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DOI: 10.1002/adfm.200500624

Stable, Superhydrophobic, and Conductive Polyaniline/Polystyrene Films for Corrosive Environments**

By Ying Zhu, Jingchang Zhang, Yongmei Zheng, Zhongbing Huang, Lin Feng,* and Lei Jiang*
A polyaniline/polystyrene composite film with a lotus-leaf-like structure is prepared via a simple electrospinning method. The film shows stable superhydrophobicity and conductivity, even in many corrosive solutions, such as acidic or basic solutions over a wide pH range, and also in oxidizing solutions. The special surface composition and morphology are the two important aspects that induce such unusual properties. The polystyrene content can strongly influence the morphology of the composite films, which thus display different superhydrophobicities and conductivities.

1. Introduction
The wettability of a solid surface is a very important property that is governed by both the chemical composition and the geometrical microstructure of the surface. It is known that a flat surface with a low surface energy tends to exhibit a water contact angle (CA) greater than 90. However, even a surface with the lowest surface free energy, that of closest hexagonal packed CF3 groups, shows a CA of only 119,[1] which is insufficient to produce a superhydrophobic surface, i.e., a surface with a CA of greater than 150. In recent years, it has been found that, if a surface with a rough or microtextured structure has a low interfacial free energy, the CA can reach almost 180, and the surface will remain dry as a water droplet easily slides across it.[28] The typical example is the self-cleaning of natures lotus leaf, on which the CA is about (161.0 2.7) and the sliding angle (SA) only 2.[9ac] The micro- and nanoscale hierarchical structures on the surface of the lotus leaf, i.e., branch-like nanostructures on the top of micropapillae, contribute to this unique property. According to this finding, biomimic superhydrophobic surfaces have been widely developed by constructing micro- and nanostructures on surfaces composed of various materials.[9d,e] A superhydrophobic surface is needed for many applications in biotechnology and for textiles and antifouling

[*] Dr. L. Feng, Prof. L. Jiang, Dr. Y. Zhu, Dr. Y. Zheng, Dr. Z. Huang Center of Molecular Sciences, Institute of Chemistry Chinese Academy of Sciences Beijing 100080 (P.R. China) E-mail: fenglin@iccas.ac.cn; jianglei@iccas.ac.cn Dr. Y. Zhu, Prof. J. Zhang School of Science Beijing University of Chemical Technology Beijing 100029 (P.R. China) [**] The authors thank the Natural Science Foundation of China (50 533 030, 20 125 102, 90 306 011, 20 421 101), the Innovation Foundation of the Chinese Academy of Sciences, and the Cooperation Lab of the National Center for Nanoscience and Technology for providing support.

coatings, etc.[10] However, such a surface can easily bring about static-charge accumulation, possibly causing a fire or an explosion in practical applications under dry conditions. Inspired by the conducting materials used for static-charge dissipation, we believe that a superhydrophobic surface prepared using such a material would be one of the most effective approaches for eliminating the disastrous drawback of static-charge accumulation. Conducting polyaniline (PANI) has attracted much attention as a result of its controllable conductivity, ease of synthesis, low density compared to metals, good environmental stability,[1114] and use in various possible applications.[1517] On the other hand, there is a limit in the practical applications of the staticcharge dissipation of PANI, because its conductivity is easily influenced by acidic or basic ambiences that arise under certain weather conditions, such as rain or snow, and from surrounding contaminants. The aim of our work is to fabricate a superhydrophobic surface utilizing conducting PANI blended with polystyrene (PS), so as to combine stable conductivity with superhydrophobicity, which would make this surface useful as an antistatic coating for use under a range of environmental conditions. To the best of our knowledge, there has been no report on this unique surface to date. Herein, a novel composite film of PANI doped with azobenzenesulfonic acid (ABSA) blended with PS was obtained by a simple and inexpensive electrospinning method.[1820] The PANI/PS composite film shows a structural similarity to the surface of a lotus leaf, resulting in a superhydrophobic surface with a CA larger than 150 and a SA lower than 5, i.e., it has a self-cleaning effect. Importantly, the prepared PANI/PS composite film exhibits conductive and excellent superhydrophobic properties, and remains stable, not only in pure water, but also in corrosive nitric acidic and sodium hydroxide solutions, as well as in oxidizing solutions. Such a PANI/PS composite film can have practical uses, such as in antistatic coatings, electromagnetic-interference shielding, and as an anticorrosion protection in various environments, especially in harsh conditions. It can also save time and money for maintenance, as well as prolonging the life span of film materials. The present findings

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are of crucial significance for conductive coatings and for maintaining their stable conductivity and superhydrophobicity, from both theoretical and practical aspects.

2. Results and Discussion

2.1. Surface Morphology and Surface Properties of PANI/PS Composite Films First, PS (3.72 wt.-%) dissolved in a dimethylc d formamide (DMF) solution of PANI doped with ABSA was electrospun to obtain PANI/PS films with a lotus-leaf-like structure on clean glass slides. The films are green because the composite contains the conductive form of PANI. The morphology of the conductive PANI/PS composite film was examined using scanning electron microscopy (SEM). A typical SEM image (Fig. 1a) exhibits a web of nanofibers with many sub-micrometer-sized spheres over the whole substrate. A higher magnification (Fig. 1b) indicates that in the hierarchical structure there are many nanoknots linking the nanofibers together, as well as many nanoscale protuberances covering each e f sub-microsphere. The corresponding atomic force microscopy (AFM) images (Figs. 1c,d with different magnifications) confirm the special structure of this composite film. The formation of this structure would most likely be caused by the insufficiently fast stretching during the whipping and bending process of the jet. The diameters of the sub-microspheres, nanoknots, and nanofibers are about 820300, 10040, and 4020 nm, respectively. These special structures on the film are Figure 1. a) SEM image of an electrospun PANI/PS composite film with lotus-leaf-like somewhat similar to those on the surface of the structure prepared from a 3.72 wt.-% PS:ABSA/DMF solution. b) Magnified view of a single sub-microsphere from (a). c,d) Atomic force microscopy images of the electrospun self-cleaning lotus leaf, and are expected to show PANI/PS composite film. e) The shape of a water droplet on a PANI/PS composite film unusual wettabilities. Figure 1e shows the shape with CA of 166.5. f) The sliding behavior of a water droplet on a PANI/PS composite film. of a pure water droplet (about 4 lL in volume) on a PANI/PS composite film with a CA of about desired pH on top of the film. Over a wide pH range, from 0.25 166.5 2.4; the obtained film is superhydrophobic. Moreover, to 13.68, no obvious fluctuation in CA was observed, within a much smaller SA (less than 5 for the water droplet) was oberror, and the CAs ranged from 162.0 1.1 to 162.4 2.9, inditained on such a film (Fig. 1f). Water droplets can roll easily on cating that pH has no effect on the superhydrophobicity of the a slightly tilted surface. PANI/PS composite film. A low SA of less than 5 for the acidic and basic droplets was also obtained. These results indicate that the PANI/PS composite film has stable superhydro2.2. Stable Superhydrophobicity and Conductivity of PANI/PS phobicity, not only in pure water, but also in corrosive acids Composite Films and bases, which is very important for expanding its application. Our work focuses on the superhydrophobicity and conducThe other valuable result is that there was no change in the tivity of PANI/PS composite films in nitric acidic, sodium green color of the PANI/PS composite film on the addition of hydroxide solution, and oxidizing solutions because the tradithe acidic and basic droplets, although the conductivity of the tional, conductive form of PANI can be de-doped to the insulating state via oxidation or treatment with a base.[16] Figure 2a original PANI may change easily by acid doping/base de-doping. The conductivities of the PANI/PS composite films were shows the relationship between pH and CA on a PANI/PS measured by using a standard four-probe method at the same films; the CA was measured by placing a water droplet with the

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quickly, within several seconds, showing a superhydrophilic surface with a 1.6 CA of 0 (Fig. 2d). Moreover, the conductive state of the flat PANI/PS film 1.4 160 can be de-doped to the blue, insulating 1.2 state via treatment with a base or oxidizing solution. The flat film made by 1.0 140 spin-coating fails to produce a positive 0.8 result both in its conductivity and 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 superhydrophobicity. pH Values pH Values UV-vis absorption spectra of a PANI/PS composite film and those d c treated by acidic, basic, and oxidizing solutions were measured, and are shown in Figure 2e. Three bands at about 315 nm, 432 nm, and 800 nm were observed. The band around 315 nm can be attributed to the overlap of the pp* transition of the benzoid rings of PANI and the azobenzene moiety.[21] The band at about 432 nm is related to the np* transi0.8 1.6 tion of the azobenzene moiety. The 315nm e f 1.4 318 nm 0.7 band at about 800 nm with a long tail 1.2 is assigned to the polaron transition, 0.6 1.0 which typically characterizes protona0.5 0.8 tion, and is identical to that of the 442 nm 621 nm 0.6 4 432nm 0.4 emeraldine salt form of PANI. For the 800nm 0.4 1 flat PANI/PS film, on the other hand, 0.3 2 3 2 0.2 3 the bands for untreated and acidic-so1 4 0.2 0.0 lution-treated samples are similar to 300 400 500 600 700 800 900 1000 300 400 500 600 700 800 those of the PANI/PS composite films. Wavelength (nm) Wavelength (nm) However, three bands at about 318 nm, 442 nm, and 621 nm corresponding to Figure 2. a) The relationship between pH and the CA on a PANI/PS composite film prepared from 3.72 wt.-% PS solution. b) The relationship between pH and conductivity of a PANI/PS composite film the typical PANI and ABSA absorpprepared from a solution of 3.72 wt.-% PS. c) The shape of a 1 mol L1 ammonium persulfate solution tions were observed in the UV-vis abdroplet on a PANI/PS composite film, with a CA of about 161.3. d) The shapes of water droplets on a sorption spectrum of the samples flat PANI/PS film with a CA of about 0. e,f) UV-vis spectra of PANI/PS composite films (e) and flat treated with basic and oxidizing soluPANI/PS films (f): 1: untreated film; 2: with a droplet of 0.2 M hydrochloric acid; 3: with a droplet of 1.0 % ammonia; and 4: with a droplet of 1.0 % hydrogen peroxide solution. tions (Fig. 2f), indicating the de-doped state. The absorption peaks at around 318 nm and 621 nm are attributed to the pp* transition and the exciton-like transition from the position as that used to measure the CAs at room temperature. benzenoid rings, to the quinoid rings, respectively, while that at Figure 2b shows the relationship between conductivity and pH, 442 nm is assigned as the np* transition of the azobenzene from which we can see that there is no evident fluctuation of moiety.[22,23] conductivity, within error, over a wide range of pH conditions. These results confirm that both the superhydrophobicity and conductivity of the film are stable over a wide pH range. In addition, the superhydrophobicity and conductivity of PANI/PS 2.3. Mechanism for the Special Surface Properties composite films are maintained even when oxidizing solutions, The obtained PANI/PS composite films have excellent, such as ammonium persulfate and hydrogen peroxide stable superhydrophobicity and conductivity over a wide pH solutions, are dropped on it (Fig. 2c). These results were reprorange and also in oxidizing solutions. There are two reasons for ducible, even after the film was kept in an ambient environthis: i) the surface composition and ii) the surface morphology. ment for several months, which shows their excellent stability. On the one hand, the rough PANI/PS composite film and the For comparison, a PANI/PS film with a flat surface was preflat PANI/PS film have different surface compositions, which pared by spin-coating, using the same precursor as that used to form the lotus-leaf-like PANI/PS composite film. However, can be confirmed by angle-resolved X-ray photoelectron spectroscopy (ARXPS). As can be seen from Figure 3a of the surwhen a water droplet touches the surface of this film, it spreads
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vey XPS spectra of the PANI/PS composite film collected at a takeoff angle 90, the characteristic signals of carbon, oxygen, nitrogen, and sulfur were detected. The conjugated backbone of PANI is the only nitrogen-containing component of the composite, thus the ratio of carbon to nitrogen can be used as an unambiguous marker for the surface component. Figures 3b,c present the C 1s and N 1s regions, respectively, in the XPS spectra of the composite film collected at takeoff angles of 90, 30, and 15 relative to the sample surface. The C 1s spectra display a main peak at 284.6 eV, which can be assigned to carbon atoms bonded only to carbon or hydrogen atoms, and an additional peak at 291.5 eV attributed to multielectronic transitions involving pp* transitions arising from the presence of the aromatic rings. The N 1s region shows two peaks at 400.1 and 399.9 eV, at a takeoff angle of 15, which are characteristic of doped PANI. As can also be seen from Figures 3b,c, the inten-

sity of the C 1s peaks increases while that of N 1s peaks decreases with decreasing takeoff angle. The ratio of carbon to nitrogen, which was easily calculated from the survey spectra, was 68.70, 73.98, and 76.97, respectively, for takeoff angles of 90, 30, and 15. Because the effective sampling depth decreases with decreasing takeoff angle,[24] it can be deduced that the component in the top surface is mainly low-surface-energy carbon, coming from both PANI and PS, probably based on the self-organization effect caused by electrospinning.[18,19] As a result, the surface free energy of the composite film is reduced, and its conductivity remains stable. For comparison, it can be calculated from the survey spectra of the flat PANI/PS film in Figure 3d that the ratio of C to N is 12.41:1 on the surface, which is higher than that of the PANI/PS composite film. This demonstrates that there is a significant increase in N content, possibly caused by the exposure of the PANI of the flat PANI/

C1s

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I

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405 400 395 Binding Energy (eV)

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900 800 700 600 500 400 300 200 100 Binding Energy (eV)

Figure 3. a) Survey XPS spectrum of a PANI/PS composite film prepared from a solution of 3.72 wt.-% PS at a takeoff angle of 90 relative to the surface of sample. b) ARXPS spectra of C 1s of the PANI/PS composite film, which shows the dependence of the C 1s peak of the composite film on the takeoff angle as measured at 90, 30, and 15. Inset: magnification of the 284.6 eV peak. c) ARXPS spectra of N 1s of the PANI/PS composite film for takeoff angles of 90, 30, and 15 relative to the surface of sample. d) Survey XPS spectrum of the flat film (formed by spin-coating using the same solution as (a)) at a takeoff angle 90 relative to the surface of sample.

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PS film on the surface, resulting in superhydrophilicity and an insulating state in basic and oxidizing solutions. On the other hand, regarding the surface morphology, the PANI/PS composite film exhibits a special hierarchical structure, which is rough enough to let air fill in the vacancies between individual nanostructures, so that the contact area between water and the film can be minimized. For a thorough understanding of the hydrophobicity of the PANI/PS composite film, theoretical considerations are necessary. The CA on the hierarchical surface structure of the PANI/PS composite film (hr) can be expressed by Equation 1.[25] coshr = f1coshf2 (1)

Here (h) and (hr) are the CAs of the flat PANI/PS film and of the hierarchical surface structure of the PANI/PS composite film, respectively, and 1 and 2 are the fractions of PANI/PS surface and air in contact with water, respectively (i.e., 1 + 2 = 1). It is easy to deduce from Equation 1 that increasing 2 increases hr, that is, the fraction of air in the surface is an important factor in determining the superhydrophobicity of the film. According to Equation 1, the value of f2 of the PANI/PS composite film can be calculated to be 0.986, indicating that the fraction of air in the surface is high enough to result in superhydrophobicity. This indicates that the special hierarchical morphology of the PANI/PS composite film plays an important role in its superhydrophobicity.

Figure 4. SEM images of PANI/PS composite films prepared from solutions with different concentrations of PS [wt.-%]: a) 4.53; b) 5.26; c) 6.09; and d) 7.10.

2.4. Controllable Surface Morphology and Surface Properties It is important that the morphology can be well controlled by changing the PS content. A PS content ranging from 3.72 to 7.10 wt.-% allows eletrospinning; in other words, when no PS or too much of PS is added to a PANI:ABSA solution, the solutions viscosity is not suitable for eletrospinning, and thus nanofibers will not form. The SEM images in Figures 4ad show the variation in morphology as the PS concentration in solution increases (i.e., at 4.53, 5.26, 6.09, and 7.10 wt.-%, respectively). It can be seen that the number of microspheres on the nanofibers decreases with an increasing concentration of PS in the electrospinning solution. This is because changing the concentration of the electrospinning solution can vary the solutions viscosity,[20] which increases as the concentration of PS increases. As the viscosity of the solution increases, the microspheres becomes bigger, and the average distance between the microspheres on the fibers also increases, as can be seen in Figures 4a,b. Meanwhile, the microspheres change from being spherical to being spindle-like, and the surface of the nanofibers becomes smooth when the PS concentration in solution is 6.09 wt.-% (Fig. 4c). Finally, the microspheres disappear at a PS concentration of 7.10 wt.-% (Fig. 4d). As the surface morphology is a very important factor in the determination of surface properties, changing the PS content can also control the superhydrophobicity and conductivity of the PANI/PS composite film. The conductivity depends strongly on the fraction of PANI in the composite. The solid 572 www.afm-journal.de

line in Figure 5 indicates the relationship between PS concentration in solution and the conductivity. The conductivity of the PANI/PS composite films decreases with the addition of PS to the electrospinning solution, and there is no significant change in conductivity after the concentration of PS reaches at about 5 wt.-%. The obtained conductivities are in the range of 104 105 S cm1. The dashed line in Figure 5 shows the relationship between PS concentration and superhydrophobicity: the CA for water decreases slightly from 166.5 2.4 to 154 2.1 because of the decrease in roughness caused by increasing the PS content in the electrospinning solution. However, a surface with a high CA does not always show a low SA. The SA of these PANI/PS composite films changes with increasing PS content, and a typical water droplet on the surface rolls off easily, even when there is little tilt on the surface, with films made from solutions with 3.72 and 4.53 wt.-% PS. In contrast, a typical water drop placed on a composite film formed from a solution with 7.10 wt.-% PS clings to the surface of the film, even when the film was tilted until vertical. The observed behavior of different SAs can be understood in terms of the contact-line structure formed at the interfaces between solid, liquid, and

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12 10 8 6 4 2 0 4 5 6 PS Content (wt-%) 7

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Figure 5. The relationship between the PS concentration in solution and the CAs ( , dotted line) and conductivity ( , solid line).

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air.[3,8a] For films with a low SA, it is expected that the threephase contact lines are contorted on the surface and extremely unstable, owing to the hierarchical structure of the surface, which effectively traps sufficient air to reduce the sliding resistance drastically. For films with a high SA, however, the proper surface roughness makes the three-phase contact lines change into solidliquid contact lines on the surface, which are comparatively smooth and stable, resulting in the effective intrusion of water into the surface nanostructures because of the droplets weight. Accordingly, the experimental results show that the SA is strongly affected by the surface structure. For comparison, the flat morphology and the superhydrophilicity of the spin-coated film did not change by varying the PS content. Furthermore, it is known that other electrospinning parameters, such as elecrospinning voltage, surface tension, and solution conductivity, significantly influence the morphology of the electrospun film, and therefore affect the superhydrophobicity and conductivity of PANI/PS composite films. Detailed results will be reported elsewhere.

electrode. The working distance (WD) between the tip and collector was 10 cm. A voltage of 18 kV was applied, and composite films with different PS content were collected on glass slides placed on the surface of aluminum foil. The composite films were green. The structural features of the electrospun PANI/PS composite films were verified using a JEOL-6700F field-emission scanning electron microscope and Seiko-3800N atomic force microscope. UV-vis spectra were recorded on a HITACHI 4100 UV-vis spectrophotometer. XPS spectra were conducted on a VG ESCALAB 220i-XL instrument with a monochromatic Al Ka X-ray source (1486.6 eV). CAs and SAs were measured on a dataphysics OCA20 contact-angle system at ambient temperature. Average CAs and SAs were obtained by measuring the same sample at five different positions. The conductivity of the PANI composite films were recorded using a standard four-probe method at room temperature. Precise pH values were measured using DELTA 320 pH meters at ambient temperature. Received: July 13, 2005 Final version: October 13, 2005 Published online: January 19, 2006

[1] T. Nishino, M. Meguro, K. Nakamae, M. Matsushita, Y. Ueda, Langmuir 1999, 15, 4321. [2] a) T. Onda, S. Shibuichi, N. Satoh, K. Tsujii, Langmuir 1996, 12, 2125. b) S. Shibuichi, T. Onda, N. Satoh, K. Tsujii, J. Phys. Chem. 1996, 100, 19 512. c) L. Zhai, F. C. Cebeci, R. E. Cohen, M. F. Rubner, Nano Lett. 2004, 4, 1349. d) X. Zhang, F. Shi, X. Yu, H. Liu, Y. Fu, Z. Wang, L. Jiang, X. Li, J. Am. Chem. Soc. 2004, 126, 3064. [3] a) W. Chen, A. Y. Fadeev, M. C. Hsieh, D. ner, J. Youngblood, T. J. McCarthy, Langmuir 1999, 15, 3395. b) T. J. McCarthy, D. ner, Langmuir 2000, 16, 7777. [4] a) H. Y. Erbil, A. L. Demirel, Y. Avci, O. Mert, Science 2003, 299, 1377. b) N. J. Shirtcliffe, G. McHale, M. I. Newton, C. C. Perry, Langmuir 2003, 19, 5626. c) B. He, N. A. Patankar, J. H. Lee, Langmuir 2003, 19, 4999. d) J. Genzer, K. Efimenko, Science 2000, 290, 2130. [5] a) E. Nun, M. Oles, B. Schleich, Macromol. Symp. 2002, 187, 677. b) N. A. Patankar, Langmuir 2004, 20, 8209. c) A. Marmur, Langmuir 2004, 20, 3517. d) J. Han, D. Lee, C. Ryu, K. Cho, J. Am. Chem. Soc. 2004, 126, 4796. [6] a) J. Bico, C. Marzolin, D. Qur, Europhys. Lett. 1999, 47, 220. b) R. Blossey, Nat. Mater. 2003, 2, 301. c) A. Lafuma, D. Qur, Nat. Mater. 2003, 2, 457. d) S. Herminghaus, Europhys. Lett. 2000, 52, 165. [7] a) K. Tadanaga, N. Katata, T. Minami, J. Am. Ceram. Soc. 1997, 80, 1040. b) S. Veeramasuneni, J. Drelich, J. D. Miller, G. Yamauchi, Prog. Org. Coat. 1997, 31, 265. c) Y. Wu, H. Sugimura, Y. Inoue, O. Takai, Chem. Vapor Deposition 2002, 8, 47. [8] a) S. Li, H. Li, X. Wang, Y. Song, Y. Liu, L. Jiang, D. Zhu, J. Phys. Chem. B 2002, 106, 9274. b) L. Feng, Z. Yang, J. Zhai, Y. Song, B. Liu, Y. Ma, Z. Yang, L. Jiang, D. Zhu, Angew. Chem. Int. Ed. 2003, 42, 4217. c) L. Jiang, Y. Zhao, J. Zhai, Angew. Chem. Int. Ed. 2004, 43, 4338. [9] a) W. Barthlott, C. Neinhuis, Planta 1997, 202, 1. b) C. Neinhuis, W. Barthlott, Ann. Bot.London 1997, 79, 667. c) L. Feng, S. Li, Y. Li, H. Li, L. Zhang, J. Zhai, Y. Song, B. Liu, L. Jiang, D. Zhu, Adv. Mater. 2002, 14, 1857. d) Q. Xie, J. Xu, L. Feng, L. Jiang, W. Tang, X. Luo, C. C. Han, Adv. Mater. 2004, 16, 302. e) R. Furstner, W. Barthlott, C. Neinhuis, P. Walzel, Langmuir 2005, 21, 956. [10] a) A. Nakajima, K. Hashimoto, T. Watanabe, Monatsh. Chem. 2001, 132, 31. b) M. Miwa, A. Nakajima, A. Fujishima, K. Hashimoto, T. Watanabe, Langmuir 2000, 16, 5754. c) Z. Z. Gu, H. Uetsuka, K. Takahashi, R. Nakajima, H. Onishi, A. Fujishima, O. Sato, Angew. Chem. Int. Ed. 2003, 42, 894. [11] J. Yue, A. J. Epstein, J. Am. Chem. Soc. 1990, 112, 2800. [12] S. J. Pomfret, P. N. Adams, N. P. Comfort, A. P. Monkman, Adv. Mater. 1998, 10, 1351. [13] A. J. Epstein, A. G. MacDiarmid, Synth. Met. 1995, 69, 179.

3. Conclusions
A PANI/PS composite film with a lotus-leaf-like structure has been prepared by simple electrospinning on a large scale at low cost. The film is superhydrophobic, with both a high CA and low SA, showing a self-cleaning effect. It is very significant that the superhydrophobicity, self-cleaning effect, and conductivity are well maintained over a wide range of pH conditions and also in oxidizing solutions. Results show that the PS content can strongly influence the morphology of the PANI/PS composites film, which thus display different superhydrophobicities and conductivities. This is the first example of a superhydrophobic surface with conductivity available in acidic and basic solutions, as well as in oxidizing solutions, using the conductive state of PANI; this may give rise to new perspectives in practical applications. Furthermore, the strategy used herein may provide an easy method for fabricating superhydrophobic films made of self-cleaning, functional polymers for use in many fields.

4. Experimental
Emeraldine-base (EB) PANI (3 g; JiLin Zheng Ji Science and Technology Development Ltd.), was added to DMF (200 mL) with stirring at 40 C. This solution was stirred for 12 h and then filtered using absorbent cotton to remove any particulate matter. A DMF solution of EB was doped with about 0.45 wt.-% ABSA (Shanghai Chemical Reagent Co.), and the green conducting form was obtained (PANI:ABSA). Different amounts of PS (Aldrich), ranging from 3.72 to 7.10 wt.-%, were then poured into the doped PANI over a period of 4 h, with magnetic stirring, to obtain a homogeneous solution. All chemicals were used as received without any further purification. The electrospinning solution was loaded into a 2 mL hypodermic syringe perpendicular to a 0.8 mm diameter stainless-steel needle. The positive electrode of a high-voltage power supply was placed onto the tip of the needle. The negative electrode was connected to a metallic collector wrapped with aluminum foil, which served as the counter

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Adv. Funct. Mater. 2006, 16, 568574