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Concurrent dyeing and finishing of cotton with natural

colour and citric acid in the presence of NaH2PO4 as
catalyst under thermal treatment
a b c
S. Ray Maulik , D. Das & S.C. Bhattacharya
a
Visva Bharati University , Silpa Sadana , India
b
National Institute of Fashion Technology , Kolkata , India
c
Jadavpur University , Kolkata , India
Published online: 08 Feb 2011.

To cite this article: S. Ray Maulik , D. Das & S.C. Bhattacharya (2011) Concurrent dyeing and finishing of cotton with natural
colour and citric acid in the presence of NaH2PO4 as catalyst under thermal treatment, The Journal of The Textile Institute,
102:6, 491-499, DOI: 10.1080/00405000.2010.491984

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 The Journal of The Textile Institute
Vol. 102, No. 6, June 2011, 491–499

Concurrent dyeing and finishing of cotton with natural colour and citric acid in the presence
of NaH2PO4 as catalyst under thermal treatment
S. Ray Maulika*, D. Dasb and S.C. Bhattacharyac
a
Visva Bharati University, Silpa Sadana, India; bNational Institute of Fashion Technology, Kolkata, India; cJadavpur University,
Kolkata, India
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(Received 31 March 2009; final version received 5 May 2010 )

Taylor and Francis Ltd

10.1080/00405000.2010.491984

Cotton fabric was simultaneously modified and dyed with citric acid and Camellia sinensis, and citric acid and
Punica granatum in the presence of sodium di-hydrogen phosphate (NaH 2PO4) as the catalyst using a pad–dry–cure
technique. Treatment with 10% citric acid, 15% NaH2PO4 and any of the above-mentioned dyes at 100% wet pick-
up, followed by drying at 95°C for 5 min and curing of the dried fabric at 140°C for 5 min produced most balanced
improvements in respect of the depth of shade, wrinkle recovery and colour fastness to light, wash and rubbing with
retention of more than 70% of the original strength. Infrared analysis of the dyed cotton fabric indicated that the
treatment of cotton with citric acid and either Camellia sinensis or Punica granatum under the influence of an
esterification catalyst led to the esterification of carboxyl groups of citric acid and of hydroxyl groups of cotton
cellulose and with that of both the dyes. The said process also led to some degree of cross-linking of polymeric chains
of cotton.
Keywords: citric acid; Camellia sinensis; esterification; Punica granatum; sodium di-hydrogen phosphate

Introduction they are commonly capable of dyeing cotton at a poor

Citric acid offers a cheap alternative to the use of toxic
formaldehyde condensate as a cross-linking agent of
cotton in view of its environment-friendly, non-toxic and
safe character (Schramm, Rinderer, & Bobleter, 1997;
Welch, 1992). Citric acid and other polycarboxylic acid
compounds establish ester linkage by reaction of their
carboxylic acid groups with the hydroxyl groups of cellu-
losic chains of cotton in the presence of different sodium
salt of phosphorous-containing minerals acids as cata-
lysts such as NaH2PO2, Na2HPO3, NaH2PO3, NaH2PO4,
Na2H2P2O7, Na4P2O7, and so on (Welch, 1992).
Camellia sinensis is cultivated for its leaves from
which commercial tea is made. The chief biochemical
colouring compounds present in the tea are theaflavin and
thearubigins, which have a polyphenol structure (Sarma,
1999), as shown in Figure 1. Pomegranate is the name
given to a sweet juicy fruit obtained from the cultivated
species of genus Punica granatum and Punica protopu-
nica. The rind of such fruit contains ellagi-tannin-
level, giving poor all-round colour fastness properties.
Such dyes, however, are capable of dyeing wool and silk
fibres appreciably from an acidic dye bath (pH ∼4), giving
much improved colour fastness properties (Das, Bhatta-
charya, & Ray Maulik, 2005; Das, Ray Maulik, & Bhat-
tacharya, 2006). Results of applications of such dyes done
at different pH following the exhaust technique are given
in Table 1. In this context, we thought it of interest to
investigate whether the use of citric acid could prove to
be worthy and efficient in bringing about the esterifica-
tion reaction with the hydroxyl groups of cotton and with
that of the dyes in a manner that would lead to improve-
ment in colour yield and all-round fastness properties, in
addition to improvement in wrinkle recovery of the cotton
fabric, when the cotton fabric is dyed with the dyes in
the presence of citric acid under the influence of an ester-
ification catalyst following a pad–dry–cure technique.
Results of related investigations done on bleached cotton
fabric are reported in the present article.
Figure 2.
1. (a) Theaflavin
Flavogallol: colouring
and (b) thearubigins:
component ofcolouring
Punica granatum
component
. of Camellia sinensis .

flavogallol (Gulrajani, Gupta, Agarwal, & Jain, 1992) as

the colouring component, which also has a polyphenol
structure (Figure 2). Both the above-mentioned colouring Experimental
compounds contain phenolic hydroxyl groups in their Materials
structure and are soluble in water. When such dyes are Plain-weave loom-state cotton fabric with yarns of 15
applied following an exhaust technique, it appears that tex warp and 14 tex weft, having 245 ends/dm and

*Corresponding author. Email: s_r_moulik@yahoo.co.in

ISSN 0040-5000 print/ISSN 1754-2340 online

Copyright © 2011 The Textile Institute
DOI: 10.1080/00405000.2010.491984
http://www.informaworld.com
 492 S. Ray Maulik et al.

Table 1. Effect of variation in dye bath pH on K/S value and colour fastness properties for cotton dyed with Camellia sinensis
and Punica granatum.
Dye Colour fastness
Cotton dyed with bath pH K /S Washing to light Rubbing
Camellia sinensis 4 0.67 3 3 4–5
7 0.43 2–3 2–3 4–5
10 0.29 2–3 2–3 4–5
Punica granatum 4 0.68 2–3 2 4–5
7 0.51 2–3 2 4–5
10 0.24 2–3 2 4–5
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Figure 1. (a) Theaflavin and (b) thearubigins: colouring component of Camellia sinensis.

granatum and Camellia sinensis were further extracted

and purified in a Soxhlet apparatus using methanol as
solvent, filtered and finally recrystallised before they
were used as colourant.

Figure 2. Flavogallol: colouring component of Punica
granatum.
180 picks/dm and an average area density of 50 g/m2,
were used in this study.
Analytical reagent-grade citric acid obtained from
M/s Loba Chemie Pvt. Ltd., Mumbai, India, was used
without any treatment or purification. All other chemi-
cals used in this study were of laboratory reagent grade.
Punica granatum obtained from M/s ALPS Indus-
tries Ltd., India, in the form of powder and commercial-
grade CTC tea (Camellia sinensis) obtained from M/s
Tata Tea, India, were also used in this study. Punica
Methods
Desizing, scouring and bleaching of loom-state
cotton fabric
In order to remove size and other chemicals from the
cotton fabric, the latter was desized, scoured and
bleached prior to dyeing. Desizing of cotton fabric was
performed using a 0.25N hydrochloric acid solution at
the temperature of 50°C for 2 hrs at a fabric-to-liquor
ratio of 1:20 (w/v) in a laboratory winch machine. The
desized cloth was washed thoroughly using hot water,
which was followed by a cold wash prior to a scouring
treatment.
The scouring treatment of the desized cotton cloth
was performed by the pad–steam technique (Das &
Munshi, 2006). Sodium hydroxide was applied by
padding the fabric with 10% sodium hydroxide solution
containing 2% of an anionic detergent in a two-bowl
 The Journal of The Textile Institute
padding mangle and the squeezing pressure for the
padding operation was adjusted to enable a wet pick-up
rate of 100%. The caustic padded fabric was subse-
quently steamed in a laboratory steamer at 100°C for 10
min. After steaming, the cotton fabric was washed thor-
oughly with hot water and again washed with cold
water.
Bleaching of the scoured fabric was performed
using a solution containing hydrogen peroxide (0.1%),
sodium meta-silicate (0.08%) and sodium hydroxide
(0.05%) at a temperature of 80°C for a period of 1 hr in
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the laboratory winch machine. The bleached fabric was
washed thoroughly with hot water, which was followed
by a cold wash, neutralised with dilute acetic acid,
washed again with water and dried in air.
Application of natural dye on cotton
In the absence of inorganic salt (mordant)
Dyeing of the cotton fabric with an aqueous solution of
Punica granatum and Camellia sinensis was done at a
fabric-to-liquor ratio of 1:50. The dye bath temperature
was kept at 90°C for 1 hr. The pH of the dye bath was
adjusted as specified using acetic acid and sodium
carbonate separately. Soaping of all the dyed fabric
samples was done using a 2 g/l non-ionic detergent at a
temperature of 60°C for 10 min. Finally, the fabric
samples were cold-washed and dried.
In the presence of inorganic salt (mordant)
The aqueous solution of Camellia sinensis and Punica
granatum was also selectively applied in the presence
of inorganic salts or mordants such as magnesium
sulphate, aluminium sulphate and ferrous sulphate
following a pre-salt application technique. The salt
concentration for all such applications was kept at 5 g/l
of dye liquor. In the pre-salt application (mordanting)
method, the fabrics were first immersed in an aqueous
solution of inorganic salt for 45 min at 70°C. The
mordanted fabrics were then dyed separately with an
aqueous solution of Camellia sinensis and Punica
granatum at 90°C for 1 hr at a fabric-to-liquor ratio of
1:50. Soaping of all the dyed fabric samples was done
using a 2 g/l non-ionic detergent at 60°C for 10 min.
Finally, the fabric samples were cold-washed and dried.
Simultaneous application of natural dye and citric acid
The aqueous solution of Camellia sinensis and Punica
granatum in the presence of citric acid was applied
under different specified conditions following a pad–
dry–cure technique. For this purpose, the impregnation
of the cotton fabrics in solutions containing natural
493
dyes, citric acid and the specified catalyst was
performed at nearly 100% wet pick-up in a miniature
laboratory model two-bowl padding mangle. The
impregnated fabrics were dried at 95°C for 5 min and
finally cured at a temperature of 140°C for 5 min using
a dry heat method in a laboratory drying and curing
chamber. The concentration of natural dyes for all these
applications was commonly maintained at 20% of the
weight of the fabric. Soaping of all the dyed fabric
samples was done using a 2g/l non-ionic detergent at
60°C for 10 min. Finally, the fabric samples were cold-
washed and dried.
Measurement of K/S
Dye receptivity of the cotton fabrics as estimated in
terms of K/S (Kubelka–Munk function) was deter-
mined. The value is based on measuring the reflectance
of each dyed fabric sample at the respective wavelength
of maximum absorption (λmax) in a Macbeth 2020-plus
reflectance spectrophotometer and converting the
reflectance value (R) to the corresponding K/S value
using the Kubelka–Munk equation (Billmeyer &
Saltzman, 1981), that is, (K/S) = (1 − Rλ)2/2Rλ, where K
is the coefficient of absorption, S is the coefficient of
scattering and Rλ is the reflectance of the dyed substrate
at wavelength λ.
Assessment of colour fastness to washing
Colour fastness to washing of cotton fabrics (modified/
unmodified) dyed with Camellia sinensis and Punica
granatum was assessed in a Launder-O-Meter in
accordance with a method prescribed in IS: 3361-1984
(ISO-II).
Assessment of colour fastness to light
Colour fastness to light of cotton fabrics (modified/
unmodified) dyed with Camellia sinensis and Punica
granatum was assessed on a mercury bulb tungsten
filament (MBTF) light fastness tester following the
method prescribed in IS: 2454-1984.
Assessment of colour fastness to rubbing
Colour fastness to rubbing was determined using a
motorised Crockmeter following the method prescribed
in IS: 766-1984.
Determination of weight gain
For the determination of gain in weight of a known
weight of fabric after modification, the dry weights of
 494 S. Ray Maulik et al.
each sample were recorded before (W2) and after (W1) a
specific treatment and the weight gain data are expressed
as the percentage of initial dry weight. The weight gain
percentage was then calculated on the basis of initial dry
weight of cotton using the following relationship (Das
& Munshi, 2006): weight gain (%) = (W1 − W2) / W2 ×
100. For citric acid treatment, each of the fabric samples
were soap-washed following the method prescribed in
ISO-II and dried to a constant weight at 100°C to record
the weight of the fabric after treatment (W1).
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Tensile properties
Tensile strength of selected unmodified/modified cotton
fabric samples as specified were measured according to
the method (Handbook of Textile Testing, 1981)
prescribed in IS: 1969-1968 in a Zwick/Roell Z010
CRT universal tensile testing machine. The test strip
specimens were ravelled to a size of 50 mm × 20 mm
between the jaws of the machine and the tests were
performed with a traverse speed of 300 mm/min and
with a pre-tension of 2 N.
Determination of fabric stiffness
Fabric stiffness, as expressed by the bending length,
was measured as per IS: 6490-1971 (cantilever test)
Figure 3. Reaction scheme showing the modification of cotton cellulose with citric acid, Camellia sinensis and Punica granatum
under the influence of NaH2PO4 as the esterification catalyst.
in a SASMIRA stiffness tester at a specimen size of
25 mm × 200 mm.
Measurement of wrinkle recovery angle
The wrinkle recovery angle (warp + weft) of the selected
fabric sample was measured using a SASMIRA crease
recovery tester in accordance with IS: 4681-1972.
IR spectroscopy
Infrared (IR) spectra of bleached and selectively modi-
fied cotton samples were obtained following the KBr
pellet technique (Das, Datta, Chavan, & Datta, 2005)
using Perkin–Elmer FT-IR spectrometer, spectrum
RX1. The dried fibre samples were crushed to a size
finer than 20 mesh before pelletising with KBr. About
0.003 g of each of crushed fibre samples was considered
for pelletisation and test KBr pellets contained about 1%
powdered fibre.
Summary and discussions
It would be helpful if we consider, at the outset, the
mechanism of modification of cotton, Camellia sinensis
and Punica granatum dyes with citric acid following
the pad–dry–cure technique under the influence of
NaH2PO4 (sodium di-hydrogen phosphate) used as the
esterification catalyst (Figure 3). The sequence of
 The Journal of The Textile Institute
reactions shown in Figure 3 would be expected to take
place, ultimately leading to notable gain in weight,
colour yield and changes in the chemical nature and
physical properties of cotton during the overall process.
NaH2PO4 is known to be an efficient esterification cata-
lyst, and reactions 1(a) and 1(b), producing citric acid
esters of cotton and dye, respectively, through the pad–
dry–cure technique, would be the direct consequence of
its catalytic action. The said esterification reaction
would also expectedly lead to cross-linking of dye and
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that of cotton, as shown in reactions 1(a) and 1(b).
However, citric acid esters of cotton and dye shown by
the structure I and III in Figure 3 may then react further
with hydroxyl groups of dye and cotton (cellulose),
respectively, leading to subsequent linking of cotton
and dye via an ester bridge formed by the citric acid
moiety, as shown by reaction 1(c), during the drying
and curing step. Moreover, additional reactions leading
to further esterification (due to limited establishment
of ester linkages between the third unreacted carboxylic
[−COOH] group of a citric acid bound to cotton and/or
dye molecules and alcoholic [−OH] groups of the dye
and cellulose) may also take place. When the cotton
fabric would be padded with a solution containing the
dye, citric acid and the esterification catalyst and would
subsequently be dried and cured, all the reactions shown
Figure 4. Infrared (IR) spectra of (a) bleached cotton and of bleached cotton modified with (b) only citric acid, (c) citric acid
and Camellia sinensis, and (d) citric acid and Punica granatum.
495
in Figure 3 and discussed above are likely to take place
simultaneously and successively, leading to a weight
gain for the fibre–fabric system and enhancement in the
colour yield of the cotton substrate.
Figure 3. Reaction scheme showing the modification of cotton cellulose with citric acid, Camellia Sinensis and Punica granatum under the influence of NaH 2PO4 as the esterification catalyst.
IR analysis
The IR spectra of bleached cotton fibre (spectrum – a)
and of the cotton fibre modified with citric acid using
NaH2PO4 as the esterification catalyst in the absence of
any dye (spectrum – b), in the presence of Camellia
sinensis (spectrum – c) and in the presence of Punica
granatum (spectrum – d) are shown in Figure 4. A
broad absorption band over 3500–3000 cm−1, character-
istic of hydrogen-bonded O-H stretching vibration, is
common to all the four spectra. Two notable absorption
bands in the regions of 1565 cm−1 and 1749 cm−1
appearing at different intensities in the spectra (b–d) are
characteristic of carboxylate (anion) stretching and
ester stretching vibration, respectively. In the spectrum
of undyed bleached cotton (cellulose), absorption band
over 1500–2000 cm−1 are practically non-existent.
Citric acid treatment of cotton in the presence of
NaH2PO4 catalyst (spectrum – b) results in the appear-
ance of a new strong absorption band at 1565 cm−1 for
the carboxylate anion and also a new absorption band at
 496 S. Ray Maulik et al.

1749 cm−1 for ester stretching (due to the esterification the application of Camellia sinensis and Punica grana-
reaction between carboxyl groups of citric acid and tum following the pad–dry–cure technique, it appeared
hydroxyl groups of cotton cellulose – Reaction 1a, that with increasing dose level of citric acid, shade
Figure 3). Treatment of cotton with citric acid under the depth (expressed in terms of K/S) and wrinkle recovery
influence of an esterification catalyst and in the pres- of the cotton fabric followed a common increasing
ence of Camellia sinensis (spectrum – c) and Punica trend, with the final leveling off effect in most cases at
granatum (spectrum – d), however, commonly resulted a citric acid application level of 10% of the weight of
in intensification of absorption bands at 1749 cm−1 cotton fabric. It is interesting to note that the weight
corresponding to ester stretching and substantial weak- gain data followed a common increasing trend for appli-
ening of the carboxylate anion band at 1565 cm−1 (due cations of both of the dyes, with an increase in the dose
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to significant disappearance of carboxylic acid groups), level of citric acid in each case, and the values for
indicating overwhelming esterification of carboxyl weight gain in all the cases were observed to be substan-
groups of citric acid accomplished through the pad– tially higher than the respective citric acid application
dry–cure technique, with hydroxyl groups of cotton levels (Tables 2 and 3). Such high weight gains
cellulose and hydroxyl groups of each of Camellia achieved at and above a citric acid application level of
sinensis or Punica granatum dyes during the final 10% is the consequence of improved uptake of both of
stage of drying and curing induced by heat. The results the dyes considered in our study, which is much higher
of the IR analysis are in tune with the mechanism than that achieved when cotton was dyed in the absence
proposed. of citric acid, as is evident from the weight gain and K/
S data of the corresponding dyed cotton fabrics given in
Figure 5.
4. Infraredfabrics
Cotton (IR) spectra
dyed with
of (a)natural
bleached
dyescotton
in theand
presence
of bleached
of different
cottonagents.
modified with (b) only citric acid, (c) citric acid and Camellia sinensis, and (d) citric acid and Punica granatum.

Tables 2 and 3.
Effect of citric acid application level However, a dropping trend in retention of tensile
Cotton fabrics were separately dyed with Camellia strength of the cotton fabric followed with increasing
sinensis and Punica granatum dyes following the pad– dose level of citric acid. This fall in the tensile
dry–cure technique in the presence of varying concen- strength of the cotton fabric is considered to be low
trations of citric acid taken in the padding liquor as and of little practical significance for the application
specified, maintaining a dose ratio of citric acid and of the dyed fabric in the area of apparel, where wrin-
NaH2PO4 catalyst fixed at 1:1.5 (weight/weight) kle resistance property is of importance and is usually
according to a procedure described in the experimental promoted at the cost of even up to 50% of the original
section. Relevant data are shown in Tables 2 and 3. For strength of the cotton fabric (Shank, 2002). The higher

Table 2. Effect of citric acid application level on dye receptivity and mechanical properties of cotton fabric dyed with Camellia
sinensis.
Citric NaH2PO4 Weight K/S at Wrinkle recovery Tensile strength Bending
acid (%) (%) gain (%) (λ = 420 nm) angle (°) retained (%) length (cm)
0 0 4.1 0.83 126 90.50 2.24
5 7.5 12.21 3.91 200 78.24 2.24
10 15 17.93 8.72 223 70.12 2.24
15 22.5 21.30 8.73 226 66.13 2.29
20 30 23.98 8.75 227 61.00 2.32
Note: Citric acid and NaH2PO4 doses given are in weight percent of dry cotton; pad–dry–cure temperature: 140°C.

Table 3. Effect of citric acid application level on dye receptivity and mechanical properties of cotton fabric dyed with Punica
granatum.
Citric NaH2PO4 Weight K/S at Wrinkle recovery Tensile strength Bending
acid (%) (%) gain (%) (λ = 420 nm) angle (°) retained (%) length (cm)
0 0 4.30 0.91 126 91.30 2.24
5 7.5 11.26 3.41 210 76.51 2.24
10 15 17.80 8.11 234 71.32 2.26
15 22.5 20.21 8.13 236 65.28 2.28
20 30 23.83 8.15 237 62.86 2.30
Note: Citric acid and NaH2PO4 doses given are in weight percent of dry cotton; pad–dry–cure temperature: 140°C.
 The Journal of The Textile Institute 497

shade depth and wrinkle recovery angle attained for
the fabric dyed with Camellia sinensis and Punica
granatum dyes in the presence of citric acid than that
dyed with these dyes in the absence of the acid is the
consequence of efficient esterification reactions that
possibly took place between the carboxyl groups of
citric acid and the hydroxyl groups of dye and cotton
cellulose in a manner that ultimately led to the estab-
lishment of linkage between the dye and the fabric via
citric acid.
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Fabric stiffness, expressed in terms of bending length
of the cotton fabric dyed with the above-mentioned
dyes in the presence of citric acid and NaH2PO4 cata-
lyst, remains unaltered, however, for almost all the
dose levels of NaH2PO4. Considering all data for
dyed cotton fabrics in Table 4, including K/S value,
wrinkle recovery, tensile properties and fabric stiff-
ness, it appears that the application of 10% citric acid
with 15% NaH2PO4 as catalyst, each on the basis of
fabric weight, produced optimum or the most

balanced improvements in the properties of the cotton

Effect of variation in NaH2PO4 dose level
Relevant data for 10% citric acid application at
different dose levels of NaH2PO4 are given in
Table 4. For the application of Camellia sinensis and
Punica granatum following the pad–dry–cure tech-
nique, a higher dose of NaH2PO4 as catalyst
commonly produced higher K/S values and wrinkle
recovery angle in view of the consequent higher
degree of esterification. A higher dose of NaH2PO4
evidently caused a higher degree of linking between
the dye and the cotton fibre by esterification via
citric acid moieties in addition to cross-linking of
cellulosic chain molecules of cotton that ultimately
resulted in enhanced K/S value and wrinkle recovery
angle and a falling trend in retention of the tensile
strength for the cotton fabric (Table 4). During the
application of Camellia sinensis and Punica grana-
tum following the pad–dry–cure technique, the pres-
ence of the esterification catalyst at high temperature
(> 90°C) caused carboxyl acid groups of citric acid
to establish ester linkage with the hydroxyl groups of
cotton and dye molecules in a manner that ulti-
mately led to higher colour yield, as is evident from
the K/S value of the respective dyed cotton fabrics.
fabric.
Comparison of properties of cotton fabrics dyed with
Camellia sinensis and Punica granatum in the
presence of inorganic salts and citric acid
Table 5 gives data about the properties of cotton
fabrics dyed with Camellia sinensis and Punica
granatum following the exhaust dyeing technique in
(1) the absence and (2) the presence of inorganic
salts. Table 5 also gives data about the properties of
cotton fabrics dyed with the above-mentioned dyes
following the pad–dry–cure technique in (3) the
absence and (4) the presence of citric acid. It clearly
indicates that dyeing of the cotton fabrics with both
the dyes following the pad–dry–cure technique in the
presence of citric acid produced much overall
improvements in the fabric quality in each case; citric
acid under the catalytic influence of NaH2PO4 specifi-
cally and commonly imparts higher K/S (colour yield)
value and higher wash and light fastness rating, with
appreciably improved wrinkle recovery for the
respective dyed cotton fabrics. However, wrinkle
recovery achieved in such a study (223–234°) using
citric acid is somewhat less than what is usually

Table 4. Effect of variation in NaH2PO4 dose level on dye receptivity and mechanical properties of cotton fabric dyed with
Camellia sinensis and Punica granatum.
Cotton fabric NaH2PO4 Weight K/S at Wrinkle recovery Tensile strength Bending
dyed with (%) gain (%) (λ = 420 nm) angle (°) retained (%) length (cm)
Camellia sinensis 0 4.27 0.88 130 91.30 2.24
5 11.10 3.37 164 82.32 2.24
10 13.26 5.32 189 76.40 2.24
15 17.93 8.72 223 70.12 2.24
20 18.47 8.75 225 64.10 2.26
Punica granatum 0 5.26 0.97 130 92.0 2.24
5 12.62 3.91 168 83.0 2.25
10 13.21 5.36 200 78.43 2.25
15 17.80 8.11 234 71.32 2.26
20 19.0 8.13 234 61.21 2.28
Nil 15 8.36 0.16 252 64.16 2.27
Note: Cure temperature: 140°C; citric acid used: 10% (fixed).
 498 S. Ray Maulik et al.

Table 5. Comparison of properties of cotton fabric dyed with natural dyes in the presence of inorganic salts and citric acid.
Colour fastness
properties
Dyeing technique K/S at Colour appeared Wrinkle recovery
Cotton dyed with followed In the presence of (λ = 420 nm) on substrate angle (°) WF LF RF
Camellia sinensis Exhaust Nil 0.67 Beige 126 3 3 4–5
Ferrous sulphate 2.60 Grey-brown 126 3–4 4 4–5
Aluminium sulphate 1.31 Yellowish-brown 126 3 3–4 4–5
Magnesium sulphate 0.76 Beige 126 3 3 4–5
Pad–dry–cure Nil 0.83 Beige 128 3 3 4–5
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Citric acid and 8.72 Dark brown 223 4–5 5 4–5

NaH2PO4
Punica granatum Exhaust Nil 0.68 Beige 126 2–3 2 4–5
Ferrous sulphate 2.67 Grey-brown 126 3 3–4 4–5
Aluminium sulphate 2.04 Greenish-yellow 126 2–3 3 4–5
Magnesium sulphate 0.69 Beige 126 2–3 2–3 4–5
Pad–dry–cure Nil 0.91 Beige 126 2–3 2–3 4–5
Citric acid and 8.11 Dark brown 234 4 4–5 4–5
NaH2PO4
Notes: WF: wash fastness, LF: light fastness, RF: rubbing fastness.

achieved (261–280°) using DMDHEU as the conven- Conclusion

tional finishing agent (Welch, 1992). From the visual
assessment of perceived colour difference in differ-
ent portions of all the dyed samples, it appears that
the applied colours are uniform. Instrumental assess-
ment of the same gives a ∆E value of ≤ 0.20 for all
the samples.
Citric acid under the influence of an esterification
catalyst introduces ester linkages between the cotton
fabric and the dye molecule under the treatment condi-
tion in consequence to reaction of its carboxyl groups
with hydroxyl groups of the dye and cotton cellulose
under the catalytic action in addition to the establish-
ment of cross-linkages between the polymeric chains
of cotton and that between the dye molecules. Such
cross-linked dye molecules and chemically bound dye
molecules to the cotton fabric offer high resistance to
the action of washing, leading to improvement in fast-
ness to washing of the dyed fabrics. The high level of
light fastness exhibited by the cotton fabric dyed in the
presence of citric acid is explained by the fact that the
diffusion of oxygen and moisture becomes difficult in
the cross-linked structure of the cotton, which nega-
tively affects the initiation of the photofading mecha-
nism (Allen, 1987). Such establishment of ester
linkage of citric acid with cotton and the dye molecule,
leading finally to the (1) cross-linking of cotton cellu-
lose, (2) joining of two dye molecules together and (3)
joining of cotton with the dye molecule by the estab-
lishment of ester bonds, makes all the differences in
the properties of the correspondingly dyed fabrics,
including colour yield, wrinkle recovery and colour
fastness to wash and light.
Application of Camellia sinensis and Punica granatum
as natural dyes on cotton in the presence of citric acid
as the esterifying agent and NaH2PO4 as the esterifying
catalyst following the pad–dry–cure technique was
done. Padding of the cotton fabric with aqueous solu-
tions containing 10% citric acid, 15% NaH2PO4 and
any of the above-mentioned dyes maintaining 100%
wet pick-up, followed by drying of the padded fabric at
95°C for 5 min and curing of the dried fabric at 140°C
for 5 min produced optimum effects in respect of
improvements in the depth of shade, wrinkle recovery,
all-round colour fastness properties (light, wash and
rubbing), retention of tensile strength and flexibility
(bending length). IR analysis and changes attained in
the properties of the dyed cotton fabric indicated that
the treatment of cotton with citric acid under the influ-
ence of an esterification catalyst in the presence of
either Camellia sinensis or Punica granatum led to the
esterification of carboxyl groups of citric acid with
hydroxyl groups of cotton cellulose and also with that
of both the dyes during the pad–dry–cure technique
followed. Substantial improvement in wrinkle recovery
angle effected during applications of the dyes in the
presence of citric acid was however associated with a
loss of some tensile strength (∼30%) of the cotton
fabric.
References
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solution and polymer media. Review of Progress in
Colouration, 17, 61–71.
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