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Preparation of superhydrophobic coating films using silica nanoparticles and

trimethylethoxysilane

Article in Korean Journal of Chemical Engineering · February 2021

DOI: 10.1007/s11814-020-0723-y

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Korean J. Chem. Eng., 38(3), 635-644 (2021) pISSN: 0256-1115
DOI: 10.1007/s11814-020-0723-y eISSN: 1975-7220
INVITED REVIEW PAPER INVITED REVIEW PAPER

Preparation of superhydrophobic coating films using silica nanoparticles

and trimethylethoxysilane
Dong Gu Kim, Tae Hyoung Kim, and Ki Chang Song†

Department of Biomedical Materials, Konyang University, 158 Gwanjeodong-ro, Seo-gu, Daejeon 35365, Korea
(Received 29 October 2020 • Revised 15 November 2020 • Accepted 24 November 2020)

AbstractSuperhydrophobic coating solutions were prepared using fumed silica nanoparticles and trimethylethoxysi-
lane (TMES) as precursors. At this time, the surface of silica nanoparticles was modified by TMES from hydrophilic to
hydrophobic in various types of catalysts and organic solvents. The prepared coating solutions were coated on a cold
rolled steel sheet by using a spin coater, and then superhydrophobic coating films were prepared by thermal curing. In
this process, the effects of the amount of silica nanoparticles added, the type of catalysts, and the type of organic sol-
vents were observed on the hydrophobicity of the coating films. As the content of silica nanoparticles added increased
from 0 g to 0.08 g, the contact angle of the coating films increased from 93o to 151o, and when 0.08 g of silica nanopar-
ticle was added, it showed superhydrophobicity of 151o. On the other hand, when nitric acid and hydrochloric acid,
strong acids, were used as catalysts, the coating films showed low hydrophobicity of 73o and 86o, respectively. However,
when oxalic acid, a weak acid, was used, the coating film showed superhydrophobicity of 151o. In addition, with meth-
anol as an organic solvent, the coating film showed superhydrophobicity of 151o, while when i-propanol and n-butanol
were used, the coating films exhibited low hydrophobicity of 97o and 91o.
Keywords: Silica Nanoparticles, Trimethylethoxysilane, Superhydrophobic, Coating Films, Surface Modification

INTRODUCTION sive and hazardous to humans and the environment. Substitutes

for fluorine compounds with low surface energy include wax, par-
Recently, superhydrophobic surfaces with water contact angles affin, polyurethane, dendrimer, and silicone. Among them, silicon
of 150o or more have attracted great interest due to their impor- compounds have the lowest surface energy after the fluorine com-
tance for applications such as self-cleaning, anticorrosion coatings, pounds, so a siloxane (Si-O-Si) structure is introduced on the sub-
oil/water separation, and fluid drag reduction [1]. In 1997, Bartho- strate surface to make the surface water-repellent [6,7]. More
lott and Neinhuis discovered that the self-cleaning properties of specifically, silicone compounds have a very stable chemical struc-
lotus leaves were due to their specialized surface morphology and ture and are considered the most stable water-repellent compounds
hydrophobicity [2]. The specialized surface morphology prevents after fluorine compounds [7].
dirt from forming intimate contact with the surface, while its high Trimethylethoxysilane (TMES), a type of silicon compound, can
hydrophobicity makes the leaves water-repellent. Lotus leaves show be used as a capping material to modify the surface of hydrophilic
that a combination of micro and nano-hierarchical structures and silica nanoparticles. Because TMES has a single ethoxy (-OC2H5)
low surface energy components is required to form superhydro- group, it effectively reduces the amount of OH groups on the sur-
phobic surfaces [3]. This can be achieved by depositing a layer face of silica nanoparticles.
with surface-modified silica nanoparticles on the substrates. Recently, we prepared water-repellent coating solutions using
Silica nanoparticles can be used to form micro and nano-hier- TMES and methyltrimethoxysilane (MTMS) by the sol-gel method
archical structures with superhydrophobicity through surface mod- [8,9]. The solutions were coated on a cold rolled steel sheet by using
ification. Since silica nanoparticles are hydrophilic due to hydroxyl a spin coater, and non-fluorine water-repellent coating films were
groups on the outer surfaces of particles, some hydrophobic mate- prepared by thermal curing. However, the water repellency of the
rials with low surface energy, such as fluorine compounds or sili- coating films was limited, and the water contact angle did not
con compounds, are used to modify the surface of silica nano- exceed 120o because no specific structure was given to the coating
particles. Since fluorine atoms can form very stable covalent pairs films. From this observation, we concluded that the chemical compo-
when combined with carbon to form low surface energy, fluorine sition of the coating solutions just turned the substrate surface
compounds have been most frequently used to make superhydro- from hydrophilic to hydrophobic, but not superhydrophobic.
phobic coating films [4,5]. In this study, the surface of hydrophilic silica nanoparticles was
However, fluorine compounds are limited because they are expen- modified by TMES using various types of catalysts and organic sol-
vents in a colloidal solution to make a superhydrophobic coating
†
To whom correspondence should be addressed. film. To the best of our knowledge, no studies have been conducted
E-mail: [email protected] on the effects of different types of catalysts and organic solvents
Copyright by The Korean Institute of Chemical Engineers. used during the surface-modification of silica nanoparticles on the

635
636 D. G. Kim et al.

superhydrophobicity of coating films. The purpose of this study is

to prepare a superhydrophobic coating film using silica nanoparti-
cles whose surfaces have been modified by TMES with various
types of catalysts and organic solvents. In this process, the effects
of the amount of silica nanoparticles added, the type of catalysts,
and the type of organic solvents on the superhydrophobicity of the
coating film were studied.

EXPERIMENTAL

1. Materials
Hydrophilic fumed silica nanoparticles (nanopowder, 10-20 nm,
99.5%) and trimethylethoxysilane [TMES, C2H5OSi(CH3)3, 98%]
were purchased from Sigma Aldrich. Methanol (MeOH, CH3OH,
99.5%, Samchun Chemical), ethanol (EtOH, C2H5OH, 95%, Sam- Fig. 1. Schematic illustration of the preparation of superhydropho-
chun Chemical), i-propanol (i-PrOH, i-C3H7OH, 99%, Sigma bic coating films by doping TMES-modified silica nanopar-
ticles on the cold rolled steel sheet.
Aldrich), n-butanol (n-BuOH, n-C4H9OH, 99%, Sigma Aldrich),
ethyl acetate (EA, CH3COOC2H5, 99%, Sigma Aldrich), and methyl
ethyl ketone (MEK, C2H5COCH3, 99%, Sigma Aldrich) were used observe the surface morphology of the coating films. The accelera-
as organic solvents for the dispersion of silica nanoparticles. In tion voltage was set to 10 kV and the surface of the coating film
addition, oxalic acid (C2H2O4, 99.5%, Jin Chemical), hydrochloric was magnified to 15,000 times to observe the morphology.
acid (HCl, 99%, Sigma Aldrich), nitric acid (HNO3, 99%, Sigma 3-2. Contact Angle Measurement
Aldrich), and ammonia water (NH4OH, 95%, Sigma Aldrich) were The contact angle to water on the coating films was observed
used as catalysts for the hydrolysis and condensation reactions of using a contact angle meter (Phoenix 10, Surface Electro Optics).
TMES. The reagents were used without purification or chemical A zoom microscope was used to enlarge the surface image to the
treatment. optimal magnification. Next, water droplets were added to the sur-
2. Preparation of Coating Films face of the coating films, and the contact angle was measured by
Several solutions were prepared by dissolving TMES in various quantitative analysis using a monitor and a SurfaceWare9 program.
types of organic solvents and then stirring these at room tempera- The average value of five measurements of the samples was recorded
ture (RT) for 5 min. After H2O and various types of catalysts were as the contact angle value.
added to the prepared TMES solutions, the solutions were stirred at 3-3. FR-IR Analysis
RT for 12 h to perform hydrolysis and condensation. Finally, fumed The bond vibration of C-H, O-H and Si-C in silica nanoparti-
silica nanoparticles were added and stirred at RT for 24 h to pre- cle and TMES was observed by Fourier transform infrared spec-
pare hydrophobic coating solutions. After a certain amount of the troscopy (FT-IR, Cary 630, Agilent Technologies).
hydrophobic coating solutions was dropped on a cold rolled steel
sheet, spin-coating was performed at 1,000 rpm for 1 min. Then, RESULTS AND DISCUSSION
hydrophobic coating films were prepared through thermal curing
at 120 oC for 2 h. The preparation process is illustrated in Fig. 1. 1. Effect of the amount of Silica Nanoparticles Added on the
3. Characterization Hydrophobicity of Coating Films
3-1. SEM Analysis Fig. 2 shows a schematic illustration of TMES modification on
High resolution FE-SEM (MIRA3-LM, Tescan) was used to hydrophilic silica nanoparticles dispersed in methanol solvent. TMES

Fig. 2. Schematic illustration of the preparation of TMES-modified silica nanoparticles.

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 Superhydrophobic coating films using silica nanoparticles and trimethylethoxysilane 637

metric stretching of the Si-O-Si bond [12]. For the TMES-modi-

fied silica nanoparticles in Fig. 3(c), the Si-O-Si absorption band at
1,077 cm1 and the -CH3 and Si-C stretching vibration bands at
2,956 and 847 cm1, respectively, appear, but the stretching vibra-
tion of Si-OH groups at 946 cm1 disappears. This suggests that
the reaction between TMES and the hydroxyl groups of silica
nanoparticles has occurred to form Si-O-Si(CH3)3 species on the
silica nanoparticle surface, and the surface of silica nanoparticles
was successfully modified with TMES.
Table 1 shows the composition of the coating solutions pre-
pared as a function of the amount of silica nanoparticles added to
the methanol solvent with an oxalic acid catalyst. Fig. 4 shows the
SEM surface morphology of coating films prepared by changing
the amount of silica nanoparticles added from 0 g to 0.12 g in Table
1. As shown in Fig. 4(a), when silica nanoparticles were not added,
the smooth surface could be obtained because there was no silica
nanoparticle present on the surface of coating films. As the load-
ing of silica nanoparticles increased in the coating solutions, the
surface of the coating films was gradually covered with a layer of
silica nanoparticles, resulting in uneven clusters on the surface.
When a small amount of 0.03 g of silica nanoparticles was added,
a small amount of nanoparticles was formed on the surface of the
coating films, as seen in Fig. 4(b). However, when the amounts of
added nanoparticles were 0.06 g and 0.08 g, as seen in Figs. 4(c)
and (d), the coating films showed a rough surface with randomly
distributed particles over the entire coating surface and a closely
packed structure. On the other hand, the coating film with an excess
of 0.12 g of nanoparticles added showed a loosely packed struc-
Fig. 3. The FT-IR spectra of (a) silica nanoparticles, (b) TMES, and ture with grooves due to significant aggregation between silica nano-
(c) TMES-modified silica nanoparticles. particles, as seen in Fig. 4(e).
Fig. 5 shows the water contact angles of the coating films as a
function of the amount of silica nanoparticles added. The coating
can be immobilized on the surface of the silica nanoparticles through films, in which the amount of silica nanoparticles was changed to
dehydration of water molecules with an oxalic acid catalyst. The 0 g, 0.03 g, 0.06 g, 0.08 g, and 0.12 g, showed contact angles of 93o,
modification was investigated by FT-IR measurement. 108o, 143o, 151o, and 150o, respectively. When the silica nanoparti-
Fig. 3 shows the FT-IR spectra of silica nanoparticles, TMES, cles were not added, the contact angle of the coating film was as
and TMES-modified silica nanoparticles, which were obtained after low as 93o. The reason for this low contact angle is that the hydro-
surface modification of silica nanoparticles by TMES. The broad phobicity was only affected by the methyl group of TMES that
band of silica nanoparticles around 3,438 cm1 in Fig. 3(a) is due existed on coating films, since there was no surface roughness due
to the stretching of various hydroxyl (-OH) groups, e.g., those on to the absence of nanoparticles in the coating film, as shown in
silica nanoparticles or water [10]. The absorption band at 946 cm1 Fig. 4(a). As the amount of silica nanoparticles added increased, the
is assigned to the stretching vibration of Si-OH groups on surfaces contact angles of coating films also increased. When a small amount
of silica nanoparticles [11]. The -CH3 and Si-C stretching vibra- of 0.03 g of nanoparticles was added, the contact angle in Fig. 5(b)
tions of TMES in Fig. 3(b) are shown at 2,956 and 847 cm1, respec- was 108o, which was an increase compared to 93o without the addi-
tively [12]. The absorption band at 1,077 cm1 is due to the asym- tion of nanoparticles. This seems to be due to the surface rough-

Table 1. The composition of the coating solutions prepared as a function of the amount of added silica nanoparticles
TMES H2O MeOH Oxalic acid Silica nanoparticle
Sample code
(mole) (mole) (mole) (mole) (g)
Sl 0.00
S2 0.03
S3 0.02 0.01 0.06 0.0008 0.06
S4 0.08
S5 0.12

Korean J. Chem. Eng.(Vol. 38, No. 3)

638 D. G. Kim et al.

Fig. 4. The SEM surface morphology of coating films prepared by varying the amount of added silica nanoparticles. (a) 0 g, (b) 0.03 g, (c)
0.06 g, (d) 0.08 g, and (e) 0.12 g.

ness formed by the addition of silica nanoparticles. However, since that the superhydrophobicity is due to the surface roughness formed
the amount of nanoparticles added was small, it was not distrib- by the addition of modified silica nanoparticles. However, it was
uted over the entire surface, so the contact angle of the surface did remarkable that when an excess amount of 0.12 g of nanoparticles
not increase significantly. When the amount of added nanoparti- was added, the contact angle of the coating film in Fig. 5(f) was
cles was 0.06 g and 0.08 g, the modified nanoparticles were uni- 150o and was not improved due to significant aggregation between
formly distributed over the entire surface, resulting in high contact nanoparticles despite the increase in the amount of nanoparticles
angles of 143o and 151o, respectively, as seen in Figs. 5(c) and (d). added. This result is consistent with Toh et al., who did not observe
Especially, in the case of 0.08 g, the coating film showed a contact an improvement in the contact angle despite an increase in the
angle of 151o, which showed the superhydrophobicity. It seems amount of silica nanoparticles added due to significant aggrega-

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 Superhydrophobic coating films using silica nanoparticles and trimethylethoxysilane 639

Fig. 5. Water contact angle of the coating films as a function of the amount of added silica nanoparticles on the hydrophobicity. (a) 0 g, (b)
0.03 g, (c) 0.06 g, (d) 0.08 g, and (e) 0.12 g.

tion between nanoparticles [13]. From these observations, it can a condensation reaction to yield a dimer called hexamethyldisilox-
be concluded that superhydrophobic coating could be successfully ane (HMDS), as shown in Eq. (2).
fabricated on a cold rolled steel sheet via the addition of TMES-
(CH3)3-Si-OH+HO-Si-(CH3)3(CH3)3-Si-O-Si-(CH3)3++H2O (2)
modified silica nanoparticles. However, when the amount of silica
nanoparticles exceeded 0.08 g, significant aggregation occurred In the case of surface modification of silica nanoparticles, it is well
between silica nanoparticles and the contact angle was rather known that hydrolyzed TMES adsorbs more on the surface of sil-
reduced. ica nanoparticles than HDMS dimer [14].
2. Effect of Type of Catalyst on the Hydrophobicity of Coat- Chang et al. studied the hydrolysis and condensation reactions
ing Films of TMES at different pH values [11]. They reported that the hydro-
When TMES is added to silica nanoparticles dispersed in metha- lyzed TMES monomers combined with each other to form a
nol, the ethoxy group (Si-OC2H5) of TMES hydrolyzes with water dimer (HMDS) through a condensation reaction. They also found
in methanol to form a silanol group (Si-OH), as shown in Eq. (1). that little conversion to form HMDS occurred when the pH value
was higher than 1.3. However, when the pH value was lowered to
(CH3)3-Si-OC2H5+H2O(CH3)3-Si-OH+C2H5OH (1)
0.8 or less, the hydrolysis and condensation reactions occurred
Then, the silanol group in the hydrolyzed TMES tends to undergo rapidly and the product was mainly composed of HMDS.

Korean J. Chem. Eng.(Vol. 38, No. 3)

640 D. G. Kim et al.

Table 2. The composition of coating solutions prepared with different types of catalysts in methanol
TMES H2O MeOH Catalyst Silica nanoparticle
Catalyst types
(mole) (mole) (mole) (mole) (g)
Oxalic acid
Hydrochloric acid
0.02 0.01 0.06 0.0008 0.08
Nitric acid
Ammonia

Fig. 6. The SEM surface morphology of the coating films prepared by using different catalysts of (a) oxalic acid, (b) hydrochloric acid, (c)
nitric acid, and (d) ammonia.

Table 2 shows the composition of coating solutions to reveal the Fig. 7 shows the effect of type of catalysts on the contact angles
effect of various types of catalysts in methanol solvent on the hy- of the coating films. The coating films prepared with different cat-
drophobicity of the coating films. Fig. 6 shows the SEM surface alysts of oxalic acid, hydrochloric acid, nitric acid, and ammonia
morphology of the coating films prepared using different catalysts show contact angles of 151o, 86o, 73o, and 143o, respectively. As ob-
of (a) oxalic acid, (b) hydrochloric acid, (c) nitric acid, and (d) served by Cheng et al. [11], when oxalic acid, a weak acid catalyst,
ammonia. When oxalic acid, a weak acid, was used as a catalyst, was used, there was almost no condensation reaction between the
silica nanoparticles were evenly distributed and coated on the entire hydrolyzed TMES monomers, so the solution was composed of
substrate. However, when hydrochloric acid and nitric acid, strong hydrolyzed TMES monomers, showing preferred adsorption on
acids, were used as catalysts, wide uncoated areas without nano- the surface of silica nanoparticles. Therefore, the modified silica
particles appeared on the surface. On the other hand, when ammo- nanoparticles were evenly distributed on the substrate surface,
nia, a base, was used as a catalyst, silica nanoparticles were uni- showing a superhydrophobicity of 151o. However, when hydro-
formly distributed on the coating films, but the particles were larger chloric acid and nitric acid, strong acid catalysts, were used, the
than that of oxalic acid and severe aggregation between nanoparti- coating films showed low hydrophobicity of 86o and 73o, respec-
cles was observed. tively. In this case, the hydrolysis and condensation reactions of

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 Superhydrophobic coating films using silica nanoparticles and trimethylethoxysilane 641

Fig. 7. Water contact angles of the coating films prepared by using different catalysts of (a) oxalic acid, (b) hydrochloric acid, (c) nitric acid,
and (d) ammonia.

TMES occurred rapidly, as mentioned by Cheng et al. [11]. The pylene glycol, and acetone, they form a stable, low viscosity sol
solution was composed of HMDS dimer, so it was less adsorbed with no aggregation between nanoparticles [15]. It is known that
on the surface of silica nanoparticles. Therefore, the silica nanopar- the hydrogen bonding between silanol group (Si-OH) on the sur-
ticles with less surface modification were not well coated on the face of silica nanoparticles and the polar organic solvent contrib-
surface, as shown in Figs. 6(b) and (c), resulting in low contact utes to the formation of this stable sol [16]. However, hydrophilic
angles of 86o and 73o. In the case of ammonia, which is a base cat- silica nanoparticles, dispersed in non-polar organic solvents with-
alyst, the contact angle of the coating film was 143o, which was out hydroxyl groups, undergo gelation due to direct bonding be-
slightly lower than that of oxalic acid of 151o. It is presumed that tween silanol groups on the surface of silica nanoparticles [15]. On
the aggregation between the nanoparticles was severe in ammo- the other hand, when the surface of hydrophilic silica nanoparti-
nia catalyst and the surface roughness was less than that of oxalic cles is modified by TMES as the capping agent, the TMES moiety
acid, resulting in a lower contact angle of the coating film. [-Si(CH3)3] on the surface of nanoparticles effectively prevents the
3. Effect of Type of Organic Solvents on the Hydrophobicity formation of bonds between the silica nanoparticles. As a result,
of the Coating Films the modified nanoparticles can be dispersible in various types of
When hydrophilic silica nanoparticles are dispersed in polar organic solvents, including polar and non-polar solvents [11].
organic solvents with hydroxyl groups such as alcohols, polypro- Chang et al. prepared hydrophilic silica nanoparticles from tetra-

Table 3. The composition of coating solutions prepared with different types of organic solvents under oxalic acid along with the solubility
parameters of organic solvents in this study
Solubility parameter TMES H2O Solvent amount Oxalic acid Silica nanoparticle
Solvent types
 (MPa1/2) (mole) (mole) (mole) (mole) (g)
Methanol 29.6
Ethanol 26.5
i-Propanol 23.6
0.02 0.01 0.06 0.0008 0.08
n-Butanol 23.1
Methyl ethyl ketone 19.1
Ethyl acetate 18.1

Korean J. Chem. Eng.(Vol. 38, No. 3)

642 D. G. Kim et al.

Fig. 8. The SEM results of surface microstructure of the coating films prepared with (a) methanol, (b) ethanol, (c) i-propanol, (d) n-butanol,
(e) methyl ethyl ketone, and (f) ethyl acetate.

ethylorthosilicate by the sol-gel method, after modifying the sur- Table 3 shows the composition of coating solutions prepared
face of silica nanoparticles using TMES, a capping agent [11]. They with various types of organic solvents with an oxalic acid catalyst,
found that the TMES-modified silica nanoparticles could be dis- and the solubility parameters of organic solvents used in this study
persible in a variety of organic solvents (polar and non-polar sol- [17]. Fig. 8 shows the SEM results of surface microstructures of
vents), with the dispersibility depending on the amount of TMES the coating films prepared with (a) methanol, (b) ethanol, (c) i-
bound to the silica nanoparticles. They also observed that the size propanol, (d) n-butanol, (e) methyl ethyl ketone, and (f) ethyl ace-
of the silica nanoparticles, dispersed in various organic solvents, tate. In the case of coating films prepared with methanol and etha-
decreased as the solubility parameter of organic solvents increased nol, as shown in Figs. 8(a) and (b), the silica nanoparticles are evenly
[11]. coated over the whole substrate to form a rough surface. How-

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 Superhydrophobic coating films using silica nanoparticles and trimethylethoxysilane 643

Fig. 9. Water contact angles of the coating films prepared with (a) methanol, (b) ethanol, (c) i-propanol, (d) n-butanol, (e) methyl ethyl
ketone, and (f) ethyl acetate.

ever, the coating films prepared with i-propanol and n-butanol in show that silica nanoparticles are evenly coated on the entire sub-
Figs. 8(c) and (d) shows regions that were not extensively coated strate, as shown in Figs. 8(e) and (f). Therefore, the coating films
with nanoparticles on the substrates. In addition, in the coating prepared with methyl ethyl ketone and ethyl acetate exhibit rela-
films, prepared with methyl ethyl ketone and ethyl acetate, ketone tively high contact angles of 119o and 126o, respectively. However,
solvents in Figs. 8(e) and (f), the nanoparticles are evenly coated as shown in Table 3, the solubility parameters of the ketone sol-
on the entire substrate. vents are lower than those of methanol and ethanol, and the nano-
Fig. 9 shows the effect of different types of organic solvents on particles in the solutions are larger than those of methanol and
the contact angles of coating films. The coating films prepared with ethanol, resulting in a less rough structure on the coating films. For
methanol and ethanol exhibit high contact angles of 151o and 149o, this reason, unlike methanol and ethanol, high hydrophobicity
respectively, as the nanoparticles are evenly distributed on the sur- above 149o was not observed in the coating films of methyl ethyl
faces, as shown in Figs. 8(a) and (b). However, i-propanol and n- ketone and ethyl acetate.
butanol show low contact angles of 97o and 91o, respectively, due
to the broad areas not covered with silica nanoparticles, as shown CONCLUSION
in Figs. 8(c) and (d). On the other hand, when methyl ethyl ketone
and ethyl acetate, ketone solvents were used, the coating films A superhydrophobic coating film was successfully prepared by

Korean J. Chem. Eng.(Vol. 38, No. 3)

644 D. G. Kim et al.

forming a rough structure of silica nanoparticles modified with the coating films of methyl ethyl ketone and ethyl acetate.
TMES on the surface of the cold rolled steel sheet. The surface char-
acteristics of the coating film were studied by SEM, FT-IR, and ACKNOWLEDGEMENT
static contact angle measurements. FT-IR analysis confirmed that
the reaction between TMES and the hydroxyl groups of silica This paper was supported by the Konyang University Research
nanoparticles occurred to form Si-O-Si(CH3)3 species on the sil- Fund in 2019.
ica nanoparticle surface, and the surface of silica nanoparticles was
modified by TMES. The coating film, prepared without silica nano- REFERENCES
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