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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
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
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%.
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).
B.B.J. Basu, A.K. Paranthaman / Applied Surface Science 255 (2009) 44794483
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[9]
[10]
[11]
[12]
[13]
4. Conclusions
[20]
[21]
[22]
[23]
[24]
[14]
[15]
[16]
[17]
[18]
[19]
[25]
[26]