Applied Surface Science 257 (2010) 16661671

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Applied Surface Science

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

Preparation and properties of super-hydrophobic coating on magnesium alloy

Bo Yin a , Liang Fang a,b, , Jia Hu a , An-Qiong Tang a , Wen-Hou Wei a , Jiang He a
a b

Department of Applied Physics, Chongqing University, Chongqing 400044, China National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing 400044, China

a r t i c l e

i n f o

a b s t r a c t
The super-hydrophobic coating was successfully fabricated on the surface of magnesium alloy AZ31 by chemical etching and surface modication. The surface morphologies, compositions, wettability and corrosion resistance of the coating were investigated with SEM, XPS, contact angle measurement and electrochemical method, respectively. It shows that the rough and porous micronano-structure was presented on the surface of magnesium alloy, and the contact angle could reach up to 157.3 0.5 with sliding angle smaller than 10 . The super-hydrophobic coating showed a long service life. The results of electrochemical measurements showed that anticorrosion property of magnesium alloy was improved. The super-hydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it nds that only about 10% of the water surface is contacted with the metal substrate and the rest 90% is contacted with the air cushion. 2010 Elsevier B.V. All rights reserved.

Article history: Received 21 June 2010 Received in revised form 23 August 2010 Accepted 31 August 2010 Available online 9 September 2010 Keywords: Magnesium alloy Corrosion resistance Super-hydrophobic coating Electrochemical measurement

1. Introduction Wettability of solid surfaces is a very important property and is governed by both the chemical composition and the geometric structure of the surface [14]. The surface with a water contact angle (WCA) of more than 150 that repels water extremely is called a super-hydrophobic surface. Such surfaces have attracted much attention in recent years because of the superior aspects of physicochemical properties and important applications, such as water repellency, lubricity, self-cleaning and antifouling properties [2,58]. The super-hydrophobic phenomenon can be commonly observed in many plants in nature such as the lotus leaf, which is known as the Lotus effect. The recent studies demonstrate that super-hydrophobicity of lotus leaves principally results from the presence of binary structures at both micro- and nano-meter scales and the low energy wax-like materials on the surfaces [2,8]. The development of various fabrication techniques for superhydrophobic surfaces by simulating the surface of the lotus leaf is a pertinent subject. Super-hydrophobicity can be achieved by a combination of surface roughing and lowering surface energy [9,10]. Various fabrication methods have been reported, such as chemical etching [9], phase separation [11], plasma enhanced chemical vapor deposition [12], solgel processing [10], and so on. But, these techniques all require either special equipment or complex process control. A simple method of fabricating a super-hydrophobic sur-

Corresponding author at: Department of Applied Physics, Chongqing University, Chongqing 400044, China. Tel.: +86 023 65105870. E-mail address: fangliangcqu@yahoo.com.cn (L. Fang). 0169-4332/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2010.08.119

face on aluminum and its alloy was developed by Qian and Shen [9], but the procedure took a long time. In this way, the developments of super-hydrophobic surfaces on engineering materials become important, particularly in corrosion protection technology. Recently, owing to the low density, high-specic strength and good castability, research on ultralight magnesium and its alloys are enjoying a renaissance [13]. As the important structural materials for automotive and aerospace applications, magnesium and its alloys are one of the lightest engineering materials [14,15]. However, they have a drawback: extremely low corrosion resistance. This corrosion behavior prevents magnesium and its alloys from being used in practical applications. Up to now, many different methods have been developed to improve the corrosion resistance of magnesium alloys. Most of the strategies applied to the improvement of corrosion resistance of magnesium alloys have, as a target, the introduction of diamond-like carbon, Al, Ni, and other coatings on the surface of alloys, which will increase the weight of magnesium alloys [16,17]. A super-hydrophobic coating can suppress the contact of magnesium alloys with water to depress the progress of corrosion, so it is regarded as a promising technology for improving anticorrosion performance because it would inhibit the contact of a surface with water and environmental humidity. Therefore, the fabrication of super-hydrophobic coating on magnesium and its alloys is considered to be worthwhile. By now, a few methods have been reported about super-hydrophobic treatment on magnesium and its alloys surface. Jiang and co-workers fabricated a super-hydrophobic surface on MgLi alloy through chemical etching, followed by modication and annealing processes using uoroalkylsilane (FAS) molecules [18]. The super-hydrophobic sur-

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face greatly improved the corrosion resistance of the MgLi alloy. Nevertheless, this procedure also took a long time (about 14 h). Although the chemical etching method took a very short time to create surface texture, the time required to prepare the FAS coating was too long. Liang et al. obtained a stable biomimetic superhydrophobic surface on magnesium alloy by microarc oxidation pretreatment and chemical modication [19]. But this technique required complex process control. Therefore, a facile, simple and time-saving fabrication method which would be very advantageous for industrial large-scale production is needed. Herein, we described a simple and efcient method, which combines chemical etching and subsequent modication with oxosilane for the fabrication of super-hydrophobic coating on magnesium alloy. The procedure was fairly easy to carry out, and no special equipment was required. Moreover, the procedure was used without heat treatment and can be completed within several tens of minutes. In addition, the chemical stabilities of the super-hydrophobic coating on magnesium alloy were also examined from the viewpoints of durability and corrosion resistance. 2. Experimental 2.1. Materials Magnesium alloy AZ31 (composition: Al of 2.53.5 wt.%, Zn of 0.71.3 wt.%, Mn of 0.38 wt.%, Si of 0.0135 wt.%, Cu of 0.001 wt.%, with the balance being Mg) with a size of 20 mm 20 mm 1.5 mm was used as the substrate. Nitric acid (HNO3 , 65%, A.R.), copper nitrate trihydrate (Cu(NO3 )2 3H2 O, A.R.), triethoxyoctylsilane (KH832, Shanghai Ruicong Analytical Instrument Co., Ltd.). 2.2. Methods The magnesium alloy foils were ultrasonically cleaned in water, acetone and absolute ethanol for 10 min, and dried. The cleaned magnesium alloy substrates were etching with an aqueous solution of 5 wt.% HNO3 and 1 mM Cu(NO3 )2 at room temperature, then rinsed in ultrapure water and ethanol, respectively, and dried at about 150 C for 10 min. Finally, the magnesium alloy surfaces were modied with a 2.0 wt.% ethanol solution of KH-832 for 0.5 h and subsequently heated at 150 C for 1 h. 2.3. Samples characterization The surface morphologies of the obtained samples were observed on a scanning electron microscope (SEM, TESCAN VEG-

AII LMU, Czech) at 20 kV. Contact angles were measured with a contact angle meter (Drop Meter TM A-100P) at ambient temperature and the sliding angle was measured by the conventional tilting plate method. The volume of water drops was 5 L. The contact angles were measured at ve different spots for each sample, and the average value was adopted as the nal result of the contact angle. Besides, the error analysis of the data of WCA was analyzed by arithmetic mean of the root mean square error. A PHI-multifunctional X-ray photoelectron spectroscope (XPS, Kratos Corp., England) operating with MgK irradiation (h = 1253.6 eV) was performed to analyze the chemical states of some typical elements distributed on the super-hydrophobic surface. The energy scale was internally calibrated by referencing to the binding energy (Eb ) of the C1s peak of a carbon contaminant at 284.6 eV. The electrochemical measurements were carried out in a three-electrode cell. The super-hydrophobic coating on AZ31 magnesium alloy with a size of 1 cm 1 cm was used as the working electrodes. A platinum plate and saturated calomel electrode (SCE) were used as counter and reference electrode, respectively. Measurements were performed in 3.5 wt.% NaCl solutions at room temperature using a LK98BII potentiostat/galvanostat system. Scan was conducted with a constant rate of 10 mV/s. Potentiodynamic anodic polarization curves were established and the corrosion potential (Ecorr ) and corrosion current density (icorr ) were determined using the Tafel extrapolation method.

3. Results and discussion 3.1. Morphological analyses of the coating The SEM morphologies with different magnication of the sample surface of AZ31 before chemical etching are given in Fig. 1. The surface microstructure of the modied sample is observed by SEM with different magnication, as shown in Fig. 2a and b. It can be seen that the magnesium alloy surface is rather rough and covered by a relatively uniform micro- and nano-porous structure (Fig. 2a and b). It is clear that many apertures with average diameters of 5 m are distributed uniformly across the magnesium alloy surface (Fig. 2b). Fig. 2c and d are the typical SEM images of lotus with different magnication [10,20]. Large-scale SEM image (Fig. 2b) shows randomly distributed papillae in micrometer size range that is similar to the lotus leaf. Such regularly ordered porous structure can trap a large amount of air, which is expected to reveal super-hydrophobicity of the magnesium alloy surface [2].

Fig. 1. The SEM morphologies of the surface on AZ31 before chemical etching.

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Fig. 2. The SEM morphologies of the super-hydrophobic surface on AZ31 and lotus surface: (a) and (b) are the SEM images of the as-prepared coating, (c) and (d) are the SEM images of lotus [10,20].

3.2. Wettability of the coating The photographs of water droplets on the modied and bared AZ31 magnesium alloy substrate are given in Fig. 3. It obviously demonstrates that the wettability of the AZ31 substrate changes after it is coated with the coating. Magnesium and its alloy is a type of hydrophilic material with a native oxidized layer, showing the contact angle of 47.4 (Fig. 3a and b), while after super-hydrophobic treatment, the surface exhibits a high WCA about 157.3 0.5 with a small sliding angle of less than 10 (Fig. 3c and d). The contact angle we obtained is a little smaller than the observation of 160 on MgLi alloy by Jiang and co-workers [18], but slightly larger than (155 1.6 ) which is reported by Liang et al. through microarc oxidation pretreatment and chemical modication [19]. It is also found that magnesium alloy through chemical etching and without modication in silane show the characteristics of super-hydrophilic, water droplets are fully spreaded and the contact angle is 0 . This veries the assumption proposed by Wenzel [21] that rough surface structure could make the hydrophilic surface more hydrophilic. These results reveal that the micro- and nano-porous structure and the low surface free energy matter of KH-832 are signicantly responsible for the super-hydrophobicity of the magnesium alloy surface. In addition, the super-hydrophobicity can be maintained at least for three months of storage in air, the values of contact angles vary little, just reduce by 46 , indicating good stability in air, shown in Fig. 4.

3.3. Chemical composition of the surface on the magnesium alloy XPS measurements are performed to investigate the chemical composition of the surface before and after modifying with KH-832. The elements of C, O, Si, and Mg are detected from both samples are shown in Fig. 5. It can be seen from Table 1 that the composition of element C and Si increase remarkably while those of the rest elements decrease after modication, which implies that the surface has been covered with silane lm. In addition, the Si2p peak of the magnesium alloy samples before and after modied with silane is given in Fig. 6. It should be pointed out that the Si signal is detected from the sample without silane treatment, but this Si2p peak is quite weak with low S/N ratio, and its binding energy is 101.4 eV, which can be assigned to Si element in magnesium alloy substrate; however, the silanized sample has a pronounced Si2p peak with a binding energy of 102.1 eV, implying that the silane grafted on the magnesium alloy substrates [2224].

Table 1 The element composition of magnesium alloy surface with and without modication. Element Element composition (at.%) Without modication C O Si Mg 32.51 43.02 1.52 22.94 After modication 43.88 32.78 4.42 18.92

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Fig. 3. The photograph of water contact angle on AZ31: (a) and (b) are the images of the untreated substrate, (c) and (d) are the images of super-hydrophobic surface AZ31 by chemical etching and modication.

3.4. Corrosion resistance of super-hydrophobic coating The potentiodynamic polarization curves of (a) a bare magnesium alloy and (b) a super-hydrophobic coating on magnesium alloy in 3.5 wt.% NaCl solution using the Tafel extrapolation method are given in Fig. 7. The corrosion potential (Ecorr ) and the corrosion current density (icorr ) derived from the potentiodynamic polarization curves are shown in Table 2. As clearly seen in Fig. 7, the corrosion potential positively increases from 1.48 0.03 V of the bare magnesium alloy to 1.17 0.03 V of the super-hydrophobic coating. The shift of the Ecorr in the positive direction could be linked to an improvement of the protective properties of the superhydrophobic coating formed on the AZ31 magnesium alloy. The corrosion current density, icorr , of the super-hydrophobic coating

(6.77 105 mA/cm2 ) decreased by more than 3 orders of magnitude as compared to that of the bare one (7.94 102 mA/cm2 ). These results indicate that the super-hydrophobic coating on magnesium alloy has better corrosion resistance.

60000
O1s

50000 40000

MgKLL

OKLL

Intensity (a.u.)

C1s

30000 20000 10000 0

200 180 b after modification a without modification 0 200 400 600 800 1000

Water contact angle ()

160 140 120 100 80 60 40 0 20 40 60 80 100

Mg2p Mg2s Si2p

Binding Energy (eV)

Fig. 5. XPS survey of the AZ31 magnesium alloy surface unmodied (a) and modied with KH-832 (b).

Table 2 The results of potentiodynamic corrosion test of the magnesium alloy with and without coating in 3.5 wt.% NaCl solution. Sample The bare sample The sample with coating Ecorr (V) 1.48 0.03 1.17 0.03 icorr (mA/cm2 ) 7.94 102 6.77 105

Time (day)
Fig. 4. Inuence of laying up time on hydrophobicity of super-hydrophobic coating.

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2000 1900 1800 b after modification a without modification

102.1 eV

Si2p

4. Summary (1) Super-hydrophobicity lies in two core factors: the rst is the chemical etching, which allowed the formation of suitable surface roughness on magnesium alloy, and the second is the modication with a low surface energy material, which created a lower surface energy surface. (2) Super-hydrophobic surfaces with the WCA of 157.3 0.5 and the sliding angle of 10 have been successfully fabricated by means of chemical etching and subsequent coating of triethoxyoctylsilane on AZ31 magnesium alloy substrates. (3) The SEM shows that the magnesium alloy surface is rather rough and covered by a relatively uniform micro- and nanoporous structure. Such regularly ordered porous structure can trap a large amount of air, which is expected to reveal superhydrophobicity of the magnesium alloy surface. (4) The results of electrochemical measurements show that the corrosion potential of the super-hydrophobic coating increased, and the corrosion current density of the superhydrophobic coating decrease by more than 3 orders of magnitude as compared to that of the uncoated one. These results indicate that the super-hydrophobic coating on magnesium alloy has better corrosion resistance. (5) The super-hydrophobic phenomenon of the prepared surface is analyzed with Cassie theory, and the result shows that only about 10% of the water contact surface is contacted with the metal substrate and the rest 90% is contacted with the air cushion. Acknowledgements This work was supported by the Science and Technology Key Foundation of Chongqing under Grant No. CSTC, 2009AC4045, the Graduate Innovation foundation (No. CDJXS10 10 22 07), the Third Stage of 211 Innovative Talent Training Project (No. S09109) and sharing fund of large-scale equipment of Chongqing University. References

Intensity (a.u.)

1700

b 101.4 eV

1600 1500 1400 1300 90 92 94 96 98 100 102 104 106 108 110

Binding energy (eV)

Fig. 6. Si2p XPS spectrum of the AZ31 magnesium alloy unmodied (a) and modied with KH-832 (b).

-1.0 -1.1 -1.2

a bare magnesium alloy b magnesium alloy with coating

E (V)

-1.3 -1.4 -1.5 -1.6 -1.7 -8 -7 -6 -5 -4

-3

-2

-1

logi (mA/cm2)
Fig. 7. Polarization curves of the AZ31 magnesium alloy with and without coating.

3.5. Analysis on the formation of super-hydrophobicity According to what we have learned, the micro- and nano-meter porous structures have probably already trapped enough air to prevent the penetration of water droplets into the cavities and grooves, which bestowed the super-hydrophobicity on the magnesium alloy surface (Figs. 2 and 3). To further understand the wettability of the interface between the surface and a water droplet, a contrast experiment for the measurement of contact angle on a smooth surface was performed. The contact angle in terms of the Cassie and Baxter equation is described as follows (Eq. (1)) [25,26]: cos
c

= s (cos

+ 1) 1

(1)

is the apparent contact angle of the rough surwhere c face, e (105.0 ) is the contact angle of a smooth surface modied with the same coating, and s is the fraction of the solid surface in contact with the liquid. According to the above mentioned equation the s value of the micro- and nano-structure is estimated to be about 0.10. Herein, the area fraction of the air trapped within the interstices of the surface is 0.90. This extremely large portion of air exposed to water droplet, preventing the penetration of water droplets into the surface, increasing the CA and enhancing the super-hydrophobicity. This result is better than that of Wangs (85%), which is got on magnesium substrate by Wet chemical method [27].

(157.3 )

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