coatings
Article
Design and Characterization of Electroconductive
Graphene-Coated Cotton Fabric for Wearable Electronics
Nujud Mohammed Badawi 1 , Khalid Mujasam Batoo 2, *, Sajjad Hussain 3,4 , Namrata Agrawal 5 ,
Mrutunjaya Bhuyan 1 , Shahid Bashir 6 , Ramesh Subramaniam 1,7, * and Ramesh Kasi 1
Citation: Badawi, N.M.; Batoo, K.M.;
Hussain, S.; Agrawal, N.; Bhuyan, M.;
Bashir, S.; Subramaniam, R.; Kasi, R.
Design and Characterization of
Electroconductive Graphene-Coated
Cotton Fabric for Wearable
Electronics. Coatings 2023, 13, 1601.
https://doi.org/10.3390/
coatings13091601
Academic Editor: Yiping Guo
Received: 26 July 2023
Revised: 9 August 2023
Accepted: 31 August 2023
Published: 13 September 2023
Copyright: © 2023 by the authors.
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, 1601. https://doi.org/10.3390/coatings13091601
1 Centre for Ionics University of Malaya, Department of Physics, Faculty of Science, Universiti Malaya,
Kuala Lumpur 50603, Malaysia; lyde467@hotmail.com (N.M.B.); bunuphy@um.edu.my (M.B.);
rameshkasi@um.edu.my (R.K.)
2 King Abdullah Institute for Nanotechnology, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
3 Institute of Nano and Advanced Materials Engineering, Sejong University, Seoul 05006, Republic of Korea;
shussainawan@gmail.com
4 Graphene Research Institute, Sejong University, Seoul 05006, Republic of Korea
5 Department of Physics, Swami Shraddhanand College, University of Delhi, Delhi 110036, India;
namrata@ss.du.ac.in
6 Higher Institution Centre of Excellence (HICoE), UM Power Energy Dedicated Advanced
Centre (UMPEDAC), Level 4, Wisma R&D, Universiti Malaya, Jalan Pantai Baharu,
Kuala Lumpur 59990, Malaysia; shahidbashirbaig@gmail.com
7 Department of Chemistry, Saveetha School of Engineering, Institute of Medical and Technical Science,
Saveetha University, Chennai 602105, Tamilnadu, India
* Correspondence: kbatoo@ksu.edu.sa (K.M.B.); ramesh@um.edu.my (R.S.)
Abstract: Efficient energy storage is becoming a serious niche area nowadays due to exponential
growth in energy consumption. Different approaches have been developed and implemented to
improve the performance of the devices, in which improving conductivity is a major issue. In the
present work, cotton fabric was converted into a conductive material by incorporating graphene,
using the Layer-by-Layer (LBL) method, followed by heating at 100 ◦ C. The electrical conductivity
of the cotton using different concentrations of graphene was studied. The graphene-coated cotton,
at the 17th layer, with a concentration of 168.36 wt.% resulted in a surface resistance of 0.644 Ω/sq
and retained the maximum resistance even after two months. Scanning electron microscopy (SEM)
and Energy-dispersive X-ray spectroscopy analysis (EDX) were employed to comprehend the surface
morphology and elemental compositions. Fourier transform infrared (FTIR) spectroscopy, UV-vis
absorption, and X-ray diffraction (XRD) were used to determine the structural analysis, which
revealed a good dispersion of graphene in the cotton samples obtained through dimethyl sulfoxide
(DMSO) doping, which reduced the ripple of the cotton. The cotton fabric treated with graphene was
thermally stable, as shown through thermal analysis. From the results obtained, it is evident that
graphene-treated cotton fabric materials show tremendous potential for use in smart textiles and also
as protective clothing.
Keywords: graphene; pure cotton; conductive cotton; resistance; smart textile
1. Introduction
Due to their numerous uses in biomedical devices, sensing and actuation, data process-
ing and communications, energy conversion and storage like batteries and supercapacitors,
and electromagnetic shielding, smart electronic textiles, including conductive textiles, have
attracted a lot of attention. Some of the most important features, apart from the ease of use
of smart and wearable electronic textiles, are electrical conductivity, light weight, and high
flexibility [1]. Repeating cellobiose units give natural cellulosic fibers like cotton their cool,
supple, and biodegradable qualities, which make them useful in a variety of industries [1,2].
Their hydrophilic structure gives them a superior adsorption capacity that is 24–27 times
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Coatings 2023, 13, 1601 2 of 21

their mass. In contrast, cotton’s low UV protectivity, hygroscopicity, and nonconductive

characteristics limit its use in a number of industries. Cotton fabrics with graphene coatings
may be an efficient way to not only remove the restrictions while retaining the comfort of
wearing them but also to add other desired functionalities. A proportion of 95% of cotton
fiber consists of cellulose I (β-1,4-D-anhydroglycopyranose), which is the primary cell wall.
The unique properties of cellulose fibers make them ideal for use in smart textiles due to
their high absorption, low price, and low impurity content, as well as their good mechanical
properties. In the design of smart active materials that conduct electric current, cellulose
fibers are an ideal matrix [2]. Textiles are coated and printed to obtain a functional surface
with different properties using different allotropes of carbon such as graphene [3], carbon
black [3,4], and carbon nanotubes [5] to enhance textile conductivity, of which electrical
conductivity is of great importance for smart textile applications. Among the various textile
materials, cotton is one of the most widely used materials for textiles and clothing. Cotton
has good elasticity and high breathability [3,4]. Cotton is a comfortable fabric and is more
breathable when abraded compared to other fabrics. Cotton has a chemical structure that
consists of active hydroxyl groups, which makes it easy to adjust and hence improve the ad-
hesion and distribution of active substances on the fabric [6,7]. On the other hand, graphene
can meet most of the requirements for use in conductive fillers, ink, and coatings [8] due to
its high mobility [9], mechanical durability [10], and environmental stability. In addition
to the possibility of production at a low cost, the oxygen-containing groups enhance the
action of the treated tissues of both graphene and cotton to form hydrogen bonds with each
other, thus enhancing the adhesion. Some methods for manufacturing conductive fabrics
have been reported, including the layer-by-layer as well as dip drying method [11]. These
are the most frequently used processes in which graphene is absorbed on the surface of
tissues by the action of capillaries, forming hydrogen bonds with the cloth [12,13].
Graphene-modified fabrics have drawn a lot of interest due to their numerous func-
tional attributes. Particularly, cotton fabrics coated with graphene show great promise for
a range of applications, including smart textiles, protective clothing, and sensors. With
hexagonally arranged carbon atoms that are sp2 -hybridized, graphene is a monotonically
thick 2-D nanomaterial. It has an exceptionally high surface area, Joule heating capacity,
mechanical strength, thermal stability, UV protectivity, and electrical conductivity. A po-
tential strategy for fully utilizing graphene’s special qualities is to coat it onto fabrics. The
unique properties of graphene can be transferred to fabrics modified with graphene if it
can be coated on them with a high bonding strength [1,8]. Each cotton cellulosic monomer
consists of three chemically reactive hydroxyl groups that can interact with graphene. As
active binding sites for 3 chemical bonding between cotton, graphene, and coupling agents
as well as for interfacial interaction, significant amounts of hydroxyl groups on cotton’s
surface and the oxygen-64-bearing groups in graphene are present. To ensure a durable
coating, it is essential to strengthen the bond between graphene and cotton. According
to some studies, silane coupling agents were used to increase the adhesion of minerals
to polymers [10,11]. The 3-glycidyloxypropyl tri methoxy silane, an organosilane with
hydroxy on the surface, acts as a coupling agent to reinforce the bonding force between
graphene and cotton through a layer of the single-molecule membrane [12,13]. As a result,
bacteria may come in contact with cotton surfaces, defeating the antibacterial properties of
the fabric [14]. Thus, it has become necessary to modify cotton fabric so that the drawback
of conventional cotton fabric can be addressed and the antibacterial activity can be given a
boost [15].
Increasing the layers/coatings of graphene on fabric leads to an increase in conduction
or equivalently a reduction in resistivity or resistance. Several researchers have contributed
to this interesting and flourishing field of conducting fibers in recent times. Graphene
Oxide (GO) was applied to cotton fabric by Khalilabad et al. [16] before being reduced by
Na2 S2 O4 to produce graphene. It was discovered that the surface resistance decreased by
almost three orders of magnitude from 201.1 to 0.374 k cm−1 as the number of graphene
coatings was increased up to 20. When they used C6 H8 O6 as a reducing agent, similar
Coatings 2023, 13, 1601 3 of 21

results were obtained. The surface resistance was found to reduce to 0.84 from 400.2 kΩ/sq
as the number of coatings was increased to 20 [17].
Ba et al. [18] prepared few-layer graphene (FLG)-coated cotton cloth and measured its
conductivity. It was observed that the electrical conductivity increased (or surface resistivity
decreased) from 1500 S m−1 to 7000 S m−1 when the amount of FLG was changed from
3 wt% to 6 wt% in the composite.
Modified cotton fabrics were prepared by Kowalczyk et al. [19] through xerogel
coatings of Gr or rGO. The Gr coating of 1.5 wt% was found to result in the lowest surface
and volume resistance of about 3.0 × 105 Ω and 1.7 × 104 Ω, respectively, after calendering.
Woltornist et al. [20] used an interfacial trapping method to fuse fabric with FLG/graphite
(though cotton was not used by them). The sheet resistance measured was lowest at an
FLG loading of 10.7 wt%, while at 2.5 wt%, it was four orders of magnitude higher.
The brush-coating-drying method was used by Alamer et al. [21] to prepare conductive
textiles from cotton using graphite and solvents DMSO and dimethylformamide (DMF).
The lowest value of sheet resistance obtained by them was 0.47 kΩ/sq.
In the current work, the conductive cotton fabric was made by coating it with graphene
layer-by-layer; treating it with sodium dodecylbenzene sulfonate (SDBS) as a dispersing
agent and dimethyl sulfoxide (DMSO) to weaken the ripple of the cotton fibers, allowing
for the better incorporation of graphene on cotton fibers; and then heating it for an hour at
100 ◦ C. The structural, morphological, and thermal characteristics of the graphene-coated
cotton fabric were determined using experimental techniques like SEM, EDX, XRD, FTIR,
TGA, and DSC. To assess the potential use of the coated material as smart wearable clothing
and in the design of contemporary electrical/electronic circuitry, the conductivity of the
materials was determined using a four-line probe and was monitored for two months.

2. Materials and Methods

2.1. Materials and Chemicals
The initial flake size of the graphene that was purchased from Sigma Aldrich was
100 mesh. Dimethyl sulfoxide (DMSO) (assay 99.9%; Sigma Aldrich, Glasgow, UK) was
used as an additive to increase the conductivity of graphene, and 100 gm−2 of 100% pure
cotton fabric was provided from Egypt. From Sigma Aldrich in the UK, sodium dodecyl
benzene sulfonate (SDBS) was bought. As a solvent, deionized water (DI) was employed.

2.2. Preparation of Graphene

The graphene solution was prepared in a beaker containing 1 g of graphene, which
was mixed with 50 mL of deionized (DI) water for 30 min with the help of a sonicator at
50 ◦ C until the mixture turned into a homogenous black solution. An amount of 1 mL of
DMSO was added to the solution while gently stirring it at 45 ◦ C for 5 min. An amount of
0.5 g of the anionic surfactant and a few drops of sodium dodecylbenzene sulfonate (SDBS)
were added to the mixture, to exfoliate the graphene. The surfactant acted as an exfoliant
and stabilizer by binding it to the graphene surface, after which the solution was ready
and applied directly to the pure cotton. The procedure of graphene solution preparation is
shown in Figure 1.
At room temperature, water has a high surface tension of 72.8 mJ m−2 . Therefore, ex-
foliating graphene with just water is not possible. The range of 40–50 mJ m−2 is considered
good for the same. Interfacial tension needs to be minimized between graphene and the
solvent, which is achieved through the addition of DMSO (DMSO has a surface tension of
42.9 mJ m−2 at room temperature). A binary mixture of water and DMSO, along with high
temperature, helps to reduce surface tension [22].
Surfactant is further added to water to reduce its surface tension. It is achieved with
the help of SDBS. The water/surfactant system helps in the exfoliation and stabilization of
graphene. Water is also a good dispersion medium for graphene [23].
Coatings 2023, 13, 1601 4 of 21

Figure 1.
Figure 1. Diagram
Diagramofofgraphene
graphenesolution preparation.
solution preparation.

2.3. Fabrication of Graphene-Coated Cotton

The prepared graphene solution was deposited on cotton using the Layer-by-Layer
(LBL) method, which is eco-friendly. In this method, graphene was distributed on the
cotton layer-by-layer at room temperature. As the layers increased, the amount of material
adhering to the cotton increased, up to the 17th layer. Hence, the number of suitable
drop casting was determined to be 17. By using this (LBL) technique, the sample had a
comparatively high level of water resistance after modification. The first layer of graphene
was coated on cotton fabric using drop-casting followed by drying, to obtain electrical
resistance, with an effective area of 1 × 1 cm2 for the cotton sample. Different concentra-
tions of graphene were applied to the cotton material to evaluate the effect on electrical
conductivity. To calculate the amount of graphene loading, the cloth was weighed before it
was dipped in graphene ink and after it had dried completely. The treated sample was left
at room temperature for 25 min to ensure that the cotton was impregnated with the solution
and then dried in oven air for 1 h at 100 ◦ C to increase the concentration of graphene on
the cotton sample (Figure 2). The resistance of cotton fabric treated with graphene was
measured using a four-line probe. The same steps were followed until data from
Coatings 2023, 11, x FOR PEER REVIEW 1716layers
2 of
were tabulated.

Figure 2.
Figure 2. Diagram
Diagramofofdeposition
depositionof of
graphene solution
graphene on cotton.
solution on cotton.
Coatings 2023, 11, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/coatings
Coatings 2023, 13, 1601 5 of 21

2.4. Characterization and Measurement

After the cotton was subjected to LBL coating, the surface morphology of graphene-
coated cotton and pure cotton was examined using scanning electron microscopy (SEM;
JEOL, JSM-6380LA). In addition, energy-dispersive X-ray analysis (EDX) was performed
on pure and graphene-treated fabric to ensure the purity of the samples.
The Fourier transform infrared spectroscopy (FTIR) spectra of pure cotton and cotton
with 17 layers of graphene were used to identify the functional groups of the two types of
cotton, and the Hewlett Packard HP-8453 spectrophotometer was used to conduct the UV-
vis spectroscopy. The structural analysis of the pure and coated cotton was conducted using
X-ray diffraction (XRD) technology. A Paralytical X-ray instrument with monochromatic
X-ray Cu Kα of wavelength λ = 1.541874 Å was used for the same. Scherrer’s formula was
used to estimate the size in the vertical direction [24].

Kλ
D= (1)
βcosθ

where K = 0.98, λ is the X-ray wavelength, β is the full-width at half-maximum, and θ is the
diffraction angle in radians.
On pure cotton and cotton fabrics treated with graphene solution, thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC) were also carried out using
TGA 1000 and DSC 8000 instruments, respectively. To study the electrical properties of the
pure and treated cotton fibers, the four-probe method was used. The electrical resistances
of the samples were calculated from I-V curves, at a temperature of 25 ◦ C and relative
humidity of 65%. The probes tapped the head at predetermined intervals, and the sweep
resistances of the threads were determined by applying Ohm’s law to the I-V profile. I-V
characteristics were run on each 2.5 cm distance to confirm the results. The sheet resistance
was calculated using the formula:
w
Rs = R (2)
d
where w is the sample’s width (2.5 cm), d is the distance between the leads (0.35 cm), and
R is the resistance [13]. An HP 34401A multimeter was used to measure the potential
difference after applying current using a Keithley 2400 m. The concentration of graphene
in the conductive cotton after each layer was calculated using Equation (3):

C2 − C1
C (wt %) = × 100 (3)
C1

where C2 is the weight of the conductive graphene cotton and C1 is the weight of the
pristine cotton.
Cotton fabrics treated with graphene have exceptional electrical and mechanical
properties. As a result, these can be utilized in industry in place of conductive wires. To
power an LED, a conductive cotton fabric was incorporated into an electrical circuit.

2.5. Mechanical Testing

Tensile tests were performed using Microster (N200, Duben), (Norwood, MA, USA)
on cotton samples treated with graphene with a thickness of 0.6 mm.
Stress is defined as the force per unit area and is expressed as N/m2 or Pascal (Pa), an
SI unit. Tensile stress can be calculated using this formula:

F
σ= (4)
A
where σ is stress (in newton per square meter), F is the force, and A is the cross-sectional
area of the sample.
Coatings 2023, 13, 1601 6 of 21

Extension per unit length is the definition of strain. Furthermore, because it is a ratio
of lengths, it lacks units [13].

∆L
ε= and ∆L = L − L0 (5)
L0

where L0 is the length of the fiber before stretching, L is the length after stretching, and ε is
the strain. The distance between these two lengths is denoted by ∆L.

3. Results and Discussion

3.1. Graphene-Coated Cotton Fabric Preparation
Graphene can form chemical bonds with cotton, making it a potential material for
smart textiles. Here, the graphene-coating was performed on the cotton using a layering
method where the chemical bonds of the graphene sheets on the surface of the fabric have
fixed structures. Graphene with its hydroxyl, epoxy, and carboxylic functional groups
makes it easily dispersible in water. Some specific functional groups present in graphene
such as carboxylic acid, carbonyl moieties, C-OH, C-O-C, as well as C-O facilitate the prepa-
ration of graphene-modified cotton fabrics. The graphene is absorbed into the cotton fabric
layer-by-layer, and the resulting fabric is called cotton-graphene due to the bonding of the
graphene sheets on cotton, as depicted in Figure 3. Finally, the cotton is heated to activate
the bonds between the graphene and cotton fibers to form a crosslinking network that
includes graphene particles, hence causing chemical crosslinking. As shown in Figure 3b,
after being treated with graphene, the color of cotton fabric changed from white to black,
demonstrating that this material bonds with cotton via the electrons in the hydroxyl
Coatings 2023, 11, x FOR PEER REVIEW 3 ofgroup
16
in cellulose, breaking one of the C-O bonds in the graphene sheets [24].

Figure 3.
Figure 3. The
The chemical
chemicalstructure:
structure:(a)(a)
graphene and
graphene cotton,
and andand
cotton, (b) the
(b) color of pure
the color cotton
of pure changing
cotton to
changing
black after being treated with graphene.
to black after being treated with graphene.

Cotton obtained from graphene-coating can incubate nanostructured energy materials.

The LBL method, which is one of the methods used to make different materials, is effective
with cotton fabric (Figure 3). In addition, conductive cotton was prepared using 17 layers of
graphene solution because of the strong interaction of the π–π bond between graphene and
pure cotton. Graphene is a good conductor and, due to the non-positional electrons in the π-
orbitals, graphene is formed through sp2 -hybridization. The acidity of the β and γ hydroxyl
groups increased after the first layer of graphene was applied to cotton through the electron
recovery chain. To increase the likelihood of bonding between the bacterial cell and the
graphene sheet, the graphene solution was uniformly coated on the stable and pure cotton to
Coatings 2023, 13, 1601 7 of 21

a total of 17 layers. Pore formation plays a significant role in DMSO’s mechanism of action,
which accounts for both DMSO’s significant enhancement of membrane permeability to
hydrophilic molecules and its cryoprotectant activity. Strong dynamic charge pairing
between the phosphate and choline groups can be seen in phosphatidylcholine bilayers that
lack DMSO. There is thinning and expansion of the bilayer through DMSO. This encourages
the permeation of solutes, particularly hydrophobic substances, across the membrane. The
path length is shortened and there is increased fluidity in the interior of the membrane,
leading to easy diffusion.
By incorporating graphene into cotton, agglomeration on the cotton surface is reduced
to an optimal ratio, which is necessary to achieve desired properties. Due to the strong
interaction of bonds between graphene and cotton fabric, the electron transfer efficiency of
cotton is greatly improved, and the graphene solution prepared using DMSO and SDBS
can reduce the stacking of cotton fiber, making it suitable for many potential applications
including protective clothing, health monitoring, motion sensing, and sportswear.

3.2. Surface Micro-Morphology of the Cotton Fabric

SEM was used to examine the surface morphology of the cotton that had been treated
with graphene and pure cotton. Figure 4a shows an image of a pure cotton fiber. The
surface of the cotton was found to be smooth and clean before it was treated with graphene
and the fiber was reverse-twisted along the longitudinal direction. Pure cotton has a tightly
woven, fibrous structure, as shown in Figure 4a. Graphene affects the shape of the surfaces
of the fibers. Figure 4b presents the first layer of the coating. With the increase in the
proportion of graphene, we observed better dispersion and adhesion to the cotton fibers.
The surface of the cotton-treated sample showed the distribution of a graphene layer on
the cotton surface. When dipped in graphene solution, the surface of the cotton fabrics
maintained their original pure structure, suggesting that a single layer of graphene did
not affect the fabric structure, while it became rough as more graphene layers were added.
The cotton surface became rougher after being covered by 17 layers of graphene, as seen in
Figure 4c. When treated with graphene, the surface of the cotton showed graphene clusters,
making the cotton surface rough, thus generating a dual-size cotton surface structure. Due
to the bonds between graphene and the cotton fiber, the electron transfer efficiency in the
composite fibers greatly improved (Figure 5) [24]. Graphene reduced the stacking of the
textile fibers through the perfect distribution of the graphene on the cotton sample. It is
observed that the graphene coating was well distributed on the cotton surface [25]. Also, a
decrease in cotton fiber ripple was observed due to the presence of DMSO with graphene.
The dip-coating continued to form the layers, and a high concentration of coating was
formed on the cotton fibers [26]. It is necessary to note a wide distribution of the size of the
cotton sample after processing with graphene layers, and with more layers, the average
size of the diameter of the cotton increased and remained very stable.
 Coatings 2023, 11, x FOR PEER REVIEW 4 of 16

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Figure 4. Scanning electron microscopy images of pure cotton fiber (a) before treatment and (b,c) after
Figure 4. Scanning electron microscopy images of pure cotton fiber (a) before treatment and (b,c) after
treatment.
treatment.

Figure5.5.
Figure Schematic
Schematic representation
representation of the formation
of the formation of bondsgraphene
of bonds between between graphene
and and cellulose
cellulose (cotton)
fiber.
(cotton) fiber.

3.3. EDX Analysis

On pure cotton and cotton treated with graphene, energy-dispersive X-ray spec-
troscopy measurements were made to ascertain the purity and elemental makeup of the
samples. As shown in Figure 6a, the spectra of the pure cotton samples have peaks at
energies of 0.277 keV and 0.525 keV, respectively, indicating the presence of the elements
carbon and oxygen [27]. Figure 6b shows the EDX pattern of the graphene-treated cotton.
An additional peak, apart from carbon and oxygen peaks, is seen at 2.307 keV for the
element sulfur, which is due to the presence of graphene along with DMSO and SDBS.
Coatings 2023, 13,
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x FOR PEER REVIEW 6 of 16 9 of 21

Figure 6. (a) EDX pattern of the untreated cotton and (b) EDX pattern of the graphene-coated cotton
Figure 6. (a) EDX pattern of the untreated cotton and (b) EDX pattern of the graphene-coated cotton
after the 17th layer.
after the 17th layer.
3.4. FTIR Characterizations of the Graphene Cotton Fabric
Fourier transformation infrared (FTIR) spectroscopy was performed in the frequency
range of 700–1800 cm−1 for both pure cotton and graphene-treated cotton, as shown in
Figure 7. The peaks observed at 1300 cm−1 , 1320 cm−1 , 1120 cm−1 , and 1680 cm−1 are
attributed to the C-OH, C-OH, C-O, and C-H bonding groups, respectively. It should
be noted that the O-H bonds have significantly higher stretching frequencies than their
heavy-atom equivalents.
Coatings
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Figure 7. FTIR
Figure spectra
7. FTIR of (a)of
spectra pure
(a) cotton and (b)and
pure cotton cotton
(b) that hasthat
cotton beenhas
coated
beenwith graphene
coated with after 17
graphene after
layers.
17 layers.

Due to the stretching of the C-H, C-O vibrational modes, and -OH, the spectrum of
pure cotton exhibits significant peaks at 1300 cm−1 , 1100 cm−1 , and 1000 cm−1 , respectively.
The C-H vibrational modes, C-H bending (deformation stretching), and C-H vibrational
modes, which are weak signals, are also seen at 900, 868, and 800 cm−1 , respectively.
Further, the bands seen in pure cotton at 750 and 710 cm−1 are attributed to the I and I
phases, respectively. In contrast, cotton treated with graphene layers displays a strong
band at 1730 cm−1 due to the C-O stretching vibrations, and the signals at 1270, 1680, and
810 cm−1 are attributed to the symmetric and asymmetric stretching vibrations of the C-O
bond, which are absent from the original cotton sample. In addition, peaks observed at
1400 and 1125 cm−1 correspond to the asymmetric and symmetric stretching vibrations of
the C-H bond [28,29].
Other bands at 1730 and 1372 cm−1 are represented by symmetric and asymmetric
stretching vibrations of C=O and C-O-C, respectively. Additionally, the non-oxidized
graphitic domain’s aromatic bending vibration of unsaturated C=C is blamed for the
1637 cm−1 peak. Although the FTIR spectrum of cotton with 17 layers of graphene is
similar, the intensities of the diffraction peaks decrease as a result of the connection between
the cotton and the graphene sheets. With the characteristic transmittance bands for oxygen
functional groups, such as C=O (1700 cm−1 ) and C-O-C (1226 cm−1 and 1047 cm−1 ) found
in graphene, the carbon materials further support the XRD findings. Further, medium
bands are observed in the region from 1375 to 1280 cm−1 due to the C-H bending from
the CH2 group [24]. The peaks at 1730, 1680, and 1270 cm−1 in the spectrum of the cotton
sample indicate the presence of graphene in the grafted cotton fibers. Although these
ranges did not change after treatment with graphene, the results indicate that the ratio
Iα /Iβ increased with the addition of graphene to pure cotton. The outcomes are consistent
with the X-ray data [25].

3.5. UV-Vis for Graphene-Based Cotton

The photoreduction of RZ as a function of UV light (350 nm) exposure time was used
to assess the photocatalytic activity of graphene-coated cotton fabrics. Redox indicator RZ
is utilized in a variety of biological assays.
Figure 8 depicts the UV-vis spectroscopy of graphene, with the maximum absorption
peak at 246 nm, which is attributed to the aromatic C-C bond π–π * transitions. The band gap
energy of 3.26 eV, in the UV range, is determined from the UV-vis absorption spectra [25,26].
Coatings 2023, 13, 1601 11 of 21

The figure displays the UV-vis spectrum of cotton fabrics made from pure cotton and cotton
fabrics coated with graphene [28]. Due to the good UV absorbance property of graphene,
Coatings 2023, 11, x FOR PEER REVIEW 8 of 16
the absorbance of UV light (200–400 nm) in the spectrum of graphene-coated cotton fabrics
is significantly higher than that of pure cotton fabrics.

Absorbance

Cotton
Graphene
Cotton/Graphene

200 300 400 500 600 700

Coatings 2023, 11, x FOR PEER REVIEW 9 of 16
Wavelength(nm)

Figure
Figure 8. UV–vis
8. UV–vis spectrum
spectrum of graphene
of graphene andspectra
and UV–vis UV–vis of spectra of pure
pure cotton fabriccotton fabric and graphene-
and graphene-coated
cotton.
coated cotton.

3.6. X-ray
3.6. X-rayDiffraction
Diffraction
Figure99presents
Figure presents
thethe XRD
XRD pattern
pattern of pure
of the the pure cotton
cotton and treated
and treated cotton sample
cotton sample with 17 with
17 layers
layers of graphene.
of graphene. TheThe
XRDXRD pattern
pattern reflects
reflects the changes
the changes in characteristic
in the the characteristic diffraction
diffraction
peak
peak after
aftertreatment
treatmentwith
withgraphene.
graphene.

X-raydiffraction
Figure9.9.X-ray
Figure diffraction pattern
pattern of of pure
pure cotton
cotton strands
strands (the(the black
black line)line) and graphene-coated
and graphene-coated cottoncotton
with 17
with 17layers
layers(the
(thered
red line).
line).

The strong diffraction peaks at 2θ = 19.6◦ , 21.5◦ , 22.5◦ , and 36.5◦ are the characteristic
peaks of pure cotton with major reflections at Miller indices (1–10), (110), and (020), re-
spectively. The peaks at 2θ = 12.2◦ , 25.9◦ , and 36.8◦ represent (111), (200), (220), and (222)
planes of cotton with 17 layers of graphene, respectively. The XRD pattern of graphene
has a strong and well-defined peak at 2θ = 25◦ and 27◦ . At 2θ = 26.6◦ , there is a low peak
with lower intensity in the graphene parent sample, demonstrating that the introduction
of oxygen functional groups, such as epoxide, hydroxyl, and carboxylic groups, increased
the interlayer spacing between the graphene layers. For cotton with 17 layers of graphene,
a narrow, sharp peak is observed at 22.22◦ , with inter-crystalline spacing d = 0.399 nm,
Coatings 2023, 13, 1601 12 of 21

due to the presence of a typical graphene crystal structure [29,30]. As observed from the
high-intensity peak of the graphene-coated sample, the diffraction peak disappears and
a new diffraction peak appears at 15.08◦ , with an inter-crystal spacing d value equal to
0.8945 nm, which indicates the introduction of oxygen functional groups [31,32]. These
oxygen-containing groups combine with water molecules and cotton fiber samples through
hydrogen bonding with graphene, which has a hydrophilic property.

3.7. Thermal Analyses (TGA and DSC)

To investigate the thermal stability and pattern of material degradation of pure cotton
samples and cotton treated with graphene, TGA and DSC analyses are crucial tools. The
thermogravimetric measurements were carried out within the 25–600 ◦ C range depicted
in Figure 10 (a,b). The thermal patterns of cotton and cotton with 17 layers of graphene
are shown in these graphs. The figure makes it clear that all of these materials burned
completely and without leaving any residue in the air atmosphere before 550 to 600 ◦ C,
indicating their high purity. The thermogram of pure cotton in Figure 10 (a) demonstrates
that the initial phase of weight loss takes place between 100 and 380 ◦ C. Based on the
decomposition temperatures of the key mass loss events in the sample—roughly <100 ◦ C
for water elimination—the events can be explained. The second stage of weight loss is
observed at 400 ◦ C due to the removal of oxygen functional groups and 400–600 ◦ C can
be linked to the oxidative pyrolysis of the carbon framework, such as epoxy (C–O–C),
which turns into molecules of gas like CO2 and H2 O and hydroxyl (–OH) [28]. The thermal
stability of graphene-coated cotton was analyzed, which reveals the higher thermal
Coatings 2023, 11, x FOR PEER REVIEW 10 ofstability
16
and decomposition of coated cotton at high temperatures.

Figure 10.
Figure 10. TGA
TGAthermograms
thermogramsofof
(a)(a)
pure cotton
pure andand
cotton (b) (17-layer) graphene-coated
(b) (17-layer) samples.
graphene-coated samples.

Additionally, cotton with 17 layers of graphene is highly thermally conductive, and the
Seebeck coefficient and figure of merit of graphene are high, which facilitates the conversion
of electrical current to heat [28].
The treated cotton decomposes in two stages, the first stage (20 to 150 ◦ C) in which
the absorbed water molecules leave and the second stage (450 to 490 ◦ C) in which the
coated graphene starts to decompose. In comparison, it is seen that the weight loss in the
pure cotton sample is significantly less than that in the graphene-coated cotton [29]. This
is because the number of oxygen-containing functional groups in graphene fiber, such as
hydroxyl (OH) and epoxy (C-O-C), is higher in the coated sample than in the pure sample.
Also, there is combustion of carbon present in graphene that leads to a loss in weight.
In the DSC analysis, it is noted that graphene-treated cotton fibers are flame-retardant
when the decomposition temperature is above 400 ◦ C. Also, it is observed that the pure
cotton fiber yarns are subjected to changes in the heat flow pattern when the temperature
 graphene starts to decompose. In comparison, it is seen that the weight loss in the pure cot-
ton sample is significantly less than that in the graphene-coated cotton [29]. This is because
the number of oxygen-containing functional groups in graphene fiber, such as hydroxyl
(OH) and epoxy (C-O-C), is higher in the coated sample than in the pure sample. Also, there
is combustion of carbon present in graphene that leads to a loss in weight.
Coatings 2023, 13, 1601 In the DSC analysis, it is noted that graphene-treated cotton fibers are flame-retardant 13 of 21
when the decomposition temperature is above 400 °C. Also, it is observed that the pure cot-
ton fiber yarns are subjected to changes in the heat flow pattern when the temperature falls
from 360 °Cfrom
falls to 340360
°C, ◦as
Cshown
to 340 in Figure
◦ C, 11. The
as shown inresults
Figureindicated
11. The that the thermal
results stability
indicated that the thermal
of the graphene-treated cotton improved with the increase in graphene layers.
stability of the graphene-treated cotton improved with the increase in graphene Hence, gra- layers.
phene-treated cotton has better thermal stability and a higher decomposition temperature.
Hence, graphene-treated cotton has better thermal stability and a higher decomposition
temperature.

-1
Heat Flow (mw)

-2

-3

-4
(b)
(a)
-5

-6

-7

-8
0 50 100 150 200 250 300 350 400 450
T °C

Figure 11. DSC thermograms of the (a) pure cotton and (b) graphene-coated samples after 17 layers.
Figure 11. DSC thermograms of the (a) pure cotton and (b) graphene-coated samples after 17 layers.
3.8. Electrical Conductivity of the Cotton Fabrics
The four-line probe method, at a temperature of 25 ◦ C, was used to investigate the
effective resistance of cotton with 17 layers of graphene and to study the electrical properties
of composite cotton, using the relation Rs = R (w/d). The pure cotton sample showed no
electrical conductivity since it is an insulating material. However, after treatment with
graphene, the surface resistance was found to be between ~370.8 Ω/sq and ~0.09 Ω/sq, as
in Figure 12 and listed in Table 1 [28]. The higher conductivity of graphene-treated cotton
is attributed to the presence of co-activators (DMSO), which catalyze the morphological
changes. It organizes the cotton fibers, allowing greater penetration of graphene into
the cotton fibers, resulting in better charge transport. Additionally, it might be because
cotton and graphene’s various functional groups successfully form a chemical bond [26–28].
The effective use of graphene is also demonstrated by the high electrical conductivity of
treated cotton. Considering the higher electrical properties of treated cotton, excellent
potential applications of the material are expected in the fields like sensors, supercapacitors,
the electronic industry, and smart clothing as wearable textiles [29,33]. Moreover, both
DMSO and SDBS also act as plasticizers that redirect cotton fibers in addition to stabilizing
graphene at higher temperatures and allowing a regulated conduction mechanism deep
inside through the improvement of bonds between cotton and graphene [34]. Increasing
the concentration of graphene layers increases the stability of graphene in the cotton sample
and fills the spaces between the fibers, thus enhancing the electrical conductivity of the
fabric, as listed in Table 1.
 tronic industry, and smart clothing as wearable textiles [29,34]. Moreover, both DMSO and
SDBS also act as plasticizers that redirect cotton fibers in addition to stabilizing graphene at
higher temperatures and allowing a regulated conduction mechanism deep inside through
the improvement of bonds between cotton and graphene [35]. Increasing the concentration
of graphene layers increases the stability of graphene in the cotton sample and fills the
Coatings 2023, 13, 1601
spaces between the fibers, thus enhancing the electrical conductivity of the fabric, as listed14 of 21
in Table 1.

Figure 12.
Figure 12.(a)
(a)The
Thesheet
sheetresistance
resistanceof cotton fabric
of cotton treated
fabric with with
treated different concentrations
different of graphene
concentrations at
of graphene
17 layers. (b) Nyquist plots of the cotton/graphene and (c) fitting the spectra of the cotton fibers
at 17 layers. (b) Nyquist plots of the cotton/graphene and (c) fitting the spectra of the cotton fibers treated
with graphene with an electrical equivalent circuit.
treated with graphene with an electrical equivalent circuit.

Table 1. Dependence of conductive cotton fabric sheet resistance and graphene cotton resistance.

Layer C (wt.%) R (Ω) RS (Ω/sq)

1 10.7 370.8 2649
2 12.5 149 1065.5
3 14 104.9 749.
4 25 34 243.6
5 26.5 28.8 206
6 28.6 20.9 149.5
7 34 10 72
8 46 5.89 42
9 50 1.50 10.7
10 54.6 1 10
11 55.8 0.66 4.7
12 77 0.4 3
13 83.7 0.19 2.9
14 102 0.17 2.5
15 135.5 0.15 2.06
16 173.8 0.1 1.8
17 186 0.09 0.6

The impregnation process also leads to isotropic electrical conduction throughout

the cotton [34,35]. The nanoparticles behave like an electrical insulator that shows a plate
resistance higher than 370.8 Ω corresponding to a sheet resistance of 2649.1 Ω/sq. Also, a
sudden change in conductivity corresponds to an increase in the graphene concentration at
168.36 wt.%, where electro-filtration occurs, leading to a surface resistance value around
0.0901 Ω at the 17th layer. At this concentration, the composite sample behaves like
an ohmic conductor and exhibits the lowest resistance value, as mentioned in Table 2.
Improvements in the resistance value are of great importance for practical purposes. A
comparison of previously reported work on cotton/graphene-treated samples with the
Coatings 2023, 13, 1601 15 of 21

present work based on their method of preparation and electrical resistivity is presented
in Table 3. Additionally, the graphene-treated cotton fibers’ ionic conductivity at room
temperature was calculated. Because graphene enhances ionic conduction and supports
ionic diffusion through polymer networks along cellulose strands in pure cotton, the
electrode acts like an ionic conductor as a result of its presence [36]. Due to the high
absorbency of the composite cotton and graphene, the three-dimensional structure’s high
porosity increases its capacity to hold water, resulting in smoother pathways for ion
transport. As a result, cotton around the charged groups is easily permeable to electrolytic
ions, increasing ionic conductivity. At room temperature, the cotton treated with graphene
has an ionic conductivity of 9.2 × 10−2 S cm−1 , as shown in Figure 12b. A straight line
that is parallel to the hypothetical axis is visible [37,38]. An equivalent circuit (shown in
Figure 12c) represents the impedance characteristic of the observed impedance of the coated
cotton with graphene, where a RC parallel group having resistance R in Ω, is connected
in series with a capacitor in electrical circuit. Angles less than 90◦ cause vertical straight
lines to appear for capacitors. The observed linear trend that is increasing steadily can be
explained by the large surface area of graphene.

Table 2. The sheet resistance of graphene cotton fabric at an optimum concentration at 17th layer.

C (wt%) R (Ω) Rs (Ω/sq) log c log Rs

168.3 0.090 0.644 2.226 −0.1909

Table 3. Comparing the current work to previously published research on cotton and graphene.

Material Method Electrical Resistivity References

Cotton cellulose coated with graphene Dip-pad-dry 91.8 kΩ/sq [39]
Cotton fabric (SCF)/graphene oxide (rGO) Dip coated 40 Ω/sq [40]
Graphene oxide (RGO)-coated-copper (Cu)/silver
Dip-coating approach 16.70 KΩ/sq [41]
(Ag) nanoparticle-incorporated cotton fabrics
Graphene oxide/cotton/sodium dithionite (Na2 S2 O4 ) Dipping method ±0.92 kΩ sq−1 [42]
Knitted cotton fabrics/GO/sodium nitrate/H2 SO4
Dipping method 0.19 MΩ/sq [43]
and KMnO4 .
Simple spraying and
rGO/ZnO-coated cotton 8.4 10−2 S/cm [44]
drying process
Graphene/cotton fabric (HC-GCF) Coating method 7 Ω sq−1 [45]
Graphene Oxide/Silver Nanoparticles/Cotton Fabric Dip-coating ~10−13 S cm−1 [46]
Graphene nanoribbon/cotton fabric Wet coating approach ~80 Ω [47]
Graphene oxide (GO) nanosheets\cotton fabric Dip and dry method 1015 Ω/sq [48]
Graphene/pure cotton fabric Dip-coating 0.0901 Ω~0.644 Ω/sq Present work

To determine the electrical stability of the graphene-treated cotton fibers, the conduc-
tivity of coated cotton was measured in terms of bulk resistance over two months at room
temperature using a four-probe method. The results are shown in Figure 13. The treated
samples demonstrated good electrical stability, as the electrical resistance values remained
almost unchanged over two months.
 Coatings2023,
Coatings 2023,13,
11, 1601
x FOR PEER REVIEW 13 of 16 16 of 21

Current (I)
4

2
1Day
1Month
1 2Month

2 4 6 8 10
Voltage (v)

I-VI-V
Figure13.13.
Figure measurement
measurement at Day
at Day 1, after
1, and and after 1 month
1 month and 2 months.
and 2 months.

The reliability of the higher-concentration-treated cotton sample was studied with a

change in temperature between 25 and 100 ◦ C, as shown in Figure 13. The results indicate
that the resistance of the graphene-treated cotton sample initially increases with increasing
temperature. This shows that the samples exhibit metallic behavior. However, above 80 ◦ C,
the resistance starts to decrease sharply with increasing temperature. Two reasons could be
possible for this sharp increase in current above 80 ◦ C. First, as the temperature increases,
the DMSO solution evaporates, and the graphene sheets come closer to each other, thereby
increasing the possibility of conduction. Second, each carbon atom in the two-dimensional
plane of graphene is connected to three other carbon atoms via strong covalent bonds, and
there is also a weak van der Waals bond perpendicular to these bonds that is available for
future atom-to-atom bonds. As the graphene planes and DMSO come close to each other,
the π bonding occurs between carbon and DMSO in the perpendicular direction. With
an increase in temperature, DMSO evaporates between graphene planes; thus, the planes
condense and get closer to each other, leading to charge transportation [27,39]. It is seen
that an increase in the graphene content reduces the surface resistance, while it increases the
thermal stability of the composite cotton [49]. To study the stability and thermal response,
samples were kept for two months at 25 ◦ C and the relative humidity was around 65%.
It was observed that the sample retained its maximum resistance value of 0.6 Ω/sq over
the period.
The 17 layers of graphene/cotton have a temperature-dependent performance in
terms of resistance. It can be found that the delay increases with increasing temperature.
Resistance increases with temperature up to approximately 65 ◦ C and thereafter decreases
as the temperature is further increased. The transition in behavior taking place at 75 ◦ C
is independent of the concentration of graphene, suggesting that this transition from
metallic (25 to 75 ◦ C) to semiconductor (75 to 100 ◦ C) behavior is a feature of the graphene
themselves and is independent of the amount of material present in pure cotton [46].
Treated cotton with 17 layers of graphene has good thermal stability as there was very little
variation in the electrical conductivity when it was heated from 25 ◦ C to 100 ◦ C and tested
over 3 months, as shown in Figure 14.
 Coatings 2023,13,
Coatings2023, 11, 1601
x FOR PEER REVIEW 14 of 1617 of 21

Figure
Figure14.14.
Resistance variation
Resistance with temperature
variation from 25 °C
with temperature to 100
from ◦ Cfor
25°C, 100 ◦coated
tocotton C, for with optimum
cotton coated with
graphene at 17 layers.
optimum graphene at 17 layers.

3.9. Mechanical Properties of the Cotton Sample: The Tensile Test

The mechanical properties of the composite cotton sample were evaluated through
the tensile strength test, as shown in Figure 15. In general, carbon-based materials often
become hardened [50]. It was observed that cotton impregnated with graphene exhibited
an increase in material hardness and strength. The treated sample showed three types of
strengths, yield strength (1), ultimate strength (2), and fracture strength (3), where (1) yield
Coatings 2023, 11, x FOR PEER REVIEW 15 of 16
strength is the stress that the material can withstand without permanent deformation,
(2) ultimate strength is the maximum stress that the material can withstand, and (3) fracture
strength is the maximum value of strain where the material breaks.

2.5
cotton
cotton/graphene
(3)
2.0
Stress(Mpa)

1.5

1.0
(2)

0.5

(1)
0.0

0 5 10 15 20 25
Strain%

Figure 15. Stress–strain curves of pure cotton and graphene-coated cotton after 17 layers.
Figure 15. Stress–strain curves of pure cotton and graphene-coated cotton after 17 layers.

Tensile test results reveal that the treatment with 17 layers of graphene solution
improved the mechanical properties of the elastic cotton. The presence of graphene may
have increased the bonding strength between pure cotton and conductive cotton, leading
to an improvement in the strength of the thread [51,52].

4. Application of Conductive Cotton/Graphene

To verify the potential use of the composite cotton as an alternative to the conductive
wires, an LED lamp was illuminated by powering the graphene-coated cotton at 17 layers in
 Coatings 2023, 11, x FOR PEER REVIEW 16 of 16

Coatings 2023, 13, 1601 18 of 21

4. Application of Conductive Cotton/Graphene
To verify the potential use of the composite cotton as an alternative to the conductive
a seriesan
wires, LED lamp was
configuration to ailluminated
DC powerby powering
supply of 12the graphene-coated
V. The cottonwith
lamp illuminated at 17nolayers
decrease
in a series configuration to a DC power supply of 12 V. The lamp illuminated with no de-
in its intensity when tested for 35 min, as shown in Figure 16. The experiment demonstrated
crease in its intensity when tested for 35 min, as shown in Figure 16. The experiment demon-
the ability of the material to be used as an alternative to a conductive wire in a typical
strated the ability of the material to be used as an alternative to a conductive wire in a typical
electrical system [53]. The proof of concept and all the studied results show that graphene-
electrical system [54]. The proof of concept and all the studied results show that graphene-
treated cotton fabric has promising applications such as mechanical sensors, actuators [54],
treated cotton fabric has promising applications such as mechanical sensors, actuators [55],
electromagnetic shielding [55], flexible heating elements, and supercapacitors [56,57].
electromagnetic shielding [56], flexible heating elements, and supercapacitors [57,58].

Figure 16. (a) DC LED illuminated by conductive-graphene-treated cotton fabric after 17 layers; (b)
Figure 16. (a) DC LED illuminated by conductive-graphene-treated cotton fabric after 17 layers;
circuit diagram as an alternative to a conductive wire.
(b) circuit diagram as an alternative to a conductive wire.

5. Conclusions
Graphene-coated pure cotton fabrics with 17 layers can be used as smart textiles for
multiple applications. The results revealed that the graphene/cotton had a resistance of
0.644 Ω/square meter. Graphene bonding was confirmed on the cotton surface through
SEM, FTIR, and XRD, while EDX testing ruled out the presence of any unwanted elements
in the samples. In addition, the graphene/cotton sample was tested by connecting it in
series to a 12 V power supply and lighting a bulb, given the importance of technology
and personal protective equipment. The coated sample showed remarkably stable thermal
and electrical properties because of the electrostatic attraction between the cotton substrate
and the graphene particles. The results demonstrate potential commercial benefits and
technological advantages, especially in the design of electrical devices and smart conductive
fabrics. However, the functioning of the surface effects in graphene networks is still
debatable and further studies are warranted.

Author Contributions: Conceptualization, N.M.B.; Methodology, N.M.B.; Validation, S.B.; Formal

Analysis, N.M.B. and M.B.; Investigation, N.M.B.; Resources, N.A.; Writing—Original Draft, N.M.B.;
Writing—Review and Editing, K.M.B., S.H., N.A., M.B., S.B., R.S. and R.K.; Supervision, M.B., R.S.
and R.K.; Funding Acquisition, K.M.B. All authors have read and agreed to the published version of
the manuscript.
Funding: The authors extend their appreciation to the Deputyship for Research and Innovation, Ministry
of Education in Saudi Arabia for funding this research work through project no. (IFKSUOR3-281-2).
Institutional Review Board Statement: Not applicable.
Coatings 2023, 13, 1601 19 of 21

Informed Consent Statement: Not applicable.

Data Availability Statement: Research data can be provided on request to the corresponding author.
Acknowledgments: Authors would like to thank Universiti Malaya for providing the facilities and
SATU research grant ST031-2021. The authors extend their appreciation to the Deputyship for
Research and Innovation, Ministry of Education in Saudi Arabia.
Conflicts of Interest: The authors declare that they have no conflict of interest between them.

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