Progress in Organic Coatings 131 (2019) 73–81

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

The study of glass superhydrophobicity by modified SiO2- T

hexadecyltrimethoxysilane (SiO2-m-HDTMS) nanoparticles and mixture of
surfactants
⁎
Beheshteh Sohrabi , Fereshteh Mansouri, Sanaz Zirak Khalifan
Department of Chemistry, Surface Chemistry Research Laboratory, Iran University of Science and Technology, P.O. Box 16846-13114, Tehran, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: Indeed, which changes will be produced in hydrophobicity behavior of superhydrophobicity glasses when they
Superhydrophobic surfaces are in contact with surfactants which are as a detergent? The most prominent point of this paper is study of
Catanionic mixtures surfactant nanostructures interactions with superhydrophobic surfaces and investigation of interactions effect on
Silane containing substances the superhydrophobicity of these surfaces. To answer the question above, it is necessary to prepare hydrophobic
Contact angle
surfaces alongside materials having silane and improve their superhydrophobic property by modified SiO2-
Hexadecyltrimethoxysilane (SiO2-m-HDTMS) in various concentrations followed by the interaction of surfac-
tants nanostructures with these surfaces and finally, we should study the impact on contact angle. What our
studies about the interaction of anionic and cationic-rich solutions showed is that a change in the percentage of
surfactants and also their change in concentration caused a change in superhydrophobicity. Additionally, our
investigations on βσ and βM parameters illustrated that in cationic-rich region before CMC, because of existing
monomers in cationic-rich region by raising concentration, contact angle contrast to wettability of surface in-
creases. While in anionic-rich region, surfactants monomers are much more stable than aggregates; thus, with an
increase in concentration, the number of monomers on surface and therefore the wettability of surface increase.
In fact, we demonstrated that surfactant concentration and also the structure of nanomaterial, especially in the
anionic-rich region, affect the superhydrophobic surface.

1. Introduction revealed that hierarchical micro-nanostructures and low surface energy

In recent years, great deal of studies in the field of super-
hydrophobic (SH) surfaces has been implemented because of its diverse
applications in various fields. [1–7] The superhydrophobic surfaces are
defined as every surface possessing a high static contact angle above
150° and hysteresis angle (the difference between the advancing and
receding contact angles) of less than 10° which exhibit extreme water
repellency and self-cleaning properties. Water droplets may roll in ad-
dition to sliding at a low value of contact angle hysteresis, which sim-
plifies the removal of contaminant particles. These surfaces have gen-
erally been produced by adsorption of some materials as coating on
substrates and by combining nanomaterials as raspberry-like nano-
particles with coatings for creating roughness. [8–10] Additionally,
hierarchical structure of these surfaces leads to multifunctional using of
them. Thus, these surfaces have extensive applications in various in-
dustrials e.g. in electronic and optical devices, photonic materials, and
templates for making chemical sensors [11]. Investigations have
are two main reasons for appearing of superhydrophobicity phenom-
enon on SH surfaces [12]. Thus, we can use both reducing energy and
roughness of surface for producing superhydrophobic surfaces. Various
materials are used for fabricating the multifunctional superhydrophobic
surfaces and among these materials, silanes due to suitable price and
performance are significantly used [13]. Silane nanoparticles could be
applied for the creation of roughness on the surface [13–15]. What the
camparison between hierarchical surfaces and mono-scale roughness
surfaces shows clearly is that hierarchical surfaces are more appropriate
than other for fabricating superhydrophobicity surfaces. In fact, on
these surfaces, the water droplets could readily sit on the apex of the
nanostructured parts, because of air bubbles which fill the valleys of the
structure under the droplet. Accordingly, considerable super-
superhydrophobicity is exhibited by these surfaces. Once the water
droplets roll off on these surfaces, remove any contaminant particles
from the surface which in turn leads to self-cleaning. Reportedly, na-
nostructures are created by using silane nanoparticles. To this end,

⁎
Corresponding author.
E-mail addresses: sohrabi_b@iust.ac.ir, sohrabi_b@yahoo.com (B. Sohrabi).

https://doi.org/10.1016/j.porgcoat.2019.02.010
Received 31 October 2018; Received in revised form 31 January 2019; Accepted 4 February 2019
Available online 25 February 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
B. Sohrabi, et al. Progress in Organic Coatings 131 (2019) 73–81

Fig. 1. Preparation of nanoparticles modified by HDTMS.

Fig. 2. The interaction of glass with MTCS.

Fig. 3. Placing of modified nanoparticles (SiO2- m-HDTMS) on the glass surface.

Fig. 4. The diagram of contact angle versus modified nanoparticles wt%.

silane nanoparticles were placed on the surface by functionalizing them
[16]. A complex interplay among the surface structure, the morphology
and physical and chemical properties affects the properties of surfaces.
Also, studies of Kumar and et al. show if a drop of water was placed on a
clean silica surface spreads uniformly to form a film.While, a drop of
CTAB solution initially spreads and then retracts to form a drop. [17] In
the other word, contact angle changes with increase surantfacts to so-
lution because the interface tension and surface energy in the droplet
interface change. Also, the investigations show surfactants, depending
on their concentrations and structures, play an important role in

74
B. Sohrabi, et al.
controlling the spreading of solutions on superhydrophobic surfaces
[18,19].
Various investigations have been done about the interaction of
surfactants and other materials with polar and dipolar surfaces and by
measuring hysteresis (H) angle, contact angle and surface energy, these
interactions have been studied. Barey et al investigated contact angle
and H, advance and receding angles of various polymeric materials and
surfactants with polymeric and silica surfaces. The obtained results
showed that H angle and surfactant dispersion on the surface depends
on the surfactant concentration and advance, receding and H angles
confirmed it. By studying the interaction of diverse surfactants in the
contact area of solid-liquid-air, the impact of concentration on the ad-
sorption of these materials on hydrophobic surfaces such as silane
coated surfaces could be observed [20].
In the present work, we investigate the impact of surfactants mix-
ture on the behavior of hydrophobicity of superhydrophobed glass with
silane materials and also explain the surfactants orientation on these
surfaces. The changes in contact angle will be explored to determine β
parameter.
2. The study of Surfactants interactions to superhydrophobic
surfaces
Surfactants widely are used for aggregation between interfaces
[21–25] difference of interaction energy between the chain and the tail
of a surfactant molecule causes to aggregation of these materials be-
tween phases. Surfactants, in the phase interfaces, change interface
tension and consequently contact angle is changed. The role of single
and mixed surfactants in control of superhydrophobic surfaces wett-
ability has been investigated [25]. Despite existence of diverse articles
in the field of the surfactants adsorption on superhydrophobic surfaces,
still, numerous studies for utilization of their potential applications are
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Progress in Organic Coatings 131 (2019) 73–81
Fig. 5. Contact angle images of modified su-
perhydrophobic surfaces with SiO2-m-HDTMS
with composition ratio: a) pure MTCS, b) su-
perhydrophobic glass modified by 0.1% SiO2-
m-HDTMS, c) superhydrophobic glass modified
by 0.3% SiO2-m-HDTMS, d) superhydrophobic
glass modified by 0.5% SiO2-m-HDTMS, e) su-
perhydrophobic glass modified by 0.7% SiO2-
m-HDTMS, f) superhydrophobic glass modified
by 0.9% SiO2-m-HDTMS.
continued to be carried out. It is worth pointing out that wetting of
hydrophilic surfaces depends on decrease in surface tension and solid-
liquid interfacial tension that this change in surface tension depends on
the type and the structure of surfactants. Surfactants increase wett-
ability of the surfaces which are hardly become wet by adsorption in
solid-liquid and liquid-air interface [25]. This phenomenon takes place
because of decrease in interfacial tension resulted from surfactants.
Surfactants, depending on their concentrations and structures, play
an important role in controlling spreading of solutions on super-
hydrophobic surfaces [21].
In recent years, wetting and spreading processes in which surfactant
solutions are involved have been widely used in numerous industrial
and practical applications. Performance of various single surfactants
has been widely investigated and their wettability has been studied
[21]. Addition of mixed surfactants to water has been proven to be an
important factor in enhancement of wetting, even on superhydrophobic
surfaces [25].
2.1. Interaction of the mixed surfactants
We consider two surfactant materials which are similar in terms of
structure and chemical properties; we evaluate the interaction of these
two surfactant materials by measuring parameter β. The interactions
and in conclusion the values of parameter β, usually are affected by
electrostatic interactions among hydrophilic heads of two surfactants.
Surfactants mixtures such as the mixture of anionic and cationic
surfactants show deviation from ideal state. Some factors such as su-
perhydrophobic chain length and the volume of polar head can be ef-
fective factors which could cause the surfactants mixture deviation
from ideal state.
B. Sohrabi, et al.
Fig. 6. SEM images related to the surface hydrophobed by MTCS (left) and then modified by 0.9% SiO2-m-HDTMS (right) a) 200 μm, b) 50 μm, c) 10 μm, d) 1 μm.
2.1.1. Intermicelar interaction parameter β
Molecular interactions between two different surfactants in micelle
mixture are defined by parameter β which is indicator of this interac-
tion power and nature. In attraction interactions, β is negative and in
repellence interactions β is positive. Hence, negative amount means
that because of mixing two surfactants, present attraction interaction is
higher or the repellence after mixing is lower than before mixing
[26–28]. Approaching β parameter to negative amount means that the
interactions because of mixing are low. To calculate molecular inter-
action in agglomerated particles in the mixture of two different sur-
factants, Rubbing law has been used. According to this law, it can be
written:
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Progress in Organic Coatings 131 (2019) 73–81
(X1M )2 ln (α1 C12M / X1 C1M )
=1
(1 − X1M )2 ln[(1 − α1) C12M /(1 − X1M ) C2M ] (1)
ln [α1 C12M / X1 C1M ]
βM =
(1 − X1M )2 (2)
where X1Mis the mole fraction of surfactant 1 in the mixed surfactant
solution and C1M , C2M and C12M are the CMCs for surfactant 1, surfactant 2
and their mixture, respectively, at the mole fraction α1.
2.1.2. Mixed monolayer interaction parameter β σ
Interaction power of the two surfactant materials in the mixture
one-layer depends upon the surface nature and molecular properties
such as temperature and the solution ionic strength. Studies show that
B. Sohrabi, et al. Progress in Organic Coatings 131 (2019) 73–81

Fig. 7. a) AFM images related to a normal glass (b) AFM images related to the surface superhydrophobed by the MTCS and modified by 0.9% SiO2-m-HDTMS.

Table 1 Table 3
Selected concentrations from conductometry data for performing the reaction. Information of surface tension and contact angle related to the full of cation and
full of anion conditions.
SDS:CTAB 90:10 10:90
(Wt%) SDS:CTAB (Wt%) C (mM) γLA (mN/m) θ (◦)
C(mM) 2.03 1.37
2.75 2.53 0.3 46.9 98.57
90: 10 0.5 40.57 100.16
1.37 30.61 102
Table 2 2 31.10 87.07
0.3 48.68 130
Average size of nanoparticles in cationic and anionic-rich mixtures.
10:90 0.5 40.57 135
α Concentration Average Size 2.03 30.61 136.88
(mM) (nm) 2.75 31.10 119.35

SDS:CTAB 90:10 2.03 673.2

(Wt%) 90:10 2.75 655.4
means that in case of mixing two surfactants in the surface, the inter-
CTAB: SDS 90:10 1.37 3256
(Wt%) 90:10 2.53 6067 action is higher, or after mixing, it is lower than before mixing. To
calculate molecular interaction in one-layer formed by two surfactants
mixture in different surface, following equations are used [26,27].
the interactions, which are at the mixture one-layer, are stronger in
comparison with the interactions of intra-micelle under similar condi- Z12 ln(α1 C12/ Z1 C1σ )
=1
tions. By using of Rubbing theory, the molecular interactions between (1 − 2
Z1) ln[(1 − α1) C12/(1 − Z1) C2σ ] (3)
two surfactants in various surface absorbed on different intersections
can be determined. For attraction interactions, β σ is negative and for ln(α1 C12/ Z1 C1σ )
repelling interactions, β σ is positive. Accordingly negative amount of β σ βσ =
(1 − Z1)2 (4)

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B. Sohrabi, et al. Progress in Organic Coatings 131 (2019) 73–81

Table 5
Interaction parameters table of the monomers on the surface and in micellar
solution.
SDS:CTAB (Wt%) βM f1 f2 X1 f2S βσ f1S

90:10 −5.72 0.23 0.24 0.49 0.485 −6.55 0.053

10:90 −5.92 0.72 0.03 0.76 0.21 −3.96 0.57

3. Experimental

3.1. Materials and methods

All the solvents, chemicals and reagents were purchased from

Merck, Fluka and Aldrich. Surface tension was measured by a tension
measurement-sigma 700. Phase transfers and concentrations were
Fig. 8. Contact angle changes versus the surfactants concentration in cationic-
identified by Jenway conductometer. Atomic force spectroscopy (AFM)
rich and anionic-rich mixtures.
was obtained by Ara research co AFM instrument. Dynamic light scat-
tering was investigated by ZETAPLUS (Brookhaven). Contact angles
Table 4 were measured by using Data Physics OCA15 plus Contact Angle-meter.
Data related to solid-liquid surface tension. The roughness factor that obtained
from Eq. (7) is 0.94.
3.2. Synthesis of supersuperhydrophobic surfaces
SDS:CTAB(Wt.%) C(mM) θ (◦) γlv(mN/m) γslSL(mN/m)

90:10 0.3 130 42.68 40.57

Initially, silicate nanoparticles were synthesized via Stöber process.
0.5 135 40 41.46 [29] 50 mL ethanol and 2 mL double distilled water were poured in a
2.03 133.88 37.2 38.80 250 mL round-bottom flask. Then, tetraethyl-ortho-silicate (0.024 mol,
2.75 119.35 36.10 30.19 5 g) was added to the flask and the mixture was stirred by a magnetic
10:90 0.3 98.57 46.9 13.22
stirrer till the mixture is completely homogenous. Next, temperature
0.5 100.16 40.57 13.24
1.37 102 30.61 12.40 was increased to 50 °C by an oil path and 1 mL, 28% ammonia (as a
2.53 87.02 31.10 3.91 catalyst) was added to the mixture for reaching pH to 11. Reaction was
continued for 5 h. Then, the reaction mixture was cooled to room
temperature. The resulted sediment was separated from the mixture. It
Here Z1 is the mole fraction of surfactant 1 in total mixed monolayer was washed with ethanol for other three times. At last step, the sedi-
(on a surfactant-only basis); β σ , is interaction parameter for mixed ment was placed at 60 °C inside oven to be completely dried.
monolayer formation at the aqueous solution/air interface and C1σ , C2σ
and C12 are the molar concentrations in the solution phases of surfactant 3.3. Synthesis of modified silicate nanoparticles with
1, surfactant 2, and their mixture, respectively, at the mole fraction α1 Hexadecyltrimethoxysilane (HDTMS)
of surfactant 1 required to produce a given γ value. In our experiments,
we determined C1σ , C2σ and C12, which correspond to a surface tension of 0.5 g synthesized white silicate nanoparticles and 4 mL HDTMS
σ = 40 mN m−1 for the cationic-rich mixture. were loaded into a round-bottom flask and the reaction mixture was
exposed to ultrasound waves to be dispersed. The flask was placed at
f1σ = exp(β σ χ12 ) (5) 50 °C and stirred for 30 min by a magnetic stirrer. The reaction mixture
was alkaline by addition of 1 mL ammonia 25%. The reaction was
f 2σ = exp[(β σ (1 − χ1 )2] (6) continued for 12 h and the flask was then cooled and white sediment
was separated by centrifuge. To wash unreacted silanes, the sediment
Interaction parameter β σ , f1σ and f 2σ just like intra-micelle interac- was washed with ethanol and separated and ultimately it was dried at
tion parameter are obtained by simultaneous solution of Eqs. (3) to (6) 50 °C [30]. Synthesis steps of modified silicate nanoparticles with
by using of Matlab software. Hexadecyltrimethoxysilane (HDTMS) have been peresented in Fig. 1.

Fig. 9. The schematic for the surfactants monomers and aggregates place in liquid-air and solid-liquid interfaces.

78
B. Sohrabi, et al.
3.4. Preparation of glass base for coverage
Initially, the slides were washed with water and detergents [31,32].
Then, they were placed in a solution of sulphuric acid and chromic acid
for removal of any kind of impurities and fat. Next, glasses were washed
with distilled water and exposed to ultrasound waves in ethanol solu-
tion for 15 min and were washed again with water and dried [33–35].
Preparation of hydrophobic coverage by methyltrichlorosilane (MTCS)
via chemical vapor deposition method. In this method, prepared glasses
were previously hung in an isolated system. A little pot placed in this
system was loaded with 1 mL (MTCS) and the bottom of this system was
filled with 2 mL ethanol 5%. The reaction vessel door was closed firmly
and placed on a heater at 50 °C for 48 h. At this conditions glass is
hydrophobic via chemical vapor deposition method. (see Fig. 2) Then,
the glasses were prepared for measuring contact angle.
3.5. Modification of hydrophobic surface by modified SiO2-HDTMS
nanoparticles with various weight percents
At this step, after measuring contact angle for comparison with
modified state, the hydrophobic glasses were modified by plunging in
the desired solution. SiO2-m-HDTMS solution with weight percents
from 0.1% to 1.1% were dissolved in ethanol and placed in ultrasonic
and then the hydrophobic glasses were placed in these solutions for
5–15 min (according to Fig. 3). Next, they were exited from solution
and dried and then their contact angle was measured. Suitable time and
concentration were optimized with regard to contact angle.
3.6. Preparation of surfactants
In the present study, ionic surfactants mixtures, which have syner-
getic effects and produce the wide range of microstructures in solution
various composition, were used. To this end, 90:10 mixture of CTAB/
SDS as cationic-rich and 90:10 mixture of SDS/CTAB as anionic-rich
with 10 mM concentration were prepared. Initially, critical micelle
concentration (CMC) of solutions was measured by Tensiometer. Then,
the phase transfers and concentrations were identified by using con-
ductometery. Concentrations of the solutions were prepared and after
performing dynamic light scattering (DLS) test, their contact angle with
the surface was investigated. The desired concentrations were con-
sidered to be selected after critical concentrations to be able to in-
vestigate the concentration effect and mixture effect on the contact
angle. The contact angle of the superhydrophobic glasses in peresence
and absence surfactants was measured by Digimizer program. To this
end, 2 μL water and surfactant solution, respectively was placed on the
glass surface by a Hamiltonian syringe and a photograph was captured
and its contact angle was measured with software. The contact angle
between the glass surface with anionic surfactant and another one with
cationic surfactant was compared. Then, the interaction between the
surface and surfactant nanostructures was investigated.
4. Results and discussion
4.1. Contact angle of water droplet
The superhydrophobic glass surface prepared by MTCS and also by
SiO2-m-HDTMS in different percentages, which are used for the im-
provement of the glass surface superhydrophobicity, obtained and their
contact angles were measured. Fig. 4 shows the contact angle variations
of superhydrophobic surface to increase in nanoparticles percentage
[36].
Fig. 5 shows the contact angle of modified surfaces increases by an
increasing in composition of SiO2-m-HDTMS. It is figured out that the
maximum contact angle is for the glass containing 0.9 wt. % of nano-
particles and has a contact angle of 162.5 ° showing super-
hydrophobicity of the glass surface. The minimum contact angle is for
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Progress in Organic Coatings 131 (2019) 73–81
the conditions in which the coated glass contains 0.1 wt. % of nano-
particles and has a contact angle of 139.5 °. The above presented images
and diagram demonstrate that contact angle increases with an increase
in SiO2-m-HDTMS percentage. In the present study, 0.9 wt. % is the
level which is applied for investigation of surfactants impact.
4.2. Glass superhydrophobic surface investigation and its roughness using
SEM and AFM
To investigate the morphology of superhydrophobic surface and
also to observe the exact roughness present on its surface, scanning
electron microscopy (SEM) was used. According to Fig. 6, SEM images
show the glass surface coated by the MTCS and also show the super-
hydrophobic glass surface modified by SiO2-m-nanoparticles 0.9 wt. %.
In addition to surface roughness, the existence of layers in the range
115–123 nm on the SiO2-m-HDTMS 0.9%, is a solid reason for why it is
superhydrophobic in comparison with MTCS conditions (Fig. 2).
Atomic force microscopy (AFM) [37] images related to a clean glass
and the superhydrophobic glass prepared by MTCS which is modified
by nanoparticles are shown at Fig. 7. Indeed, Fig. 7 demonstrates that
superhydrophobic glass, in comparison with a normal glass, is not
completely smooth and various rough points are discernable on it. By
comparing these two values it can be concluded that the super-
hydrophobic glass surface has a rough cover which gives rise to such
significant superhydrophobicity. Consequently, AFM images also like
other characterization methods reveal the presence of roughness on the
glass surface which superhydrophobic glass surface.
4.3. Interaction of mixed surfactants
To investigate the interaction of surfactants with the super-
hydrophobic surface, initially, CMC of cationic-rich and anionic-rich
mixed surfactants were obtained by measuring the interfacial tension
changes of every mixed surfactant to the concentration increase. The
CMC related to cationic-rich was obtained 0.56 mM and that amount for
anionic-rich was obtained 1.07 mM. By using of electrical conduction,
the changes of electrical conductivity by an increase in concentration
were recorded. With an increase in concentration of surfactants and
followed by an increase in the size of micelles or changing in their
shapes, phase transfer was carried out. In the present paper, con-
centrations of which phase transfer happens are selected to investigate
interaction of surfactants on superhydrophobic surfaces. Size of other
particles in high concentrations of CMC for every surfactant was mea-
sured by DLS. In Table 1, a data related to the total information of both
mixed surfactants have been reported.
In Table 2, α shows the molar fraction of surfactant in total con-
centration of aggregates.
In cationic-rich mixture, with an increase in surfactants concentra-
tion, the monomers aggregation increases and their size is getting
larger. In the sizes ranging from about 500 nm and surfactants form
stable vesicles and because the used solution contains anionic and ca-
tionic surfactants, the possibility of the vesicle formation in the solution
is high. The positive charge of cation on the nitrogen atom is placed on
the hydrophilic head of surfactant and this atom is surrounded by
methyl molecules which in turn reduces the impact of positive charge;
that’s why the vesicles size resulted from cationic-rich surfactant is
larger. On the one hand, with regard to negative being of β in cationic-
rich mixture (has bee presented in next section), it can be inferred that
the interaction between CTAB and SDS is an attraction type. On the
other hand, due to the interaction of hydrophilic head of surfactants
and opposite charge of CTAB and SDS heads, the attraction force be-
tween them increases which in turn causes to an increase in the size of
aggregates in cationic-rich conditions. According to data Table 3 the
impact of mixed surfactants in two regions CTAB: SDS (90:10) and
CTAB: SDS (10:90) on contact angle indicates that there is a linear re-
lation between them. While, surfactants in the variuos compositions
B. Sohrabi, et al.
and concentrations demonstrate different behavior because there are
different interactions between their aggregations and monomers in
various interfacial tensions. Fig. 8 shows the relation of cos θw with
concentration changes in cationic- and anionic-rich regions. In con-
centrations lower than CMC, the surfactants monomers cause to a de-
crease in liquid-air interfacial tension and have less impact on surface
wettability; this has been proved by data of solid-liquid and liquid-air
interfacial tensions in Table 4. Aggregating and locating of surfactants
on solid-liquid interface in concentrations higher than CMC, cause to
surface wettability. The superhydrophobic glass surface is non-polar
and surfactants are located on the surface through hydrocarbon chains
and their hydrophilic head is toward water and that’s why they give rise
to the hydrophilicity of the surface. Surfactants are located as mono-
mers on the surface and make a hydrophilic layer and if they are as
aggregation, they will cause to an increase in wettability. Figs. S1 and
S2 shows contact angle of the glass superhydrophobed by MTCS and
modified by 0.9% SiO2-m-HDTMS in the presence of cationic- and an-
ionic-rich surfactant solutions, respectively. Contact angle measure-
ment of the water drop on the superhydrophobed glass surface proved
that the glass surface was hydrophilic after addition of the surfactant;
thus, the contact angle was reduced.
4.4. Investigation on impact of mixed surfactants in solid-liquid interfacial
tension
As we know, for wettability phenomenon, addition to liquid-air
interfacial tension, solid-liquid interfacial tension also is effective. This
problem in high concentrations of CMC, in which liquid-air interfacial
tension approximately is constant, is getting more and more important.
Table 4 shows the amount of solid-liquid interfacial tension and ac-
cording to the obtained data, the amount of surface wettability and in
other words the presence of surfactants in liquid-solid interface could
be proved. In Fig. 4 solid-liquid interfacial tension for specified con-
centrations in both cationic-rich and anionic-rich mixtures by using Eq.
(7) and critical surface tension was calculated.
γ − γsl ⎞
cos θ = r ⎛⎜ sv ⎟
⎝ γlv ⎠ (7)
To this end, the critical surface tension (γC) was determined by
using a plot of the contact angle cosine of the pure surfactants aqueous
solutions on the superhydrophobic glass surface vs. the reciprocal of the
surface tension of the solution (γlv) in cationic-rich and anionic-rich
regions. From obtained line equation, it results that if θ = 0 the surface
tension of the solution (γlv) will be equal to γC. From Young equation it
results that if θ = 0, the difference between the glass surface tension
and glass-solution interfacial tension (γsl) should be equal to γC. In this
case when γsl = 0, γC should be equal to the glass surface tension γsv.
To investigate the solid-liquid interfacial tension, the data were
separated into two parts: before CMC and after CMC. According to the
data obtained from liquid-air interfacial tension and their contact angle
in anionic-rich region before and after CMC and also according to the
data resulted from solid-liquid interfacial tension obtained from Eq. (7),
it can be concluded that how surfactants monomers place in liquid-air
and in solid-liquid interfaces. It is noteworthy that in any surface in
which there are surfactants, they reduce its interfacial tension. Before
CMC, with an increase in concentration, contact angle is increased and
solid-air interfacial tension is decreased, which shows the surface un-
wettability. After CMC in which liquid-air interfacial tension is constant
and air-liquid interface is full of the surfactants monomers, monomers
are aggregated and are formed as aggregation and monomeric. Mono-
mers will give rise to a decrease in solid-liquid interface whether in
aggregation form or monomeric form. In higher concentrations, ag-
gregations are adsorbed on the solid surface and in the result solid-
liquid interfacial tension is decreased. Also, in cationic-rich region be-
fore and after CMC according to the data resulted in Table 4 solid-air
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Progress in Organic Coatings 131 (2019) 73–81
interfacial tension is decreased, which shows surfactants were adsorbed
on the solid surface before CMC as monomer and after CMC as ag-
gregate.
4.5. Effect of β parameter on the wettability of surface
To figure out how placing surfactants in solid-liquid and liquid-air
interface (Fig. 9) and its impact on surface wetting from the parameter
βM has been used. According to the Table 5 the parameter βM (the in-
teraction of monomers in micelle state) is −5.92 in cationic-rich region
and indicates that monomers interaction in micelle state is attraction
and stable vesicles are formed. The βσ value shows that monomers
adsorb together at surface because of existing opposite charges of hy-
drophilic head of mixed surfactants. On the one hand, comparing βσ
and βM shows that in cationic-rich region before CMC due to existing
monomers at the medium by increasing concentration, contact angle
increases. Additionally, after CMC, monomers in micelle state are more
stable than the state in which they are on the surface. As a result, the
surfactants aggregate on surface solid-liquid gives rise to contact angle
decreases and wettability of the glass surface increases. On the other
hand, the data of Table 5 indicates that surfactants monomers are more
stable than aggreates in anionic-rich region and with an increase in
surfactants concentration, the number of monomers on surface increase
which in turn cause to an increase in the wettability of surface. Hence,
it is possible to determine placing type of surfactants on the anticipated
surface by using the comparing of βM and βσ parameters.
5. Conclusion
A novel method successfully was demonstrated for super-
hydrophobicity of glass by Hexadecyltrimethoxysilane (HDTMS) na-
noparticles. The efficiency of this method was investigated by AFM,
contact angle, zeta potential and DLS techniques. Additionally, the
current study was performed to explore the optimal concentration and
composition of surfactants for their interaction with SH glass surfaces
by modification with TEOS as a low surface energy material. In the
present study, through an experimental study, the effect of a mixture of
surfactant on the surface of superhydrophobic glass has been in-
vestigated. The surface of the glass reached a high contact angle
through the modification and so-called superhydrophobic. The study of
the interaction of anionic- and cationic-rich solutions showed a change
in the percentage of surfactants or their change in concentration caused
a change in superhydrophobicity. The surface of the glass is super-
hydrophobic and this superhydrophobicity is due to changes in the
parameter β in anionic- and cationic-rich solutions and the direction of
anionic and cationic surfactants beside each other on the surface.
Comparing βσ and βM parameters show that in cationic-rich region
before CMC due to existing monomers by increasing concentration,
contact angle increases and wettability of surface decreases. Since,
surfactants momomers are more stable than aggregates in anionic-rich;
therefore, with an increase in concentration, the number of monomers
on surface increases and the wettability of surface increases.
Acknowledgement
The financial support from Iran Science and Technology University
is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.porgcoat.2019.02.010.
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