coatings
Article
Sustainable Dyeing and Finishing of Cotton Fabrics
with Layer-by-Layer Technique
Şule Sultan Uğur
Citation: Uğur, Ş.S. Sustainable
Dyeing and Finishing of Cotton
Fabrics with Layer-by-Layer
Technique. Coatings 2023, 13, 1129.
https://doi.org/10.3390/
coatings13061129
Academic Editor: Chi-wai Kan
Received: 12 May 2023
Revised: 12 June 2023
Accepted: 17 June 2023
Published: 20 June 2023
Copyright: © 2023 by the author.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2023, 13, 1129. https://doi.org/10.3390/coatings13061129
Department of Textile Engineering, Faculty of Engineering, University of Süleyman Demirel,
32260 Merkez, Turkey; suleugur@sdu.edu.tr
Abstract: Large amounts of water, synthetic dyestuffs and chemicals are used in the wet processes of
textile finishing, and at the end of these processes, liquors containing chemical substances create a
waste load. For this reason, it is of great importance to develop new wet-finishing processes that use
less water, dyestuffs and chemicals. For this purpose, the layer-by-layer deposition method (LbL)
was used in this research as an environmentally friendly, sustainable method that can be used in wet-
finishing processes to minimize chemical, water and energy consumption. The dyeing and functional
finishing of cotton fabrics were carried out in one process by the LbL method. Cotton fabrics were
pre-treated with a commercial cationic dye fixation agent and cationic charges were produced on
the fabric surfaces. Reactive and direct dyestuff groups were used in the dyeing process of cotton
fabrics and fluorocarbon was used in the functional finishing process. Eight and 12 dye/fluorocarbon
layered structures were obtained by LbL deposition using a laboratory-type padder. Cotton fabrics
were dyed and finished with the same dyes and fluorocarbon via the padding method and both
samples were compared. The washing, rubbing and light color fastness properties, color strength
and color difference of the dyed samples were tested. Tensile strength, air permeability, SEM graphs,
contact angle, water and oil repellency analyses were performed for the treated fabrics.
Keywords: layer-by-layer; cotton; sustainable; dyeing; functional finishing
1. Introduction
When we look at the textile industry in terms of sustainability, water, chemical and
energy consumption are indisputably the three main issues. Textile dyeing processes
consume excessive amounts of water and leave a large amount of untreatable hazardous
waste, such as salts, hydroxides and unreacted dyes, in the environment. Environmental
pollution associated with the textile industry is seen as a critical global problem and new
technologies and alternative environmentally friendly processes need to be developed to
alleviate this situation [1–7].
The most used dyestuffs in the dyeing processes of cotton textile materials are reactive
and direct dyestuffs. Large amounts of salt are required to increase the adsorption of
dyestuffs used in dyeing cotton, and large volumes of water are required to clean hy-
drolyzed dyes [8,9]. The amount of salt used in the recipe varies between 5 and 125 (o.w.f.)
depending on the weight of the fabric [10].
Different textile dyeing technologies (anhydrous supercritical dyeing, solvent dyeing,
dyeing with liquid ammonia, reverse microemulsion dyeing methods, etc.) have been
developed to prevent water pollution caused by the textile dyeing industry due to excessive
water use. However, these technologies do not provide a solution for reactive dyeing
processes due to the insoluble dyestuff in carbon dioxide or the use of environmentally
unfriendly hydrocarbon solvents [11–17].
Studies to minimize salt and water consumption in dyeing processes include applying
enzymatic processes in fabric preparation, using biodegradable organic salts and different
surface modifications of cotton [18–21].
https://www.mdpi.com/journal/coatings
Coatings 2023, 13, 1129 2 of 11

Generally, weak hydrogen and Van der Waals bonds are effective in binding the reac-
tive dyestuff to cellulose. Through surface modifications of cellulose, such as cationization,
stronger ionic bonds can be obtained that promote dye binding [11]. While the new, posi-
tively charged groups obtained by cationization increase the substantiveness between the
dye and fabric, the uptake of anionic dyes increases significantly [22,23].
The LbL method is based on the alternating deposition of anionic and cationic groups
to form nanometer-sized multilayer coatings on the surface of a charged material through
electrostatic interactions. Nanoparticles, dyes, proteins, polymers, biomolecules, sensors,
etc., can be incorporated into the surfaces of different materials to impart functional proper-
ties. It can be seen that non-planar textile fabrics are studied widely with the LbL technique
because the surface, size and shape of the material to be coated are not limiting factors. In
recent years, researchers have used the LbL method to impart many properties, such as
dyeability [24], antifouling [25], X-ray shielding, electromagnetic shielding and electrical
conductivity [26], antimicrobial [27], flame retardancy [28], UV protection [29], water and
oil repellency and self-cleaning, strength [30], to fabrics containing natural and synthetic
fibers. Regarding the dyeing processes of textiles with LbL, a few papers have been pub-
lished. Cotton fabrics dyed with brightening agents [31], reactive dyes and acid dyes [32]
have been studied in the literature via the LbL method. In some other studies, the LbL
process is used as a pretreatment before dyeing to prevent dye aggregation and to increase
dye uptake for cotton [33] and polyester fibers [24].
The development of an environmentally friendly dyeing process is essential to con-
tribute to the sustainable development of the textile industry. This study aimed to carry
out both the dyeing and finishing of cotton simultaneously with the layer-by-layer coat-
ing method, to minimize water, auxiliary chemical and energy consumption. Reactive
dyestuffs as well as direct dyestuffs are negatively charged; therefore, a positively charged
fluorocarbon was used to achieve the functional finishing properties.

2. Materials and Methods

Bleached woven cotton fabric (plain woven; 138.84 g m2 ; 56 thread cm−1 warp and
31 thread cm−1 weft; yarn count 50/1) was used in the dyeing and finishing processes
(Table 1). Reactive and direct dyes were purchased from NF Chemical, Türkiye, and the
Dyeset Chemical Technologies Joint Stock Company, Türkiye, respectively. Dye fixing agent
Aysol Mordan T (polyamine) was provided by Ayteks Chemical, Türkiye. Fluorocarbon
solution (Rucostar EEE6, C6 -fluorocarbon resin with hyperbranched polymers in a hydro-
carbon matrix, PFOA and PFOS-free, cationic, liquid) was purchased from Rudolf Duraner,
Türkiye. Commercially used chemicals and dyestuffs were used both in the dyeing and
finishing processes according to the classical impregnation principle and in the dyeing and
finishing processes performed according to the layer-by-layer deposition system. For the
impregnation and LbL processes, a laboratory-type horizontal padding machine was used
with a fabric speed of 2 m per minute and 2 bar pressure.

Table 1. Experimental details of the pad–dry–cure and LbL processes.

Dyestuff Process Layer Number

8 (RR/F)8
LbL
Reaktoset Red RFT 12 (RR/F)12
Padding - RR/F
8 (RY/F)8
LbL
Reaktoset Yellow RFT 12 (RY/F)12
Padding - RY/F
Coatings 2023, 13, 1129 3 of 11

Table 1. Cont.

Dyestuff Process Layer Number

8 (RB/F)8
LbL
Reaktoset Brilliant Blue BRF 12 (RB/F)12
Padding - RB/F
8 (DR/F)8
LbL
Direct Scarlet Red F2G 12 (DR/F)12
Padding - DR/F
8 (DY/F)8
LbL
Direct Yellow PG 12 (DY/F)12
Padding - DY/F
8 (DB/F)8
LbL
Direct Blue B2R 12 (DB/F)12
Padding - DB/F

2.1. LbL Dyeing and Finishing Processes

First, the fabric was washed with a non-ionic washing agent and then padded with a
cationic dye fixing agent (Aysol Mordan T) to impart cationic sites to the surfaces of the
cotton fibers. Reactive and direct dyes with three primary colors were used for the dyeing
process with 2 wt %. Reactive dyes that were used for the dyeing contained one –N N–
(azo) bond, vinyl sulfone and monochlorotriazine for the red color, anthraquinone for the
blue color and monochlorotriazine for yellow dye as reactive groups. Direct dyes contained
azo groups, benzothiazoles as reactive groups and SO3 Na as solubilizing groups.
A fluorocarbon solution was used for cationic layers with 50 g/L and pH 4.5. A
laboratory-type padding machine was used for continuous processes for the reactive or
direct dye/fluorocarbon multilayer film deposition process. In the deposition process, the
positively charged cotton fabrics were padded by the following solutions alternately: (a) the
anionic dye solution, (b) deionized water, (c) the cationic fluorocarbon solution, (d) deion-
ized water. This deposition cycle was repeated until 8 and 12 multilayer dye/fluorocarbon
films were deposited on the cotton fabrics; then, the fabrics were cured at 150 ◦ C for 5 min.

2.2. Pad-Dyeing and Finishing Process

The same dyes and fluorocarbon were also applied to the cotton fabric through the
conventional pad-dyeing technique for comparison purposes. In the impregnation method,
the dyeing process was applied first, followed by washing processes, and then impregnation
with fluorocarbon was performed. Dyeing was done according to the impregnation method
with a mixture containing 25 mL silicate, 7.5 mL of caustic soda, 1.5 mL of wetting agent
and 2% of the dyestuff to be used. The unfixed dyestuff was removed by pickling with
0.8 g/L acids and performing 2 hot, 1 warm and 1 cold rinses. Afterward, the fluorocarbon
prepared at 50 g/L with 1 mL/L acetic acid at pH 5 was applied and the fabrics were dried
at 165 ◦ C for 1.5 min and fixed at 165 ◦ C for 2 min. For the process name, “LbL” is used
for the layer-by-layer dyeing and finishing process and “padding” refers to the classic
pad–dry–cure method.
Colorfastness Tests: Dyeing performance was assessed in terms of dry and wet rubbing
fastness (AATCC-8-1996), washing fastness (ISO 105 C06 A1S) with 3 repeats and light
fastness (TS EN ISO 105-B06). The gray scales were used to determine the color change
and staining, yielding the color difference below the samples for rubbing and washing
fastness. The blue wool scale was used to determine the color differences in the samples
for light fastness.
Coatings 2023, 13, 1129 4 of 11

Color Strength and Color Difference: Color strength (K/S) values of the samples were
determined using the Kubelka–Munk formulation (Equation (1), where R: the decimal
fraction of the reflectance of fabric, K: the absorption coefficient, S: the scattering coefficient),
which was programmed in a Minolta 3600d Spectrophotometer (illuminant D65, 10 stan-
dard observers) based on reflectance measurements. The color difference in the treated
sample compared to untreated fabric was evaluated using the L*, a* and b* coordinate
values according to CIELAB; see Equation (2).

1 − R2


K/S = (1)
2R
q
∗
∆ECIELAB = (∆L∗ )2 + (∆a∗ )2 + (∆b∗ )2 (2)
Tensile Strength: The breaking strength of samples in the warp direction at fracture
was tested according to the TS EN ISO 13934-1 Standard (Textiles—Tensile properties of
fabrics, strip method) with a Lloyd LR5K Plus electronic tensile strength machine. The
specimens were prepared in 350 mm × 70 mm dimensions according to the standard and
5 tests were done.
Scanning Electron Microscopy: Microscopic investigations of the selected samples
were carried out using a Quanta 400F scanning electron microscope (SEM) at an acceleration
voltage of 10 kV. The fabric samples were sputter-coated with a 10 nm Au/Pd layer prior
to SEM observation.
Air Permeability: Air permeability was examined with a TexTest Instruments FX 3300
Air Permeability Tester III instrument at 100 Pa pressure, according to the EN ISO 9237
Standard. A circular specimen holder, with an orifice included, was used for the tests,
carried out on an area of 20 cm2 . Ten tests were done for each sample and the average
values were calculated.
Water Repellency: The water repellency of the samples was evaluated according to the
ISO 4920 Standard (Textile fabrics—Determination of resistance to surface wetting—Spray
test) using a spray tester. This test method evaluated the fabric’s resistance to wetting using
a specified volume of distilled or fully deionized water. The spray rating was determined by
comparing the appearance of the samples with a five-grade scale of photographic standards
for resistance to surface wetting (0–5) [34,35].
Oil Repellency: The oil repellency of the samples was evaluated according to the
AATCC 118-2007 Standard (Oil repellency—Hydrocarbon resistance test) via a series of
standard hydrocarbons of different surface tensions, numbered 1 to 8. Hydrocarbon test
liquid drops were placed on the sample surface and the highest numbered test liquid that
did not wet the fabric gave the grade of oil repellency.
Static Contact Angle Measurement: The static contact angle was measured on the
samples using an optical goniometer apparatus; 10 µL distilled water droplets were applied
to the samples at 20 ◦ C. Five different measurements were performed on the samples and
the average values were calculated.
Washing Durability: The samples were washed according to ISO method 105-C10:2006(C)
with 5 g/L nonionic soap solution (with a liquor ratio of 50:1) at 50 ◦ C for 45 min; they
were then rinsed and dried for 5 cycles.

3. Results and Discussion

Due to the pad–dry–cure and LbL dyeing processes, the color strength values (K/S) and
color differences ∆E of the fabrics were measured by spectrophotometer measurements
and the test results are given in Figure 1. The ∆E values obtained for dyeing processes
performed with the pad–dry–cure method and the K/S values of the untreated fabric were
taken as a reference. The ∆E values obtained with direct dyestuffs were much higher than
those for the reactive dyestuffs. In the processes performed with the LbL method, the
number of layers was recorded in all dyed samples in the difference in the ∆E values that
they obtained. The color strength values (K/S) of fabrics dyed by the pad–dry–cure method
Coatings 2023, 13, 1129 5 of 11

with direct dyestuffs could be obtained in approximately four layers by the LbL method
and approximately six layers in reactive dyestuffs. K/S values obtained with DY, DB and
Coatings 2023, 13, x FOR PEER REVIEW
DR were 66.11, 20.34 and 78.52, respectively. With RY, RB and RR, K/S values5 ofof 12
74.86,
24.52 and 52.63, respectively, were measured.

Figure 1.
Figure 1. The
The color
color strength
strengthvalues
values(K/S)
(K/S)and color
and differences
color (ΔΕ)
differences of the
(∆E) fabrics.
of the fabrics.

In general, one of the factors governing the surface wetting behavior is the surface
roughness, and the other is the surface chemical composition. Cotton fabrics create a
coarse, porous, micrometer-sized layer, while the surface roughness required for the hy-
drophobic property can only be achieved with a low-surface-energy coating. In both
 Coatings 2023, 13, 1129 6 of 11

gs 2023, 13, x FOR PEER REVIEW In general, one of the factors governing the surface wetting behavior 6 of 12 is the surface
roughness, and the other is the surface chemical composition. Cotton fabrics create a coarse,
porous, micrometer-sized layer, while the surface roughness required for the hydrophobic
property can only be achieved with a low-surface-energy coating. In both applications
applications performed
performedwithwiththe
thefluorocarbon,
fluorocarbon,ititwas
wasseen
seenthat
thatthe
thefiber
fibersurfaces
surfaceswere
werecov-
covered well and
ered well and smoothly,
smoothly, asas seen
seen in
in the
theSEM
SEMgraphs
graphsgiven
givenininFigure
Figure2.2.However,
However, in in
thethe
LbL
LbL deposition
deposition processes, it was determined that the fibers were more densely coated in such
processes, it was determined that the fibers were more densely coated in such a way that
a way that they were
they connected
were connectedwith each
with other.
each other.

Untreated cotton fabric

(RB/F)12 (DY/F)12

RB/F DY/F
Figure 2. SEM images
Figure of
2. the
SEMuntreated,
images ofLbL- and pad–dry–cure-treated
the untreated, samples.
LbL- and pad–dry–cure-treated samples.

As a result of the
As adyeing
result processes performed
of the dyeing processeswith pad–dry–cure
performed and LbL methods,
with pad–dry–cure and LbL methods,
washing (staining
washing (staining and color change), rubbing (wet and dry) and color
and color change), rubbing (wet and dry) and light fastness fast-
light fastness color fast-
ness tests were carried
ness tests out
wereand the results
carried out andarethe
given in Table
results 2. In in
are given dyeing
Tableaccomplished
2. In dyeing accomplished
with reactive dyestuffs, similar
with reactive test results
dyestuffs, were
similar testfound
resultsbetween both between
were found methods,both
especially
methods, especially
between 12 layers and pad–dry–cure.
between In eight-layer dyeing,
12 layers and pad–dry–cure. the value
In eight-layer differences
dyeing, the valuebetween
differences between
the methods were generallywere
the methods not greater
generallythan
nothalf the value.
greater In the
than half theevaluations
value. In theperformed
evaluations performed
on direct dyestuffs, it was
on direct seen that
dyestuffs, the washing,
it was seen that rubbing and light
the washing, fastness
rubbing values
and light were values were
fastness
much higher andmuchbetter with
higher andthebetter
LbL with
method
thethan
LbL with thethan
method pad–dry–cure method. The method. The
with the pad–dry–cure
main reason that direct dyestuffs are used less often than reactive dyestuffs in commercial
applications is that lower brightness and fastness results are obtained. With the results
obtained, it can be seen that these disadvantages can be partially eliminated with the LbL
Coatings 2023, 13, 1129 7 of 11

main reason that direct dyestuffs are used less often than reactive dyestuffs in commercial
applications is that lower brightness and fastness results are obtained. With the results
obtained, it can be seen that these disadvantages can be partially eliminated with the LbL
method and the commercial applicability of direct dyestuffs with the LbL method may
be increased.

Table 2. Washing, rubbing and light color fastness results.

Washing Fastness Rubbing Fastness

Fabrics Light Fastness
Staining Color Change Dry Wet
(RR/F)8 3/4 4 4/5 3/4 3
(RR/F)12 3/4 4 4/5 3/4 3
RR/F 3/4 4 4/5 4 3/4
(RY/F)8 3 4 4 3/4 3/4
(RY/F)12 3/4 4 4 4 4
RY/F 3/4 4 4/5 4 4+
(RB/F)8 3/4 4 4 4/5 3/4
(RB/F)12 3/4 4 4 4/5 4
RB/F 4 4 4 4/5 4+
(DR/F)8 3 3/4 4/5 4 2/3
(DR/F)12 3 3/4 4/5 4 3
DR/F 2 1/2 1/2 1 2/3
(DY/F)8 3 4 3/4 3 3/4
(DY/F)12 3/4 4 3/4 3 4
DY/F 2 1/2 1/2 1 3
(DB/F)8 3 3/4 3/4 4 3
(DB/F)12 3 3/4 3/4 4/5 3
DB/F 1/2 2 1/2 1 2/3

The untreated cotton fabric did not show water- and oil-repellent properties as ex-
pected. The treated fabrics’ water-repellent properties were measured in the spray test
method and contact angle measurements. While, with the spray test method, textile ma-
terials’ real-time behavior can be tested, contact angle tests show the surface free energy
changes. Spray tests of the treated fabrics were evaluated using the ISO 4920:2012 Standard.
All samples were assessed according to the ISO rating scale, as shown in Table 3. Compared
with the untreated fabric, treated fabrics (after LbL or padding treatment) had good water
repellency, with around ISO 3–4. For LbL-treated samples, with an increase in the number
of layers, the test grade increased too. According to the contact angle results, all the treated
fabrics exhibited good hydrophobic properties, greater than 130◦ for direct dyes and 140◦
for reactive dyes. After five washing cycles, fabrics still showed hydrophobic properties
and the largest angles were found with 12-layer LbL-treated fabrics. The oil repellency
properties of the samples were evaluated using different standard hydrocarbons. Test
results were given according to the largest amount of test liquid that did not wet the fabric.
In particular, with the reactive dyed samples, 7-n-octane degrees were obtained for both
methods. As can be seen from the obtained color yield and fastness values, the reactive
dyestuffs could be coated more successfully with the LbL coating process. With the addition
of more reactive dye in each layer, the number of charged groups to which the fluorocarbon
structure could be attached was also increased. For this reason, it was concluded that the
obtained oil repellency and contact angle values were higher in coatings produced with
reactive dyestuffs compared to direct dyestuffs.
 Coatings 2023, 13, x FOR PEER REVIEW 8 of 12
Coatings 2023, 13, 1129 8 of 11

Table 3. Water repellency, oil repellency and contact angle measurement test results.
Table 3. Water repellency, oil repellency and contact angle measurement test results.
Water Repellency
Water Repellency Grade OilRepellency
Oil RepellencyGrade
Grade ContactAngle
Contact Angle
Fabrics Grade
Fabrics 5 Washing
Treatment Washing Treatment 5 5Washing
5 WashingTreatment 55Washing Washing
TreatmentCycles Treatment Cycles Treatment Cycles
Cycles Cycles Cycles
Untreated fabric
Untreated ISO 0 - - - - -
ISO 0 - - - - -
fabric
(RR/F)8 ISO 4 ISO 3 5 4 141.4 139.8
(RR/F)
(RR/F) 8
12 ISO 4ISO 4 ISOISO 3 4 5 5 44 143.2
141.4 142.4
139.8
(RR/F) RR/F
12 ISO 4ISO 4 ISOISO 4 3 5 6 44 142.7
143.2 138.2
142.4
RR/F(RY/F)8 ISO 4ISO 3 ISOISO 3 3 6 6 45 142.7
143.7 138.2
141.3
(RY/F)
(RY/F)
8 12 ISO 3ISO 4 ISOISO 3 3 6 7 57 143.7
142.9 141.3
142.2
(RY/F) RY/F
12 ISO 4ISO 3 ISO 3
ISO 3 7 7 7 6 142.9
143.4 142.2
137.4
RY/F(RB/F)8 ISO 3ISO 4 ISOISO 3 4 7 6 65 143.4
144.8 137.4
143.1
(RB/F)8 ISO 4 ISO 4 6 5 144.8 143.1
(RB/F)12 ISO 4 ISO 4 7 6 146.6 144.7
(RB/F)12 ISO 4 ISO 4 7 6 146.6 144.7
RB/F ISO 4 ISO 4 7 6 144.9 140.3
RB/F ISO 4 ISO 4 7 6 144.9 140.3
(DR/F)8 ISO 4 ISO 3 3 3 134.0 129.3
(DR/F) 8 12
(DR/F) ISO 4ISO 4 ISOISO 3 3 3 3 33 134.0
134.7 129.3
131.4
(DR/F)12 ISO 4 ISO 3 3 3 134.7 131.4
DR/F ISO 4 ISO 3 4 3 136.3 132.5
DR/F ISO 4 ISO 3 4 3 136.3 132.5
(DY/F)
(DY/F)8 8
ISO 4ISO 4 ISO
ISO 3 3 5 5 4 4 134.2
134.2 132.3
132.3
(DY/F)12
(DY/F) ISO 4ISO 4 ISOISO 3 3 6 6 55 136.9
136.9 132.7
132.7
12
DY/F DY/F ISO 3ISO 3 ISO
ISO 2 2 6 6 5 5 135.4
135.4 131.2
131.2
(DB/F)
(DB/F) 8 8 ISO 3ISO 3 ISO ISO
3 3 4 4 4 4 133.2
133.2 129.7
129.7
(DB/F)
(DB/F)
12 12 ISO 4ISO 4 ISOISO 3 3 5 5 44 134.3
134.3 131.9
131.9
DB/F DB/F ISO 4ISO 4 ISOISO 3 3 5 5 44 133.9
133.9 131.1
131.1

InInorder
order to
to evaluate
evaluate the
theeffect
effectofof
thethe
pad–dry–cure
pad–dry–cure andand
LbLLbL
methods applied
methods to cotton
applied to
fabrics, their air permeability properties were examined and the results are
cotton fabrics, their air permeability properties were examined and the results are given ingiven in Figure
3. As a3.result
Figure of the of
As a result dyeing and finishing
the dyeing processes
and finishing applied,
processes the airthe
applied, permeability values
air permeability
decreased in both methods, but the decrease in these values did not reach significant
values decreased in both methods, but the decrease in these values did not reach significant levels
that affected the comfort properties of the fabrics. As the number of layers increased
levels that affected the comfort properties of the fabrics. As the number of layers increased in the
inLbL
themethod, the values
LbL method, decreased
the values more, more,
decreased especially for thefor
especially results obtained
the results with reactive
obtained with
dyestuffs,
reactive provingproving
dyestuffs, the presence of inter-fiber
the presence connections,
of inter-fiber as shown
connections, in the SEM
as shown in theimages.
SEM
Since cotton
images. fabricsfabrics
Since cotton contain hydrophilic
contain fibersfibers
hydrophilic with with
weakweak
hydrogen
hydrogenbonds, during
bonds, wet
during
processes
wet in industrial
processes in industrialapplications,
applications,they show
they showshrinkage, andand
shrinkage, their air air
their permeability
permeability val-
ues may
values maydecrease
decreaseasasa aresult.
result.

300
Air Permeablity

200
(cm3/s/cm2)

100

0
Untr RR/F RY/F RB/F DR/F DY/F DB/F
eate
d
Padding 276.4 267.2 266.5 269.3 270.7 271.4 273.1
LbL-8 layer 240.6 243 232.8 246.1 249.4 252.6
LbL-12 layer 221.5 220.6 221.8 234.3 230.6 232.7

Padding LbL-8 layer LbL-12 layer

Figure3.3.Air
Figure Airpermeability
permeabilitytest
testresults
resultsofofthe
theuntreated,
untreated,pad–dry–cure-
pad–dry–cure-and
andLbL-treated
LbL-treated fabrics.
fabrics.
Coatings 2023, 13, x FOR PEER REVIEW 9 of 12
Coatings 2023, 13, 1129 9 of 11

The strength properties of untreated and dye-finished samples were measured and
The strength properties of untreated and dye-finished samples were measured and
compared to determine whether the applied treatments weakened the fabrics (Figure 4).
compared to determine whether the applied treatments weakened the fabrics (Figure 4).
It was seen that the tensile strength values decreased by 5.88% for reactive dyestuffs and
It was seen that the tensile strength values decreased by 5.88% for reactive dyestuffs and
4.58% for direct dyestuffs in the process carried out according to the pad–dry–cure
4.58% for direct dyestuffs in the process carried out according to the pad–dry–cure method.
method. The fluorocarbon left the fabric stiff as it cross-linked with the O-H group in the
The fluorocarbon left the fabric stiff as it cross-linked with the O-H group in the amorphous
amorphous region of the cotton. In addition, since the cross-linking reaction of the fluoro-
region of the cotton. In addition, since the cross-linking reaction of the fluorocarbon
carbon
occurred occurred with acid
with acetic aceticadded
acid added
to thetobath
the bath
in theinacidic
the acidic region,
region, it caused
it caused a decrease
a decrease in
in strength
strength [36–38].
[36–38]. AsAsa aresult
resultofofthe
theprocesses
processescarried
carriedout
outaccording
according to to the
the layer-by-layer
layer-by-layer
deposition
deposition principle, it was
principle, it was determined
determined that that there
there was
was anan increase
increase inin the
the breaking
breaking strength
strength
values of 5.41% for reactive dyes and 4.24% for direct dyes. The
values of 5.41% for reactive dyes and 4.24% for direct dyes. The difference here difference hereis is thought
thought to
to be because no extra chemicals were used besides the chemical
be because no extra chemicals were used besides the chemical groups used for dyeing groups used for dyeing
and
and water-repellent
water-repellent finishing.
finishing. Notably,
Notably, therenowas
there was neednotoneed to useacid,
use acetic acetic acid,iswhich
which requiredis re-
to
quired to obtain appropriate
obtain appropriate pH valuespH in anvalues inenvironment.
acidic an acidic environment.
As a result,Asthea result,
greatest the greatest
difference
difference
was the usewas the use
of much of much
fewer fewer chemicals,
chemicals, the creationthe of creation
less waste of and
less the
waste and the
absence of absence
a loss in
of a loss in the physical properties of the textile material. The product
the physical properties of the textile material. The product obtained was dyed and obtained wasgained
dyed
and gained water-repellent properties in a single step, and we also increased
water-repellent properties in a single step, and we also increased its life cycle by increasing its life cycle
by increasing
its strength. its strength.

367.7 368.5 369.3

370 364.4 363.7 365.2
Tensile Strength (N)

360
349.6
350
340 332.6 333.8 334.4
329.1 328.8 329.2
330
320
310
300

Padding LbL-12 layer

Figure 4. Tensile strength test results of the untreated, pad–dry–cure- and LbL-treated fabrics.
Figure 4. Tensile strength test results of the untreated, pad–dry–cure- and LbL-treated fabrics.

4. Conclusions
With the
the development
developmentofoftechnology,
technology,the thefocus
focusof many
of many researchers has has
researchers beenbeen
on sus-
on
tainable andand
sustainable environmentally
environmentally friendly
friendlyproduction
production methods.
methods.While Whilethere
thereare
aremany
manytech-
tech-
nological innovations
innovations that
thatfacilitate
facilitatethe
thedyeing
dyeingandand finishing
finishing treatments
treatments of cotton
of cotton prod-
products,
which are the most used natural fibers in the world, most of the environmentally
ucts, which are the most used natural fibers in the world, most of the environmentally sustainable
options are more
sustainable optionscostly.
are Although
more costly. theAlthough
use of treatment
the useand disposal systems
of treatment by the industry
and disposal systems
is preferred
by as a is
the industry solution,
preferredthese
as asystems
solution,dothese
not offer low-cost
systems do not and fully
offer environmentally
low-cost and fully
friendly approaches.
environmentally For approaches.
friendly this reason, it is this
For necessary
reason,toitdevelop
is necessarymore tosustainable
develop more dyeing
sus-
and wet-finishing
tainable dyeing and technologies.
wet-finishingThe LbL technique
technologies. The offers a new alternative
LbL technique offers a newwhere both
alterna-
dyeing
tive andboth
where functional
dyeingfinishing can be combined
and functional in a be
finishing can single processin
combined and the process
a single processcanand
be
applied with simple modifications on currently used padding
the process can be applied with simple modifications on currently used padding ma-machines.
Commercial chemicals and dyestuffs currently used in the industry were used in all
chines.
processes. In this study,
Commercial the layer-by-layer
chemicals and dyestuffs deposition
currently used method,in thewhich promises
industry weresustainabil-
used in all
ity, was carried
processes. In thisout withthe
study, a padding machine
layer-by-layer used in the
deposition method,finishing
which industry.
promises In sustaina-
this way,
both existing chemicals and technology were used and an innovative LbL
bility, was carried out with a padding machine used in the finishing industry. In this way, dyeing–finishing
process
both was presented
existing chemicals forand
the textile industry
technology withused
were much andlessan water, chemical,
innovative LbLanddyeing–
energy
use, in an eco-friendly manner.
Coatings 2023, 13, 1129 10 of 11

The obtained dyeing performance results gave the same or better values than the
classical pad–dry–cure method. Since the process is completed without adding any textile
auxiliaries to the dyeing solutions used, the dye baths can be reused or a much smaller
waste load can be achieved. The dyestuff color yield values are much higher than those
of the classical method, and the dyestuff usage efficiency also increases. As a result of
the conventional reactive dyeing process, there is no need for multi-step washing steps
that require large amounts of water, chemicals and heating. Fastness properties, which are
the reason that direct dyestuffs are less preferred, could be obtained at very high levels
with the LbL technique. In the processes performed with the fluorocarbon, the same water
repellency, oil repellency and contact angle results were obtained with the classical method;
in particular, the washing durability reached higher levels with the LbL treatment. In the
evaluation of the physical properties of the fabrics after treatment, the losses experienced
for the classical method in terms of the strength values were seen in the LbL technique.
However, improvements in the strength properties were determined due to the fact that
the dyeing process was carried out at an ambient temperature and the fluorocarbon could
be bonded to the cotton fibers without the need for an acidic environment. As a result, by
using only a dyestuff and fluorocarbon, the use of unnecessary auxiliary chemicals was
eliminated and no waste load was created. It can be concluded that the LbL technique is
much better than the conventional pad–dry–cure method in terms of cost, performance,
efficiency and sustainability. For the textile wet-finishing industry, the LbL technique is an
ideal solution for cotton fabrics. Future studies can be carried out on products mixed with
different fiber types so that the method can be adopted at an industrial level.

Funding: This research received no external funding.

Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: This work was supported by the Scientific Research Fund of Suleyman Demirel
University. Project Number: 4496-YL2-15.
Conflicts of Interest: The author declares no conflict of interest.

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