Applied Surface Science 255 (2009) 44794483

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Applied Surface Science

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

A simple method for the preparation of superhydrophobic PVDFHMFS

hybrid composite coatings
Bharathi Bai J. Basu *, Ashok Kumar Paranthaman
Surface Engineering Division, National Aerospace Laboratories, Bangalore 560017, India

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 18 August 2008
Received in revised form 7 October 2008
Accepted 18 November 2008
Available online 3 December 2008

A superhydrophobic surface was obtained by embedding hydrophobically modied fumed silica (HMFS)
particles in polyvinylidene uoride (PVDF) matrix. The water contact angle (WCA) on the PVDFHMFS
hybrid composite coating is inuenced by the content and nature of silica particles in the coating. As the
silica concentration in PVDF matrix was increased from 33.3% to 71.4%, WCA increased from 1178 to 1688
and the sliding angle decreased from 908 to <18. Surface topography of the coating was examined using
scanning electron microscopy. An irregular rough surface structure composed of microcavities and
nanolaments was found to be responsible for the superhydrophobicity. The method is simple and costeffective and can be used for preparing self-cleaning superhydrophobic coating on large areas of different
substrates.
2008 Elsevier B.V. All rights reserved.

Keywords:
Superhydrophobic
Polyvinylidene uoride
PVDF
Coatings
Hydrophobically modied fumed silica
Water contact angle

1. Introduction
In recent times, superhydrophobic surfaces (surfaces with
water contact angle (WCA) higher than 1508) have attracted
attention because of their self-cleaning, anti-icing, anti-sticking
and anti-contamination properties [122]. A perfect example of
superhydrophobic surface from nature is the lotus leaf, on which a
water droplet forms a sphere and rolls off. This is called lotus
effect which is accomplished by a surface topography with micro
and nano-structures [23]. By mimicking this effect, surfaces can be
modied to develop articial superhydrophobic coatings. Even
though several methods are reported in literature to obtain
superhydrophobic surfaces, many of them may not be feasible for
large area application.
Many methods have been reported in literature for the
preparation of hydrophobic and superhydrophobic surfaces [1
22]. Recent reviews focus on the progress in the various methods of
preparation, theoretical modelling and applications of superhydrophobic surfaces in the last decade [15]. The preparation
methods are categorized as bottom-up, top-down, and combination approaches. These methods are mainly based on two
approaches: either make a rough surface from a low surface
energy material or modify a rough surface with a material of low

* Corresponding author. Tel.: +91 80 25086251; fax: +91 80 25210113.

E-mail address: bharathi@css.nal.res.in (B.B.J. Basu).
0169-4332/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2008.11.065

surface energy [6]. However, some of these methods are substrateselective and some other methods involve complicated multi-step
processes or expensive instruments.
Fluorinated polymers are of special interest in the creation of
superhydrophobic surfaces due to their extremely low surface
energies [711]. Roughening these polymers in different ways
leads to superhydrophobicity directly. For example, Peng et al.
have obtained a highly hydrophobic porous PVDF by using a
modied phase inversion method [7]. It is reported that
peruoroalkyl polymer can provide a surface with very low
surface energy and displays good hydrophobicity [8]. Many such
uorinated materials have not been used directly but linked or
blended with other materials to make superhydrophobic surfaces.
PVDF is a commercially available uoropolymer with low surface
energy (25 dynes/cm) and good physical, chemical, and mechanical properties. Also, being an engineering thermoplastic, PVDF has
better stiffness and strength than those of most uorine-containing polymers. It has exceptional chemical stability and excellent
resistance to aging and durability. Many superhydrophobic
surfaces reported in the literature are made by using a combination
of very low surface energy materials and very high surface
roughness characteristics.
A superhydrophobic surface can also be made by introducing
roughness to a hydrophobic surface with a contact angle larger
than 908. It has been reported in the literature that incorporation of
nanoparticles and microparticles in solgel matrix or hybrid
polymer matrix can lead to superhydrophobicity [916]. Li et al.

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B.B.J. Basu, A.K. Paranthaman / Applied Surface Science 255 (2009) 44794483

obtained a superhydrophobic surface on a PVDF macroporous lm

through self-assembled silica colloidal templates [9]. Chang et al.
prepared organic superhydrophobic lms by utilizing TA-N
uoroalkylate and methyl methacrylate copolymer as waterrepellent materials and inorganic silica powder as surface roughness material [10]. Superhydrophobic properties of polymer based
nanocomposite coatings prepared by dispersing nanoCaCO3 in
PVDF matrix have been reported [11]. The coating surface is
characterized by microspheres with bumpy surface similar to the
topological structure of lotus leaf and a water contact angle (WCA)
of 1538 was obtained for this coating. Su et al. have embedded
nanosilica particles on epoxy-coated glass surface, but superhydrophobicity is achieved by subsequent uoroalkyl silane
coating [12]. Fluoroalkyl silanes are either incorporated in the
hybrid mixture or applied as a top-coat in some of the reported
work in order to decrease the surface energy [1113]. Qu et al. have
prepared a hybrid lm by emulsion polymerization but the
procedure is tedious and involves multi-steps [14]. Superhydrophobic nanocomposite coating was obtained by using a mixture of
small anatase and large boehmite particles and its hydrophobicity
depended on the surface roughness and micropore fraction [15].
A superhydrophobic surface of PEEK/PTFE composite coating
has been reported very recently [17]. The microstructure is
controlled by varying the curing temperature and superhydrophobic surface is obtained when the coating is cured at 300 8C.
Though PTFE has lower surface energy than PVDF, it is difcult to
prepare coatings with it due to its limited solubility in solvents.
We found that surface roughness can be created in PVDF-based
coating matrix by embedding hydrophobically modied silica
(HMFS) particles in the matrix so that the surface becomes
superhydrophobic. Li et al. have reported that superhydrophobic
nanosilica can be prepared by surface modication using
hexamethyldisilazane [18]. In this study, we have used commercially available hydrophobically modied fumed silica particles as
ller to prepare superhydrophobic composite coatings. In a
previous work by Yan et al., CaCO3 nanoparticles were added as
ller to PVDF matrix to create superhydrophobic composite
coatings. Since CaCO3 is hydrophilic, uoroalkyl was added to
render it hydrophobic and prolonged stirring of the mixture for
about 13 days was required. In this study, there was no need to
include expensive reagents like uoroalkyl silanes in the coating
mixture as the silica particles were highly hydrophobic and the
stirring time was about 30 min to 1 h. Spray coating was employed
because of its advantages for preparing coatings of desired
thickness with minimum wastage of precursor solution. Hence
it is a simple and cost-effective approach for creating superhydrophobic and self-cleaning surfaces.
2. Experimental
Commercial grade PVDF powder was procured from M/s
Pragathi Chemicals, India. HMFS silica was procured from M/s
ABCR GmbH, Germany. Dimethylformamide (DMF) and toluene
were purchased from SigmaAldrich. Static contact angles were
measured by using Contact Angle Goniometer instrument,
Ramehart, Inc. The water droplet used for measurements was
10 mL. The average of ve measurements made at different
positions on the coating surface was adopted as the value of WCA.
Sliding angles were measured using home-built tilting table with a
protractor using a 10 mL water drop. The reported sliding angle is
the average of ve measurements. All measurements were
performed at ambient conditions. Surface morphology of the
composite coatings was examined using Leo 440I Scanning
electron microscope.
PVDF solution (5%) was prepared by dissolving PVDF powder in
DMF and heating to about 50 8C for complete dissolution. A known

amount of HMFS silica particles were dispersed in toluene by

ultrasonication, mixed with PVDF solution while magnetically
stirring for about 30 min to 1 h till a homogenous mixture was
obtained. Then the precursor mixture was transferred to a spray
gun and sprayed on to clean dry glass slides or other substrates.
The coating was dried at room temperature.
3. Results and discussion
The WCA of a blank PVDF coating without HMFS was about 908.
HMFS silica particles were used as ller for the preparation of PVDF
composite coating. These particles are highly hydrophobic in
nature. It is amorphous hexamethyldisilazane treated fumed silica
with a surface area of 200 m2/g and an ultimate particle size of
0.02 mm (as per the specications given in the Gelest catalog).
However SEM study of these silica particles dispersed in toluene
has shown particles of 1 mm along with agglomerates of 25 mm.
The effect of the concentration of HMFS on the hydrophobicity
of PVDFHMFS composite coating was studied. The results are
shown in Table 1. It was found that WCA increased and sliding
angle decreased with increase in HMFS content in the coating.
When HMFS concentration was 50%, WCA increased above 1508
and sliding angle (SA) decreased to about 38 so that superhydrophobicity was obtained. Due to experimental difculties for
measuring advancing and receding contact angles for these
coatings, contact angle hysteresis could not be obtained and
hence sliding angles were measured. In the case of PVDFHMFS
coatings with silica content 50% and above, water drops actually
rolled off from the coating surfaces. When the silica content was
66.7% and above, water drops rolled off from the coating surfaces
even before tilting the surface. Hence the sliding angle for these
coatings was nearly zero or <18 as given in Table 1. Maximum
superhydrophobicity was achieved at HMFS concentrations of
66.7% and above with a WCA of 1671688 and SA < 18. Thickness of
the coatings was in the range of 1020 mm. Images of a water
droplet on PVDFHMFS composite coatings with different silica
concentrations are shown in Fig. 1. It can be seen that the water
drop is nearly spherical at higher HMFS concentrations.
It was found that adhesion of the coating could be improved by
heating the coatings at 100 8C for 1 h. The coating can be applied on
metallic surfaces and also on epoxy-painted surfaces. We have also
sprayed the PVDFHMFS mixture as a top-coat on epoxy-coated
aluminium sheets. Since DMF attacks epoxy paint coatings, the
precursor mixture should have another milder solvent like toluene
so that the DMF to toluene ratio of the mixture was about 1:1.
Spraying on epoxy substrate was done carefully so that coating was
deposited layer by layer.
The surface morphology was examined by using scanning
electron microscopy (SEM). The SEM images of the composite
coatings are shown in Figs. 2 and 3. It can be seen that the coatings
are free from cracks and showed aggregates of silica particles.
Aggregate size and distribution increased with increase in silica
concentration. The microstructure was affected by the method of
preparation of the precursor, stirring, ultrasonication and spraying
Table 1
Contact angles and sliding angles of PVDFHMFS coatings with different ller
concentrations.
Concentration of
HMFS silica (%)

PVDF to HMFS
weight ratio

Water contact
angle (8)

Sliding
angle (8)

0
33.3
50
60
66.7
71.4

2:1
1:1
2:3
1:2
2:5

95
117
160
164
167
168

>90
90
3
2
<1
<1

B.B.J. Basu, A.K. Paranthaman / Applied Surface Science 255 (2009) 44794483

4481

Fig. 1. Images of water drop on PVDFHMFS coatings with different silica concentrations: (a) 33.37%, (b) 50%, (c) 60%, (d) 66.67% and (e) 71.42%.

conditions. It was found that the PVDFHMFS (1:1) composite

coating prepared from a precursor aged for 3 days exhibited a
porous structure with long nanolaments (Fig. 2c and d). The
composite coating with PVDF:HMFS (1:2) was more rough and
displayed porous structure. When the precursor was ultrasonicated before spraying, SEM images showed micro-scale bumps
interspersed with honeycomb-like structure as shown in Fig. 3c
and d. The areas surrounding the honeycomb contained silica
particles. The aggregates of particle were smaller for coating
prepared with ultrasonicated precursor. The bumps also had a
microporous structure. In all the four cases, the composite coatings
exhibited superhydrophobicity irrespective of the differences in
their microstructure. Hsieh et al. have proposed that water
droplets cannot penetrate easily into micropores on a repellent
surface and therefore rough surfaces with a high fraction of

micropores enhance superhydrophobicity [19]. Thus the microstructure of the coatings was found to depend on the silica content,
aging time and spraying parameters of the precursor mixture.
It was found that solvent (DMF)nonsolvent (toluene) ratio is
an important parameter. If the amount of toluene used for
dispersing silica particles is high, PVDF gets precipitated. Hence an
optimum amount of toluene should be used to dilute the PVDF
solution since excess toluene precipitates PVDF. The precipitated
PVDF can be redissolved by adding more DMF to the solution and
by warming.
The usefulness of a superhydrophobic coating is determined by
its stability. The surface should retain its water-repellent properties after immersion in water. It was found that the coating
appeared as a silver mirror when it was immersed in water and
viewed at a glancing angle as shown in Fig. 4. Similar optical

Fig. 2. SEM images of PVDFHMFS (1:1) composite coatings prepared under different conditions (a) with freshly mixed precursor, magnication 500; (b) higher
magnication of (a); (c) after aging the precursor, magnication 500; (d) higher magnication of (c).

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B.B.J. Basu, A.K. Paranthaman / Applied Surface Science 255 (2009) 44794483

Fig. 3. SEM images of PVDFHMFS (1:2) composite coatings prepared under different conditions (a) with freshly mixed precursor, magnication 500; (b) higher
magnication of (a); (c) after ultrasonicating the precursor, magnication 500; (d) higher magnication of (c).

property has been reported earlier for superhydrophobic surfaces

[20,21]. The mirror-like appearance is due to an air layer between
water and superhydrophobic surface. It was found that the PVDF
HMFS (1:1) coating was not wetted after 6 h of immersion in water
and there was no change in WCA but an increase in SA to about 158
was observed in the immersed area. The coating regained its
superhydrophobic property after drying at room temperature.
PVDFHMFS (1:2) coating was not wetted after 30 h of immersion
in water. But SA increased to 108 while there was no change in
WCA. Drying at room temperature resulted in complete regaining
of the superhydrophobic property. Composite coatings with higher
silica concentration showed better water repellency than coatings
with lower silica concentration. Zimmerman et al. also have noted
the increase in sliding angles of silicone-based superhydrophobic
coatings [22]. They have proposed that increased sliding angle is
related to the pinning of the contact due to surface inhomogeneities. It is presumed that hydrophilic defects on the surface are
generated during immersion that lead to an increase in sliding
angle without inuencing the static contact angle.

Fig. 4. Total internal reection of PVDFHMFS coatings on glass substrate when

immersed in water.

These composite coatings exhibited self-cleaning property. It

was found that the water droplets removed any dust particles
sprinkled on the coating. The coatings were stable for long periods if
stored under ambient conditions. The rst batch of our coatings
prepared one year ago still continue to retain their superhydrophobic property. Coatings were exposed to sunlight and wind to
study the effect of weather on the performance of coatings. Even
after continuous exposure for several days, there was no deterioration in performance and the coatings were superhydrophobic.
Generally superhydrophobic surfaces are easily damaged by
scratching and abrading due to their high surface roughness [22]. To
our knowledge, no superhydrophobic coating with high abrasion
resistance has been reported so far. The coating integrity was tested
qualitatively by cotton swab abrasion test [24]. The ratings criteria
were as follows: Rating 1the substrate was exposed; Rating 2
signicant amount of material was removed, substrate not exposed,
thick abrasion line seen; Rating 3less material was removed, the
abrasion line was less thick; Rating 4abrasion line was very thin;
Rating 5no abrasion line observed. The composite coatings showed
rating 3. The rubbed area was not wetted by water but displayed an
increase in SA of about 208. After annealing at 100 8C for 1 h coating
exhibited rating 4. Surprisingly, mechanical property of the coating
was good even at higher silica concentrations. On the contrary, PVDF
blank coating showed poorer adhesion and abrasion resistance than
the composite coatings.
The condensation of water droplets on the composite coating
surface was studied. Recent studies have shown that many of the
superhydrophobic surfaces, both natural and articial may not be
truly superhydrophobic depending on how water gets on to their
surfaces [25,26]. It was shown that if water vapor inltrates into
the microvoids on the surface of lotus leaf, water drops can stick to
their surface and they do not roll off even after tilting the surface at
any angle. Superhydrophobic behaviour of such surfaces is termed
to be metastable [26]. Hence it is important to consider how water
gets on to and evolves on the surface. We have carried out a simple
water condensation test on the PVDFHMFS composite coating by
exposing it to fog by keeping outside overnight. An epoxy paint
coating was also kept for comparison. The temperature was about

B.B.J. Basu, A.K. Paranthaman / Applied Surface Science 255 (2009) 44794483

4483

cavities and nanobers was found to be responsible for the

superhydrophobicity. The method is simple and cost-effective and
can be used for preparing self-cleaning superhydrophobic coating
on large areas on different kinds of substrates for practical
applications.
Acknowledgement
The authors are grateful to Dr. A.R. Upadhya, Director, NAL, Dr.
Kota Harinarayana, Raja Ramanna Fellow, NAL and Dr. K.S. Rajam,
Head, Surface Engineering Division, NAL for their constant support
and encouragement for this work. We wish to thank Prof. A.
Venkateswara Rao, Shivaji University, Kolhapur, India for static
contact angle measurements, and Raghavendra, Materials Science
Division, NAL for technical assistance with SEM studies.
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Fig. 5. Photographs of condensed water drops on (a) epoxy paint coating; and (b)
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4. Conclusions

[20]

Creation of surface roughness by embedding hydrophobically

modied fumed silica particles in PVDF matrix resulted in
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