Article

pubs.acs.org/JPCC

Organization of SiO2 and TiO2 Nanoparticles into Fractal Patterns on

Glass Surface for the Generation of Superhydrophilicity
Nainsi Saxena, Tapaswinee Naik, and Santanu Paria*
Interfaces and Nanomaterials Laboratory, Department of Chemical Engineering, National Institute of Technology, Rourkela 769008,
Orissa India
*
S Supporting Information

ABSTRACT: The superhydrophilic surfaces have many

important practical applications such as antifogging, antifoul-
ing, self-cleaning, etc. The present study demonstrates a simple
and facile template-assisted dip-coating approach for the
organization of silica (SiO2) and titania (TiO2) nanoparticles
(NPs) into fractal patterns on the glass surface. The pure NPs
suspension showed a “coffee ring effect” and did not form any
organized pattern on the glass surface after drying. In this
reported method, NPs were organized into fractal patterns
using a template consisting of sodium carboxymethyl cellulose
(CMCNa) and oxalic acid mixture in the presence of a cationic
surfactant (CTAB). The presence of surfactant plays a major
role to alter the coffee ring effect because of a Marangoni flow in the direction of droplet edge to its center induced by the surface
tension gradient and surface potential of the particles, which eventually helps to get a uniform fractal pattern. Finally, the fractal
patterns of only SiO2 and TiO2 NPs were attained on the glass surface after calcining the CMCNa template at 450 °C. The
obtained fractal patterns of SiO2 and TiO2 coated glass surfaces showed the average water contact angle of ∼6° and ∼8°
respectively, whereas coating of only NPs without pattern could not achieved such low average contact angle. These coated
surfaces were found to have an excellent antifogging property (transparency of the surface) in the presence of water vapor.

1. INTRODUCTION available for the surface modification along with creation of

The wettability of the solid surfaces is an attractive and
emerging research field of study in recent years because of its
many advanced practical applications and academic inter-
ests.1−5 The term superhydrophilicity refers to the strong
affinity of water toward any surface with water droplet contact
angle (θ) < 10°, in contrast, superhydrophobicity refers to the
poor affinity of water with contact angle (θ) > 150°. The
superhydrophilic and superhydrophobic states of the solid
surfaces are very important from the practical perspective than
the intermediate stage between these two (10°< θ < 150°). The
topic of superhydrophilicity is younger comparative to that of
superhydrophobicity. The superhydrophilic surfaces are having
unique properties such as fast water spreading and drying,
antifogging,6 antifouling,7 etc., which are mainly useful for
automobile mirror and glasses,8,9 dental mirror,10 bioactive
implantation,11,12 biocompatible materials,13,14 humidity sen-
sor,15 microfluidic devices,16,17 heat transfer enhancement,18,19
and so on. Because of these wide varieties of applications of
superhydrophilic surfaces, the topic has been drawing
significant attention in recent years. There are mainly two
strategies for generating a superhydrophilic surface. The first
strategy is to develop surface modifications by various
treatments (mentioned below) along with the surface rough-
ness. The second one is by creating only micro/nanometer
level roughness on the surface. There are many techniques
surface roughness. Among these surface modification techni-
ques, some important techniques are photo induced hydro-
philicity (PIH) using UV light20 and ion irradiation,21 plasma
treatment,22 laser ablation,23 and fluorine induced super-
hydrophilicity (FIS).24 Photo induced hydrophilicity was first
reported in 1997 using polycrystalline TiO2 thin film on glass
surface.25 When the TiO2 coated surface was exposed to the
UV radiation, the coating with submicron roughness was
generated on the surface, and it became superhydrophilic.
Later, coatings of other inorganic nanomaterials such as SnO2,
ZnO, and WO3 made through PIH were also reported by
several researchers.26−29 The disadvantage of this method is the
functionalization can be made under irradiation of a specific
light condition only. Plasma and corona treatments are also
important techniques mainly applicable in the oxidation of
polymer surfaces.22 Recently, FIS based surfaces via oxy-
fluoridation were also reported, in which fluorine atoms were
linked to metal and semimetal atoms and a superhydrophilic
surface was obtained.24 In spite of the fact that the FIS surfaces
show excellent antifogging property but the fabrication steps
are tedious and complex.
Received: September 20, 2016
Revised: January 5, 2017
Published: January 5, 2017

© 2017 American Chemical Society 2428 DOI: 10.1021/acs.jpcc.6b09519

J. Phys. Chem. C 2017, 121, 2428−2436
The Journal of Physical Chemistry C
Figure 1. (a) Optical microscopic image of a full drop of SiO2 NPs suspension after drying scale bar = 500 μm; (b) SEM image SiO2 after dip-
coating of glass slide (inset magnified view of NPs) scale bar = 10 μm; and (c) optical microscopic image of SiO2 NPs suspension drop in the
presence of 0.1 × CMC (critical micellar concentration) of CTAB (0.1 mm) after drying scale bar = 500 μm.
As surface roughness plays a vital role in modification or
controlling the surface wettability, another universal approach
for creating superhydrophilic surface is to create micro or nano
level roughness.5 The first study of wetting phenomena on
rough surfaces was conducted by R. N. Wenzel in 1939 and it
was reported that the liquid can wet all the surface irregularities
if the surface is rough.30,31 The surface roughness enhancement
by the hierarchical structures is an effective and well-known
method. Water can be absorbed on such rough surface into the
internal spacing due to the 3D capillary flow. Until now various
nanoparticles such as SiO2,32,33 TiO2,34,35 ZnO,36 and SnO237
coated surfaces have been reported. Various methods have been
frequently used for depositing the nanoparticles on a flat
substrate such as sol−gel,33,38 structure growth in solution,39
inkjet printing,40 chemical vapor deposition,27,41 chemical and
hydrothermal methods,1 etching,42 electrochemical,43 electro-
spinning,44 and phase separation of polymers.45 The disadvan-
tages of the above processes are that some processes require
multisteps, require expensive techniques, and are not useful for
the larger area. Some other approaches for generating different
micro to nano patterns on the surfaces can also be directly
achieved by using lithography and self-assembly techniques.
The lithographic based structured micropillars array with
switchable wettability has been reported earlier.46,47 However,
the process is again expensive and complex. To overcome such
drawbacks, researchers have shown continuously increasing
interest into self-assembly based processes to generate
superhydrophilic surfaces during the past few years. Various
self-assembly processes like layer by layer assembly,6,33,48
electrostatic self-assembly,15 and template-assisted assem-
bly49,50 of colloidal and nanoparticles are mainly used for
generating roughness which in turn effectively change the
wettability of a surface. Various types of hierarchical structures
can be generated using these self-assembly processes.
Among several organized structures, the organization of
nanoparticles into the fractal pattern is drawing researchers
attention in recent years because of their several promising
applications such as solar cells,51 surface enhanced Raman
spectroscopy,52 catalysis,53 electronics,54 and so on. A well-
organized fractal pattern on the solid surface can also be used
easily to generate higher roughness factor of a surface. Using
this concept, in this work, we attempt to organize the NPs into
fractal pattern over a large area of a flat surface using an
inexpensive and easy route which can be utilize for generating
superhydrophilic surfaces or other potential applications. The
fractal patterns originated from the mixture of CMCNa and
oxalic acid were used as a template to organize SiO2 and TiO2
NPs in the presence of CTAB (cetyltrimethylammonium
bromide). These fractal patterns can be generated either over a
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small area from an evaporating sessile droplet or over a large
area from the evaporation film after dip coating of the surface.
This process can also be used for the organization of other NPs.
In this process, we explore an easy and inexpensive method-
ology for the generation of fractal patterns over a small as well
as a large surface area to produce a superhydrophilic surface
which is probably reported for the very first time.
2. EXPERIMENTAL SECTION
2.1. Materials. The (following) materials used in this study
were purchased from the following companies, oxalic acid
(H2C2O4.2H2O), 99% from Merck. (India); cetyltrimethylam-
monium bromide (CTAB) 99%, from Fluka Analytical; sodium
carboxymethylcellulose (CMCNa) 99% from Loba Chemie
Pvt. Ltd.; tetraethylorthosilicate (TEOS) 99% from Sigma-
Aldrich; aqueous ammonia (25%) Merck (India); and absolute
ethanol (99.5%), Merck (India). The TiO2 NPs (particle size
21 nm) were purchased from Sigma-Aldrich. All these
chemicals were used as received, without any further
purification. Glass slides were purchased from Borosil Glass
Works Ltd. Ultrapure water of 18.2 MΩ. cm resistivity was used
for all experiments.
2.2. Methods. The silica nanoparticles used in this
experiment were synthesized by modified Stober’s method55
at 25 ± 3 °C using TEOS in ethanol, in the presence of
ammonia as a condensation catalyst. In this method, 7.5 mL of
ethanol, 0.4 mL of (0.6 M) aqueous ammonia, and 1.5 mL of
deionized water were mixed together and stirred well for 5 min.
Then 0.6 mL of TEOS was added dropwise into the reaction
mixture under magnetic stirring condition and continued
stirring for 3 h when, finally, a white color 0.2 M silica
suspension was obtained. The glass slides were washed with
ultrapure water and ethanol and then dried in a hot air oven for
2 h. For the generation of self-assembled structure, a mixture of
oxalic acid (40 mM) and CMCNa (0.4 wt %) was prepared and
stirred well for 30 min at room temperature and denoted as D.
Then the as synthesized NPs suspension was added (5:1 v/v
mixture: NPs) and termed as D5. Finally, the cleaned glass slide
was dipped for 10 min in the D5 suspension and dried inside
the closed chamber of a dry block heater (Genetix Biotech
Asia) for 1 h at 35 °C. After that, the slides were heated at 450
°C for 2 h in a muffle furnace to remove the organic molecules
and observed under both optical (Leica-DM-2500M) and
electron microscopes (JEOL-JSM6480LV, SEM and FEI-
NOVA Nano SEM, FE-SEM). The particle size and zeta
potential were measured using dynamic light scattering (DLS,
Malvern Zeta size analyzer, Nano ZS). The contact angle
measurements were done using a video-based contact angle
meter (Data Physics, OCA 30). The height profile was
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measured by an atomic force microscope (AFM), Veeco-diCP
II (model no. AP-100).
3. RESULTS AND DISCUSSION
3.1. Organization of Silica NPs on the Glass Surface. In
this work, our final objective is to produce fractal patterns of
Figure 2. (a) Optical microscopic image of CMCNa + oxalic acid after
drying of a sessile droplet (Arrow indicating the drop periphery), scale
bar = 500 μm. (b) Magnified view of the self-assembled pattern on the
glass surface through SEM, scale bar = 10 μm.
silica NPs on the glass surface. However, when a particle
suspension is dropped on a flat surface, in most of the cases the
“coffee ring” structure is formed at the periphery of the droplet
after drying. Coffee ring structure is defined as the formation of
a ring like pattern on a flat surface after drying of a coffee drop
(or a colloidal suspension).56 For the understanding of the
organization behavior of silica NPs suspension, a sessile droplet
(5 μL) of silica NPs suspension (average size ∼270 nm Figure
S1, Supporting Information) was gently placed on the glass
surface with the help of a micropipette and kept for drying at 35
°C inside a dry block heater for 10 min. After evaporation of
the droplet, the surface was examined microscopically, and the
formation of a ring structure at the initial pinned pining line of
the contact line was observed as shown in Figure 1a. This ring
type structure formation was because of the coffee ring effect
(CRE), which occurs after deposition of the particles at the
triple point of drop periphery.57 When a droplet of nonzero
contact angle is placed on a flat surface, the rate of evaporation
of liquid at the edge is higher compared to that of center of the
droplet. Because of the evaporative flux, the silica NPs moved
toward the edge from the interior of the drop. The particles
Figure 3. Optical microscopic images of: (a) full drop view of suspension D5, (b) full drop view of suspension D5S0.1, (c) full drop view of
suspension D5S1.5, (d) dip-coated glass surface of suspension D5, (e) dip-coated glass surface of suspension of D5S0.1 (marked region indicates
agglomerated particles), and (e) dip-coated glass surface of suspension of D5S1.5. Scale bars are 500 μm for (a−c) and 200 μm for (d−f).
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Table 1. Surface Tension of Different Mixtures and
Respective Contact Angle Values on Glass Surface
component surface tension (mN/m) contact angle (deg)
D 56.37 39.5
D5 43.84 24.5
D5S1.5 34.70 46.3
1.5 mM of CTAB 31.74 71.0
Figure 4. (a) TGA curve for reaction mixture (b) SEM image
(magnified view) of self-assembled SiO2 NPs after burning of coated
slide, scale bar =5 μm.
continued to move toward the drop periphery until the particle
diameter was less than the liquid film thickness or height from
the surface. When the particles were very close to the drop
boundary, the adhering liquid film brought the particles to a
closer distance because of the capillary force and finally at the
closer distance van der Waals force of attraction helped them to
deposit at the drop periphery to form a coffee ring structure.
During evaporation of the droplet, the height of the droplet was
reduced gradually with the shrinking of the drop volume
compared to that of the initial stage.
In this study, our prime objective is to generate a uniform
organized structure over a large area. However, initially, we
tested the organization ability of NPs using a small evaporating
drop of NPs suspension, and then it was tested for the large
area via dip-coating. Now, to know the behavior of the SiO2
NPs suspensions on a large area, a glass slide was dipped into
the NPs suspension for 10 min and dried at 35 °C inside a dry
block heater. The microscopic structure presented in Figure 1b
clearly shows that the NPs are deposited randomly without
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Figure 5. FE-SEM images of CMCNa (D5S1.5) mediated fractal patterns of SiO2 NPs after burning at 450 °C: (a,b) single coating, (b,c) double
coating, scale bar = 300 μm for (a,c) and scale bar = 5 μm for (b,d). (e) AFM image of double coated SiO2 NPs on glass surface and (f) height
profile of the image.
formation of any organized patterns on the surface. In this case,
we believe that during the evaporation of liquid film, the SiO2
particles were not organized as it was showing the CRE during
the evaporation droplet.
To eliminate the CRE as well as to organize the NPs on the
flat surface, the role of surfactant was also studied. Surfactant
molecules are generally used to get better dispersion of
nanoparticles in aqueous media, which in turn also affect the
particle deposition behavior on a flat surface. So, a cationic
surfactant (CTAB) solution of 0.1 mM concentration (0.1 ×
CMC) was mixed and the evaporating drop study was
performed. The optical microscopic characterization depicts a
uniform deposition of particles without the formation of a
coffee ring structure, as shown in Figure 1c. The reasons for the
elimination of CRE can be attributed as follows: (i) negative
charges of both particles and glass surface neutralizes in the
presence cationic surfactant, which in turn helps the hydro-
phobic (van der Waals) interaction between the surface and
particles. (ii) The presence of surfactant induces a Marangoni
flow in the direction of droplet edge to its center because of the
surface tension gradient. The surface tension gradient arises
because of the higher concentration of the surfactant molecules
at the drop periphery (low surface tension) than that at the
central region (high surface tension) during the evaporation of
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the drop. The presence of Marangoni flow favors depinning of
the contact line and finally elimination of the coffee ring effect.
3.2. Organization of SiO2 Nanoparticles into Fractal
Pattern on Glass Surface. It has been observed in our
previous studies58,59 and several other studies that different
additives have a significant role in organizing the nanoparticles
on a flat surface from the evaporating drops. In our work, we
have reported that sulfur nanoparticles can be organized into
the different fractal patterns in the presence of different organic
and inorganic acid salts.59 In addition, recently we have also
observed in our ongoing unpublished work about the formation
of fractal pattern by CMCNa after evaporation of a sessile drop
in the presence of oxalic acid. Here, it is noteworthy to mention
that only CMCNa is not forming any organized structure after
drying (details are given in Figure S2, Supporting Information),
however, the presence of oxalic acid helps to form the
organized structure because of similar reasons mentioned in our
previous study.58 In this study, we found pure SiO2 NPs were
unable to generate any patterned structure in the presence of
only oxalic acid. So, we attempt to use the previously studied
CMCNa pattern in the presence of oxalic acid as a template to
organize the SiO2 NPs.
The optical and electron microscopic images of the mixture
of CMCNa and oxalic acid (D) after drying of a sessile droplet
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Figure 6. Microscopic images of organized TiO2 NPs on glass surface mediated by CMCNa in the presence of CTAB (1.5 mM). (a) Optical
microscopic image of single coated surface before calcination, scale bar = 200 μm (b)SEM image of single coated surface after calcination, scale bar =
50 μm, (c) magnified view of the same surface, scale bar = 1 μm, (d) Optical microscopic image of double coated surface before calcinations, scale
bar = 200 μm, (e) SEM image of double coated surface after calcinations, scale bar = 50 μm, (f) magnified view of the same surface, scale bar = 1 μm.
HRTEM image (g) stem part of assembled pattern (h) magnified view of small area (i) magnified view of TiO2 nanoparticle (size of particles 21 nm
d-spacing of 0.352 nm).

Table 2. Contact Angle of Pure Water on Glass Surfaces the second contact line and oriented toward the center. There
Under Different Conditions was no organized structure between the first and second
contact lines. Generally, the formation of the second ring is
contact angle (deg)
called as inner coffee ring deposits (ICRD).60 As our main aim
NPs double coated NPs single coated fractal double coated fractal is to organize the silica nanoparticles over the full drop area, we
SiO2 21.85 17.47 6.22 studied the effect of surfactant again on the elimination of
TiO2 23.50 19.50 8.02 ICRD and the results are presented in (b) and (c) parts of
Figure 3. From Figure 3b,c it can be seen that in the presence
of 0.1 and 1.5 mM of CTAB concentrations full drop area is
are presented in Figure 2. The Figure 2a shows that during
covered by the fractal patterns after elimination of ICRD.
drying of the droplet, the drop was squeezed toward the center
Finally, to check the organization pattern on a larger area of a
from the original periphery without pinning or forming any
structure up to a certain distance. After some time at a certain surface due to the evaporation of the liquid film, the glass
concentration of solute, the drop was started pinning with the surface was dipped in both the above-mentioned conditions in
formation of fractal patterns. The patterns of CMCNa were the presence and absence of CTAB. Later, the film was dried at
started from pinning line and converge toward the central 35 °C. It can be seen from the optical microscopic images that
region of the drop. The magnified view of the branches is under both conditions fractal patterns are formed on the
shown in Figure 2b. surface. Figure 3d shows that the pattern does not cover the
Further, we mixed SiO2 NPs with D to see whether the NPs surface fully in the absence of CTAB, while the particles are
can also be organized along with the CMCNa pattern. A sessile agglomerated on the surface in the presence of 0.1 mM CTAB
droplet of 5 μL volume of D5 suspension was gently placed on (below CMC) as illustrated in Figure 3e. A comparison
the glass surface with the help of a micropipette and allowed to between these two indicate there is no significant difference in
dry at 35 °C inside the dry bath heater. A full drop view (Figure the appearance. However, in the presence of 1.5 mM CTAB
3a) clearly shows that the drop was pinned at the first contact (Figure 3f), the patterns are uniform and dense without any
line, and then the fractal patterns formation was started from agglomeration of particles in comparison to that of 0.1 mM
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Figure 7. Drop view of pure water on glass surfaces (a) untreated surface (CA = 42°), (b) double coated SiO2 NPs (without organization) (CA =
21.85°), (c) double coated TiO2 NPs (without organization) (CA = 23.50°), (d) double coated organized SiO2 NPs (CA = 6.22°), (e) double
coated organized TiO2 NPs (CA = 8.02°). Antifogging test of the (f) Silica coated glass surface (g) normal glass (h) TiO2 coated glass surface.
CTAB (Figure 3e). From these observations, it is very clear that
the SiO2 NPs are organized along the pathway of CMCNa and
formed similar fractal patterns. The Mullins−Sekerka instability
during the evaporation of the droplet because of the presence
of salt in the mixed media is also important for the formation of
organized structure.61 This instability is mainly attributed to the
crystallization of formed sodium oxalate salt. The presence of
sodium oxalate salt in the mixture leads to the crystallization
process and act as a building block for the arrangement of SiO2
NPs.
As surface charge (ζ potential) of the particles is an
important parameter in the organization process, we measured
the ζ potential under different conditions. The ζ potential
values of SiO2 NPs in aqueous media, CMCNa + oxalic acid
mixture, CMCNa + oxalic acid +0.1 mM CTAB mixture
(D5S0.1), CMCNa + oxalic acid +1.5 mM CTAB mixture
(D5S1.5) are −41, −0.96, +0.32, and +0.83 mV, respectively.
The reduction of surface charge of SiO2 NPs in the presence of
CMCNa is mainly because of the adsorption of CMCNa
molecules onto the nanoparticles surface. In the presence of
CTAB, the surface charge becomes positive but because of the
neutralization of the positively charged headgroup (trimethy-
lammonium group) of CTAB with the negatively charged oxalic
acid, the value of surface charge is low. Since the electrostatic
repulsive forces between the particle−particle and particle−
surface are reduced after suppression of the surface charge, the
particles are easily organized along with the CMCNa pattern.
From the surface charge analysis, it is also clear that better
dispersion of particles in the presence of surfactant is mainly
because of the steric repulsion. We have also measured the
surface tension and contact angle of all prepared suspensions
for the better understanding of the surfactant effect on
nanoparticles suspension. Table 1 shows the surface tension
and contact angle values on glass surface under different
conditions.
From the Table 1 it is clear that the surface tension of D, D5,
and D5S1.5 decreases gradually and the value of D5S1.5 is
slightly higher than pure CTAB. The value of surface tension of
solution D is lower than pure water (72 mN/m) because of the
presence of organic molecules like CMCNa, the contact angle
is also less than pure water because of lowering of surface
tension. After addition of NPs into the mixture D (denoted as
D5), both surface tension and contact angle reduces and the
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reason for the reduction was well explained in our previous
study.62 In brief, the presence of the particles affects the
cohesive force among the water molecules at the interface,
which causes the surface tension reduction at the interface. The
reduction in contact angle on the hydrophilic glass surface in
the presence of SiO2 NPs is attributed to surface tension
reduction and development of the disjoining pressure. Later,
when CTAB is added to the suspension, the surface tension of
D5S1.5 further reduces because of the presence of surfactant. In
spite of surface tension reduction, the contact angle increases
because of strong adsorption of cationic surfactant molecules
onto the particles and glass surfaces through the positively
charged headgroup of the surfactant molecules. Finally, all these
combined effects help to organize the NPs on the glass surface.
After the formation of organized structure, the surface was
heated at 450 °C for 2 h to burn all the associated organic
molecules in order to get the patterns of only SiO2 NPs. To
support this, we performed thermogravimetric analysis (TGA)
and the weight loss (%) vs temperature graph is presented in
Figure 4 for the template forming mixture (CMCNa + oxalic
acid + CTAB).
From the TGA curve, it can be observed that there is a sharp
change within 100 °C because of the evaporation of unbound
moisture, and then between 100 and 350 °C almost 90%
decomposition of organic molecules occurs gradually. Finally,
between 350 and 450 °C there is a slow change in
decomposition and beyond that the change is negligible. The
trace amount of residue present is mainly because of the
formation of sodium superoxide (NaO2) or sodium carbonate
(Na2CO3).63 We also observed the coated glass surface with
template mixture without NPs after heating at 450 °C through
SEM and it was found that most of the areas were clean and
there were some residues on some areas. The elemental analysis
(EDS) also shows the presence of only Na and O. (SEM and
EDS analysis are provided in Figure S3, Supporting
Information.) From the TGA study it can be concluded that
the pattern shown after calcination is mainly because of the
particles. After burning, organized structure of SiO2 NPs was
confirmed from the microscopic analysis (Figure 4b) with trace
amount of the salt. We have also studied the effect of multiple
coatings with the same suspension of D5S1.5 and the
microscopic images of the surfaces are presented in Figure
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5a−d. It is observed that the fractal density increases after
double coatings compared to that of single.
Further to get an idea about the height profile of the
deposited particles a small portion of SiO2 double coated
surface was analyzed using AFM (Figure 5e). The height profile
obtained through a line from the surface topography is
presented in (Figure 5f). The line profile shows that in most
of the places the height is close to a single particle layer (∼300
nm). It can also be concluded that after double coating,
particles are organized in empty places of the surface instead of
multiple layers, which can also be seen from the SEM images.
3.3. Organization of TiO2 Nanoparticles Using CMCNa
Template on Glass Surface. To see the versatility of the
method TiO2 NPs was also used to organize on glass surface by
CMCNa template. The water suspension of 21 nm TiO2 NPs
(0.798 g/L concentration) was mixed with solution D (5:1 v/v
D: NPs) noted as D5. In this process, CTAB was also mixed
with D5 to maintain the final concentration of 1.5 mM. Then
the glass surface was dip coated with the final TiO2 suspension
and analyzed under optical and electron microscopes, after
drying and calcined at 35 and 450 °C respectively. It can be
observed from the images presented in Figure 6 that similar
types of fractal patterns are also formed in the presence of TiO2
NPs. The patterns are also retained after calcinations and dense
after double coatings. From this study, it can be concluded that
similar fractal pattern can be generated over a large surface area
using other NPs also.
Since the particle size of TiO2 is more than 10 times smaller
than SiO2 the presence of particles is not clearly visible from
the FE-SEM images. That reason the formed fractal patterns
were also characterized using HR-TEM to ensure the branches
of the fractal pattern are made with TiO2 NPs. Formed pattern
on the glass surface after calcination was scratched with a sharp
blade and dispersed in isopropanol, and then dropped on a
carbon coated copper TEM grid. The low and high
magnification TEM images of a small portion of a branch are
presented in Figure 6g,h. Figure 6h clearly shows the branch is
made of small TiO2 particles the sizes of the particles are also
matching with that mentioned by Sigma-Aldrich. A HR-TEM
image (Figure 6i) clearly indicates the size of the particle is
21.03 nm with spherical morphology. The lattice fringes with
an interlayer spacing of 0.352 are matching with the (101)
planes of anatase TiO2.
3.4. Effect of Organized Structure on Wettability of
the Glass Surface. In spite of several possibilities of practical
applications of these fractal patterns, we tested the effect of
these structures on the wettability of the glass surface. In
general, wettability of a flat surface can be changed by creating
the roughness on the surface. In this study, we used these
patterns as an inexpensive technique to enhance the roughness
factor at the nanoscale to improve the wettability of the surface.
For determining the wettability of these NPs assembled glass
surfaces, pure water contact angle measurements were done,
and the results are presented in Table 2. Pure water shows the
contact angle of 42° on the glass surface. After simple dip
coating of NPs on the glass surface, when the particles are
unorganized on the surface the contact angle reduces for both
particles, but the reduction is more in the case of SiO2 NPs.
When the particles were organized into the fractal pattern after
single coating, further reduction of contact angle was observed
(∼5° lower) than that of the normal dip coated surface into the
NPs suspension. Finally, further significant reduction of contact
angle was observed for both particles after double coating.
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Keeping in mind the residue after burning may also change the
hydrophilicity of the surface, we measured the contact angle of
the glass surface after the formation of pattern with mixture D +
CTAB and calcination at 450 °C. The water contact angle was
decreased on the coated surface to 27° from that of 42° on
normal glass slide. So, the change is significant but little higher
than the silica coated unpattern surface. However, it was also
found that the deposited residue having high solubility in water,
so the mixture D + CTAB coated surface was dipped in water
and taken out immediately than the contact angle again
increased to 38.11°. So, the change in contact angle is not
significant when the residue salts are removed. We also
measured the contact angle after washing on the fractal surface,
but no significant change in contact angle was found. Figure 7
shows the pure water drop view on glass surfaces under
different mentioned coatings conditions. It is noteworthy to
mention that both cases after double coating the surfaces
become superhydrophilic as the contact angle is <10°. The
maximum lowering of the contact angle after the double coated
fractal pattern is mainly because of the formation of dense
structure as mentioned before.
In general, there are two models offered theoretically for the
prediction of contact angle on the rough surfaces, Wenzel’s30
and Cassie−Baxter’s64 models. In Wenzel’s model a rough
surface is entirely wetted by liquid without any trapped air in
between the roughness. However, in the Cassie−Baxter model
air is trapped between the rough asperities of the solid surface.
cos θ* = r cos θ (1)
where θ* is the contact angle on the rough surface, θ is the
equilibrium contact angle on flat smooth surface, and r is the
roughness factor defined as the ratio between the actual surface
area of surface to the projected area. From the equation, the
roughness factor values on double coated fractal surfaces are
1.338 and 1.332 for SiO2 and TiO2 coatings, respectively.
To see the practical applicability of these superhydrophilic
surfaces we performed antifogging test. For the analysis of the
antifogging property the coated glass samples were placed
above a beaker filled with hot water. Figure 7f,g,h shows the
physical appearances of treated and untreated glass surfaces in
the presence of water vapor. From Figure 7g, the foggy
appearance over the untreated glass surface is clearly visible,
whereas, the appearance of SiO2 and TiO2 coated fractal
patterned surfaces are very clear because of the formation of
continuous thin liquid films on these superhydrophilic surfaces.
4. CONCLUSIONS
In summary, well organized fractal patterns of SiO2 NPs on the
hydrophilic glass surface were generated using CMCNa and
oxalic acid mixture template via dip coating method. Used SiO2
NPs alone were unable to form any patterns because of the
coffee ring effect. However, when these particles were mixed
with CMCNa and oxalic acid, gave fractal patterns at the central
region of the droplet leaving the drop peripheral region blank
because of ICRD. The formation of fractal structure is mainly
because of the dendritic crystallization of sodium oxalate salt,
Marangoni flow, and van der Waals attractive force between the
particles. The ICRD was eliminated by adding a cationic
surfactant (CTAB) into the mixture. Additionally, the structure
was also uniform throughout the surface without any
agglomeration of particles. Organized fractal patterns of only
SiO2 were successfully obtained after calcination of the
CMCNa + oxalic acid template at 450 °C. The same
DOI: 10.1021/acs.jpcc.6b09519
J. Phys. Chem. C 2017, 121, 2428−2436
The Journal of Physical Chemistry C
methodology was also applied to get organized fractal pattern
of TiO2 NPs. Furthermore, these organized structures on glass
surface showed superhydrophilic nature with water contact
angles ∼6 and ∼8° for SiO2 and TiO2 NPs, respectively. The
fabricated superhydrophilic surfaces were also showed the
antifogging property in the presence of water vapor.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b09519.
FE-SEM image of as synthesized SiO2 NPs, microscopic
images of oxalic acid and CMCNa solution after drying,
and microscopic analysis of the surface coated by a
mixture D + CTAB after burning (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: sparia@nitrkl.ac.in or santanuparia@yahoo.com. Fax:
+91 661 246 2999.
ORCID
Santanu Paria: 0000-0002-3053-7277
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We acknowledge Indian Association for the Cultivation of
Science, Kolkata, India, for giving us the opportunity to access
their AFM facility.
■
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2436 DOI: 10.1021/acs.jpcc.6b09519

J. Phys. Chem. C 2017, 121, 2428−2436