98 J. Math. Fund. Sci., Vol. 56, No.

2, 2024, 98-117

Bioinspired Superhydrophobic Finishing of Cotton Fabric

Using Carnauba Wax and Biosilica Nanoparticles with a
Layer-by-layer Deposition Method
Mohamad Widodo1,*, Rino Rakhmata Mukti2, Sri Yuliani3 & Amalia Putri4,5

1
Postgraduate Program, Master of Applied Sciences in Textile Engineering and Apparel
Technology, Politeknik STTT Bandung (Polytechnic of Textile Technology), Bandung,
Indonesia
2
Department of Chemistry, Bandung Institute of Technology, Bandung, Indonesia.
3
Center for Agroindustry Research, National Research and Innovation Agency,
Indonesia
4
Department of Textile Chemistry, Politeknik STTT Bandung (Polytechnic of Textile
Technology), Bandung, Indonesia
5
PT. Hilon Indonesia, Tangerang, Indonesia
*
E-mail: [email protected]

Abstract. Hydrophobic surface modification has great potential for applications

in everyday life, particularly in textiles such as sportswear, health, protection, and
other non-clothing textiles. Improving water repellence and high-level
hydrophobicity in textile materials has so far been difficult to achieve with
chemicals other than PFAS (per- and polyfluoroalkyl substances) due to
environmental and health concerns. In this research, biosilica nanoparticles from
rice husk ash (RHA) and carnauba wax were deposited alternately using a layer-
by-layer (LBL) method to create a surface with a combination of nanoscale
roughness and hydrophobicity resembling the lotus effect. Chitosan was used to
cationize the surface of cotton fibre and bridge the negatively charged
nanobiosilica particles and carnauba wax. The hydrophobicity increased with the
number of layers of nanosilica-chitosan-wax (SNP/CHI/SCW), reaching a contact
angle of 140.2° (close to superhydrophobic) with three layers of SNP/CHI/SCW,
followed by decreased air permeability from 19.4 cm3/cm2/s for untreated cotton
to 13.3 cm3/cm2/s for treated cotton, with a total decrease of 31.44%. Cotton fabric
was successfully modified from hydrophilic to superhydrophobic using an LBL
coating of RHA silica nanoparticles and carnauba wax.

Keywords: carnauba wax; layer-by-layer (LBL); RHA silica nanoparticles; self-

assembly; superhydrophobic; water repellent.

Received August 27th, 2024, Revised October 4th, 2024, Accepted for publication October 7th, 2024
Copyright © 2024 Published by ITB Institut for Research and Community Service, ISSN: 2337-5760,
DOI: 10.5614/j.math.fund.sci.2024.56.2.2th
 Bioinspired Superhydrophobic Finishing of Cotton 99

1 Introduction
Chemical modification of superhydrophobic surfaces has become a popular
research topic and has great application potential in daily life, notably in textiles
and clothing for protection against the elements [1],[2],[11],[12],[3]-[10]. Such
surfaces repel water with contact angles larger than 150° and the water rolls off
easily when the surface is inclined to less than 10° [13],[14]. Nature, particularly
the plant kingdom, make use of this particular ability for protection, inspiring the
so-called “lotus effect” that was used for the first time when Wilhelm Barthlott
and Ehler described the self-cleaning and ultrahydrophobic properties of micro-
nanostructured surfaces in a paper published in 1977 [15],[16]. In general, low
surface energy and a degree of roughness (micro to nano) on the surface of
materials are important characteristics of superhydrophobic surfaces [17].

Yamamoto et al. [18] demonstrated this concept by reverse engineering. They

removed the wax by dipping a lotus leaf in ethanol and evaluated the results and
effects of the removal. The water contact angle decreased significantly from 161°
for the original surface to 122° for the ethanol-treated leaf. Fractal analysis
showed that the untreated original surface of the lotus leaf is divided into two
fractal regions, which comprise a smaller-sized roughness region of 0.3 to 1.7 μm
with a larger fractal dimension of D = 1.48 and a larger roughness region of 1.7
to 19 μm with a smaller fractal of D = 1.36. Dipping the leaf in ethanol led to the
removal of the region with larger D, which is characterized by wax tubes, and left
only the smaller D region. This analysis is in line with a dual-scaled model of the
hierarchical structure on superhydrophobic surfaces [11],[14],[19]-[22].

Cotton is still the number one material of choice for clothing because it easily
absorbs moisture/sweat and provides comfort. However, there are situations
where water repellent and quick-drying properties are needed along with the
comfort offered by cotton, particularly for sportswear and medical textiles (e.g.
surgical gowns), which leads to the need for the modification of the cotton’s
surface properties from hydrophilic to hydrophobic and even superhydrophobic.
Fluorochemical compounds, collectively known as PFAS (per- and
polyfluoroalkyl substances), have long been primary choice and are regularly
used for high-performance water repellent textiles. However, under strict
regulations, out of environmental and consumer safety concerns, the use of PFAS
has been banned in many countries. In the textile industry, these chemicals are
known collectively as C8 (perfluorooctanoic acid or PFOA and perfluorooctane
sulfonate or PFOS) and C6 (perfluorohexanoic acid or PFHxA). Finding
substitute chemicals that are safe and still provide the same functionality is not
an easy task, but alternative chemicals and different strategies are available.
100 Mohamad Widodo, et al.

Recently, a considerable interest has risen in the use of silica nanoparticles to

produce nanostructured surfaces for strong water repellence in textiles [6],[23]-
[31]. However, only a few studies were concerned with silica nanoparticles from
rice husk ash (RHA), which is a form of agricultural waste and is abundantly
available in Indonesia [32],[33]. Borah et al. obtained water contact angles of
101.7° on eri silk [24] and 145° on eri silk/wool fabrics [23] from the treatment
with RHA nanosilica. Tavakoli et al. [25] obtained a water contact angle of 140°
for cotton fabric treated with RHA nanosilica.

Inspired by the presence and role of nanostructured wax on the lotus leaf,
researchers have studied and explored the use of waxes, including those from
natural origin, to create a surface with low surface energy. Bashari et al. [34]
reported the use of carnauba wax nanoparticles (CNP) from the carnauba palm
tree (Copernicia prunifera) together with chitosan for a water repellent finishing
of cotton fabrics. Five bilayers of CNP/chitosan produced a surface with a water
contact angle of 130.9° before washing and 101.7° after washing. Forsman et al.
[35],[36] obtained water contact angles of 138-152° on cotton fabrics by using
two bilayers of carnauba wax and poly-L-lysin (PLL). By using a combination of
carnauba wax and alkyl-silane modified (hydrophobic) silica nanoparticles Celik
et al. [37] obtained a water contact angle of 175° with a sliding angle of 3° on a
glass surface, thus creating a superhydrophobic surface. The hydrophobotization
was carried out via silanization of silica nanoparticles by dodecyltrichlorosilane
prior to the deposition, which turned the nanoparticles from hydrophilic to
hydrophobic (Figure 1).

Figure 1 The silanization of silica nanoparticles by dodecyltricholorosilane.

In this study, based on the works of Bashari et al. [34], Forsman et al. [35],[36]
and Celik et al. [37], a safe and environmentally alternative approach using a
combination of silica nanoparticles, chitosan, and carnauba wax is presented. The
study shows the feasibility of LBL self-assembly deposition for use in the existing
textile processing method (pad-dry) of superhydrophobic finishing of cotton
fabric. The wetting properties, washing durability, and comfort aspects of the
fabric were evaluated as a function of the number of coatings or layers seeking
for its practical application in the industry.
 Bioinspired Superhydrophobic Finishing of Cotton 101

2 Experimental Section

2.1 Materials
100% cotton fabric (100 g/m2, 43 ends/cm  39 ends/cm, Ne1 30s) was donated
by the Laboratory of Textile Printing and Finishing at Politeknik STTT Bandung.
The fabric was ready for dyeing/printing, which means it had been through the
process of desizing, scouring, and bleaching.

RHA silica nanoparticles were produced and donated by the Centre of Research
for Post Harvest at the Ministry of Agriculture in Bogor, Indonesia. The silica
nanoparticles were amorphous with an average crystallinity degree of 58.5% and
a bulk density of 0.67 to 0.81 g/mL, and had particle sizes in the range of 25.1 to
40.6 nm [38].

Carnauba wax (CAS Number: 8015-86-9) and Tween 80 (polyoxyethylene-20-

sorbitan monooleate, CAS No. 9005-65-6) nonionic surfactant were purchased
from Sigma-Aldrich (Singapore). Rucoperse NPA is a polymeric dispersing agent
based on acrylic acid homopolymer and was donated by Rudolf-Chemie
Indonesia (Bandung, Indonesia). Food-grade chitosan with a deacetylation degree
of 80% was purchased from Bio Chitosan Indonesia (Surabaya, Indonesia).

2.2 Methods
The general methodology employed in this research was as follows. The cotton
fabric was first grafted with chitosan for surface cationization and then immersed
successively in the dispersion of RHA silica nanoparticles (SNP), solution of
chitosan (CHI), and dispersion of solid carnauba wax (SCW), creating a
SNP/CHI/SCW trilayer on the chitosan grafted cotton (Figure 2). To create the
next SNP/CHI/SCW trilayer, the cotton fabric was first immersed in chitosan
prior to each layer in the repeating order of SNP, CHI, and SCW. Chitosan is
required to provide a cationic bridge between each of the layers.

Figure 2 The layer structure of silica nanoparticles (SNP), chitosan (CHI), and
solid carnauba wax (SCW) on the surface of chitosan-grafted-cotton fabric (CHI-
g-CO).
102 Mohamad Widodo, et al.

2.2.1 Preparation of Chitosan Solution (CHI)

Chitosan solution was prepared by stirring a dispersion of chitosan flakes (8.0 g)
in 400 ml of 2% (v/v) aqueous acetic acid solution at pH 4 for 1 h at 60 °C. Two
such solutions were prepared: one for the grafting of chitosan onto cotton fabric,
the other for the layer-by-layer (LBL) deposition of silica nanoparticles and
carnauba wax.

2.2.2 Preparation of Solid Carnauba Wax Particles (SCW)

SCW was prepared by the organic solvent-free method described by Bashari et
al. [34]. Principally, the wax was heated to melting and then dispersed with the
use of surfactant to form a stable emulsion of solid lipid particles in the submicron
range (Figure 3). Firstly, 0.3 g of carnauba wax was put into a 250-mL beaker
glass and heated in a water bath above its melting temperature at 90 °C.
Separately, the polyoxyethylene-20-sorbitan monooleate (Tween 80) surfactant
was added to 10 mL of water under magnetic stirring at 90 °C for 2 min, which
was then transferred to the molten carnauba under magnetic stirring at 90 °C until
the formation of a white mixture. To obtain a stable and fine emulsion, the
mixture was sonicated in a sonication bath (Bransonic ultrasonic cleaner, Branson
2510EMTH) at a frequency of 30 KHz and 100 W power for 4 min. The obtained
emulsion was poured under mild magnetic stirring into 100 mL of cold water (2-
5 °C) and then stirred for 3 min to facilitate the solidification of lipid
nanoparticles. Lastly, the mixture was homogenized by ultrasonic homogenizer
(Bandelin SONOPULS Digital Ultrasonic Homogenizer) at 20 W power in a
pulse regime of 10 seconds on and 5 seconds off for 60 seconds. Extra water was
removed by using a centrifuge at 6000 rpm 4 times for 15 min to obtain a more
concentrated SCW suspension.

Figure 3 Step-by-step preparation of the solid carnauba wax.

 Bioinspired Superhydrophobic Finishing of Cotton 103

2.2.3 Preparation of Dispersion of Silica Nanoparticles (SNP)

Alkali (NaOH) was added to 500 mL of water to adjust the pH to 11, where silica
nanoparticles are negatively charged and repel each other, followed by the
addition of 4 mL of Rucoperse NPA. 4.0 g (2 g/L) dispersing agent to RHA silica
nanoparticles under magnetic stirring until a stable dispersion was obtained.

2.2.4 Grafting of Chitosan onto Cotton Fabric using Sodium

Periodate
The grafting of cotton with chitosan follows the methods described by Ramadan
et al. [40] and Winiati et al. [41]. A solution of 100 mL containing 50.0 g sodium
periodate (NaIO4) (0.5 mg/ml) was added to the solution of chitosan prepared in
2.1.1, making up a 500-ml solution of chitosan and sodium periodate. Cotton
fabric samples measuring 30 cm x 30 cm (approximately 9 g) were dipped in the
solution of chitosan at 60 °C with constant stirring for 2 h. The samples were
subsequently washed three times with Tween 80 (2 g/L) in deionized water,
followed by soaking for 24 h in 500 mL of deionized water with constant stirring
at ambient temperature to remove ungrafted chitosan from the cotton fiber surface
and make sure that the grafted chitosan became durable to washing. The samples
were then dried under vacuum at 60 °C for 6 h to produce chitosan grafted cotton
fabric (CHI-g-CO in Figure 2).

2.2.5 Layer-by-Layer Deposition of Silica Nanoparticles and

Carnauba Wax
The chitosan grafted cotton (CHI-g-CO) fabric was first dipped in a solution of
HCl 0.1 N (pH 3.5) for 5 minutes, which was followed by drying in an oven at
60 °C for 15 minutes. The dried cotton fabric samples were alternately dipped for
5 minutes in a dispersion of silica nanoparticles (2.1.3), solution of chitosan
(2.1.1), and aqueous solution (2% w/v) of carnauba wax (2.1.2). The fabrics were
impregnated with a wet pick up (WPU) of 100% after each dipping procedure
and subsequently dried in an oven at 70 °C for 15 min. This sequence of processes
(Figure 4) was repeated to obtain two and three trilayers of SNP/CHI/SCW on
each sample as shown in Table 1.

Table 1 Sample description and codes (n = 3).

Sample Code Description
CHI-g-CO Chitosan-grafted cotton fabric
SNP/CHI/SCW(1) Cotton fabric coated with 1 layer of SNP/CHI/SCW
(silica nanoparticles/chitosan/ solid carnauba wax)
SNP/CHI/SCW(2) Cotton fabric coated with 2 layers of SNP/CHI/SCW
(silica nanoparticles/chitosan/ solid carnauba wax)
SNP/CHI/SCW(3) Cotton fabric coated with 3 layers of SNP/CHI/SCW
(silica nanoparticles/chitosan/ solid carnauba wax)
104 Mohamad Widodo, et al.

Figure 4 The LBL deposition of SNP/CHI/SCW trilayers onto chitosan-grafted

cotton fabric samples.

2.3 Characterization of Treated Fabric

2.3.1 ATR-FTIR Spectroscopy

Attenuated total reflectance Fourier-transform infra-red (ATR-FTIR)
spectroscopy was carried out on a IRAffinity-1S Shimadzu to identify the
characteristic functional groups on the surface of the treated cotton fabric
samples. Measurements of the fabrics were done with 32 scans and a resolution
of 4 cm-1.

2.3.2 Water Repellence Measurements

The water repellence of the treated samples was evaluated by the spray test
method according to SNI ISO 4920:2012 (Figure 6), which is an Indonesian
national standard adoption of ISO 4920:2012 Textile fabrics – Determination of
resistance to surface wetting (spray test) and is similar to the AATCC Test
Method 22 Water repellence test (spray method). In principle, under the specified
conditions and procedures, water is sprayed through a funnel on a tight sample to
form a wetting pattern on the surface, the size of which is related to the water
repellence of the fabric (Figure 5). The evaluation result is determined by
comparing it with a standard pattern (Figure 6). Higher ratings indicate greater
water repellence.
 Bioinspired Superhydrophobic Finishing of Cotton 105

Additionally, the water repellence was also quantified by measurement of the

contact angle (CA) (Kyowa Contact Angle Goniometer DMs-401, Centre of
Textile Research, Bandung). The static contact angle was measured by placing a
droplet (5 µL) of deionized water on at least three positions on each sample. An
image of each drop was taken with a 15-s delay after the drop. From the shape of
the drop, the CA was analyzed and determined using the Low-Bond
Axisymmetric Drop Shape Analysis (LBADSA) [42],[43] plugin for ImageJ, a
free image analysis software package.

Figure 5 Spray test apparatus (left) and spray testing of fabric (right).

Figure 6 Standard spray test rating SNI ISO 4020:2012.

106 Mohamad Widodo, et al.

2.3.3 Air Permeability

Air permeability was measured following the ASTM D737-18(2023) Standard
Test Method for Air Permeability of Textile Fabrics using an air permeability
tester (Testex). The results were expressed in the amount of air (cm3) that
penetrated and went through the fabric across a given area (cm2) in a unit of time
(s) and also in terms of air permeability reduction according to Equation (1):
𝐴𝑈− 𝐴𝐿𝐵𝐿
Air permeability reduction (%) 𝑋 100 (1)
𝐴𝑈

where AU and ALBL are the air permeabilities (cm3/cm2/s) of the untreated and the
LBL samples, respectively.

3 Results and Discussion

3.1 FTIR Analysis: Surface Chemical Properties

Figure 7 shows the ATR-FTIR spectra of the untreated and the treated cotton
fabrics (after grafting of chitosan and LBL deposition of SNP and SCW). For the
untreated cotton fabric (Figure 7a), peaks characteristic of -OH groups were
found at 3,336 cm-1 and 1,030 cm-1 in the cotton structure. It must be noted,
however, that these two peaks can be seen in all other spectra because -OH groups
are present in chitosan, silica nanoparticles (in the form of silanol), and in
carnauba wax.

Figure 7b shows the spectrum of the cotton fabric after being grafted with
chitosan as described in Sub-section 2.1.4. As shown in Figure 8, cotton
undergoes ring opening via oxidation by NaIO4, leading to the formation of
aldehyde (II), which is then available for the formation of a chemical bond with
the amine (-NH2) groups of the chitosan (III) forming a Schiff base (-C=N). On
chitosan grafted cotton fabric, the expected characteristic absorption band of
chitosan must come from the Schiff base C=N double bond at 1,690 to 1,640
cm-1. Closer examination of that area of the spectrum revealed an absorption band
that constituted stretching of C=N at 1,684 cm-1. Some of the aldehyde groups
must still have been available so that the spectrum shows a peak that represents
C=O stretching at 1,716 cm-1. The FTIR spectrum of the chitosan grafted cotton
after the deposition of silica nanoparticles (SNP) is shown in Figure 7c. The OH
stretching vibrations of the SiOH group absorb in the same region as alcohols,
3,700 to 3,200 cm-1. Strong Si-O bands are present in the region 830-1,110 cm-1
[6],[44]-[46]. Riaz et al. [6] observed two sharp peaks at 1,094 cm-1 and 807 cm-1
that correspond to symmetric and asymmetric stretching vibrations of Si–O–Si in
cotton fabric treated with silica nanoparticles. As shown in Figure 7c, a peak
corresponding to Si-O appears at 1,055 cm-1 in the treated chitosan grafted cotton.
 Bioinspired Superhydrophobic Finishing of Cotton 107

Figure 7 ATR-FTIR spectra of the untreated and the treated cotton fabric by LBL
deposition of chitosan (CHI), silica nanoparticles (SNP), and carnauba wax
(SCW).

Figure 8 The oxidation of cotton by NaIO4 (II) and grafting with chitosan (III)
[47].
108 Mohamad Widodo, et al.

Carnauba wax is a mixture of at least three groups of long hydrocarbon

compounds. The composition consists primarily of 80-85% C24 and C28 esters,
10-15% C32 and C34 straight-chained primary alcohols, and 3-6% hydroxy-fatty
acids [34],[48]. Main spectral features of esters with a carbonyl (C=O) stretching
at 1,735 cm-1 and C-C(=O)-O stretching at 1,165 cm-1 can be identified as the
characteristic spectra of carnauba wax, whereas the peak at 1,604 cm-1 indicates
the presence of carboxylate [46]. Additionally, the methylene vibration at 2,916
cm-1 and 2,848 cm-1 (stretching), 1,472 cm-1 and 1,463 cm-1 (scissoring), 729 cm-
1
and 719 cm-1 (rocking) are also present [48].

According to the scheme in Figure 2, the topmost layer of the treated cotton
samples must be carnauba wax. Therefore, two strong peaks from methylene at
2,916 cm-1 (vibration) and at 2,848 cm-1 (stretching) should be visible in Figure
7. Close examination of the spectrum in Figure 7d reveals an almost unnoticeable
but pronounced (compared to the other three spectra in Figure 7) presence of a
weak peak of methylene vibration only at 2,903 cm-1, confirming the presence of
carnauba wax.

3.2 Water Repellence and Air Permeability

Table 2 shows a series of black-white images obtained from the greyscale images
of the spray tests of the chitosan grafted cotton coated with different numbers of
SNP/CHI/SCW trilayers. The black color within the circle boundary (the hoop
diameter) represents the water pattern on the fabric after spraying. Increasing the
number of coatings or SNP/CHI/SCW trilayers from one to three increased the
water repellence rating of the unwashed samples from 70 to 90, which is normally
expected from a good water-repellent finish. However, after washing (2.2.4), the
rating dropped to 50 for all fabrics, which raises questions regarding the durability
of the treatment in relation to washing. However, the water repellence in terms of
water contact angle (Table 3) was much more promising, with contact angles of
137.43°, 142.56°, and 152.19° before washing and 129.61°, 132.81° and 140.17°
after washing for 1, 2 and 3 SNP//CHI/SCW trilayers, respectively.

The general consensus is that superhydrophobic surfaces must have a water

contact angle > 150°. However, in a study that redefined the basic terminology in
surface wetting, Law [49] proposed a lower threshold. A surface is
superhydrophobic when its water contact angle is ≥ 145°. This is when the surface
has practically no affinity with water. The water contact angle obtained from the
three layers of SNP/CHI/SCW (140.2°) is close enough to the proposed new
threshold showing a promising result toward superhydrophobicity. The most
promising route to increase the contact angle is by adding more layers. However,
even with three layers, the air permeability of the fabric was already reduced by
as much as 31.44% from 19.42 cm3/cm2/s for the untreated cotton to 13.30
 Bioinspired Superhydrophobic Finishing of Cotton 109

cm3/cm2/s for the treated cotton (Figure 9). Besides, as shown by Bashari et al.
[34], the deposition of layers increases the fabric stiffness, which is not desirable.

Table 2 Results from spray tests of untreated and treated cotton fabrics.
Number of Coatings
Before/After
Untreated Fabric SNP/CHI/SCW(1) SNP/CHI/SCW(2) SNP/CHI/SCW(3)
Washing
SPRAY TEST

Before

0 70 (ISO 2) 80 (ISO 3) 90 (ISO 4)

After

0 50 (ISO 1) 50 (ISO 1) 50 (ISO 1)

Table 3 Contact angles of treated cotton fabrics.

Number of Coatings
Before/After Untreated
Washing Fabric SNP/CHI/SCW(1) SNP/CHI/SCW(2) SNP/CHI/SCW(3)

WATER CONTACT ANGLE (O)

Before

0 137.43  0.32 142.56 0.63 152.19  0.23

After

0 129.61  0.79 132.81 0.88 140.17  0.25

Therefore, adding more layers beyond three in this particular case does not seem
to be the solution for a larger contact angle of at least 145°. At this point, although
110 Mohamad Widodo, et al.

not quite superhydrophobic by the formal definition, it is safe to conclude that the
treated cotton fabric was in the transition region from high hydrophobic to
superhydrophobic.

Figure 9 Air permeability of treated cotton with an increasing number of

SNP/CHI/SCW layers. The bar refers to air permeability (cm3/cm2/s) and the lines
refer to the air permeability reduction (%).

In this study, unless the carnauba wax was successfully broken down to nanosized
particles and self-assembly took place as expected, the deposition of the carnauba
wax, which was preceded by the deposition of chitosan, bore the risk of reducing
the critical roughness factor brought about by the nanoscale structure underneath
and failed to build the dual-scale hierarchy that is a prerequisite for
superhydrophobicity. The high water repellence (140.2°) produced by the layer
system of SNP/CHI/SCW is much larger than the contact angles reported by
Bashari et al. [34] but comparable to those of Forsman et al. [35]. This supports
the existence of a dual hierarchy in the nanostructure of layers on the surface of
the cotton fabric. At this point, it is necessary to revisit the idea about the layering
and the structure of layers that is responsible for the large contact angles.

The layer structure shown in Figure 2 follows the idea of layering continuous
films one at a time on the substrate surface. With that structure, there is only one-
scale roughness, as shown in Figure 10a. Each of the layers is in fact not a
continuous film but an array of solid (SNP and SCW) and polymeric particles
(CHI). During deposition, in each of the successive layers, the particles that came
later actually should cover an individual or a collection of particles deposited
 Bioinspired Superhydrophobic Finishing of Cotton 111

previously, creating a two-scale hierarchical structure like in fractal surfaces

(Figure 10b). The method of LBL deposition employed in this study is dip-pad-
dry (Figure 4), which tends more to create structure (a). However, it is also
probable that the layering took the form of structure (b). The documentation from
one of the preliminary experiments showed that cotton fabric covered with only
one layer of modified hydrophobic silica nanoparticles (one-scale roughness)
produced a water contact angle of 127°, suggesting that the layering may be
somewhere between structure (a) and (b) or transition between them.

Figure 10 Structure of layers with (a) one-scale roughness and (b) two-scale
roughness.

With that observation, it is suggested that a larger contact angle would be

obtained when structure (b) is predominant. In the deposition method employed
by Bashari et al. [34] and Forsman et al. [35], the fabric is dipped successively in
separate solutions/emulsions of SNP, CHI, and SCW. This is not quite self-
assembly and presumably leads to the formation of structure (a). Rather than
using this dipping method, the route to superhydrophobic should start with the
modification of silica nanoparticles by LBL self-assembly deposition of chitosan
and carnauba wax, followed by the deposition of modified silica nanoparticles
using the conventional pad-dry process on chitosan-grafted cotton (Figure 11).
112 Mohamad Widodo, et al.

Figure 11 Alternative strategy/route for superhydrophobic finishing of cotton by

silica nanoparticles and carnauba wax.

4 Conclusions
An environmentally friendly and safer process of superhydrophobic finishing of
cotton fabrics with a static contact angle of 140.2° was successfully developed
with naturally available materials from rice husk ash silica nanoparticles and
carnauba wax using a layer-by-layer deposition self-assembly method. The
contact angle increased with the number of trilayers and reached 140.2° with three
trilayers. This was followed by 31.44% reduction of air permeability due to the
blocking of fabric pores by the multiple layers. Washing decreased water
repellence quite substantially in terms of spray testing from 70-90 down to 50 but
remained highly hydrophobic to superhydrophobic based on the definition given
based on contact angle from 137-152° to 129-142°.

5 Recommendations for Further Works

The route of improvement for a contact angle larger than 140° for a truly
superhydrophobic water-repellent finish of textiles involves ensuring that the
deposition creates a two-scale hierarchically nanostructure on the surface of the
fabric. A recommendation for further study is to investigate the surface properties
of the fabric after each of the successive depositions of silica nanoparticles,
chitosan, and carnauba wax in order to better understand the transformation of
the surface’s chemical morphology following the coating and its relation with the
wetting properties. Secondly, to investigate different process routes, i.e., surface
modification of silica nanoparticles by chitosan and carnauba wax and
 Bioinspired Superhydrophobic Finishing of Cotton 113

silanization of silica nanoparticles looking at multifunctional groups that provide

anchors for chemical bonding with cotton and superhydrophobicity.

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