Journal of Colloid and Interface Science 326 (2008) 465470

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

UV and thermally stable superhydrophobic coatings from solgel processing

Yonghao Xiu a,b , Dennis W. Hess a, , C.P. Wong b,
a b

School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, GA 30332-0100, USA School of Materials Science and Engineering, Georgia Institute of Technology, 771 Ferst Drive, Atlanta, GA 30332-0245, USA

a r t i c l e

i n f o

a b s t r a c t
A method for the preparation of inorganic superhydrophobic silica coatings using solgel processing with tetramethoxysilane and isobutyltrimethoxysilane as precursors is described. Incorporation of isobutyltrimethoxysilane into silica layers resulted in the existence of hydrophobic isobutyl surface groups, thereby generating surface hydrophobicity. When combined with the surface roughness that resulted from solgel processing, a superhydrophobic surface was achieved. This surface showed improved UV and thermal stability compared to superhydrophobic surfaces generated from polybutadiene by plasma etching. Under prolonged UV tests (ASTM D 4329), these surfaces gradually lost superhydrophobic character. However, when the as-prepared superhydrophobic surface was treated at 500 C to remove the organic moieties and covered with a uoroalkyl layer by a peruorooctylsilane treatment, the surface regained superhydrophobicity. The UV and thermal stability of these surfaces was maintained upon exposure to temperatures up to 400 C and UV testing times of 5500 h. Contact angles remained >160 with contact angle hysteresis 2 . 2008 Elsevier Inc. All rights reserved.

Article history: Received 11 April 2008 Accepted 15 June 2008 Available online 28 June 2008 Keywords: Silica Thin lm Superhydrophobicity Fluoroalkyl silane UV stability Thermal stability Accelerated UV weathering test

1. Introduction The water repellent properties of many biological surfaces, especially plant leaves, have prompted great research interest since, when water drops fall on certain leaf surfaces, they can easily pick up contamination, roll off the surface, and thereby clean the leaves. Because the rst observation of this self-cleaning phenomenon was on lotus leaves, the effect is generally termed lotus effect. Detailed inspection of the leaves showed that micron and submicron structures as well as hydrophobic materials exist on the leaf surface [1]. The combination of these factors leads to superhydrophobicity. Wenzel [2,3] showed that surface roughness produces a physical enhancement of hydrophobicity which was described by cos A = r cos Y . (1)

very rough surfaces with Y (at) > 90 ; rather, the droplet effectively resides on a composite surface. In this case Cassies equation applies [4]. cos A = f 1 cos Y f 2 , (2)

In Eq. (1), A is apparent contact angle, Y is the contact angle on a at surface and r is the ratio of the actual to the projected area. This expression predicts that the wetting behavior of a surface is enhanced by roughness; thus, creation of roughness on a at surface with an equilibrium contact angle Y (at) > 90 increases the contact angle, while the same roughness on a surface with Y (at) < 90 decreases the contact angle. In practice, intimate contact is not usually maintained between liquid and solid on

Corresponding authors. Faxes: +1 404 894 2866 (D.W. Hess), +1 404 894 9140 (C.P. Wong). E-mail addresses: dennis.hess@chbe.gatech.edu (D.W. Hess), cp.wong@mse.gatech.edu (C.P. Wong). 0021-9797/$ see front matter doi:10.1016/j.jcis.2008.06.042

where f 1 and f 2 are the fractions of the surface occupied by solid/ liquid and air/liquid, and f 1 + f 2 = 1. Self-cleaning surfaces have many potential applications, for example, surface decontamination on microelectronic equipment or devices, water repellent coatings, biocompatible surfaces, and friction reduction. Such surfaces have been created on a variety of materials such as silicones [5], alumina [68], silicon [9], silica [1014], polyelectrolytes [15,16], carbon nanotubes [17], polystyrene [18], PTFE (polytetrauoroethylene) [19] and uorocarbons [20], and polybutadiene [21]. Several criteria have been used to characterize these surfaces including contact angle (>150 ), contact angle hysteresis (<10 ) and roll off angle. However, limitations exist when polymeric materials are exposed to atmospheric conditions where degradation in superhydrophobic properties occurs due to UV irradiation, and to exposure to impurities, O2 , and moisture present in the environment. Also, because organic polymers are easily deformed when a force is applied, the surface structure is not stable when the surface undergoes abrasion from friction, handling, or dust particles. Solgel processes offer a method to fabricate porous glass lms under ambient conditions. The mild preparation conditions offer the ability to incorporate a wide range of labile organic species into a glass composite. In addition to the mild processing condi-

2008 Elsevier Inc. All rights reserved.

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tions, solgel derived materials exhibit tunable porosity [14,2224], transparency [25], hardness, and good thermal stability. However, UV stability has not been addressed extensively, especially for long times, which is a requirement for outdoor applications. Such applications are especially problematic, since the surface hydrophobicity imparted is usually due to the presence of hydrocarbons [10,14]. In the current paper, porous silica generated by solgel processing followed by surface uoroalkyl substitution is invoked to improve the thermal and long term UV stability of superhydrophobic lms. This approach to the fabrication of inorganic superhydrophobic silica lms uses tetramethoxysilane and isobutyltrimethoxysilane as precursors. When isobutyltrimethoxysilane is incorporated into silica, the surface contains hydrophobic isobutyl groups, resulting in the ability to ne tune hydrophobicity and adhesion. Furthermore, this method does not use supercritical drying which is frequently employed for the preparation of superhydrophobic materials [10]. The porosity and thus surface structure can be controlled by parameters such as reaction conditions, solvent evaporation rate and precursor ratio. In addition, due to the fact that CF bonds are stronger than CH bonds, it is expected that the incorporation of uoroalkyl groups will impart improved UV stability to the coating and thereby make possible a variety of outdoor applications. Therefore, by designing both surface hydrophobicity and surface structure into the lm, it should be possible to prepare an inorganic coating with stable superhydrophobicity. 2. Experimental details 2.1. Bulk silica formation The initial solution was prepared using a two-step (acid/base catalyzed) procedure. Tetramethoxysilane (TMOS), isobutyltrimethoxysilane (IBTMOS), ethanol, and water were mixed in the volumetric ratio of 1:1:2:1 in a 30 ml vial. The pH was adjusted to 1.51.8 by adding hydrochloric acid, and the mixture stirred for 120 min at 60 C to form silica sol. Ammonium hydroxide (NH4 OH) was subsequently added to the sol, followed by mixing for 5 min at room temperature. The resulting gel was allowed to age for 1 week. Slow evaporation of ethanol and water was permitted through a small slit (6 mm 3 mm) in the vial cap, thereby forming bulk silica within the vial. 2.2. Silica lm formation by casting Glass slides were used as substrates for the casting of silica lms. The slides were cleaned in Piranha solution (70:30 (vol/vol) mixture of 96% sulfuric acid and 30% aqueous hydrogen peroxide) and subsequently rinsed extensively with de-ionized water and ethanol. Film casting was performed by invoking two glass slides. One slide served as the substrate, and the other, which was treated with trimethylchlorosilane (TMCS) to prevent gel from bonding to it, served as the cover. A chromium lm of 300 nm thickness was sputtered onto the surface of the substrate glass slide prior to gel formation. Bulk silica sol was prepared according the procedure described above; after NH4 OH was added to the sol, the solution was stirred for 3 min. Several drops of the sol were then dispensed onto the substrate glass slide and the sol covered with the TMCS treated glass slide. After gelation, aging and evaporation of the solvent, a silica lm resulted. 2.3. Preparation of superhydrophobic polybutadiene lms A polybutadiene/toluene solution (5 wt% with 2% UV stabilizer TINUVIN 1577FF from Ciba and 1.5% antioxidant IRGANOX 1010FF from Ciba) was dispensed onto a silicon substrate at a spin speed

Fig. 1. Morphology of a superhydrophobic polybutadiene surface formed by an SF6 plasma treatment.

of 2000 rpm to cast polybutadiene lms (10 m). The lm surface was subsequently exposed to an SF6 plasma at 150 mTorr and 150 W for 10 min to form a superhydrophobic uorinated polybutadiene surface as shown in Fig. 1. 2.4. Characterization Contact angle measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) were used to characterize the superhydrophobic surfaces. Water droplets of 1 mm diameter were placed onto surfaces using a microsyringe and static images were recorded from which the contact angle of the droplet on the solid surface was determined. For SEM inspection, samples were xed to aluminum stubs with conductive tape prior to coating with 20 nm of gold in an Ernest Fullam sputter coater. The samples were then imaged using a LEO 1530 SEM. An Explorer AFM from Veeco was invoked for roughness determination; measurements were performed in contact mode. A cantilever with a nominal spring constant of 0.1 N/m was used with minimum force. For TGA analysis, a TGA 2050 thermogravimetric analyzer from TA Instruments was used. An approximately 10 mg silica sample was placed in a ceramic pan, and the pan positioned in the TGA furnace; a temperature ramp was applied from room temperature to 800 C with an air ow of 100 SCCM. 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 ushed with dry air continuously before and during FTIR measurements. 2.5. Accelerated UV weathering test UV tests were performed by adhering to standard tests for the uorescent UV exposure of plastics (ASTM D 4329). A UVA-340 uorescent lamp was used to simulate the short and middle UV wavelength region corresponding to daylight exposure. The test cycle was 8 h UV with the uninsulated black panel temperature controlled at 60 3 C, followed by 4 h condensation with the uninsulated black panel temperature controlled at 50 3 C. A radiometer was used to monitor and control the amount of radiant energy that impinged on the sample. A thermometer was used to monitor the temperature in the test chamber. 3. Results and discussion Solvent evaporation of the solution-cast coating results in lm surface roughness. The presence of hydrophobic chemical groups on the silica surface as illustrated schematically in Fig. 2, along with the surface roughness generated from solvent evaporation,

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Table 2 Contact angles on surfaces resulting from various formulations of bulk silica TMOS (ml) 1 2 3
a

IBTMOS (ml) 3 2 1

Ethanol (ml) 4 4 4

H2 O (ml) 2 1.9 2

1 M HCl (ml) 0.03 0.1a 0.03

NH4 OH (ml) 0.5 1 1

Contact angle ( ) 160.8 156.1 75.3

HCl concentration is 0.1392 M.

Fig. 2. Illustration of hydrophobic groups on a treated silica surface. Table 1 Physical characteristics of solutions resulting from different sol formulations TMOS/IBTMOS/ethanol/H2 O (volume ratio) 3:1:4:2 1:1:2:1 1:3:4:2 Phase separation during hydrolysis No No Yes Transparency during gelation Yes No No Precipitation after gelation No No Yes

yields an enhanced surface contact angle. As described below, a superhydrophobic silica lm can be prepared from solgel processing using TMOS and IBTMOS. 3.1. Acidbase catalyzed solgel process Table 1 indicates that chemical reactions can occur that result in changes in the physical solution characteristics during the bulk silica formation process. When the concentration of IBTMOS was increased, e.g., TMOS/IBTMOS ratio of 1:3, phase separation occurred during hydrolysis as evidenced by the fact that the solution became cloudy (white) upon stirring. After the addition of ammonium hydroxide and equilibration, a separate viscous phase appeared at the bottom of the vial. After removal of the upper liquid phase, the viscous solution remaining in the vial underwent slow gelation and bulk silica formed. For a TMOS/IBTMOS ratio (v/v) of 1:1, no phase separation occurred; even after 120 min of reaction, the sol was still transparent. After gelation by addition of the ammonium hydroxide solution (1.1 M), the sol became

turbid/white and the solution gelled to form bulk silica. The time needed for this to occur depended on the amount of ammonium solution added; the more ammonium, the shorter the time to develop a turbid sol. During the controlled evaporation of solvent, the volume of silica was gradually reduced. Table 2 indicates the solgel process conditions and the nal contact angles on the asprepared silica surfaces. The creation of superhydrophobic surfaces requires control of the surface roughness. For surfaces formed from mixtures of TMOS/IBTMOS with a ratio of 1:3, superhydrophobicity was achieved with large pore sizes of 10 m as shown in Fig. 3. In addition to the pores generated by evaporation of solvent, the particle size also contributes to the surface roughness as shown in Fig. 3d. Surfaces from mixtures of TMOS/IBTMOS with a ratio of 1:1 still show superhydrophobicity although the isobutyl trimethoxysilane content is reduced. Furthermore, the pores are not spherical due to the increase of solvent solubility in the silica and the pore size is much reduced. Surfaces from mixtures of TMOS/IBTMOS with a ratio of 3:1 did not display superhydrophobicity because of the lower ratio of IBTMOS used; that is, the surface is generally at with insucient voids, and the contact angle is only 75.3 . After fracture of bulk silica formed from a 1:1 mixture of TMOS/IBTMOS, the fractured surface still displayed superhydrophobicity because the surface remained rough; the water contact angle on this fractured surface was also above 150 . 3.2. Creation of superhydrophobic thin lms by solgel processing In addition to bulk silica, cast silica thin lms were also prepared. Water droplet contact angles on different thin lm surfaces

Fig. 3. SEM images of surfaces of as-synthesized bulk silica. (a) TMOS/IBTMOS = 1:3, 1 M hydrochloric acid: 0.03 ml, 1.1 M ammonia: 0.5 ml; (b) TMOS/IBTMOS = 1:1, 0.1392 M hydrochloric acid: 0.1 ml, 1.1 M ammonia: 1 ml; (c) TMOS/IBTMOS = 3:1, 1 M hydrochloric acid: 0.03 ml, 1.1 M ammonia: 1 ml; (d) high resolution SEM image of the structures on a superhydrophobic silica surface from a mixture of TMOS/IBTMOS = 1:3. Inset: images of the shapes of water droplets in contact with the prepared silica surfaces.

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Table 3 Thin silica lms cast from different ratios of TMOS/IBTMOS TMOS/IBTMOS (v/v) 1:3 1:1 3:1 Contact angle ( ) 101.0 167.8 73.6 Contact angle hysteresis ( ) Not measurable 23 Not measurable

Fig. 5. TGA results for silica from different TMOS/IBTMOS ratios. Temperature ramping rate: 4 C/min. Table 4 EDS analysis results of the thin lm from TMOS/IBTMOS = 1:1 Element C O Si Totals Wt% 25.13 44.56 30.31 100.00 At% 35.13 46.76 18.11 100.00

Fig. 4. High resolution SEM image of a silica lm cast from TMOS/IBTMOS = 1:1.

are shown in Table 3. For a TMOS/IBTMOS ratio of 1:3, although superhydrophobicity was observed on bulk silica, 300 nm lms cast from this mixture were not superhydrophobic. A possible reason for this result is that large pores such as those observed in the bulk materials cannot form in thin lms. However, with a TMOS/IBTMOS ratio of 1:1, a superhydrophobic thin lm with a contact angle of 165170 was achieved. Fig. 4 shows the surface microstructure of a 300 nm silica lm cast onto a glass slide from a TMOS/IBTMOS ratio of 1:1; the surface consists of globules (20 50 nm in diameter) surrounding a network of pores (submicron size) formed by evaporation of solvent from the sol. These observations also indicate that surface roughness exists in two scales: the pores contribute to the submicron scale roughness, and the silica particles contribute to the nanoscale roughness. This twoscale surface roughness combined with the hydrophobic surface that resulted from the isobutyl groups in IBTMOS, generated a superhydrophobic lm surface. 3.3. Stability of superhydrophobic surfaces The hydrocarbon side group contained in the superhydrophobic silica can decompose (or be oxidized in air) at elevated temperature and thus cause the loss of superhydrophobicity. TGA studies of samples synthesized with TMOS/IBTMOS ratios of 1:1 and 1:3, demonstrate that the onset of weight loss is 200 C and 207 C, respectively, as shown in Fig. 5. With continued heating above the onset temperature, the organic groups in the silica structure begin to degrade due to oxidation or bond cleavage of the isobutyl groups. TGA results showed that 27.7% loss is observed for a TMOS/IBTMOS ratio of 1:1. EDS results in Table 4 and Fig. 6 also indicated that the isobutyl group content was 28.5 wt% in the 1:1 silica (H atoms were included in the calculation) which agrees well with TGA data. For a TMOS/IBTMOS ratio of 1:3, similar results were observed to those with a TMOS/IBTMOS ratio of 1:1. Table 5 shows the contact angle data on the heat-treated surfaces at different temperatures. Contact angle decreased with increasing heat treatment temperature and contact angle hysteresis increased. When the heat treated surface was again treated with IBTMOS/hexane solution, the surface superhydrophobicity was recovered (CA 165 and hysteresis <5 ). This suggests that thermal

Fig. 6. EDS spectrum of the thin lm from TMOS/IBTMOS = 1:1. Table 5 Thermal stability of the as-prepared superhydrophobic surfaces after heating for 2 h at different temperatures Heat treatment temperature ( C) 200 300 400 Contact angle ( ) 165.3 91.7 15.2 Contact angle hysteresis ( ) 12.6

>60
Not measurable

degradation of the surface is primarily due to a change in surface chemistry rather than to a change in the surface roughness. FTIR analysis of the silica lm after a heat treatment at 400 C indicated that hydrocarbon absorptions were absent as shown in Fig. 7; CH3 and CH2 stretching vibration (29752840 cm1 ) and deformation vibration (1232 cm1 , 1173 cm1 , 894 cm1 and 839 cm1 ) intensities were below the detectability limit after the heat treatment, conrming decomposition of the organic groups. Organic polymers with reactive (e.g., double bonds) or low energy (e.g., tertiary hydrogen) structures in the polymer main chain, are vulnerable to UV irradiation. When impurities (i.e., catalyst) and UV absorbing groups are present, the polymer can undergo a photo-oxidation process to form carbonyl or hydroxyl groups on the surface and thus degrade (unzip) into smaller chains [26]. The introduction of these hydrophilic groups leads to the loss of super-

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Table 6 Effect of UV irradiation on contact angle and hysteresis for a thin lm formed from TMOS/IBTMOS = 1:1 UV weathering test of silica lm 8 days 12 days Contact angle 159162 158 Hysteresis 35 1520

Fig. 7. FTIR spectra of the silica superhydrophobic silica thin lm before and after heat treatment at 400 C for 1 h.

Fig. 9. FTIR comparison of silica thin lms before and after prolonged UV irradiation. Top curve: silica lm from TMOS/IBTMOS = 1:1 before UV test; bottom curve: the same silica lm after UV testing for 12 days.

Fig. 8. UV moisture weathering of superhydrophobic PB and silica thin lm surfaces. Bottom curve: SF6 RIE etched PB + UV absorber TINUVIN 1577FF (2%) + antioxidant IRGANOX 1010FF (1.5%); top curve: silica lm from TMOS/IBTMOS (1:1) using a two step acidbase catalyzed solgel process.

hydrophobicity. As described previously, when the surface is hydrophilic, surface roughness enhances the hydrophilicity to superhydrophilicity. For the silica lm, only small side groups (isobutyl groups) exist on the surface; these moieties are more UV stable than are polymers because negligible impurities and less UV-fragile defects exist on the silica surface; thus the silica lm exhibits better UV stability than do organic polymers (polybutadiene uorinated in SF6 plasma) as shown in Fig. 8. In addition, the silica main chain is comprised of SiO bonds, which have higher bond strength and thus better UV stability than organic polymer materials. Other commercially available polymers such as ethylenevinyl acetate copolymer, polydimethyl siloxane and Teon, all show surface degradation after long time UV aging tests. When a superhydrophobic surface begins to degrade, the hysteresis changes more rapidly than does the contact angle. This observation is shown in Table 6, where contact angles changed very little, while hysteresis changed signicantly. Therefore, contact angle hysteresis can be used to evaluate the surface chemistry change when the contact angles remain almost unaltered. The surface fraction that is air beneath the water drop becomes smaller and smaller, until it ultimately disappears, and the Cassie model no longer accurately describes the surface/water contact. Instead, the contact interface is better described by the Wenzel state. The FTIR spectrum in Fig. 9 shows that after UV irradiation, the SiOCH3 deformation vibration band at 1444 cm1 disappeared due to continued hydrolysis. The CH deformation vibration band at 1352 cm1

Fig. 10. Superhydrophobic silica thin lm AFM surface image after PFOS treatment; inset, water droplet image on the surface; contact angle, 168 ; hysteresis, 2 .

also disappeared while the OCH2 vibration band at 1330 cm1 appeared after UV irradiation because of oxidative degradation of the isobutyl groups specically on tertiary carbons. In order to mitigate the thermal and UV stability degradation of the superhydrophobic TMOS/IBTMOS surfaces, a heat treatment was performed on the silica thin lms immediately after formation, to decompose/oxidize the organic moieties; subsequently, a uoroalkyl silane treatment was carried out. AFM was used to probe the surface morphology of PFOS-treated superhydrophobic silica lms. Fig. 10 shows the surface morphology of a silica lm produced from a 1:1 TMOS/IBTMOS mixture, that was heat treated at 500 C and then PFOS treated; the root mean square (RMS) surface roughness from AFM was 330 nm. On the rough surface, air can still be effectively trapped between the water droplet and the substrate. Thus, the Cassie state can be maintained to achieve a superhydrophobic surface with both high contact angle and low hysteresis as shown in the inset in Fig. 10. Acceler-

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SF6 plasma etched polybutadiene lms but lost superhydrophobicity due to the oxidative degradation of the isobutyl groups. When the superhydrophobic surfaces from TMOS/IBTOMS mixtures were heated to 500 C, the surface became superhydrophilic. When a PFOS treatment was performed on the surface, the attachment of uoroalkyl groups resulted in superhydrophobicity. This surface is much more stable than a surface with isobutyl groups; after a UV testing time of 5500 h, no degradation of either contact angle or contact angle hysteresis was observed for the PFOS-treated surface. Thermal stability of the PFOS-treated rough silica surfaces was also much improved at temperatures up to 400 C. The PFOS-treated superhydrophobic surface is one of the most stable surfaces reported to date. This approach to the generation of superhydrophobic surfaces may have much signicance for the successful application of self-cleaning surfaces in a variety of environments.
Fig. 11. UV stability of a PFOS-treated rough silica thin lm surface. Table 7 Thermal stability of a PFOS-treated superhydrophobic thin lm surface after heating for 2 h at different temperatures Temperature ( C) 400 450 500 Contact angle ( ) 166.3 160.4 0 Contact angle hysteresis ( ) 2.1

Acknowledgments The authors acknowledge nancial support from the National Science Foundation (NSF CMMI #0422553) and the National Electric Energy Testing Research and Applications Center (NEETRAC) at Georgia Institute of Technology. References
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>30
Not measurable

ated UV and thermal stability test results are shown in Fig. 11 and Table 7. Because of the attachment of uoroalkyl groups on the surface, improved thermal and UV stability were achieved due to the presence of a linear uorocarbon chain on the silica surface. UV tests showed a stable superhydrophobic surface after a 5500 h testing period without degradation of either contact angle or contact angle hysteresis. A thermal treatment at 400 C demonstrated that the surface is stable to this temperature, which is a signicant improvement relative to the results obtained with a superhydrophobic surface that contained isobutyl groups. Further temperature increases resulted in a decrease of the contact angle and an increase of contact angle hysteresis. When the treatment temperature was 500 C, the surface was no longer superhydrophobic (contact angle = 0 ) as a result of the decomposition/oxidation of the surface uoroalkyl groups. To our knowledge, this is one of the most stable superhydrophobic surfaces reported to date. This nding demonstrates that it may be possible to use superhydrophobic/self-cleaning surfaces in harsh environments such as high UV irradiation, high temperature, and outdoor applications. 4. Conclusions Superhydrophobic bulk silica materials and analogous silica thin lms were prepared by TMOS/IBTMOS two-step acid base catalyzed solgel processing. Thermal analysis shows that these superhydrophobic materials begin to lose superhydrophobicity when heated above 200 C. UV weathering tests (ASTM D 4329) indicate that the silica materials demonstrate better stability compared to