Superhydrophobicity and UV stability of polydimethylsiloxane/polytetrafluoroethylene

(PDMS/PTFE) coatings
Yonghao Xiu', Lingbo Zhu', Dennis Hess', C. P. Wong2
'School of Chemical and Biomolecular Engineering
2School of Materials Science and Engineering
Georgia Institute of Technology, Atlanta, GA 30332
Telephone: +1 404-894-8391, Fax: +1 404-894-9140
Email: cp.wonggmse.gatech.edu

Abstract To date a variety of superhydrophobic surfaces have been

The incorporation of polytetrafluoroethylen (PTFE)
nanoparticles in curable polydimethylsiloxane (PDMS) matrix
allows the formulation of superhydrophobic films with
contact angles of 155-160°. Evaluation of the effect of PTFE
particle size on the superhydrophobicity was conducted by
using a larger particle size (2-5 ptm); the resulting film yielded
a contact angle of 140°. However, after UV irradiation, the
surface gradually lost superhydrophobicity. Changes in
surface chemistry resulting from these processes were
investigated using X-ray photoelectron spectroscopy (XPS)
and Fourier transform infrared spectroscopy (FTIR).
Applications for this superhydrophobic film include the
coating of microelectronic devices for self-cleaning and
moisture protection.
1. Introduction
The creation of superhydrophobic surfaces that mimick
lotus leaves is a relatively new research field that has attracted
considerable attention. Generally two requirements must be
satisfied in order to achieve superhydrophobicity. First, the
surface must be hydrophobic with a contact angle greater than
90°. Second, the surface needs to have a two-tiered
roughness; that is, it has to display both micro and nano
structures. Such surface roughness converts the hydrophobic
surface to a superhydrophobic surface.
The effect of surface roughness on contact angle was
modeled by several investigators approximately 50 years ago.
Wenzel's equation[ 1] was developed to account for roughness
through r, the ratio of the actual to projected surface area.
COSOrough=rCOSOtrue (1)
From equation (1) it is evident that contact angles (0) less
than 90° are decreased by roughness, while contact angles
greater than 90W are increased by roughness. In addition, if the
contact angle is large and the surface sufficiently rough, the
water droplet may trap air and thus yield a compound surface
effect with an apparent contact angle described by Cassie-
Baxter equation [2], equation 2:
CoSOapparent=rfcoOOiS +fi-1, (2)
where Oapparent and 01 are the Cassie-Baxter contact
angle and Young contact angle. fl is the fraction of the
projected area of the surface that is wet by water, and r is the
roughness (actual area to projected area) of the water contact
surface..
In this regime, a superhydrophobic surface can be
achieved.
98 1-4244-0261-1/06/$20.oo A©2006 IEEE.
fabricated from materials ranging from organic polymers
(e.g., polystyrene[3], fluorinated polyelectrolytes[4, 5],
polypropylene[6]) to inorganic materials (e.g., silica[7],
alumina[8, 9]). However, an important issue that will be
addressed in the current paper is the UV stability of
superhydrophobic surfaces. For organic polymers, the UV
stability is poor, especially within top several nanometers of
the polymer surface[10], which plays a critical role in surface
properties such as adhesion, decontamination, and moisture
repellency. Silicone is a UV stable polymer with low surface
energy (-2 1mJ/cm2) and a strong Si-O-Si (siloxane)
backbone, which provides enhanced chemical inertness and
exceptional flexibility;in fact, little degradation is expected
for long term applications. The unique stability of silicone
rubbers has been a driving force for their continued use in a
variety of applications. In this paper, superhydrophobic
surfaces were created using curable PDMS (Sylgard 184) and
PTFE particles, the superhydrophobic surfaces characterized,
and the UV degradation of the surfaces investigated.
2. Experimental
Materials
Substrates (lxi cm2) were p-type (100) silicon wafers
(Electronic Materials, Inc.). Allyl triethoxysilane (ATES) and
hexane were purchased from Sigma-Aldrich, Inc. Hexane was
used as solvent for the solution of ATES. Deionized (DI)
water (>18MQ), acetone, dilute hydrofluoric acid (HF/DI
H20 = 1:36 by volume), piranha solution (2 parts
concentrated (96%) H2SO4 mixed with 1 part H202 (3000 in
water) by volume), were used for the silicon wafer surface
cleaning. Silicone Sylgard 184 (two parts: PDMS elastomer
base and curing agent ), and Dow Coming 1-2577, provided
by Dow Coming Corp., were used as a curable polymer. Then
suspension of silicone, PTFE particles and toluene (weight
ratio: 1:3:7) was preapred and the film was derived by
spincoating the suspension on silicon wafer at 2000 rpm and
subsequent evaporation of the solvent at 100 °C for 30 min.
Two types of PTFE particles: polytetrafluoroethylene Zonyl
fluoroadditive ZONMP 1100 (particle size range: 150-250
nm, spherical) and ZONMP 1300 (particle size range: 2-5 ptm,
irregular shape) were used to make superhydrophobic films
on the silicon wafer.
PDMS Sylgard 184 ingredients
Base:
Dimethyl siloxane, dimethylvinyl-terminated
Dimethylvinylated and trimethylated silica
Tetra(trimethylsiloxy) silane
 Curing agent: condensation with the uninsulated black panel temperature
Dimethyl, methylhydrogen siloxane controlled at 50 ± 3°C. A radiometer was used to monitor and
Dimethyl siloxane, dimethylvinyl-terminated control the amount of radiant energy that impinged on the
Dimethylvinylated and trimethylated silica sample. A thermometer was used to monitor the temperature
Tetramethyl tetravinyl cyclotetrasiloxane in the test chamber.
The base resin and the curing agent were mixed in a ratio 3. Results and discussions
of 10:1 (weight) to achieve good mechanical strength. 3.1 Comparison of results with different PTFE particle
Cleaning of the silicon wafer surface sizes
First the surface of the silicon wafer is cleaned in acetone For PDMS/ZONMP 1300 surface, the particle size is
by sinication for 30 min at room temperature. The native around 2-5 ptm, and the contact angle for this surface is
surface oxide layer is then removed using 1:50 HF:H20 dilute around 136.4° as shown in Figure 1.
hydrofluoric acid and the sample rinsed in DI water. The
substrates are then placed in a piranha solution at -80°C for
30 min to reoxidize and hydroxylate the surface. Finally, the
substrates are rinsed in DI water and dried with pure nitrogen.
The water contact angle for this surface is 15° compared to
48° for a wafer surface prior to the cleaning and surface
conversion treatment. The lower angle is consistent with the
presence of an increased concentration of hydroxyl groups on
the surface.
Surface Functionalization. The hydroxylated silicon
wafer surface is functionalized by exposure to allyl
trimethoxysilane (ATES). The silicon wafer is immersed in a
ATES/hexane solution (1OmM) for 30 min, and then rinsed Figure 1. SEM image of PDMS/ZONMP 1300 (weigth
with IPA. Finally, the wafer is heated at 150°C for lhr in air. ratio is 1:3), contact angle: 136.4'
The surface was then functionalized with allyl groups.
Film Formation
Sylgard 184 (the ratio of PDMS elastomer resin to curing
agent is 10:1) or Dow Coming 1-2577, was added to PTFE
nanoparticles, with toluene as the solvent. The mixture was
stirred for 30 min to homogenize the solution. The solution
was then spincoated onto the wafers at 2000 rpm to form
films.
Surface characterization
Contact angle measurements, Scanning Electron
Microscopy (SEM), UV Visible spectroscopy and Fourier
Transform Infrared spectroscopy (FTIR) were used to
characterize the superhydrophobic surfaces. For contact angle
measurements, water droplets (4pt size) were introduced Figure 2. Low concentration of ZONMP 1100 (weight
using a microsyringe and static images were recorded from ratio is 1:1.5) Contact angle: 132.0°
which the contact angle of the droplet on the solid surface
was determined. For SEM inspection, the samples were fixed
to aluminum stubs with conductive tape before being coated
with -20nm of gold in an Ernest Fullam sputter coater. The
samples were then imaged using a HITACHI S 800 SEM.
FTIR spectra were obtained using a Nicolet magna IR 560
with an ATR accessory. Samples were stored in a drybox to
prevent moisture absorption. The spectrometer was flushed
with dry air continuously before and during FTIR
measurements.
UV exposure testing
UV exposure tests were performed according to standard
tests for the fluorescent UV exposure of plastics["] . A UVA- Figure 3. PDMS/ ZONMP 1100 (weight ratio is 1:3),
340 lamp (xenon lamp) was used to simulate the short and Contact angle: 161.2°
middle UV wavelength region corresponding to daylight For PDMS/ZONMP 1100 surface, the diameter of the
exposure[12]. The test procedure is as follows. The test cycle ZONMP particle is 150-250 nm, and a contact angle depends
used was 8 h UV with the uninsulated black panel on the concentration of the particle concentration in the
temperature controlled at 60 ± 3°C, followed by 4 h water composite surface. When the weight ratio of PDMS/ZONMP
1-4244-0261-11061'$20.00 A©2006 IEEE. 99
1100 is 1:1.5, the contact angle is only 132.0° as shown in That is, the synergistic effect of two scale roughness is
Figure 2. However, when the weight ratio increases to 1:3, a necessary to achieve superhydrophobicity in the presence of
water contact angle as high as 157° can be achieved as shown micron-scale roughness.
in Figure 3, with an advancing/receding contact angle
hysteresis of 5-7°. From the SEM pictures of films from
PDMS/ZONMP 1100 (figure 3), it is obvious that the surface
displays a two-scale roughness. The one roughness scale is in
the nanometer range and is due to the PTFE particles. The
other roughness level is due to micron sized pores that were
formed by the evaporation of solvent (toluene) during curing.
For the PDMS/PTFE film with a PTFE particle diameter in
the micron range, (ZONMP 1300 with a particle size of 2-5
microns), the contact angle is 130-140°, and the SEM image
indicates that the particle surface is very smooth. Although
the surface is still rough at the micron scale, the roughness Figure 5. SEM picture ot a tflm with a ratio ot 1:1 tor
does not effectively enhance the contact angle. 1300/1100. Contact angle: 138.3°
3.2 Bimodal process for the PDMS/PTFE system 3.3 UV stability of silicones
In this set of studies, two types of fluorocarbon particles: PDMS shows improved contact angle retention after the
ZONMP 1300 (2-5microns) and ZONMP 1100 (150-250 nm) UV weathering performed according to ASTM D 4329.
were used simultaneously. Figure 4 shows a plot of contact However, for silicone 1-2577 (room temperature curable), the
angle as a function of different ZONMP 1300 to 1100 ratios. surface no longer displayed superhydrophobicity after the
Clearly, the incorporation of nano sized particles results in same time of the UV weathering test. A possible reason for
larger contact angles (superhydrophobicity). this difference is that in PDMS there are no phenyl groups,
which have strong UV absorption peaks in the UV-A region
160- (320-400 nm). When these groups absorb UV light, they
cannot efficiently dissipate the energy via physical processes
155-
(e.g., fluorescence, phosphorescence); instead, the energy
2 150
absorbed causes chemical reactions such as bond cleavage.
Table 1. Comparison of UV stability of different silicones
145- Contact
Contact
() 140- Silicone/PTFE angle before angle after
0
135-
UV
~~~hrs)
1-2577 156.20 132.1°
130
0.0 05 1.0 1.5 20 (polyphenylmethylsiloxane)
fluorocarbon 1300/1100 ratio 184
(polydimethylsiloxane) 158W 156.2
Fig 4. Ratio of different PTFE particle size mixtures on
the contact angle of PDMS/PTFE Figure 6 shows the UV-VIS spectra of these two different
As mentioned above, previous studies have demonstrated silicones. The existence of phenyl groups in silicone 1-2577
that the creation of superhydrophobicity similar to that of causes absorption of UV light, which leads to degradation of
lotus leaves requires a surface texture with two scale the silicone surface, causing it to be more hydrophilic.
roughness'13'l51. However, the combination of submicron and However, PDMS shows minimum UV absorption, especially
micron sized PTFE particles does not permit the generation of in the UV-A range, indicating that it is more stable under UV
superhydrophobic surfaces. It can be noted from the SEM irradiation.
images in figure 5, that the micron sized PTFE is very
UV absorbance of silcone 1-2577 and 184
smooth. Most of the nano sized particles reside between the
micron sized particles, and an insufficient number of the nano 0.6-
particles are located on top of the micron sized particles.
From figure 4, it is also shown that when the particle size 0.4

ratio of 1300/1100 is increased, the contact angle on the film e~~~~~~~~~~~

'M 0.2
decreased steadily, and when the ratio is higher than 2, the
contact angle is almost the same as the film of PDMS/1300. 0
Under this condition, the nano particles do not contribute to 300 350 400 450 500

the surface roughness because most of the particles are in the wavelength, nm

valleys formed by the micron-sized particles. In order to

achieve the desired effect, the nanorough surface should be on Figure 6. UV Vis spectra of 184 and 1-2577
top of the micro rough surface as is observed on lotus leaves.
100 1-4244-0261-1/06/$20.00 A©2006 IEEE.
 Although the UV absorption of PDMS is low, compared
to a chromophore-containing silicone such as polyphenyl r r 35001

methyl siloxane, degradation still occurs. The contact angle

decreased slowly with time during the UV weathering test. In
order to investigate the long term UV stability of 31111

PDMS/PTFE surfaces, a prolonged UV aging test was O0O)O

performed. Figure 7 shows the contact angle change over a
period of 44 days UV aging time; clearly, the PDMS/PTFE D0

surface slowly degrades. After 44 days, the contact angle 296 294 292 290 288 288 284 282 280 278 278 27

decreased to 140, and the superhydrophobic properties were D0

Binding Energy (eV)

,.

eliminated. That is, a water droplet placed on the surface does

not roll across the surface and fall off, rather, it simply sticks
to the surface. However, the UV stability of the PDMS/PTFE
surface is much improved relative to that of organic
polymeric surfaces, such as superhydrophobic fluorinated
polybutadiene, which loses superhydrophobicity after only 3-
4 days of the UV weathering test.
D0

o298 290 288 288 284 282 280 278 278 27

C(1s)

aO
D0
176 -

168 -

0) 160-
'a

- 152- 3011 64 5 250 58 58 54 52 50 58 58 54 5

144-

- 136-
0 o
544 542 540 538 538 534 532 530 528 528 524 52
Binding Energy (eV)
1-zo oru
D0

1L
128

10 20 30 40 50

Time,days

Figure 7. Long term UV stability of PDMS with respect to the

contact angle retention D0 _ ._ _ _ ___ ___ __ ___ ___ ___ ___ __ _.

Generally, PDMS is a very stable polymer, and it is

transparent to UV light at wavelengths above 300 nm. 0 (Is)

However, upon long term UV exposure, the surface chemistry

of the film is altered. In order to evaluate the surface
chemistry changes due to UV exposure, high resolution X-ray
Photonelectron Spectroscopy (XPS) was performed to
investigate changes in the surface chemical bonding states.
XPS spectra for carbon, oxygen and silicon are shown in
figure 8. For each element, the XPS peak intensities at lower
binding energy increases with UV exposure time. With UV
degradation time, the FWHM of carbon peak increased from
2.16 (initial surface), to 2.64 (96hrs UV degradation) and 2.95
(144 hrs UV degradation). For the higher binding energy
C(ls) peak (Si-C or SiCH2-CH2Si), the peaks will decrease
which shows the photooxidation process that caused the
broken of Si-C and SiCH2-CH2Si bonds and incorporation of
oxygen to Si and C. For silicon peaks, initially, there is no
peak at 529eV, during the UV degradation, the peak at 529eV
(Si-OR) appeared and increased with time due to the Si (2p)

photooxidation. At the same time, the C content for the three Figure 8. High resolution XPS spectra of PDMS surfaces as a

samples decreased from the intial 62.3% to 60.2% (96 hrs) function of UV irradiation time 1: Original PDMS film before

and 54.50 (144 hrs). These XPS results indicate that during UV test; 2: 96 hrs UV test; 3: 144 hrs UV test.

UV exposure, Si-C and C-C bonds are broken, and under

oxygen atmosphere (especially under UV, reactive ozone will Si-O-C new chemical species increases the surface energy and
be formed), Si-O-C bonds are formed. The generation of the decreases the contact angle of this surface and ultimately
1-4244-0261-1/06/$20.00 A©2006 IEEE. 101
leading to the formation of silica like surfaces[16] and the loss
of surface superhydrophobicity (loss of hydrocarbon).
FTIR analysis of the PDMS/PTFE surface was also
performed before and after the UV test. Because polydimethyl
siloxane is vinyl terminated, Si-H reacts with the vinyl groups
during curing to form Si-CH2-CH2-Si structures. In the FTIR
spectra shown in figure 9, there are five absorption peaks at
844, 864, 906, 1015 and 1080 cm-'. The peaks at 864 and 906
cm'i can be attributed to the Si-CH2-CH2-Si deformation
vibration and the Si-C stretching vibration, respectively. the
FTIR spectra demonstrate that as the UV exposure time
increases, these two peaks decrease which suggests the loss of
these groups due to oxidation during UV exposure. The peak
at 844 cm-' can be attributed Si-O-CH2-CH2 stretching
absorption. It increases with time of the UV weathering test,
and therefore represents a product of UV degradation. The
two FTIR peaks at 1015 and 1080 cm-' can be attributed to
Si-O stretching vibrations. Because the peak at 1080 cm-'
increases with time of UV weathering, this peak is attributed
to Si-O-CH3 vibration due to the incorporation of oxygen into
silicone during the photooxidation process. These Si-OR
polar bond leads to the loss of superhydrophobicity
ultimately.
I Wavenub-r (c-1)
Figure 9. The FTIR spectra of the PDMS with respect to the
UV irradiation time 1 Original PDMS film before UV test; 2:
96 hrs UV test; 3: 144 hrs UV test; 4: 1000 hrs UV test
Conclusions
By incorporation of PTFE nanoparticles in PDMS films,
superhydrophobic surfaces were created. Through the
comparison of different sized PTFE particle, it showed that
the surfaces with micron particle were not superhydrophobic
due to the smoothness of the particle surface. And the
combination of the nano and micron sized particles showed
that when the smaller scale roughness is not on top of the
larger scale roughness, the superhydrophobic surface cannot
be achieved. The UV stability test showed that when there are
102 1-4244-0261-1/06/$20.00 A©2006 IEEE.
UV absorbing groups (e.g., phenyl groups) present in the
polymer, the surface degradation occurs much faster than the
surface of UV transparent materials. In order to achieve UV
stable superhydrophobic surfaces, the UV absorbing groups
should be avoided in the system. The XPS and FTIR analysis
of the superhydrophobic surfaces after UV degradation
showed that the possible product after UV degradation is Si-
O-R, which is polar and showed high surface energy and
leading to the increase of the surface energy and thus the loss
of superhydrophobicity.
Acknowledgments
We would like to appreciate the support from National
Electric Energy Testing Research and Applications Center
(NEETRAC). In addition, we thank Frank Lambert for the
help in the standard UV weathering test.
References
1. R. N. Wenzel, "Resistance of Solid Surfaces to Wetting
By Water", Ind. Eng. Chem., (1936) 28, 988.
2. A. B. D. Cassie, "Contact Angles", Disc. Faraday Soc.,
(1948) 3, 11.
3. Jau-Ye Shiu, Chun-Wen Kuo, Peilin Chen, and Chung-
Yuan Mou, "Fabrication of Tunable Superhydrophobic
Surfaces by Nanosphere Lithography", Chemicstry of
Materials, 2004, 16(4), 561-564
4. Zhai, Lei; Cebeci, Fevzi C.; Cohen, Robert E.; Rubner,
Michael F., "Stable Superhydrophobic Coatings from
Polyelectrolyte Multilayers", Nano Letters 2004, 4(7),
1349-1353.
5. Jisr, Rana M.; Rmaile, Hassan H.; Schlenoff, Joseph B.,
"Hydrophobic and Ultrahydrophobic Multilayer Thin
Films from Perfluorinated Polyelectrolytes", Angewandte
Chemie, International Edition (2005), 44(5), 782-785.
6. Erbil, H. Yildirim; Demirel, A. Levent; Avci, Yonca;
Mert, Olcay. "Transformation of a Simple Plastic into a
Superhydrophobic Surface", Science, 2003, 299(561 1),
p1377.
7. Xiu, Yonghao; Lingbo Zhu; Hess, Dennis W.; Wong, C.
P., "Coprecursor Approach to the Fabrication of
Superhydrophobic Durable Self-cleaning Films", 7th
Electronics Packaging Technology Conference,
Singapore, 2005.
8. Tadanaga, Kiyoharu; Morinaga, Junichi; Matsuda,
Atsunori; Minami, Tsutomu. "Superhydrophobic-
Superhydrophilic Micropatteming on Flowerlike Alumina
Coating Film by the Sol-Gel Method", Chemistry of
Materials (2000), 12(3), 590-592.
9. Nakajima, Akira; Fujishima, Akira; Hashimoto, Kazuhito;
Watanabe, Toshiya. "Preparation of Transparent Super-
hydrophobic Boehmite and Silica Films by Sublimation of
Aluminum Acetylacetonate", Advanced Materials
(Weinheim, Germany) (1999), 11(16), 1365-1368.
10. Authur W. Adamson, Alice P. Gast, Physical Chemistry
of Surfaces (6th edition), John Wiley & Sons Inc (1997).
11. Standard Practice for Fluorescent UV Exposure of
Plastics, ASTM D 4329-99.
12. Standard practice for Operating Fluorescent Light
Apparatus for UV Exposure of Nonmetallic materials,
ASTM G 154-OOa.
13. W. Barthlott, C. Neinhuis, "Purity of the sacred lotus, or
escape from contamination in biological surfaces", Planta,
(1997), 202, 1-8.
14. Neelesh A. Patankar, "Mimicking the Lotus Effect:
Influence of Double Roughness Structures and Slender
Pillars", Langmuir, (2004), 20, 8209-8213.
1-4244-0261-1/06/$20.00 A©2006 IEEE.
15.Lingbo Zhu, Yonghao Xiu, Jianwen Xu, Prabhakar A.
Tamirisa, Dennis W. Hess, and Ching-Ping Wong,
"Superhydrophobicity on Two-Tier Rough Surfaces
Fabricated by Controlled Growth of Aligned Carbon
Nanotube Arrays Coated with Fluorocarbon", Langmuir,
(2005), 21(24), 11208-12.
16. Jeffrey W. Gilman, David S. Schlitzer, and Joseph D.
Lichtenhan, "Low earth orbit resistant siloxane
copolymers", Journal ofApplied Polymer Science, (1996),
60, 591-596.
103