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Superhydrophobic Fluorinated
Polyurethane Films
a b c d
D. Wu , W. Ming , R. A. T. M. van Benthem & G. de With
a
Laboratory of Materials and Interface Chemistry, Eindhoven University
of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
b
Laboratory of Materials and Interface Chemistry, Eindhoven University
of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands,
Nanostructured Polymers Research Center, Materials Science Program,
University of New Hampshire, Durham, NH 03824, USA; , [email protected],
Email: [email protected]
c
Laboratory of Materials and Interface Chemistry, Eindhoven University
of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
d
Laboratory of Materials and Interface Chemistry, Eindhoven University
of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

Version of record first published: 02 Apr 2012.

To cite this article: D. Wu, W. Ming, R. A. T. M. van Benthem & G. de With (2008): Superhydrophobic
Fluorinated Polyurethane Films, Journal of Adhesion Science and Technology, 22:15, 1869-1881

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 Journal of Adhesion Science and Technology 22 (2008) 1869–1881
www.brill.nl/jast

Superhydrophobic Fluorinated Polyurethane Films

D. Wu a , W. Ming a,b,∗ , R. A. T. M. van Benthem a and G. de With a

a
Laboratory of Materials and Interface Chemistry, Eindhoven University of Technology,
P.O. Box 513, 5600 MB Eindhoven, The Netherlands
Downloaded by [University of Saskatchewan Library] at 23:36 23 September 2012

b
Nanostructured Polymers Research Center, Materials Science Program,
University of New Hampshire, Durham, NH 03824, USA

Abstract
A superhydrophobic polyurethane-based film is described, on which the water advancing and reced-
ing contact angles are 150◦ and 82◦ , respectively. The film was prepared from surface-fluorinated
polyurethane (PU), obtained from a well-defined fluorinated isocyanate, with silica particles incorporated
within the film. In the absence of the silica particles, smooth fluorinated PU films with about 2 wt% flu-
orine demonstrate water advancing and receding contact angles of 110◦ and 63◦ , respectively. A major
cause for the large contact angle hysteresis, similar to the so-called ‘sticky’ superhydrophobic behav-
ior, on the roughened PU films is believed to originate from the surface reorganization of the fluorinated
PU upon contact with water, which is characteristic for the partially fluorinated PU film. When a similar
poly(dimethylsiloxane) (PDMS)-based roughened film was made, the water contact angle hysteresis could
be reduced significantly, since the long PDMS chain can effectively suppress the surface reorganization
upon contact with water.
© Koninklijke Brill NV, Leiden, 2008

Keywords
Superhydrophobicity, polyurethane, contact angle hysteresis, surface reorganization

1. Introduction
Mother Nature has demonstrated many elegant examples of superhydrophobic sur-
faces. For instance, many plant leaves (such as lotus leaf [1]) and insects (such
as water strider [2] and Namib Desert beetle [3]) have ‘smartly’ adopted a dual-
size or even multi-length-scale surface roughness to effectively generate super-
hydrophobicity. The superhydrophobicity is attributed to a smart combination of
low surface-energy species and the peculiar topographic feature based on dual-
size roughness. Due to the potential applications in a variety of areas, an exten-
sive interest has been revived in superhydrophobic surfaces in the past decade
[4–10]. Inspired by the lotus leaf structure, we have recently prepared epoxy-based,

*To whom correspondence should be addressed at the University of New Hampshire. Tel.: 001-603-
8621446; Fax: 001-603-8624892; e-mails: [email protected], [email protected]

© Koninklijke Brill NV, Leiden, 2008 DOI:10.1163/156856108X320023

 1870 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881

poly(dimethylsiloxane)-surface-modified, superhydrophobic films with dual-size

hierarchical structure originating from well-defined raspberry-like particles [11].
On this surface, the advancing contact angle for water is about 165◦ and the roll-off
angle of a 10-µl water droplet is <3◦ .
Another inspirational example from Mother Nature is the gecko, which can
climb vertically even on smooth substrates [12, 13]. Even though a gecko can
adhere strongly to a surface, surprisingly its tiptoe, comprising millions of setae,
demonstrates superhydrophobic behavior [13]. Recently, there have been a few re-
ports on so-called ‘sticky’ superhydrophobic surfaces [14, 15], obtained via aligned
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polystyrene hollow nanotubes [14] or etched hydrophilic aluminum alloy [15].

Here we report another type of sticky superhydrophobic surface from roughened,
partially fluorinated polyurethane films. It is well known that a fluorinated polymer
has low wettability due to its low surface energy [16, 17], and can, therefore, be
used as an ideal building block to develop superhydrophobic coatings. On the other
hand, wettability is basically a surface property, so it is unnecessary to have flu-
orinated species in the bulk. Surface segregation provides an excellent strategy to
create a coating with a fluorine-rich surface. In such an approach, due to its low sur-
face energy, the fluorinated species would migrate toward the air/film interface to
minimize the interfacial energy [18–27]. Thus, only a small quantity of fluorinated
species is needed to provide a surface with low surface energy. Here, we report the
synthesis of a well-defined fluorinated isocyanate, the preparation of partially flu-
orinated polyurethane (PU) films using the fluorinated isocyanate, and the sticky
superhydrophobic behavior of roughened fluorinated PU films. The origin of the
sticky superhydrophobic behavior and possible ways of suppressing this phenom-
enon will be discussed.

2. Experimental Section
2.1. Materials
A solventless liquid oligoester (SLO, Scheme 1) was synthesized according
to a previously published procedure [22]. Two different perfluoroalkyl alco-
hols, Cn F2n+1 –CH2 CH2 OH (n = 6 and 8, denoted as F6 -OH and F8 -OH), were
kindly supplied by Clariant GmbH (Frankfurt am Main, Germany), with trade-
marks of Fluowet EA 600 and EA 800, respectively. 3/4-Isocyanatomethyl-
1-methyl-cyclohexylisocyanate (IMCI, Scheme 1) was generously supplied by
DSM (Geleen, The Netherlands). Zirconium(IV) butoxide was purchased from
Fluka (Milwaukee, WI, USA). A polyisocyanate cross-linker, under the trade-
mark Desmodur N3300, was obtained from Bayer AG (Leverkusen, Germany).
α,ω-Vinyl-terminated poly(dimethylsiloxane) (PDSM, MW of about 6000) and
tetrakis(dimethysiloxy)silane (a 4-functional cross-linker) were obtained from
ABCR (Karlsruhe, Germany), and the catalyst cis-dichlorobis(diethyl
sulfide)platinum(II) was obtained from Strem Chemicals (Newburyport, MA,
USA). Silica particles (diameter: ∼0.9 µm, with a trademark of Nyasil 6200) were
 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881 1871
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Scheme 1. Molecular structures of SLO, IMCI and N3300.

generously provided by Nyacol Nano Technologies (Ashland, MA, USA). Alu-

minum panels were purchased from Q-Panel Company (Cleveland, OH, USA).

2.2. Synthesis of Fluorinated IMCI

The well-defined fluorinated IMCI (Fn -IMCI, n = 6 or 8) was synthesized via

a one-step reaction between IMCI and a perfluoroalkyl alcohol (F6 -OH or F8 -OH)
catalyzed by zirconium(IV) butoxide, and the overall OH/NCO molar ratio was
0.8/2 or 1/2 under a dry N2 atmosphere at 80 or 60◦ C for 1 h.

2.3. Preparation of Partially Fluorinated PU Films

The well-defined fluorinated isocyanate (F6 -IMCI or F8 -IMCI) was mixed with
appropriate amounts of SLO and N3300 (cross-linker) in butyl acetate. The overall
OH/NCO molar ratio was maintained at about 1.1 to ensure full conversion of the
NCO groups. After a homogeneous mixture was formed, a coating was applied onto
a clean aluminum panel by spin coating. The coating was then cured at 80◦ C for 2 h.
Because of the steric hindrance, the tertiary NCO group in Fn -IMCI was much
less reactive than the NCO groups in the cross-linker N3300. So, alternatively,
Fn -IMCI was first reacted with SLO at an NCO/OH molar ratio of 1/20, before
adding N3300 to the reaction mixture. Otherwise, NCO groups in N3300 may con-
sume all the OH groups in the SLO before Fn -IMCI can have a chance to be grafted
onto the SLO.
 1872 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881

2.4. Preparation of Roughened Fluorinated PU Films

First, F8 -IMCI was mixed with SLO, and the overall NCO/OH molar ratio was
maintained at 1/20 to make sure there were enough OH groups remaining in SLO
after all the NCO groups were consumed. The product mixture was dissolved in
butyl acetate. Next, the cross-linker N3300 was added to the silica particle suspen-
sion in butyl acetate. Finally, the solution of F8 -IMCI, SLO and the suspension of
SiO2 were mixed together, and the OH/NCO molar ratio was about 1.1. The SiO2
particle concentration for the mixture was varied from 30–60 wt%. Films were
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applied onto clean aluminum panels by an automatic film applicator (Coatmaster

509 MC, Erichsen, Germany) and cured at 80◦ C for 1 h. The thickness of dry films
was about 6 µm.
2.5. Preparation of Roughened PDMS-Based Films
First, a mixture of vinyl-terminated PDMS and SiO2 particles (0.9 µm) was dis-
persed in toluene by a sonifier for 2 min, then the cross-linker tetrakis(dimethy-
siloxy)silane and the catalyst cis-dichlorobis(diethyl sulfide)platinum(II) were
added to the mixture. The SiO2 particle concentration in the final film was about
50 wt%. Films were applied onto clean aluminum panels by an automatic film
applicator and cured at 60◦ C for 3 h.
2.6. Characterization Techniques
1 H-NMR analyses were performed using a Varian 400 MHz spectrometer at room
temperature. Samples were dissolved in CDCl3 (5 wt%). MALDI-TOF MS mea-
surements were carried out on a Voyager-DE-STR instrument (Applied Biosystems,
Foster City, CA, USA). Trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]
malononitrile was used as the matrix, which was dissolved in tetrahydrofuran (THF)
at a concentration of approximately 40 mg/ml. Sodium trifluoroacetate (Aldrich,
98%, Milwaukee, WI, USA) was used as the cationization agent and was added to
THF at a concentration of 5 mg/ml. Samples were dissolved in THF at a concen-
tration of 2 mg/ml. In a typical measurement, the matrix, cationization agent and
sample solution were premixed in a 5:1:1 ratio. Approximately 0.5 µl of the mix-
ture obtained was hand-spotted on the target plate and left to dry. Mass spectra were
recorded in the reflector mode.
X-ray photoelectron spectroscopy (XPS) measurements were performed with a
VG Escalab 200 using a standard aluminum anode (Al, Kα = 1486.6 eV) operating
at 240 W and with a background pressure of 2 × 10−7 Pa. Spectra were taken at
takeoff angles of 30◦ and 90◦ , corresponding to the probe depths of about 5 and
10 nm, respectively.
Contact angles (CAs) were measured with deionized water using a Dataphysics
OCA 30 instrument (Filderstadt, Germany) at room temperature. All the contact an-
gles were determined by averaging the values measured at three different locations
on each sample surface. Dynamic advancing and receding angles were recorded
while the probe fluid was added to and withdrawn from the drop, respectively.
 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881 1873

Atomic force microscopy (AFM) measurements were performed on a Veeco

Multimode SPM Nanoscope III instrument (Santa Babara, CA, USA). The can-
tilever of choice was no-contact gold-coated NSG 11 (NT-MDT, Russia). Scanning
electron microscopy (SEM) was performed on a Philips XL-30 ESEM FEG instru-
ment (Philips, now FEI Co., The Netherlands).

3. Results and Discussion

3.1. Synthesis of Fn -IMCI
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IMCI consists of two isocyanate groups: one is directly bonded to a carbon atom
in the cyclohexane ring, resulting in considerable steric hindrance, while the other
(primary) isocyanate group is separated from the ring by a methylene spacer and is,
therefore, more accessible. When zirconium(IV) butoxide is used as the catalyst for
the reaction between an alcohol and IMCI, the selectivity of the reaction between
the alcohol and the primary isocyanate group is as high as 99% [28]. Therefore,
by controlling the Fn -OH/NCO molar ratio at 1:2, a perfluoroalkyl chain could
be selectively grafted onto IMCI, leaving the other isocyanate group for further
reaction.
Both IMCI and Fn -IMCI were characterized by 1 H-NMR, as shown in Fig. 1.
The following peaks can be identified. For IMCI, δ = 3.30 (m, 2H, –CH 2 –NCO);
and for F6 -IMCI, δ = 2.45 (m, 2H, –CH2 CH 2 CF2 –), 3.10 (m, 2H, –CH 2 –NHC(O)–
O–), 4.40 (t, 2H, –O–CH 2 CH2 CF2 –), 4.90 (m, 1H, –CH2 –NHC(O)–O–). F8 -IMCI

Figure 1. Proton NMR spectra of F6 -IMCI and IMCI.

 1874 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881

has the same spectrum as F6 -IMCI. After the fluorination, the peak at 3.30 ppm
in the IMCI spectrum disappeared completely, indicating that the primary NCO
had reacted completely. The well-defined structure of Fn -IMCI enables an easy and
accurate adjustment of the fluorine content in the polymeric film created by cross-
linking Fn -IMCI, SLO and N3300.
According to the stoichiometry for the reaction between IMCI and Fn -OH and
the selectivity of the Zr-catalyst [28], the OH/NCO molar ratio just needs to be
1/2 to obtain well-defined Fn -IMCI. When a coating was prepared with F8 -IMCI
synthesized as such (together with SLO and N3300), the water contact angles on the
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coating varied significantly before and after the samples were rinsed with acetone.
The advancing and receding CAs on the film before rinsing were 120◦ and 60◦ ,
respectively; after the acetone rinse and being dried in air at 80◦ C for 15 min, the
advancing/receding CAs on the film decreased to 97◦ /55◦ . To find out the reason for
this large decrease, the fluorine concentration at the sample surface before and after
rinsing with acetone was checked with XPS at takeoff angles of 30◦ and 90◦ . Before
the acetone rinse, the F/C atomic ratios in the top 5 and 10 nm of the film were
0.57 and 0.46, respectively; after rinsing, these values reduced to 0.19 and 0.13,
respectively. These results indicate that there is a fluorine-rich layer on the surface
that can be easily rinsed away. A likely reason is that some fluorinated species are
not chemically bonded to the cross-linked polymer network, which may include
non-reactive fluorinated species and, to a lesser extent, unreacted F8 -OH. So we
examined the synthesized F8 -IMCI with MALDI-TOF MS.
In the MALDI-TOF mass spectrum of the F8 -IMCI, two peaks were found at
m/z = 681 and 1145, corresponding to the species [F8 -IMCI + Na]+ and [F8 -
IMCI-F8 + Na]+ , respectively, which indicated that a side reaction had occurred
(Scheme 2). The by-product F8 -IMCI-F8 has no NCO group available to react fur-
ther with SLO, so it cannot be cross-linked to the bulk of the film. On the other
hand, F8 -IMCI-F8 will migrate to the surface of the film very easily during the film

Scheme 2. Reactions between IMCI and F8 -OH.

 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881 1875

formation, and can be rinsed away by acetone. Therefore, the fluorine concentration
at the film surface decreased dramatically after rinsing with acetone.
To eliminate the by-product F8 -IMCI-F8 , the molar ratio between OH and NCO
was reduced from 1/2 to 0.8/2 and the reaction temperature was decreased from 80
to 60◦ C. Under these conditions, there will be only a small amount of unreacted
IMCI present at the end of reaction. Since the primary NCO is much more reactive
than the tertiary NCO in the presence of the Zr-catalyst we used (the selectivity is
above 99% [28]), there should be no F8 -IMCI-F8 present in the final product. The
remaining IMCI can act as a chain extender in the following film formation. The
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new product was examined with MALDI-TOF MS, and the peak at m/z = 1145
indeed completely disappeared, indicating that there was no F8 -IMCI-F8 left in the
new product.
3.2. Wettability of Smooth Polymeric Films
Smooth PU films were prepared by thermal curing of a mixture containing
Fn -IMCI, SLO and N3300 at 80◦ C for 2 h, as detailed in the Experimental Sec-
tion. The wettability of a film is reflected by the contact angle (CA) of water on the
surface. The advancing (θA ) and receding (θR ) water CAs on the smooth films, after
being rinsed with acetone, were measured, as given in Table 1. For the film free of
fluorine (Film-NF), the advancing water CA on the film surface was about 87◦ . Af-
ter adding a small amount of fluorinated species, the advancing water CA increased
to 110◦ for Film-A containing F8 -IMCI. It is interesting to notice that Film-A was
more hydrophobic than Film-B containing F6 -IMCI, even though the latter had
a slighter higher bulk fluorine concentration. Similar results have been obtained in
our previous studies [22, 24–27]. The reason is that the driving force for the surface
enrichment by the fluorinated species is stronger for F8 -IMCI than for F6 -IMCI,
due to the longer perfluoroalkyl chain in the former. Film-A was also rinsed by
acetone and subsequently dried; the water contact angles remained essentially the
same as those before acetone rinsing, indicating that the perfluoroalkyl chains were
chemically bonded to the bulk of the film.
Table 1 also indicates that a large water CA hysteresis (CAH) is present for the
partially fluorinated films. It is well known that contact angle hysteresis arises from

Table 1.
Water CAs on smooth films from SLO, Fn -IMCI and N3300

Film Film composition F content Water contact angle θA Water contact angle θR
(wt%)∗ (◦ ) (◦ )

Film-NF N3300, SLO 0 86.7 ± 0.8 41.1 ± 1.1

Film-A F8 -IMCI, N3300, SLO 2.1 110.4 ± 1.7 63.1 ± 1.6
Film-B F6 -IMCI, N3300, SLO 3.8 99.3 ± 1.2 56.2 ± 0.5
∗ wt% was calculated from the film composition, assuming all the added fluorinated species were
chemically bonded to the network.
 1876 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881
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Figure 2. AFM non-contact mode images of the surface of Film-A: (a) height image and (b) phase
image.

three sources [29]: surface roughness, surface chemical heterogeneity and surface
reorganization. To find out what caused the high water CAH on these films, the
topography of the films was examined by AFM; typical height and phase AFM
images are shown in Fig. 2. For Film-A, the surface roughness in the area of
0.5 µm × 0.5 µm is <5 nm (Fig. 2a), so the surface roughness is not likely to be
the source for the high CAH. Furthermore, the AFM phase image in Fig. 2b clearly
shows that there is no phase contrast at the film surface, which indicates that the
distribution of the fluorinated species is quite homogeneous even at the nanome-
ter scale at the film surface. Therefore, the surface chemical heterogeneity is not
expected to contribute significantly to the large CA hysteresis, either.
We have prepared other low surface energy polyurethane (PU) films with surface
enriched by fluorinated species [24, 26], on which CAH as high as 50◦ was also ob-
served. We examined the top atomic layer of the fluorinated PU surface containing
1 wt% of fluorine [22] by low energy ion scattering [30, 31] (a unique technique
that analyzes the composition of only the outermost atomic layer), and found that
only fluorine and carbon atoms were present, suggesting that oxygen and nitrogen
atoms were primarily located beneath the top atomic layer. The very large CAH is
likely due to the fact that the fluorinated chain (e.g., C8 F17 –) is not long enough to
prevent the surface reorganization (i.e., to shield the polar urethane group from the
interrogating liquid) upon contact with water during the CA measurements [32]:
when the water droplet is in contact with the film surface, the urethane group that
originally sits below the top fluoroalkyl layer has the opportunity to interact with
water, leading to a low θR and a large CAH. We believe, therefore, that the large
CAH observed in the films containing Fn -IMCI also originates from the surface
reorganization upon contact with water during contact angle measurements. The
surface reorganization can be facilitated by the fact that the PU films we prepared
had a relatively low Tg (about 15◦ C), so the polymer network and the perfluoroalkyl
chains had some degree of mobility. On the as-prepared surface, the perfluoroalkyl
chains were oriented preferentially towards the coating–air interface, leading to
 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881 1877

high advancing water contact angles. Upon contact with water, however, water may
penetrate into deeper layers and ‘drag out’ some polar groups (e.g., urethane), lead-
ing to low receding contact angles, due to the insufficient shielding of the polar
groups by the short perfluoroalkyl chain.
3.3. Wettability of Roughened Fluorinated Polyurethane Films
It is well known that surface roughness can alter the surface wettability significantly.
We incorporated a certain amount of silica particles into the partially fluorinated PU
films, with the aim to generate sufficient roughness to obtain superhydrophobicity.
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Since the surface energy of silica particles is much higher than the individual com-
ponents used for the preparation of the PU films, the polymer solution is able to wet
the silica particle surface easily. Therefore, we assume that the silica particles will
be covered by a thin layer of PU after film formation. The silica particles we used
had an average particle diameter of ∼0.9 µm. The highest content of silica particles
we could use was 60 wt%, above which continuous films could not be obtained. On
the other hand, for a SiO2 concentration below 30 wt%, a smooth film was formed.
The water CA data on the roughened fluorinated PU films are given in Table 2.
Obviously, as the silica content (relative to the total solid content) increased to 50
and 60 wt%, the advancing CA increased significantly up to 150◦ . On the other
hand, there was only marginal increase in the receding CAs (Film-C and Film-D).
Film-C was examined by SEM and AFM. Both the SEM image (Fig. 3) and AFM
height image (Fig. 4a) showed that Film-C had a rough surface, with a typical peak-
to-valley distance of ∼0.5 µm (Fig. 4b). Film-D, which contained 10 wt% more
silica particles than Film-C, demonstrated even higher surface roughness (Fig. 5),
with a typical peak-to-valley distance reaching ∼0.9 µm.
A possible cause for the large CAH for Film-C and Film-D is the surface reorga-
nization upon contact with water, as discussed above. Also, the surface roughness
for these films may not be high enough. If the surface roughness is not sufficiently
high, the wetting may well be located in the Wenzel regime [33, 34], where a higher
liquid/solid interfacial area would effectively increase the CAH; more on this will
be discussed in the following section. The observed large CAH is similar to what
has been termed ‘sticky’ superhydrophobic behavior [15].

Table 2.
Water CAs on roughened films from SLO, F8 -IMCI and N3300

Film∗ SiO2 content Water contact angle θA Water contact angle θR

(wt%) (◦ ) (◦ )

Film-A 0 110.4 ± 1.7 63.1 ± 1.6

Film-C 50 136.3 ± 0.6 70.2 ± 0.8
Film-D 60 150.2 ± 1.2 82.1 ± 1.1
∗ The fluorine content in all the films was 2.1 wt% (excluding the weight of silica particles for
Film-C and Film-D).
 1878 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881
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Figure 3. SEM image of Film-C.

3.4. Wettability of Roughened PDMS Films

To examine if the surface reorganization of the roughened fluorinated PU film was
the major cause for the large CAH observed, we chose to use PDMS to obtain a
roughened surface. PDMS has a low surface energy, with a water CA of typically
about 105◦ and a CAH of <10◦ . In addition, due to its relatively long chain length
(compared to C8 F15 –), PDMS has been successfully used to make smooth PDMS-
modified PU films with a relatively low CAH [35], where a PDMS chain length of
60–70 repeating units appears to be long enough to prevent the surface reorganiza-
tion during the CA measurements.
We first attempted to deposit a PDMS layer based on vinyl-terminated PDMS
and tetrakis(dimethysiloxy)silane on a roughened fluorine-free PU film (containing
60 wt% SiO2 ), but the surface coverage of PDMS layer on the PU film was found
to be very poor, leading to a very low receding water CA (∼20◦ ).
For the sake of proving principles, we decided to make a roughened PDMS film
with silica particles incorporated on an aluminum panel, as outlined in the Experi-
mental Section. A continuous film was obtained with advancing and receding water
CAs of 150◦ and 105◦ , respectively. The CAH (45◦ ) was significantly lower than
that (68◦ ) for Film-D, although the two films demonstrated similar surface rough-
ness. In the case of the roughened PDMS film, the surface reorganization upon
contact with water was eliminated, which is believed to be the main reason that
the receding water CA increased substantially. On the other hand, the receding
CA was still not as high as the value we obtained on a dual-size PDMS-modified
surface made from raspberry-like particles with a CAH of as low as 2◦ [11]. The
dual-size surface roughness [11] leads to an effective transition from the Wenzel
wetting regime to the Cassie regime [36], allowing us to obtain successfully non-
sticky superhydrophobic surfaces. For the roughened PDMS surface in this study,
 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881 1879
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Figure 4. AFM height image of Film-C (a) and the topographical profile (b) along the line indicated
in (a).

the single-size silica particles obviously cannot provide sufficiently high surface
roughness to lead to a truly self-cleaning surface. Nonetheless, this investigation
does indicate that the surface reorganization of the roughened fluorinated PU film
 1880 D. Wu et al. / Journal of Adhesion Science and Technology 22 (2008) 1869–1881
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Figure 5. AFM height image of Film-D.

upon contact with water is a major cause for the observed sticky superhydrophobic
behavior.

4. Conclusions
It has been demonstrated in this study that by incorporating silica particles, a par-
tially fluorinated polyurethane film can be turned superhydrophobic, despite a large
water contact angle hysteresis (sticky superhydrophobic behavior). One major
cause for the large CAH is the surface reorganization of the fluorinated polyurethane
film upon contact with water. A long PDMS chain can be used to effectively sup-
press the surface reorganization upon contact with water.

Acknowledgements
This research was sponsored by DSM Research, The Netherlands. We thank
Dr. E. Currie and Dr. J. Thies (DSM Research) for beneficial discussions and Mar-
ion A. van Straten for MALDI-ToF MS measurements.

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