Clean Techn Environ Policy

DOI 10.1007/s10098-017-1425-y

ORIGINAL PAPER

Cationization of cotton for industrial scale salt-free reactive

dyeing of garments
Nallathambi Arivithamani1 • Venkateshwarapuram Rengaswami Giri Dev1

Received: 18 December 2016 / Accepted: 19 September 2017

Ó Springer-Verlag GmbH Germany 2017

Abstract Reactive dyeing of cotton garments involves two Keywords Reactive dyes  Cotton  Salt  Cationization 
stages, namely exhaustion and fixation of dyes. The Exhaust method  Salt-free garment dyeing
exhaustion stage in reactive dyeing requires high quantity
of salt. After dyeing process, the highly saline coloured
effluent is discharged and the treatment of this effluent at Introduction
present is not economically viable and making industries
look for other alternatives for usage of salt. Cationization Cotton fibre is the most widely used textiles for apparel
of cotton is one of the effective alternatives to overcome production in the world due to its excellent physical and
the usage of the salt. The present work focuses on the chemical properties such as dimensional stability, comfort
exhaust method of cationization of garments at an indus- to wear, high moisture absorbency, dyeability and
trial scale using 3-chloro-2-hydroxypropyl trimethylam- biodegradability (Chattopadhyay et al. 2007). To satisfy
monium chloride as a cationic agent. Two commercially the consumers aesthetically, cotton garments have been
popular reactive dyes namely Navy Blue and Green dyes dyed with varieties of colour with good level of fastness
were chosen for dyeing the garments at 10% shade. The properties. In industrial practice, reactive dyes are one of
results of dyeing were evaluated on the basis of colour the most preferred colourant for dyeing cotton garments
strength, dyeing levelness and colour fastness. The uni- due to their brilliancy, wide gamut of colour, ease of
formity of dye on the fabrics was evaluated based on application and high wet fastness properties (Shore 1995).
dyeing levelness and was found to be good for cationized However, reactive dyeing process requires a high amount
cotton dyed garments. The fastness properties of dyed of electrolyte like common salt (NaCl) or Glauber’s salt
fabrics to washing and light were good. The dye utilization (Na2SO4) to reduce electrostatic repulsion which arises due
in the cationized cotton dyed garments was twice as that of to the surface charge on the wet cotton fabric and the
the conventionally dyed cotton garments. The environ- anionic nature of the reactive dye molecules (Chen et al.
mental hazard posed by the highly saline coloured effluent 2015; Farha et al. 2010; Suesat 2008). Even with the
could be easily mitigated by the salt-free reactive dyeing required addition of salt, only 60–65% of dyes are utilized
process. during dyeing remaining 30–35% of dyes along with added
salt are removed as a coloured effluent at the end of the
dyeing process (Allègre et al. 2006; Ma et al. 2015).
Numerous attempts have been made to reduce or elim-
Electronic supplementary material The online version of this inate the usage of salt in the reactive dyeing process. It can
article (doi:10.1007/s10098-017-1425-y) contains supplementary
material, which is available to authorized users. be summarized under these categories namely modification
of dyeing machinery, dye chemistry and cotton substrate.
& Venkateshwarapuram Rengaswami Giri Dev Exhaust dyeing machines which can operate at an ultra low
vrgiridev@yahoo.com
liquor level of 1:1 to 1:5 have led to the reduction in the
1
Department of Textile Technology, Anna University, water consumption and salt consumption in the reactive
Chennai 600 025, India dyeing process to a certain extent. To further reduce the

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 N. Arivithamani, V. R. G. Dev

usage of salt modification of the functionality of dye was Materials and methods
attempted and has not been commercially successful due to
their higher molecular weight, poor dye migration, poor Materials
dye penetrability and poor dyeing levelness and they are
restricted only to lighter shades (Aktek and Millat 2017; 100% Cotton-scoured, bleached and ready for dyeing plain
Taylor 2000). Cationization of cotton substrate is one of weave woven garments with a cover factor of 180 g/m2
effective alternatives to eliminate the usage of salt. Various with ends per inch (EPI) and picks per inch (PPI) of 88 and
cationic agents for modification such as polyamide-based 100 were used for this study. The cationic agent CHPTAC
epichlorohydrin type of polymers, dendritic polymers, used in this study was procured from a local chemical
poly-(4-vinylpyridine) quaternary ammonium compounds, supplier in Tiruppur. Hot brand reactive dyes namely Navy
glycidyltrimethyl ammonium chloride (Glytac), chlorotri- Blue and Green dyes were used for the study, and the
azine type quaternary compounds, choline chloride, dyeing recipe is given in Table 1. Other chemicals such as
N-methylolacrylamide, epichlorohydrin-based quaternary sodium chloride (NaCl), sodium carbonate (Na2CO3),
ammonium compounds (Aktek and Millat 2017; Khatri sodium hydroxide (NaOH) were procured from Fisher
et al. 2015; Lewis and Mcllroy 1997) and biopolymers like Scientific Chemicals Ltd., Chennai, India.
chitosan, starch and their derivatives, keratin hydrolysate
from chicken feather, horn and hoofs have been reported in Cationization of cotton garments
literature (Arivithamani et al. 2014; Lim and Hudson 2004;
Wang and Liu 2014; Zhang et al. 2007). Among them 5 kg ready for dyeing cotton garment was loaded into the
quaternary ammonium-based cationic agent 3-chloro-2- garment dyeing machine at 1:20 material to liquor ratio.
hydroxypropyl trimethylammonium chloride (CHPTAC) is The garment was first subjected to warm wash at 50 °C for
widely used for cationization of cotton fabric as it is eco- removing any residue finishes in the fabric. The cation-
friendly and atoxic in nature (Choudhury 2014; Varadara- ization process was started by the addition of 24 g/L
jan and Venkatachalam 2015; Wang and Lewis 2002). The sodium hydroxide to the wetted fabric at 40 °C. The
cationized cotton fabric can be dyed with reactive dyes machine was operated for 10 min followed by the addition
under neutral or mildly acidic conditions without the of cationic agent (80 g/L CHPTAC) in the same bath, and
addition of salt. But the major limitation in the application the machine was run for 15 min. The temperature of the
of cationic agent to the cotton fabric is that it has to be bath was raised to 80 °C, and it was held for 30 min. Then
applied by a batch process which is a time-consuming one the bath was drained out and the cationized cotton gar-
(Hauser and Tabba 2001). It is difficult to translate at ments were subjected to the after-treatment process such as
industrial scale as most of the industries adopt the exhaust hot wash, neutralization at 70 °C followed by the cold
method of dyeing (Montazer et al. 2007; Wang et al. 2009). wash to remove the physically adsorbed cationic agent in
The objective of the paper is to carry out cationization of the garments. The pH of the cationized garment was
garments by exhaust technique followed by reactive dye- maintained at 6.5, and the dyeing process was started in the
ing. The application of cationic agent by exhaust process same bath.
would make the industries adopt this process without
modification of existing setup. Characterization of cationized cotton garment
In this study, cationization of cotton garments was car-
ried out by exhaust method with a conventional garment FTIR was used to assess the presence of functional groups
dyeing machine using CHPTAC as a cationic agent. The of the cationic agent on the cotton garment after the
cationization process parameters were optimized to achieve cationization process. The measurements were taken using
the higher degree and uniform level of cationization in the a Nicolet-460 FTIR machine under standard operating
cotton garments. The produced cationized cotton garments conditions. The samples were loaded in the pellet form, and
were dyed with Navy Blue and Green dye for a darker the pellets were made by mixing fibrous tuft with the
shade of 10% without the addition of salt. The colour potassium bromide (KBr).
strength of the produced cationized cotton dyed garment X-ray diffraction (XRD) patterns of normal and
was compared with that of the conventionally dyed cotton cationized cotton were measured using X-ray powder
garments. The results obtained are discussed in the fol- diffractometer system by monitoring the diffraction angle
lowing sections. from 10° to 70° (2h) using monochromatized Cu Ka

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Cationization of cotton for industrial scale salt-free reactive dyeing of garments

Table 1 Dyeing recipe and its

Dyeing specifications Navy blue Green
specifications
Shade (%) 10% 10%
Dye combination Navy blue GDB—7.5% Navy blue GDB—6.5%
Blue GDN—2% Yellow GDB—2.5%
Red GDB—0.5% Turquoise blue GDB—1%
NaCl (g/L) 40 60
Na2CO3 (g/L) 20 30
Dyeing method Temperature raise method

(k = 1.54051 Å) radiation. The crystalline index (CI) of Evaluation of colour strength and dyeing levelness
each sample was calculated by following Eq. (1), accord-
ing to methods described by Segal et al. (1959). The colour strength of the dyed garment was expressed as
I200  Iam K/S value which is obtained from the Kubelka–Munk
CIð%Þ ¼  100 ð1Þ Eq. (2). The colour strength was measured at the minimum
I200
reflectance of the dyed fabric using a UV–Visible spec-
where I200 is the maximum intensity of the (200) lattice trophotometer, and the value for Navy Blue dye was
diffraction peak, and Iam is the intensity scattered by the 580 nm and for Green dye was 680 nm. The other dyeing
amorphous fraction of the sample. parameters such as relative colour strength (RCS) per-
The effect of cationization treatment on morphological centage, colour co-ordination values CIE Lab values (L*,
characteristics of the cotton fabrics was studied with a a* and b*), hue angle (h°) and chroma values (C*) were
high-resolution FESEM analyser. The samples were sputter measured using a following Eqs. (3)–(8).
coated with a thin layer of gold for better electric con-
ductivity. The FESEM was taken with a working distance ð1  RÞ2
Colour strengthðK=SÞ ¼ ð2Þ
of 9 mm with a magnification of 2.5 kX at an acceleration 2R
voltage of 20 kV. Relative colour strengthð%Þ
K=S value of cationized cotton dyed fabric
Dyeing of cotton garments ¼  100
K=S value of conventional dyed cotton fabric
ð3Þ
The modified cotton garments were dyed separately as per
dye recipe mentioned in Table 1 for Navy Blue—10% L ¼ 116 ðY=Y0 Þ1=3  16 ð4Þ
shade and Green—10% shade in exhaust garment dyeing h i
machine with the liquor ratio of 1:20. The cationized cotton a ¼ 500 ðX=X0 Þ1=3 ðY=Y0 Þ1=3 ð5Þ
garments were run with the respective dye solution at h i
60 °C for 20 min without the addition of salt; then the b ¼ 200 ðY=Y0 Þ1=3  ðZ=Z0 Þ1=3 ð6Þ
recommended amount of alkali (Na2CO3) was added into qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
the bath. The dyeing temperature was gradually raised to Chroma ðC Þ ¼ ða Þ2 þðb Þ2 ð7Þ
80 °C for fixation of reactive dyes into the cationized  
cotton fabric and run for 40 min. At the end of the dyeing o 1 b
Hue ðh Þ ¼ tan ð8Þ
process, the garments were subjected to the after-treatment a
process to remove unfixed dyes from the garments by where L*—lighter/darker; a*—redder/greener; and b*—
carrying out cold wash, neutralization, hot wash and yellower/bluer tone of the fabric. The hue angle (h°)
soaping process. After dyeing process, the garments were denotes tone of the colour, and chroma (C*) values denote
introduced into a solution containing 0.5 g/L of silica for the saturation of colour in terms of dullness to brightness.
finishing at room temperature for 10 min and then the The levelness of the dyed garments was measured using
garments were subjected to hydro-extraction and tumble relative unlevelness index (RUI) for which the colour of
dried at 60 °C for 20 min. Similarly the cotton garments the garment was measured at eight different places and the
were dyed using conventional method of dyeing with the RUI value was measured using Eqs. (9) and (10). The
recommended addition of salt and alkali. lower value indicates the better levelness in the dyed
garments.

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 N. Arivithamani, V. R. G. Dev

Fig. 1 Cationization process

cycle for cotton material

X
700 ‘‘etherification reaction’’ to produce cationized cotton
RUI ¼  k
ðSk =RÞV ð9Þ garment. The cationized cotton garments strongly attract
k¼400 the anionic reactive dyes without the addition of salt.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Pn ffi
2 The reaction of cationic agent with cotton garment was
i¼1 ðRi  RÞ carried out in situ by the reaction of quaternary ammonium
Sk ¼ ð10Þ
ð n  1Þ compound with alkali at 80 °C for 70 min. Based on the
where Sk—Standard deviation of reflectance values mea- previous trials (Arivithamani and Dev 2016, 2017a, b), the
sured at specific wavelengths, n—number of spots mea- optimized conditions for achieving a higher degree of
sured at each wavelength, Ri—reflectance value of the ith cationization in the cotton garments by exhaust method
measurement for each wavelength, R—mean  of the were fixed as 1:2 molar ratio of cationic agent to alkali. The
reflectance value of n measurements for each wavelength, process cycle for cationization of cotton is given in Fig. 1.
Vk—photopic relative luminous efficiency function. The
visual appearance of levelness and the grading of RUI Characterization of cationized cotton
values for dyed fabrics were calculated as per the standard
(Chong 1992). FTIR study of the cationized cotton garment

Assessment of fastness properties The IR spectrum of the cotton garment and cationized
cotton garment is presented in Fig. 2. The cotton garment
All the dyed cotton garments were tested for fastness showed a characteristic cellulosic peak at 945–1200 cm-1,
properties such as washing, rubbing and perspiration strong absorption peak for –OH stretching at
according to ISO 105-C06-C2S, ISO 105 X 12 and ISO 105 3100–3686 cm-1, C–H stretching at 2771–3000 cm-1, C–
EO4 standards. The colour change was rated according to H rocking vibration at 1386 cm-1 and C–O stretching
the appropriate grey scale value. Colour fastness to light vibration at 1120 cm-1 (Khalil-Abad et al. 2009). Com-
was tested according to ISO 105 B02, and the degree of pared with cotton garment, cationized cotton garment
fading was assessed by the Society of Dyers and Colourist showed narrow hydrogen bonded O–H stretching peak at
blue wool scales. 3100–3686 cm-1 and aliphatic C–H stretching at
2917 cm-1, C–N stretching vibration at 1200 cm-1 (Zhang
et al. 2015). A sharp peak at 1494–1510 cm-1 corresponds
Result and discussion to the presence of quaternary ammonium (3R–N?–) groups
(Zhang et al. 2007). The peaks confirm the fixation of the
The cationization process was carried out in two steps; in CHPTAC on the cotton garments.
the first step, the cationic agent CHPTAC was converted
into 2,3-epoxypropyl trimethylammonium chloride X-ray diffraction analysis for cotton and cationized cotton
(EPTAC) in an alkaline medium. In the second step, the fabric
formed EPTAC was ring-opened in an alkaline medium to
react with the primary hydroxyl group of the cotton by X-ray diffraction analysis was carried out to study the
effect of cationization on crystal structural changes. From

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Cationization of cotton for industrial scale salt-free reactive dyeing of garments

Fig. 2 FTIR spectrum of cotton

and cationized cotton

the results shown in Fig. 3, it can be seen that typical cationized cotton garments. The fibres in the cotton gar-
diffraction peaks of cotton existed at 2h of 14.8°, 16.4°, ment have convoluted morphology, which is the charac-
22.9°, and 33.8° for both cotton and cationized cotton teristic feature of cellulosic materials. The fibres in the
fabric (Fig. 3). It corresponds typically to cellulose I cationized cotton garments show rounded rod-like mor-
crystalline form (Klemm et al. 2005). The crystallinity of phology due to the addition of alkali during cationization
cotton was found to be 66%, whereas for cationized cotton process. This confirms the fixation of CHPTAC on the
fabric it was slightly reduced to 63%. The XRD spectra cotton garments. The EDX result shows the presence of
result reveals that the cationization process has not altered carbon and oxygen content in the cotton garment; on the
the crystallinity and crystal form in cotton. other hand the cationized cotton garment showed nitrogen
content in addition to the carbon and oxygen content,
Surface morphology analysis of the cationized cotton thereby confirming fixation of CHPTAC in the cationized
garment cotton garment (Fig. 5).

Figures 4 and 5 give the FESEM images and EDX (En- Dyeing of cotton and cationized cotton garment
ergy-Dispersive analysis of X-rays) results for cotton and
All the garments (cotton and cationized cotton) were dyed
based upon the temperature raise method suggested by the
dye manufacturer, and the dyeing cycle for conventional
and salt-free dyeing process is given in Fig. 6. The process
cycle was divided into three sections, namely cationization,
dyeing and after-treatment process, while comparing the
conventional and salt-free dyeing process, the salt-free
dyeing process should have taken a long time since this
process contains additional cationization process. But
Fig. 6 shows that conventional dyeing process takes
517 min (8 h, 37 min) and on the other hand salt-free
dyeing process takes 502 min (8 h, 22 min) to complete
the process. It can be inferred from Fig. 6 that both the
conventional and salt-free dyeing consumes almost equal
processing time, even though the salt-free dyeing process
consists of additional cationization process. The reason
behind is that the salt-free dyeing process eliminates the
salt dosage time of 20 min, salt migration time of 20 min
Fig. 3 XRD spectra for cotton and cationized cotton fabric

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 N. Arivithamani, V. R. G. Dev

Fig. 4 FESEM images of a cotton and b cationized cotton

and also the number of washing cycles is decreased. This is garments and it suggests that the tone of the fabric is not
due to better dye utilization in the case of cationized cotton altered due to the cationization treatment. Table 2 gives the
dyed garment during salt-free dyeing process. colour strength and dyeing levelness (RUI) values of the
cationized cotton dyed garment with two different reactive
Evaluation of dyeing parameters and levelness dyes. The cationized cotton dyed with Navy Blue showed
colour strength of 24.26 which is almost twice the colour
The cationized cotton garments were dyed without the strength of the conventionally dyed cotton garment which
addition of salt, and cotton garments were dyed with the had the colour strength of 10.31. Similarly for Green dye,
recommended dosage of salt (Navy Blue—40 g/L and cationized cotton dyed garments showed five times higher
Green—60 g/L of NaCl) and the dyeing mechanism is colour strength (25.46) than the conventionally dyed cotton
given in Figs. 7 and 8. The reflectance curves for all dyed garment with the colour strength (5.06). The colour coor-
garments are given in Fig. 9. From the figure, it can be seen dinate values (L*, a*, b*, h°) for both the dyes were
that the cationized cotton dyed garments have lower assessed in which the cationized cotton dyed garments
reflectance values than the conventionally dyed cotton showed decreased lightness values (L* = 16.3 for Navy
garments. It reveals that the colour strength of the cation- Blue and 19.4 for Green) compared to the conventionally
ized cotton dyed garments is higher than the conventional dyed cotton garments (L* = 28.9 for Navy Blue and 44.3
dyed cotton garments. At the same time, the curves follow for Green). It reveals that the cationized cotton dyed gar-
a similar trend to that of the conventionally dyed cotton ments have a higher depth of shade compared to the

Fig. 5 EDX images of a cotton and b cationized cotton

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Cationization of cotton for industrial scale salt-free reactive dyeing of garments

Fig. 6 Comparison of dyeing cycles for conventional and salt-free dyeing process

conventionally dyed cotton garment. The a* and b* values cationic sites which attract the oppositely charged anionic
did not significantly altered for Navy Blue and Green dyed reactive dyes in the exhaust dyeing process. This would
garments, and it suggests that the tone of the fabric is not greatly increase the concentration of reactive dyes inside
altered. the cationized cotton garment which in turn enhances dye-
The dyeing mechanism of reactive dye in a cationized fibre fixation in the cationized cotton garment during the
cotton garment is illustrated in Fig. 8. It was found that subsequent addition of alkali (Na2CO3) in the dyeing pro-
most of the reactive dyes were easily absorbed and diffused cess. The cationic sites of the cationized cotton garment
into the cationized cotton garment due to the presence of could also temporarily restrict the movement of dye anions

Fig. 7 Dyeing mechanism of reactive dye on cotton Fig. 8 Dyeing mechanism of reactive dye on cationized cotton

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 N. Arivithamani, V. R. G. Dev

20
30
18
25
Cotton with Navy Blue
15
Cationized cotton with Navyl Blue
Reflectance (%)

Reflectanc e(%)
20 13

10
15

8 Cotton with Green

10
5 Cationized cotton with Green

5
3

0 0
400420440460480500520540560580600620630660680700
400
420
440
460
480
500
520
540
560
580
600
620
630
660
680
700
Wavelength (nm) Wavelength (nm)

Fig. 9 Reflectance curve for cotton and cationized cotton dyed garments

Table 2 Colour parameters for cotton and cationized cotton dyed garments
Dyes, shade (%) Samples K/S RCS (%) L* a* b* h° C* RUI values

Navy blue—10% Cotton (with salt) 10.3 100 28.9 3.5 - 14.1 76.0 14.5 0.35 (good levelness)
Cationized cotton (salt-free) 24.3 235 16.3 3.5 - 6.6 61.7 7.5 0.39 (good levelness)
Green—10% Cotton (with salt) 5.1 100 44.3 - 17.3 11.4 33.4 20.7 0.33 (good levelness)
Cationized cotton (salt-free) 25.5 503 19.4 - 8.5 3.9 24.7 9.4 0.19 (excellent levelness)

Fig. 10 Images of a conventional and b cationized cotton dyed garments

resulting in the decreased hydrolysis of reactive dyes and is given in Table 2. Cationized cotton dyed garments with
increased utilization of reactive dyes by the cationized Green dye showed the excellent levelness value, whereas
cotton garments. This ensures the dyeing levelness of the all other garments showed good levelness value.
cationized cotton. The dyeing levelness of the dyed gar- Thus, the dyeability of cationized cotton dyed garments
ments expressed in terms of the relative unlevelness index with the two different reactive dyes (Navy Blue—10% and

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Cationization of cotton for industrial scale salt-free reactive dyeing of garments

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Acknowledgements The authors would like to express sincere derivative to cotton fabric as a zero-salt dyeing auxiliary. Color
gratitude to Mr. G. Ramesh Kanna, Managing director Motherland Technol 120:108–113. doi:10.1111/j.1478-4408.2004.tb00215.x
Garments Pvt. Ltd., SIDCO Industrial Estate, Chennai, India, for Ma W, Wang T, Li H, Zhang S (2015) Cotton fabric modification
permitting us to carry out this study in his industry and special thanks through ceric (IV) ion-initiated graft copolymerisation of
to University Grants Commission (UGC) for financial support (Grant 2-methacryloyloxyethyltrimethyl ammonium chloride to
number F1-17.1/2012-13/RGNF-2012-13-SC-TAM-31034). enhance the fixation of reactive dyes. Cellulose 22:4035–4047.
doi:10.1007/s10570-015-0713-0
Montazer M, Malek RMA, Rahimi A (2007) Salt free reactive dyeing
of cationized cotton. Fibers Polym 8:608–612. doi:10.1007/
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