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Electrochimica Acta 50 (2005) 50835089

Study on a hydrophobic nano-TiO2 coating and its properties for corrosion protection of metals
G.X. Shen a , Y.C. Chen a , L. Lin a , C.J. Lin a, , D. Scantlebury b
a

State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen 361005, China b Corrosion and Protection Center, UMIST, P.O. Box 88, Manchester M60 1OD, UK Received 22 November 2004; received in revised form 1 April 2005; accepted 1 April 2005 Available online 11 July 2005

Abstract A uniform TiO2 nanoparticle lm has been coated on the surface of 316L stainless steel by using solgel and dip-coating technology. A hydrothermal post-treatment method has been developed to eliminate the crack defects in the coatings, and to improve the structure and property for the coating. A self-assembly of uoroalkylsiane (FAS-13) has been conducted to enhance the surface hydrophobic property of the nano-TiO2 coatings. The distribution of particle sizes of TiO2 sol has been analyzed by -potential analysis, and the surface morphology and structure have been characterized by contract angle, XRD, and SEM measurements. The results indicate that the surface of coatings is uniform and dense, with approximately 375 nm thickness. The diameter of particles of TiO2 anatase is in the range of 1518 nm. The contact angle of the super-hydrophobic surface is 150 1 . It shows, from the electrochemical tests, that the super-hydrophobic coatings on 316L stainless steel exhibit an excellent corrosion resistance in chloride containing solution at the room temperature. 2005 Elsevier Ltd. All rights reserved.
Keywords: Hydrophobic coatings nano-TiO2 ; 316L stainless steel; Corrosion resistance

1. Introduction Various surface techniques have been developed to improve the corrosion resistance of metals. One of the most effective methods is to deposit a protective ceramic coating on the metal surface, e.g., nitrides, carbides, silicides or transition metal oxides [1]. The coatings with very low electronic conductance, such as SiO2 [2], TiO2 [3], non-conducting coatings Al2 O3 [4] or mix-oxides coating of TiO2 , SiO2 , and Al2 O3 [5] have been reported as the corrosion protections in the literatures. Up to now, there are two kinds of methods for preparing the coatings on metal surfaces, viz. from gaseous phased (PVD [6] and CVD [7]) methods and from the liquid phase (solgel method [8] and electrodeposition process [9]) methods. And most of the ceramic coatings are formed by solgel method, because the solgel techniques require considerably less equipment, can be amenable to any

Corresponding author. E-mail address: cjlin@xmu.edu.cn (C.J. Lin).

accessories in a large and complex shape, and are applicable to substrates that cannot withstand high temperature [10]. However, the coatings fabricated by solgel process are encountered a technical problem, that is there always exists pores and cracks in the coatings resulting from the sintering in a high temperature, which may become a detrimental factor to cause delamination and corrosion at the interface of coating and substrates [11]. Since the discovery of photo-electrochemical property of TiO2 lms, it has been noted that the TiO2 lm, as a photoanode, might provide metals cathodic protection under illumination [12]. It is believed that the TiO2 coating as a ceramic coating might provide a good corrosion protective property for the metals [13]. An attempt has been made in this work to deposit a nano-TiO2 composite coatings on 316L stainless steel to enhance the barrier corrosion resistance and hydrophobicity. The investigation on the modication of nano-TiO2 composite coatings on metal for enhancing and lasting its photogenerated cathodic protection will be reported otherwhere.


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calomel reference electrode (SCE), a platinum auxiliary electrode, and the samples as working electrodes was used in the experiments. The working electrodes (samples) were enveloped by epoxy resin and only remained an exposure area (0.5 cm 0.5 cm) for testing. The Tafel polarization curves were measured between 15 mV at the open circuit potential at the rate of 0.167 mV/s and started after 10 min immersion of samples in the solution. The EIS were performed at open circuit potential. The applied frequencies were ranged from 105 to 103 Hz using ve points/decade. The impedance data were analyzed by Autolab analysis systems [15]. All experiments were executed in a Faraday cage in order to minimize the external electronic interference with the system at the room temperature. 2.4. Surface composition analysis by XPS The nano-TiO2 coating surface before and after being immerged in Ringers solution for 1008 h was analyzed by XPS (Physical Electrons Quantum 2000 Scanning Esca Microprob). The X-ray in XPS was generated at 15 kV and 10 mA, using Al K radiation. The air pressure in the vacuum chamber was lower than 5 107 Pa and the analysis area was 2 mm 1 mm. The depth prole were analyzed by Ar+ sputter etching the thin lm 200 and 400 nm using 5 keV at a beam current 2040 mA. The XPS were corrected for charge shifting by taking C 1s at 285.0 eV.

2. Experimental methods 2.1. Preparation of TiO2 colloidal solution In our experiments, all regents were purchased from Chinese Chemical Regent Co. Using EAcAc as a chelating agent, the TiO2 sol was prepared from tetra-n-butyl titanate (Ti(On-Bu)4 ) in the following process: rstly, 20 ml ethanol and 1 ml EAcAc without further dehydration were mixed, 2 ml Ti(O-n-Bu)4 were added and the solution was continuously stirred for 1 h. Within 30 min, 0.2 ml distilled water was carefully added to the solution for hydrolysis and kept stirring for 10 h. The yellow transparent solution was aged for 24 h before conducting coating on metal surface. 2.2. Fabrication of the hydrophobic nano-TiO2 coatings In the preparation of a uniform nano coating, the pretreatment of the substrate surfaces is important. The 316L stainless steel sheet (0.5 cm 0.5 cm) were ground with No. 3201500 emery papers gradually, polished with 1 and 0.3 m Al2 O3 powder, and then ultrasonically cleaned in acetone, ethanol, and distilled water for 10 min, respectively. After hot air drying, it was coated with nanoparticle TiO2 coatings by a dip-coating method. In this procedure, the substrate was immersed in the sol solution for 5 min, and withdrawn at a speed of 0.51 mm/s. After drying naturally in the ambience, the specimens were heated in an oven at 150 C for 30 min. Such an operation as mentioned above was repeated for four times to increase the coating thickness. Then, the samples were heat-treated at 450 C for 30 min to enable the oxide conversion and removal of solvent and residual organics in the coating. However, during the procedure of densication, crystallization of TiO2 and removal of residual hydroxyl and organic groups, the nano coatings were usually prone to cracking. In order to eliminate the creak defects in the coating and to optimize the coating structure and properties, the nano-TiO2 coated samples were immersed in a boiling water for 1050 min, and then thermal-treated in the mufe oven again at 450 C for 10 min. FAS-13 was used as a water-repellent agent. A methanol solution of 1% FAS-13 was hydrolyzed by adding a threefold-molar excess of water at room temperature and then kept stirring for 3 h. The nano-TiO2 coatings were immersed in the solution for 3 h and dried at 140 C for 1 h [14]. 2.3. Electrochemical tests The polarization curves and electrochemical impendence spectroscopy (EIS) for the prepared coatings were carried out in an oxygen-saturated Ringers solution (NaCl 8.6 g/dm3 , KCl 0.3 g/dm3 , and CaCl2 0.48 g/dm3 ) by using Autolab PGSTAT30 Electrochemical Measurement System. At the same time, the effects of the hydrophobic post-treatment on corrosion resistance of the nano-TiO2 coatings were investigated. A three-electrode cell including a saturated

3. Results and discussion 3.1. Formation mechanism of the sol In this work, ethyl acetoacetic (EAcAc) was used as a catalyst and chelating agent. The form mechanism of ultra ne particles of TiO2 sol may be explained as the followings: Firstly, the titanium alkoxide species react with EAcAc producing hex-cyclic molecules, then the hex-cyclic molecules form tri-dimensional network macromolecular in a polymerization process. When adding H2 O into the solution, the hydrolysis rate of the macromolecules is slower than that of titanium alkoxide, which may control effectively size particles of the sol. Besides, because of EAcAc partly hydrolysis, on the surface of the sol particles hold the same property charges, which may reduce aggregation of the particles. Fig. 1 shows a distribution of the sol particle diameter measured by -potential analysis. The diameter of ultra ne particles is mostly 1 nm in scale and no aggregation phenomenon is observed. And the sol is stable and transparent and can be kept for a long period. 3.2. Inuence of hydrothermal post-treatment on properties of nano-TiO2 coatings Fig. 2 shows the SEM images of nano-TiO2 coatings before (a and c) and after (b and d) hydrothermal post-


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Fig. 1. Particle diameter distribution of the TiO2 sol.

treatment, indicating that there are some crack defects on the coating surface due to the shrinkage occurring during the thermal process. Though, these crack defects appear little inuence on the mechanical and adhesive properties of the coatings, as a protective coating for the metals, these crack defects may become a potential risk to cause local corrosion of metals. In order to eliminate the cracks or other defects, various methods, such as PEG [16], polyvinyl alcohol (PVA) [17], and hydroxypropyl-cellulose (HPC) [18], etc. have been reported to add into the colloidal solution to improve

the drying properties of the gel, adjust the viscosity of the sol, and increase the strength of the material to prevent crack formation [19]. However, those methods have made a little progress in prevention from cracks defects in the coatings, and the procedures are considerably complicated. Comparing the SEM images in Fig. 2, it shows that after being treated in boiling water for 10 min, the surface of coatings become smooth and uniform and the cracks disappear, and the aggregation becomes less and diameter of particles tends to uniform. The hydrothermal post-treatment method developed in this work may not only eliminate the cracks or other defects in the coatings successfully, but also make the structure and morphology of the coatings more perfect. The inuence of disposed time for the TiO2 coatings exposed in boiling water on their morphology, hydrophobic properties, and particle size of was deliberatively investigated, and the results were listed in Table 1. It is interesting to note that, as shown in Table 1, the coatings kept in boiling water for 10 min appear free of crack defects, and its particles and pores are ranged in 1518 and 48 nm, respectively. However, when the immersion time increases to 20 min, the aggregation phenomenon of particles is observed and the surface becomes coarse. And then if the immersion time is longer than 30 min, the morphology and size of particles become uniform again, similar to that of the sample treated for

Fig. 2. SEM images of the nano-TiO2 coated 316L before hydrothermal post-treatment (a and c) after post-treatment (b and d).


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Table 1 Inuence of the immersion time in boiling water on morphology, size, and hydrophobic property of the titania coatings No. 1 2 3 4 5 6 Time (min) 0 10 20 30 40 50 Conguration Porous, aggregation, cracks Porous, evenly, no cracks Porous, aggregation, no cracks Porous, evenly, no cracks Porous, aggregation, no cracks Porous, evenly, no cracks Diameter (nm) 3021 1518 3918 1821 1825 1821 Thick (nm) 375 375 375 375 372 370 Contact angle ( ) 41.5 104.4 78.5 90.5 64.8 78.5

10 min. The structure of the nano-TiO2 coatings is varied with the hydrothermal post-treatment time periodically for about every 10 min. We believe that a process of the restructure and recrystallization of titania might play an important role in morphology, size and hydrophobic property of lm during the hydrothermal post-treatment process. The thickness of the coatings does not change too much in the course of the whole hydrothermal treatment, implying that the interaction and bond strength between the coatings and the substrates are very rmly. Besides, the hydrophobic properties of the coatings are closely associated with the morphology of the nano coating, the contact angle of water on the fresh TiO2 surface is nearly 0 1 . It was found that the nano coatings treated for 10 min were kept in dark for 2 months, the contact angle of water increased to 104.4 1 . The mechanism of the hydrophobic property of the nano-TiO2 coatings is remained unapprehended up to now. It could not be simply explained by removing of the hydroxide radical and the contamination of dusty on the coatings [20]. Tadanaga et al. studied on the formation of super-water-repellent Al2 O3 coatings, and proposed that the hydrophobic property was resulted from the nano-size particles and the existence of air in the pores on the surface [21]. The XRD analytic results (in Fig. 3) show that the strong diffraction peaks were originated from (1 0 1), (0 0 4), (2 0 0), (2 1 1), etc., which are the character peaks of anatase phase. After conducting a self-assembly of FAS-13 on coatings, its contact angle to water increased to 150 1 , indicating that the hydrophobic property of the coating is further strengthened.

3.3. Corrosion resistance of the hydrophobic coatings According to the mechanism of corrosion protection of metals, the hydrophobic coatings with low wettability are possible to effectively prevent the water onto the substrate surface, and exhibit an excellent corrosion resistance in the wet environments. Fig. 4 shows the polarization curves of bare 316L stainless steel, nano-TiO2 coated and FAS/nanoTiO2 coated 316L stainless steel electrodes in Ringers solution. The nano-TiO2 coated electrodes were placed in the dark for more than 1 month before measurements, and all the experiments were carried out in a dark room to avoid from the photoelectrochemical inuence. The nano-TiO2 and FAS/nano-TiO2 coated 316L stainless steel electrodes exhibit relatively lower current densities, icorr decreases two to three order of magnitudes compared to the bare 316L stainless steel electrode in the same condition. The anodic corrosion slope of the FAS/nano-TiO2 coated electrode inclines to level and current densities are clearly lower than that of the bare 316L electrode. It is noted furthermore that the corrosion potential of the nano-TiO2 and FAS/nano-TiO2 coated electrodes are much noble than that of the 316L stainless steel, the corrosion potential shifting positively from 0.21 to 0.083 V and 0.04 V (versus SCE), respectively. The reason caused the potential positive shift does not clear, which may be explained by the different effect of hydrophobicity of the coating. The

Fig. 3. XRD spectrum of the TiO2 coatings.

Fig. 4. Polarization curves for bare 316L and lms in oxygen-saturated Ringer solution. (a) Bare 316L; (b) TiO2 /316L coatings; (c) FSA/TiO2 /316L coatings.


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Fig. 5. EIS spectra of the bare 316L and coated 316L electrodes in ringer solution, at the open circuit potential, the frequency range is 105 103 Hz. (a) Bare 316L; (b) TiO2 coated 316L; (c) FSA/TiO2 coated 316L.

hydrophobicity of the porous coatings attributed to air trapped in the nanopores limits water accessibility and concentration of corrosive species in the stainless steel holes, and hence cause a retardation of the anodic dissolution process. The transportation of oxygen to the pores through the trapped gas is usually not inuenced or is even increased, thus resulting in similar or even higher oxygen concentrations in the pores and an enhancement of the cathodic process (oxygen reduction). The different effect of hydrophobicity of the coating on the position of the cathodic and anodic branches in the polarization curves may then be explained why it is not only the decrease in corrosion current but the shift in corrosion potential when applied nano-TiO2 coatings. The EIS spectra have also been obtained at the open circuit potential from bare 316L, nano-TiO2 and FAS/nano-TiO2 coated 316L stainless steel electrodes in Ringer solution (Fig. 5). The Bode diagrams evidently show a clear difference of corrosion resistance between the bare 316L and the nano-TiO2 coated 316L electrodes, noting the peak at the high frequency in Fig. 5(b and c). In general, ac impedance at high frequencies represents the responses of coatings in the solution, and at low frequencies reects the Faraday reaction resistance Rt and double-layer capacitance. So in the equivalent circuits, two electrochemical interface reactions are used to the system of the coated 316L stainless steel. The Nyquist plots presented here illustrate that the nano-TiO2 and FAS/nano-TiO2 coated 316L stainless steel present an excellent corrosion resistance compared to the bare 316L stainless steel. The results are in accordance with those of polarization curves. The EIS spectra are analyzed with equivalent circuit in Fig. 6, where Q stands for constant phase element (CPE) in

circuit description code, which is commonly used to replace capacitance, because it is hardly pure capacitance in the real electrochemical process and it is dened by admittance Y and power index number n, given by Y = Y0 (j)n . This is a general dispersion formula, for n = 0 it stands resistance, while it is capacitance if n = 1. In all cases of study, n is close to 1, representing a capacitive characteristic of the interfaces. In Fig. 6, Rs delegates the solution resistance and a pair of elements of Qc (CPE of coatings) and Rc in parallel replace the dielectric properties of the coatings. Qdl (CPE of double layer) and Rt (react resistance) are adopted to describe the charge transfer process happening at the solution/steel interface in the pinholes of coating. Using the equivalent circuits, the curve tting performed for both nano-TiO2 and FAS/nano-TiO2 coating systems and for the bare 316L yields the values of parameters for the circuit elements (Table 2). From Table 2, it is interesting to note that the apparent capacitance of the coatings Qc is very low (approximately 108 ). This lower value is consistent with the insulating nature of the coatings. Rt (i.e., corrosion resistance) of the nano-TiO2 coated and the FAS/nano-TiO2 coated electrodes have been improved nearly 15 and 1000 times, respectively. It is demonstrated that the corrosion resistance for FAS/nano-TiO2 coating system is much higher than that for the TiO2 coated system.

Fig. 6. Equivalent circuit for the bare 316L (a) and the coated 316L (b) in ringer solution.


5088 G.X. Shen et al. / Electrochimica Acta 50 (2005) 50835089 Table 2 EIS parameters in the equivalent circuit for the bare and coated 316L systems Electrodes Rs ( ) Qdl Y0 316L TiO2 /316L FAS/TiO2 /316L 30.9 45.8 29.0 (108 ) n 0.705 0.7213 2152 884 Rc ( ) Qdl Y0

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Rt ( ) n 0.863 0.873 0.845 1.32 105 1.68 106 1.74 108

(106 )

4.4 2.7

6.08 19.0 1.25

3.4. The results of XPS analysis Fig. 7 shows the XPS depth prole spectra of the hydrophobic TiO2 coating before (a) and after immerged in the solution for 1008 h (b). Because the organic FSA layers is only one or two molecule layers, the surface of the coatings is made up of TiO2 particles. The XPS spectra show that the 400 nmdepth layer is 316L substrate. We did not nd and chloride element in the coatings, indicating that the nano coating is possible to obstruct from Cl penetration. There is a distinct difference for the elements distribution of in the 200 nmdepth layer before and after immerged. After immerged 1008 h, only some Fe and a little Cr elements, but

no metallic oxides is observed in the coatings, implying that no corrosion has taken place during the immerging.

4. Conclusions We have prepared nano-TiO2 coatings on metal by solgel method, and developed a hydrothermal post-treatment method to effectively eliminate the cracks defects in the coating to optimize structure and properties for the coatings. Using self-assembly of FAS-13, organic and inorganic hybrid nano coatings with high hydrophobic properties has been fabricated. The results of electrochemical test indicate that the hydrophobic coatings exhibit an excellent corrosion resistance in Ringer solution. The corrosion potentials shift positively, icorr decreases three order of magnitudes, and the corrosion resistance Rt increases one to three order of magnitudes. It is expected that the surface modication by nano-TiO2 coatings may become a promising technique in improvement of corrosion resistance of metals.

Acknowledgements Financial support for the National Natural Science Foundation of China (Grant numbers: 20127302, 20021002) is gratefully acknowledged.

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Fig. 7. XPS depth prole spectra of the hydrophobic nano-TiO2 coatings before (A) and after (B) being immerged in Ringers solution (a) 0 nm; (b) 200 nm; (c) 400 nm depth.


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