INSTITUTE OF PHYSICS PUBLISHING Nanotechnology 17 (2006) 32593263

NANOTECHNOLOGY doi:10.1088/0957-4484/17/13/030

Super-hydrophobic surfaces from a simple coating method: a bionic nanoengineering approach

Yuyang Liu, Xianqiong Chen and J H Xin1
Nanotechnology Center, ITC, The Hong Kong Polytechnic University, Hong Kong, Peoples Republic of China E-mail: tcxinjh@inet.polyu.edu.hk

Received 28 March 2006, in nal form 9 May 2006 Published 12 June 2006 Online at stacks.iop.org/Nano/17/3259 Abstract Inspired by the self-cleaning behaviour of lotus leaves in nature, we developed a simple coating method that can facilitate the bionic creation of super-hydrophobic surfaces on various substrates, thus providing a feasible way of fabricating super-hydrophobic surfaces for civil and industrial applications. Micronanoscale binary structured composite particles of silica/uoropolymer were prepared using an emulsion-mediated solgel process, and then these composite particles were applied to various substrates to mimic the surface microstructures of lotus leaves. Super-hydrophobic surfaces with a water contact angle larger than 150 are obtained, and these super-hydrophobic surfaces are expected to have potential applications for rusting-resistant, anti-fog and self-cleaning treatments. (Some gures in this article are in colour only in the electronic version)

1. Introduction
Learning from nature is an important source of new techniques and advanced materials. A typical example of this is the creation of super-hydrophobic surfaces by bionic copying of the microstructure of lotus leaves [1, 2]. The super-hydrophobic behaviour of lotus leaves, known as the lotus-leaf effect or self-cleaning effect, is found to be a result of the hierarchical rough structure, as well as the wax layer present on the leaf surface [3]. It has been well-established that the wettability of a solid surface is governed by both the surface chemical composition and the surface geometrical microstructures [35]. Inspired by the novel repellent properties of lotus leaves, scientists have created articial super-hydrophobic surfaces by tailoring the surface topography and using techniques such as anodic oxidation [69], electrodeposition and chemical etching [1012], plasma etching [13, 14], laser treatment [15, 16], electrospinning [1719], chemical vapour deposition [2023], solgel processing [2426], and so on. To fabricate a surface with a water contact angle larger than 150 , two key factors must be considered. Surface energy and surface roughness are
1 Author to whom any correspondence should be addressed.

the dominant factors for wettability. When the surface energy is lowered, the hydrophobicity is enhanced. However, even a material with the lowest surface energy gives a water contact angle of only around 120 [27]. For higher hydrophobicity, providing an appropriate surface roughness is required. To create a super hydrophobic surface, a common two-step process has been developed and utilized by many researchers. In this two-step process, they usually create a rough surface (e.g. with a fractal structure) and then modify the surface with materials of low surface free energy, such as uorinated or silicon compounds. This two-step process has been widely used for the fabrication of super-hydrophobic surfaces on special solid substrates. However, either special equipment or complex process control is required in many of the above cited cases. Little research is focused on the development of a simple way of fabricating super-hydrophobic surfaces on various substrates. Up to now, there have been few previous report on the fabrication of super-hydrophobic surfaces via simple coating methods that can simultaneously construct a solid surface with appropriate surface roughness and low surface energy. The development of nanotechnology and nanoengineering has provided a promising way of constructing the surface properties of a solid surface at atomic, molecular, and 3259

0957-4484/06/133259+05$30.00

2006 IOP Publishing Ltd Printed in the UK

Y Liu et al

supramolecular levels. Several critical research elds (such as processing, catalytic, optical, actuation, electrical, mechanical, etc) have already started to benet from new technological advancements in the area of nanotechnology, particularly through the use of nanomaterials. Recently, materials with micronanoscale binary structures have received increasing attention, mainly due to their potential applications in photocatalysis, surface-enhanced Raman scattering, electron storage, and the fabrication of super-hydrophobic and superhydrophilic surfaces [28]. A super-hydrophobic surface of micronanoscale binary structured composite particles provides a convenient way of realizing the simultaneously combination of low surface energy and surface roughness at the micro-to nano-levels. Shi et al [28] reported the fabrication of a lotus-like micronanoscale binary structured surface with super-hydrophobic behaviour from copper phosphate dehydrate materials. To extend the application of this new technique to a more extensive eld, more scalable and achievable methods are desired. Herein, we developed a new one-step method for the fabrication of super-hydrophobic surfaces from micronanoscale binary structured composite particles of common commercial raw materials.

3. Results and discussion

The morphologies of the composite particles and lms formed from the composite particles are shown in gure 1. Figure 1(a) shows the SEM picture of the lm formed from the composite particles. It reveals that the lms are composed by assembling microsized particles, and these microsized particles will provide an appropriate surface roughness for the treated substrates. Figure 1(b) presents an amplied SEM picture of the composite particles, indicating that the surfaces of the microsized particles are studded with nanoparticles, thus forming the resultant micronanoscale binary structures. These micronanoscale binary structured composite particles have beautiful strawberry-like shapes. Figure 1(c) shows the amplied section of the particles surface selected from gure 1(a), indicating that the surfaces of the microsized particles are covered with ne nanoparticles whose diameters are in the range 3050 nm. The pictures in gure 1 indicate that, after using the emulsion-mediated solgel procedure, the silica matrix and uoropolymer are combined together at the nanoscale, forming the nal micronanoscale binary structured compsite particles. A potential mechanism for the formation of the micronanoscale binary structured composite particles is proposed in gure 2. As shown in gure 2, when the silica precursor methyltrimethoxysilane (MTMS) was introduced into uoropolymer latex, MTMS oil drops were rst surrounded and stabilized by emulsier molecules and polymer latex particles (gure 2, step 1) [30]. In this step, the superuous emulsier molecules existing in the emulsion system assemble around the drops of MTMS, stabilizing the MTMS drops in the system. At the same time, part of the polymer nanoparticles can also be adsorbed onto the oilwater interface [30], working as a solid dispersant to stabilize the MTMS drops in the system. So, the particle size of silica spheres is inuenced greatly by the emulsier concentration of the latex. As shown in gure 2, the particle size of the silica solid particles can also be adjusted through the addition of emulsiers. However, emulsiers are hydrophilic species, and the increase in emulsiers would reduce the hydrophobicity of the resultant coating greatly. With the progress in hydrolysis and condensation of MTMS, silica solid particles formed, and then these surface-surrounded uoropolymer particles were immobilized onto the surface of the nal silica microparticles, thus forming the micro nanoscale binary structured composite particles (gure 2, step 2). Because of the crosslinking reaction of 3-GPTS with the hydroxy group of the silica matrix and the hydroxy group of the uoropolymer, these uoropolymer nanoparticles are immobilized onto the surface of silica microspheres. The wettabilities of the composite particle lms were evaluated using a water contact meter (Tantec, Schaumburg, IL, USA). Figure 3 records the relationship between the surface roughness and water contact angle of the tinplate substrates. Figure 3(a) shows the surface morphology of the original tinplate substrate and the image of the corresponding water contact angle. It reveals that the surface of the original tinplate substrate is considerably smooth, and the water contact angle of the original tinplate substrate is about 22 . The water drop is fully spread on the substrate. Figure 3(b) presents the surface morphology of the tinplate substrate, having been

2. Experimental section
Two uoropolymer latices containing hydroxyl groups were used in this research. Latex A is a lab-synthesized latex according to a method in the literature (cationic, 30% solid content by weight, with particle size changing from 60 to 158 nm) [29]. The particle size of the latices can be controlled by changing the weight ratio of monomers to emulsiers. The particle sizes of the latices were determined by dynamic light scattering (DLS) using a 90 Plus particle size analyser (Brookhaven Instruments Corp.) equipped with a diode laser operating at 658.0 nm at 20 C after the latex was diluted by deionized water. Latex B, in contrast, is a commercial product from AGC Chemicals America Inc. under the trademark AG710 (nonionic, 30% solid content by weight). The preparation of the micronanoscale binary structured silica/uoropolymer composite particles can be accomplished as follows. In a typical procedure, a 10 ml emulsion of latex A (or latex B) was diluted with 90 ml of water, and then the pH value of the emulsion was adjusted to 5 using acetic acid. A 2.5 ml silica precursor methyl-trimethoxysilane (MTMS, Aldrich, 98%) was dropped into the diluted emulsion of latex A (or latex B) and then stirred for 24 days at room temperature to form the micronanoscale binary structured particles. The particle size of the silica spheres can be controlled by changing the weight ratio of silica precursor to latex. To improve the coalescence between the silica particles and the uoropolymer matrix, 0.1 g of crosslinking agent 3-glycidoxypropyltrimethoxysilane (3-GPTS) was introduced into reaction system. The nal solid content of the nal suspension was measured using a drying-weighing method. The silica/uoropolymer composite suspensions were diluted to 25% (weight, %) and were then applied to tinplate substrates using a spin-coating method (KW-4A Spin Coater, Xiamen, China; 2000 rpm, 20 s). The morphologies of the composite particles and the lms were investigated using eldemission scanning electron microscopy (FE-SEM, JEOL JSM6335F). 3260

Super-hydrophobic surfaces from a simple coating method

(a)

(b)

(c)

Figure 1. The surface morphology of the micronanoscale binary structured silica/uoropolymer composite particles ((a) bar = 10 m; (b) bar = 500 nm; (c) bar = 200 nm).

treated with uoropolymer latex, indicating that the surface of the tinplate substrate becomes smoother because of the polymer coatings and that the water contact angle of the treated tinplate substrate has been improved greatly (from 22 to approximately 110 ). Figure 3(c) shows that the surface structure of the tinplate substrate have been treated with the silica/uoropolymer micronanoscale binary structured particle composite and a corresponding water contact angle. It reveals that the surface of the tinplate substrate has been covered with assembling silica/uoropolymer composite particles, which provides an appropriate surface roughness of the substrate. Because the surface of the silica micro-particles are covered with low-surface-energy uoropolymer, as a synergistic result, the water contact angle has been improved to 161 correspondingly. For comparison, a mixture of silica nanoparticles and uoropolymer latex was also applied to the same substrate using the same spin-coating method. Figure 3(d) shows the surface morphology of the substrate covered with a layer of silica nanoparticles/uoropolymer blended coating. It reveals that silica nanoparticles have assembled together, binding by the uoropolymer latex, correspondingly, with a water contact angle of about 146 . The results in gure 3 reveal that the wettability of a solid surface is not only governed by the surface energy of the material but also by the surface roughness of the solid. Obviously, the micronanoscale binary structured composite particles can give a higher water contact angle. As lots of air was trapped in the cavities between binary structured particles, a water drop on such a coating could only make contact with the tips of the nanosized uoropolymer particles. Therefore, air itself served as part of the surface, and the interface beneath the

fluoropolymer latex particles

Silica precursor

(1)

(2)

emulsifier molecules

Silica solid particles

Figure 2. A potential mechanism for the formation of the micronanoscale binary structured composite particles.

water drop could be considered a composite surface. Thus, the water put on the super-hydrophobic surface was likely resting on an air cushion. The microstructure of the coating and the corresponding high water contact angle conrmed that we had successfully mimicked the lotus leaf using a simple coating method. What is more, such a super-hydrophobic surface was obtained by using just common commercial raw materials without complex procedures. As an example of a practical application, we explored the application of this technique in protection from iron rusting. Iron is one of the most widely used metal materials in the world, from tin cans to steel bridges. The rusting of iron materials occurs frequently in nature and greatly reduces the strength of iron and steel structures, and is, therefore, a major economic and safety problem. Every year, the economic importance of rusting is such that it has been estimated that the cost of corrosion is over 1% of the worlds economy. 3261

Y Liu et al

(a)

(b)

(c)

(d)

Figure 3. The relationship between surface roughness and water contact angle on tinplate substrates. Surface morphology of the original substrate ((a) bar = 5 m), uoropolymer surface coated substrate ((b) bar = 5 m), silica/uoropolymer micronanoscale binary structured composite particles treated substrate ((c) bar = 5 m), and silica nanoparticles/uoropolymer mixture coated substrate ((d) bar = 2 m). Optical images of the water contact angles were inserted in the top-right corner of the SEM images, respectively.

Figure 4. Optical image of drying water beads on iron substrate treated with the silica/uoropolymer micronanoscale binary structured composite particles.

a new super-hydrophobic surface on iron substrates for the protection of iron materials from rusting. Figure 4 shows an optical image of water drops on an iron substrate whose surface has been treated with the silica/uoropolymer micronanoscale binary structured composite particles. The picture reveals that water drops converge together, forming drying water beads. Given a small slope angle of 13 , these water beads will slip away easily from the iron substrate. The water-repellent behaviour of surfaces created using this simple coating method hints that this new technique can easily be applied to various substrates to create super-hydrophobic coatings for rustingresistant, anti-fog and self-cleaning applications. The mechanical stabilitiy of the composite coating (e.g. fastness, impact strength) on different substrates is of great importance for the practical application of this new technique. To improve the mechanical stability of the composite coating on different substrates, two general procedures can be employed to perfect the use of the composite coating. On the one hand, the composite coating can be cured at 120170 C to enhance the fusion between the silica and the uoropolymer matrix and the adhesion between the uoropolymer and the substrates. On the other hand, a commercial crosslinking agent can be used as a reinforcing ingredient, adding to the silica/foluopolymer micronanoscale binary structured composite to improve the mechanical stability of the superhydrophobic surface coating on different substrates.

Various techniques have been proposed and developed for the protection of iron materials from rusting, including protective coatings, the alloying method and the electrochemical method. The rusting of iron consists of the formation of hydrated oxide, Fe(OH)3 or FeO(OH), and is an electrochemical process that requires the presence of water, oxygen and an electrolyte. In the absence of any one of these three conditions, rusting does not occur to any signicant extent. In air, a relative humidity of over 50% provides the necessary amount of water and, at 80%, corrosion is severe. On the basis of the above principle, we can utilize the mechanism of the so-called lotus effect to produce 3262

Super-hydrophobic surfaces from a simple coating method

4. Conclusions
Micronanoscale binary structured composite particles have been synthesized by using a novel emulsion-mediated sol gel process. Surface composite coatings of micronanoscale binary structured composite particles can mimic the surface microstructures of lotus-leaves and thus provide superhydrophobic behaviour. These micronanoscale binary structured particle composites can be applied to various common substrates by using simple spray-coating or spincoating methods to create super-hydrophobic surfaces with a water contact angle larger than 150 . Compared with other complex processes, this surface coating method is simpler and manoeuverable for practical rusting-resistant, anti-fog and selfcleaning applications.

Acknowledgment
This project was supported by the Innovative Technology Funding ZP0D from the Hong Kong SAR government.

References
[1] Sun T L, Feng L, Gao X F and Jiang L 2005 Acc. Chem. Res. 38 644 [2] Sun M H, Luo C X, Xu L P, Ji H, Qi Q Y, Yu D P and Chen Y 2005 Langmuir 21 8978 [3] Marmur A 2004 Langmuir 20 3517 [4] Barthlott W and Neinhuis C 1997 Planta 202 1 [5] Neinhuis C and Barthlott W 1997 Ann. Bot. 79 667 [6] Tsujii K, Yamamoto T, Onda T and Shibuichi S 1997 Angew. Chem. Int. Edn 36 1011 [7] Shibuichi S, Yamamoto T, Onda T and Tsujii K 1998 J. Colloid Interface Sci. 208 287 [8] Narita M, Kasuga T and Kiyotani A 2000 J. Japan. Inst. Light Met. 50 594

[9] Thieme M, Frenzel R, Schmidt S, Simon F, Hennig A, Worch H, Lunkwitz K and Scharnweber D 2001 Adv. Eng. Mater. 3 691 [10] Shirtcliffe N J, McHale G, Newton M I and Perry C C 2005 Langmuir 21 937 [11] Zhang X, Shi F, Yu X, Liu H, Fu Y, Wang Z Q, Jiang L and Li X Y 2004 J. Am. Chem. Soc. 126 3064 [12] Shi F, Wang Z and Zhang X 2005 Adv. Mater. 17 1005 [13] Ogawa K, Soga M, Takada Y and Nakayama I 1993 Japan. J. Appl. Phys. 2 32 L614 [14] Olde Riekerink B M, Terlingen J G A, Engbers G H M and Feijen J 1999 Langmuir 15 4847 [15] Khorasani M T, Mirzadeh H and Kermani Z 2005 Appl. Surf. Sci. 242 339 [16] Khorasani M T and Mirzadeh H 2004 J. Appl. Polym. Sci. 91 2042 [17] Jiang L, Zhao Y and Zhai J 2004 Angew. Chem. Int. Edn 43 4338 [18] Acatay K, Simsek E, Ow-Yang C and Menceloglu Y Z 2004 Angew. Chem. Int. Edn 43 5210 [19] Ma M, Hill R M, Lowery J L, Fridrikh S V and Rutledge G C 2005 Langmuir 21 5549 [20] Lau K S, Bico J, Teo K B, Chhowalla M, Amaratunga G A, Milne W I, McKinley G H and Gleason K K 2003 Nano Lett. 3 1701 [21] Liu H, Feng L, Zhai J, Jiang L and Zhu D 2004 Langmuir 20 5659 [22] Wu Y, Bekke M, Inoue Y, Sugimura H, Kitaguchi H, Liu C and Takai O 2004 Thin Solid Films 457 122 [23] Huang L, Lau S P, Yang H Y, Leong E S, Yu S F and Prawer S 2005 J. Phys. Chem. B 109 7746 [24] Tadanaga K, Kitamuro K, Matsuda A and Minami T 2003 J. Sol-Gel Sci. Technol. 26 705 [25] Nakajima A, Fujishima A, Hashimoto K and Watanabe T 1999 Adv. Mater. 11 1365 [26] Shirtcliffe N J, McHale G, Newton M I and Perry C C 2003 Langmuir 19 5626 [27] Nishino T, Meguro M, Nakamae K, Matsushita M and Ueda Y 1999 Langmuir 15 4321 [28] Wu X and Shi G 2005 Nanotechnology 16 2056 [29] Ha J W, Park I J and Lee S B 2005 Macromolecules 38 736 [30] Binks B P and Lumsdon S O 2001 Langmuir 17 4540

3263