Indian Journal of Fibre & Textile Research

Vol. 37, September 2012, pp. 265-272

Effect of pH on the coloration of synthetic fibres with indigo blue

Gulzar A Baiga
Department of Textile Chemistry, College of Textile Engineering & Technology, BZU Multan 68000, Punjab, Pakistan

Received 13 February 2011; revised received and accepted 4 November 2011

Various synthetic fibres, viz. PET (polyethylene terephthalate), nylon 6.6, acrylic and lycra (polyurethane), have been
dyed with indigo blue at various pH. The pH values are achieved by controlling the relative amounts of sodium dithionite
and sodium hydroxide in the dyebath. PET, nylon 6.6, acrylic and lycra are dyed at 120, 100, 100 and 80 °C respectively for
30 min through an exhaust technique. The results show that leuco vat acid molecules exhaust well on all of these synthetic
fibres in the appropriate acidic region (pH being 5.5 – 6). Lycra produces the highest shade depth followed by acrylic, nylon
and then PET. On either side of this pH region, substantivity decreases. In the highly acidic region indigo molecules are
precipitated while in the alkaline region dye molecules are ionized, and the fibre polymeric material is hydrolyzed.
Reflection spectra show that the absorption maxima of indigo molecules are at 610 nm for PET, nylon and lycra while for
acrylic it is 560 nm. It is also suggested that dye molecules exist as single molecules in the fibre matrix because when indigo
is dissolved in dimethyl formamide it absorbs at 610 nm as well.

Keywords: Acrylic fibre, Dye-fibre chemistry, Indigo blue, Lycra fibre, Nylon 6.6 fibre, PET fibre, Reflection spectra

1 Introduction weight (sp. gravity 1.18). These fibres find

Indigo, a natural dye, has been in use for the
coloration of textiles since ages. The highest
consumption of indigo is in the denim industry where
reduced indigo is applied to cotton warp threads by
the multiple dips-cum- oxidation steps. In addition to
cotton, other fibres such as silk and wool are also
dyed with indigo in the past. Some of the work has
been published about the application of vat colorants
on synthetic fibres mainly PET (polyethylene
terephthalate)1-8. A recent work has been published
about the application of indigo on PET and nylon9,10.
There are various synthetic fibres available in the
market. These fibres include PET, nylon 6.6, nylon 6,
acrylic and spandex. PET is the most abundantly
manufactured synthetic fibres in the world. Its
production was 18 million tonnes per year in 2000
(ref. 11). The fibres are strong, lightweight, easily
dyeable and crease-resistant as well as have good
wash and wear properties. Polyesters are dyed with
disperse dyes. Nylons include mainly nylon 6.6 and
nylon 6 fibres. Nylons are very important fibres and
find applications in the apparel and hosiery industry.
These are mainly dyed with acid dyes. Acrylic fibres,
also known as artificial wool because of their
excellent bulk and warmth properties, have reduced
_______
a
E-mail: gabaig@bzu.edu.pk
applications in knitwear, socks, blankets and
upholstery. Acrylic fibres are also blended with wool.
Acrylic fibres are dyed with basic dyes. Spandex
(polyurethanes) known for their high stretchability
and elastic recovery, are sold under various brands.
These include Lycra®, Elaspan® (Invista), Dorlastan®
(Asahi Kasei) and ESPA® (Toyobo) to name a few.
Lycra fibres are mostly blended with other fibres e.g.
cotton. Cotton- lycra yarns are manufactured such that
lycra forms the core surrounded by a sheath of cotton
fibres. These fibres can be dyed with disperse or
acid dyes.
The synthetic fibres mentioned above have
specialized dye classes for each of them. Some of the
work was carried out to modify the fibres, the dyes or
the process so that fibres in a blend could be dyed
with a single dye simultaneously12-16. The present
work suggests that the vat dyes are universal as these
colorants can be applied to any class of fibres. Natural
fibres are already known to be dyed with vat dyes;
however, a little work has been published with regard
to the application of vat colorants on synthetic fibres.
One of the unique features, explored during the
present research work of vat colorants is their
pH-dependant behaviour during dyeing. Depending
on pH these colorants may behave as either disperse
or acid dyes. Since most of the synthetic fibres could
266 INDIAN J. FIBRE TEXT. RES., SEPTEMBER 2012
be dyed with disperse dyes, vat dyes could qualify as
universal colorants because of their being applied to
natural as well as synthetic fibres.
In the present work, indigo dye has been applied to
PET, nylon 6.6, acrylic and lycra through an exhaust
technique to study the dyeability of these fibres with
vat dyes. The pH of the fresh and spent-dyebaths has
been measured and the results are presented. Effects
of varying pH on the dyebath composition, colour
strength and on the chemistry of the fibres were
discussed. A theoretical approach has been used to
correlate the substantivity of leuco vat acid with
fibres. Various interactions are proposed between the
leuco vat acid and the polymeric materials of the
synthetic fibres.
2 Materials and Methods
2.1 Materials
High temperature (HT) dyeing machine 75231-
1992 was used to dye samples of synthetic fibres.
Dyebath pH was measured at the start and at the end
of dyeing using Henna Digital pH Meter PH-210.
Reflectance and colour strength of dyed samples were
measured on GretagMacbeth ColorEye – 7000A
Spectrophotometer. Synthetic indigo dye (85%) in
granular form was procured from the DyStar Pakistan.
Sandopan DTC (non-ionic detergent) was obtained
from Clariant Pakistan. Sodium dithionite, sodium
hydroxide and sodium carbonate used were of
laboratory grade. The specifications of various fabrics
used are given in Table 1.
2.2 Methods
Pretreatment
Synthetic fibres contain little impurities in the bulk
of the material. Some of the added impurities, e.g.
lubricants and anti-stats applied during spinning have
to be removed. A light scouring treatment with 2 g/L
sodium carbonate at 60 oC for 20 min was given. The
samples were then rinsed with cold water followed by
drying overnight under ambient conditions.
Table 1 — Specifications of fabrics used in the study
Yarn (filament) Warp den Weft den Warp density
ends/inch
PET 88 177 124
Nylon 6.6 210 94 160
Acrylic 88 177 124
Lycra 620 dtex 40
(wales density)
Dyeing
Samples were dyed with Indigo to 1% o.w.f shade
depth. Sodium dithionite 10 g/L, temperature (PET
120 oC17, nylon 100 oC, acrylic 100 oC, and lycra
80 oC), time 30 min and liquor-to-material ratio 40:1
were fixed while pH was varied from acidic to
alkaline regions by varying the amount of sodium
hydroxide. All the samples after dyeing were
subjected to cold water rinsing. When dyeing cotton,
samples are oxidized and then soaped. However, in
the case of synthetic fibres soaping followed the
oxidation. The samples were soaped with Sandopan
DTC 5 g/L (non-ionic washing aid) at 80 °C (for lycra
40 °C) for 10 min. Since synthetic fibres have a
compact and crystalline structure, the dye was
oxidized in hot air (oxygen from air) at 110 °C for
5 min., air dried and then tested for colour values.
Figure 1 shows the complete dyeing cycle and
Scheme 1 shows the reduction-oxidation cycle of
indigo during dyeing. Scheme 1 also shows
various fractions of leuco vat acid produced as a
function of pH.
pH Measurement
The pH values of the fresh as well spent dyebaths
were measured at room temperature. ∆pH (difference
in pH between any two adjacent pH values) was
measured and presented along with the pH values –
derivative of pH curve.
Fig. 1 — Process profile of indigo dyeing
Weft density Mass density Weave
ends/inch gsm
78 109 Plain
80 37 Plain
78 109 Plain
24 3800 Single jersey
(courses density)
 BAIG: EFFECT OF PH ON COLORATION OF SYNTHETIC FIBRES
Scheme 1 — Schematic reactions of Indigo reduction
Colour Measurement
Reflectance and colour strength were measured
on GretagMacbeth ColorEye – 7000A Spectrophoto-
meter. Colour strength (K/S) was measured by single
wavelength method at a specified wavelength (λ)
using the following equation17:
K/S= [(1.0-Rλ)2]/2.0 Rλ
where K is the coefficient of absorption of dye at λmax;
Sλ, the coefficient of scattering at λmax; and Rλ,
reflectance of the specimen at λmax. Reflection of the
samples has been measured from 400 nm to 700 nm at
intervals of 20 nm.
3 Results and Discussion
3.1 Dyebath pH Analysis
Figure 2 shows pH values of the fresh as well as
spent dyebath. The graph exhibits a continuous
change in pH from the start to the end of the sodium
hydroxide concentrations. It is apparent from the start
graph that the changes in pH are very slow at the start;
increase sharply, then slow down and finally become
stable. It is known that the temperature and reaction
rate have a direct relationship. Sodium dithionite is
very unstable in solution in the presence of oxygen
and alkalies. Some of the chemical reactions that
sodium dithionite undergo with these reactants under
different conditions have been reported in the
previous work9,10.
At room temperature, sodium dithionite
decomposes slowly and hence upto sodium hydroxide
concentrations of 0.6 – 0.8 g/L, pH varies slowly and
then increases rapidly in between 0.8 g/L and 1.2 g/L
alkali concentrations. The acidic products, produced
by sodium dithionite, are in so high quantities that
they consumes whole of the alkali leaving pH in the
267
Fig. 2 — Dyebath pH at the start and end with different alkali
concentrations
acidic side. As the alkali concentration crosses a
certain limit set by the acidic impurities, there is a
large change in pH at this point represented as hump
by the differential-start curve. Further increase in
alkali concentration beyond 1.2 g/L does not lead to
any appreciable increase in pH. During the
experiment it has been observed that color of the
dyebath changes to light green, which is an indication
that dye has started converting into the reduced form,
but surely not completely because the fully reduced
indigo has yellow color. Since it is the start of dyeing,
dyebath shows the same sort of behavior for all of
the fibres.
Figure 2 also shows the pH of spent-dyebath, i.e. at
the end of dyeing. At the very start because of the
presence of acidic impurities, pH remains in the acidic
side but now the length of the tail decreases, the later
is due to a complete reaction among the acidic
impurities and the sodium hydroxide. After the
impurities are consumed, a sudden change is observed
at 0.8 g/L alkali concentration that leads to an
increase in the pH. This change indicates the
formation of leuco vat acid. From 1.2 g/L to 3.2 g/L
alkali concentrations, pH curve exhibits very slow
change and this shows that alkali is consumed. Here,
the leuco vat acid reacts with sodium hydroxide and is
converted into the mono-sodium phenolate form
(Scheme 1). Since leuco vat acid is a week acid and
sodium hydroxide is a strong alkali, a week buffer is
formed and hence pH changes slowly. In the next
region, from 3.2 g/L to 3.6 g/L alkali concentration,
another change represented as a hump can be seen.
This sharp change shows a steep increase in pH that
means vat acid has completely been consumed and
268 INDIAN J. FIBRE TEXT. RES., SEPTEMBER 2012
now mono-sodium phenolate solely exists at this
point. This mono-ionic form then starts converting
into di-sodium phenolate form. It can be seen from
the figure that the end-graph becomes stable once
again. During this, di-ionic form starts appearing in
equilibrium with mono-ionic form. We finished here
because pH values beyond this were ineffective for
dyeing of synthetic fibres. Average value of pH is
found to be approx. 11.1 in the region upto the
concentrations studied, however it definitely increases
upto pH 12 – 13 when di-ionic form is completed.
Dyebath pH behaviour of acrylic fibres at the end is
quite different from that of the other fibres. At higher
alkali concentrations cyano groups (-C≡N) are
hydrolyzed. Hydrolysis of cyano groups leads to the
formation of carboxylic acid groups that are
neutralized with sodium hydroxide. Due to
consumption of alkali, pH of the dyebath does not
increase appreciably toward the end of the graph.
It is possible to calculate different fractions of
leuco vat acid (Scheme 1) which is present at a
particular pH by using the Eqs (1) – (3)18. It can be
seen from Fig. 3 that leuco vat acid remains as the
major fraction upto pH 6 and after this its
concentration drops down steeply. This is bound to be
in line with our results. As the pH increases, di-
sodium form also starts appearing. At pH 9, both the
curves of the leuco vat acid and mono-phenolate form
cross each other. Beyond this, leuco vat acid
diminishes steeply and converts into the mono-
sodium phenolate form. At a pH of 11, di-sodium
form starts appearing, although it is in minute amount.
Fraction II = 1/ (1+10a+10b)
where a = (pH – pK1) and b = (2pH – pK1 – pK2)
Fig. 3 — Factions of vat acid at various pH values
Fraction III = 1/ (1+10c+10d) …(2)
where c = (pK1 - pH) and d = (pH – pK2)
Fraction IV = 1/ (1+10e+10f) …(3)
where e = (pK1 +pK2 – 2pH) and f = (pK2 - pH)
3.2 Dyebath pH vs. Colour Strength
Figure 4 shows the colour strength of indigo on
various synthetic fibres dyed at various pH values.
The shade depth decreases steeply at pH values lower
than 5.5 – 6. When indigo is reduced with sodium
dithionite, acidic inorganic products are generated
which are highly soluble in aqueous solution. Leuco
vat acid, being a very week acid, is sparingly soluble
in aqueous medium. Because of the presence of
highly soluble acidic impurities, the solubility of
leuco vat acid is reduced. If these acidic products are
not consumed, then according to the Le Chatlier’s
principle the reaction should have not proceeded
further. It is suggested that below pH 4 – 4.5, acidity
is so high in the dyebath that most of the leuco vat
acid is precipitated and this is supported by the
observations that at the end of dyeing in this region, a
black dispersion is produced and therefore very little
dye exhausted onto the fabric. Although in the pH
range 3 – 5, leuco vat acid is the sole product of
reduction reaction, most of it is precipitated from the
solution.
An increase in pH beyond 5 leads to proper
colloidal solubilisation of leuco vat acid. The
presence of dispersing agents helps stabilize the
…(1) dispersion of leuco vat acid. Around pH 6 leuco vat
Fig. 4 — Colour strength (K/S) versus pH (1% o.w.f, 10 g/L
Na2S2O4, 120 oC, 40:1, 30 min)
 BAIG: EFFECT OF PH ON COLORATION OF SYNTHETIC FIBRES 269

acid still shares 98% of the strength in the dyebath below pH 4 – 5 hence; pH should have to be
solution (Fig. 3), and therefore a maximum shade controlled carefully and never be dropped down blow
depth is produced on all of the synthetic fibres as 5. The pH-dependant behaviour of synthetic fibres
shown in Fig. 4. The shade depth produced on various exhibits that pH could be used as a
fibre is in the following increasing order: lycra > retarder/exhaustion-controller during vat dyeing of
acrylic > nylon > PET (Table 2). Lycra fibres are not these fibres. Unlike PET, nylon and acrylic form a
highly crystalline fibres. The highly amorphous wide plateau between pH 5 and approximately
regions in lycra are the main reason for high shade (Table 2). This shows that while dyeing these fibres,
depth being produced. In the case of PET, shade depth pH variations in that regions could be tolerated. High
decreases sharply after pH 6. In the case of lycra, colour yield on lycra fibres is simply due to the high
acrylic and nylon fibres, dye exhausts upto pH 8 as amorphousity of the polyurethane polymers.
well. When pH increases the mono-sodium phenolate
form also starts appearing that leads to decrease in 3.3 Colorimetric Properties
dye build up. This decrease in shade build-up Figure 5 shows the reflection spectra and
continues to decrease until pH 9. Beyond this pH colorimetric properties of indigo on PET, nylon,
range, the mono-sodium phenolate form acrylic and lycra fabrics. The samples were dyed to
predominates, while the vat acid remains in very 1% (o.w.f). Reflection spectra shows that the
minor quantity. This minor quantity of vat acid absorption maxima of indigo in PET, nylon, acrylic
continues to tint all of the synthetic fibres. It is and lycra are at 610, 610, 560 and 610 nm
evident from Fig. 4 that there is little shade depth respectively. When applied to cotton fibres, indigo
Table 2 — Effect of optimum pH range and average colour
absorbs maximally at 660 nm7. There is a shift
strength of indigo on various fibres towards shorter wavelengths in maximum absorption
of 50 nm for PET, nylon and lycra and 100 nm for
Fibre λmax, nm Optimum pH Average K/S acrylic. It is known that indigo molecules exist as
aggregates in the cotton fibres and that this
PET 610 6 7.5
Nylon 6.6 590 5.5 – 7.75 12 aggregation increases during soaping of dyed fabric.
Acrylic 610 5.5 – 7.0 17.5 When Indigo is dissolved in dimethyl formamide and
Lycra 610 6 – 7.5 25 light absorption is measured spectrophotometrically,

Fig. 5 — Colorimetric properties of indigo (1% owf) on various synthetic fibres

270 INDIAN J. FIBRE TEXT. RES., SEPTEMBER 2012
the absorption maximum is found at 610 nm like most
of the synthetic fibres. It can be deduced from these
results that indigo molecules exist in the synthetic
fibres as single molecules. Dyeing of polyester with
disperse dyes is explained on solid-solution theory.
Since indigo absorbs at 610 nm when dissolved in
dimethyl formamide where it forms a true solution, it
is proposed that indigo molecules also form a solid
solution with synthetic fibres. Figure 5 also presents
colorimetric properties of indigo on various synthetic
fibres. It can be observed from the graphs that shade
is redder-bluer on lycra while on all others fibres it is
greener-bluer in tone. Highest chroma is exhibited on
lycra and the least one on PET. Nylon and acrylic
remain between these two fibres.
3.4 Dyebath pH vs. Fibre Chemistry
Scheme 2 shows some of the chemical reactions
that synthetic fibres may undergo during dyeing. PET
contains a large number of ester groups in the
backbone of their macromolecules. Ester groups are
stable at pH 5 - 5.5 and this is one of the reasons why
PET fibres are dyed on commercial scale around this
pH region. However, alkaline pH is detrimental to the
integrity of these fibres. In the alkaline pH region
polyester fibres are hydrolyzed and this hydrolysis
rate is directly related to processing temperatures.
Hydrolysis of PET leads to the formation of free
alcoholic and carboxylic acid groups at the end of
Scheme 2 — Hydrolysis of synthetic fibres
newly generated polymer chains. The free carboxylic
acid groups are neutralized with the alkali present in
the dyebath. This neutralization leads to negative
potential being developed on the surface of fibres,
which cause repulsion of ionized leuco vat acid
molecules. If processed for longer duration at higher
temperature in the alkaline regions, polyester fibres
lose much of their mechanical properties. Nylons and
lycra fibres contain amide groups in the backbone of
their polymer chains. Amide groups, like esters, are
also vulnerable to hydrolysis that leads to the
formation of free amine and carboxylic acid groups.
These later groups could then consume alkali present
in the dyebath and become charged negatively.
Acrylic fibres are the most susceptible to hydrolysis
than any others. Acrylic fibres contained cyanide,
chlorine, acetate and acrylamide groups pendants to
polymer chains. Cyano groups are the main groups
while other functional groups are introduced to reduce
crystallinity of the fibres. Cyano groups are unstable
in the acidic as well alkaline region, more in the later.
In the alkaline region cyano groups are hydrolyzed to
carboxylic acid groups. These acidic groups are then
neutralized with the dyebath alkali and lead to the
formation of carboxylates. It can be concluded that in
the alkaline pH region synthetic fibres are degraded
and because of acquiring negative potential the dye
molecules do not adsorb into fibres. Since, all of these
 BAIG: EFFECT OF PH ON COLORATION OF SYNTHETIC FIBRES
Scheme 3 — Synthetic fibres – indigo interactions
synthetic fibres can be dyed around pH 5.5 – 6, there
are no worries of fibre degradation in this region.
3.5 Dye-Fibre Interactions
Indigo molecules exhibit good substantivity for
synthetic fibres. No doubts, substantivity depends on
the form of indigo molecules. Oxidized indigo
molecules do not have substantivity, while as the
dyebath pH increases the substantivity decreases. It is
an appropriate acidic pH region where indigo
molecules exhaust well to the synthetic fibres. From
Fig. 4, it is clear that even at a particular pH (6 for
example), color strength is not the same. It can be
inferred from the previous discussion that dye
molecules and fibre chemistry have great influences
on dyeing properties. Scheme 3 shows some of the
possible interactions that may give rise to
substantivity forces between fibres and dye
molecules. Indigo molecules have ketonic groups in
the oxidized state.
After reduction, ketonic groups are converted into
hydroxyl groups. These hydroxyl groups are ionized
depending on pH, as shown in Fig. 3. PET fibres have
aromatic rings and carbonyl groups in the backbone
of their macromolecules. Acrylic possesses cyanide,
acetate and acrylamide pendant groups while nylons
have amide and amine groups. Lycra has amide
groups in their polymer backbone. All of these groups
are polar because of electro-negativity differences in
constituting atoms. From the results presented and
discussed in previous sections and that there is little
271
color strength in the highly acidic and alkaline pH
regions, it can be inferred that the hydroxyl groups in
leuco vat acid molecules contribute to substantivity.
Other possible interaction can be between the
aromatic nuclei of PET and hydroxyl groups of dye
molecules9. In the alkaline pH region, dye molecules
are ionized and develop negative charge. In addition
to hydrogen bonding, nylon could interact with leuco
vat acid molecules through ionic bonds10.
4 Conclusion
Synthetic fibres, viz. polyester, nylon, acrylic and
lycra, could be dyed with vat dyes. Dyebath pH is one
of the main potential factors during dyeing that must
be chosen and controlled properly. Leuco vat acid
dispersions are unstable at too low pH values while in
the alkaline region dyes molecules are ionized and
synthetic fibres developed negative potential. Water
solubility of the ionized dye molecules and the
negative potential attained by fibres at higher pH
values are the main reasons for little exhaustion of
dye molecules in the alkaline media. Appropriate pH
region for dyeing is observed as 5.5 – 6, though some
fibres absorbed dye upto pH 8 as well. At a sodium
dithionite concentration of 10 g/L, 0.6 – 0.8 g/L
concentration of sodium hydroxide is sufficient to
attain pH in the range of 5.5 - 6. Sodium dithionite is
a reducing agent that produces inorganic acidic
products on decomposition; therefore, higher
concentrations of sodium dithionite may require
higher amounts of sodium hydroxide to achieve the
required pH. So, there is a direct relationship between
concentration of sodium dithionate and sodium
hydroxide to achieve a specific pH. Indigo molecules
do not exist as aggregates within the fibre matrix that
leads to exhibiting different light reflection properties.
On the commercial scale, polyester-cotton blends are
dyed mostly with disperse-reactive dye systems. The
present work suggests that a single bath dyeing of
polyester-cotton blends could be carried out with vat
dyes that could save energy and processing time.
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