. The results
gm/l Na2S2O4, 1 gm/l NaOH, 120 oC, 30 exhibit how the fiber structure affects the washing
minutes) and rubbing properties for the same dye. The more
hydrophobic and compact the structure, the better
3.6 Reflection Spectra its wash & crock fastness. The decrease in light
fastness might be due to indigo molecules being
The reflection spectra of indigo dyed polyester present within the fibre matrix as individual
fabric are shown in Figure 9. It can be seen from molecules.
these curves that the absorption maxima lie at 610
nm. When measured spectrophotometricaly in the
Table 1. Light & Rubbing Fastness
dimethyl formamide solution, indigo absorbs at
610 nm as well (Katsushi et al., 2005). Rubbing Light
Dry Wet
This shows that indigo dye molecules exist in the
4 4 2
fibre matrix in the unassociated form as they do in
solution. It can be said that indigo dye molecules

Table 2. Washing fastness

Colour change Staining
Acetate Cotton Nylon Polyester Acrylic Wool
4 GS 3-4 4 3–4 4 4–5 4

24
RJTA Vol. 15 No. 4 2011

Table 3. Sublimation fastness (01 min)

o
160 C 180 oC 200 oC 220 oC

Staining

Staining

Staining

Staining
change

change

change

change
Shade

Shade

Shade

Shade
3-4 4 2-3 1-2 2 2-3 1-2 1-2

4. Conclusion competition’, Textile Chemist and Colorist, vol.

21, no. 12, pp. 25–31.
All-polyester fabrics can be dyed with indigo [6] Hongyo, S. 2001, ‘Dyeing Technology by
through the exhaust technique by reducing it in Indigo Base Dyestuff’, Senshoku Kenkyu, vol.
situ. Sodium dithionite concentration of 6 gm/l is 45, pp. 30–35.
sufficient when alkali is 0.6 gm/l. When reducing [7] Hongyo, S., Kunitou, K. & Maeda, S. 1999,
agent has been optimized, the alkali concentration ‘Dyeing of Synthetic Fibre Garments by Indigo
should bear a certain relationship with sodium Dyes’, Okayama-ken Kogyo Gijutsu Senta
dithionite. pH should be in the acidic range and be Hokoku, vol. 25, pp. 53-54.
monitored strictly. Indigo does not exist as [8] Hongyo, S. & Maeda, S. 2000, ‘Dyeing of
aggregates within the fiber matrix might leads to Synthetic Fibres with Vat Dyes’, Senshoku
its having poor light fastness; however washing Kogyo, vol. 48, no. 12, pp. 3–8.
and crocking are good. This poor light fastness [9] Hongyo, S. & Moriwaki, H. 1990, ‘Dyeing of
can be taken advantage of in producing Cotton Garments and Synthetic Fibres with
faded-effects on indigo-dyed polyester fabrics. Indigo Dyes’, Senshoku Kogyo, vol. 47, pp.
55–62.
REFERENCES [10] Instrumental Colour Measurement, AATCC
Evaluation Procedure 6, AATCC Technical
[1] Baig, G.A. 2008, ‘Single Bath dyeing of PC Manual, 2006, pp. 386 – 391.
Blended Fabrics with Indigo’, 4th International [11] James, A., Greer & Turner, G.R. 1983, ‘Indigo
Textile, Clothing & Design Conference Denims: The Practical Side’, Textile Chemist
(ITC&DC), pp. 299–304, Dubrovnik, Croatia. and Colorist, vol. 15, no. 6, pp. 101–103.
[2] Brennan, C.M. & Bullock, J.F. 1996, [12] Katsushi K., Setsuaki, H., Shingo M. & Kenji
Physicochemical for Colour Chemistry, Peters, M. 2005, ‘Dyeing Polyester Fabrics with
A.T. & Freeman, H.S., Chapman & Hall: Indigo’, Textile Research Journal, vol. 75, no. 2,
London, UK, pp. 58. pp. 149–153.
[3] Chao, Y.C. & Lin, S.M. 2000, ‘A Single-Dye [13] Koshida, H. & Nakayama, T. 1987, ‘New
System for Polyester-Wool Blends’, Research Application Technologies of Vat Dye’,
Journal of Textile and Apparel, vol. 4, no. 2, pp. Senshoku Kogyo, vol. 35, pp. 199–225.
37-46. [14] Pierce, J.H. 1985, ‘The indigo phenomenon: its
[4] Chevli, S.N. & Lewis, D.M. 1999, ‘The history and application’, International Dyer and
Application of Vat Pigment Dispersions and Printer, vol. 170, no. 7, pp. m20.
Leuco Vat Acid Dispersions to Polyester Fibres’, [15] Susan C. & Druding, 2008, Dye History from
Advan. Colour Sci. Technol, vol. 2, pp. 2600 BC to the 20th Century,
148–151. http://www.straw.com/sig/dyehist.html.
[5] Etters, J.N., Annis, P.A., Baughman, G.L., [16] Textiles – Tests for Colour fastness – Part X12:
Farmer, J.C., Lindsay, J.N. & Perkins, W.L. ISO 105-X12, Ref # ISO 105-X12: 2001 (E).
1989, ‘South-eastern section, Effect of Dyebath [17] Textiles – Tests for Colour fastness – Part C03:
pH on color yield in indigo dyeing of Cotton ISO 105-03, Ref # ISO 105-X12: 1989 (E).
Denim Yarn, 1989 Intersectional Paper [18] Textiles – Tests for Colour fastness – Part B02:
Xenon arc fading lamp test, Ref # ISO 105-B02:
1994 (E).

25