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Colloids and Surfaces A: Physicochem. Eng. Aspects 313–314 (2008) 411–414

Preparation of superhydrophobic polystyrene

membranes by electrospinning
Minsung Kang, Rira Jung, Hun-Sik Kim, Hyoung-Joon Jin ∗
Department of Polymer Science and Engineering, Inha University, Incheon 402-751, South Korea
Received 28 October 2006; accepted 26 April 2007
Available online 9 June 2007

Abstract
In this study, N,N-dimethylformamide (DMF), which is a non-volatile solvent, was selected to dissolve polystyrene (PS) (190,000 g/mol) and
the concentration of the PS solution (∼35 wt%) was maximized to retard the evaporation of the solvent under electrospinnable conditions. Unlike
the porous morphology observed on the surface of the fibers electrospun from the PS solution in tetrahydrofuran (volatile solvent), the electrospun
PS fibers obtained from the highly viscous solution of PS in DMF exhibited an intriguing surface morphology with numerous protuberances. The
contact angle measurements indicated that the electrospun fibrous membranes were superhydrophobic with a water contact angle of 154.2 ± 0.7◦ .
This superhydrophobicity was attributed to the combined effects of the regular nanostructural protuberant morphology formed on the surfaces of
the individual fibers during electrospinning and the microstructural surface roughness of the electrospun membrane itself.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Superhydrophobic; Polystyrene; Electrospinning; Surface energy

1. Introduction cleaning effect caused by superhydrophobicity is useful for

The wettability of solid surfaces is a momentous property
for many industrial and biological techniques and it depends
on both their chemical composition and geometrical structure
[1]. As regards the chemical composition, the hydrophobicity
of a solid surface can be enhanced by lowering the surface
energy component using such methods as the introduction of
CF3 -groups. Although CF3 -groups, which have the lowest sur-
face free energy, were functionalized onto a flat solid surface to
increase the water contact angle, the highest value obtained was
only 120◦ , which is difficult to define as “superhydrophobic-
ity” [2,3]. The phenomenon in which a surface is hydrophobic
with a water contact angle greater than 150◦ is called superhy-
drophobicity [4]. As a typical example, the lotus leaf (Nelumbo
nucifera) found in nature has a unique property called self-
cleaning, because the water contact angle is 160.4 ± 0.7◦ [5].
This high water contact angle is caused by its hierarchical struc-
ture, which consists of nanoscale cylinder-like shapes on the
rough micro-surface and a low surface energy [6]. The self-
∗ Corresponding author. Tel.: +82 32 860 7483; fax: +82 32 865 5178.
E-mail address: hjjin@inha.ac.kr (H.-J. Jin).
various applications such as anti-fouling coatings and biomedi-
cal materials [7].
In recent studies, surface modification or reducing the surface
energy have been tried to produce superhydrophobic materials
via solution casting [3], and the introduction of inorganic com-
ponents including carbon nanotubes [8,9] or polymers [10] onto
the surfaces of films and electrospinning [11–14]. For example,
superhydrophobic films were fabricated using organic poly-
mers such as isotactic polypropylene [3] or inorganic materials
such as aluminum oxide [14] and polyelectrolytes [15]. Aligned
polystyrene (PS) nanotubes [10] and carbon nanotubes [9] were
found to exhibit superhydrophobic properties.
Electrospinning is a simple method of producing contin-
uous fibers with diameters ranging from the nanometer to
the submicron scale. It is also appropriate to make super-
hydrophobic non-woven membranes owing to the roughness
introduced during their spinning [11–14]. Rutledge et al.
reported that electrospun poly(␧-caprolactone) with the chem-
ical vapor deposition of polymerized perfluoroalkyl ethyl
methacrylate and electrospun poly(styrene-b-dimethylsiloxane)
exhibited superhydrophobic properties [11,14]. Jiang et al. also
succeeded in preparing porous and protuberant microsphere-
embedded nanofibers with a superhydrophobic surface via

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doi:10.1016/j.colsurfa.2007.04.122
412 M. Kang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 313–314 (2008) 411–414
electrospinning using PS/N,N-dimethylformamide (DMF) solu-
tion [12].
We recently reported the preparation of electrospun PS fibers
with a unique surface morphology using a non-volatile solvent
(DMF) [16]. These fibers have a uniform protuberant surface
morphology, whereas electrospun fibers produced with volatile
solvents such as tetrahydrofuran (THF) have a porous surface
morphology. In this study, the electrospun PS fibers were found
to exhibit superhydrophobicity because of the unique protuber-
ant structure formed on their surface, which is similar to the
hierarchical structure of lotus leaves, and which is expected to
affect their superhydrophobic behavior.
2. Experiment
PS (Mw ; 190,000 g/mol), THF, chloroform (CHCl3 ) and
DMF (HPLC grade) were purchased from Scientific Polymer
Products, Inc. or Sigma-Aldrich, Inc. and were used as received.
To prepare the PS films, 5 wt% PS was dissolved in THF and
CHCl3 . The PS solutions, 30 wt% in THF or CHCl3 and 35 wt%
in DMF, were prepared in a warm water bath (∼40 ◦ C) with
about 2 h of mild stirring for electrospinning.
The PS films were prepared from the 5 wt% THF and CHCl3
solutions by spin casting them on a cleansed silicon wafer. The
electrospinning apparatus was composed of several components;
a high voltage supplier (Gamma High Voltage Research, E3
Fig. 1. FESEM images of electrospun PS fibers from 30 wt% PS solution in (a) THF and (b) CHCl3 ; and the images of the water droplet on the surface of the
electrospun PS membranes from 30 wt% PS solution in (c) THF and (d) CHCl3 .
30P-5W, USA), a capillary tube with a stainless steel needle
(16 gage), a syringe pump (Harvard Apparatus, USA), and a
stainless steel collecting plate (diameter; ∼10 cm), as described
in a previous work [17]. The PS solutions in THF and CHCl3
were electrospun using a 10 mL syringe with a 1.2 mm diameter
spinneret at a flow rate of 30 ␮L/min under applied voltage dif-
ferences of 16 and 20 kV over a distance of 30 cm (E = 0.53 and
0.67 kV/cm), respectively. The electrospinning of the PS solu-
tion in DMF was carried out using the same equipment under
an applied voltage difference 16.0 kV and a distance of 21 cm
(E = 0.76 kV/cm) at 150 ␮L/min.
The water contact angle on the spin cast film or the elec-
trospun membrane was measured with an FTÅ200 contact
angle instrument (First Ten Angstroms, USA) at room tem-
perature. The morphology of the fiber and its surface structure
were observed by field emission scanning electron microscopy
(FESEM) (S-4300, Hitachi, Japan). The samples were platinum
coated for 45 s to minimize the charging effect. The accelera-
tion voltage and working distance for each image were 15 kV and
6 mm, respectively. Optical microscopy (OM) (BX51, Olympus,
Japan) was used to examine the internal structure of the electro-
spun fibers as well as the fiber diameters. The fiber diameters
were measured from the electronic OM and FESEM images
using image analysis software. The cross-sections of the fibers
were observed by transmission electron microscopy (TEM) (CM
200, Philips, Netherlands). The fibers were placed in an epoxy
 M. Kang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 313–314 (2008) 411–414
resin and hardened in an oven at 60 ◦ C for 2 days. The micro-
tomed slice of a fiber embedded in epoxy resin was placed on a
copper grid and observed by TEM.
3. Results and discussion
In order to measure the intrinsic hydrophobicity of the PS,
it was dissolved in good, volatile solvents such as THF and
CHCl3 . From the solutions of PS in THF and CHCl3 with a
concentration of 5 wt%, homogeneous smooth PS surface films
were easily fabricated by spin-casting on a silicon wafer. The
water contact angle values of the spin cast PS films made using
THF and CHCl3 were 91.6 ± 1.9◦ and 89.8 ± 1.1◦ , respectively.
PS is chemically hydrophobic, so that its water contact angle
was higher than that of other hydrophilic polymers. However,
the value of the water contact angle was not sufficient to exhibit
superhydrophobic behavior. We suggest that a rough surface
morphology as well as a hydrophobic chemical structure is
required for superhydrophobicity.
Concentrated solutions of up to 30 wt% were electrospun
to obtain a fibrous form, as shown in Fig. 1. The electrospun
fibers obtained from the PS/THF solution were randomly ori-
ented and each fiber had a flat surface with a regular porous
surface morphology and a diameter of 129.9 ± 27 nm (N = 100),
as Rabolt and co-workers reported [18,19]. This porous mor-
phology results from the high rate of evaporation of the volatile
solvent, THF (vapor pressure 129 mmHg at 20 ◦ C, b.p.; 66 ◦ C),
during electrospinning. The electrospun fibers had an aver-
age diameter of 12.7 ± 1.6 ␮m (N = 100) (Fig. 1(a)). Fig. 1(b)
shows the surface morphology of the electrospun PS fibers
obtained from the 30 wt% solution in CHCl3 , which produced
continuous and randomly oriented electrospun fibers with a
diameter of 12.9 ± 1.5 ␮m (N = 100), and large-scale grooves
were observed on the individual fibers. Both of the non-woven
electrospun membranes had a rougher surface morphology than
Fig. 2. (a) FESEM images of electrospun PS fibers from 35 wt% solution in DMF, (b) water droplet on electrospun PS fibers from 35 wt% solution in DMF, and (c)
variation of water contact angles depending on surface structures (1; PS film, 2; electrospun PS fibers using THF, 3; electrospun PS fibers from DMF).
413
the spin cast films. As a result, they were found to have
much higher water contact angle values of 138.1 ± 0.7◦ (THF)
and 138.8 ± 0.5◦ (CHCl3 ). This result supports our hypoth-
esis that the hydrophobicity largely depends on the surface
morphology. According to Cassie and Baxter, when a water
droplet is placed on a heterogeneous surface consisting of mate-
rial and air, it can be held up by the trapped air [20]. It is
known that the air trapped at the surface is very important
for hydrophobicity, because the water contact angle of air is
considered to be 180◦ [12]. The fibrous membranes we pre-
pared also include much air between the individual electrospun
fibers. Nevertheless, the water contact angle value obtained from
the electrospun fibers was not sufficient for them to exhibit
superhydrophobicity, because the electrospun fibers had a large
diameter, so that the water droplet came into contact with
a large area of the fibers compared with superhydrophobic
materials. This phenomenon is able to be explained using the
Cassie and Baxter equation (Eq. (1)) describing the relation-
ship between the water contact angles of smooth and rough
surfaces.
cos θr = f1 cos θ − f2 (1)
where θ and θ r are the water contact angles on a smooth
surface and rough surface, respectively, that is, the spin cast
films and fibrous membranes in this study, and f1 and f2 are
the fractions of the solid surfaces, i.e., the electrospun fibers
with porous surfaces or grooves and the air in contact with
water on the rough surface (f1 + f2 = 1). Given the water con-
tact angles of the spin cast films (θ) and fibrous mats (θ r ),
f2 can be calculated by Eq. (1). It was found to be 0.77 or
0.75, respectively, when THF or CHCl3 was used as a sol-
vent. Note that the values of f2 of superhydrophobic surfaces
should be more than 0.90 [9,12]. These values also show that
it is difficult to observe superhydrophobic behavior on electro-
spun membranes. The surface morphology of an electrospun
414 M. Kang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 313–314 (2008) 411–414
Fig. 3. (a) Optical microscopy image (1500 magnification) of the electrospun
PS fiber from 35 wt% solution in DMF and (b) TEM image of the cross section
of the electrospun PS fiber from 35 wt% solution in DMF.
fiber depends on the solvent used for its electrospinning and
PS is regarded as a model polymer to investigate the solvent
effect.
We previously reported that protuberant electrospun PS fibers
could be produced from a 35 wt% PS/DMF solution by the
solvent effect [16]. Fig. 2 illustrates the electrospun PS fibers
obtained from a 35 wt% PS/DMF solution. As shown in Fig. 2, a
lot of protuberances were observed on the individual electrospun
fibers. This surface structure resulted from the presence of resid-
ual solvent entrapped inside a single fiber during electrospinning
by its slow evaporation rate. The solvent entrapment inside the
fibers was observed by optical microscopy and TEM, in order to
confirm our hypothesis. As shown in Fig. 3(a), several hundred
nanometer-size bubbles were observed inside the single fiber
electrospun from the 35 wt% PS solution, and the TEM image
of the cross-section of the PS fiber electrospun from the 35 wt%
PS solution clearly shows the presence of several solvent bub-
bles having different diameters (Fig. 3(b)). We supposed that the
PS fibers would have a much higher water contact angle value,
because of the existence of the regular nanoscale protuberant
structures on their surfaces. Indeed, the water contact angle of
the electrospun membrane having a protuberant morphology on
each fiber was remarkably increased to 154.2 ± 0.7◦ . Accord-
ing to the results we previously mentioned, we found that the
physical surface structure is an important factor determining the
superhydrophobic property as well as the intrinsic hydrophobic
chemical structure of such materials as PS.
4. Conclusion
Recently, many researchers have tried to mimic lotus leaves
through various methods. ‘Superhydrophobicity’ is a phe-
nomenon wherein a solid surface has a water contact angle
greater than 150◦ . We prepared electrospun fibers from PS solu-
tions with several solvents, viz. THF, chloroform and DMF. It
was found that the hydrophobicity of the solid surface depends
on the surface morphology. When PS solutions in THF or CHCl3
were electrospun, the water contact angles were 138.1 ± 0.7◦
and 138.8 ± 0.5◦ , respectively, whereas the smooth films pre-
pared from the same solutions showed lower water contact
angles of 91.6 ± 1.9◦ (THF) and 89.8 ± 1.1◦ (CHCl3 ). Fur-
thermore, the water contact angle was remarkably increased
to 154.2 ± 0.7◦ , when the electrospun PS fibers obtained using
DMF as a solvent had a protuberant secondary structure on their
surface, which was derived from the intrinsic properties of the
non-volatile DMF.
Acknowledgements
The authors of this paper would like to thank the Korea
Science and Engineering Foundation (KOSEF) for sponsoring
this research through the SRC/ERC Program of MOST/KOSEF
(R11-2005-065).
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