Electrochimica Acta 53 (2008) 59135922

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

The synergistic combination of bis-silane and CeO2 ZrO2 nanoparticles on the electrochemical behaviour of galvanised steel in NaCl solutions
M.F. Montemor a, , W. Trabelsi a,b , S.V. Lamaka c , K.A. Yasakau c , M.L. Zheludkevich c , A.C. Bastos c , M.G.S. Ferreira a,c
a b c

ICEMS, Instituto Superior T ecnico, Technical University of Lisbon, Av. Rovisco Pais Lisboa 1049 001, Portugal ENIT, Unit e de Recherche de Corrosion, Tunes, Tunisia CICECO, University of Aveiro, Department of Ceramic and Glass Engineering, Aveiro 3810 193 Portugal

a r t i c l e

i n f o

a b s t r a c t
Bis-1,2-[triethoxysilylpropyl]tetrasulde silane lms containing CeO2 ZrO2 nanoparticles were deposited by dip-coating on galvanised steel substrates. The morphological features of the coated substrates were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The anti-corrosion performance of the modied silane lm applied on galvanised steel substrates was studied by electrochemical impedance spectroscopy (EIS). The ability of nanoparticles to mitigate localized corrosion activity at articially induced defects was investigated via the scanning vibrating electrode technique (SVET) and by the scanning ion-selective electrode technique (SIET). The results showed that the addition of nanoparticles provides good corrosion protection of the galvanised steel substrates pre-treated with the modied silane solutions. The corrosion activity was reduced by more than one order of magnitude. Complementary d.c. experiments, using zinc electrodes exposed to NaCl solutions containing the nanoparticles were also performed in order to better understand the role of the nanoparticles. An ennoblement of the corrosion potential and polarisation of the anodic reactions could be detected. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 7 March 2008 Accepted 26 March 2008 Available online 10 April 2008 Keywords: Silanes Ceria Zirconia Nanoparticles SVET SIET

1. Introduction The need of alternatives to replace the very effective but environmentally harmful chromate-based surface treatments promoted the investigation of several classes of new pre-treatment systems. Among these, pre-treatments based on organosilanes attracted considerable interest as they provide the formation of a thin organic coating that confers surface functionalisation. Therefore, silane pre-treatments work as adhesion promoters for improved paintability. The corrosion resistance of the painted system is mainly controlled by the anti-corrosion properties of the paint scheme, which includes the pre-treatment layer. Thus, this layer plays an important role, since it is the one in direct contact with the metal. The pre-treatment layer must provide adhesion, good barrier properties [14], and if possible, corrosion inhibition ability. The major drawback of the silane pre-treatments is their inert character regarding the corrosion processes. The silane coating, by itself, does not provide any active protection when the aggressive species reach the metallic surface and initiate the cor-

Corresponding author. E-mail address: mfmontemor@ist.utl.pt (M.F. Montemor). 0013-4686/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2008.03.069

rosion activity. Recent research efforts have been focused on the modication of the bulk properties of silane coatings by adding active anti-corrosion species in order to further improve the corrosion resistance, or to introduce self-healing ability in the silane coating. Some corrosion inhibitors were employed as active additives like tolyltriazole [4], benzotriazole [4], phenylphosphonic acid [5] and cerium [69], zirconium [8] and lanthanum [9] salts. The organic inhibitors added to the silane coatings improved the corrosion resistance but did not impart self-healing activity. Conversely, cerium salts present potential as additives since they seem to provide self-healing ability [4,79]. New pre-treatments for galvanised steel substrates based on bis-[triethoxysilylpropyl] tetrasulde doped with small amounts of cerium nitrate or zirconium nitrate were studied in a previous work [8] and it was found that the corrosion resistance of the treated substrates before painting was signicantly improved by addition of those dopants. This effect could be associated to reduced porosity and increased thickness of the coatings [8,9]. It was shown that the presence of zirconium ions provided very good barrier properties, whereas the presence of cerium provided better corrosion inhibition ability. Nanoparticles of several oxides are very promising llers for coating materials. Generally, these small oxide particles provide

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improved resistance to oxidation, corrosion, erosion and wear. Many efforts have been made to enhance the corrosion resistance of metallic substrates by using ZrO2 [10,11], CeO2 [12,13], SiO2 [14,15], Al2 O3 [16], and other mixed oxides. Among these, CeO2 and ZrO2 , particularly, are very interesting due to their resistance to high temperature oxidation, corrosion, mechanical abrasion and wear [12,13,17]. Cerium oxides and cerium hydroxides are also reported as cathodic inhibitors [1820] and have been proposed as effective species for the protection of metals from corrosion. Zirconium oxides also possess very attracting properties, such as improved resistance to wear and corrosion, biocompatibility, heat resistance and good adhesion to metallic surfaces [2132]. ZrO2 thin lms have been applied for corrosion protection of metals. Chemical vapour deposition [25], eletrophoretic deposition [26] and solgel deposition by dip coating procedure [24,27,33] are common routes to prepare ZrO2 coatings for anti-corrosion purposes and for the improvement of mechanical properties [2832]. Non-active SiO2 [3438] or CeO2 [38] nanoparticles have been applied as additives in silane coatings, leading to composite systems with improved anti-corrosive resistance. ZrO2 CeO2 lms were deposited on metals by solgel processing [39]. Their improved corrosion behaviour was attributed to a decreased ow of aggressive species through the coating. The extent of the improvement depended upon the thermal treatment of the sample and coating thickness [40]. New hybrid solgel coatings containing ZrO2 nanoparticles and doped with cerium ions, provide longer corrosion protection, since the ZrO2 particles could play the role of nanoreservoirs for storage and controllable release of the inhibitor [41]. Despite the large number of works published in literature that explored the unique properties of CeO2 and ZrO2 very little has been published using a combination of both in the eld of the pre-treatments. The present work reports the anti-corrosion properties of a new pre-treatment for galvanised steel obtained by dipping the metallic substrate in a silane solution modied with 250 ppm of CeO2 ZrO2 nanoparticles. Two approaches are reported: the rst one investigates the morphological features and the electrochemical behaviour of silane coatings containing the CeO2 ZrO2 nanoparticles, whereas the second approach examines the corrosion activity of zinc electrodes immersed in NaCl solutions containing the nanoparticles. Furthermore, we present an electrochemical study in which advanced localised electrochemical techniques (SVET and SIET) are combined with conventional d.c. measurements in order to better understand the corrosion mechanisms. The results show that silane coatings modied with nanoparticles enhanced the corrosion protection of galvanised steel substrates. The role of the nanoparticles is analyzed and discussed.

in the silane solution was 250 ppm. The solution was stirred for one hour and then stored for a few days before use. Galvanised steel coupons, having a zinc coating weight of approximately 140 g/m2 were used. No post annealing was performed on this material. Pure zinc coupons (Goodfellow; 99.9%) were also prepared. The coupons (either galvanised steel or zinc) were degreased using an alkaline cleaner (Novomax ) for 45 min at 50 C, washed with distilled water, dried in air and immersed in the modied silane solution for 10 s. The treated coupons were cured in the oven at 120 C for 40 min. 2.1.2. Nanoparticles added to aqueous solutions Aqueous solutions of 0.005 M NaCl containing 250 ppm of nanoparticles were prepared and continuously stirred. d.c. electrochemical experiments were performed under stirring. Two test solutions were prepared: 0.005 M NaCl pH 6 and 0.005 M NaCl plus NaOH pH 10. The nanoparticles were CeO2 ZrO2 or, for comparative purposes, CeO2 (30 < < 40 nm), both obtained from SigmaAldrich. 2.2. Electrochemical techniques 2.2.1. EIS The EIS measurements were carried out using a Gamry FAS1 Femtostat with a PC4 Controller Board. The experiments were performed at room temperature, in a Faraday cage, at the open circuit potential, using a three-electrode electrochemical cell, consisting of the working electrode (3.15 cm2 of exposed area), saturated calomel electrode (SCE) as reference and platinum as counter electrode. The measuring frequency ranged from 100 kHz down to 5 mHz. The rms voltage was 10 mV. The EIS experiments were performed during immersion of the pre-treated galvanised steel substrates in solutions of 0.005 M NaCl for one week. Spectra were treated using the Z-view Software using the adequate equivalent electric circuits. 2.2.2. SVET The SVET measurements were performed using Applicable Electronics equipment, controlled by the ASET program (Sciencewares). The vibrating electrode was made of platinumiridium covered with polymer, leaving only an uncovered platinum black tip with a diameter of 2030 m. The average distance of the tip to the surface was kept at 200 m and the scanned area was 2 mm 2.5 mm, with maps of 50 50 points. To evaluate the corrosion inhibition performance of the modied silane lm, a scratch was made on the surface using an edge knife. The dimensions of the scratch were approximately 1 mm (length) 0.1 mm (wide). The zinc surface was exposed in the scratch. Silane treated galvanised steel or silane treated zinc coupons were immersed in the aggressive solution (0.005 M NaCl) and measurements were taken periodically. 2.2.3. SIET The SIET measurements were performed with Applicable Electronics equipment, controlled by the ASET program (Sciencewares). The pH micro-potentiometric electrodes were made in the laboratory as described in reference [42] using hydrogen I cocktail B ionophore (Fluka, Ref. 95293). These electrodes have a linear potentialpH response from pH 5.512. The microelectrodes were calibrated before and after the measurements with commercial pH buffers. Maps with 30 30 points were obtained in a plane 50 m above the samples surface. SIET measurements were performed on the silane treated zinc coupons immersed in 0.005 M NaCl. Prior to immersion a scratch of approximately 1 mm length by 0.1 mm wide was performed on the silane coating, exposing the zinc substrate.

2. Experimental procedure 2.1. Materials 2.1.1. Silane coatings Bis-[triethoxysilylpropyl]tetrasulde silane (BTESPT) was chosen because it forms lms with very high hydrophobicity and therefore good potentialities for corrosion protection, as reported in previous works [8,9]. The silane solution was prepared by dissolving 5% (v/v) of BTESPT (SigmaAldrich) in a mixture of methanol (90%, v/v) and aqueous dispersion of nanoparticles (5%, v/v). The aqueous dispersion was produced by dispersing ultrasonically, in water, CeO2 ZrO2 (CAS number 53169247) nanoparticles (SigmaAldrich) with purity 99% and an average diameter around 25 nm (measured by XRD). The nal concentration of nanoparticles

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2.2.4. d.c. polarization Current vs. time experiments were performed on galvanised steel substrates. The applied potential was 50 mV above the open circuit potential. Potentiodynamic polarization experiments were performed in solutions of 0.005 M NaCl and NaOH (pH 10) containing 250 ppm of CeO2 ZrO2 or 250 ppm of CeO2. These experiments aim at understanding the behaviour of the zinc surface under pH conditions identical to those generated by the cathodic activity when the galvanised steel substrate coated with silane is corroding. Thus, the experiment intends to simulate a cathodic delamination process and to investigate the role of the nanoparticles in such process. The potentiodynamic polarization curves were performed using a RADIOMETER-VOLTALAB PGZ 100 apparatus. The scan rate was 1 mV/s in the anodic or in the cathodic direction, starting from the open circuit potential after different stabilization times. The working electrode was pure zinc with dimensions 10 mm 10 mm 1 mm. The samples were mounted in an epoxy

resin mould, polished with SiC papers (Buehler) until 1200 grit, washed with deionised water and ethanol and nally dried with compressed air. The electrochemical cell used in the d.c. experiments was similar to the one described for the EIS measurements. 2.3. Microscopic techniques 2.3.1. SEM/EDX The microstructure, qualitative chemical composition and thickness of the bis-1,2-[triethoxysilylpropyl]tetrasulde-based lms containing CeO2 ZrO2 nanoparticles before immersion in NaCl solution were studied by scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy. Semi-in-lens Hitachi SU70 UHR Schottky (Analytical) FE-SEM microscope with an electron beam energy of 15 keV or 5 keV was used. The sample for crosssection analysis was prepared by embedding a coated coupon into epoxy resin. The sample was polished sequentially with 400, 800,

Fig. 1. (a) SEM image of the Zn coupon coated with the silane coating containing CeO2 ZrO2 nanoparticles, (b) overall EDX spectrum of the image presented in (a), (c) cross-section image and (d) EDX mapping of the same coating deposited on zinc substrates, (e) SEM image and (f) EDX mapping of CeO2 ZrO2 nanoparticles incorporated into silane coating.

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1200, 2400 and 4000 grade sand paper in ethanol. The sample was then polished with CafroTM diamond paste down to 0.5 m and cleaned ultrasonically in ethanol. 2.3.2. AFM The morphology of the pre treated Zn surface was assessed using a PicoLETM Atomic Force Microscope from Molecular Imaging. Measurements were done in AC Mode using Si probes highly doped to dissipate surface charge with tip radius <10 nm. 3. Results 3.1. Morphological Investigation The SEM/EDX images depicted in Fig. 1 show the plane view (a), the overall EDX spectrum (b) of the area presented in (a), the cross-section representation (c) and the EDX mapping (d) of a nanoparticles-doped silane coating applied on zinc coupons. The lm is uniform, without relevant defects. All elements of the coating and nanoparticles were identied by EDX analysis (b). No cracks induced by addition of CeO2 ZrO2 were visualized on the surface of the coating. Some agglomerates of nanoparticles could be observed at low magnication (Fig. 1a) and the EDX analysis of this region clearly shows the presence of cerium and zirconium peaks. A closer view (Fig. 1e) and the respective EDX maps taken at low accelerating voltage (5 keV) to avoid the cracking of the coating revealed

the presence of cerium and zirconium, conrming the presence of CeO2 ZrO2 nano-sized particles agglomeratesFig. 1(e and f) and a relatively uniform distribution of nanoparticles in the coating. The thickness of the bis-1,2-[triethoxysilylpropyl]tetrasulde silane lm deposited on the Zn substrate was around 0.81.1 micrometers. The EDX analysis of the cross-section zones revealed that the main components of the coating were Si and S together with Zn from the substrate Fig. 1(b and d). Fig. 2 presents atomic force microscopy (AFM) topography and the phase images taken on the zinc coupons coated with the nanoparticles-modied silane coating and on the coating without addition of nanoparticles, which was used as a reference. The single nanoparticles cannot be clearly seen in the topography image (Fig. 2a), however, the phase image presented in Fig. 2b shows the presence of agglomerates and very small nanoparticles. These nanoparticles appear to be 4060 nm in diameter. The size difference between the initially added nanoparticles and the values measured by AFM can be explained by the presence of a silane layer on the top of the nanoparticles. Thus, AFM measures the convexity of the surface originated by the underlying nanoparticles. Apart from single nanoparticles, some agglomerates (ranging from 100 to 600 nm) are visible on the topography map. The phase image does not show signicant differences between the matrix and agglomerates, which can be explained by the presence of the silane lm at the top of CeO2 ZrO2 agglomerates. The roughness (RMS) of the topographic images presented in Fig. 2 are 85 and

Fig. 2. AFM topography (a) and phase (b) maps obtained at the silane lms containing CeO2 ZrO2 nanoparticles and on silane lms without nanoparticles (c and d), before immersion in 0.005 M NaCl. Z height of images (a) and (c) is 23 nm and 144 nm, respectively.

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31 nm for samples with addition of nanoparticles and without, respectively. The differences in roughness are caused by the addition of the nanoparticulated mixed oxides to the silane solution in the course of synthesis. 3.2. Electrochemical investigation 3.2.1. Barrier properties The role of the nanoparticles in the barrier properties of the silane coating applied on galvanised steel substrates was evaluated via EIS in 0.005 M NaCl solutions. The concentration of the NaCl solution is low because the main goal of this work is to understand how the nanoparticles affect the corrosion behaviour. Therefore, it is necessary to delay the corrosion processes to get as much information as possible. Fig. 3 depicts the electrochemical impedance spectra obtained on the galvanised steel substrates pre-treated with the silane lm lled with CeO2 ZrO2 nanoparticles. Spectra for a silane lm without nanoparticles (blank silane) and for untreated galvanised steel were also included in Fig. 3 for comparative purposes. One broad time constant could be observed. The impedance spectra show a resistive behaviour at very high frequencies followed by a capacitive response and, in the low frequency domain, a resistive plateau with impedance values around 108 cm2 . With further increase of the immersion time, a small drop of the low frequency impedance values was observed. At the end of the tests no signs of corrosion activity could be detected on the pre-treated surface. In previous works [8] we proposed three different equivalent circuits, for the tting of the EIS data obtained on doped silane lms. The number of time constants depended upon the dopants and immersion time as previously reported [8]. Since in this work EIS was used to evaluate the barrier properties of the nanoparticles lled coating the impedance spectra were tted using the equivalent circuit shown in Fig. 4. Only one time constant was considered due to the very high impedance values. This option gave the smallest error in the tting routines. The equivalent circuit includes the electrolyte resistance and a R/CPE contribution to simulate the capacitive and low frequency resistive behaviour. The tting of the capacitive part of the spectra was made using a constant phase element (CPE). Generally the CPE is associated with

Fig. 3. Impedance Bode plots obtained on the galvanised steel sample pre-treated with the silane lm lled with CeO2 ZrO2 nanoparticles. Spectra for the blank silane lm and for untreated galvanised steel (HDG) obtained after one day of immersion are also presented for comparative purposes.

Fig. 4. Equivalent circuit used for numerical tting of the EIS spectra and tted spectra for the silane coatings containing CeO2 ZrO2 nanoparticles after one day of immersion in 0.005 M NaCl.

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Fig. 5. Evolution of the CPE parameters during immersion of the treated galvanised steel coupons in 0.005 M NaCl. Values obtained for a blank silane coating are also presented.

a distribution of the capacitance over the surface or to changes of the capacitance with frequency [43]. One example of the tting procedure adopted is presented in Fig. 4. The evolution of the tting parameters obtained from the numerical simulation of experimental spectra are depicted in Figs. 5 and 6. Generally the n exponent of the CPE element was in the range 0.950.9. Fig. 5 shows a very small increase of the coating capacitance during the rst day of immersion. This increase was due to electrolyte uptake through conductive pathways that developed inside the lm. However, changes were limited to a few nF/cm2 sn1 suggesting a very high stability of the silane coating during the test period. The silane coating also presented very high resistances, that decreased during immersion from 100 M cm2 , down to 10 M cm2 (Fig. 6). These values are about three orders of magnitude higher than those observed in a blank silane lm. The thickness of modied silane lms deposited on galvanised steel substrates is generally higher than those of the blank lms (0.51 m). These differences could contribute to the improved barrier properties, but other factors like lower porosity and lower conductivity of the lled lms can also contribute to the improved behaviour. This result shows that the presence of CeO2 ZrO2 nanoparticles enhanced the barrier properties of the silane coating, delaying corrosion onset.

3.2.2. Corrosion inhibition at localized defects Electrochemical impedance spectroscopy provides data about the average response over the entire sample surface. However, the scanning vibrating electrode technique (SVET) and the scanning ion-selective electrode technique (SIET) allow local electrochemical information to be obtained in the form of local current density maps or pH maps, respectively, over the exposed metallic surface. SIET measures potentiometrically the concentration of specic ions in solution (pH in this work) at selected distances from the surface [42,44,45]. These local measurements are very useful to understand the ability of the nanoparticles to inhibit corrosion activity in localized defects, such as scratches. The measured distributions of current or potential can be represented as two or three dimensional maps or as current plots across lines. The SVET maps give quantitative information about anodic and cathodic currents densities and show how the anodic vs. cathodic activity changes during immersion. The SIET maps allow monitoring the changes of the pH, both in the anodic and cathodic areas when the corrosion activity proceeds. The combination of both techniques is a relatively new approach in corrosion studies and constitutes a strong tool to understand corrosion and corrosion inhibition mechanisms at the microscale level. Fig. 7 shows the SVET maps obtained on the galvanised steel substrates pre-treated with blank silane and with a silane coating lled with CeO2 ZrO2 nanoparticles. Prior to immersion a defect was made on the specimen surface in order to expose the substrate. This procedure ensures that corrosion activity starts at the same time in both substrates. Therefore, it allows a better comparison of the results and a better understanding of the role of the nanoparticles. After one hour of immersion, the SVET maps showed signicant differences. The substrate coated with the blank lm (Fig. 7A) developed strong anodic activity over the scratch; the remaining surface behaving essentially as cathodic. Since oxygen reduction is the main cathodic reaction expected, the large cathodic areas revealed that oxygen could easily access the inter-

Fig. 6. Evolution of the coating resistance (Rc) during immersion of the treated galvanised steel coupons in 0.005 M NaCl. Values obtained for a blank silane coating are also presented.

Fig. 7. SVET maps obtained in the scratched BTESPT silane lms (A) and CeO2 ZrO2 lled BTESPT silane lms (B) after one hour of immersion in NaCl 0.005 M. Scan size: 2 mm 2.5 mm. Current units: A/cm2 .

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Fig. 8. SVET maps (ionic currents left and surface images right) obtained in the scratched BTESPT silane lms (images A and B), CeO2 ZrO2 lled BTESPT silane lms (images C and D) after 24 and 48 h of immersion in NaCl 0.005 M, respectively. Scan size: 2 mm 2.5 mm. Current units: A/cm2 .

face. The surface of the system pre-treated with the silane coating lled with CeO2 ZrO2 nanoparticles (Fig. 7B) showed much lower anodic/cathodic current densities, revealing much weaker corrosion activity on the exposed surface. The anodic current densities were about one order of magnitude below those measured in the blank lm. This trend was observed during the whole experiment that lasted for 48 h of immersion. For the blank silane lm, with time, there was a decrease of the current density on the initial active area due to precipitation of zinc corrosion products, but several new anodes developed and, after 24 h, signicant delamination could be observed around the initial scratch (Fig. 8A and B). After 48 h of immersion the blank coating was strongly deteriorated and generalised corrosion activity was observed. For the coating modied with the nanoparticles, the anodic current densities were always below 10 A/cm2 and after 48 h (Fig. 8C and D) the rst signs of delamination could be observed around the scratch. The SVET results indicated that the galvanised steel substrates pre-treated with the silane coatings containing CeO2 ZrO2 nanoparticles provide a signicant delay of the corrosion activity at localized scratches. Fig. 9 shows the current vs. time curves obtained on the galvanised steel substrates treated with the blank silane coating and with the silane coating modied with CeO2 ZrO2 nanoparticles. Prior to measurement a scratch was made on the surface. For the blank coating the current increased and attained stable values around 100 A/cm2 . However, in the presence of nanoparticles the initial shift was followed by a slow decrease and stabilisation at values around 1 A/cm2 , two orders of magnitude below those of the blank lm. Although this measurement gives an average value of the electrode behaviour, it showed a very good agreement with the localised SVET measurements. The previous electrochemical results clearly showed that the nanoparticles delay the development of the corrosion activity of

galvanised steel substrates. They provide better barrier properties and delay corrosion activity at localised defects. In order to better understand the role of the nanoparticles a number of SVET, SIET and potentiodynamic polarisation tests were carried in coated and uncoated zinc samples immersed in NaCl solutions. 3.2.3. Role of the nanoparticles The mechanisms associated with the corrosion inhibition in the presence of nanoparticles were studied in pure zinc electrodes coated with the silane lm modied with the nanoparticles, using the SVET and SIET measurements. The study was complemented

Fig. 9. Current vs. time curves recorded for the scratched blank silane lm and CeO2 ZrO2 lled silane lm during immersion in NaCl 0.005 M.

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Fig. 10. SVET maps (A and C) and SIET pH maps (B and D) obtained on scratched BTESPT silane lms lled with CeO2 ZrO2 nanoparticles applied on zinc substrates after different immersion times in NaCl 0.005 M. Scan size: 2 mm 2.5 mm.

with potentiodynamic polarisation curves carried using untreated zinc electrodes in solutions containing the nanoparticles. The SVET and SIET maps obtained on pure zinc electrodes coated with the CeO2 ZrO2 nanoparticles modied coating are depicted in Fig. 10. The SVET map (Fig. 10A) obtained six hours after immersion revealed some anodic activity over the scratched area, as expected and in good agreement with the results obtained for the galvanised steel substrates. For the early stages of immersion the anodic currents densities were very low and the pH at the anodic sites was around 6. The cathodic sites were characterised by higher pH values, which attained 8.5. After three days of immersion the behaviour was signicantly different. The anodic currents increased to values that are one order of magnitude above the initial ones and new anodic sites appeared on the surface, extending the corroded area. The pH around these areas was nearly neutral since zinc corrosion does not lead to signicant acidication. The cathodic activity became more localised as it can be seen in the left bottom. The pH starts to increase in the neighbours of the cathodic zones and attained 10.5, at the centre of the cathodic area. It should be noted that the pH measurements were made 50 m above the surface which means that the pH of the solution in direct contact with the metal is even higher in the cathodic regions. The SIET maps

reveal that the increased anodic activity at the scratched area is accompanied by a stronger alkalinisation at the cathodic sites. In a complementary experiment, the zinc electrodes where immersed in a solution of NaCl 0.005 M plus NaOH at pH 10, simulating the conditions that were observed at the cathodic areas (see Fig. 10D), where precipitation of zinc hydroxides takes place. Fig. 11 shows the potentiodynamic polarisation curves obtained under these conditions. In this experiments tests were performed using the CeO2 ZrO2 nanoparticles and, for comparative purposes, CeO2 nanoparticles, too. For the zinc electrode immersed in the solution containing the CeO2 nanoparticles a clear passivation range, extending from the corrosion potential up to 0.7 V could be observed. Above 0.7 V the current increased due to zinc dissolution. An identical trend could be observed for the solution modied with the CeO2 ZrO2 nanoparticles. In this case, the corrosion potential was slightly more negative, but the current densities were identical. For the blank solution (without nanoparticles) the corrosion potential was 1.0 V. A clear passivation range could not be observed; however, the current changes were very small for the potential range between 0.9 and 0.8 V, suggesting an incipient passivation range. In this case the anodic current densities were more than one order of magnitude higher

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Fig. 11. Anodic potentiodynamic polarisation curves obtained in solutions of 0.005 M NaClpH 10, with and without addition of 250 ppm of nanoparticles using pure zinc electrodes.

comparatively to the electrodes polarised in the solutions containing the nanoparticles. The potentiodynamic polarisation results revealed that the presence of nanoparticles improves the self-passivation of zinc electrodes in alkaline environments, decreasing the anodic current densities and shifting the breakdown potential towards more positive values. The polarisation measurements showed that the behaviour of zinc electrodes exposed to solutions containing the CeO2 ZrO2 or CeO2 nanoparticles revealed an identical behaviour. Therefore, it seems that the zirconia component of the nanoparticles probably do not provide signicant corrosion inhibition effects. Conversely, the cerium oxide plays the role of active element. The benecial effects of CeO2 in improving the passivation range of stainless steels electrodes immersed in aggressive conditions have been previously reported [46]. 4. Discussion The modication of functional coatings, like silanes or solgel coatings with species able to inhibit corrosion or to impart self healing ability as well as improved barrier and mechanical properties is nowadays a big challenge in the corrosion protection eld. An attracting route to incorporate this active species in the coating is through doping with nanoparticles or with organic or inorganic inhibitors or through encapsulation of reservoirs containing the inhibitor [5,47,4952]. This last approach consists on the use of silica nanoparticles covered layer-by-layer with polyelectrolyte layers and layers of inhibitor (benzotriazole) that is slowly released to the electrolyte solution due to pH changes [51]. The use of nanoparticles directly covered with ions able to provide corrosion inhibition properties, like cerium ions [38,41,48,52], is also another approach that makes silane and solgel coatings smarter face to the corrosion processes. These procedures raise some important questions: Which nanoparticles shall be chosen? How stable are these nanoparticles and do they have an active role? In previous works [38,52] we demonstrated that CeO2 nanoparticles were more effective in terms of corrosion protection comparatively to SiO2 nanoparticles.

These nanoparticles enhanced the barrier properties of the silane coatings comparatively to a blank lm and, furthermore, it was demonstrated that the CeO2 nanoparticles, by themselves provided a delay of the corrosion activity, starting at defects. Additionally, in a previous work [8] we reported that Zr-modied silane lms presented very good barrier properties, but no signicant corrosion inhibition ability. Therefore, in this work, we proposed another approach, which aims at creating a synergistic effect, by the combination of zirconia and ceria nanoparticles. The results demonstrated that the use of CeO2 and ZrO2 nanoparticles as llers in silane coatings resulted in a very effective procedure to improve both the barrier properties of the coating and to reduce corrosion activity. The EIS measurements revealed that the coating modied with the nanoparticles could attain impedance values near 100 M cm2 , much higher than the values measured for a blank lm and also higher than the values measured for lms modied with CeO2 only [38]. The enhancement of the barrier properties can be attributed to the presence of the inorganic component and probably to lower porosity and conductivity as proposed in previous works [52]. In this work the SVET and d.c. measurements revealed a signicant decrease of the corrosion activity in the presence of nanoparticles. This means that the nanoparticles behave not only as llers for enhanced barrier properties as observed by EIS, but also as active llers, which reduce the corrosion activity. The d.c. polarization tests carried in solution, revealed two important features: the open circuit potential was shifted towards nobler values and there was a clear decrease of the anodic current density in the presence of nanoparticles. Furthermore, by comparing the potentiodynamic polarisation results obtained in the presence of CeO2 nanoparticles and in the presence of CeO2 ZrO2 nanoparticles, the inhibition effect could be assigned to the CeO2 component in the CeO2 ZrO2 nanoparticles rather than the ZrO2 component. However, the ZrO2 component also plays an important role, contributing for the enhancement of the barrier properties. We demonstrated in previous works [8] that zirconium ions led to very good barrier properties, whereas the addition of cerium led to more effective corrosion inhibition ability. To interpret the improved corrosion resistance of the silane coatings modied with the nanoparticles the following explanation can be drawn: the CeO2 ZrO2 nanoparticles are homogeneously dispersed in the lm as demonstrated by SEM/EDX and AFM. When a scratch is made on the surface, there is development of anodic (exposed sites) and cathodic activity (around the scratch) where oxygen is available. In the conditions tested in the present work, the main cathodic reaction is oxygen reduction with production of hydroxyl ions. The Zn2+ ions produced at the anodic areas migrate to the cathodic places where they combine with OH to form zinc corrosion products, which in the presence of chloride ions also lead to the formation of simonkolleite and/or other zinc chloride charged ions as reported in literature [53,54]. Simultaneously to these processes, and under the increased pH that attained values higher than 10 as demonstrated by SIET, the silica component of the silane coating starts to decompose into an hydrated and expansive gel, because silica is not stable at increased pH values. Conversely, the CeO2 ZrO2 nanoparticles are very stable under those alkaline conditions. The CeO2 nanoparticles are characterised by a uorite structure that easily develop oxygen vacancies, making these nanoparticles highly reactive. Furthermore, literature reports that the maximum of defects concentration develops at pH values between 10 and 11 [55]. The high surface reactivity of ceria has been explored for several applications like for example to remove ionic species in water treatment routines or for the xation of metallic cations, like Zn2+ in the formulation of sunscreens. Generally, the species formed are very stable ceria-based oxides. Therefore,

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the CeO2 nanoparticles may complex with the zinc charged species formed during anodic polarisation, stabilising the layer of protective zinc corrosion products. When the nanoparticles are embedded in the silane coating, the mechanism can be assumed as similar. Thus, at the cathodic areas, where the pH reaches values over 10, the silica network decomposes, releasing the nanoparticles that precipitate on the electrode surface, forming complexes with the zinc charged species and reinforcing their protective role. These more stable corrosion products decrease the active area available for the half-cell reactions, therefore slowing down the corrosion activity. The results obtained in this work evidence that CeO2 ZrO2 nanoparticles play an active role in the corrosion protection performance when they are added as llers to hybrid silane coatings. Therefore, the reinforcement of silane coatings with such nanoparticles, leads to the formation of more protective surface layers, which improve the lifetime of the metallic substrate. 5. Conclusions Bis-1,2-[triethoxysilylpropyl] tetrasulde silane coatings modied with CeO2 ZrO2 nanoparticles applied by dipping procedures can be used as llers to improve the corrosion resistance of silane pre-treatments for galvanised steel. The addition of nanoparticles to the silane solution enhanced the barrier properties of the modied silane coatings. In the presence of defects the corrosion activity was delayed for the coatings containing the CeO2 ZrO2 nanoparticles. The polarization measurements suggest that the inhibition effects are mainly due to the presence of the CeO2 component of the nanoparticles. The nanoparticles in solution induce an important polarization of the anodic reactions and a decrease of more than one order of magnitude on the corrosion current density. The increased anodic activity observed around the scratched areas was accompanied by an increased pH over the cathodic regions. The presence of nanoparticles improves the passivity range of zinc in alkaline medium, therefore delaying the breakdown of the lms under chloride attack. References
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