Original article

Textile Research Journal

2020, Vol. 90(19–20) 2245–2257

Effects of UV absorbers and reducing ! The Author(s) 2020

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agents on light fastness of cotton DOI: 10.1177/0040517520911372
journals.sagepub.com/home/trj
fabrics pre-dyed with sodium copper
chlorophyllin and gardenia yellow

Zhong Zhao1,2, Mingwen Zhang1, Chris Hurren1, Liming Zhou3,

Jihong Wu2 and Lu Sun1,2

Abstract
In this study, inorganic and organic UV absorbers, as well as reducing agents, were employed to treat cotton fabrics that
were pre-dyed with two natural dyes (sodium copper chlorophyllin and gardenia yellow) to improve light fastness. The
performance of UV absorbers and reducing agents was evaluated by comparing
E (CIELAB) of the treated samples
caused by their exposure to simulated sunlight irradiation. Results show that both inorganic and organic UV absorbers
present unsatisfactory effects on inhibiting the photo-fading of dyes, while the reducing agents (i.e. sodium citrate and
glucose) exhibit distinctive effects on improving their light fastness. The protection was enhanced when the amount of
the two reducing agents was increased from 1% to 5% o.w.f. Sodium citrate was found to be more efficient than glucose
in this regard. Change in shade of gardenia yellow and sodium copper chlorophyllin pre-dyed fabrics with a treatment of
5% o.w.f. sodium citrate after 10 h exposure to simulated sunlight were
E 3.95 and 2.46, while for the controls were
E
10.34 and 8.11, respectively.

Keywords
gardenia yellow, glucose, light fastness, reducing agent, sodium citrate, sodium copper chlorophyllin, UV absorber

Natural dyes have been used to color manmade tex- gallic acid, vitamin C, and vitamin E) and organic
tiles since ancient times; however, their dominance UV absorbers (phenyl salicylate, benzophenone, and
in the textile dyeing industry has been gradually lost benzophenone 6) on the light fastness of cotton yarns
to synthetic dyes over the last decades.1 Natural dyes dyed with three natural dyes: weld, woad, and madder.
in general are more biodegradable,2,3 renewable,4,5 and The results show that neither the UV absorbers nor the
less harmful to the human body than their synthetic antioxidants are effective additives for inhibiting the
counterparts.6 These advantages have redrawn research
attention7 owing to the urgent need for and pressure
on alleviating the environmental pollution derived from
1
massive exploitation of synthetic dyes in the modern Institute for Frontier Materials, Deakin University, Australia
2
School of Textile Science and Engineering, Wuhan Textile University,
textile industry.8 To improve the confidence in using
China
natural dyes, a number of primary drawbacks of nat- 3
Group R&D Center, Guang Dong Esquel Textiles Co. Ltd, China
ural dyes9,10 should be tackled, such as poor color fast-
ness—that is, rapid color fading.11 Corresponding authors:
Treating the dyed fabrics with functional additives Jihong Wu, School of Textile Science and Engineering, Wuhan Textile
such as UV absorbers and antioxidants in the finishing University, China.
Email: [email protected]
process is a prevalent strategy for improving the light Lu Sun, Institute for Frontier Materials, Deakin University, Geelong,
fastness of natural dyes.12 Cristea and Vilarem13 inves- Victoria 3216, Australia.
tigated the effects of antioxidants (cafeic acid, Email: [email protected]
2246 Textile Research Journal 90(19–20)

photo-fading rates of weld and madder on cotton yarn. semiconductors like ZnO and TiO2 will cause degrad-
However, all the antioxidants and one UV absorber ation of the dye molecules due to the interactions
(benzophenone 6) show dramatic contributions to pro- between intermedia generated during photocatalysis
tecting the cotton yarn dyed with woad from of semiconductors and the chromophores of dyes.23
photo-fading. Oda carried out a series of studies14–17 Apart from ZnO, reducing agents, which also have
on the inhibitory feasibility of organic UV absorbers antioxidant properties and are much cheaper than anti-
on photo-fading of two natural dyes: red carthamin oxidants, can be a promising alternative to antioxidants
and gardenia blue. The results show that UV absor- in inhibiting the photo-fading of natural dyes.
bers 2-hydroxybenzophenone (HBP), 2-(20 -hydroxy- Previous research on inhibiting the photo-fading of
50 -methylphenyl) benzotriazol (HMBT) and natural dyes has focused mainly on the ability of organic
2,20 ,4,40 -tetrahydroxybenzophenone (TBP) have a UV absorbers to block UV rays24–26 and the ability of
minor effect on protecting red carthamin from photo- antioxidants27,28 to prevent photo-oxidation in dyes.
fading, while other additives like nickel p-toluenesul- Neither inorganic UV absorbers nor common reducing
phonic acid, derivatives of 5-(2H-benzotriazole-2- agents have been used in the studies of inhibiting photo-
yl)2,20 ,4,40 tetrahydroxybenzophenone, dibenzotriazo- fading of natural dyes. In this study, fabrics pre-dyed with
lylbenzophenone derivatives, and dibenzotriazolylben- two natural dyes, sodium copper chlorophyllin (green
zophenonesulphonic acid derivatives are significantly dye) and gardenia yellow (yellow dye), were treated with
effective against the photo-fading of red carthamin. an inorganic absorber (ZnO), a commercial organic
Regarding gardenia blue, UV absorbers also show absorber (UV FASTÕ ), and four kinds of reducing
poor inhibition on photo-fading rate. Similarly, nickel agents, respectively. Figure 1 illustrates the preparation
salts-based UV absorbers display better performance in processes of ZnO nanoparticles (NPs) (a) and the pre-
preventing the photo-fading than that of each corres- dyed fabrics treated with ZnO NPs via in-situ synthesis
ponding UV absorber. (b), the direct dip-coating and electrostatic adsorption (c)
Results from Cristea and Vilarem and Oda show that methods, and the pre-dyed fabrics treated with reducing
organic UV absorbers may exhibit limited effects on agents/UV FASTÕ via the dipping and padding method.
inhibiting photo-fading of some natural dyes, as such Effects of UV absorbers and reducing agents on
an ability of organic UV absorbers varies from one nat- inhibiting photo-fading of the dyes were evaluated by
ural dye to another. Besides, some organic UV absorbers measuring color differences of the treated fabrics as a func-
are highly likely to cause environmental issues18 if the tion of their exposure to simulated sunlight irradiation.
wastewater generated in the dyeing process is directly
poured into natural water systems. Other effective addi-
tives like antioxidants, which are commonly used as medi- Experimental
cines to scavenge reactive oxygen species (ROS)—the
oxygen-containing free radicals such as singlet oxygen,
Materials
hydroxyl radical, and superoxide, generated in living Two single jersey 100% cotton fabrics pre-dyed with
organisms19—are too expensive to be widely applied in sodium copper chlorophyllin and gardenia yellow
the textile dyeing industry. More importantly, progressive with the same density of 270 g/m2 (kindly supplied by
degradation of organic UV absorbers during exposure to the Esquel Group, Foshan, China) were used without
sunlight will shorten the durability of UV-blocking further processing prior to any treatment. Sodium sul-
finishes and thus affect light fastness properties of treated fite was obtained from BDH Chemicals Ltd (Dorset,
fabrics. Therefore, seeking alternative economical and UK). Citric acid monohydrate, ethanol, and sodium
environment-friendly ways to improve the light fastness hydroxide were purchased from Chem-Supply Pty Ltd
of textiles dyed with natural dyes is still necessary. (SA, Australia). Zinc acetate dihydrate and D-glucose
Since the first report of photo-activity of semicon- anhydrous were purchased from AJAX Chemicals Ltd
ductors in the 1970s, inorganic semiconductors like (NSW, Australia). UV FASTÕ was purchased from
TiO2 and ZnO have dramatically developed in the last Huntsman Corporation (Texas, USA). The 20% w/v
decades. One of the major applications of these inor- poly(diallyldimethylammonium chloride) (PDDA)
ganic semiconductors is as a UV-blocking finish on tex- solution, sodium citrate dehydrate, and sulfurous acid
tiles due to their ability to absorb UV rays.20 Among were purchased from Sigma-Aldrich (NSW, Australia).
these UV absorbers, ZnO is a semiconductor with a The UV FASTÕ was of commercial grade. Other chem-
broad UV absorption spectrum. It is safe for the icals were all of analytical grade. All the chemicals were
human body21 and stable under UV irradiation.22 used as received. Filters with the capability to absorb
Although ZnO has been proved to be an efficient UV UV rays and visible light within different wavelength
absorber that can improve light fastness of fabrics dyed ranges were purchased from Purshee Optical Elements
with reactive dyes, there are still chances that Co., Ltd (Yixing, China).
Zhao et al. 2247

Figure 1. Diagram for preparation of ZnO nanoparticles (a), the pre-dyed fabrics coated with ZnO nanoparticles via in-situ synthesis
(b), the direct dip-coating and electrostatic adsorption methods (c), and the pre-dyed fabrics treated with reducing agents/UV FASTÕ
via the dipping and padding method (d).

Effects of light within different wavelength ranges

on photo-fading
To investigate the effects of light irradiation with dif-
ferent wavelength ranges on the photo-fading of the
two pre-dyed fabrics, the simulated sunlight irradiation
was filtered by covering the fabrics with four different
filters made from transparent glass plates with different
colors during their exposure to the irradiation. The
color change of the two fabrics caused by simulated
sunlight irradiation filtered by four filters, which can
shield the light within different wavelength ranges,
was measured and compared to investigate the contri-
bution rate of each wavelength on the photo-fading of
the two dyes. The transmittance spectra of the four fil-
ters are presented in Figure 2. The specific wavelength Figure 2. Transmittance spectra of the filters.
ranges of the filters are listed in Table 1.

Treatments of ZnO nanoparticles to the ZnO NPs were prepared by dispersing

Zn(CH3COO)2  2H2O in NaOH ethanol solution
pre-dyed fabrics under continuous stirring as reported previously.29
ZnO NPs were applied to 1.35 g green and yellow The ZnO NPs precipitated from the NaOH ethanol
fabrics in dimensions of 5  10 cm via three different solution were first collected via repeated rinse with
methods: dip-coating, electrostatic adsorption, and ethanol and centrifugation to remove residual NaOH
in-situ synthesis on fabric. In the first two methods, (illustrated in Figure 1(a)). Finally, ZnO NPs
2248 Textile Research Journal 90(19–20)

Table 1. Wavelength range of the filters dried at room temperature overnight. The fabrics trea-
ted by this method were designated as Fabrics #3.
Transmitting
wavelength
Filters ranges Characterization of ZnO NPs. The crystal properties, UV
absorbance ability, and particle size of ZnO NPs were
1 >355 nm investigated via XRD test, UV–vis spectrophotometry,
2 >380 nm and particle size analysis, respectively. The X-ray dif-
3 >410 nm fraction spectrum of ZnO NPs was obtained by scan-
4 >460 nm ning the ZnO NPs with Cu Ka radiation generated by
an Ultima IV X-ray diffractometer (Rigaku
Corporation). The UV–vis absorbance spectrum
(within the wavelength range 250–600 nm) of ZnO
dispersions were prepared by dispersing the prepared NPs was recorded by scanning its ethanol dispersion
ZnO NPs in ethanol. In the third method, in-situ with a UV–vis spectrophotometer (Varian Cary 300,
hydrolysis of Zn(CH3COO)2  2H2O was carried out Agilent). Particle size distribution of ZnO NPs was
upon the surface of pre-dyed fabrics (illustrated in obtained by scanning the ZnO ethanol dispersion
Figure 1(b)) via the same method with minor (4 mg/mL) with a particle size analyzer (Nanotrac
modification. Wave II, Microtrac).

Direct dip-coating of ZnO NPs. In the dip-coating method, Thermogravimetric analysis. The final amount of ZnO NPs
the green and yellow fabrics were dipped into 4 mg/ml deposited on the two fabrics via the three methods were
ZnO ethanol dispersions, respectively. The excess determined by measuring the residual weight percent-
liquor contained by the soaked fabrics was squeezed age obtained from thermogravimetric analysis. The
out by a Rapid PA0 pad mangle (Rapid Labortex samples were ground into powder and subjected to a
Co. Ltd.) to maintain a pickup rate of 100% and a thermogravimetric analyzer (Mettler Toledo TGA/
5% o.w.f. of ZnO NPs. Treated samples were dried in DSC 1). The weight percentage of the samples was rec-
darkness at room temperature overnight and desig- orded from the initial temperature of 50 C and the rec-
nated as Fabrics #1. ording process was terminated at 800 C. The heating
rate was 10 C/min. Oxidization of the samples occurred
Electrostatic adsorption of ZnO NPs. In the electrostatic under continuous oxygen flow.
adsorption method, the green and yellow fabrics were
first immersed in 1% w/v PDDA aqueous solution
at a liquor ratio of 1:20 for 30 min. Then, the soaked
Treatments of UV FASTÕ
fabrics were thoroughly rinsed with distilled water UV FASTÕ is a commercial UV absorber, and the typ-
and dried at room temperature. After the drying pro- ical usage is recommended at 1–2% o.w.f. for fabrics
cess, the fabrics were submerged in the ZnO aqueous that will be facing high exposure to light. First, 1.35 g
dispersion (1 mg/ml) at a liquor ratio of 1:50 to allow green and yellow fabrics of 5  10 cm were immersed
for the deposition of ZnO NPs onto the fabrics. in the UV FASTÕ aqueous solution (2 wt.%) at a
The fabrics were immersed in the dispersion under solid/liquid ratio of 1:10 for 2 min. The excess
slow stirring for 2 h. Subsequently, the soaked fabrics liquid retained in the fabrics was removed by the pad-
were retrieved, gently rinsed with distilled water, ding mangle. The final pickups of the fabrics were
and dried in darkness at room temperature. Treated maintained at 100  5% w/w via padding to ensure
fabrics obtained via this method were designated as the loading amount of UV FASTÕ was 2  0.1%
Fabrics #2. o.w.f. The blank control sample was soaked with deio-
nized water. Finally, the treated fabric samples were
In-situ synthesis of ZnO NPs on cotton fabrics. The green cured in the dark at room temperature overnight. The
and yellow fabrics were submerged in the prepared fabrics treated by this method were designated as
Zn(CH3COO)2  2H2O ethanol solution at a liquor Fabrics #4.
ratio of 1:30 for 30 min. Then, 0.04 mol/L NaOH etha-
nol solution was added to the zinc acetate solution drop
by drop with constant stirring to prepare a transparent
Treatments of reducing agent to pre-dyed fabrics
sol-gel. The whole suspension in which the fabric was Protective effects of reducing agents. Four types of reducing
immersed was heated at 80 C for 3 h. After the heating agents—sodium sulfite (Na2SO3), citric acid, sodium
process, the fabrics were taken out, thoroughly rinsed citrate, and glucose—were applied in this study.
with distilled water to remove residual NaOH, and Aqueous solutions of the reducing agents were
Zhao et al. 2249

prepared: 3 wt.% Na2SO3 (designated as S-3), 3 wt.% Photo-fading under standard irradiation. The fabrics were
Na2SO3 neutralized by H2SO3 (designated as SN-3), directly exposed to the standard irradiation conditions
3 wt.% citric acid (designated as C-3), 3 wt.% sodium following ISO 105-B02, over a total irradiation time
citrate, neutralized by citric acid (designated as CN-3), length of 72 h. An untreated fabric sample was exposed
and 3 wt.% glucose (designated as G-3). Then, 1.35 g under the same conditions as a control.
pre-dyed fabrics of 5  10 cm were treated with these
aqueous solutions of reducing agents, following the
same procedures as the treatment of UV FASTÕ . The
Color difference measurement
processes of treating the pre-dyed fabrics with reducing The level of color fading during the exposure process
agents/UV FASTÕ are presented in Figure 1(d). was evaluated by the
E value to compare the color
difference between the treated samples and the control
Protective effects of reducing agents with different usages. The in a numeric manner.
E values were both recorded
effects of loading amount of sodium citrate and glucose under D65 light source emitted by a spectrophotometer
were further investigated. A series of samples were pre- (Datacolor SF 600 Plus-CT Spectraflash) at a measure-
pared by treating 1.35 g green and yellow fabrics of ment angle of 10 . The CIE L*, a*, b* of ZnO NPs/UV
5  10 cm with 1 wt.%, 3 wt.%, and 5 wt.% sodium cit- FASTÕ treated fabrics and the
E between the
rate and glucose solutions following the same steps untreated fabric and each treated fabric were also rec-
described above. The pre-dyed fabrics treated with orded with the spectrophotometer to investigate the
1 wt.%, 3 wt.%, and 5 wt.% sodium citrate and glucose effect of ZnO NPs treatment via the three methods
solutions were designated as CN-1, CN-3, CN-5, G-1, and UV FASTÕ on the color of pre-dyed fabrics.
G-3, and G-5.
SEM images of fabrics treated with ZnO NPs
Treatments of reducing agents and commercial UV
Morphology of the green fabrics treated with ZnO NPs
absorber via the three methods and the three reducing agents was
Combinations of both reducing agents and commercial investigated by scanning electron microscopy (ZEISS
UV absorber at different concentrations, including 5% Supra 55 SEM VP).
o.w.f. neutralized sodium citrate with 2% o.w.f. UV
FASTÕ (designated as CN-UV), as well as 5% o.w.f.
Color fastness
glucose with 2% o.w.f. UV FASTÕ (designated as
G-UV), were applied to 1.35 g two pre-dyed fabrics of Color fastness to laundering, color fastness to per-
5  10 cm. spiration, color fastness to water, and color fastness
to light of the two fabrics treated with 5% o.w.f. neu-
tralized sodium citrate was evaluated according to the
Evaluation of photo-fading rates AATCC Test Method 61 (2013), AATCC Test Method
Light fastness of the pre-dyed fabrics treated with dif- 15 (2013), AATCC Test Method 107 (2013), and
ferent additives (reducing agents, organic and inorganic AATCC Test Method 16 (2012) respectively.
UV absorbers) was evaluated by measuring the
E of Untreated green fabric and untreated yellow fabric
the fabric under simulated sunlight irradiation and the were subjected to the same fastness tests as a control.
standard irradiation at certain time intervals. All the
samples were exposed to standard irradiation unless
otherwise specified. Results and discussion
Effects of filters on the photo-fading of pre-dyed
Photo-fading under simulated sunlight irradiation. Fabrics
fabrics
were directly subjected to simulated sunlight irradi-
ation generated by a solar radiometer (Atlas Suntest The surface absorbance spectra of both sides of the
CPS1) equipped with a 1500 W air-cooled xenon arc fabrics are presented in Figure 3. It can be seen from
lamp (light wavelength range 300800 nm). The tem- Figure 3 that in the visible light range, the absorption
perature inside the chamber was maintained at 35 C. peaks of green dye appeared at around 630 nm and
The intensity of the irradiation was 400 W/m2. The dis- 406 nm, and the absorption region of the yellow dye
coloration level of the fabric sample was measured at a mainly ranges from 430 nm to 470 nm. In the UV
1-h interval, and the total irradiation time was 10 h. light range (200–400 nm), strong absorption is also
Untreated green and yellow fabrics were exposed to observed in yellow and green fabrics.
the simulated sunlight under the same conditions as Results of the effects of the four filters on photo-
control ones. fading of the two pre-dyed fabrics are shown in Figure 4.
2250 Textile Research Journal 90(19–20)

It can be seen from Figure 4 that the filters have light and part of the visible light (below 460 nm) spec-
moderate effects on inhibiting photo-fading of the two trum have been shielded by filter 4. It is also notable
dyes. The color change differences between the control that filters 1 and 2, which block UV and allow the
samples and the filter-covered samples after 10 h transmittance of visible light, exhibited minor effects
of simulated sunlight irradiation were
E 10.34 (con- on decreasing the color difference of yellow fabric
trol, yellow),
E 9.75 (filter 1, yellow),
E 9.27 (filter 2, caused by simulated sunlight irradiation. Different
yellow),
E 7.84 (filter 3, yellow),
E 7.06 (filter 4, color difference results were recorded for the green
yellow),
E 8.11 (control, green),
E 6.66 (filter fabric under the same conditions as lower
E values
1, green),
E 6.17 (filter 2, green),
E 5.39 (filter 3, were recorded in the presence of filters 1 and 2.
green), and
E 4.54 (filter 4, green). The inhibiting Results from this test are consistent with those from
effect of the filters can be sorted in the order filter UV absorbers and further prove that UV rays are not
4 > filter 3 > filter 2 > filter 1. the only root cause of photo-fading of the two dyes.
Therefore, the protection level of discoloration Specifically, the yellow fabric is more sensitive to visible
improved with the increasing absorbent region of the light while UV irradiation plays a more important role
filters. However, the best protection against color in the photo-fading of green fabric. One possible reason
fading for yellow and green fabrics increased by only why UV and visible light behave differently in the
31.7% and 44.0% respectively, even after 85% of UV photo-fading of the two fabrics is that as a carotenoid,
the yellow dye is more prone to photo-oxidation caused
by visible light, while the porphyrin structures in the
molecules of green dye will be activated to triplet
states under UV irradiation.

Effects of organic and inorganic UV absorbers on

inhibiting photo-fading
XRD spectrum featuring characteristic diffraction
peaks of ZnO can be observed from Figure 5(a), indi-
cating the successful synthesis of ZnO NPs with high
purity. The diffraction peaks match the crystal param-
eters of hexagonal wurtzite ZnO, a common crystal
structure of ZnO which has been reported previ-
ously.30,31 The UV–vis spectrum (Figure 5(b)) con-
firmed that the ZnO NPs exhibit distinctive UV
Figure 3. Surface UV–vis absorbance spectra of the fabrics pre- absorbance within the wavelength range 250–370 nm.
dyed with gardenia yellow and sodium copper chlorophyllin. The ability of ZnO NPs to absorb UV light can be

Figure 4. Discoloration of (a) yellow fabric and (b) green fabric caused by filtered simulated sunlight radiation generated by a xenon
light source with an intensity at 400 W/m2. Transmittance wavelength ranges of filters 1–4 are >355 nm, >380 nm, >410 nm, and
>460 nm, respectively.
Zhao et al. 2251

Figure 5. XRD spectrum (a), UV–vis spectrum (b), and particle size distribution of ZnO NPs prepared via hydrolysis of
Zn(CH3COOH)2 under alkaline conditions in ethanol (c).

Table 2. Effect of ZnO treatments via the three methods on the color of pre-dyed fabrics

Yellow Green

Sample L* a* b*
E L* a* b*
E

Control 77.46 3.64 34.06 – 51.16 8.61 11.53 –

Fabric #1 78.61 2.60 33.22 1.88 51.63 8.34 11.79 0.95
Fabric #2 78.83 0.10 37.12 5.05 50.43 8.46 11.60 0.83
Fabric #3 80.10 1.46 32.53 5.96 51.87 8.06 11.79 0.99
Fabrics #4 79.14 1.39 34.88 5.65 51.55 8.41 11.57 0.74

attributed to its energy band gap (3.37 eV32), a prom- and the ZnO NPs have minor absorbance of visible
inent characteristic that enables metal oxide semicon- light (Figure 5(b)), they are not likely to cause severe
ductors to absorb photons and release electrons.33 color change after the treatments. Similarly, UV
Minor absorbance of light in the blue light region FASTÕ has very limited effect on the color of treated
by ZnO NPs can also be observed from the UV–vis fabrics as it is a colorless and transparent liquid and its
spectrum, indicating that ZnO NPs will not affect the usage in the treatment was at a low o.w.f. (2%). The
original color properties of the substrate (dyed fabric difference in the color change between the green fabric
in this case) with a low o.w.f. of ZnO NPs coatings. and the yellow fabric was mainly caused by the solubil-
The channel (%) bar chart and passing (%) curve in ity of the dyes in ethanol and water. Generally, a pro-
Figure 5(c) jointly show a particle size distribution fea- portion of the dye molecules of gardenia yellow were
turing a diameter range from 36.1 to 72.3 nm and an dissolved in ethanol or water during the treatment pro-
average diameter of 47.5 nm. This indicates that the cesses, therefore, resulting in an obvious color change
ZnO NPs in the ethanol dispersion are mainly nano- of the treated yellow fabrics.
scale, with minor aggregation behavior. The actual amount of ZnO NPs loaded on the fab-
The CIE L*, a*, b* of ZnO NPs coated fabrics and rics was determined by determining the weight percent-
the
E between the untreated control and each ZnO age of the final inorganic material left on the sample
NPs coated fabric are listed in Table 2. after continuous heating in the TGA tests. TGA curves
Distinct color changes resulted mainly from the for the two fabrics are presented in Figure 6. Y1, Y2,
decrease in the value of a* of yellow fabrics coated Y3, and YC represent the yellow fabrics treated via
with ZnO NPs via the three methods or treated with direct dip-coating, electrostatic adsorption, and in-situ
UV FASTÕ . However, minor color change of the green synthesis, as well as the blank control, respectively
fabrics was recorded as the
E between the control and (Figure 6(a)). The mass of the four samples all
each treated sample is lower than 1, indicating that decreased quickly within the temperature range 200–
treatments have a minor effect on the color of pre- 450 C due to the oxidization of cellulose, and then
dyed green fabric. As the amount of ZnO NPs coated gradually reached stable stages when the temperature
on the dyed fabrics is maintained at a low level (5%) was further increased. Due to the existence of metal
2252 Textile Research Journal 90(19–20)

ions contained in the dye molecules and the mordants were
E 8.37, 7.81, and 5.87, respectively, while the
introduced during the dyeing process, the final weight UV FASTÕ was
E 6.17 at 2% o.w.f. For the green
percentage of YC was above zero (2.01%) as the metal fabrics, a similar color change trend was observed: the
elements remained stable even after reaching the high-
E of the control sample was 8.11 after 10 h of irradi-
est temperature (800 C). The final residual weight ation, while color change of fabrics with ZnO NPs
percentages of Y1, Y2, and Y3 at 800 C were 6.68%, coated through direct dip-coating, electrostatic adsorp-
6.87%, and 7.12%. The difference of final weight per- tion, and in-situ synthesis around 5% o.w.f. were
E
centages between the treated sample and the blank con- 7.71, 7.04, and 6.83, respectively, and UV FASTÕ was
trol indicated the existence of a ZnO NPs coating, as
E 5.79 at 2% o.w.f.
the inorganic material also remains stable. Therefore, Owing to the much lower usage of UV FASTÕ ,
the effective loading of ZnO NPs on Y1, Y2, and Y3 organic UV absorber was more effective compared
was 4.67%, 4.86%, and 5.11% o.w.f., respectively. with ZnO NPs in the protection against photodegrada-
Similar trends are observed in Figure 6(b). G1, G2, tion. In addition, the in-situ synthesis method provided
G3, and GC represent the green fabrics treated via a better protective effect than direct dip-coating and
direct dip-coating, electrostatic adsorption, and in-situ electrostatic adsorption methods, which may be attrib-
synthesis, as well as the blank control, respectively. The uted to a higher coverage of ZnO NPs. However, both
final weight percentages of G1, G2, G3, and GC at inorganic and organic UV absorbers were not satisfac-
800 C were 7.83%, 7.98%, 8.26%, and 3.61%, which tory for effective UV protection of either of the two
indicates the effective loading of ZnO NPs on G1, G2,
and G3 are 4.22%, 4.37%, and 4.65% o.w.f., respect-
ively. These percentages were similar in pickup rate and
trend to those seen for the yellow fabric. Table 3.
E of yellow and green fabrics treated with ZnO
The color change of ZnO-treated samples with dif- nanoparticles via direct dip-coating (Fabric #1), electrostatic
ferent methods and UV FASTÕ , as well as the adsorption (Fabric #2), in-situ synthesis (Fabric #3), and UV
FASTÕ (Fabric #4)
untreated control, caused by exposure to simulated
sunlight irradiation, are presented in Table 3. Yellow Green
It can be seen from Table 3 that ZnO NPs and UV
FASTÕ showed different effects on inhibiting the dis- Loading Loading
coloration of the pre-dyed fabrics caused by simulated amount amount
Sample (o.w.f.)
E (o.w.f.)
E
sunlight irradiation. For the yellow fabrics, the discol-
oration of the control sample was
E 10.34 after 10 h Control 0% 10.34 0% 8.11
of irradiation, which was very severe. Four types of Fabric #1 4.67% 8.37 4.22% 7.71
treated samples indicated reduced discoloration to dif- Fabric #2 4.86% 7.81 4.37% 7.04
ferent degrees. Particularly, the discoloration of ZnO Fabric #3 5.11% 5.87 4.65% 6.83
NPs coated through direct dip-coating, electrostatic
Fabric #4 2% 6.17 2% 5.79
adsorption, and in-situ synthesis around 5% o.w.f.

Figure 6. TGA curves of (a) yellow samples and (b) green samples. The number 1–3 and the letter C after Y and G represent the
yellow/green fabrics treated via direct dip-coating, electrostatic adsorption, in-situ synthesis, and the blank control, respectively.
Zhao et al. 2253

natural dyes evaluated. One possible reason is that (d)), the two dyes are extremely sensitive to the reduci-
photo-fading of the two dyes was caused by photo-oxi- bility and pH value of the additives. After the treatment
dation from both UV and visible irradiation. This rein- with the reducing agents, the acidity of citric acid
forces the degradation levels observed using filters to caused rapid color change of the yellow fabric (from
block the UV portion of the irradiated light. light yellow to orange) and the desorption of the mol-
Overall, despite the ZnO NPs having prominent UV ecules of green dye from cotton. A chemical reduction
absorbance, their photocatalytic activity will also cause of the dye was evident with each of the reducing agents
photo-fading of the two natural dyes as a proportion of trialed, to varying levels. Na2SO3 had the largest effect
energy of the absorbed UV rays will be delivered to the with a significant bleaching reduction of intensity of
dye molecules. However, the organic UV absorber (UV both dyes. For the weaker reducing agents (sodium cit-
FASTÕ ) molecules degrade and ‘‘sacrifice’’ themselves rate and glucose) this effect was still apparent but at a
to protect the dye molecules from photo-fading, thus reduced rate. The pH state of the fabric had a large
generating a better inhibiting effect than the inorganic effect on the reducing effect during coating. With the
counterparts. citric acid treatment, the yellow dye was more sensitive
to this effect than the green (yellow:
E 14.92; green:

E 3.33). Control of the pH to neutral conditions
Effects of reducing agent during the coating minimized this change in color
Protective effects of reducing agents. A number of different (yellow:
E 2.27; green:
E 0.87).
strength-reducing agents were trialed to see if they
could reduce the photo-oxidation of the natural dye. Protective effects of reducing agents at different usages. As
The glucose and neutralized sodium citrate were the the neutralized sodium citrate and glucose treatments
most effective of the reducing agents used for inhibiting showed the best protection levels of the reducing agents
light-induced discoloration of the two pre-dyed fabrics trialed, further experiments were conducted to examine
(Figure 7). For both the yellow and the green fabrics, the optimum concentrations for treatment (Figure 9).
the neutralized sodium citrate exhibited the lowest The neutralized sodium citrate treatment showed
color change during light exposure of each of the redu- increased light fastness protection for both fabrics as
cing agents tested (yellow:
E 5.03; green:
E 3.64). its concentration was increased: 5% neutralized sodium
The glucose-treated samples also performed similarly citrate provided the highest protection for both dyes.
(yellow:
E 5.26; green:
E 4.47). The glucose also provided an improvement in light fast-
Apart from protecting the dyed fabrics from photo- ness proportional to the amount of treatment material
fading, the additives themselves can also cause fading used; however, optimum protection was already
of the dye molecules. Due to the occurrence of damage achieved at 1% for the yellow dye. As seen in earlier
and ring-opening of the unstable porphyrin structures work, the photo-fading mechanism was different for
in the two major components of the green dye (whose each dye, so reducing agents exhibit better effects
molecular structures are presented in Figure 8(a) and on inhibiting the photo-fading of yellow fabric as it is
(b)), and the reduction of conjugated carbon chains in more sensitive to photo-oxidation caused by visible
the two major components of the yellow dye (whose light, which can be relieved by the treatment of redu-
molecular structures are presented in Figure 8(c) and cing agents.

Figure 7.
E of control and (a) yellow and (b) green fabrics treated with various types of reducing agents (3% o.w.f.) under simulated
sunlight irradiation generated by a xenon light source at an intensity of 400 W/m2.
2254 Textile Research Journal 90(19–20)

Figure 8. Molecular structure of the major components (a) sodium copper chlorin e6 and (b) sodium copper chlorin e4 in the green
dye, and (c) crocin and (d) crocetin in the yellow dye.

Figure 9.
E of control, neutralized sodium citrate, and glucose treated (a) yellow and (b) green fabrics with various dosages under
simulated sunlight irradiation generated by a xenon light source at an intensity of 400 W/m2.

Effects of reducing agents together with a the commercial light fastness protecting agent UV
FASTÕ had limited protection of the two dyes. This
commercial UV absorber
section examines if the inclusion of the reducing agent
Yellow and green fabrics were treated with glucose with with the commercial protecting agent would improve
2% o.w.f. UV FASTÕ (UV fast/G-5) and subjected to protection levels. Each of the reducing agents alone
standard irradiation. Earlier experiments showed that performed better than the combined reducing agent/
Zhao et al. 2255

UV FASTÕ treatments (Figure 10). The neutralized

SEM images of the treated samples
sodium citrate treatment was the best performer for Morphology of ZnO NPs and reducing agents depos-
both dyes, but in combination glucose/UV FASTÕ ited on the green fabrics are shown in Figure 11. It can
was the best performer of the treatments including UV be seen from Figure 11 that among the three different
FASTÕ . The difference between the glucose/UV FASTÕ treatment methods, both direct dip-coating and in-situ
and the neutralized sodium citrate/ UV FASTÕ may be synthesis methods resulted in severe aggregation of
due to the interaction between the sodium citrate and the ZnO NPs, while the electrostatic adsorption method
commercial protecting agent allowing electron transfer provided a more even dispersion of ZnO NPs. The
and hence photocatalytic oxidation. in-situ synthesis method showed the highest coverage
of ZnO NPs, and dip-coating indicated the lowest
one. In addition, the lowest amount of ZnO NPs depos-
ited on the green fabric can be observed from Figure
11(a). Layers formed by the reducing agents recrystal-
lized during the drying process after the dipping and
padding treatment, which can also be observed on the
cotton fiber of the green fabrics (Figure 11(d)–(f)).

Color fastness
The results of the color fastness tests are listed in
Table 4. During the dipping and padding process in
the treatment of the yellow fabric, a small amount of
the water-soluble dyes dissolved in the aqueous solution
of neutralized sodium citrate, resulting in a lighter
Figure 10.
E of control and fabrics treated with 5 % o.w.f.
shade and poorer wash fastness of the treated yellow
neutralized sodium citrate (CN-5), 5 % o.w.f. glucose (G-5), 2 %
o.w.f. UV FASTÕ, 5 % o.w.f. neutralized sodium citrate with 2 %
fabric compared with the untreated yellow fabric.
o.w.f. UV FASTÕ (UV fast/CN-5), and 5 % o.w.f. glucose with 2 % Compared with the yellow dye, the molecules of green
o.w.f. UV FASTÕ (UV fast/G-5) caused by their exposure to dye contained more hydroxyl groups (shown in
standard radiation for 72 h following ISO 105–B02. Figure 7), which can form electrostatic interactions

Figure 11. SEM images of the green fabrics treated with ZnO NPs via (a) direct dip-coating, (b) electrostatic adsorption, and
(c) in-situ synthesis, and green fabrics treated with 5% o.w.f. (d) neutralized sodium citrate, (e) glucose, and (f) neutralized Na2SO3,
respectively.
2256 Textile Research Journal 90(19–20)

Table 4. Color fastness properties of the fabrics treated with 5% o.w.f. neutralized sodium citrate

Color fastness to Color fastness to Color fastness

laundering perspiration to water
Color
Color Color Color fastness
Samples change Staining change Staining change Staining to light

Untreated green fabric 3.5 3.5 3.0 3.0 3.5 4.0 3.0
Green fabric treated with 5% 4.0 4.0 3.5 3.0 4.5 4.0 3.5
o.w.f. neutralized sodium citrate
Untreated yellow fabric 4.0 3.0 2.0 3.0 4.0 4.0 2.5
Yellow fabric treated with 5% 3.5 3.0 2.0 3.0 4.0 3.5 3.5
o.w.f. neutralized sodium citrate

with the protonated binding sites of the cationic cotton. slow down the fading process, and the protection level
Therefore, the amount of dye molecules lost in the of discoloration was improved with the concentration
treatment via the dipping and padding method was of the reducing agents. It is notable that dipping the
lower than for the yellow one. For the green fabric, yellow fabric in the aqueous solution of neutralized
the color change caused by the wash fastness test was sodium citrate caused minor color change of the treated
contributed to the loss of unfixed dye molecules and the yellow fabric as a portion of molecules of yellow dye
dye molecules’ bond to the cationic cellulose via electro- were dissolved in the solution. Compared with controls,
static interaction. In addition, a proportion of unfixed application of 5% o.w.f. glucose and neutralized sodium
dye molecules were already lost in the dipping and pad- citrate reduced the photo-fading rates of the green dye
ding process, and thus fewer unfixed molecules of the by 51.1% and 69.7%, respectively. For yellow fabrics,
green dye were lost during the laundering, resulting in the reduction percentage in photo-fading rates is 55.4%
a minor improvement in wash fastness. Similar results and 61.8% respectively. The application of reducing
were recorded in the color fastness to perspiration and agents can improve the photo-stabilities of both yellow
color fastness to water due to the same reason. and green dyes so that they have a better usability in
The results of color fastness to light are consistent textile garments; however, further work needs to be con-
with the photo-fading curves presented in Figure 8 and ducted to understand how to retain them in the fabric.
further confirm the effects of sodium citrate on inhibit- Treating the dyed fabrics with reducing agents has minor
ing the photo-fading of the two fabrics. effects on the wash fastness properties of the treated
Overall, wash fastness results of the fabrics treated samples, as no further fixation of dye molecules occurred
with 5% o.w.f. neutralized sodium citrate suggest that in the treatment.
treating the dyed fabrics with reducing agent via the
dipping and padding method has minor effects on the
Declaration of conflicting interests
wash fastness of treated samples as no further fixation
of the dye molecules or the fixation of reducing agents The authors declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
occurred during the treatment.
article.

Conclusions Funding
Organic and inorganic UV absorbers are not efficient in The authors disclosed receipt of the following financial sup-
inhibiting the photo-fading rate of the dyed fabrics (in port for the research, authorship, and/or publication of this
green and yellow) as the former may cause degradation article: This work was supported by a commercial fund pro-
of the dye molecules due to its photocatalytic activity vided by the Guangdong Esquel Textiles Co. Ltd (No.
while the latter will be degraded and gradually lose its 230701-3029999).
inhibiting effect after absorbing the energy of UV rays.
In addition, filtering UV rays in simulated sunlight with ORCID iD
UV filters was also an ineffective inhibitor in terms of
Lu Sun https://orcid.org/0000-0003-2999-1250
photo-fading. Those findings indicate that photo-
fading was caused by both UV rays and visible light.
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