Journal of Cleaner Production 251 (2020) 119728

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Sustainable indigo dyeing and improvement of rubbing fastness of

dyed cotton fiber using different fixing agents for obtaining eco-
friendly cowboy products
Yuni Luo b, Liujun Pei a, b, *, Jiping Wang a, b, **
a
School of Fashion Engineering, Shanghai University of Engineering Science, No.333 Longteng Road, Songjiang District, Shanghai, 201620, PR China
b
Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Zhejiang Sci-Tech University, Hangzhou, Zhejiang, 310018, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Indigo dyeing for cotton fibers can achieve ideal color depth in silicone non-aqueous medium dyeing
Received 14 September 2019 system and solve some environmental pollution problems which were caused by the traditional water
Received in revised form bath dyeing. However, the rubbing fastness of indigo-dyed cotton fiber is poor, which will influence the
12 November 2019
spinning process. In this investigation, three fixing agents commonly used in the market were screened
Accepted 13 December 2019
Available online 17 December 2019
to treat the indigo-dyed cotton fibers and their working mechanism was also studied. The results of GPC
and FTIR showed that all the three fixing agents were polyurethanes which have a similar narrow
Handling editor: Jian Zuo molecular weight distribution and they could combine with indigo-dyed cotton fiber with intermolecular
forces (hydrogen bonds) and ionic bonds with indigo-dyed cotton fiber. Compared with these fixing
Keywords: agents, fixing agent J has a better effect on reducing the friction coefficient of fiber because cotton fiber
Eco-friendly was the smoothest after fixing. After adding some cationic surfactant during fixing, the effect of fixation
Indigo was influenced because there was a competition relation between the fixing agent and surfactant. From
Silicon non-aqueous medium the spinning process, the rubbing fastness of fiber treated with fixing agent can meet the spinning re-
Rubbing fastness
quirements. 100 kg/d industrial application provides compelling proof of indigo dyeing in non-aqueous
Surface charge
medium dyeing system, because this dyeing technology can change the complex process of traditional
indigo dyeing, the monotonous style, and the serious waste water pollution for cowboy wear production.
© 2019 Published by Elsevier Ltd.

1. Introduction wastewater discharge is outstanding in the indigo dyeing industry

Clothing made from cellulosic fabrics such as cotton and in
particular indigo dyed denim fabrics have been common items of
clothing for many years (Haaf et al., 2018). The dark blue dyes are
still extensively employed for dyeing cotton yarn in the manufac-
ture of textiles. In view of the widespread of indigo dyeing for
dyeing textiles, some attempts are constantly being made to
improve existing dyeing processes and conserve dye and time as
well as optimize color yield and shade control. (Saikhao et al., 2011,
2018). However, the problem of dyeing-water consumption and
* Corresponding author. School of Fashion Engineering, Shanghai University of
Engineering Science, No.333 Longteng Road, Songjiang District, Shanghai, 201620,
PR China. Tel./fax: þ86 021 67791454.
** Corresponding author. Schhool of Fashion Engineering, Shanghai University of
Engineering Science, No.333 Longteng Road, Songjiang District, Shanghai, 201620,
PR China.
E-mail addresses: liujunpei2017@zstu.edu.cn, peilj@sues.edu.cn (L. Pei).
(Venkatraman and Liauw, 2019). In order to reduce pollution
emissions and reaction by-products, non-aqueous media dyeing
technology such as organic solvent dyeing (Chen et al., 2016; Tang
et al., 2017; Thi et al., 2017) and CO2 supercritical fluid dyeing (Abou
Elmaaty and Abd El-Aziz, 2018; Fan et al., 2017; Liu et al., 2019b)
had been developed to solve these problems, which is in line with
the concept of green development.
Solvent dyeing is the substitution of organic liquid for water in
the process of application and fixation of dyes on fiber. In organic
solvent dyeing system, the dye can dissolve in organic liquid, and
the reuse of dyeing media is difficult after dyeing. Furthermore, this
dyeing technology is often carried out by using hydrocarbon sol-
vents as continuous phase media such as hexane, cyclohexane and
n-heptane which are not environment-friendly (Fan et al., 2017).
CO2 supercritical fluid dyeing technology is generally operated at
temperature up to 140
C under considerable pressure
(250e300 bar). However, indigo reduced solution is nearly insol-
uble in CO2 supercritical fluid whereas disperse dye exhibits a

https://doi.org/10.1016/j.jclepro.2019.119728
0959-6526/© 2019 Published by Elsevier Ltd.
2 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728
measureable solubility (Dos Santos et al., 2018).
For the indigo dyeing, it is well known that the dyed cotton yarn
or fabric has excellent light fastness and rubbing fastness which is
dyed with indigo under a multiple pad dyeing in the traditional
water bath (Park et al., 2013). However, cotton fiber cannot dye
with indigo in traditional water bath because such multiple
padding processes have a serious effect on the fiber entanglement,
which will influence the spinning. In our previous investigations (Li
et al., 2016; Pei et al., 2017a, 2017b), non-aqueous medium dyeing
technology for dyeing cotton fiber with indigo had been success-
fully prepared by taking siloxane non-aqueous medium as a
continuous phase. After dyeing, the silicon non-aqueous medium
will remain on the fiber, which was recycled with pressure drying
machine. On the other hand, there is a small amount of dyeing
effluent after dyeing. As the surface tension of non-aqueous silicon
medium (19.52 dyn/cm) is very low and its density is lower than
water, silicon non-aqueous medium and dyeing effluent can be
naturally separated after 2e3 h. However, the condition of indigo
dyeing for cotton fiber is about a high concentration of reducing
solution and a little of water in the silicon non-aqueous dyeing
system, which is different from the traditional water bath. These
high concentration leuco may be easily to aggregate and oxidize in
the form of indigo aggregates on the fiber surface, which may result
the fiber surface become more rough than the cotton fiber dyed in
the traditional water bath (Li et al., 2016; Surita and Tansel, 2014;
Hossain et al., 2017) and lead a poor rubbing fastness of dyed fiber.
In this work, the silicone non-aqueous/indigo dyeing system
was successfully prepared with a small amount of aqueous solution,
together with a small amount of alkaline agent and sodium
hydrosulfite. The indigo dyeing performance and rubbing fastness
of dyed cotton fiber were analyzed in silicone non-aqueous dyeing
system. The influence of fixing agent on the rubbing fastness of
dyed cotton fiber under different conditions was studied. The
mechanism between the fixing agent and dyed cotton fiber was
systematically studied. Moreover, scale-up test of indigo dyeing in
the silicone non-aqueous dyeing system was amplified to 25kg/
cylinder in our cooperative enterprise to achieve different styles
indigo yarn and denim materials.
2. Experimental
2.1. Materials
Cotton fiber: A combed velveteen cotton fiber (linear density:
1.8d, length: 28.5 mm, Micronaire: A) was used for the indigo
dyeing which was collected from Shaoxing Furun Dyeing and Fin-
ishing Co., Ltd. Cotton fabric: A 100% cotton woven fabric (127.2 g/
m2, yarn count: 40 S  40 S, yarn density: 146  287) was collected
from Shaoxing Furun Dyeing and Finishing Co., Ltd. Indigo dye,
weak acid flavine G and xylidine ponceau 2R (granular, industrial
grade) were purchased from Changzhou Lantu Chemical Co., Ltd.
The molecular structures of dyes are shown in Fig. 1. Sodium
dithionite (Na2S2O4), sodium hydroxide (NaOH), tetrahydrofuran,
potassium chloride (KCl) and acetic acid, all with purity above
99.7%, were purchased from Hangzhou Gaojing Chemical Reagent
Co., Ltd. Siloxane non-aqueous media (purity>98%) was purchased
from GE Toshiba Silicone Ltd. High concentration acid fixing agent
HF(Fixing agent H) and wet fastness fixing agent JYE961 (fixing
agent J) was purchased from Guangzhou Asahi Chemical Co., Ltd.
Dry and wet rubbing fastness fixing agent TS-HT (Fixing agent T)
was purchased from Qingyuan Junyu Chemical Co., Ltd. Octadecyl
trimethyl ammonium chloride (OTAC), Dodecyl dimethylamine
oxide (OB-2) and Lauroamide propyl betaine (CAPB) were pur-
chased from Shanghai Winsono New Material Technology Co., Ltd.
2.2. Dyeing method in silicone non-aqueous medium dyeing system
Preparing for indigo reduction: 6% the weight amount of fiber
(owf), indigo, 8% (owf) NaOH and 19% (owf) Na2S2O4 were mixed
using silicone media for liquid seal to isolate air at 60
C for 20 min.
Dyeing method: 1 g cotton fiber with 1 g water and dyed with
1 g indigo reduction in the silicone non-aqueous medium at a liquor
ratio of 20:1. The dyeing process was carried out on DYE-24 dyeing
machine (ShangHai Chain-Li Automation Equipment Co., Ltd). The
dyeing temperature was started at 15
C and raised to 70
C at 2
C
min1 keeping warm for 60min. After dyeing, the cotton fiber were
oxidized in the air for 12 h, then using 5% (owf) acetic acid to wash
cotton fiber at liquor ratio of 30:1 at 25
C for 5 min.
2.3. Fixing method
The fixing process for dyed cotton fiber was carried out at 45
C
for 30min with 3% (owf), fixing agent. Then the pretreated cotton
fiber were pre-dried at 80
C for 5 min and baked at 120
C for
3 min.
2.4. Dyeing method with acid dye
The cotton fabric were pretreated by fixing agent in the con-
centration of 0, 1, 5, 10 and 20 g/L as same as the fixing method.
Dyeing method was shown in Fig. 2, it was started at 15
C and
then raised to 60
C at 4
C min1 keeping warm for 30min. 1 g
cotton fabric with 5% (owf) acid dye in water bath at a liquor ratio of
50:1. The pH of acid dye solution was adjusted during dyeing (the
pH value of weak acid flavine G was about 3, the pH value of xyli-
dine ponceau 2R was about 6). After dyeing, the dyed cotton fabric
was washed at the liquid ratio of 30:1 at 25
C and dried at 80
C for
2 h.
2.5. Analysis and characterization
2.5.1. Measurement of color yield
K/S value of the fabric and fiber were analyzed by a Datacolor SF-
650 plus color testing in 10
from the observer with D65 illuminant.
Every sample was measured in three different places, and the color
data was the average value of the three different places (Liu et al.,
2019b).
2.5.2. Rubbing fastness testing
According to the standard of LVS EN ISO 105-X12,25 (Dos Santos
et al., 2018), the rubbing fastness of cotton fabric or fiber was
evaluated by a white fabric (100 mm  40 mm) against the dyed
cotton fiber under wet and dry condition using Crocmeter 238 A of
SDLA (Shirley Development Laboratories Atlas Inc., USA). After
rubbing, the b* value of white fabric was measured with Datacolor
SF600X at the maximum absorption wavelength. The rubbing
fastness of sample was represented by the b* value of white fabric,
because that the higher of the b* value, the worse is the rubbing
fastness of cotton fiber.
2.5.3. FTIR analysis
FTIR spectra of the samples were examined by KBr pellet
(Fourier Transform Infrared Spectrometer Nicolet 5700, USA) at a
wave number range of 400e4000 cm1 with 64 scans and a 4 cm1
resolution (Liu et al., 2019a).
2.5.4. GPC analysis
The molecular weight of fixing agent was determined by a GPC
instrument (Brookhaven, USA) at a 40
C column temperature, and
the flowing velocity was 1 ml/min. The fixing agent emulsion
 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728
Fig. 1. The molecular structures of dyes: (a) Indigo; (b) Weak acid flavine G; (c) Xylidine ponceau 2R
concentration was 0.1 mg/ml with the flow phase THF. The mea-
surement can test the molecular weight of the polymer ranges from
1000 to 200000 g/mol1.
2.5.5. Surface zeta potential of fiber analysis
After fixation, the surface charge of cotton fiber was measured
using a solid surface zeta potentiometer (SurPASS, Anton Paar,
Austria). The electrolyte solution was potassium chloride (KCl) with
a concentration of 0.001 mol L1 (Aboltakhty et al., 2018; Correia
et al., 2012). The pH value of the test was 7.28 which was same as
the pH of fixation process. The streaming current mode was used
during testing.
3. Results and discussion
3.1. GPC analysis
According to the result of GPC analysis, the molecular weight of
three fixing agents is shown in Fig. 3. The weight average molecular
weight and number average molecular weight of fixing agent J are
6176 and 7154, respectively, which are larger than that of other
fixing agents (H: Mn ¼ 5204, Mw ¼ 5949; T: Mn ¼ 5198,
Mw ¼ 5837). And it was found that the polydispersity of fixing
agent J is 1.14 (Fig. 3d), which is very close to the polydispersity of
fixing agent H (1.15) and fixing agent T (1.12), indicating that all of
the three fixing agents have the narrow distribution of molecular
weight.
3.2. Infrared spectroscopic analysis
To characterize the presence or absence of characteristic ab-
sorption peaks in the fixing agents, the structures of three fixing
agents were investigated with FTIR spectra analysis which was
Fig. 2. Dyeing method with acid dye.
3
confirmed in Fig. 4a. The tensile vibration peaks at 3330 cm1 and
1716 cm1 are the stretching vibration of the free NeH and the
stretching vibration of eNH on the amide bond, respectively (Zhu
et al., 2016). Obviously, the characteristic absorption peak of
stretching vibration and deformation of eNH on the amide bond
was at 1540 cm1. The peaks at 3449 cm1 and 2875 cm1 can be
identified as the stretching vibration peak of eOH and character-
istic absorption peak of symmetric stretching vibration of eCH2-,
respectively. Moreover, the C¼O stretching vibration of the amide
in the fixing agent H shifts to an absorption peak at 1671 cm1, but
the fixing agent J and the fixing agent T have a characteristic ab-
sorption peak at 1725 cm1 (Xu et al., 2014). In addition, the
characteristic absorption peak at 941 cm1 is contributed to the
characteristic of benzene. Furthermore, the bending vibration peak
of CH2 connected with quaternary ammonium cationic was found
at 1236 cm1. The characteristic absorption peaks of CeOeC and
eOH at 1108 cm1 stretching vibrations indicating the polyether
was existed in these fixing agents. So these results of FTIR analysis
indicated that all of three fixing agents were polyurethane (Fu et al.,
2008; Khattab et al., 2018; Zhao et al., 2019).
As shown in Fig. 4b, compared with the infrared spectra of
control cotton fiber, the characteristic absorption peak which were
appeared at 1540 cm1 could be identified to the tensile vibration
and deformation of eNH on amide bond after fixing, indicating that
the dyed cotton fiber had been treated with the fixing agents. There
are no other characteristic peaks in Fig. 4b, indicating that the fixing
agent and the dyed fiber were mainly combined by intermolecular
forces (hydrogen bonds).
3.3. Influence of the fixing agents concentration on the rubbing
fastness of dyed fiber
The effect of fixing agent concentration on the rubbing fastness
4 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728

Fig. 3. GPC analysis of three fixing agents (a) H; (b) J; (c) T; (d) Polymer dispersity index.

of dyed fiber was shown in Fig. 5. As can be seen, with the increase
of fixing agent concentration, the b* value of the white fabric
increased from 4.67 to 0.14 (fixing agent H), 1.18(fixing agent J)
and 0.74 (fixing agent T), respectively, indicating that the rubbing
fastness of dyed fiber was improved. Obviously, the effect of fixing
agent J was better than the other fixing agents.
As shown in Fig. 6, the coefficient of static friction increased
from 0.0163 to 0.0179 by comparing the control cotton fiber and the
dyed cotton fiber (Correia et al., 2012; Teidelt et al., 2012), indi-
cating that the presence of dye particles on the surface of indigo-
dyed cotton fiber lead the surface of the fiber more rougher. The
static friction coefficient of cotton fiber was decreased and the
surface of the fiber became smooth after treating with the fixing
agents. However, with the increase of fixing agent concentration,
the surface of cotton fiber became rough. For example, when the
concentration of fixing agent H was increased from 1 g/L to 20 g/L,
the friction coefficient of dyed fiber was increased from 0.0191 to Fig. 5. The rubbing fastness of dyed fiber under different concentration of fixing
0.0217. Obviously, according to the static friction of the fiber in agents.

Fig. 4. FTIR analysis: (a) fixing agents; (b) indigo dyed cotton fiber after fixation.
 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728
Fig. 6. Coefficient of friction about cotton fiber after treated with different concentration fixing agents: (a) 1 g/L; (b) 20 g/L.
Fig. 6, the cotton fiber treated with fixing agent J was the smoothest
than cotton fibers treated with other fixing agents.
3.4. Effect of fixing agent ionicity on the rubbing fastness of dyed
fiber
In order to investigate the effect of ionicity on the bonding force
between fixing agent and fiber, cotton fiber were treated with three
different surfactants. Brief analysis, the more content of surfactant,
the better was the rubbing fastness of fiber (Fig. 7a). Compared with
these three different surfactants, the effect of OTAC on fiber rubbing
fastness was the best. It could be noted from Fig. 7b that the
combination of the surfactant and the fixing agent would influence
the fixing effect of fixing agent. For example, the b* value of white
fabric was 2.96 when the fixing agent T was used alone, but it was
decreased to 3.80 when OTAC surfactant was added in the solu-
tion of fixating agent T. Therefore, the cationic surfactant would
influence the effect of fixing agent, because there was a competition
relation between the fixing agent and surfactant.
3.5. Zeta potential analysis
As shown in Fig. 8a, the zeta potential of cotton fiber was
changed from 25.73 mV to 6.78 mV, 16.51 mV and 14.22 mV
after treating with OTAC, OB-2 and CAPB, respectively. It means that
the surface charge of cotton fiber was increased by the cationic
surfactants (Luxbacher et al., 2014; Lei et al., 2012), which may
result a better rubbing fastness of dyed fiber. As shown in Fig. 8b
and c, the surface charge of fiber was changed from 20.73 mV
to 16.56 mV, 21.30 mV to 13.27 mV, 22.40 mV to 18.91 mV
when the dyed cotton fiber was treated only by three fixing agents
(Fig. 8b) or treated by the combination of fixing agent and surfac-
tant (Fig. 8c), respectively. From these results, it concluded that the
OTAC had a better effect on the fixing agent T.
As shown in Fig. 9, when a positive charged surfactant and a
fixing agent were simultaneously added to the water bath, the
Fig. 7. The b* value of white fabric: (a) treated by surfactant; (b) treated by surfactant and fixing agent.
5
surfactant and the fixing agent would compete to attract with the
negatively charged on cotton fiber (Shi et al., 2011; Sharif et al.,
2007). Therefore, this would weaken the fixing effect of fixing
agent. The results of the surface zeta potential indicated that the
binding force of fixing agent T in water was not as good as the fixing
agent J and the fixing agent H. Moreover, the rubbing fastness and
zeta potential mean the binding force of fixing agent on the fiber in
water bath is affected by the cation: fixing agent J< fixing agent H<
fixing agent T, indicating that fixing agent J had a better ability to
bond with cotton fiber.
3.6. The washing ability of fixing agent
In order to investigate the affinity between the fixing agent and
the fiber, the fabric was dyed with Weak acid Flavine G and Xylidine
Ponceau 2R after the fabrics pretreating with fixing agent. As we all
know, fabric can hardly be colored with acid dyes, but fabric can be
colored by acid dyes after fixing, which means the acid dyes are
combined with cationic fixing agent on the fabric.
As shown in Fig. 10 and Fig. 11, the K/S value of fabric were
changed by different concentration of fixing agents after dyeing
with acid dyes. The higher concentration of fixing agent, the more
dyes were combined with the fixing agent, indicating the film was
hardly to dissolve into water.
For the fixing agent J, the K/S value of fabric was maximum at
5 g/L and 10 g/L which were dyed with Weak acid Flavine G and
Xylidine Ponceau 2R, respectively. When the concentration of fixing
agent was lower, the fixing agent had a good fluidity and was easy
to enter the pores of fiber to produce precipitate. When the con-
centration of fixing agent was higher, the molecules of fixing agent
were difficult diffuse into the fiber pores (Wang et al., 2018; Zhou
et al., 2019), but they might easy to cross-link the film on the sur-
face of fiber. For the Weak acid Flavine G, the K/S value of fabric was
the largest at concentration of 10 g/L, because the good directness
of the Weak acid Flavine G made it difficult to diffuse into the
interior of fiber. Furthermore, most of agents were combined with
6 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728

Fig. 8. Zeta potential of cotton fiber: (a) treated with surfactant; (b)treated with fixing agent; (c) treated with surfactant and fixing agent.

Fig. 9. The schematic of fixing agent and surfactant treated the dyed-fiber.

Fig. 10. The K/S value after dyeing pretreated cotton fabric with acid dye: (a) Weak acid Flavine G; (b) Xylidine Ponceau 2R
 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728 7

Fig. 11. Samples of acid dyeing with different pretreatments.

Fig. 12. Indigo/silicon non-aqueous medium dyeing-fixing process. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of
this article.)

fixing agent on the surface of fabric, resulting that most of fixing
agents were adsorbed on the surface of fabric. When the fabric dyed
with Xylidine Ponceau 2R, the K/S value of fabric was the largest at a
concentration of 20 g/L, because the poor directness of the Xylidine
Ponceau 2R made itself was easy to diffuse into the interior of fiber
and combined with fixing agent on the surface of fabric.
3.7. 25 kg cotton fiber/indigo dyeing in the silicone non-aqueous
dyeing system
The process of 25 kg cotton fiber/indigo dyeing in silicone non-
aqueous dyeing system is shown in Fig. 12. Firstly, cotton fiber was
dyed and oxidized. After pickling process, the dyed cotton fiber was
fixed to meet spinning. The pilot test of dyeing 25 kg cotton fiber at
one time has been successfully completed in cooperative enter-
prise. As shown in Fig. 13, a 100 kg/d pilot production line had been
completed for indigo dyeing of cotton fiber in Haining Green Uni-
verse Textile Technology Co. Ltd. In order to obtain different styles
of yarns and fabrics, these dyed cotton fibers were spun after
pickling and fixing (Fig. 4). Indigo dyeing in the silicone non-
aqueous dyeing system greatly enriches the style of indigo dyed
products in the market, and simplifies the dyeing process and re-
duces water pollution. This is a favorable dyeing technology which
can solve the current environmental problems in the textile in-
dustry. The success of 25 kg pilot production indicates that the
dyeing method is expected to be further industrialization (see
Fig. 14).

Fig. 13. The dyeing pilot plant of 25 kg.

8 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728
Fig. 14. Different styles of products which was produced by indigo dyed cotton fiber.
3.8. Comparison chemical additives and wastewater in silicon non-
aqueous dyeing system and traditional water bath
The traditional dyeing of warp yarns on sizing and dyeing
combined machines was used for cotton yarn/indigo dyeing. Cotton
yarn was repeatedly dipped into the dyebath and was padded to
remove excess reducing solution, and finally was oxidized in the air.
The consumption of reagents to dye 1t products in both traditional
water dyeing system and silicon non-aqueous medium dyeing
system are listed in Table 1.
The cotton yarns usually repeated dyeing for 8e10 times and
multiple washing in traditional water bath. Thus the amount of
additives, dyes, water, etc., which are more than in silicon non-
aqueous medium dyeing system. It is obviously the water con-
sumption and wastewater in the traditional water is three times
that of in silicon non-aqueous dyeing system. In order to keep the
indigo in the reduced state, a large amount of alkali agent and
reducing agent are used in traditional water bath, thus the con-
sumption of sodium hydroxide and sodium dithionite is 2e3 times
and 1e2 times that of in silicon non-aqueous dyeing system
respectively. A large amount of auxiliaries would cause high pH,
CODCr, BOD5 of wastewater during dyeing., these results are shown
in Table 2. Furthermore, the conductivity of wastewater in tradi-
tional water bath is nearly four times that in silicon non-aqueous
dyeing system. Compared with the traditional indigo dyeing, low
water consumption, low auxiliaries and low wastewater in the
silicon non-aqueous dyeing system will greatly simplify the dyeing
processes, reduce costs and the pressure on the textile industry due
to the environmental legal system.
Table 1
Comparing the consumption of reagents in two different dyeing systems for 1t products.
Indigo (kg)
Sodium hydroxide (kg)
Sodium dithionite (kg)
Water Consumption(t)
Wastewater(t)
Depth of product (K/S Value)
Water Consumption: Dyeing þ Washing; Wastewater: Dyeing þ Washing.
Table 2
The parameters of wastewater produced in silicon non-aqueous dyeing system and
traditional water bath.
Parameters Silicon non-aqueous medium Traditional water bath
pH 10.36 12
CODCr (mg/L) 915 1208
BOD5 (mg/L) 210 300
Conductivity (u˛ s/cm) 1203 4360
Chroma, multiple 320, Navy blue 2500, Navy blue
4. Conclusions
In summary, the results of GPC and FTIR showed that all the
three fixing agents were polyurethanes which have a similar nar-
row molecular weight distribution and they could combine with
indigo-dyed cotton fiber without covalent bond. From the b* value
of white fabric and the coefficient friction of cotton fiber, it can be
concluded that the dyed cotton fiber had a good rubbing fastness
which was treated with the fixing agent J. The rubbing fastness and
zeta potential mean that the binding force of fixing agent on the
fiber in water bath is affected by the cation: fixing agent J< fixing
agent H< fixing agent T, indicating that fixing agent J has a better
ability to bond with cotton fiber. After fixation, the rubbing fastness
of dyed cotton fiber was greatly improved and the surface of dyed
fiber became much smoother, because the molecular weight of
fixing agent J was larger than the other fixing agents. Furthermore,
the combination of fixing agent J with cotton fiber was stronger
than the other fixing agents. These three polyurethane fixing
agents and dyed fibers were mainly combined by intermolecular
forces (hydrogen bonds) and ionic bonds. Compared with these
fixing agents, fixing agent J has a better effect on reducing the
friction coefficient of fiber because cotton fiber was the smoothest
after fixing. After adding some cationic surfactant during fixing, the
effect of fixation was influenced because there was a competition
relation between the fixing agent and surfactant From the spinning
process, the rubbing fastness of fiber treated with fixing agent can
meet the spinning requirements. 100 kg/d industrial application
can fundamentally change the current situation of the complex
process of traditional indigo dyeing, the monotonous style, and the
serious waste water pollution for cowboy wear production. We
believe that this dyeing technology will greatly broaden the
imagination of cowboy products designers, and enhance the
ecological and environmental protection.
Fundings
This work was supported by the National Key Research and
Development Program of China (2017YFB0309600), Key Technol-
ogy Research and Development Project of Zhejiang Province
(2017C03016) and Key Research and Development Program of
Xinjiang Production and Construction Corps (2019AA001).
Silicon non-aqueous medium Traditional water bath
60 60
80 200
190 320
2 þ 30  1 0.8 þ 30  3
0.5 þ 28 0.6 þ 87
25.09 20.99
 Y. Luo et al. / Journal of Cleaner Production 251 (2020) 119728
Author contributions section
Yuni Luo: Data curation, Writing- Original draft preparation.
Liujun Pei: Conceptualization, Methodology,Writing- Review-
ing and Editing.
Jiping Wang: Investigation, Supervision, Project administration.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.119728.
References
Aboltakhty, H., Rashidi, A., Yazdanshenas, M.E., Shahidi, S., 2018. Effect of nitrogen
plasma treatment and direct dye on zeta potential of cotton fabric. Oriental
Journal of Chemistry 34 (1), 301e313.
Abou Elmaaty, T., Abd El-Aziz, E., 2018. Supercritical carbon dioxide as a green
media in textile dyeing: a review. Text. Res. J. 88 (10), 1184e1212.
Chen, L.Y., Wang, B.J., Chen, J.G., Ruan, X.H., Yang, Y.Q., 2016. Characterization of
dimethyl sulfoxide-treated wool and enhancement of reactive wool dyeing in
non-aqueous medium. Text. Res. J. 86 (5), 533e542.
Correia, M.S., Miranda, A.S., Oliveira, M.C., Capela, C.A., Pouzada, A.S., 2012. Analysis
of friction in the ejection of thermoplastic mouldings. Int. J. Adv. Manuf. Tech.
59 (9e12), 977e986.
Dos Santos, C., Brum, L.F.W., de F atima Vasconcelos, R., Velho, S.K., dos Santos, J.H.Z.,
2018. Color and fastness of natural dyes encapsulated by a sol-gel process for
dyeing natural and synthetic fibers. J. Sol-Gel. Sci. Technol. 86 (2), 351e364.
Fan, Z., Li, Q., Cai, X., Li, Z., 2017. Synthesis of reactive waterborne polyurethane
modified with quaternary ammonium chain extender and its color fixation
properties. J. Text. I. 108 (7), 7.
Fu, X., Maruyama, T., Sotani, T., Matsuyama, H., 2008. Effect of surface morphology
on membrane fouling by humic acid with the use of cellulose acetate butyrate
hollow fiber membranes. J. Membr. Sci. 320 (1e2), 483e491.
Haaf, M.P., Piemonte, K.M., McQuade, D.T., Cotton, L., Blackburn, R.S., 2018. In-situ
fabric coloration with indigo synthesised in flow. Color. Technol. 135 (2),
127e132.
Hossain, M.D., Khan, M.M.R., Uddin, M.Z., 2017. Fastness properties and color
analysis of natural indigo dye and compatibility study of different natural
reducing agents. J. Polym. Environ. 25 (4), 1219e1230.
Khattab, T.A., Rehan, M., Hamouda, T., 2018. Smart textile framework: photochromic
and fluorescent cellulosic fabric printed by strontium aluminate pigment.
Carbohyd. Polym. 195, 143e152.
Lei, N., Zhong, N., Shi, Y., Ling, X., 2012. Researches on the fixation performance of
chitosan and its derivative. Adv. Eng. Mater. 55e547, 1547e1551.
Li, D., Li, X., Liu, J., Wang, L., Shao, J., 2016. Indigo dye/D5 system for cotton fiber
dyeing. Dyeing Finishing 4, 9e13.
9
Liu, X., Liu, F., Liu, S., Cui, M., Deng, J., 2019a. Relationship on structure and prop-
erties of polyurethane modified Diels-Alder addition polymer. J. Appl. Polym.
Sci. 136 (15).
Liu, Y., Xia, L., Zhang, Q., Guo, H., Wang, A., Xu, W., Wang, Y., 2019b. Structure and
properties of carboxymethyl cotton fabric loaded by reduced graphene oxide.
Carbohydr. Polym. 214, 117e123.
Luxbacher, T., Curlin, M., Petrinic, I., Buksek, H., Pusic, T., 2014. Assessing the quality
of raw cotton knitted fabrics by their streaming potential coefficients. Cellulose
21 (5), 3829e3839.
Park, S., Lee, J.-H., Cho, Y.-J., Chun, J., Hur, F.G., 2013. Draft genome sequence of
Pseudomonas sp strain G5, isolated from a traditional indigo fermentation. Dye
Vat. J. Korean Soc. Appl. Bi. 56 (3), 339e341.
Pei, L., Liu, J., Cai, G., Wang, J., 2017a. Study of hydrolytic kinetics of vinyl sulfone
reactive dye in siloxane reverse micro-emulsion. Text. Res. J. 87 (19),
2368e2378.
Pei, L., Liu, J., Wang, J., 2017b. Study of dichlorotriazine reactive dye hydrolysis in
siloxane reverse micro-emulsion. J. Clean. Prod. 165, 994e1004.
Saikhao, L., Suwanruji, P., Jantip, S., Porntip, S., 2011. Preparation and character-
ization of the blended film from silk fibroin and regenerated cellulose fiber
residue. Adv. Mater. Res. 332e334, 1666e1669.
Saikhao, L., Setthayanond, J., Karpkird, T., Bechtold, T., Suwanruji, P., 2018. Green
reducing agents for indigo dyeing on cotton fabrics. J. Clean. Prod. 197, 106e113.
Sharif, S., Ahmad, S., Izhar-ul-Haq, M.M., 2007. Role of quaternary ammonium salts
in improving the fastness properties of anionic dyes on cellulose fibres. Color.
Technol. 123 (1).
Shi, Y., Jin, S., Guo, Z., 2011. Applied researches of chitosan and silicon sol as fixing
agent on ramie. Adv. Mater. Res. 332e334, 1369e1373.
Surita, S.C., Tansel, B., 2014. Emergence and fate of cyclic volatile poly-
dimethylsiloxanes (D4, D5) in municipal waste streams: release mechanisms,
partitioning and persistence in air, water, soil and sediments. Sci. Total. Environ.
468, 46e52.
Tang, A.Y.L., Wang, Y.M., Lee, C.H., Kan, C.W., 2017. Computer color matching and
levelness of PEG-based reverse micellar decamethyl cyclopentasiloxane (D5)
solvent-assisted reactive dyeing on cotton fiber. Appl Sci-Basel 7 (7).
Teidelt, E., Starcevic, J., Popov, V.L., 2012. Influence of ultrasonic oscillation on static
and sliding friction. Tribol. Lett. 48 (1), 51e62.
Thi, V.H.T., Lee, B.K., Ngo, C.V., 2017. Durable superhydrophobic cotton filter pre-
pared at low temperature for highly efficient hexane and water separation.
J. Taiwan. Inst. Chem. E. 71, 527e536.
Venkatraman, P.D., Liauw, C.M., 2019. Use of a carbon dioxide laser for environ-
mentally beneficial generation of distressed/faded effects on indigo dyed denim
fabric: evaluation of colour change, fibre morphology, degradation and textile
properties. Opt. Laser. Technol. 111, 701e713.
Wang, S., Sun, P., Hao, X., Li, Z., Liu, G., Jin, L., Yin, X., 2018. Ferric sulfophenyl
phosphate bonded with phosphotungstic acid as a novel intercalated high-
temperature inorganic-organic proton conductor. Mater. Chem. Phys. 213,
35e43.
Xu, C., Cai, Z., Xing, J., Ren, Y., Xu, W., Shi, W., 2014. Synthesis of polypropylene
carbonate polyol-based waterborne polyurethane modified with polysiloxane
and its film properties. Fiber. Polym 15 (4), 665e671.
Zhao, C., Wang, C., Wang, Y., Yao, D., 2019. Super stretchable chromatic poly-
urethane driven by anthraquinone chromogen as a chain extender. Rsc. Adv. 9
(5), 2332e2342.
Zhou, Y., Yu, J., Biswas, T.T., Tang, R.-C., Nierstrasz, V., 2019. Inkjet printing of
curcumin-based ink for coloration and bioactivation of polyamide, silk, and
wool fabrics. Acs. Sustain. Chem. Eng. 7 (2), 2073e2082.
Zhu, K., Li, X., Wang, H., Fei, G., Li, J., 2016. Properties and paper sizing application of
waterborne polyurethanemicroemulsions: effects of extender, cross-linker, and
polyol. J. Appl. Polym. Sci. 133 (25).