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Applied Surface Science 255 (2008) 29782984

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Applied Surface Science


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

Structure stability and corrosion inhibition of super-hydrophobic lm on aluminum in seawater


Yansheng Yin a,*, Tao Liu b, Shougang Chen b, Tong Liu b, Sha Cheng b
a b

Institute of Ocean Materials and Engineering, Shanghai Maritime University, Shanghai 200135, China Institute of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China

A R T I C L E I N F O

A B S T R A C T

Article history: Received 23 January 2008 Received in revised form 13 August 2008 Accepted 24 August 2008 Available online 4 September 2008 Keywords: Super-hydrophobic Aluminum Corrosion inhibition Seawater Electrochemistry

A novel and stable super-hydrophobic lm was prepared by myristic acid (CH3(CH2)12COOH, mya) chemically adsorbed onto the anodized aluminum surface. The static contact angle for seawater on the surface was measured to be 1548. As evidenced by molecular dynamics (MD) simulations and electrochemical impedance spectroscopy (EIS), the effect of ethanol solvent on the lm stability was proved. The surface structure and composition were then characterized by means of scanning electron microscopy (SEM) with energy dispersive X-ray spectrum (EDS) and atomic force microscope (AFM). The electrochemical measurements showed that the super-hydrophobic surface signicantly decreased the corrosion currents densities (icorr), corrosion rates and double layer capacitance (Cdl), as simultaneously increased the values of polarization resistance (Rct) of aluminum in sterile seawater. 2008 Elsevier B.V. All rights reserved.

1. Introduction Aluminum is an important subject of research because it is abundant in nature, easy to handle and represents an important category of materials due to their high technological value and wide range of industrial applications, especially in aerospace and household industries. In addition, aluminum is characterized by low price, high electrical capacity and high energy density [1]. The most important feature of aluminum is its corrosion resistance due to the presence of a thin, adherent and protective surface oxide lm. Aluminum and its alloy, however, are reactive materials and are prone to corrosion in seawater [2]. The use of super-hydrophobic surfaces is one of the novel methods for protection against corrosion. Recently, much attention has been attracted to surface with super-hydrophobic properties [3] (hydrophobic surface with water contact angle above 1508 is called super-hydrophobic surface [4]). This strategy is perfectly exhibited by the lotus leaf whose surface is structured on two length scales by micron and nano-sized wax protrusions [5]. Because of their interesting properties and important applications in fundamental research and industrial applications [6,7], various fabrication methods have been reported

* Corresponding author. E-mail address: yys2003ouc@163.com (Y. Yin). 0169-4332/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2008.08.088

[811]. All these methods have a common feature that they were obtained through a combination of surface roughness and hydrophobic materials. In other words, both the surface geometrical structure and the chemical composition control the wettability of the solid surface. The anodic oxidation of aluminum materials has clearly gained enormous importance since the 1920s, both from a scientic point of view and for technology and industrial production. Schwabe, who devoted much of his scientic productivity to corrosion and passivity, took up issues concerning not only iron metals, but also the specic behavior of aluminum and other valve metals [12]. The importance of the anodic oxidation of Al has continued into present developments of acid-generated anodic layers with selfordered nano-porous structures as a template for data storage [13]. Interestingly, the anodization will open up another promising application eld in our research: it is possible to generate microrough surface, then by means of subsequent xation of hydrophobic organic compounds, super-hydrophobic surface is formed [1416]. Such surface is of great importance for many industrial applications, and may present a solution to the long-standing problems of environmental contamination and corrosion of metals. Nevertheless, the stability of super-hydrophobic surface is very important for the application in corrosion prevention. Former studies reveal that thicker lms from longer-chained adsorbate offer greater protection to the underlying metal surface than the thinner lms, in terms of their performance and lifetimes

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[17,18]. However, there is little knowledge about the effect of solvent on the lm stability. Therefore, we attempt to discuss the factors that inuence the lm state in seawater and then use electrochemical analysis to determine the coating capacitances and resistances for these lms as a function of their exposure to sterile seawater. 2. Experimental 2.1. Molecular dynamics (MD) simulations All molecular dynamics simulations were run at experiment temperature (343 K); all of them were minimized and calculated under the NVT (constant numerator, temperature and volume) ensemble. A simulation box (3.5 nm 3.6 nm 7.3 nm) with periodic boundary conditions was used to model a representative part of the interface devoid of any arbitrary boundary effects. The box consisted of an aluminum oxide slab with xed spatial positions and a liquid phase consisting of a layer of molecules. The Al2O3 crystal with (0 1 2) plane used for simulations, was prepared from a small unit cell, which was obtained by cleaving the Al2O3 crystal structure along the (0 1 2) plane with O atom on top. Thus, vacant O sites were introduced at the liquidsolid interface. The simulation box comprised 980 Al and 1470 O atoms. The starting point in our simulated system was an ideally single myristic acid molecule and the one surrounded by a proper number of ethanol molecules, respectively. Cutoff-based electrostatic coulomb interactions as well as van der Waals energies were used and the cutoff radius was 1.8 nm. Interactions between atoms and molecules were accounted for by use of the COMPASS force eld [19], which was optimized for the simulation of condensed phases including metal oxides. COMPASS force eld is a powerful force eld supporting atomistic simulations of condensed phase materials. This force eld enables accurate and simultaneous prediction of structural, conformational, vibrational, and thermophysical properties for a broad range of molecules in isolation and in condensed phases, and under a wide range of conditions of temperature and pressure. 2.2. Super-hydrophobic surface The aluminum samples with a purity of 99.9% were used in this experiment. Before anodizing, the specimens were annealed at 500 8C for 3 h to remove the mechanical stress, and then cooled spontaneously. The front surface was polished by silicon carbide papers (from 400 to 1600 grade), then degreased with acetone, washed with distilled water, dried. The natural oxide lm on the aluminum sheet was dissolved in 1 mol/L sodium hydroxide for 2 min at 25 8C, and then put it into 1 mol/L nitric acid for 1 min to counteract remnant lye, washed in deionized water. The anodization was carried out under a constant current of 1.3 A/cm2 in a 15-wt% sulphuric acid, and the temperature was kept constant at 25 8C for 2 h. During this process, the electrolyte was vigorously stirred. Subsequently, the sheets were chemically modied in myristic acid with 10 wt% ethanol and 100 wt% melting myristic acids for 30 min at 70 8C. Subsequently, the sheets were washed in ethanol at 70 8C, deionized water in turn, and then were dried in oven at 80 8C for 1 h. The contact angles were measured by a JC2000A CA system at ambient temperature, the surface morphology measurements were carried out with scanning electron microscopy (SEM) (JEOL JSM-6700F) and atomic force microscopy (AFM) (SPI3800N). An energy dispersive X-ray spectrum (EDS) was also used to analyze the microzone composition of the surface.

2.3. Electrochemical measurements The working cell was a standard three-electrode cell having a Pt net as a counter electrode and saturated calomel electrode (SCE) as reference electrode whose potential was +241 mV vs. NHE at 25 8C. The area of work electrode was 1 cm2. All the measured potentials presented in the paper were referred to this electrode. All tests were performed at ambient temperature (25 8C) in the seawater from Tsingtao sea area (E1208180 , N368040 ), which was autoclaved at 121 8C and 20 psi for 20 min (32% NaCl, pH 8.02). Prior to potentiodynamic polarization and electrochemical impedance spectroscopy measurements, 1 h immersion was given to ensure the steady state. For potentiodynamic polarization experiments, the potential was scanned from 600 to +600 mV at a scan rate of 2 mV s1. Electrochemical impedance spectroscopy (EIS) was performed by IM6 electrochemical workstation under open circuit conditions. The experimental temperature was kept at 25 8C. EIS measurements were performed in the frequency range between 10 mHz and 100 kHz with a sine-wave amplitude of 10 mV. The experimental EIS spectra were interpreted on the basis of equivalent electrical analogs using the program Zview2.0 to obtain the tting parameters. 3. Results and discussion 3.1. Study of lm stability in seawater Firstly, we studied the effect of the ethanol solvent on the lm stability in sterile seawater. In Fig. 1, the contact angle as a parameter of the immersion time and concentration of myristic acid are plotted. The experiment shows that the specimens modied in myristic acid with 10 wt% ethanol solvent (Type B) is, as a rule, hydrophilic after 24 h exposure to the sterile seawater, whereas, the surface modied in 100 wt% myristic acid (Type A) only shows a slight decrease in water repellency. These observations are conrmed by the results of EIS. At the beginning of immersion (1 h), the sample modied in 100 wt% myristic acid (Type A) shows a prominent semicircle in the Nyquist plot, whose diameter value is around a few hundreds of kV cm2. When the immersion time increases to 24 h, the semicircle diameter decreases by no more than one order of magnitude, which is still larger than that of specimen modied in 90 wt% myristic acid (Type B) exposed to seawater for 1 h (Fig. 2).

Fig. 1. Super-hydrophobic surface stability in seawater with and without ethanol solvent.

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with EAl2 O3 and Emya being the total potential energy of the aluminum oxide crystal and the myristic molecule, respectively. The mean value of interaction energy EAl2 O3 mya reads 2822 kJ mol1 for type A and 2424 kJ mol1 for type B. Obviously, the increase of jEAl2 O3 mya j for type A as compared to type B results from the increase of the van der Waals forces due to the closer contact of the alkyl tail of the molecule being attached at the surface. So the enhanced structural stability of type A is likely due to the greater number of intermolecular interactions within the hydrocarbon chains for these lms. The results of EIS and MD suggest that the ethanol solvent is not for the benet of lm stability; hereinafter, the 100 wt% myristic acid is used to modify anodized surfaces in order to improve their corrosion resistance. 3.2. Characteristics and features of super-hydrophobic surface Subsequently, the super-hydrophobic surface structure and composition are characterized. The AFM images of the specimens surface morphology are shown in Fig. 5. It can be seen that the Al surface becomes quite rough (surface roughness Ra is about 3 mm) and develops mountain-like structure when the sample is anodized in a 15-wt% sulphuric acid for 2 h (Fig. 5a). After chemical modied in 90 wt% and 100 wt% myristic acid, however, the surface roughness slightly decreased (surface roughness Ra is about 2 mm) because the myristic acid may ll some holes of anodized surface (Fig. 5b and c). And compared with type B lm surface (modied in 90 wt% myristic acid), type A lm surface (modied in 100 wt% myristic acid) is more uniform. We can have a conclusion that the super-hydrophobic lm can be formed on the Al surface more compactly and uniformly without the effect of the ethanol. Fig. 6 shows the untreated and super-hydrophobic surfaces observed by SEM with different magnications. Compared with the oc-like structure on the untreated surface, the anodization and chemical modication make the surface a specic morphology by characterized into a regularly ordered elieve-like structure. On the modied surface, many cracks and venations are observed at low magnication, and multilayer aggregates and small holes at high magnication observation. The chemical composition of the untreated and modied surfaces are analyzed using EDS. Fig. 7a shows the occule on the

Fig. 2. Nyquist plots of the samples exposed to seawater for different time without (Type A) and with (Type B) 10 wt% ethanol solvent.

The reason for the change is probably the effect of ethanol solvent employed in the phase of preparation and an effective way of studying these complex processes is to use molecular dynamics simulations of suitable models accounting for the liquidsolid interface [2023]. Fig. 3 shows the end conguration of two different orientated myristic acid molecules adsorbed on the polar Al2O3 (0 1 2) surface with and without the ethanol. Type A (Fig. 3a) is zigzag with some methylene groups and the polar carboxyl head attached to the surface and the residual unpolar tail perpendicular to the surface, but type B (Fig. 3b) where only carboxyl head is near to the surface accompanied by a longer upright tail. In Fig. 4, a detailed analysis of the whole trajectory is given, Fig. 4a referring to type A and Fig. 4b to type B. The interaction energy EAl2 O3 mya of the myristic acid molecule with the aluminum oxide surface is calculated according to the following equation: EAl2 O3 mya EAl2 O3 mya EAl2 O3 Emya (1)

with EAl2 O3 mya being the total potential energy of the aluminum oxide crystal together with the adsorbed myristic acid molecule, and

Fig. 3. Ball and stick model of an adsorbed myristic acid molecule studied via MD simulations (a) in the absence and (b) the presence of ethanol solvent (250 small molecules). The different colors correspond to different atom types with white symbolizing hydrogen, red oxygen, green carbon, and violet aluminum. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)

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Fig. 4. Analysis over a period of 5 ps of the interaction energy EAl2 O3 mya (a) Type A and (b) Type B.

untreated surface are mainly composed of Al and O elements; Fig. 7b indicates that the as-prepared surface is composed of other oxygenous compounds on the surface besides A12O3. Reference to other research [24], the C peak may come from [CH3(CH2)12COO]3Al. During the process of chemical modication, the released aluminum ions can be immediately captured by coordination with ntetradecanoic acid molecules, forming aluminum carboxylate, according to the following equation: Al3 3CH3 CH2 12 COOH ! CH3 CH2 12 COO3 Al 3H (2)

And the S peak probably results from remnant aluminum sulphate. 3.3. Study of corrosion protection behavior with electrochemical analysis Lastly, the ability of the super-hydrophobic surface to protect aluminum from corrosion in sterile seawater was studied by electrochemical experiments. The changes observed in the polarization curves in the absence and the presence of the superhydrophobic lm is shown in Fig. 8. It can be seen that both the cathodic and anodic currents are shown to decrease and the corrosion potential (Ecorr) value is shifted in the positive direction in presence of super-hydrophobic surface (Fig. 8, curve 3). The corrosion current densities of untreated electrode and that of lm-covered electrodes are obtained by Tafel extrapolation of
Fig. 5. AFM of (a) aluminum surface anodized for 2 h in a 15-wt% sulphuric acid, (b) anodized surface modied in 90 wt% myristic acid and (c) anodized surface modied in 100 wt% myristic acid.

polarization curves to the corrosion potentials (Ecorr). The inhibition efciency (IE) is calculated using the following formula [25]: IE i i0 100 i (3)

where i and i0 mean the corrosion current densities of aluminum electrodes covered with and without super-hydrophobic lms,

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Fig. 6. SEM of untreated surface with different magnications (a) 1500 and (b) 10,000 and super-hydrophobic aluminum surface (c) 1500 and (d) 10,000.

respectively. The inhibition efciency of the anodized aluminum surface is 61%. After modifying by the myristic acid, the inhibition efciency increases to 96%. The super-hydrophobic surface produced positive results mainly on the aluminum anodic reaction, whose currents are reduced by about three orders of magnitude; the corrosion

potential (Ecorr) shifts positively for about 0.2 V when the anodized aluminum is covered with the myristic acid lm. This suggests that the myristic acid lm mainly retards the dissolution of aluminum between the interface of the aluminum surface and seawater. The Bode plots obtained from the untreated anodized and super-hydrophobic specimens in the sterile seawater for 1 day are

Fig. 7. EDS result of (a) untreated surface and (b) super-hydrophobic surface.

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Table 1 Electrochemical model impedance parameters and coverage of lm derived from EIS at 25 8C Samples Rct (kV) 10.18 27.94 337.6 Cdl (mF) 1.708 1.168 0.078 n1 0.86 0.92 0.77 Rc (kV) 0.003 0.367 Cc (mF) 0.218 0.019 n2 0.50 0.67 Rs (V) 2.02 1.50 5.04

u
63 97

Untreated Anodized Super-hydrophobic

Fig. 8. Potentiodynamic polarization curves of untreated, anodized and superhydrophobic samples for 24 h in sterile seawater at 2 mV s1.

two time constants in the corresponding impedance spectrum, as it is shown in Fig. 10b. RctjjCdl would represent the impedance connected with the interface reactions and the solid state conduction in the barrier layer otherwise the resistance Rc could be ascribed to the electrolyte resistance within the nano-sized pores of the porous sub-layer (governed mainly by pore dimensions). Cc would normally be assigned to the capacitance of a surface lm (a function of factors such as lm thickness and defect structure). The resistance Rc of super-hydrophobic specimen increased considerably in comparison with the anodized specimen (Table 1). It appears reasonably to conclude that the oxide-related nano-porosity has been modied by the penetrating organic agent, and the pores are mostly sealed. The Rct values in low frequency increase rapidly when the super-hydrophobic lm formed on the surface (seen from Fig. 9 and Table 1). It is proved that the hydrophobicity plays an important role in improving the anticorrosion of the aluminum. The constant phase elements (CPE, Cdl) with their n values close to 1.0 represent double layer capacitors with some pores; the CPE decreases upon addition of super-hydrophobic lm, which is expected to cover the charged surface reducing the capacitive effect. Because areas covered with the lms are electrochemically inert and all the current is passed via pinholes on the electrode [26], coverage (u) of lm on aluminum surfaces is given by 1u Rt0 Rt (4)

Fig. 9. Bode plots of untreated, anodized and super-hydrophobic samples after immersion in sterile seawater (32% NaCl, pH 8.02) for 24 h.

represented in Fig. 9 (25 8C). The equivalent circuits are shown in Fig. 10 and the tted parameters are summarized in Table 1. Fig. 10a indicates the equivalent circuit representing the electrochemical behavior of the untreated surface, which shows one time constant. In this circuit, Rct the charge transfer resistance, Cdl the double layer capacitance, Rs the solution resistance. In the case of the electrode passivated by means of anodization and chemical modication, the equivalent circuit should consider

where u is the fraction of lm coverage, and 1 u is the total fraction of pinholes. Rt (Rt = Rct + Rc) is the charge transfer resistance of the modied Al and Rt0 is the resistance of the untreated Al. The coverage of anodized aluminum surface and the surface modied in myristic acid is 63% and 97%, respectively. The result shows that the myristic acid molecules may play a lling role in decreasing the defects of the anodized aluminum surface. From results obtained by potentiodynamic polarization and electrochemical impedance spectroscopy, it can be concluded that porous anodic aluminum oxide is easily penetrated by the Cl in the seawater. So it cannot improve the corrosion resistance obviously. However, once the anodized surface was chemical modied by myristic acid, the specimen can show excellent anticorrosion properties because of the adsorption of organic

Fig. 10. Equivalent circuits of the studied system (a) untreated and (b) anodized and super-hydrophobic specimens.

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matter, which leads under different experimental conditions to water-repelling effects. 4. Conclusions In conclusion, super-hydrophobic surface on aluminum is successfully generated by anodization process and chemical modication. The impact of ethanol for stability is studied by MD and EIS. The anodization for 2 h and 100 wt% myristic acid is ideal for the formation of the stable super-hydrophobic surface. The specic morphology of surface and chemical composition are characterized by the experiments of AFM, SEM and EDS. The analysis of potentiodynamic polarization, EIS and appropriate equivalent circuit models reveal that the aluminum corrosion is effectively inhibited by the formation of a stable super-hydrophobic lm. It is believed that this method should be easily applied to large-scale production of super-hydrophobic engineering materials with ocean industrial applications if the lm stability is improved further. Acknowledgments We thank the nancial support from the National Natural Science Foundation of China (Nos. 50672090 and 50702053) and

the excellent mid-youthful scientist encouraging Foundation of Shandong Province (2006BS04021). References
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