Article

International Journal of
Green Nanotechnology
Application of Nanosols in Textile 1:1-7
ª The Author(s) 2013
Industry DOI: 10.1177/1943089213506814
nan.sagepub.com

Amirhosein Berendjchi, PhD1, Ramin Khajavi, PhD2, and

Mohammad Esmaeil Yazdanshenas, PhD3

Abstract
Inorganic metal oxide nanoparticles are mainly synthesized by sol–gel process. The most important beneficial advantage of
mentioned process is facile and the time-consuming route. The resultant meta-stable synthesized inorganic nanoparticles can
easily modify different substrates and alter their performance. The presented review investigates the possible applications of
nanosols (especially silica and titanium dioxide sols) in the field of textile industry, including the formation of hydrophobic,
bioactive or protective metallic oxide coatings on textiles by physical or chemical modifying of nanosols.

Keywords
sol–gel, inorganic nanoparticles, modifying, textile industry

Introduction in the formation of an amorphous network that is called

These days applying nanoparticles especially in the field of
chemistry science has many advantages. By using very small
compounds under 100 nm scale with high activity (because
of their high specific area) bulk or surface properties of
various substrates could be changed. Synthesizing metal
oxide nanoparticles using conventional methods because of
time- and energy-consuming process could not be an appro-
priate approach. It seems that preparing colloidal metal oxide
solutions under ambient conditions would be more benefi-
cial. Nanosols are colloidal solutions of nanometer-sized
metal oxide particles in aqueous or organic solvents. Because
of very high surface area, the nanosols are metastable, thus,
during a coating process a three-dimentional (3D) network
would be formed due to aggregation of particles and
subsequent evaporation of the solvent.1 Nanosol coatings are
usually prepared by using the sol–gel process. This process
can be basically divided into three steps: formation of the nano-
sol by hydrolysis of the precursor material and subsequent con-
densation reactions, the coating process, and drying or curing.
The precursors are either inorganic metal salts or metal organic
compounds such as metal alkoxides or acetylacetonate. Alkoxy
derivatives of metals or semimetals are most widely used,
whereby hydrolysis transforms them into the corresponding
hydroxides. These hydroxides are mostly unstable in higher
concentrations and therefore tend to undergo subsequent
condensation reactions. The condensation reactions lead to the
formation of particles with sizes in the nanometer range.
Frequently used precursors are, for example, tetraethoxysilane
Si(OC2H5)4 (TEOS), titanium(IV)isopropoxide Ti(OC3H7)4,
or Al(OC4H9)3. It should be taken into account that insuffi-
cient heat treatment after applying nanosol coatings will result
‘‘xerogel.’’1
Eqs 1 and 2 show an example of possible reactions during
the synthesis of colloidal silica nanoparticles from an alkoxy
silane precursor:
Si(OC2H5) +H2O Si(OH)4 + 4C2H5OH ð1Þ
2SiðOHÞ4 ! 2ðSi  O  SiÞ þ 4H2 O ð2Þ
The above-mentioned colloidal solution has a low viscosity
(in the range of 1–6 mPas) in liquid dispersion containing nano-
sized particles. Synthesized metal oxide nanoparticles can be
easily applied on the surface of a variety of materials, leading
to the formation of dense layers once the solvent evaporates.1
Modification of Nanosols
Prepared sols are modified using two major methods: chem-
ical and physical routes. In chemical modifying method,
1
Department of Textile Engineering, Science and Research Branch, Islamic
Azad University, Tehran, Islamic Republic of Iran
2
Department of Textile Engineering, South Tehran Branch,, Islamic Azad
UniversityTehran, Islamic Republic of Iran
3
Department of Textile Engineering, Yazd Branch, Islamic Azad University,
Yazd, Islamic Republic of Iran
Corresponding Author:
Amirhosein Berendjchi, Department of Textile Engineering, Islamic Azad
University, Science and Research Branch, Tehran, Islamic Republic of Iran.
Email: amirhosein.br@gmail.com
2 International Journal of Green Nanotechnology 1(0)
Figure 1. Transmission electron microscopic images of (a) unmo-
dified silica nanoparticles and (b) chemical modified with copper
(Cu) nanoparticles.3
usually active chemical substances such as polysiloxanes,
alkylsilanes, organic domains, and so on are introduced
inside the network of nanoparticles by forming covalent or
even physical bonds. Ibrahim et al. used hexamethyldisila-
zane for surface modification of synthesized silica
nanoparticles.2 Alkylsilane chemical modifier resulted in the
formation of monodisperse colloidal solution as a result of
prevention of silica nanoparticle agglomeration and reduced
surface energies. Berendjchi et al by dopping Cu nanoparti-
cles inside inorganic silica network obtained grape-like clus-
ters with the capability of trapping air inside (Figure 1). Due
to the potential ability of complex forming copper nanopar-
ticles, the morphology of resultant network was changed.3
By adding macromolecular compounds such as dyestuffs,
proteins, polymers, and so on in the physical modifying route
the actual encapsulation procedure occurs, resulting in the
formation of the corresponding compound during or after the
hydrolysis process of the precursor.1 Miao et al prepared
silica microcapsules containing butyl-stearate by emulsify-
ing butyl-stearate inside silica network and obtained core
shell microcapsules that have beneficial applications in
energy-saving building materials.4
One of the most important factors for applying nanosol
coatings onto textile fibers is adhesion between substrate and
coating material. This is especially the case for most of the
synthetic polymeric fibers. Several methods such as cross-
linking agents, corona, or plasma treatments, high temperature
processing, and so on, are used for activating such surfaces.1
After preparing the corresponding coatings usually using
padding process and appropriate heat treatment, metal oxide
nanoparticle networks would be fixed on the textile
surfaces.2–15 In the presented review, we will investigate the
possible applications of nanosols for changing the perfor-
mance of textile fibers.
Fiber Spinning
It has been reported that glass fibers could be produced using
dry spinning of silica sols. By doing so, inorganic composite
fibers based on silicon dioxide (SiO2) and also other metal
oxides or mixtures of both would be prepared. Spinning of
nano fibers from sol–gel-based solutions using electrospin-
ning method is also reported. Electrospinning process has
some advantages because of simplicity of producing of fiber
sheets based on the inorganic fibers. Preparing the inorganic
fleeces could be advantageous for certain applications
including preparation of catalytic materials, promising a
good solvent and temperature stability, combination of light-
weight and high surface area, and so on. Nanofibers are also
of interest for the preparation of certain filter materials for
filtering very small particles.1
Fiber Protection
Fire Resistance. As mentioned before, a combination of a
lightweighted and flexibility with high tensile strength is one
of the advantages of using textile materials. Flame-retardant
finishes in textile industry have attracted great interest
because every year enormous number of people all around
the world die due to fire accidents. For technical textiles
employed in high-temperature applications or aggressive
zones, there is also a huge demand for modifying them to
withstand high temperatures and delay the burning rate. The
purely inorganic nanosol networks are themselves inflamma-
ble; therefore, they are not expected to increase the inflam-
mability of fiber materials. It is expected that enhanced
flame-retardant activity achieved by coating inorganic
nanosols would be the result of a barrier effect. On one hand,
applying the nanosol coatings as thin as possible will make it
more effective; and on the other hand, as xerogel matrices
are porous the coatings cannot probably act as a sufficient
oxygen barrier because of the above-mentioned limiting fac-
tors that reduce the effectiveness of thermal shielding
ability.1
In the field of textile industry, there are two mechanisms
for creating the fire-retardancy effect on textile materials.
One of them is to prevent the possible reactions of active free
hydroxyl or hydrogen radicals generated from burning pro-
cess. In this area, chlorine- or bromine-containing substances
are often used for fire protection. By decomposition of these
compounds during a fire, hydrogen chloride and hydrogen
bromide will be released. Then these compounds react with
highly reactive hydroxyl and hydrogen radicals, forming less
energetic chlorine or bromine radicals. Hydrogen and
hydroxyl radicals promote the radical processes in the flame,
which are mainly responsible for the propagation of a fire. As
a result, the initial burn rate will be slowed down because of
reduction of these radicals, thereby increasing the time to
flashover. Frequently used brominated species as flame
retardants are polybrominated diphenyl ether, polybromi-
nated biphenyl, or brominated cyclohydrocarbons.1
Another major approach is to create a protective char
layer having nonporous and dense structure characteristic.
For example, using phosphate esters incorporated in a
Berendjchi et al.
coating (or forming the coating itself) and converting to char
by a fire, a protective layer will be formed. The transport of
oxygen into the polymer would be hindered by these barrier
layers, and simultaneously they will act as a shield against
the heat. During decomposition, the expansion of some
compounds is observed based on ammonium polyphosphates
or dicyandiamide. This action will cause forming a thick char
layer that acts as the shield against oxygen and heat.1
UV Protection. Apart from the well-known perils on human
beings due to exposure to the sun’s radiation, there are
enormous synthetic fiber polymers that are decomposed by
UV-light, examples are polyester, p-aramide, or poly-p-
phenylenebenzobisoxazole (PBO) fibers. Most of the time
the UV protection is expected in textiles of darker shades
because the dyestuffs inside would absorb UV as well as visi-
ble light strongly; however, the protection against these
radiations is limited. Although the light stability of polyester
fabrics is sufficient in the field of clothing, an improved
resistance is needed for certain applications. Improving the
UV resistance could be achieved by modifying the fiber
polymer with UV-absorbing pigments or even employing
organic molecules that act as radical scavengers. As men-
tioned earlier, absorption of UV radiation would be neces-
sary since the number of people with skin cancer has
increased dramatically within the last decades. In textile
industry, the main aim of coating of a textile by nanosols
is to absorb or reflect visible, UV, or IR light over a broad
range of the spectrum or even at certain wavelengths. In sin-
gle molecules, the optical properties are determined by the
energetic gap between molecular orbitals especially the
highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbitals (LUMO). The absorption of
bulk semiconductor materials is estimated by the band gap
between the unoccupied conduction and the occupied
valence band. It is clear that in nanoparticles, the number
of located orbitals in the valence and the conduction band
is dramatically reduced. Therefore, in comparison with bulk
materials, the number of orbitals in nanoparticles is low.
Generally the gap between the HOMO and the LUMO
orbitals is determined by repelling the occupied as well as the
unoccupied orbitals. Because of fewer number of orbitals in
the nanoparticles, the repulsion is lower. As a result, the
energy gap between HOMO and LUMO becomes larger.
In general, for colored nanoparticles with decreasing size,
the absorption band will shift to shorter wavelength.
Therefore, the use of nanometer-sized particles is considered
more beneficial. It has been reported that nanosols contain-
ing inorganic particles such as zinc oxide (ZnO) or titania
(TiO2) are able to absorb UV radiation. In addition, it is
reported that the preparation of nanosol coatings filled with
TiO2 or ZnO particles smaller than 50 nm is advantageous
because these coatings are colorless and transparent. Embed-
ding of the organic UV absorbers such as phenylacrylates or
benztriazols into coatings based on silica–sol has also been
3
reported. Chemical bonding between the organic UV
absorbers and the silica networks for achieving an improved
durability might be useful. To increase the UV-absorption in
the UV-A region, it would be effective to use fluorescent
whitening agents in combination with a TiO2 sol.1
Changing Hydrophobicity
Cotton is probably the most common natural fiber in textile
industry. For many applications creating a hydrophobic sur-
face on cotton textiles is a major challenge. Most of the syn-
thetic fibers that are usually used in textile industry are fairly
hydrophobic. Thus, most of the time, water-repellent finishing
is applied on natural fibers. Before revealing the scanning
electron microscopes (SEMs) the term ‘‘hydrophobicity’’ was
presented based on fundamental wetting theories (Yang, Wen-
zel and Cassie - Baxter equations).5–7
Yang presented a formula for measuring the so-called
‘‘static contact angle (CA)’’ when a droplet is placed on a
solid surface:
cos yy ¼ ðgSA  gSLÞ=gLA: ð3Þ
Where gSA and gSL are the surface energies of the solid
against air and liquid, respectively, and gLA is the surface
energy of liquid against air.5 yy is called static water CA
in the Yang’s equation.
Based on the above equation, less surface energy equals to
more hydrophobicity, but the static CA will decrease up to a
certain value. Actually by chemically modifying a surface,
we cannot create a super-repellent surface.
The possibility of producing a superhydrophobic surface
was proposed by Wenzel in 1936.6 Based on eq 4, we can
conclude that beside chemical modification, physical proper-
ties of materials (roughness) can play an important role with
respect to the surface hydrophobicity:
cos yw ¼ Rf cos yy: ð4Þ
Rf (roughness factor) is equal to the ratio of the solid
surface area and its flat projected area.
In 1944, another theory was presented by Cassie and
Baxter.7 Based on this theory (eq 5), the hydrophobicity of
a surface can be enhanced by trapping air inside the valleys
of a rough surface at the triple contact line (composite inter-
face between air, liquid, and solid substrates):
Cos ycb ¼ Rf Cos yy  fLAðRf Cos yy þ 1Þ: ð5Þ
The fraction of trapping air (fLA) plays a major role. With
higher air pockets fraction (flA), the amount of cos ycb
decreases, enhancing the superhydrophobicity effect on the
roughened surfaces.
According to the above-mentioned explanation, for the
creation of a superhydrophobic surface two factors are
necessary: low surface energy (chemical factor) and rough-
ness (physical factor).
4 International Journal of Green Nanotechnology 1(0)
Figure 2. Altering the morphology of cotton fiber before (a) and after (b) treating with silica nanoparticles.3
Synthesized metal oxide nanoparticles in sol–gel method
have potential applications in creating the roughness on
textile surfaces. As shown in Figure 2, they are spherical
in shape; and when a surface is coated with nanoparticles, the
morphology of surface is altered.
As mentioned before, most of the water-repellent
finishing processes are applied on natural fibers especially
on cotton ones. In order to create a superhydrophobic
surface, we can reduce the surface energy of a roughened
surface or create roughness on a surface having low free
energy. In order to create roughness by the sol–gel method,
usually TEOS and its hydrolysis is used under alkaline con-
dition.8 In this way, nanoparticles created have more stability
because of their increasing size; and when placed on the sur-
face, they could create roughness on the substrate. Due to the
existence of enormous hydroxyl groups on the surface of
nanoparticles, usually through the self-assembly process and
by introducing an alkyl silane containing alkyl or flouroalkyl
side chains, the free surface energy of the substrate is
reduced and a superhydrophobic surface is created.3,9–14
Xu et al. created superhydrophobic cotton fabric by fabricat-
ing rough surfaces using both SiO2 nanoparticles and ZnO
nanorod arrays and also using low surface energy by subse-
quent modification with n-dodecyltrimetoxysilane (DTMS).
In this article, both SiO2 nanoparticles and ZnO nanorods
had similar diameter; however, the samples prepared with
ZnO nanorods had more air trapping between the adjacent
ZnO nanorods because of higher aspect ratio of ZnO nanor-
ods. As a result, slide angle was reduced when compared to
the samples treated with SiO2 nanoparticles and DTMS.
Wetability of cotton fabric showed superhydrophobic
properties with static CA of more than 150 for 5 μL water
droplets. In this article, it was concluded that lower sliding
angle of cotton fabric treated with ZnO is attributed to
discontinuous three-phase contact line that shows better
water-repellent properties.9 Yu et al. created a superhydro-
phobic complex coating for cotton fabrics based on silica
nanoparticles and perfluorooctylated quaternary ammonium
silane coupling agent (PFSC). The complex film was pre-
pared via sol–gel process. Silica nanoparticles made the tex-
tile surface much rougher, and the PFSC on the top layer
lowered the surface free energy. Fabrics coated with this
coating showed excellent water-repellent property and the
CA increased from 133 for those cotton fabric treated with
PFSC without silica sol to up to 145 . Also, the oil repellency
was improved and the CA of CH2I2 on the fabric surface
treated with SiO2 nanoparticles and PFSC increased from
125 to 131 (in comparison with fabrics treated with PFSC
only).10 Bae et al. created superhydrophobic cotton fabrics
by treating with silica nanoparticles and a cost-effective
water-repellent agent (WR agent; an emulsion consisting
of perfluroacrylate, benzyl methacrylate, water, etc.). In this
article, two types of silica nanoparticles were synthesized via
the sol–gel process and their shape, size, and composition
were characterized; and it was concluded that silica nanopar-
ticles were spherical and had diameters of about 143 and 378
nm. For cotton fabrics treated with WR agent alone in con-
centrations lower than 0.3% wt, the CAs of water remained
on cotton surface were lower than 20 . The hydrophilic silica
nanoparticles did not change the properties of cotton, and
they showed that water drops are absorbed inside fabric due
to the hydroxyl groups existing on the surface of silica nano-
particles. However, for cotton fabrics treated with silica
nanoparticles and the WR agent, even at very low concentra-
tion of WR agent (about 0.1% wt), the CA of more than 130
was obtained. Thus, it was concluded that superhydrophobic
cotton fabric can be prepared by a combination of silica
nanoparticles and a WR agent, which is inexpensive
compared to fluorosilanes.11 Erasmus and Barkhuysen cre-
ated superhydrophobic cotton fabric by modification with
flourosilane. In this article, superhydrophobic surface and
self-cleaning ability of cotton was created by 1H, 1H, 2H,
2H flouro-octyl tri etoxy silane, and it was recognized that
an increased level of treatment increases the CA and causes
Berendjchi et al. 5

Figure 3. Scanning electon microscope and scanning probe microscope micrographs of surface fabricated by (a & b; left) untreated (middle)
silica sol, (right) 0.5% copper (Cu)-doped silica; and (c) water drops on surface fabricated by 0.5% Cu-doped silica sol and its contact angle.3

self-cleaning properties.12 Li et al. created superhydrophobic
cotton fabric via sol–gel method and using water glass
(sodium silicate) as the starting material. Such surfaces were
produced first by dip coating of silica hydrosols that were
prepared via hydrolysis and condensation of water glass onto
cotton substrates. Then the silica coating was modified with a
nonfluoro compound (hexadecyltrimetoxysilane [HDTMS])
for attaining a thin film and finally superhydrophobicity with
a water CA of higher than 151 was obtained.13 Hoefnagels
et al. turned cotton fabrics from hydrophilic to superhydropho-
bic by in situ introduction of silica particles into cotton fibers
in order to generate a dual-size surface roughness, followed by
hydrophobization with polydimethylsiloxane. The treated fab-
rics exhibited a static water CA of 155 for a 10-μL droplet. In
this article, it was mentioned that the sliding angle of water
droplets depends on the droplet volume and is in the range
6 International Journal of Green Nanotechnology 1(0)
Table 1. Percentage Reduction in Bacteria on the Fabricated Silica-
Cu Surfaces.
Escherichia coli Staphylococcus
(%) Gram aureus Gram
Sample Kind negative positive
Silica-Cu (0.5%) 92.98 99.42
Silica-Cu (2%) 72.19 99.40
Undoped silica sol 0 0
Source: Reprinted from Berendjchi, A.; Khajavi, R.; Yazdanshenas, M. E. Fab-
rication of Superhydrophobic and Antibacterial Surface on Cotton Fabric by
Doped Silica-Based Sols with Nanoparticles of Copper. Nanoscale Res. Lett.
2011, 6, 594.
of 7 for a 50-μL droplet to 20 for a 7-μL droplet. Also, it was
mentioned that when perfluoroalkyl chain is introduced to the
surface of silica particles, the superhydrophobic fabric
becomes highly oleophobic, so that the static CA for a
15-mL sunflower oil droplet becomes 140 and its sliding
angle will be 24 .14
Antimicrobial Coatings
Another major finishing in textile industry refers to elimina-
tion of microorganisms from textiles. Antimicrobial coatings
have been intensively studied and probably are the commer-
cially most important finishes. There are some drawbacks
with regard to the settlement of microorganisms on textiles.
Because of specific structure and large surface of textile
materials especially in the natural ones, good adhesion and
excellent water storage properties are expected. Such textiles
in contact with the skin (under sufficient temperature and
humidity conditions) offer an ideal place for the growth of
pathogenic bacteria, because of their porous and hydrophilic
structure. Preventing the degradation of textile fibers, limit-
ing the prevalence of bacteria, reducing odor formation, and
protecting users by avoiding the transfer and spread of patho-
gens are some possible advantages of the above-mentioned
finishes. Many approaches to create an antimicrobial textile
by nanosol treatment have been proposed by researchers.
There are different methods to destroy germs using nanosol
finishes, which include the employment of photoactive
nanosol coatings containing TiO2 in anatase form or those
using the controlled release of embedded biocides or even
using composite coatings containing TiO2 and SiO2 sols.1
Xing et al. used low temperature and cost-effective process
for creating antimicrobial effect on cotton textiles based on
sol–gel method. In this study, they used water glass as
precursor and the antimicrobial treatment was performed by
treating silica impregnated cotton textiles with silver nitrate
solution. Samples had excellent antibacterial activity against
Escherichia coli bacteria even after 50 washing cycles.15
Creating both antibacterial and superhydrophobic effects
simultaneously on cotton textiles has also been reported.3 In
the previous study, by dopping Cu nanoparticles inside silica
sol, we obtained an improved superhydrophobicity (static
water CA of 155 ) accompanied with excellent antibacterial
activity against both of Gram-positive and Gram-negative
bacteria. In the first step, silica nanoparticles were synthe-
sized using general Stöber method. Then Cu nanoparticles
were dopped inside inorganic nanoparticle networks in two
different percentages (wt %). Resultant coating material was
applied on cotton fabric, and HDTMS was used for lowering
the surface energy of samples. Due to the air-trapping capa-
bility of inclined surface and extreme antibacterial activity of
Cu nanoparticles, superhydrophobicity and also antibacterial
activity of samples were promoted. In Figure 3 and Table 1,
an improved porous structure and also enhanced antibacterial
activity of cotton textiles are confirmed by scanning probe
microscope and American Association of Textile Chemists
and Colorists (AATCC) 100 method, respectively.
Conclusion
Different possible applications of metal oxide nanoparticles
prepared by sol–gel method were discussed. In all cases, sub-
sequent modifying by appropriate chemical compounds is
needed. Silica nanoparticles are used more than the other
types of inorganic metal oxide nanoparticles because of their
special shape and also higher activity.
Acknowledgments
The authors acknowledge Dr. Manafi from the Department of
Chemistry of Islamic Azad University–South Tehran Branch for his
constructive advice in this review.
Declaration of Conflicting Interests
The author(s) declared no potential conflicts of interest with respect
to the research, authorship, and/or publication of this article.
Funding
The author(s) received no financial support for the research, author-
ship, and/or publication of this article.
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