J Nanopart Res (2011) 13:541554 DOI 10.

1007/s11051-010-0044-x

RESEARCH PAPER

Release studies of corrosion inhibitors from cerium titanium oxide nanocontainers

Evaggelos D. Mekeridis Ioannis A. Kartsonakis George S. Pappas George C. Kordas

Received: 19 March 2010 / Accepted: 7 July 2010 / Published online: 23 July 2010 Springer Science+Business Media B.V. 2010

Abstract Cerium titanium oxide nanocontainers were synthesized through a two-step process and then loaded with corrosion inhibitors 2-mercaptobenzothiazole (2-MB) and 8-hydroxyquinoline (8-HQ). First, polystyrene nanospheres (PS) were produced using polymerization in suspension. Second, the PS spheres were coated via the solgel method to form a cerium titanium oxide layer. Finally, the nanocontainers were made by calcination of the coated PS nanospheres. The size of the containers was 180 10 nm as determined by Scanning Electron Microscopy (SEM). X-Ray Diffraction Analysis (XRD) showed that the nanocontainers consist of anatase and cerianite crystalline phases. The presence and loading of the inhibitors in the nanocontainers was conrmed with Fourier Transform Infrared Spectroscopy (FTIR) and Thermo Gravimetric Analysis (TGA), respectively. TGA revealed the amount of 10.43 and 4.61% w/w for 2-MB and 8-HQ in the nanocontainers, respectively. Furthermore, the release kinetics of the inhibitors from the nanocontainers was studied in corrosive environment using electrochemical impedance spectroscopy (EIS) in the presence of aluminum alloys 2024-T3 (AA2024-T3).

Keywords Nanocontainers Corrosion Inhibitors Synthesis Drug delivery Introduction Nanosized materials have been a subject of intensive investigations in variety of topics from optics and electronics to biotechnology and medicine (Zheng et al. 2006; Ding et al. 2006; Pappas et al. 2008). Materials such as nanoparticles, nanospheres, and micelles can be used as drug delivery and drugcontrolled release systems. Hollow nanocontainers are of great interest because of their ability to encapsulate substances in their hollow inner cavities and release them at a later stage (Hu et al. 2005). Recently, it has been recognized that the nanocontainers loaded with corrosion inhibitors when incorporated into coatings provide additional protection of metal alloys, such as AA2024-T3, from corrosion. AA2024-T3 is mainly used in aeronautical applications. The methods of delivery of the inhibitors to the metal surface can inuence the efciency of the inhibiting action (Lamaka et al. 2007). According to Raps et al. (2009) and Khramov et al. (2004) the addition of corrosion inhibitors in solgel coatings in one hand can improve corrosion protection, on the other hand may deteriorate the barrier properties of the lm. Encapsulating corrosion inhibitors in nanocontainers and then added them to the protective coating system is an advantageous method to unite the barrier properties of the coatings with the active action

E. D. Mekeridis I. A. Kartsonakis G. S. Pappas G. C. Kordas (&) Sol-Gel Laboratory, Institute of Materials Science, NCSR DEMOKRITOS, 153 10 Agia Paraskevi Attikis, Greece e-mail: gkordas@ims.demokritos.gr

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of the corrosion inhibitors (Kartsonakis et al. 2007; Zheludkevich et al. 2005a, 2007a). Kartsonakis et al. synthesized hollow titania spheres using cationic polystyrene lattices which were prepared by polymerization in suspension of styrene using 2.20-azobis (2-methylpropionamidine) dihydrochloride (AMPA) as an initiator (Kartsonakis et al. 2008). Zirconia and silica nanoparticles were used as reservoirs for the storage and prolonged release of corrosion inhibitors in silica and silicazirconia based coatings by Zheludkevich et al. (2005a, 2007b) and found that the nanoparticles reinforced the coating and released inhibitors during contact with moisture. Shchukin et al. presented halloysite nanotubes with inner voids loaded by 2-MB and outer surfaces layer-by-layer covered with polyelectrolyte multilayers as a mean to optimize hybrid solgel lms (Shchukin et al. 2008). Cerium molybdate nanocontainers were synthesized and loaded with corrosion inhibitors (8-HQ and 1-Hbenzosulfonic acid) by Kartsonakis and Kordas (2009) Some of the most effective and environmental friendly corrosion inhibitors for aluminum alloys are derived from cerium salts. Nanostructured solgel coatings doped with cerium ions were investigated as pretreatments for AA2024-T3 (Zheludkevich et al. 2005b). Titania-containing organicinorganic hybrid solgel lms have been developed by Poznyak et al. as an alternative to chromate-based coatings for corrosion protection of aluminum alloys (Poznyak et al. 2008). 8-HQ and 2-MB compounds were studied as corrosion inhibitors by Lamaka et al. (2007) for AA2024-T3. They found that these inhibitors provide anticorrosion protection for AA2024-T3 forming a thin organic layer of insoluble complexes on the surface of the alloy. Inhibiting action is the consequence of suppression of dissolution of Mg, Al, and Cu from the corrosion active intermetallic zones (Lamaka et al. 2007; Sanyal 1981; Zheludkevich et al. 2007c). Yasakau et al. examined the addition of 8-HQ at different stages of the synthesis process to understand the role of possible interaction of the inhibitor with the components of the solgel system (Yasakau et al. 2008). 2-MB was evaluated by Zheludkevich et al. (2005c) as corrosion inhibitor for protection of AA2024-T3 in neutral chloride solutions. Otsuka-Yao-Matsuo et al. (2004) studied the photocatalytic behavior of CeTiO4 and CeTi2O6 powders. Keomany et al. prepared thin lms of

(CeO2)x(TiO2)1-x by a solgel process involving two alcoxides (Ce(OBuS)4 and Ti(OBun)4 in BuOH) were studied by cyclic voltammetry in a lithiumconducting polymer electrolyte in order to examine the inuence of the structure on the electrochemical insertion in such lms, which are suitable counter electrode materials for lithium-based electrochromic windows (Keomany 1995). In the present study, cerium titanium oxide hollow nanospheres were synthesized and characterized by SEM, XRD, TGA, and FT-IR. After that, these nanocontainers were loaded with corrosion inhibitors 2-MB and 8-HQ to produce an inhibitor delivery system. Studies were made on the % w/w loading of the inhibitors by heat treatments and FT-IR spectroscopy. The release of the inhibitors in a corrosive environment was tested via EIS. The results suggest the use of these loaded nanocontainers into coatings on metal alloys for corrosion protection of metals used for automobiles, ships, and airplanes.

Experimental Materials and reagents All chemicals were of analytical reagent grade. Titanium tetraisopropoxide (TTIP, Aldrich), polyvinylpyrrolidone (PVP, average molecular weight: 55,000, Aldrich), cerium (III) acetylacetonate (Ce (acac)3, Aldrich), sodium chloride (NaCl, Aldrich), sodium hydroxide (Aldrich), 2,20 -Azobis (2-methylpropionamidine) dihydrochloride (AMPA, Aldrich), and absolute ethanol (Aldrich), were used without further purication. Styrene (Aldrich) was double distilled under reduced pressure prior to use. Preparation of nanocontainers Cerium titanium oxide hollow nanospheres were synthesized through a three-step process. The rst step involves the preparation of positive charged polystyrene nanospheres. Styrene was polymerized by polymerization in suspension according to the conditions shown in Table 1. The polymerization process is described in our previous study (Kartsonakis et al. 2008). In order to eliminate the result of oxygen effect, the reactions were made in nitrogen atmosphere.

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J Nanopart Res (2011) 13:541554 Table 1 The conditions used in the preparation of polystyrene latex at 80 C Material Styrene AMPA Water Nanospheres size (nm)
a

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Quantity (g) 9.06 1.3 900 195 10a

Determined by scanning electron microscopy analysis

Table 2 Conditions of preparation of coated spheres Material Ethanol (ml) PVP (g) NaCl 5 mM (ml) Polystyrene (g) TTIP (ml) Nanospheres size (nm)
a

Quantity (g) 800 8.0 20 *9 9.0 215 10a

Determined by scanning electron microscopy analysis

Polymerization lasted 12 h. The solution was centrifuged and the precipitate was washed with distilled water. During the second step, the PS nanospheres were coated via solgel method. Solgel coating were prepared with controlled hydrolysis of the alcoholic solution of TTIP jai Ce(acac)3 in the presence of PS nanospheres, NaCl, and PVP (Table 2). PVP and NaCl were added to the mixture reaction to prevent aggregation of the core particles. The positive charged polystyrene reacts with the negative charged product of the hydrolysis of TTIP and Ce(acac)3. Monomers or oligomers of hydrolyzed TTIP and Ce(acac)3 are condensed on the surface of the polystyrene. Aging of the solutions at 60 C, centrifugation, and washing of the coated nanospheres were followed. The formation of hollow nanospheres was achieved after heat treatments of the composites at 600 C with heating rate 10 C min-1, where the polystyrene cores were burned off (Kartsonakis et al. 2007, 2008). Encapsulation and release of inhibitors The obtained cerium titanium nanocontainers were loaded with the corrosion inhibitors 8-HQ and 2-MB. The loading procedure included rst the preparation of a saturated solution of the inhibitor in acetone. After that, an amount of cerium titanium oxide

nanocontainers was placed in a sealed container. The nanocontainers were placed in a vacuum system to draw out the air inside them. Then, the saturated solution of the inhibitor in acetone was inserted in the sealed container and the whole mixture was stirred at room temperature for 12 h. Finally, the cerium titanium oxide nanocontainers loaded with the inhibitor were collected through centrifugation and were dried under vacuum overnight. The release of 8-HQ and 2-MB from nanocontainers was studied via EIS. A typical three electrode cell was used in a Faraday cage. For this purpose, solutions of 0.01, 0.05, and 0.1% w/v concentration of nanocontainers loaded with inhibitors in a corrosive environment (0.05 M NaCl) were prepared. Furthermore, solutions of pure inhibitors 8-HQ and 2-MB with the same concentration were also studied for comparison reasons. Panels of AA2024-T3 were used as the working electrode, a platinum sheet as the counter while a saturated calomel electrode (SCE) served as reference electrode. The panels had been previously cleaned, under specic conditions. The AA2024-T3 panel cleaning includes the insertion of it into 2% w/w solution of NaOH for 3 min at 40 C. After that, the panel is rinsed with distilled water and is inserted into 4.33 M solution of HNO3 for 1 min at room temperature. Finally, it is rinsed with distilled water. EIS measurements were taken after 3, 6, 24, 48, 72 h of exposure in 0.05 M NaCl solution. The exposed geometric area was 2 cm2 for all the experiments. All the samples were in vertical position; the experiments were carried out at room temperature. For every result, a minimum of three repetition measurements were taken. Instrumentation The average nanocontainer size and the morphology of the substrate after 72 h of exposition in NaCl, were determined by SEM using a PHILIPS Quanta Inspect (FEI Company) microscope with W (tungsten) lament 25 kV equipped with EDAX GENESIS (AMETEX PROCESS & ANALYTICAL INSTRUMENTS). The phase of the nanocontainers was examined by XRD using a powder diffractometer (SIEMENS D-500 equipped with a Cu Ka lamp with wavelength 1.5418 A). Temperature treatments such as Thermo Gravimetric Analysis (TGA) were made using a Perkin Elmer (Pyris Diamand S II) analyzer at the heating rate

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of 10 C min-1 in air. Fourier Transform Infrared Spectroscopy (FT-IR) was made using a BRUKER EQUINOX 55-S spectrometer. Nitrogen adsorption experiments and pore size measurements were performed using a volumetric static sorption apparatus (Autosorb-1 MP, Quantachrome Instruments). The release of inhibitors from nanocontainers was studied via Impedance analyzer (Solartron Sl 1260 Impedance/ gain-phase analyzer) connected to a Solartron PGstat (Solartron Sl 1470 Electrochemical interface).

Results and discussion Scanning electron microscopy analysis As shown in Fig. 1, the polymerization process leads to polystyrene nanospheres with uniform size with an average diameter of 195 10 nm. Figure 2 shows that after calcinations, the cerium titanium oxide hollow nanospheres exhibit an average diameter of 180 10 nm. The EDX analysis shows that titanium, cerium, and oxygen constitute the spectrum of the spheres. Gold appears due to the gold coating that was applied to the spheres in order to be conductive for the SEM analysis (Fig. 3). FT-infrared spectroscopy analysis Figure 4 shows the FT-IR spectrum of the nanospheres, before and after calcination. This spectrum
Fig. 2 SEM images of cerium titanium oxide hollow nanospheres

Fig. 1 SEM images of polystyrene nanospheres

veries the formation of inorganic shells and the complete removal of the organic components. The FT-IR spectrum in Fig. 4a of the nanospheres prior to calcinations reveals well-dened bands of the phenyl group (703, 750, 1445, 1494, and 3022 cm-1) in polystyrene. The peak at 2,919 cm-1 is due to the CH2 group. The peaks at 1590, 1150, and 1163 cm-1 are the band characteristic of PVP, indicating that PVP has not been well removed during the experimental process. It can be seen that the characteristic peaks of polystyrene are missing from the spectrum after calcination. The spectra in Fig. 4b, is the one after calcination; the band characteristic of the polystyrene latex have been disappeared, indicating that polystyrene latex has been well removed from the core/shell composite particles by calcination at 600 C. Both FT-IR spectra for as-prepared and after calcination samples show absorption peaks at the wave number region between 400 and 1,000 cm-1. This region contains bands typical of metal oxygen bonding. The absorption peaks of TiO2 are at 470, 525, 540, 579, 690, 700, 790 cm-1 (Kartsonakis et al. 2008; Zheludkevich et al. 2005c; Keomany 1995; Verma et al. 2004; Mc Devitt and Baun 1964). For CeO2, the characteristic peaks are at 425 cm-1, 525 cm-1, 540 cm-1 (Kartsonakis et al. 2007; Zheludkevich et al. 2005c; Keomany 1995; Verma et al. 2004). It is mentioned that the FTIR spectra after calcinations

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J Nanopart Res (2011) 13:541554 Fig. 3 EDX analysis of cerium titanium oxide hollow nanospheres

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Fig. 4 FT-IR spectra of: a cerium titanium oxide nanospheres (before calcination), b Cerium Titanium oxide hollow nanospheres (after calcination)

depict broad band at the region between 400 and 1,000 cm-1 and the above peaks can be distinguished. The broad bands in the range of 3,2003,500 cm-1 and at 1,652 cm-1 correspond to stretching vibration of OH bond of the physically adsorbed water in the sample (Verma et al. 2004). Thermogravimetric and differential thermal analysis Figure 5 shows the TGADTA diagrams of cerium titanium oxide nanocontainers. The rst weight loss is observed in the range of 30150 oC which can be attributed to desorption of physically adsorbed water

(free and physisorbed water) (Kartsonakis et al. 2007). The second weight loss in the range of 150230 oC can be attributed to the chemisorbed water; the monolayer of H2O molecules which directly interact with the solid surface such as cerium and titanium cations and hydroxyls and to the dehydroxylation (release of OH from the structure) (Kartsonakis et al. 2007; Kartsonakis and Kordas 2009). It is observed from the TGA diagram that polystyrene is burned off between 290 and 400 C (the third sharp weight loss). The fourth weight loss between 400 and 450 C is attributed to the burn off of polyvinylpyrrolidone (Jablonski et al. 2008). Hence, calcination at 600 C in air removed the polystyrene core particles completely. DTA diagram shows an exothermic peak between 260 and 340 C. This peak is due to the condensation of hydroxyl groups. The exothermic peak between 365 and 420 C is due to crystallization of amorphous cerium and titanium oxides into crystalline (Raps et al. 2009). This was conrmed by the XRD pattern shown in Fig. 6 of the sample treated at 600 C. The sudden decrease of temperature at 400 C is due to the accuracy of the instrument and depends on the heating rate (10 C min-1) and the organic content (PS) of the sample which are both very high. X-ray diffraction analysis Crystalline phases were identied according to the JCPDS (Joint Committee on Powder Diffraction Standards) le numbers 21-1271 and 43-1002 for

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Fig. 5 TGA and DTA curves of cerium titanium oxide hollow nanospheres

Fig. 6 XRD pattern of cerium titanium oxide hollow nanospheres

distribution was calculated through the B.J.H method at desorption isotherm and the mean pore radius found to be 1.6 nm with a pore volume 0.503 cc g-1. The hysteresis through desorption (Fig. 8) is characteristic for curves of type IV (IUPAC). This fact indicates the presence of mesopores in the sample. The observation of steps at the adsorption isotherm clearly denotes the presence of different size of pores in the sample. This result is both presented in the pore size distribution diagram and in the axis of relative pressure (through hysteresis that come near to 0.2) (Figs. 7, 8). The loaded nanocontainers with 8-HQ and 2-MB were degassed at 25 C for 18 h. The measurement of the 2-MB-lled sample showed some interesting results compared to the hollow nanospheres. The total amount of the adsorbate is less in the lled sample. The specic area decreased signicantly from 129 m2 g-1 for the hollow nanospheres to 17 m2 g-1 for the nanospheres lled with 2-MB. Also the pore size distribution, calculated from desorption branch through B.J.H method, showed a decrease in the pore volume from 0.503 to 0.301 cc g-1 indicating the lling of the pores and the hollow structure with the inhibitor. The pore size distribution of the lled sample did not show any pores with radius below 4 nm. The measurement of the sample lled with 8-HQ was impossible, due to evaporation of the inhibitor under the preparation conditions (high vacuum, leak test of the instrument). Encapsulation and release of inhibitors TGA diagrams of pure 8-HQ, 2-MB, and cerium titanium oxide nanocontainers loaded with 8-HQ or 2-MB are shown in Fig. 9. Pure 8-HQ began to degrade at 120 C until 212 C where no residue left. The diagram of cerium titanium nanocontainers loaded with 8-HQ shows a rst weigh loss between 30 and 130 C corresponding to acetone and physically adsorbed water (free and physisorbed water) (Takeuchi et al. 2005), a second weight loss between 130 and 170 C due to 8-HQ that is on the surface of the nanocontainers and nally a third and forth weight loss from 170 to 850 C correspond to oxidative degradation of encapsulated 8-HQ. Pure 2-MB is completely burned off between 180 and 330 C. The diagram of loaded nanoconainers with 2-MB depicts a sharp weight loss from 200 to 330 C corresponding to

anatase and cerianite, respectively. Figure 6 shows the XRD pattern of the sample after calcination. The peaks at 2h = 25.5 (101), 38.1 (004), 48.2 (200), 55.15 (105), 55.05 (211), and 62.9 (204) represent to tetragonal anatase. According to the JCPDS Library, the above peaks are slightly moved to higher values of 2h. The presence of cerium identied from the main peak at 2h = 28.6 (111), which is characteristic of cerianite, causes stress to the crystal structure of anatase leading to the increase of peak positions that mentioned above (Verma et al. 2007). Porosity measurements The samples of the empty nanocontainers were degassed at 300 C for 18 h before the measurement. The specic area was calculated with the B.E.T method in the range of relative pressure 0.050.3 P/P0 and was found to be 129 m2 g-1. The pore size

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J Nanopart Res (2011) 13:541554 Fig. 7 BJH pore distribution of cerium titanium oxide hollow nanospheres

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Fig. 8 Isotherms of cerium titanium oxide hollow nanospheres and loaded nanospheres with 2-MB

the oxidative degradation of the inhibitor that is on the surface of the nanocontainers, a second weight loss between 330 and 850 C due to the oxidative degradation of the inhibitor that are enclosed into the nanocontainers. Comparing the TGA diagrams, it is observed that pure 8-HQ is burned off at higher temperatures in the samples of cerium titanium nanocontainers loaded with this inhibitor. This retardation (roughly 200 C higher than pure inhibitor) is attributed to the protection provided by the shell of nanocontainers. This result indicates that 8-HQ is encapsulated into nanocontainers. The same analysis can be made for the nanocontainers loaded with 2-MB. The burn off 2-MB between 330 and 850 C corresponds to inhibitor that is inside the shell of the nanocontainers. The weight losses observed by the TGA measurements were used to determine the amount of inhibitors

loaded into the nanocontainers. First, we consider the sample of nanocontainers loaded with 8-HQ. We take the weight of the sample at 170 C (G1) and at 850 C (G2), we then subtract G2 from G1 (DG = G1 - G2) and last we divide DG by G1 to obtain the ratio mass loss, rm = DG*100/G1 due to 8-HQ. In the case of CeTi nanocontainers loaded with 8-HQ, rm is about 4.37% w/w. In the case of CeTi nanocontainers loaded with 2-MB, we take G1 at 330 C because the 2-MB burns off at this temperature. Above this temperature, the weight loss corresponds to mass encapsulated in the nanocontainer. G2 is taken at 900 C. We estimate rm about 25.36% w/w for the CeTi nanocontainers loaded with 2-MB. The release of the inhibitors was studied via EIS. If the inhibitors are released from the nanocontainers, they should provide corrosion protection of the AA2024-T3 panels. This can be observed by EIS. The rst experiment was accomplished using pure inhibitors in the solution (e.g. 2-MB 0.1% w/v in a salt solution) in order to clarify the extend of corrosion protection attributed to the inhibitors (Figs. 11, 13). The second experiment was carried out using lled nanocontainers with inhibitors (8-HQ Fig. 11, 2-MB Fig. 13) in order to observe the effect of protection due to the inhibitor release from the nanocontainers. The third experiment was done using different amounts of loaded nanocontainers in the solution (e.g. 0.01, 0.05, and 0.1% w/v) shown in Figs. 10 and 12 for 8-HQ and 2-MB, respectively. One can perceive an inuence of the concentration on the corrosion protection attributed to the release of the inhibitors from the nanocontainers. The best results against corrosion were obtained for 0.1% w/v, and correspond to the

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548 Fig. 9 TGA curves of: pure 8-HQ, pure 2-MB, and cerium titanium oxide nanocontainers loaded with 8-HQ and 2-MB

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Fig. 10 Bode diagrams of AA2024 after 72 h of immersion in 0.05 M NaCl with 0.01, 0.05, 0.1% w/v of nanocontainers loaded with 8-HQ and without nanocontainers

Fig. 11 Bode diagrams of AA2024 after 72 h of immersion in 0.05 M NaCl with a 0.1% w/v of nanocontainers loaded with 8-HQ, b pure inhibitor 8-HQ, and c bare AA2024

protection provided by the same concentration of pure inhibitor (0.1% w/v of 8-HQ and 2-MB). According to TGA measurements, the concentration of 2-MB in 0.1% w/v nanocontainers is 86.1 mM and the concentration of 8-HQ is 17.2 mM. The impedance at low frequencies corresponds to the polarization resistance of the AA2024-T3 electrode and, therefore, can be

used to estimate the corrosion protection (Lamaka et al. 2007). In the low frequency region, it can be seen that the total value of impedance is about one order of magnitude higher for the specimens immersed in the NaCl solution containing the nanocontainers loaded with inhibitors (Figs. 10, 11, 12, 13). It can be clearly seen that both chemical compounds worked as

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Instead of capacitances, Constant Phase Elements (CPE) were used in all ttings procedures because the phase angle of the capacitor is different from -90. The impedance of the CPE depends on frequency according to the following equation (Kartsonakis et al. 2007; Zheludkevich et al. 2005b). The impedance of the CPE depends on frequency according to the following equation 1 Qjxn Z 1

Fig. 12 Bode diagrams of AA2024 after 72 h of immersion in 0.05 M NaCl with 0.01, 0.05, 0.1% w/v of nanocontainers loaded with 2-MB and without nanocontainers

where Z is the impedance, Q a parameter equals to (1/ |Z|) at x = 1 rad s-1, x is the frequency and n B 1 a power coefcient calculated as ratio of phase angle at maximum of corresponding time constant to -90. The capacitance of the inhibitor is calculated by the following equation: Cinh Qinh xmax ninh 1 2

Fig. 13 Bode diagrams of AA2024 after 72 h of immersion in 0.05 M NaCl with a 0.1% w/v of nanocontainers loaded with 2-MB, b pure inhibitor 2-MB, and c bare AA2024

corrosion inhibitors comparing to the solution without loaded nanocontainers. Two time constants revealed at 5 and 0.01 Hz for the solution with nanocontainers. The higher frequency time constant can be assigned to the capacitance of the double layer on the surface of the alloy. The low frequency time constant is related to a diffusion limitation of the corrosion process (Lamaka et al. 2007).

xmax is the frequency at which the imaginary impedance reaches a maximum for the respective time constant. Rsol is the resistance of the solution, Rox is the resistance of the native oxide layer, Rinh is resistance of the inhibitor layer and Rpol is the polarization resistance. Cox and nox are the parameters of constant phase element (CPE) describing the capacitance of the oxide layer, Cinh and ninh are the parameters of the CPE describing the capacitance of the inhibitor layer. Cdl and ndl are the parameters of CPE which characterize the capacitance of the double layer capacitance (Lamaka et al. 2007). For the system with the nanocontainers, two time constants are observed at high frequencies which can be attributed to the native aluminum oxide layer (at about 1 Hz) and to the layer of adsorbed inhibitor (at about 50 Hz). In the case of 2-MB, the time constant attributed to the presence of the adsorbed layer is better observed at 72 h in NaCl with 0.05 and 0.1% w/v nanocontainers. In the case of 8-HQ, a wide time constant is observed consisted of the two phases that are mentioned above. Figure 14 shows the equivalent circuit used to t the experimental data. Tables 3 and 4 summarize the parameters obtained after tting. Figures 15, 16, and 17 present the evolution of the capacitance of the inhibitor layer as a function of the time for different nanocontainer concentrations. One

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Fig. 14 Equivalent circuit used for tting experimental EIS spectra

can perceive a dependence of the capacitance from the thickness of the layer that is formed from the dielectric constant and the resistance of the inhibitor after exposure of AA2024-T3 in 0.05 M NaCl solution with nanocontainers (Lamaka et al. 2007). It is observed that each inhibitor affects the time evolution and the extend of the capacitance in a different fashion. 2-MB loaded nanocontainers exhibit
Table 3 Calculated values for EIS data obtained at different immersion times for NaCl solution with 0.01, 0.05 and 0.1% w/v CeTi oxide nanocontainers loaded with 2-MB Parameter Rsol (X cm ) Rinh (X cm2) Qinh (S cm ) Ninh Cinh (F cm-2) Rox (X cm2) Rpol (X cm )
2 -2 2

0.01% 124 3,106 1.01E-4 0.760 6.49E-5 1,310 1,747

0.05% 132 1,541 5.84E-5 0.810 3.61E-5 5,612 3,866

0.1% 130 1,677 7.25E-5 0.820 4.23E-5 8,307 8,322

much higher values than 8-HQ loaded nanocontainers (Figs. 15, 16, 17). Furthermore, the parameters of capacitance and resistance of 8-HQ do not change signicantly as the time goes by compared to 2-MB. This may be attributed to the fast formation of a stable layer of the inhibitor on the aluminum surface. A prolonged decrease of the capacitance is observed for the solution with 0.1% w/w concentration of nanocontainers which can be attributed to the increase of thickness of the inhibitor layer. Both inhibitors form a dense layer on the surface of the aluminum alloy 2024-T3. Figures 15, 16, and 17 present the direct effect of the concentration of the 8-HQ-loaded nanocontainers to the resistance of the aluminum oxide layer, Rox. Low values of Rox are obtained for concentration 0.01% w/w. The values of Rox at 0.1% w/w are one order of magnitude higher than for concentration of 0.01% w/w. In the case of 2-MB loaded nanocontainers, these shifts are also of an order of magnitude with much higher absolute values, though. One can highlight at this position, that the curves of the theta versus frequency match for the inhibitor solution and loaded nanocontainer solution. This observation is a strong support of the assumption of the release of the inhibitors from the nanocontainers. This result demonstrates that the inhibitors are not trapped permanently in the nanocontainers.

SEM images and optical observation Figures 18 and 19 show an optical visualization of the protection of the AA2024-T3 surface provided by the loaded nanocontainers after exposure for 72 h in 0.05 M NaCl solution. Figure 18 demonstrates the degradation of the bare sample exposed in the corrosive environment without the presence of nanocontainers. One can perceive a fully corroded sample with many pits. On the other hand, the addition of the nanocontainers has decreased the number of the pits on the surface of AA2024-T3. This result is in agreement with the respective EIS measurements. As it was mentioned, the action of the nanocontainers is based on the formation of chelate complexes on the aluminum surface that are difcult to be dissolved. This can be proved by the EIS measurements with the appearance of two time

Table 4 Calculated values for EIS data obtained at different immersion times for NaCl solution with 0.01, 0.05 and 0.1% w/v CeTi oxide nanocontainers loaded with 8-HQ Parameter Rsol (X cm2) Rinh (X cm2) Qinh (S cm-2) Ninh Cinh (F cm-2) Rox (X cm ) Rpol (X cm2)
2

0.01% 141.4 552.6 5.53E-4 0.790 3.75E-4 554.8 1,015

0.05% 145.8 305.7 5.67E-4 0.720 2.45E-5 351 1,414

0.1% 131.4 69.16 9.84E-5 0.780 7.64E-5 1796 8,204

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Fig. 15 Evolution of capacitance and resistance of inhibitor lm after exposure for 72 h in 0.05 M NaCl solution containing CeTi nanocontainers loaded with 2-MB

Fig. 16 Evolution of resistance of aluminum oxide layer after exposure for 72 h in 0.05 M NaCl solution containing CeTi nanocontainers loaded with: 2-MB, 8-HQ

Fig. 17 Evolution of capacitance and resistance of inhibitor lm after exposure for 72 h in 0.05 M NaCl solution containing CeTi nanocontainers loaded with 8-HQ

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Fig. 18 Visual photograph of AA2024-T3 sample after exposure for 72 h in 0.05 M NaCl

constants for the solutions with the nanocontainers assigned to the aluminum oxide layer and to the adsorbed layer of the corrosion inhibitor or to the products of the interaction of Al3?, Mg2?, or Cu2? that are formed through the initial stages of corrosion. The layer that is formed by the chelate complexes blocks the penetration of chloride ions to the native oxide layer leaving it intact (Lamaka et al. 2007; Yasakau et al. 2008). The formation of the chelate complexes on the surface of aluminum and to the active regions of 2024-T3 alloy stops the evolution of corrosion and is the cause of locally active protection Fig. 19. The totally corroded AA2024-T3 is presented in Fig. 20. On the other hand, the formation of the inhibitor layer can be observed using SEM as shown in Fig. 21 and Fig. 22.

Fig. 19 Visual photographs of AA2024-T3 panel after exposure for 72 h in 0.05 M NaCl with a 0.01%, b 0.05%, c 0.1% w/v of nanocontainers loaded with 8-HQ and d 0.01%, e 0.05%, f 0.1% w/v of nanocontainers loaded with 2-MB

Fig. 20 SEM images of AA2024-T3 panel after exposure for 72 h in 0.05 M NaCl solution without nanocontainers a magnication 1,000, b magnication 50,000 and c EDX analysis

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J Nanopart Res (2011) 13:541554 Fig. 21 SEM images of AA2024-T3 panel after exposure for 72 h in 0.05 M NaCl solution with nanocontainers loaded with 8-HQ a magnication 1,000, b magnication 50,000 and c EDX analysis

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Fig. 22 SEM images of AA2024-T3 panel after exposure for 72 h in 0.05 M NaCl solution with nanocontainers loaded with 2-MB a magnication 1,000, b magnication 50,000 and c EDX analysis

Conclusion Cerium titanium hollow nanocontainers were synthesized. Their size was characterized by SEM measurements and was 170 10 nm. XRD analysis showed that the nanospheres consist of anatase and cerianite crystalline phases. Thermal treatments with TGA and DTA proved that hollow nanospheres are produced due to burn off of polystyrene cores. The synthesized nanocontainers have different size of pores. Moreover, these nanocontainers were loaded with the corrosion inhibitors 8-HQ and 2-MB. Thermal treatments with TGA and DTA proved that nanocontainers were loaded with 4.37% w/w of 8-HQ and 25.36% w/w of 2-MB, respectively. Furthermore, the introduction of nanocontainers loaded with inhibitor to a corrosive environment to which an AA2024-T3 is exposed; shows that as the concentration of loaded nanocontainers is increased, a more effective protective layer is formed on the surface of

the metal alloy, through the release of the inhibitor from the nanocontainers. These nanocontainers can be used in a vast eld of implementations such as additives in corrosion protective coatings.
Acknowledgments This project was supported by FP7 Collaborative Project MUST. The abbreviation MUST stands for Multi-Level Protection of Materials for Vehicles by SMART Nanocontainers (EC Grant Agreement Number NMP3-LA-2008-214261).

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