Journal of Colloid and Interface Science 326 (2008) 465–470

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Journal of Colloid and Interface Science

UV and thermally stable superhydrophobic coatings from sol–gel 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 sol–gel 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 sol–gel 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 fluoroalkyl layer by a perfluorooctylsilane 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 film 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 first 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 θA = r cos θY . (1)

very rough surfaces with θY (flat) > 90◦ ; rather, the droplet effectively resides on a composite surface. In this case Cassie’s equation applies [4]. cos θA = f 1 cos θY − f 2 , (2)

In Eq. (1), θA is apparent contact angle, θY is the contact angle on a flat 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 flat surface with an equilibrium contact angle θY (flat) > 90◦ increases the contact angle, while the same roughness on a surface with θY (flat) < 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: (D.W. Hess), (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 [6–8], silicon [9], silica [10–14], polyelectrolytes [15,16], carbon nanotubes [17], polystyrene [18], PTFE (polytetrafluoroethylene) [19] and fluorocarbons [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. Sol–gel processes offer a method to fabricate porous glass films 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.

scanning electron microscopy (SEM). since the surface hydrophobicity imparted is usually due to the presence of hydrocarbons [10. which was treated with trimethylchlorosilane (TMCS) to prevent gel from bonding to it. Silica film formation by casting Glass slides were used as substrates for the casting of silica films. The test cycle was 8 h UV with the uninsulated black panel temperature controlled at 60 ± 3 ◦ C. 1. 2. atomic force microscopy (AFM). it should be possible to prepare an inorganic coating with stable superhydrophobicity. FTIR spectra were obtained using a Nicolet Magna IR 560 with an ATR accessory. Experimental details 2. Furthermore. For SEM inspection. Bulk silica sol was prepared according the procedure described above. A cantilever with a nominal spring constant of 0. A UVA-340 fluorescent lamp was used to simulate the short and middle UV wavelength region corresponding to daylight exposure. thereby forming bulk silica within the vial.8 by adding hydrochloric acid. it is expected that the incorporation of fluoroalkyl groups will impart improved UV stability to the coating and thereby make possible a variety of outdoor applications. The porosity and thus surface structure can be controlled by parameters such as reaction conditions. 2. transparency [25].2.1. Tetramethoxysilane (TMOS). Characterization Contact angle measurements. and Fourier transform infrared (FTIR) were used to characterize the superhydrophobic surfaces. 2. A radiometer was used to monitor and control the amount of radiant energy that impinged on the sample. 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. due to the fact that C–F bonds are stronger than C–H bonds.1 N/m was used with minimum force. . solvent evaporation rate and precursor ratio. After gelation. Slow evaporation of ethanol and water was permitted through a small slit (6 mm × 3 mm) in the vial cap. The presence of hydrophobic chemical groups on the silica surface as illustrated schematically in Fig. porous silica generated by sol–gel processing followed by surface fluoroalkyl substitution is invoked to improve the thermal and long term UV stability of superhydrophobic films. and good thermal stability. / Journal of Colloid and Interface Science 326 (2008) 465–470 tions. sol–gel derived materials exhibit tunable porosity [14. resulting in the ability to fine tune hydrophobicity and adhesion.5. The pH was adjusted to 1. the solution was stirred for 3 min. this method does not use supercritical drying which is frequently employed for the preparation of superhydrophobic materials [10]. after NH4 OH was added to the sol. Samples were stored in a drybox to prevent moisture absorption. especially for long times. A thermometer was used to monitor the temperature in the test chamber.22–24]. Bulk silica formation The initial solution was prepared using a two-step (acid/base catalyzed) procedure. The film surface was subsequently exposed to an SF6 plasma at 150 mTorr and 150 W for 10 min to form a superhydrophobic fluorinated polybutadiene surface as shown in Fig. Therefore. and the mixture stirred for 120 min at 60 ◦ C to form silica sol. Film casting was performed by invoking two glass slides. followed by mixing for 5 min at room temperature.14]. hardness. served as the cover. Preparation of superhydrophobic polybutadiene films A polybutadiene/toluene solution (5 wt% with 2% UV stabilizer TINUVIN 1577FF from Ciba and 1. a TGA 2050 thermogravimetric analyzer from TA Instruments was used. However. Such applications are especially problematic. by designing both surface hydrophobicity and surface structure into the film. samples were fixed to aluminum stubs with conductive tape prior to coating with ∼20 nm of gold in an Ernest Fullam sputter coater.466 Y. 2. 2. Xiu et al. measurements were performed in contact mode. which is a requirement for outdoor applications. and water were mixed in the volumetric ratio of 1:1:2:1 in a 30 ml vial. isobutyltrimethoxysilane (IBTMOS). followed by 4 h condensation with the uninsulated black panel temperature controlled at 50 ± 3 ◦ C.5–1. A chromium film of ∼300 nm thickness was sputtered onto the surface of the substrate glass slide prior to gel formation. the surface contains hydrophobic isobutyl groups. Morphology of a superhydrophobic polybutadiene surface formed by an SF6 plasma treatment. For TGA analysis.5% antioxidant IRGANOX 1010FF from Ciba) was dispensed onto a silicon substrate at a spin speed Fig. The spectrometer was flushed with dry air continuously before and during FTIR measurements. along with the surface roughness generated from solvent evaporation. ethanol. The resulting gel was allowed to age for 1 week. The samples were then imaged using a LEO 1530 SEM. In the current paper. 3. Results and discussion Solvent evaporation of the solution-cast coating results in film surface roughness. Ammonium hydroxide (NH4 OH) was subsequently added to the sol. thermogravimetric analysis (TGA). Several drops of the sol were then dispensed onto the substrate glass slide and the sol covered with the TMCS treated glass slide. 1. a silica film resulted. 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. 2. a temperature ramp was applied from room temperature to 800 ◦ C with an air flow of 100 SCCM. An approximately 10 mg silica sample was placed in a ceramic pan. When isobutyltrimethoxysilane is incorporated into silica. aging and evaporation of the solvent. Accelerated UV weathering test UV tests were performed by adhering to standard tests for the fluorescent UV exposure of plastics (ASTM D 4329). This approach to the fabrication of inorganic superhydrophobic silica films uses tetramethoxysilane and isobutyltrimethoxysilane as precursors. One slide served as the substrate.3. and the pan positioned in the TGA furnace. In addition. An Explorer AFM from Veeco was invoked for roughness determination.4. and the other. of 2000 rpm to cast polybutadiene films (∼10 μm). UV stability has not been addressed extensively.

Xiu et al. Surfaces from mixtures of TMOS/IBTMOS with a ratio of 3:1 did not display superhydrophobicity because of the lower ratio of IBTMOS used.03 ml.1 M). Acid–base catalyzed sol–gel process Table 1 indicates that chemical reactions can occur that result in changes in the physical solution characteristics during the bulk silica formation process. the sol was still transparent.5 ml. .1 ml. the more ammonium. (d) high resolution SEM image of the structures on a superhydrophobic silica surface from a mixture of TMOS/IBTMOS = 1:3. and the contact angle is only 75..1392 M hydrochloric acid: 0.g. the particle size also contributes to the surface roughness as shown in Fig.1 M ammonia: 1 ml. the shorter the time to develop a turbid sol. 3d. TMOS/IBTMOS ratio of 1:3. 1.1a 0.1. During the controlled evaporation of solvent. 3. 3.3 HCl concentration is 0. After removal of the upper liquid phase. the volume of silica was gradually reduced. (c) TMOS/IBTMOS = 3:1. even after 120 min of reaction. 1 M hydrochloric acid: 0. the viscous solution remaining in the vial underwent slow gelation and bulk silica formed. 1. / Journal of Colloid and Interface Science 326 (2008) 465–470 467 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. 3. e. Table 2 indicates the sol–gel process conditions and the final contact angles on the asprepared silica surfaces.3◦ . Fig.1 75. In addition to the pores generated by evaporation of solvent. The time needed for this to occur depended on the amount of ammonium solution added. After the addition of ammonium hydroxide and equilibration. (a) TMOS/IBTMOS = 1:3. the surface is generally flat with insufficient voids. 3. Furthermore. 1. phase separation occurred during hydrolysis as evidenced by the fact that the solution became cloudy (white) upon stirring.Y. Creation of superhydrophobic thin films by sol–gel processing In addition to bulk silica. As described below. Surfaces from mixtures of TMOS/IBTMOS with a ratio of 1:1 still show superhydrophobicity although the isobutyl trimethoxysilane content is reduced. (b) TMOS/IBTMOS = 1:1.2. superhydrophobicity was achieved with large pore sizes of ∼10 μm as shown in Fig. After gelation by addition of the ammonium hydroxide solution (1.5 1 1 Contact angle (◦ ) 160. the sol became turbid/white and the solution gelled to form bulk silica. that is. Inset: images of the shapes of water droplets in contact with the prepared silica surfaces. For surfaces formed from mixtures of TMOS/IBTMOS with a ratio of 1:3.9 2 1 M HCl (ml) 0. 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. 0. 2. Water droplet contact angles on different thin film surfaces Fig. When the concentration of IBTMOS was increased. the fractured surface still displayed superhydrophobicity because the surface remained rough. Illustration of hydrophobic groups on a treated silica surface. no phase separation occurred. After fracture of bulk silica formed from a 1:1 mixture of TMOS/IBTMOS. For a TMOS/IBTMOS ratio (v/v) of 1:1. SEM images of surfaces of as-synthesized bulk silica. 1 M hydrochloric acid: 0.1 M ammonia: 0.03 ml. a superhydrophobic silica film can be prepared from sol–gel processing using TMOS and IBTMOS. cast silica thin films were also prepared.8 156.03 NH4 OH (ml) 0.03 0. the pores are not spherical due to the increase of solvent solubility in the silica and the pore size is much reduced. the water contact angle on this fractured surface was also above 150◦ .1392 M. a separate viscous phase appeared at the bottom of the vial.1 M ammonia: 1 ml. The creation of superhydrophobic surfaces requires control of the surface roughness.

with a TMOS/IBTMOS ratio of 1:1. and the silica particles contribute to the nanoscale roughness. similar results were observed to those with a TMOS/IBTMOS ratio of 1:1.7% loss is observed for a TMOS/IBTMOS ratio of 1:1.0 167. are shown in Table 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. 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. High resolution SEM image of a silica film cast from TMOS/IBTMOS = 1:1. 5.13 44.8 73. Contact angle decreased with increasing heat treatment temperature and contact angle hysteresis increased.g. Temperature ramping rate: 4 ◦ C/min. generated a superhydrophobic film surface. tertiary hydrogen) structures in the polymer main chain. although superhydrophobicity was observed on bulk silica.00 At% 35. For a TMOS/IBTMOS ratio of 1:3. This twoscale surface roughness combined with the hydrophobic surface that resulted from the isobutyl groups in IBTMOS. 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].3. Table 4 EDS analysis results of the thin film from TMOS/IBTMOS = 1:1 Element C O Si Totals Wt% 25.468 Y. 894 cm−1 and 839 cm−1 ) intensities were below the detectability limit after the heat treatment.31 100. 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. These observations also indicate that surface roughness exists in two scales: the pores contribute to the submicron scale roughness. / Journal of Colloid and Interface Science 326 (2008) 465–470 Table 3 Thin silica films cast from different ratios of TMOS/IBTMOS TMOS/IBTMOS (v/v) 1:3 1:1 3:1 Contact angle (◦ ) 101. the organic groups in the silica structure begin to degrade due to oxidation or bond cleavage of the isobutyl groups. TGA results for silica from different TMOS/IBTMOS ratios. With continued heating above the onset temperature.7 15. TGA results showed that 27. 6 also indicated that the isobutyl group content was 28. Fig. 1173 cm−1 .. ∼300 nm films cast from this mixture were not superhydrophobic. catalyst) and UV absorbing groups are present. double bonds) or low energy (e.56 30. EDS results in Table 4 and Fig. TGA studies of samples synthesized with TMOS/IBTMOS ratios of 1:1 and 1:3. confirming decomposition of the organic groups. 6. The introduction of these hydrophilic groups leads to the loss of super- . This suggests that thermal Fig.. Organic polymers with reactive (e.3 91.2 Contact angle hysteresis (◦ ) 12. When the heat treated surface was again treated with IBTMOS/hexane solution.76 18. 4 shows the surface microstructure of a 300 nm silica film cast onto a glass slide from a TMOS/IBTMOS ratio of 1:1. 4.00 Fig. However. 3.e. For a TMOS/IBTMOS ratio of 1:3. are vulnerable to UV irradiation. CH3 and CH2 stretching vibration (2975–2840 cm−1 ) and deformation vibration (1232 cm−1 . A possible reason for this result is that large pores such as those observed in the bulk materials cannot form in thin films. Xiu et al.g. EDS spectrum of the thin film from TMOS/IBTMOS = 1:1.6 >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. 7. the surface superhydrophobicity was recovered (CA ∼ 165◦ and hysteresis <5◦ ). respectively. a superhydrophobic thin film with a contact angle of 165–170◦ was achieved. 5.5 wt% in the 1:1 silica (H atoms were included in the calculation) which agrees well with TGA data.13 46. as shown in Fig.6 Contact angle hysteresis (◦ ) Not measurable 2–3 Not measurable Fig. Table 5 shows the contact angle data on the heat-treated surfaces at different temperatures. demonstrate that the onset of weight loss is ∼200 ◦ C and ∼207 ◦ C..11 100. When impurities (i. FTIR analysis of the silica film after a heat treatment at 400 ◦ C indicated that hydrocarbon absorptions were absent as shown in Fig.

water droplet image on the surface. FTIR comparison of silica thin films before and after prolonged UV irradiation. Other commercially available polymers such as ethylene–vinyl acetate copolymer. contact angle hysteresis can be used to evaluate the surface chemistry change when the contact angles remain almost unaltered. This observation is shown in Table 6. inset. In order to mitigate the thermal and UV stability degradation of the superhydrophobic TMOS/IBTMOS surfaces. / Journal of Colloid and Interface Science 326 (2008) 465–470 469 Table 6 Effect of UV irradiation on contact angle and hysteresis for a thin film formed from TMOS/IBTMOS = 1:1 UV weathering test of silica film 8 days 12 days Contact angle 159–162◦ 158◦ Hysteresis 3–5◦ 15–20◦ Fig. When a superhydrophobic surface begins to degrade. 7. hysteresis. polydimethyl siloxane and Teflon. Therefore. where contact angles changed very little. air can still be effectively trapped between the water droplet and the substrate. all show surface degradation after long time UV aging tests. Bottom curve: SF6 RIE etched PB + UV absorber TINUVIN 1577FF (2%) + antioxidant IRGANOX 1010FF (1. the SiO–CH3 deformation vibration band at 1444 cm−1 disappeared due to continued hydrolysis.Y. only small side groups (isobutyl groups) exist on the surface. that was heat treated at 500 ◦ C and then PFOS treated. FTIR spectra of the silica superhydrophobic silica thin film before and after heat treatment at 400 ◦ C for 1 h. As described previously. 10. The surface fraction that is air beneath the water drop becomes smaller and smaller. which have higher bond strength and thus better UV stability than organic polymer materials. The ≡CH deformation vibration band at 1352 cm−1 Fig. Xiu et al. Instead. On the rough surface.5%). surface roughness enhances the hydrophilicity to superhydrophilicity. Top curve: silica film from TMOS/IBTMOS = 1:1 before UV test. these moieties are more UV stable than are polymers because negligible impurities and less UV-fragile defects exist on the silica surface. Acceler- . 10. contact angle. the silica main chain is comprised of Si–O bonds. In addition. the root mean square (RMS) surface roughness from AFM was 330 nm. bottom curve: the same silica film after UV testing for 12 days. a fluoroalkyl silane treatment was carried out. 10 shows the surface morphology of a silica film produced from a 1:1 TMOS/IBTMOS mixture. while hysteresis changed significantly. when the surface is hydrophilic. 9 shows that after UV irradiation. and the Cassie model no longer accurately describes the surface/water contact. hydrophobicity. AFM was used to probe the surface morphology of PFOS-treated superhydrophobic silica films. thus the silica film exhibits better UV stability than do organic polymers (polybutadiene fluorinated in SF6 plasma) as shown in Fig. to decompose/oxidize the organic moieties. top curve: silica film from TMOS/IBTMOS (1:1) using a two step acid–base catalyzed sol–gel process. The FTIR spectrum in Fig. Fig. Superhydrophobic silica thin film AFM surface image after PFOS treatment. the contact interface is better described by the Wenzel state. For the silica film. 8. ∼168◦ . the hysteresis changes more rapidly than does the contact angle. until it ultimately disappears. a heat treatment was performed on the silica thin films immediately after formation. Fig. 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. 8. Fig. subsequently. Thus. UV moisture weathering of superhydrophobic PB and silica thin film surfaces. 9. 2◦ . also disappeared while the OCH2 vibration band at 1330 cm−1 appeared after UV irradiation because of oxidative degradation of the isobutyl groups specifically on tertiary carbons.

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