Applied Surface Science 258 (2011) 158162

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Optically transparent, superhydrophobic methyltrimethoxysilane based silica coatings without silylating reagent
Mahendra S. Kavale a , D.B. Mahadik a , V.G. Parale a , P.B. Wagh b , Satish C. Gupta b , A.Venkateswara Rao a, , Harish C. Barshilia c
a b c

Air Glass Laboratory, Department of Physics, Shivaji University, Kolhapur, 416004, Maharashtra, India Applied Physics Division, Bhabha Atomic Research Centre (BARC), Trombay, Mumbai 400085, India National Aerospace Laboratories, Bangalore 560017, India

a r t i c l e

i n f o

a b s t r a c t
The superhydrophobic surfaces have drawn lot of interest, in both academic and industries because of optically transparent, adherent and self-cleaning behavior. Surface chemical composition and morphology plays an important role in determining the superhydrophobic nature of coating surface. Such concert of non-wettability can be achieved, using surface modifying reagents or co-precursor method in solgel process. Attempts have been made to increase the hydrophobicity and optical transparency of methyltrimethoxysilane (MTMS) based silica coatings using polymethylmethacrylate (PMMA) instead of formal routes like surface modication using silylating reagents. The optically transparent, superhydrophobic uniform coatings were obtained by simple dip coating method. The molar ratio of MTMS:MeOH:H2 O was kept constant at 1:5.63:1.58, respectively with 0.5 M NH4 F as a catalyst and the weight percent of PMMA varied from 1 to 8. The hydrophobicity of silica coatings was analyzed by FTIR and contact angle measurements. These substrates exhibited 91% optical transmittance as compared to glass and water drop contact angle as high as 171 1 . The effect of humidity on hydrophobic nature of coating has been studied by exposing these lms at relative humidity of 90% at constant temperature of 30 C for a period of 45 days. The micro-structural studies carried out by transmission electron microscopy (TEM). 2011 Elsevier B.V. All rights reserved.

Article history: Received 24 January 2011 Received in revised form 25 July 2011 Accepted 5 August 2011 Available online 11 August 2011 Keywords: Solgel process Superhydrophobic substrates PMMA Transparent coatings

1. Introduction The water repellent coatings have important feature in the industries to enhance the durability of materials. The wettability of the surface is a characteristic property of materials and strongly depends on both the surface chemical composition and surface roughness [1]. These surfaces are easy to clean, they have selfcleaning properties. In nature, many natural species exhibit water contact angle higher than 150 such as sacred lotus leaves [2], water striders legs, animal furs [3], cicada ornis wings [4], etc. These substrates are water repellent in that water droplets roll off the surface at a small tilt angle (sliding angle) and hereby removing contaminants from the substrates (self-cleaning). Lotus leaves are one of the most famous because examples among naturally occurring superhydrophobic surfaces. The microstructure of lotus leaves consists of a combination of two scales roughness: one around 10 m (rough structure) and around 100 nm (ne structure). These substrates are also referred as

Corresponding author. Tel.: +91 231 2609228. E-mail address: avrao2012@gmail.com (A.Venkateswara Rao). 0169-4332/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2011.08.023

hierarchical micro- and nanostructures. The hydrophobicity of a lotus leaf arises from the epicuticular wax secreted by the leaf itself [5]. The contact angle of water drop with lotus leaf 161 2.7 [6]. The wax has a contact angle of 110 , not highly hydrophobic; however, the lotus leaf still exhibits a superhydrophobic property. It is presumed that this combination of roughness and wax contribute to the superhydrophobicity of the lotus leaf. The rolling of water droplets and removal of the contaminants from the surface of lotus leaf is referred as the Lotus Effect. The lotus leaf therefore always exhibits a very low degree of contamination: self-cleaning. Inspired by the lotus leaf effect, many efforts have been made to fabricate such surfaces with binary hydrophobic roughness. Starting from a polymer solution, superhydrophobic coarse coatings are obtained by phase separation or electro-spinning [7,8]. Papillaemimetic polyaniline particles are assembled in the presence of peruoroocatane sulfonic acid, which can form superhydrophobic coatings in situ [9]. Assembling nano-particles followed by a post-hydrophobic modication leads to coarse superhydrophobic surfaces [10]. A superhydrophobic coating can also be obtained by controlling crystal growth dynamics from melt [11], or by means of electrochemistry onto metallic substrates [12]. Generally in solgel process hydrophobicity can be achieved by using

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silylating reagents, which replaces surface polar hydroxyl drops into non-polar alkyl groups. But this method decreases the adherence of the coatings because of the highly reactive silylating reagents. Here we have demonstrated the without use of silylating reagents superhydrophobicity can be achieved by using PMMA in the methyltrimethoxysilane based silica coatings, which enhances hydrophobic behavior.

Alcohol Condensation (3)

OH CH3 Si OH O

OH Si OH CH3 CH3 + H3CO

CH3 Si OCH3

OCH3 CH3 O Si OH O CH3 Si OCH3 OCH3 + CH3OH

2. Experimental 2.1. Preparation of coating solution For the preparation of superhydrophobic coating the chemicals used were, methyltrimethoxysilane (SigmaAldrich Chemie, Germany), methanol and Toluene (S.D. Fine Chem Ltd., Mumbai, India) and Ammonium Fluoride (Loba Chemie, India), Polymethylmethacrylate (PMMA) (Fluka, Germany). Double distilled water was used in the preparation of catalyst. All chemicals were used as received without further purication. Further, 1 to 8 g of PMMA weighed and dissolved in 100 ml of Toluene to obtain 18 wt% of the PMMA. The mixture was vigorously stirred at 50 C to get transparent and stable solution of PMMA. This wt% of PMMA added with the sol to get superhydrophobic coating. A coating sol was prepared by keeping the molar ratio of MTMS:MeOH:H2 O constant at 1:5.63:1.58, respectively with variation of PMMA from 1 to 8 wt% and 0.5 M NH4 F as a catalyst. The cleaned glass substrates were dipped vertically after addition of base catalyst in the sol and taken out after gelation. Further, these glass substrates were annealed at 150 C for 3 h to remove residual solvent.

OH Si OH
Polymerization (4) CH3 CH3 CH3
OH Si OH O Si OH O Si OCH3

CH3 + (CH3 C )

OCH3

COOCH3 PMMA

CH3 CH3 Si CH3 O

CH3 Si CH3 O

CH3 Si OCH3 OCH3 + 2CO2 + H2O + 1/2 H2

2.2. Characterizations The water drop contact angle was measured using standard goniometer (Ramehart Instrument Co., USA) equipped with CCD camera. All CAs were measured by keeping 10 L water droplet on coated glass substrate at room temperature. Surface chemical composition studies were carried out using Fourier transform infrared (FTIR, PerkinElmer 783, USA) spectroscopy and microstructural studies of the substrates coating by transmission electron microscopy (Philips, Tecnai, F20 model, Netherlands). The optical transmittance (%) of coating analyzed using UVVIS spectrophotometer (Shimadzu, UV 1800. Japan). Thermal conductivity and specic heat of the coatings quantied using CT meter (Teleph Company, France). The effect of humidity on the wetting properties of the substrates was studied in a humidity chamber (REMI Instrumentation Ltd., Mumbai, India). The thermal stability of coatings was characterized by TGA and DSC analysis in inert atmosphere.

The expected polymerization reaction between the hydrolyzed MTMS and PMMA is as shown in the reaction (4). The surface OH groups are replaced by the CH3 groups of the PMMA in order to achieve the inherent superhydrophobicity as well as nanostructured silica network resulted on the substrate surface with release of two molecules of carbon dioxide, water and hydrogen atom. This mechanism is responsible for the gelation.

3. Results and Discussion 3.1. Contact angle measurements The hydrophobic nature of the surface can be quantied by measuring the contact angle of water droplet with the surface. Fig. 1a and b shows image of water droplet on the coating prepared with MTMS as precursor without PMMA and with PMMA (7%) respectively. The water drop contact angle for these coatings was found to be increased from 116 1 to 171 1 . The hydroxyl groups are present on the surface of the coated substrate are main sources of the hydrophilicity as they promote the adsorption of water molecules. These terminal hydroxyl groups interact with water, leading to the deterioration of the non-wettability of surface whether it is aerogel or coating surface. The increase in the contact angle indicates that the increase in hydrophobicity of the silica coatings which might be due to replacement of the polar OH groups of the surface by the non polar CH3 groups of the PMMA. The static contact angle is governed by the force balance at the three phase boundary and is given by Youngs equation [13]. But the Youngs equation is applied for the at surface and not to a rough surface. The effect of surface roughness on wetting behavior is accounted by the model developed by Wenzel, where it is assumed that the space between the protrusions on the surface is lled by the liquid. Wenzel had modied the Youngs equation as in the following [14]. cos = r
sv

2.3. Reaction mechanism The hydrolysis and condensation of methanol diluted MTMS in presence of PMMA and NH4 F is as shown in following chemical reactions. Hydrolysis
4 CH3 Si(OCH3 )3 + 3H2 O CH3 Si(OH)3 + 3CH3 OH

NH F

(1)

Water Condensation (2) OH OH

OH CH 3 CH3 Si OH O

OH Si CH3 + H2O OH

lv

sl

= r cos

(5)

CH3

Si OH + OH Si OH OH

where sv , sl and lv are solidvapor, solidliquid and liquidvapor interfacial energies, respectively and is the contact angle, where

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Fig. 1. Water drop contact angle images on the silica coating. (a) Without PMMA (b) with PMMA (7%).

r is the ratio between the true surface area and its horizontal projection. In contrast, Cassie and Baxter [15] proposed an equation: cos = 1 + f (cos + 1) (6)

where f is the area fraction of the liquidsolid contact to the projected surface area. The CassieBaxter model suggested that the surface traps air in the hollow spaces of the rough surface, so that the droplet essentially rests on a layer of air. de Gennes [16] explained a threshold roughness r* for air trapping; r = 1 + tan2 4 (7)

(7%), which is the main reason for shifting the hydrophilic character to superhydrophobic nature of MTMS based silica coating. Also as wt% of PMMA increases polar groups like OH are replaced by CH3 non-polar groups and nally surface possess superhydrophobic character. 3.3. Transmission electron microscopic studies Fig. 3, shows the transmission electron micrograph of the silica coatings prepared with 7% PMMA in MTMS silica coating. The silica coating on the glass substrate selected for the TEM analysis, which showed highest contact angle of 171 1 . This study revealed that the silica particles formed a nanostructured network particles size of less than 50 nm. These studies conrm the presence of rough nanostructured protrusions and therefore these might be responsible for the superhydrophobicity of the silica coatings as suggested by the CassieBaxter model. This study revealed that well distributed nanostructured network of silica particles with size 200 nm. These studies conrm the 91% optical transmittance in the visible region and presence of rough nanostructured asperities and therefore these might be responsible for the superhydrophobicity of the silica coatings as suggested by the CassieBaxter model.

For low roughness (r < r* ), the solid/liquid interface conrms to the prole of the solid surface and the contact angle is given by Wenzels law. Beyond a threshold r* (r > r* ), air pockets are trapped and CassieBaxter equation must be used to evaluate * . 3.2. Fourier transform infrared spectroscopy studies The wetting behavior of superhydrophobic surfaces is governed by chemical composition of surface and roughness of surface. The coated material on glass substrate was removed and powder of material exposed up to 100 C for one hour for removing the moisture. Then coating powder was milled with potassium bromide (KBr) to form a very ne powder. This powder is compressed into a thin pellet for FTIR analysis in transmission mode, since KBr is transparent in the IR region. The heat treatment is helpful to remove the physically adsorbed water molecules. Fig. 2a and b shows the Fourier transform infrared (FTIR) spectra of the silica coating prepared without PMMA and with PMMA (7%), respectively. Several characteristic absorption peaks were observed in the range 4504000 cm1 indicating the presence of methyl groups in the sample. The broad absorption peak observed at 1080 cm1 which is characteristic peak of the SiOSi bond present in both samples [17]. The absorption bands were observed at 2950 and 1400 cm1 are due to stretching and bending modes of CH bond and the peaks observed at 765 and 1265 cm1 are due to the SiC bonds [18]. The 1265 cm1 peak indicates the presence of the SiC bonding. The absorption peaks at 1600 and 3400 cm1 corresponding to the polar OH bonds, the residual SiOH groups are the main source of hydrophilic character of coating. In the spectrum of without PMMA absorption peaks intensities of SiC and CH bond are less than peaks observed with PMMA (7%) coating. This conrms that numbers of SiCH3 groups are more in the coating with PMMA

Fig. 2. FTIR spectra of the superhydrophobic silica coatings.

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Fig. 5. Photograph of the superhydrophobic silica coatings on glass substrates.

Fig. 3. Transmission electron microscopic studies of the silica coatings.

3.4. Optical transmission studies The optically transparent superhydrophobic coatings nd application as a thermal insulator. Fig. 4 shows the prole of transmittance of the coatings prepared with PMMA (7%) substrate in the visible region with respect to glass. The substrate showed the 91% optical transmission. Fig. 5 shows the photograph of water droplets on silica coating; from photograph it is observed that coatings are optically transparent and hydrophobic also. The optical transmission depends on thickness of sample and particle size of the deposited silica particles. The TEM analysis shows that particle size is less than 50 nm, therefore the silica coatings are optically transparent in nature. 3.5. Thermal conductivity studies The thermal conductivity of the coating depends on the density silica network. Thermal conduction through the silica coatings

occurs through two mechanisms; solid conductivity and radiative transmission. Table 1 shows the measured thermal conductivity values for silica coatings prepared with PMMA (18%). It is observed that as wt% of PMMA increased, thermal conductivity raised from 0.068 to 0.0126 W m1 K1 . The increase in thermal conductivity might be due to increase in the density of coating. The relation between thermal conductivity and rise in temperature in coating is given by T= RI 2 L 1 4 K [ln(t) + C te ] (8)

The silica coating prepared for 7% PMMA shows thermal conductivity 0.089 W m1 K1 . Due to such low thermal conductivity, the obtained superhydrophobic coatings possess potential applications in thermal insulation systems. 3.6. Effect of humidity on superhydrophobic coatings The water repellent capability of superhydrophobic coatings gradually degrades during long-term outdoor exposure and accumulation of contaminants. Therefore stability of superhydrophobic surfaces in humid atmosphere is important factor from application point of view. Humidity is a measure of the amount of water vapors in the air. The relative humidity (H) is given by equation [19]: H= e 100 es (9)

Fig. 4. Optical Transmission studies of the silica coatings.

where e is actual vapor pressure and es is saturated vapor pressure. In humid atmosphere, it may be mentioned that the actual vapor pressure (e) is always less than the saturated vapor pressure (es ). The effect of humidity on the wetting properties of silica deposited glass substrates were carried out at relative humidity of 90% at 30 C over 45 days and contact angle values of before and after exposing to humid atmosphere are shown in Table 1. The silica coated glass substrate prepared with 7% of PMMA shows highest contact angle 171 1 and after exposing to humid atmosphere contact angle decreases to 169 . It was observed that for all silica coatings contact angle decreases slightly after 45 days. The decrease in the contact angle might be due to a slight adsorption of moisture from the atmosphere by the polar OH bonds present in the silica coating. The samples exposed to humid atmosphere for 45 days were dried at 50 C in oven and again contact angle was measured for this dried sample. It was observed that contact angle was nearly same to that of the measured before exposing to the humid atmosphere.

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Table 1 Physical Properties of the silica coatings with respect to PMMA (w/v) with MTMS. Sr. no. 1 2 3 4 5 6 7 8 9 Coating sample PMMA by (w/v) with MTMS (%) 0 1 2 3 4 5 6 7 8 Contact angle () 116 124 127 133 147 154 162 171 156 Transparency (%) 47 52 58 72 78 82 91 91 35 Thermal conductivity (Wm1 K1 ) 0.068 0.070 0.073 0.074 0.079 0.080 0.082 0.089 0.126 CA after exposing to humid surrounding () 1 104 119 123 128 143 149 156 169 155

visible region. The coatings prepared with 7% PMMA shows thermal conductivity of the order 0.089 W m1 K1 with water contact angle (CA) as high as 171 1 . The FTIR studies conrms the as wt% of PMMA increases, methyl groups in the coatings are increased. The superhydrophobic nature of coatings is thermally stable up to temperature of 457 C as revealed by the thermal analysis. Acknowledgements The authors are grateful to the Department of Atomic Energy (DAE), Board of Research in Nuclear Sciences (BRNS), Mumbai, Government of India, for the nancial support for this work through a major research project on Aerogels (No.2008/37/47/BRNS/2502). The authors, Mr. Mahendra Suhas Kavale and D. B. Mahadik are highly thankful to the DAE BRNS for the Junior Research Fellowships.
Fig. 6. TGDSC analysis of superhydrophobic silica coatings on glass substrates.

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This reveals that there was no signicant effect of humidity on the silica coatings. 3.7. TGADSC analysis Fig. 6 shows that TGA and DSC proles of the 7% PMMA modied silica coating sample. The TGA curve has small weight loss around 150 C due to evaporation of the hydroxyl groups and physically adsorbed water molecules from room temperature to around 200 C. The TGA curve shows noticeable weight loss at around 457 C accompanied with an exothermic peak in the DSC curve. The sudden weight loss in TGA curve around 457 C is due to the decomposition of alkyl (CH3 ) groups. The exothermic peak in DSC curve indicates the oxidation of alkyl groups [20]. It indicates that 7% PMMA modied silica coatings are thermal stable up to 457 C in inert atmosphere and above this temperature the silica coating becomes hydrophilic in nature. 4. Conclusion Transparent, superhydrophobic, adherent and low thermal conductive silica coatings on glass substrate were synthesized at low processing temperature using MTMS as a precursor with PMMA polymer by simple dip coating method without silylation. The use of PMMA in the MTMS based silica coatings helps to enhance the hydrophobicity and durability of the coatings. The optical transmission study shows coatings have nearly 91% transmission in the