08/24/18

Self-cleaning, Stain-resistant and Anti-bacterial Superliquiphobic Cotton Fabric

Prepared by Simple Immersion Technique
Poonam Chauhan1, Aditya Kumar1* and Bharat Bhushan2
1
Department of Chemical Engineering, Indian Institute of Technology
(Indian School of Mines) Dhanbad, Jharkhand, India, 826004
2
Nanoprobe Lab for Bio- & Nanotechnology and Biomimetics,
The Ohio State University, Columbus, OH 43210, USA

Abstract
In this paper, superliquiphobicity of cotton fabric was produced by simple immersion
method in non-fluorinated hexadecyltrimethoxysilane solution. Modified cotton fabric
showed repellency to water and oil (surface tension more than 47 mN/m) with a static contact
angle of more than 150° and tilt angle of less than 10°. The mechanical, chemical, thermal,
and UV stability of superliquiphobic cotton fabric was evaluated. Modified cotton fabric
exhibited the self-cleaning and stain-resistant properties. It also showed that it could be used
for oil-water separation application with separation efficiency of about 99%. Additionally,
the modified cotton fabric exhibited anti-bacterial properties. This approach is facile,
economical, and eco-friendly and can be applied for household and industrial applications.

Keywords: Superliquiphobic, Self-cleaning, Stain resistant, Oil-water separation, Anti-

bacterial

*Corresponding authors: adityaku43@gmail.com (Dr. Aditya Kumar);

bhushan.2@osu.edu (Dr. B. Bhushan)

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1. Introduction
The cotton fabric materials have been extensively used in various household and
industrial applications due to their unique properties such as good feel, biodegradability,
renewability, and being environment-friendly. The presence of hydroxyl groups (-OH) on the
cotton fabric surface makes it hydrophilic. Due to this hydrophilicity nature, the cotton fabric
can be quickly wetted by the liquids (including water and oil). However, this high affinity of
liquid to the cotton surface increases the probability of the stains and bacterial growth, and
subsequently it limits the usage of cotton fabric in several applications. As cotton fabric is
more prone to stains, it looks unpleasant and requires multiple washing, leading to
deterioration of life of cotton fabric and increasing the washing cost. Therefore, modification
of the cotton fabric is of interest to improve the quality of the cotton fabric and to be able to
use it for multiple applications.
Superliquiphobicity refers to a surface which repels a range of liquids (Bhushan,
2018). It includes both superhydrophobicity and superoleophobicity. Superliquiphobicity is
defined when the static contact angle greater than 150° and the tilt angle less than 10° for
both water and oil. These surfaces take their inspiration from nature, including from the lotus
leaf and water strider (Bhushan, 2018).
The superliquiphobicity on the cotton fabric is achieved by introducing the roughness
(nano/microstructures) with low surface energy materials (Bhushan, 2009). Modification on
the cotton fabric surfaces is challenging due to the inherent heterogenerous roughness with
low thermal stability. In recent work, several methods such as dip-coating (Zeng et al., 2015,
Zhu et al., 2017), solution-immersion coating (Panda et al., 2017, Li et al., 2008), sol-gel
based coating (Liu et al., 2017, Przybylak et al., 2016), wet-chemical process (Wang et al.,
2017), spray-coating (Hsieh et al., 2011) were used to develop the superliquiphobicity on the
cotton fabric. These studies mainly focused to modify cotton fabric for self-cleaning, UV-
protection, anti-bacterial, and oil-water separation. However, still a major challenge is stain
on the cotton fabric surface. For practical applications, creating the simple and facile
superliquiophobic cotton fabric becomes is of interest.
In this paper, we report a facile method to fabricate a superliquiphobicity on the cotton
fabric by simple immersing it in non-fluorinated hexadecyltrimethoxysilane (HDTMS)
solution to make it stain-resistant with properties such as self-cleaning, UV-resistance,
chemical and thermal stabilities, separation of oil of surface tension less than 47 mN/m from
its oil-water mixture, anti-bacterial properties and excellent durability. The purpose of this
paper is not only to modify cotton fabric to repel higher surface tension liquid such as water,
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but also to repel the low surface tension liquids (greater than 47 mN/m) such as milk, honey,
and ethylene glycol.

2. Experimental details
2.1 Materials
Commercially available cotton fabric (2 cm x 2 cm) was used as a substrate.
Hexadecyltrimethoxysilane (HDTMS) used as a low surface energy material was purchased
from Sigma-Aldrich. Ethanol, sodium chloride (NaCl), ethylene glycol, chloroform, toluene,
benzene, and dimethyl carbonate (DMC) were purchased from Merck Life Science Private
Ltd., India. All chemicals were used as received.

2.2 Synthesis of superliquiphobic cotton fabric

In preparation of superliquiphobic cotton fabric, as received cotton fabric was cleaned
ultrasonically to remove wax and other impurities with distilled water and ethanol for 30 min
and subsequently 1 h dried at 70°C. 5% (v/v) HDTMS was dissolved in ethanol and stirred
for 1 h at room temperature to obtain a homogeneous solution. Subsequently, cleaned cotton
fabric was immersed in HDTMS solution for 5 h and then dried at 120°C for 6 h in a hot air
oven to remove the solvent. Finally, a modified cotton fabric was taken out from a hot air
oven and left in air for cooling. The superliquiphobicity was successfully obtained on the
cotton fabric surface.

2.3 Characterization
Surface morphologies of as received and modified cotton fabric were examined with
scanning electron microscope (SEM, Supra 55V, Carl Zeiss, Germany). The wettability of
the modified cotton fabric was measured using a contact angle measurement system (DSA
25, Krüss, Germany) at the room temperature with 3-5 µL droplet of water and liquids (with
surface tension greater than 47 mN/m) such as tea, honey, milk, and ethylene glycol. Contact
angles were taken at different position on each sample. Surface tension values of these
liquids are given in Table 1 (Haynes (2014), Takamura et al. (2012), Chandan (1997),
Speight (2017), Harkins and Brown (1919)).
Functionality of the surfaces were determined using a Fourier-transform infrared
spectroscopy (FTIR, Cary 660, Agilent Technologies, USA) in the wavelength range of 400-
4000 cm-1.

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 Chemical stability of the modified cotton fabric was examined by immersing samples
in saline water (3.5 wt% NaCl) and organic solvents (toluene, chloroform and dimethyl
carbonate). At regular intervals of immersion, contact angles were measured to observe any
changes in wettability. In UV stability test, sample was exposed to UV irradiation using a
UV curer (UltraV-C1, Apex Instruments Co. Pvt. Ltd, India) with a wavelength of 254 nm
and irradiance of 6.82 Mw/cm2 for 40 h. Contact angles of the surfaces were measured at
regular intervals of UV exposure. Thermal stability of the modified cotton fabric was
evaluated by keeping the sample for 1 h in the hot air oven at different temperatures and then
the water contact angles of annealed samples were measured to examine any changes in
wettability. The durability of the modified coated fabric was evaluated by 1 h washing in
detergent, hot-water, and organic solvents by using ultra-sonication bath and water contact
angles were measured. Additionally durability of sample was evaluated by water jet test. In
this test, a water jet was sprayed on cotton fabric and the behavior of jet was recorded.
To evaluate the self-cleaning performance, as received and modified cotton fabric were
immersed into the muddy water for 10 min. The modified cotton fabric was difficult to
immerse into the mud water due to the high liquid repellence property so it was immersed by
application of force. Afterward, the impact of mud on the surfaces was recorded. In stain
resistance test, tea and color water droplets were placed on both as received and modified
cotton fabric. After that, both samples were dried in hot air oven at 80°C until complete
evaporation of liquid droplets and stain or marks on the surfaces were recorded.
The performance of the modified cotton fabric was also investigated for oil-water
separation. Before conducting an experiment, the modified cotton fabric was dipped in oil
(organic solvents). The wetted modified cotton fabric was placed onto the funnel. Later, the
oil-water mixture was poured onto modified cotton fabric which repelled the water (blue
color) and collected on its surface and oil penetrated by its own gravity. Herein, n-hexane,
kerosene, and benzene were used as oil in the oil-water mixture. Separation efficiency (ɳ)
was calculated by using this equation:
ɳ (%) = m1/m0 × 100 (1)
where, m1 and m0 are the volumes of water after and before the separation process,
respectively.
The anti-bacterial activity of both as received and modified cotton fabric were
measured with the E. coli bacteria. The inhabitation zone method (Khalilabad and
Yazdanshenas, 2013, Perera et al., 2013) was used to examine the anti-bacterial activity on
both as received and modified cotton fabric. Initially, approximate 20 ml sterilized nutrient
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agar was poured into the petri dish and left it for 30 min to get solidified before inoculating.
Five hundred microliter of the bacterial suspension with a concentration of 1×105 colony
forming unit (CFU)/ml was spread on the surface of the each sterile agar plate, and then two
holes were punched into the each plate. Both as received and modified cotton fabric of 7mm
diameter were kept in the holes and incubated at 37°C for 24 h.

3. Results and discussion

In this study, superliquiphobicity on the cotton fabric was obtained by simple
immersing it in HDTMS solution. Wettability, surface morphology, and functionality of the
modified samples will be discussed. Further, mechanical, chemical, UV, and thermal
stabilities of superliquiphobic cotton fabric will be presented. Furthermore, self-cleaning
property, oil-water separation ability, stain resistance, and anti-bacterial activity of modified
cotton fabric will also be examined.

3.1 Wettability, surface morphology, and functionality

Wettability behavior of both as received and modified cotton fabric were examined via
the contact angle measurement technique. It is found that as received cotton fabric exhibits
superhydrophilic and superoleophilic behavior with contact angle of ~0°. After modification
of cotton fabric with HDTMS, it displays outstanding water repellency with a water contact
angle of 157±5° as shown in the Fig. 1. A water droplet easily rolls off with the slide angle of
7°, indicating its superhydrophobic nature. Additionally, liquids whose surface tension is
equal or more than 47 mN/m (tea, honey, ethylene glycol, etc.) also show the good repellency
for the modified with contact angles more than 150°, revealing superliquiphobic nature of
modified cotton fabric (Fig. 2).
Mechanism of modification of cotton fabric was proposed after investigation of the
surface morphology and FTIR spectra. The surface morphologies of as received and modified
cotton fabric have been observed by using SEM as shown in Fig. 1. The SEM images of the
as received and modified cotton fabric show no significant differences due to the formation of
HDTMS monolayer, however, both surfaces show the hierarchical morphology. To confirm
the presence of functional group, FTIR spectra of both surfaces were examined as shown Fig.
3. For modified cotton surface, the absorption peaks at 796 cm-1 is attributed to Si-O-Si
stretching (. Additionally two absorption peaks at 2850-2910 cm-1 and 2910-2940 cm-1 were
found and these correspond to –CH3 and –CH2 stretching vibrations, respectively (Zhang et
al., 2012). These functional groups indicate the presence of long chain alkyl groups on the
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modified cotton fabric, which come from the HDTMS compound. The air pockets between
hierarchical microstructures and presence of hydrophobic groups on the modified surface are
likely responsible for nonwetting state (Cassie and Baxter, 1944).

3.2 Wetting stability under harsh condition

The stability of the modified cotton fabric plays a vital role. For practical application, it
should work indoor as well as in harsh environments such as high temperature, UV
irradiation, acidic/alkaline/organic contact, and washing. The durability after washing was
evaluated by immersing superliquiphobic cotton fabric into detergent solution, hot water
(80ºC) and organic solvent such as benzene, and it was ultra-sonicated for 1 h. Afterward
wettability behavior of dried fabric was examined by measuring contact angle measurement
technique. It was observed that contact angle is more than 150° and water droplets roll out
from the surface sample (Fig. 4), exhibiting washable nature of surface without any damage.
This test indicates that the HDTMS-modified cotton fabric easily sustains after washing.
A water jet experiment was also performed by spraying water. On the as received
cotton fabric, water is completely spread on the surface due the strong adhesive force
between water and the cotton fabric (Fig. 5). Whereas jet of water has bounced off the
modified cotton fabric without leaving any trace of water on its surface (Fig. 5) due to
excellent water repellent nature of the surface. In this, water is sprayed for continuously one
min on a single position of the surface, and it is found that jet is still bouncing without
leaving any trace of water on surface, showing mechanical strength of cotton fabric
modification.
The chemical stability of the modified cotton fabric was examined by immersing the
samples in organic solvents (chloroform, toluene, and dimethyl carbonate) for 7 days and in
saline water (3.5 wt% NaCl) for 24 h. The water drops on the surface, after immersion, are
formed spherical shape as shown in Fig. 6 and also contact angles are found to be more than
150°, displaying its excellent superliquiphobic nature. Modified cotton fabric is not only
suitable for organic solvents, but also it can work in the saline water, which is seriously
important for the industrial purpose.
The thermal stability experiment of the modified cotton fabric was studied by annealing
the sample at different temperatures (120 to 200°C) for 1 h in hot air oven as demonstrated by
(Nanda et al., 2017). The superliquiphobicity with (WCA=157±5°) of the modified cotton
fabric is easily sustained after annealing at 120 to 150°C (Fig. 7), exhibiting outstanding
thermal stability of the modified cotton fabric below 150°C. Further, the contact angle of
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cotton is found to be 141° after annealing at 160°C and the superliquiphobicity turns into
hydrophobicity due to the decomposition of the HDTMS (boiling point=155°C) and removal
of low surface energy material from the surface. Furthermore, after annealing at 200°C, not
only contact angle reduces (128°) and also color of fabric changes from white to brown,
indicating the damage of the fabric at this temperature.
Some of superhydrophobic surfaces can loose their superhydrophobicity when
exposing to ultraviolet (Tu et al., 2018). The ultraviolet irradiation was exposed on the
modified cotton fabric surface for 40 h. It shows that water contact angle (157±5°) after 40 h
UV exposure remains unchanged (Fig. 8). Besides, no color change of the fabric is noticed.
This shows the excellent UV stability of the superliquiphobic cotton fabric.

3.3 Applications of superliquiphobic cotton fabric

The self-cleaning experiment (Wen et al., 2017) for the modified cotton fabric was
examined by immersing as received and modified cotton fabric into the muddy water for 10
min as shown in Fig. 9. It is observed that when the modified cotton fabric does not immerse
easily in mud and remains floated on the mud water surface due to the high liquid repellence
property. Therefore, it is forcefully immersed into the mud water. After immersion, as
received cotton fabric is found to be wetted with mud water and it remains polluted even after
cleaning and drying. On the other hand, modified cotton fabric is found to be dried and fully
cleaned just after bringing out from the muddy solution, showing its excellent self-cleaning
property.
Cotton is the most favorable fabric material for our daily wearing, hospital, decoration,
and cooking purposes. Due to porous nature, it has the ability to absorb the water, moisture,
and oil. It can be stained and contaminated by liquids such as consumable food, blood, and
beverages, which is unpleasant in their use as cloths. Thus, in this paper, the efforts have been
made not only in developing the excellent superhydrophobic, but also in incorporating the
excellent stain resistance against the common household liquids such as lemon, honey,
turmeric solution, milk, and tea. Stain-resistance experiment was conducted by placing tea
droplets on both as received and modified cotton fabric (Fig. 10). It is observed that the tea
droplet is completely absorbed on the surface of as received cotton fabric. Whereas it forms a
spherical shape on the modified cotton fabric as shown in Fig. 10. It is observed that the stain
mark after drying on as received cotton fabric is clearly visible and this is unwashable. After
drying modified cotton fabric, a thin layer of tea particles is formed, but it could be removed
easily without washing. The same experiment was also repeated with colored water. In case
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of water, a color water droplet is placed on the both as received and modified cotton fabric as
shown in (Fig. 11). Color water droplet was fully absorbed on as received cotton fabric
surface while on modified cotton fabric, it left a small stain mark after drying due to the
diffusion of the dye on its surface which was difficult to remove after washing. This
experiment indicates the outstanding stain-resistance characteristics of modified cotton fabric.
Since, droplets of water and liquid of surface tension more than 47 mN/m cannot
penetrate through the superliquiphobic cotton fabric surface and low surface tension oil can
easily penetrate, this cotton fabric can be used for oil-water separation. In this study, oil (n-
hexane = 18.43 and kerosene = 30, mN/m) were used to separate from their water mixture.
Besides, oil (benzene = 28 mN/m) was used to separate from its oil mixture of ethylene
glycol (47.70 mN/m). All mixtures were taken in 1:1 ratio. Fig. 12 shows the separation of n-
hexane-water mixture using Superliquiphobic cotton fabric surface. It can be seen that oil is
separated by its own gravity. After separation, no water trace (blue color) is visible within the
penetrated oil (n-hexane), showing excellent oil-water separation efficiency. Separation
efficiency is calculated by using this equation (1). Calculated efficiency of oil separation
from its mixture for all cases (n-hexane-water (oil-water), kerosene-water (oil-water) and
benzene-ethylene glycol (oil-oil)) is found to be 99%. After a few cycles, the separation
process becomes slow due to adsorption of the oil on cotton surface. Afterward, oil adsorbed
cotton fabric is cleaned with acetone and water. It is found that the cleaned cotton fabric
shows the contact angle more than 150° and can be reused for oil-water separation process.
Cotton fabric also encounters bacterial attack, which limits its application. In this paper,
the anti-bacterial activity was also tested against the E. coli bacteria (Gram-negative bacteria)
by using qualitative measurement (inhabitation zone method) on the both as received and
modified cotton fabric. Air trapped in the interstices on the surface (Cassie-Baxter state)
which has shown in superliquiphobic surface, reduces the contact between bacteria and the
surface, and thus E.coli does not survive. No inhibition zone is observed on the as received
cotton fabric as shown in Fig. 13. Whereas inhibition zone (no growth of bacteria)
surrounding the modified cotton fabric is observed, and the diameter of Inhibition zone is
measured approximately 10mm and 14 mm including the diameter (7mm) of cotton fabric
when it is incubated for 12 hours and 24 hours respectively, revealing the excellent anti-
bacterial characteristic of superliquiphobic cotton fabric surface.

4. Conclusions

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 In this study, fluorine free superliquiphobicity on the cotton fabric is generated by
using a simple immersion technique which is inexpensive and environmental friendly.
Modified cotton shows outstanding repellency with water and liquids whose surface tension
is more than 47 mN/m such as tea, honey, and ethylene glycol. It shows good chemical
stability both in organic (chloroform, toluene, and dimethyl carbonate) as well as saline
water. Superliquiphobicity is easily sustained after 1 h washing in detergent solution, hot
water, and in organic solvent such as benzene and also remains unchanged by continuous
spraying water jet. It is also unaffected after 1 h annealing up to 150°C and 40 h exposure of
UV irradiation.
Modified cotton fabric can separate the oil from its oil-water (kerosene-water, n-
hexane-water) and oil-oil (benzene-ethylene glycol) with high separation efficiency of 99%.
It possesses the excellent self-cleaning property. It has high stain resistance. It also shows the
high anti-bacterial activity against the E. coli bacteria. The modified cotton fabric can be used
in the variety of applications.

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Comments on References:
1. References that are highlighted in yellow are not listed in the text. Please check
and delete if necessary.

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 2. (Kunken et al., 2018) and (Zhang et al., 2013) need to be listed in references

3. Chandan- need to list the city where published, in the reference

4. References for Haynes, Takamura, Chanda, Speight, Harkins and Brown are listed
for the first time in Table 1. Perhaps, they should also be mentioned in the body of
the article, where the table 1 is called out as well. .

Table 1: Surface tension values of various liquids and whether modified cotton repels the
liquid or not
Liquid Surface tension Modified cotton References
(mN/m) repels or not
Water 71.99 Repel Haynes, 2014
Glycerol 63.4 Repel Takamura et al., 2012
Milk 55-60 Repel Chandan, 1997
Ethylene glycol 47.70 Repel Haynes, 2014
Kerosene 30 Does not repel Speight, 2017
Benzene 28.80 Does not repel Harkins and Brown,
1919
n-Hexane 18.43 Does not repel Haynes, 2014

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Figure captions

Fig. 1. SEM images of as received and superliquiphobic cotton fabric. Inserts are contact
angle and high magnified SEM images.
Fig. 2. Optical image of superliquiphobic cotton fabric consisting of various droplets
(ethylene glycol, honey, color water, lemon, tea, turmeric, milk and glycerol).
Fig. 3. FTIR spectra of as received and superliquiphobic cotton fabric.
Fig. 4. Optical images of water droplets on modified cotton fabric after 60 min washing in
detergent solution, benzene and hot water (80ºC) via ultra-sonication method,
showing its excellent washing ability. Inserts are contact angle images.
Fig. 5. Water jet experiment on as received and superliquiphobic cotton fabric.
Fig. 6. Optical images of water droplet on modified cotton fabric after immersion in
chloroform for 7 days, toluene for 7 days, dimethyl carbonate for 7 days, and saline
water for 24 h, exhibiting its chemical stability. Inserts are contact angle images.
Fig. 7. Contact angle of modified cotton fabric after 1 h annealing at different temperatures,
showing thermal stability of modified cotton fabric.
Fig. 8. Optical images of water droplet on modified cotton fabric after 40 h UV exposure.
Inserts are contact images.
Fig. 9. Optical images of as received and superliquiphobic cotton fabric before and after
immersion in the mud water, demonstrating self-cleaning property of cotton fabric.
Fig. 10. Optical images of tea droplets on as received and superliquiphobic cotton fabric
before and after heating at 80°C (no stain mark), revealing stain resistance of cotton
fabric.
Fig. 11. Optical images of colored water droplets on as received and superliquiphobic cotton
fabric before and after heating at 80°C (small mark due to the diffusion of dye),
revealing stain resistant of cotton fabric.
Fig. 12. Optical images of steps before, during, and after oil-water separation by using
superliquiphobic cotton fabric. Water had blue color to visualize the difference
between oil and water mixture, showing efficiency of 99%.
Fig. 13. Optical images of as received cotton fabric after incubation time of 24 h and
superliquiphobic cotton fabric after incubation time of 12 and 24 h respectively,
with E. Coli bacteria, showing anti-bacterial activities of cotton fabric.

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