J Sol-Gel Sci Technol (2010) 53:7984 DOI 10.

1007/s10971-009-2058-3

ORIGINAL PAPER

Preparation and characterization of polyvinyl butyral/silica hybrid antireective coating: effect of PVB on moisture-resistance and hydrophobicity
Xinxiang Zhang Congrui Cao Bo Xiao Lianghong Yan Qinghua Zhang Bo Jiang

Received: 9 June 2009 / Accepted: 30 July 2009 / Published online: 13 August 2009 Springer Science+Business Media, LLC 2009

Abstract A new modied antireective coating was prepared by base catalyzed solgel process using tetraethylorthosilicate as precursor and polyvinyl butyral as modier. The properties of the silica sols and AR coatings were characterized with Fourier-transfer infrared absorption spectroscopy, particle size analyzer, transmission electron microscope, programmable rheometer, UVVis spectrophotometry, ellipsometry, atomic force microscope and contact angle measurement. It was found that addition of 4% PVB greatly enhanced moisture-resistance of the AR coating. Optical transmittance of 4% PVB modied AR coating on BK7 substrate was found to be nearly 100%. The water contact angles of normal and 4% PVB modied AR coating were 51 and 53, respectively, which indicates no signicant increase of hydrophobicity of the modied coating. The peak transmittance of 4% PVB modied AR coating was almost unaffected after being exposed to the moist surroundings while that of normal silica coating decreased sharply from 99.8 to 96.5% within 2 weeks. The excellent moisture-resistance of PVB modied AR coating may be attributed to the adsorption of PVB on the surface of AR coating. Keywords Antireective coating Polyvinyl butyral Moisture-resistance Hydrophobicity

1 Introduction Solgel process has attracted much interest since it was applied to prepare novel organicinorganic hybrid materials in 1980 [1]. Due to its advantages of good uniformity, low roughness, a large area deposition and a large-scale production, as well as a controllable microstructure in the lm preparation [2, 3], the solgel process has been widely employed to prepare antireective (AR) coatings in glasses such as automotive windows [4], solar cells [5], laser systems [6]. For AR coatings, transmittance is one of the most important properties. However, the transmittance of traditional pure silica coatings always declines in moist environment due to their property of easy absorption of water from the surroundings [79]. This problem prevents the application of these coatings in moist surroundings. Generally, moisture-resistance of the coating increases with hydrophobicity of the coating surface. In recent years, great effort has been devoted to prepare hydrophobic AR coatings to overcome this disadvantage of pure silica AR coatings. The most effective approach is to introduce organic molecules or polymers bearing hydrophobic groups into the silica sol as modiers [1013]. Using methyltriethoxysilane (MTES) co-hydrolyzed tetraethoxysilane (TEOS) in different molar ratio as precursors, Yao et al. [8] prepared optical and hydrophobic nano-porous silica coatings with low refractive index. Jeong et al. [9] have made water-repellent coatings on the surfaces of glass by solgel process using the mixtures of peruoroalkylsilane (PFAS) and tetraethoxysilane (TEOS). Besides, Hou and Chen [14] prepared super-hydrophobic silica coatings with visible light transmission using phase separation. They have successfully prepared hydrophobic silica coatings and explained the reason of increase of hydrophobicity of AR

X. Zhang C. Cao B. Xiao B. Jiang (&) Key Laboratory of Green & Technology, College of Chemistry, Sichuan University, 610064 Chengdu, China e-mail: jiangbo@china.com L. Yan Q. Zhang Research Center of Laser Fusion, China Academy of Engineering Physical, 621900 Mianyang, China

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coatings. However, few of them focused on the property of moisture-resistance of AR coatings. The aim of present work is to prepare a transparent moisture-resistant AR coating by incorporating PVB into the silica sol. In consideration of molecular structure, polyvinyl butyral (PVB) contains hydroxyl groups and alkyl groups. The former groups can react with the hydroxyl groups on the surface of silica particles and the latter groups can improve the hydrophobicity of AR coating. In addition, PVB is a good adhesive for glass and plastic, with excellent transparency and environment durability. Consequently, PVB was used as a modier to prepare high transmittance organicinorganic hybrid AR coating in this work. The optical properties as well as the moisture-resistance of the AR coating and the inuence of PVB were systematically investigated.

electron microscopy (JEM-100CX). Viscosity measurements were carried out using programmable rheometer (BROOKFIELD, DV III ULTRA), at 25 C and at a shear rate of 244.6 s-1. The transmission spectra were measured from 300 to 1100 nm with an UVVis spectrophotometer. The thickness and refractive index of the AR coatings was determined on the ellipsometry (SENTECH SE850 UV). Atomic force microscopy (AFM) (PSIA XE-100) was used to characterize the surface morphology of the AR coatings. Contact angle instrument was used to measure the hydrophobicity of the coatings. The moisture-resistance study of AR coatings was carried out at a relative humidity of 95% at 35 C.

3 Results and discussion 3.1 Particle size of silica sols

2 Experimental details 2.1 Preparation of silica coating PVB (MW & 12000) was puried by precipitation using acetone. TEOS, water and ethanol were double distilled. All the other chemicals were analytical grade and used as received. Solgel derived silica sol was prepared by the hydrolysis and condensation of TEOS catalyzed by ammonia in ethanol solution. A solution of TEOS in ethanol was rst prepared and another solution of water, ethanol and NH4OH (13.4 mol/L) was slowly added into the former solution. The mixture was stirred for 2 h at 30 C. The PVB ethanol solution was then added and stirred for another 1 h. The nal concentration of SiO2 was 3% by weight and the nal molar ratio of TEOS: H2O: EtOH: NH3 was 1: 3.25: 37.6: 0.17. The weight ratio of PVB to SiO2 was varied from 0 to 8%. The resultant sols were aged in sealed glass containers at 25 C for about 14 days before deposition. All the sols were carefully ltered through 0.22 lm PVDF lters before coating application. The silica sols were deposited on well-cleaned BK7 substrates by dip coating at the withdrawal rate of 100 mm/min. The BK7 substrates were ultrasonicated in acetone for 10 min and wiped carefully using cleanroom wipers. The silica coatings were heat treated at 160 C for 8 h under ambient atmosphere. 2.2 Characterization of solgel derived silica coatings The particle size distribution testing was performed on Malvern Zetasizer nano-ZS at 25 C using ethanol as dispersant. The TEM pictures were taken by transmittance
Fig. 1 Comparison of relationship between aging time and particle size distribution of unmodied (left) and PVB modied (right) silica sols

Particle size and its distribution is an important property for silica sol, which has many impact on the nal properties of the AR coating. Particle size was investigated with particle size analyzer. The results (Fig. 1) indicate some aggregate nature of the sols. The particle size distribution of normal silica sol is in the range of 215 nm while that of 4% PVB modied sol is in the range of 320 nm after 7 days. This is attributable to the faster particle growth of PVB modied silica sol than that of normal silica sol. The bigger particle size is possibly the results of not only PVB bridges formed between SiO2 particles, but also PVB layer formed on the surface of SiO2 particles. IR spectrum of 4% PVB modied silica xerogel (which is not listed in this paper) was unable to give evidence of direct formation of SiOC linkages between the SiO2 particles and PVB. Consequently, it is difcult to explain the reason of increase of sol particle size

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from IR spectrum basis. The mean aggregate size of modied silica sol is almost twice as large as that of normal silica sol, and the weight ratio of PVB to SiO2 is only 4%, such a low concentration of PVB is not sufcient to double the particle size of silica sol by covering PVB on the surface of silica particles. Therefore, there should be some PVB bridges formed among silica particles. The PVB bridges can be linked by COSi bonds or hydrogen bonds. The aggregate size distributions of both normal and PVB modied silica sols do not change obviously between 7 and 23 days, which indicates a slow down of the condensation process of the particles. When the aging time reaches 84 days, the mean aggregate size is larger than that of 23 days. Take modied silica sol as an example, the aggregate size distribution changes from 440 to 940 nm while the mean aggregate size changes from 9 to 16 nm. This should be attributed to the formation of bigger clusters in the sol. The viscosity of normal and modied silica sols is 2.040.02 and 2.160.02 mPaS. With the addition of PVB, the particles of the modied sol grow faster than that of normal sol which will lead to thicker coating due to the larger viscosity [15]. Besides, the larger particles will also lead to more light scattering on the surface of the AR coating caused by rougher coatings [16]. Consequently, the concentration of PVB should be kept at low level to obtain high transmittance. Figure 2 shows the TEM images of the normal and 4% PVB modied sols at 14 days aging time. To prepare the TEM samples, a droplet of the silica sols was set on a copper grid, dried under air atmosphere, and then dried under vacuum. The images reveal also that the particle size of modied sol is lager than that of normal sol which is in good agreement with the result of particle size analysis. 3.2 Optical properties All of the AR coatings are crack-free before and after heat treatment at 160 C. The coatings also appear macroscopically smooth and highly transparent. Figure 3 shows the optical transmittance spectra of normal AR coating and 4% PVB modied AR coatings on BK7 substrate. The optical transmittances of both normal and PVB modied coatings are higher than 99.5% at 700 nm, while that of bare BK7 substrate is only 92.2%. This indicates that the PVB modied organicinorganic AR coating with high transmittance is successfully obtained. Table 1 shows the effect of PVB concentration on the maximum transmittances and corresponding wavelengths of AR coatings. The maximum transmittances decrease with the increasing concentration of PVB. With the increasing PVB concentration, the particle sizes of silica

Fig. 2 TEM micrographs of silica sols without (a) and with (b) PVB

Fig. 3 Transmission spectra for the bare substrate and two AR coatings from 14 days aged sols with the withdraw rate of 100 mm/ min by dip-coating

sols increase. The increasing sizes of silica particles lead to rougher surface which lead to more light scattering of AR coatings [17]. The corresponding wavelengths of maximum transmittances increase gradually from 695 to 780 nm, which is attributed to increasing viscosity of the

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82 Table 1 Effect of PVB concentration on maximum transmittance and corresponding wavelength PVB concentration (%) 0 2 4 6 8 Maximum transmittance (%) 99.9 99.8 99.7 99.6 99.3 Wavelength (nm) 695 725 740 780 780

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sols and a corresponding increase in the thickness of the coating [18]. Results from the elliposometry show that the thicknesses of normal and 4% PVB modied AR coatings are, respectively 149 and 180 nm while the refractive indices are 1.23 and 1.19, respectively. PVB modied silica sol possesses larger particle size, which leads to bigger porosity and corresponding lower refractive index [19]. The relation between particle size, thickness, maximum transmittance, and the corresponding wavelength is clear. Increasing concentration of PVB leads to thicker and rougher coating, which results in the longer corresponding wavelength and the lower transmittance, respectively. 3.3 Surface morphology of AR coating Figure 4 shows the AFM photographs of normal and 4% PVB modied silica coatings. They are both porous, which guarantees the high transmittance of coatings. However, addition of polymer affects the morphology of AR coating. The PVB modied AR coating possesses larger pore and rougher surface. The root-mean-square (RMS) roughness values of the coatings are analyzed with AFM. RMS roughness values of the coatings increase from 0.7 to 1.4 nm. This is in good agreement with the change of the particle sizes illustrated in Fig. 2. Because PVB modied silica sol possesses larger particle size than normal silica sol, PVB modied silica coating is rougher than the normal silica coating. 3.4 Effect of PVB on hydrophobicity of AR coatings Hydrophobicity can be represented by water contact angle, with increasing values of water contact angle reecting increasing hydrophobicity. Table 2 illustrates variations in the values of water contact angle of the AR coatings as a function of the PVB concentration. The water contact angle initially increases slightly with increasing PVB concentration, reach a maximum values of 53 , then a decrease in value of water contact angle is observed with further increase of PVB content.
Fig. 4 AFM photographs of normal (a) and 4% PVB modied (b) silica coatings

Table 2 Water contact angle versus the concentration of PVB PVB concentration/% 0 2 4 6 8 Water contact angle/ 51.5 52.0 53.0 49.5 47.0

It has been well known that hydrophobic property of AR coating is controlled by both surface chemical composition and surface topology [20]. There are two effects of PVB on the water contact angle of AR coating. On the one hand, due to the introduction of alkyl groups and the reaction between PVB and silica particles which reduces the surface hydroxyl groups of AR coatings, the coating shows more hydrophobicity. On the other hand, the particle sizes of silica sols increase with the concentration of PVB. Consequently, the roughness of AR coatings is larger, which reduces the water contact angle. The relationship between contact angle and roughness can be explained by Wenzel equation [21].

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coshw R cosh0 where hw may be called the Wenzel contact angle (observed contact angle), R is the Wenzel roughness dened as the ratio of real surface area to the apparent surface area, and h0 the intrinsic contact angle on at surface. According to Wenzel equation, the observed contact angle is inversely proportional to R. The rougher surface leads to larger R, which reduces the observed value of contact angle. When the PVB concentration is lower than 4%, the former effect plays the leading role. When the concentration is higher than 4%, the later effect plays the leading role. This may be the main reason that the value of the water contact angles rst increase and then decrease with the increasing PVB concentration. 3.5 Effect of PVB on moisture-resistance of AR coating Moisture-resistance is an important property for AR coatings used in ambient environment. It can be measured through the changes of the peak transmittance of AR coatings which were kept in moist environment. The results are shown in Fig. 5. The peak transmittance of PVB modied AR coating is almost unaffected by the moist surroundings while that of normal silica coating decreased sharply from 99.8 to 96.5% within 2 weeks. The result indicates that 4% PVB modied AR coating possesses high moisture-resistance. The decrease of transmittance is attributed to decrease of porosity of the coating. The polar coating is easy to absorb water molecules from the surroundings, which leads to rupture of SiOSi bonds and pore blocking due to the absorption of water molecules. As listed in Table 2, the water contact angles of PVB modied AR coatings are close to that of normal AR

coating, but 4% PVB modied AR coating shows high moisture-resistance. Generally, the moisture-resistance of AR coatings is proportional to the hydrophobicity. In this work, a modied silica AR coating with low hydrophobicity and excellent moisture-resistance is obtained. The improvement of hydrophobicity will certainly improve the moisture-resistance of AR coating. However, it is not the only approach to improve the moisture-resistant property of the AR coating. In addition to reacting with silica particles, the PVB might be adsorbed on the surface of the AR coating, which prevents the absorption of water molecules, affording PVB modied AR coating an excellent moistureresistance. However, the mechanism of adsorption of PVB on the surface of AR coating is still unknown, further studies are necessary.

4 Conclusion PVB modied AR coating has been successfully prepared by base catalyzed solgel process using TEOS as precursor. The particle sizes of modied silica sol were larger than that of normal silica sol, which could be attributed to the hydrogen bonds or SiOC bonds formed between PVB and silica particles. The addition of PVB improved the moisture-resistance of AR coating. The transmittance of AR coating decreased with the increasing PVB concentration because of light scattering on the surface of AR coating. The optimum concentration of PVB/SiO2 was found to be around 4 wt% in order to obtain both high transmittance and moisture-resistance AR coating. The hydrophobicity of modied AR coating does not increase obviously with the addition of PVB. The phenomenon of low hydrophobicity and excellent moisture-resistance may be attributed to the adsorption of PVB on the surface of AR coating.

References
1. Philipp G, Schmidt H (1984) J Non-Cryst Solids 63:283292 2. Uhlmann DR, Suratwala T, Davidson K, Boulton JM, Teowee G (1997) J Non-Cryst Solids 218:113122 3. Sermon PA, Vong MSW, Bazin N, Badheka R, Spriggs D (1995) Recent developments in silica solgel antireection (AR) coatings. Proc SPIE. doi:10.1117/12.228295 4. Muromachi T, Tsujino T, Kamitani K, Maeda K (2006) J SolGel Sci Technol 40:267272 5. Ayllon JA, Lira-Cantu M (2009) Appl Phys A 95:249255 6. Zhang QY, Li XL, Shen J, Wu GM, Wang J, Chen LY (2000) Mater Lett 45:311314 7. Zalga A, Kazadojev I, Beganskiene A, Kareiva A (2008) Solgel synthesis of modied silica anti-reecting coatings. Springer, Netherlands

Fig. 5 Inuence of time on Transmittance of AR coatings under high humidity

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84 8. Rao AP, Rao AV, Pajonk GM (2007) Appl Surf Sci 253:6032 6040 9. Rouessac V, Ferreira P, Durand J (2003) Sep Purif Technol 32:3743 10. Smitha S, Shajesh P, Mukundan P, Warrier KGK (2007) J Sol Gel Sci Technol 42:157163 11. Yao LF, Zhu YA, Qu D, Du MF, Shen J, Wang J (2006) Optical and hydrophobic nano-porous silica thin lms with low refractive index. Proc SPIE. doi:10.1117/12.668115 12. Jeong HJ, Kim DK, Lee SB, Kwon SH, Kadonoz K (2001) J Colloid Interface Sci 235:130134 13. Pilotek S, Schmidt HK (2003) J SolGel Sci Technol 26:789792 14. Hou HF, Chen YQ (2007) J SolGel Sci Technol 43:5357

J Sol-Gel Sci Technol (2010) 53:7984 15. Mators MC, Carvallio AM, Almeida RM, Ilharco LM (1992) Inuence of processing parameters on the thickness of solgel silica lms. Proc SPIE. doi:10.1117/12.132002 16. Zhang XT, Sato O, Taguchi M, Einaga Y, Murakami T, Fujishima A (2005) Chem Mater 17:696700 17. Vincent A, Babu S, Brinley E, Karakoti A, Deshpande S, Seal S (2007) J Phys Chem C 111:82918298 18. Bautista MC, Morales A (2003) Sol Energy Mater Sol Cells 80:217225 19. Debsikdar JC (1987) J Non-Cryst Solids 91:262270 20. Cao MW, Song XY, Zhai J, Wang JB, Wang YL (2006) J Phys Chem B 110:1307213075 21. Wenzel RN (1949) J Phys Colloid Chem 53:14661467

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