Nano Materials Science 2 (2020) 281–291

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Nano Materials Science

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Durable easy-cleaning and antibacterial cotton fabrics using fluorine-free

silane coupling agents and CuO nanoparticles
Neha Agrawal a, Pearlie Sijia Low a, Jasmine Si Jia Tan a, Eileen Wen Mei Fong a, Yuekun Lai b, c,
Zhong Chen a, *
a
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore
b
College of Chemical Engineering, Fuzhou University, Fuzhou, 350116, PR China
c
College of Textile and Clothing Engineering, Soochow University, Suzhou, 215123, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Multifunctional fabrics of high durability through a scalable and eco-friendly technique remains a great challenge
Cotton fabric hindering their commercialization. In this work, we report a facile synthesis technique for the fabrication of
Superhydrophobic superhydrophobic antibacterial fabrics by employing fluorine-free silane coupling agents as cross-linkers for
Easy cleaning
enhanced durability. Three silane cross-linkers, Aminoethylaminopropyltrimethoxysilane (AEAPTMS), Amino-
Antibacterial
propyltriethoxysilane (APTES), and Methacryloyloxypropyltrimethoxysilane (MPTMS), have been investigated.
CuO nanoparticles
During the fabrication, a low surface energy polymer, polydimethylsiloxane (PDMS) was first deposited on cotton
fabrics. Subsequently, antibacterial copper oxide (CuO) nanoparticles were anchored on the PDMS coated fabrics
using the silane cross-linkers. The as-prepared fabrics displayed high superhydrophobicity and antibacterial
performance with water contact angle (WCA) > 153
, water shedding angle (WSA) < 5
, and up to 99% anti-
bacterial efficiency. Additionally, the as-prepared fabrics displayed high durability against abrasion, ultrasonic
washing, and soaking in harsh chemical environments. The air permeability and flexibility of the fabric was not
compromised after the coating. The above-reported technique is simple, cost-effective and holds tremendous
potential for large-scale production of energy-saving clothing and healthcare products.

1. Introduction improved, especially in clothing and healthcare sector [23]. In addition,

Textiles are one of the most ubiquitously used materials in industries
and households. The surface modification of textiles to impart multiple
functions has gained a lot of attention recently. Various researchers have
successfully demonstrated the functionalization of textiles for super-
hydrophobic [1-2], antibacterial [3–5], self-healing [6–8], flame retar-
dant [9–11], UV blocking [12–14], electrically conductive [15–17], and
even photocatalytic [18–20], properties for enhanced performance.
Cotton is one of the most omnipresent textile materials used extensively
due to its easy availability, breathability, inexpensiveness and biode-
gradable nature. One of the main shortcomings of cotton fabric used as
clothing is its tendency to get easily stained with food and drink spillage
which increases laundering care and growth of disease-causing microbes
[21], In hospitals, cotton fabric used as bed linen, patient gowns, and
bandages can get contaminated with blood posing a severe risk of
spreading infection [22]. By synthesizing cotton fabrics which are
superhydrophobic and antibacterial, their performance can be greatly
there will also be energy savings through reduced number of washing
and extended usage life, etc.
There are several requirements for the fabrication of super-
hydrophobic antibacterial surface, viz., the presence of dual micro-/
nanoscale roughness, low surface energy, and an antibacterial agent. A
superhydrophobic surface inspired by the lotus leaf effect displays a
water contact angle (WCA) > 150
and sliding angle (SA) < 10
[24]. A
typical strategy to construct a superhydrophobic antibacterial fabric
surface involves the use of nanoparticles to impart the nanoscale
roughness and antibacterial activity followed by treatment with a low
surface energy material to fulfil the requirements. Various
metal/metal-oxide nanoparticles like silver [25–28], copper [29–31],
titanium dioxide (TiO2) [32-33], and zinc oxide (ZnO) [34-35], have
been actively explored to impart antibacterial functionality to the fabric.
As an example, fluorinated decyl polyhedral oligomeric silsesquioxane
was used for low surface energy modification of silver nanoparticles
deposited on the cotton fabric. This yielded a highly superhydrophobic

* Corresponding author.
E-mail address: ASZChen@ntu.edu.sg (Z. Chen).

https://doi.org/10.1016/j.nanoms.2019.09.004

Available online 13 September 2019

2589-9651/© 2019 Chongqing University. Production and hosting by Elsevier B.V. on behalf of KeAi. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
N. Agrawal et al.
antibacterial surface displaying WCA of 169
and SA of 3
[36]. How-
ever, several challenges are faced by the existing technology which
hinder the commercialization of such textiles. Most of the super-
hydrophobic coatings on the fabrics involve the use of long fluoro-alkyl
chains for lowering the surface energy [37-38], which pose a health
risk to human and are harmful to the environment [39]. Therefore, the
use of fluorine-based chemicals limits the augmentation of such tech-
niques and it becomes necessary to seek alternatives like flurorine-free
silanes or low surface energy polymeric materials. While
metal/metal-oxide nanoparticles offer the simplest solution to impart the
superhydrophobic antibacterial functionality to the fabrics, poor coating
durability will result in release of nanoparticles from its surface. Upon
entering the body system through skin contact, inhalation or food items,
they can cause severe damage to the body [40-41], Loss of nanoparticles
from the fabric surface also diminishes the coating performance. It is thus
crucial to develop fabrication techniques which can anchor the nano-
particles firmly to the fabric and enhance durability. The adhesion of
these nanoparticles will translate into wash fastness during laundering, a
key consideration for cloth industry. While researchers have reported
successful synthesis of multifunctional fabrics, most do not report the
laundering durability [42-43], For example, Karimi et al. developed
self-cleaning cotton fabrics by depositing graphene oxide and TiO2 of-
fering antibacterial activity of up to 99% efficiency. However, the
washing durability of the fabrics was not considered [42]. On the other
hand, there were some reports on the loss of properties after few washes
[29,44]. Hence, there is a need for the development of facile and
eco-friendly technique for the fabrication of robust superhydrophobic
antibacterial fabrics to overcome the shortcomings of existing
technology.
Environmentally safe low surface energy polymers offer a suitable
alternative to address the toxicity concerns arising from fluorinated si-
lanes. Attia et al. successfully deposited nanoparticles like TiO2 and ZnO
on cotton fabrics by ultrasonically dispersing them in a low surface en-
ergy commercial polymer binder, thereby, eliminating the use of toxic
chemicals [43]. In our work, polydimethylsiloxane (PDMS), a
water-repellent, fluorine-free polymer was coated on the cotton fabrics
for lowering the surface energy. PDMS is also non-toxic, inexpensive, and
offers excellent chemical and mechanical stability, ideal for developing
durable coatings on fabric materials [45].
Nanoparticles, due to their large surface to volume ratio offer high
number of active sites for antibacterial reactions to take place [46]. Silver
has been one of the most extensively investigated nanoparticle for its
excellent antibacterial activity [47-48]. However, its application is
limited due to the high cost. For our work, copper oxide (CuO) nano-
particles displaying high antibacterial efficiency [49] and good economic
value were deemed to be a more suitable choice. While offering the
antifungal and antiviral properties, CuO nanoparticles do not cause any
skin-sensitization [50]. Among various types of materials, silver, copper,
ZnO and TiO2 nanoparticles have been well explored in the past, but
there was very limited investigation using CuO nanoparticles for super-
hydrophobic antibacterial textiles.
For the multifunctional fabrics to display high durability, it is essen-
tial that the nanoparticles be firmly adhered to the fabric surface. This
would reduce the risk of toxicity due to nanoparticle release, and also
stabilize the coating against laundering. For example, Zhu et al. added an
additional layer of PDMS to their superhydrophobic fabric synthesized by
depositing ZnO nanoparticles over PDMS-coated cotton surface. The
additional PDMS layer bound the nanoparticles to the fabric and pro-
vided greater durability [51]. However, to achieve antibacterial activity
along with superhydrophobicity, it is essential for the nanoparticles to be
exposed to the incoming microorganisms. An additional PDMS layer
would bury the nanoparticles and prevent bacterial interaction. To ach-
ieve this goal, we propose the use of silane coupling agents as
cross-linkers for the fabrication of durable superhydrophobic antibacte-
rial fabrics. The silane cross-linker provides additional chemical bonds
between the nanoparticles and the fabric, securing them firmly to the
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Nano Materials Science 2 (2020) 281–291
fabric surface. Moreover, the exposure of the nanoparticles to the surface
instead of dispersion in any polymer matrix ensures that the antibacterial
activity is not compromised.
The objective of this research involves developing a novel method
which is simple, inexpensive, eco-friendly, and can enhance the dura-
bility of the superhydrophobic antibacterial fabrics. To realize this aim,
PDMS was coated over the cotton fabrics, and the CuO nanoparticles
were then attached to the PDMS through a silane cross-linker. Three
types of cross linkers were evaluated in the current study. The nano-
particle loading on the fabric was optimized for maximum antibacterial
proficiency. In addition to the antibacterial activity, the durability
against abrasion, ultrasonic washing and harsh chemical environment
was also evaluated. Moreover, the air permeability and flexural rigidity
of the fabrics was assessed before and after the coating. This facile syn-
thesis strategy overcomes the shortcomings of the previous works and
displays promising potential for industrial fabrication of textile materials
imparting multiple functionalities.
2. Experimental work
2.1. Materials
Cotton fabric with an individual fibre diameter of ~15 μm
was obtained from Matex International Limited, Singapore. Aminoe
thylaminopropyltrimethoxysilane (AEAPTMS), Aminopropyltriethoxy
silane (APTES), Methacryloyloxypropyltrimethoxysilane (MPTMS),
Tetrahydrofuran (THF, anhydrous), Methanol (analytical reagent grade),
copper oxide (CuO) nanopowder (<50 nm in diameter) and non-ionic
detergent Triton X-100 were purchased from Sigma Aldrich and used
without further purification. PDMS (Slygard® 184, base and curing
agent) was purchased from Dow Corning Corporation. Escherichia coli
(E. coli, ATCC® 25922TM) and Staphylococcus aureus (S. aureus, ATCC®
25923TM) were purchased from the ATCC distribution partner Thermo
Fisher Scientific, Singapore. The cotton fabric was ultrasonically cleaned
with ethanol and deionized water to remove possible impurities and
dried for further processing.
2.2. Experimental procedure
The fabrication procedure for the superhydrophobic antibacterial
cotton fabrics is shown in Fig. 1a. First, the cotton fabrics were dip-coated
with 1 wt % PDMS (prepared by mixing the base and curing agent in the
ratio of 10:1, diluted with THF) and cured at 120
C for 30 min to obtain
PDMS coated cotton fabrics. Second, CuO nanoparticles were function-
alized with a silane coupling agent. The silane was pre-hydrolysed in
methanol (1 vol %) where CuO nanoparticles (3.2, 8.0, 16 g/m2 nominal
particle loading) were ultrasonically dispersed. Three different silanes
AEAPTMS, APTES and MPTMS were explored for their applicability
(Fig. 1b). Third, the PDMS coated cotton was immersed in the silane
solution and magnetically stirred for 1 h to allow the nanoparticle
attachment. Thereafter, the fabric was heat treated at 100
C for 1 h and
then washed with methanol to remove the unbound silane. This three-
step process resulted in the synthesis of superhydrophobic antibacterial
cotton fabrics. Different amount of nanoparticle was loaded to evaluate
the effect on superhydrophobicity and antibacterial efficiency.
2.3. Characterization
The wettability of the as-prepared fabrics was recorded using a con-
tact angle goniometer (OCA 20 Dataphysics, Germany). WCA and WSA
[52] was measured by placing 5 μL and 13 μL DI water respectively at five
equidistant positions on the fabric and an average value was reported.
The surface morphology of the fabrics was examined using a field
emission scanning electron microscope (FESEM, JEOL JSM-6340F) at an
acceleration voltage of 5 kV under secondary electron imaging mode.
Energy-dispersive X-ray spectroscopy (EDX) was performed at 20 keV
N. Agrawal et al.
Fig. 1. (a) Schematic illustration of the three-step process for the synthesis of superhydrophobic antibacterial cotton fabrics. (b) Chemical structure of the silane
coupling agents used for the fabrication.
using X-Max (Oxford Instruments). Fourier transform infrared
spectroscopy-attenuated total reflectance (FTIR-ATR, PerkinElmer
Frontier) was performed from 4000 cm-1 to 600 cm-1 to identify the
functional groups on the cotton fabric before and after the coating.
2.4. Antibacterial assessment
The antibacterial efficiency of the as-prepared fabrics was assessed
following the AATCC 100-2004 quantitative assessment technique [53]
using gram-negative and gram-positive bacteria E. coli (ATCC® 25922TM)
and S. aureus (ATCC® 25923TM) respectively. The treated and untreated
cotton fabrics were cut into circular swatches of 4.8  0.1 cm in diameter.
Luria Broth (LB) media autoclaved at 121
C for 20 min was used to
culture the microorganisms. The bacterial cells were tested for optical
density, centrifuged and re-suspended in Phosphate Buffer Saline (PBS)
solution. The fabric swatches were then inoculated with 105 colony
forming units (CFU)/ml of bacteria and incubated at 37
C for 24 h. After
the stipulated time, serial dilution was conducted for the estimated
bacterial cells inoculated. 100 μL of the inoculum was spread evenly on
the surface of the LB agar plates on a petridish and incubated at 37
C
overnight to observe the colonies. The percentage reduction of the bac-
terial cells was calculated by:
AB
% R¼  100
A a pressure of 400 Pa on a fabric area of 20 cm2. The flexural rigidity was
where R is the reduction in bacterial count, A and B are the number of
colonies observed for the untreated and treated fabrics respectively.
Three parallel runs of each test fabric was conducted and an average
value was reported.
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2.5. Durability measurements
Three durability measurements, viz., abrasion resistance, wash
fastness, and chemical stability test, were conducted on the as-
prepared fabrics. The abrasion resistance was evaluated by applying
a fixed pressure of 4 kPa with a pristine cotton fabric serving as the
abrasion material. The fabric was moved over the abradant surface
normal to the direction of applied pressure at a speed of 3 cm/s for a
distance of 11 cm in each cycle. A total of 500 such cycles were con-
ducted. For wash fastness measurement, Triton-X, a non-ionic deter-
gent (1 g/L) was added to the as-prepared fabrics at a liquor ratio of
50:1 ml/g. Thereafter, the samples were subjected to washing in an
ultrasound bath (275 W) at 40  2
C for a period of 90 min. After
every 15 min, the samples were washed with DI water and dried in an
oven at 100
C for measurement. Additionally, the chemical stability
of the as-prepared fabrics was analysed by immersing the treated
fabrics in aqueous solutions of HCl and NaOH with pH values ranging
from 1 to 13 for a period of 24 h. Contact angle was measured after the
durability tests.
2.6. Air permeability and flexural rigidity assessment
The air permeability was measured using a digital air permeability
tester (YG461E-11), supplied by Wuhan Guoliang Instrument Co., Ltd., at
tested using a fully automated fabric rigidity tester (YGB022D), manu-
factured by Shanghai Jinpeng Analytical Instrument Co. Ltd., at a fixed
bending angle of 41.5
. Three parallel tests of each test fabric was con-
ducted and the average value was reported.
N. Agrawal et al.
Fig. 2. (a) FESEM image of pristine cotton fabric (b) FESEM image of pristine cotton fibres (c) FESEM image of PDMS coated cotton fibres (d) photograph of water
droplet on a pristine cotton fabric and PDMS coated cotton fabric (e) contact angle image of pristine cotton fabric (f) contact angle image of PDMS coated cotton fabric.
3. Results and discussion
3.1. Surface morphology and contact angle analysis
A pristine cotton fabric (Fig. 2a) consists of fibres with a smooth
surface morphology (Fig. 2b) comprising of hydroxyl (–OH) groups on its
surface. The hydrophilicity induced by the hydroxyl groups causes a
water droplet in contact with the surface to be easily absorbed within the
fabric. When a uniform layer of PDMS was coated on the cotton fabric
(Fig. 2c), the fibres became water-repellent (Fig. 2d). The inherent
microscale roughness offered by the cotton fabric (due to arrangement of
the fibres) coupled with low surface energy of PDMS displayed highly
hydrophobic behaviour with WCA of 146.5  1.1
and WSA of
14.7  1.5
. However, the absence of dual scale architecture (micro and
nanoscale roughness) on the PDMS coated cotton fabric hinders the
display of superhydrophobicity. Fig. 2e and f present the WCA images of
a pristine cotton fabric and PDMS coated cotton fabric respectively.
Upon depositing CuO nanoparticles on the PDMS coated cotton by
using silane cross-linkers AEAPTMS, APTES, and MPTMS, the fabrics
displayed superhydrophobic performance with WCA >150
and WSA
<10
. The effect of nanoparticle loading on WCA and WSA for the fabrics
treated with the different cross-linkers has been shown in Fig. 3a and
Fig. 3b, respectively. A general observation was an improvement in the
superhydrophobicity (increase in WCA and decrease in WSA) of the as-
prepared fabrics with an increase in the nanoparticle loading. This
behaviour can be attributed to the higher surface roughness provided by
the increased quantity of the well-distributed nanoparticles on the fabric
surface. As an example, the surface morphology of the as-prepared fabrics
treated with APTES with nanoparticle loading of 3.2 g/m2, 8 g/m2 and
16 g/m2 has been shown in Fig. 4a, Fig. 4b and 4c, respectively. Addi-
tionally, the superhydrophobic property of the APTES-treated as-pre-
pared fabrics can be visualised from the presence of the near-spherical
water droplets over the fabric surface as depicted in Fig. 4d. For the
highest nanoparticle loading of 16 g/m2, the APTES-treated fabrics dis-
played a WCA of 154
and WSA of 5
. Similarly, the MPTMS-treated
fabrics displayed a WCA of 153
and WSA of 4
. While this behaviour
of improved superhydrophobicity with increased nanoparticle loading
was significant for APTES and MPTMS treated fabrics, an anomalous
behaviour was displayed by AEAPTMS-treated fabrics. For the
AEAPTMS-treated fabrics, there was an improvement in the super-
hydrophobic performance from 3.2 g/m2 to 8 g/m2. However, with
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Nano Materials Science 2 (2020) 281–291
further increase in nanoparticle loading to 16 g/m2, there was no notable
enhancement in WCA and there was even an increase in WSA. The
observed anomaly is likely due to the chemical structure of AEAPTMS
that consists of two amino groups on its silane chain (Fig. 1b). These
amino groups can participate in hydrogen bonding with CuO nano-
particles due to the strong affinity between them, attracting more
nanoparticles on a single chain of silane, and thereby, causing severe
nanoparticle agglomeration. This reduces the amount of air that can be
trapped in its microstructure causing a decreased superhydrophobic
performance [54]. The surface morphology of the AEAPTMS-treated
fabrics with nanoparticle loading of 8 g/m2 and 16 g/m2 are shown in
Fig. 4e and f, respectively. Additional FESEM images of the as-prepared
fabrics are shown in Section S1 of the Supplementary Information.
3.2. Chemical structure analysis
The chemical structure of the pristine cotton fabric before and after
PDMS and CuO deposition was investigated by FTIR analysis. As shown
in Fig. 5a, the cotton fabric displayed several strong peaks at 3335, 2900,
and 1105 cm-1 corresponding to –OH, C-H, and C-O-C glycosidic bond,
respectively [55]. The characteristic peaks at 1260 and 799 cm-1 of Si-C
bond appeared after coating the cotton fabric with PDMS [18,51,56]. To
evaluate the chemical structure of the PDMS-coated cotton after depo-
sition of CuO using silane cross-linkers, the responsible mechanism for
attachment was ascertained. The CuO nanoparticles consist of hydroxyl
groups on their surface. These hydroxyl groups can react with the silanol
groups of the hydrolysed silane cross-linkers by condensation reaction to
form chemical bonds [57]. In addition, the nanoparticles can also engage
in hydrogen bonding with the amino groups of the AEAPTMS and APTES
silanes [58] or with the carbonyl groups of the MPTMS silane [57,59].
This causes the firm attachment of nanoparticles to the silane
cross-linkers. The silane can then anchor the nanoparticles to the PDMS
through its silanol groups or via hydrogen bonding of amino/carbonyl
groups. To confirm the proposed mechanism, FTIR analysis was
conducted.
On performing FTIR for the as-prepared fabrics treated with amine
based silanes AEAPTMS and APTES, there exists a chemical similarity
between the as-prepared fabrics and PDMS coated cotton, causing a
substantial overlap in their infrared spectra. To observe the changes
occurring on the amine based silane-treated fabrics, the background
spectrum of PDMS coated cotton fabric was subtracted [59]. The
N. Agrawal et al. Nano Materials Science 2 (2020) 281–291

Fig. 3. The effect of nanoparticle loading on (a) WCA and (b) WSA for the as-prepared fabrics treated with AEAPTMS, APTES and MPTMS.

Fig. 4. FESEM images of APTES-treated fabrics with CuO loading of (a) 3.2 g/m2 (b) 8 g/m2 (c) 16 g/m2; (d) photograph of water droplets on the APTES-treated
fabrics with different CuO loading; FESEM images of AEAPTMS-treated fabrics with CuO loading of (e) 8 g/m2 (f) 16 g/m2.

obtained spectra was then compared with the pure silane chemicals
AEAPTMS and APTES to confirm the functional groups on the
as-prepared fabrics.
In Fig. 5b, for the after-subtraction spectra of AEAPTMS-treated fab-
rics, the peak at 1601 cm-1 corresponds to the bond deformation of the
amine (NH2) group due to hydrogen bonding [60]. The peaks at 1479,
1190 and 775 cm-1 corresponds to the CH2 deformation vibration of
–CH2NH2 primary amine, C-N-C stretching, and N-H bond vibration from
the secondary amine, respectively, confirming the role of AEAPTMS in
CuO attachment on the as-prepared fabrics [61-62].

285
N. Agrawal et al.
Fig. 5. FTIR spectra of (a) Cotton fabric, PDMS coated cotton fabric; (b) pure AEAPTMS chemical, after-subtraction spectra of AEAPTMS-treated fabric and PDMS
coated cotton fabric; (c) pure APTES chemical, after-subtraction of APTES-treated fabric and PDMS coated cotton fabric; (d) PDMS coated cotton fabric, MPTMS-
treated fabric, deconvoluted peaks 1 and 2.
In Fig. 5c, for the after-subtraction spectra of APTES-treated fabrics,
the band at 1638 cm-1 corresponds to the C¼N imine bond due to the
oxidation of the aminopropyl moiety [59]. The peaks at 1566, 1484 cm-1
corresponds to the NHþ 3 deformation due to hydrogen bonding [58-59].
The peaks at 1443, 1387 cm-1 corresponds to the asymmetric and sym-
metric deformation of the CH3 groups, respectively. These peaks are
characteristic of the pure APTES, confirming the role of APTES in
attaching CuO nanoparticles on the as-prepared fabrics [58]. Further
discussion on the after-subtraction spectra of the AEAPTMS and
APTES-treated fabrics is present in Section S2, Supplementary
Information.
In Fig. 5d, for MPTMS-treated fabrics, the peak at 1715 cm-1 corre-
sponds to the carbonyl group involved in hydrogen bonding [57]. A
cumulative peak was displayed near 1640 cm-1 which was deconvoluted
(by Gauss peak function) to produce two individual peaks. The decon-
voluted peaks named as deconvoluted peak 1 at 1643 cm-1 and decon-
voluted peak 2 at 1637 cm-1 correspond to C¼C bond of methacrylate
group [61,63], and –OH of adsorbed water [55] respectively. While the
1637 cm-1 peak due to adsorbed water was also present on the PDMS
coated cotton fabric, the 1643 cm-1 peak was absent. This indicates the
peak belongs to pure MPTMS, confirming its role in the attachment of
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Nano Materials Science 2 (2020) 281–291
CuO nanoparticles on the as-prepared fabrics.
3.3. Antibacterial activity assessment
The antibacterial activity of the as-prepared fabrics before and after
ultrasonic washing was evaluated by the AATCC 100-2004 quantitative
assessment technique [53]. The E. coli and S. aureus colonies observed on
the agar plates were counted after 24 h of incubation and the percentage
reduction was calculated (Table 1). Bacterial growth was observed for
the untreated (pristine) cotton fabric which was used as control, thereby
resulting in no antibacterial activity. The treated fabrics coated with CuO
nanoparticles displayed high reduction in the bacterial growth for both
E. coli and S. aureus, independent of the type of silane cross-linker used.
The E. coli colony reduction for the APTES-treated fabrics with different
nanoparticle loading before and after ultrasonic washing has been dis-
played in Fig. 6. Before washing of the as-prepared fabrics, with an in-
crease in the nanoparticle loading from 3.2 g/m2 to 8 g/m2, an
improvement in the antibacterial efficiency of the fabric was observed.
However, with further increase in nanoparticle loading up to 16 g/m2, no
significant improvement in colony reduction was noticed. The fabrics
with nanoparticle loading of 8 g/m2 and 16 g/m2 displayed high
N. Agrawal et al. Nano Materials Science 2 (2020) 281–291

Table 1 with nanoparticle loading of 8 g/m2 treated with different silane cross-
Percentage reduction in the bacterial growth for the as-prepared fabrics with linkers (Similar results for 3.2 and 8 g/m2 nanoparticle loading dis-
different nanoparticle loading treated with AEAPTMS, APTES, and MPTMS. played in Fig. S5, Supplementary Information). The fabrics show similar
Sample type Nanoparticle Antibacterial Efficiency (%) behaviour in WCA. These results not only prove the high durability of the
(based on loading (g/
Escherichia coli Staphylococcus aureus
as-prepared fabrics, but also manifest the reliability of this novel route of
silane- m2) fabrication across different silane cross-linkers.
crosslinker) Before After Before After
For the ultrasonic washing test, the as-prepared fabrics were sub-
Washing Washing Washing Washing
jected to harsh ultrasound treatment for a period of 90 min in the solution
AEAPTMS 3.2 97.6 96.4 96.9 95.8 of a non-ionic detergent, Triton X-100. Contact angle measurements were
8 99.2 99.8 98.0 98.6
16 99.7 98.9 97.1 96.9
taken after periodic intervals of 15 min. In Fig. 8a, the WCA for APTES-
treated fabrics with different nanoparticle loading has been shown
APTES 3.2 98.4 97.1 95.4 91.9
with respect to sonication time (Similar results for AEAPTMS and
8 98.9 99.3 97.0 96.5
16 99.4 99.3 97.4 96.2 MPTMS-treated fabrics displayed in Fig. S6, Supplementary Informa-
tion). A gradual decrease in WCA was observed with an increase in the
MPTMS 3.2 98.9 97.3 96.0 92.8
8 99.2 99.1 97.8 96.9
sonication time. This behaviour can be attributed to the sites of high
16 99.4 99.5 98.3 97.1 temperature and pressure created on the surface of the as-prepared fab-
rics due to ultrasound, weakening the coating performance. For the fabric
with 16 g/m2 nanoparticle loading, visible quantity of nanoparticles
reduction in the bacterial colonies with an efficiency greater than 99% were released into the solution resulting in sharper decrease of WCA as
for E. coli and up to 98% for S. aureus indicating high antibacterial per- compared to fabrics with 3.2 g/m2 and 8 g/m2 nanoparticle loading. The
formance of the as-prepared fabrics. weak attachment of the excess nanoparticles on the surface was
responsible for the nanoparticle release. Overall, despite the variation in
3.4. Durability assessments the nanoparticle loading, the as-prepared fabrics displayed high hydro-
phobicity up to 90 min of harsh ultrasound washing treatment. Fig. 8b
It is vital for multifunctional fabrics to display lasting durability for shows the WCA for as-prepared fabrics treated with different silane cross-
industrial and household applications. For mechanical durability linkers with 8 g/m2 nanoparticle loading (Similar results for 3.2 and 8 g/
assessment, the as-prepared fabrics were subjected to dry abrasion m2 nanoparticle loading displayed in Fig. S7, Supplementary Informa-
resistance test and wet ultrasonic washing test. For the abrasion resis- tion). The fabrics displayed comparable behaviour with a very small
tance measurement, the as-prepared fabrics were subjected to 500 cycles variation in WCA.
of abrasion with pristine cotton fabric serving as an abradant surface. In As shown in Table 1, there was a small decrease in the performance of
Fig. 7a, the WCA of APTES-treated fabrics with different nanoparticle the fabrics with 3.2 g/m2 nanoparticle loading after the washing. How-
loading has been displayed with respect to various abrasion cycles ever, the fabrics with 8 g/m2 and 16 g/m2 continued to display high
(Similar results for AEAPTMS and MPTMS-treated fabrics displayed in antibacterial efficiency showing no pronounced performance decline
Fig. S4, Supplementary Information). With an increase in the number of upon washing. Therefore, nanoparticle loading of 8 g/m2 was optimal in
abrasion cycles, there was a gradual decrease in the WCA. This was due to achieving high antibacterial performance before and after washing.
the lowering of the surface roughness against abrasion. With an increase Moreover, these results manifest the excellent performance and dura-
in the nanoparticle loading, the as-prepared fabrics offered resistance to a bility of the as-prepared fabrics through this novel route of fabrication.
higher number of abrasion cycles. The originally higher surface rough- Our results indicate the wash fastness of the as-prepared fabrics
ness attributed to the fabrics with higher nanoparticle loading was rendering them suitable for commercial applications.
responsible for the occurrence. Despite the variation in nanoparticle To confirm the retention of the CuO particles on the fibre surface,
loading, the as-prepared fabrics displayed superior hydrophobicity up to high magnification FESEM images are shown in Fig. S8. After the abra-
500 cycles of abrasion. Fig. 7b shows the WCA for as-prepared fabrics sion, most of the CuO particles remained (Fig. S8b) showing particles

Fig. 6. (a) Growth of E. coli colonies on untreated cotton fabric; Growth of E. coli colonies on APTES-treated fabrics before washing with CuO loading of (b) 3.2 g/m2
(c) 8 g/m2 (d) 16 g/m2; Growth of E. coli colonies on APTES-treated fabrics after washing with CuO loading of (e) 3.2 g/m2 (f) 8 g/m2 (g) 16 g/m.2.

287
N. Agrawal et al. Nano Materials Science 2 (2020) 281–291

Fig. 7. Effect of abrasion cycles on as-prepared fabrics (a) with different CuO loading treated with APTES; (b) treated with different silane cross-linkers with 8 g/m2
CuO loading.

Fig. 8. Effect of ultrasonic washing on as-prepared fabrics a) with different CuO loading treated with APTES; b) treated with different silane cross-linkers with 8 g/m2
CuO loading.

288
N. Agrawal et al.
Fig. 9. Effect of pH on as-prepared fabrics treated with different silane cross-
linkers with 16 g/m2 CuO loading.
attached to the cotton fiber strands. The same is true after the ultrasonic
washing (Fig. S8c). An EDX elemental analysis for Cu was performed on
the fabrics to quantitatively assess the relative levels of CuO present
(Fig. S9, Table S1). The control fabric (APTES with 8 g/m2 CuO loading)
had 5.1 wt% Cu. There was no significant change in CuO particles on the
fabric after the washing based on the elemental analysis. After the
abrasion test, the amount of Cu was slightly reduced to 4.5 wt%. Since
the sample with 3.2 g/m2 load could display very decent anti-bacterial
results (Table 1), it is reasonable to expect the antibacterial efficiency
will remain high after the abrasion test.
Apart from the mechanical durability assessments, the chemical sta-
bility of the as-prepared fabrics was evaluated after submerging them in
aqueous solutions of NaOH and HCl with pH ranging from 1-13 for a
period of 24 h (Fig. 9). The as-prepared fabrics displayed high durability
to the acidic and alkaline environments from pH values ranging from 3 to
Fig. 10. Variation of (a) air permeability (b) flexural rigidity of as-prepared fabrics with different nanoparticle loading treated with AEAPTMS, APTES and MPTMS.
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Nano Materials Science 2 (2020) 281–291
11 with no significant variation in WCA. At pH ¼ 1, the CuO nano-
particles being a weak base, were completely dissolved by the strong
acidic solution leaving the surface devoid of nanoparticles. The hydro-
phobicity, however, was retained due to the intrinsic strong resistance of
PDMS to acidic treatments. At pH ¼ 3, the acidic strength was weaker,
and the performance of CuO nanoparticles was not compromised. At
pH ¼ 13, the nanoparticles remained unaffected, however, the PDMS
coating was peeled off at a few places causing a drop in WCA. Overall, the
as-prepared fabrics showed satisfactory durability against chemical en-
vironments they are regularly exposed to in daily life.
3.5. Air permeability and flexural rigidity
The air permeability and flexural rigidity of the as-prepared fabrics
was evaluated before and after PDMS and CuO deposition (Fig. 10). It
was observed that the air permeability of the PDMS coated cotton was
higher than the pristine cotton fabric. This was probably due to the
binding of the individual cotton fibres together by the PDMS coating
which resulted in more air flow through the fabric than the pristine
cotton fabric. After incorporation of the nanoparticles, the air perme-
ability was reduced. A general trend observed was a decrease in the air
permeability with an increase in the nanoparticle loading. However, the
overall decrease in the air permeability of the as-prepared fabrics was
quite low when compared to the pristine cotton fabric, not affecting the
breathability or comfort of these fabrics for clothing applications. The
flexural rigidity of the PDMS coated cotton was lower than the pristine
cotton fabric. This was probably due to the material properties of PDMS
offering high elasticity and flexibility, thereby causing a reduction in the
rigidity of the fabric. After deposition of the nanoparticles, there was an
overall increase in the rigidity. However, it was comparable to the pris-
tine cotton fabric thereby not affecting the fabric quality or wearer
comfortability.
4. Conclusion
In this work, we report the successful fabrication of durable super-
hydrophobic antibacterial fabrics through a novel and facile procedure.
Copper oxide nanoparticles were anchored onto the surface of PDMS
coated cotton fabric by using fluorine-free silane coupling agents as cross-
linkers for improved durability. The as-prepared fabrics displayed
excellent superhydrophobicity and antibacterial activity. We found that
8 g/m2 norminal nanoparticle loading on the fabric surface was optimal
in achieving maximum overall performance. The fabrics displayed
N. Agrawal et al.
superior durability against abrasion, ultrasonic washing and harsh
chemical environments. The antibacterial performance of the fabrics was
not compromised even after ultrasonic washing. The breathability and
flexibility of the as-prepared fabrics was also preserved. This novel syn-
thesis technique displays tremendous potential for large-scale production
of multifunctional textiles due to its low-cost, environmental friendly raw
materials and improved durability, especially for clothing and healthcare
sector. Moreover, this synthesis strategy can be easily extended to other
metal-oxide nanoparticles and substrates for multifunctional coating
applications.
5. Data availability
Most of the data used in this study has been reproduced in the form of
graphs and tables and included in this paper. Additional raw/processed
data required to reproduce these findings cannot be shared at this time as
it forms a part of the ongoing study.
Acknowledgements
Financial assistance from Ministry of Education, Singapore (RG 16/
18) is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https
://doi.org/10.1016/j.nanoms.2019.09.004.
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