J Nanopart Res (2011) 13:541–554 DOI 10.



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 Ó 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 sol–gel 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 confirmed with Fourier Transform Infrared Spectroscopy (FT–IR) 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 Á Corrosion Á Inhibitors Á Synthesis Á 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 influence the efficiency 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 sol–gel coatings in one hand can improve corrosion protection, on the other hand may deteriorate the barrier properties of the film. 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 Á I. A. Kartsonakis Á G. S. Pappas Á G. C. Kordas (&) Sol-Gel Laboratory, Institute of Materials Science, NCSR ‘‘DEMOKRITOS’’, 153 10 Agia Paraskevi Attikis, Greece e-mail: gkordas@ims.demokritos.gr


polyvinylpyrrolidone (PVP. synthesized hollow titania spheres using cationic polystyrene lattices which were prepared by polymerization in suspension of styrene using 2. Inhibiting action is the consequence of suppression of dissolution of Mg. and Cu from the corrosion active intermetallic zones (Lamaka et al. Zheludkevich et al. 2008). average molecular weight: 55. In the present study. Zheludkevich et al. cerium titanium oxide hollow nanospheres were synthesized and characterized by SEM. 2007b) and found that the nanoparticles reinforced the coating and released inhibitors during contact with moisture. sodium chloride (NaCl.000. Styrene (Aldrich) was double distilled under reduced pressure prior to use. After that. 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. 8-HQ and 2-MB compounds were studied as corrosion inhibitors by Lamaka et al. Aldrich). The release of the inhibitors in a corrosive environment was tested via EIS. 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 sol–gel system (Yasakau et al. the reactions were made in nitrogen atmosphere. In order to eliminate the result of oxygen effect. which are suitable counter electrode materials for lithium-based electrochromic windows (Keomany 1995). (2005c) as corrosion inhibitor for protection of AA2024-T3 in neutral chloride solutions. 2007c). 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 sol–gel films (Shchukin et al. 123 . 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. Experimental Materials and reagents All chemicals were of analytical reagent grade. 2008). and FT-IR. Styrene was polymerized by polymerization in suspension according to the conditions shown in Table 1. 2005a. cerium (III) acetylacetonate (Ce (acac)3.20 -Azobis (2-methylpropionamidine) dihydrochloride (AMPA. Otsuka-Yao-Matsuo et al. Titanium tetraisopropoxide (TTIP. 2007a). (2004) studied the photocatalytic behavior of CeTiO4 and CeTi2O6 powders. Kartsonakis et al. Aldrich). were used without further purification. (2007) for AA2024-T3. 2008). 2007. Aldrich). (2005a. Preparation of nanocontainers Cerium titanium oxide hollow nanospheres were synthesized through a three-step process. prepared thin films of (CeO2)x–(TiO2)1-x by a sol–gel 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 influence of the structure on the electrochemical insertion in such films. Al. as an alternative to chromate-based coatings for corrosion protection of aluminum alloys (Poznyak et al. 2005b). Yasakau et al.542 J Nanopart Res (2011) 13:541–554 of the corrosion inhibitors (Kartsonakis et al. XRD. TGA. these nanocontainers were loaded with corrosion inhibitors 2-MB and 8-HQ to produce an inhibitor delivery system. 2007. Nanostructured sol–gel coatings doped with cerium ions were investigated as pretreatments for AA2024-T3 (Zheludkevich et al. 2-MB was evaluated by Zheludkevich et al. The first step involves the preparation of positive charged polystyrene nanospheres. The polymerization process is described in our previous study (Kartsonakis et al. Zirconia and silica nanoparticles were used as reservoirs for the storage and prolonged release of corrosion inhibitors in silica and silica–zirconia based coatings by Zheludkevich et al. sodium hydroxide (Aldrich). Aldrich). and airplanes. Sanyal 1981.20-azobis (2-methylpropionamidine) dihydrochloride (AMPA) as an initiator (Kartsonakis et al. 2008). Keomany et al. 2008). Studies were made on the % w/w loading of the inhibitors by heat treatments and FT-IR spectroscopy. Aldrich). Titania-containing organic–inorganic hybrid sol–gel films have been developed by Poznyak et al. Shchukin et al. ships. 2. and absolute ethanol (Aldrich). The results suggest the use of these loaded nanocontainers into coatings on metal alloys for corrosion protection of metals used for automobiles.

Furthermore. NaCl. After that. the cerium titanium oxide nanocontainers loaded with the inhibitor were collected through centrifugation and were dried under vacuum overnight.05 M NaCl solution. The solution was centrifuged and the precipitate was washed with distilled water. The panels had been previously cleaned. Temperature treatments such as Thermo Gravimetric Analysis (TGA) were made using a Perkin Elmer (Pyris Diamand S II) analyzer at the heating rate 123 . The exposed geometric area was 2 cm2 for all the experiments.0 20 *9 9. Sol–gel coating were prepared with controlled hydrolysis of the alcoholic solution of TTIP jai Ce(acac)3 in the presence of PS nanospheres.05. 72 h of exposure in 0. the panel is rinsed with distilled water and is inserted into 4. a minimum of three repetition measurements were taken. a platinum sheet as the counter while a saturated calomel electrode (SCE) served as reference electrode. 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. solutions of pure inhibitors 8-HQ and 2-MB with the same concentration were also studied for comparison reasons. The release of 8-HQ and 2-MB from nanocontainers was studied via EIS. and washing of the coated nanospheres were followed. 2007. were determined by SEM using a PHILIPS Quanta Inspect (FEI Company) microscope with W (tungsten) filament 25 kV equipped with EDAX GENESIS (AMETEX PROCESS & ANALYTICAL INSTRUMENTS). 6. 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.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. EIS measurements were taken after 3. centrifugation. the PS nanospheres were coated via sol–gel method. and 0. During the second step. Monomers or oligomers of hydrolyzed TTIP and Ce(acac)3 are condensed on the surface of the polystyrene.0 215 ± 10a Determined by scanning electron microscopy analysis Polymerization lasted 12 h. Instrumentation The average nanocontainer size and the morphology of the substrate after 72 h of exposition in NaCl.5418 A). PVP and NaCl were added to the mixture reaction to prevent aggregation of the core particles. After that. 24. The AA2024-T3 panel cleaning includes the insertion of it into 2% w/w solution of NaOH for 3 min at 40 °C. the experiments were carried out at room temperature. an amount of cerium titanium oxide nanocontainers was placed in a sealed container.06 1.1% w/v concentration of nanocontainers loaded with inhibitors in a corrosive environment (0. A typical three electrode cell was used in a Faraday cage.01. The formation of hollow nanospheres was achieved after heat treatments of the composites at 600 °C with heating rate 10 °C min-1. The nanocontainers were placed in a vacuum system to draw out the air inside them.J Nanopart Res (2011) 13:541–554 Table 1 The conditions used in the preparation of polystyrene latex at 80 °C Material Styrene AMPA Water Nanospheres’ size (nm) a 543 Quantity (g) 9. The positive charged polystyrene reacts with the negative charged product of the hydrolysis of TTIP and Ce(acac)3. For this purpose. Encapsulation and release of inhibitors The obtained cerium titanium nanocontainers were loaded with the corrosion inhibitors 8-HQ and 2-MB. solutions of 0. Then. The loading procedure included first the preparation of a saturated solution of the inhibitor in acetone. Aging of the solutions at 60 °C. it is rinsed with distilled water.33 M solution of HNO3 for 1 min at room temperature. Panels of AA2024-T3 were used as the working electrode. 48. and PVP (Table 2). All the samples were in vertical position. 0.05 M NaCl) were prepared. For every result. 2008). Finally. under specific conditions. Finally. where the polystyrene cores were burned off (Kartsonakis et al.

indicating that polystyrene latex has been well removed from the core/shell composite particles by calcination at 600 °C. 790 cm-1 (Kartsonakis et al. 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). Keomany 1995. before and after calcination. 2008. indicating that PVP has not been well removed during the experimental process. 1445. The spectra in Fig. 2005c. Fourier Transform Infrared Spectroscopy (FT-IR) was made using a BRUKER EQUINOX 55-S spectrometer. the band characteristic of the polystyrene latex have been disappeared. Keomany 1995. and oxygen constitute the spectrum of the spheres. is the one after calcination. and 1163 cm-1 are the band characteristic of PVP. This region contains bands typical of metal oxygen bonding.919 cm-1 is due to the CH2 group. 690. Verma et al. 525. 2004). FT-infrared spectroscopy analysis Figure 4 shows the FT-IR spectrum of the nanospheres. 750. It can be seen that the characteristic peaks of polystyrene are missing from the spectrum after calcination.000 cm-1. 700. 3). 4a of the nanospheres prior to calcinations reveals well-defined bands of the phenyl group (703. Both FT-IR spectra for as-prepared and after calcination samples show absorption peaks at the wave number region between 400 and 1. 2 SEM images of cerium titanium oxide hollow nanospheres Fig. Figure 2 shows that after calcinations. For CeO2. Verma et al. 2005c. Quantachrome Instruments). Gold appears due to the gold coating that was applied to the spheres in order to be conductive for the SEM analysis (Fig. 1150. 540. 2004. The EDX analysis shows that titanium. Zheludkevich et al. 4b.544 J Nanopart Res (2011) 13:541–554 of 10 °C min-1 in air. the cerium titanium oxide hollow nanospheres exhibit an average diameter of 180 ± 10 nm. Nitrogen adsorption experiments and pore size measurements were performed using a volumetric static sorption apparatus (Autosorb-1 MP. 1. 1 SEM images of polystyrene nanospheres verifies the formation of inorganic shells and the complete removal of the organic components. the characteristic peaks are at 425 cm-1. 1494. The peaks at 1590. Mc Devitt and Baun 1964). This spectrum Fig. Zheludkevich et al. The absorption peaks of TiO2 are at 470. the polymerization process leads to polystyrene nanospheres with uniform size with an average diameter of 195 ± 10 nm. The peak at 2. It is mentioned that the FTIR spectra after calcinations 123 . 2007. 525 cm-1. cerium. 579. and 3022 cm-1) in polystyrene. Results and discussion Scanning electron microscopy analysis As shown in Fig. The FT-IR spectrum in Fig. 540 cm-1 (Kartsonakis et al.

3 EDX analysis of cerium titanium oxide hollow nanospheres 545 Fig. 2007.000 cm-1 and the above peaks can be distinguished. The fourth weight loss between 400 and 450 °C is attributed to the burn off of polyvinylpyrrolidone (Jablonski et al. 6 of the sample treated at 600 °C. 2008). It is observed from the TGA diagram that polystyrene is burned off between 290 and 400 °C (the third sharp weight loss). The exothermic peak between 365 and 420 °C is due to crystallization of amorphous cerium and titanium oxides into crystalline (Raps et al.500 cm-1 and at 1.J Nanopart Res (2011) 13:541–554 Fig. 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. 4 FT-IR spectra of: a cerium titanium oxide nanospheres (before calcination). calcination at 600 °C in air removed the polystyrene core particles completely. 2007). The broad bands in the range of 3. This was confirmed by the XRD pattern shown in Fig. 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.200–3. X-ray diffraction analysis Crystalline phases were identified according to the JCPDS (Joint Committee on Powder Diffraction Standards) file numbers 21-1271 and 43-1002 for 123 . The first weight loss is observed in the range of 30–150 oC which can be attributed to desorption of physically adsorbed water (free and physisorbed water) (Kartsonakis et al. Kartsonakis and Kordas 2009). b Cerium Titanium oxide hollow nanospheres (after calcination) depict broad band at the region between 400 and 1. 2009). DTA diagram shows an exothermic peak between 260 and 340 °C. Thermogravimetric and differential thermal analysis Figure 5 shows the TGA–DTA diagrams of cerium titanium oxide nanocontainers. The second weight loss in the range of 150–230 oC can be attributed to the chemisorbed water. Hence.652 cm-1 correspond to stretching vibration of O–H bond of the physically adsorbed water in the sample (Verma et al. 2004). This peak is due to the condensation of hydroxyl groups.

The presence of cerium identified from the main peak at 2h = 28. 9. The pore size distribution of the filled sample did not show any pores with radius below 4 nm. The specific area decreased significantly from 129 m2 g-1 for the hollow nanospheres to 17 m2 g-1 for the nanospheres filled with 2-MB. Encapsulation and release of inhibitors TGA diagrams of pure 8-HQ.05–0. the above peaks are slightly moved to higher values of 2h.5° (101). 6 XRD pattern of cerium titanium oxide hollow nanospheres distribution was calculated through the B.6 nm with a pore volume 0. Also the pore size distribution.15° (105).3 P/P0 and was found to be 129 m2 g-1. 2007).2° (200). leak test of the instrument).T method in the range of relative pressure 0. 8) is characteristic for curves of type IV (IUPAC). and cerium titanium oxide nanocontainers loaded with 8-HQ or 2-MB are shown in Fig.J.J.6° (111). The specific area was calculated with the B.05° (211).503 cc g-1. and 62. 55. The pore size 123 . Pure 2-MB is completely burned off between 180 and 330 °C. causes stress to the crystal structure of anatase leading to the increase of peak positions that mentioned above (Verma et al. The total amount of the adsorbate is less in the filled sample. 7. The loaded nanocontainers with 8-HQ and 2-MB were degassed at 25 °C for 18 h. 55.2) (Figs. calculated from desorption branch through B.H method. Porosity measurements The samples of the empty nanocontainers were degassed at 300 °C for 18 h before the measurement. The measurement of the sample filled with 8-HQ was impossible. a second weight loss between 130 and 170 °C due to 8-HQ that is on the surface of the nanocontainers and finally a third and forth weight loss from 170 to 850 °C correspond to oxidative degradation of encapsulated 8-HQ. Pure 8-HQ began to degrade at 120 °C until 212 °C where no residue left. 38.1° (004). 8). The hysteresis through desorption (Fig. Figure 6 shows the XRD pattern of the sample after calcination. which is characteristic of cerianite. 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. The peaks at 2h = 25.301 cc g-1 indicating the filling of the pores and the hollow structure with the inhibitor.503 to 0.E. The diagram of cerium titanium nanocontainers loaded with 8-HQ shows a first weigh loss between 30 and 130 °C corresponding to acetone and physically adsorbed water (free and physisorbed water) (Takeuchi et al. 48. The diagram of loaded nanoconainers with 2-MB depicts a sharp weight loss from 200 to 330 °C corresponding to anatase and cerianite. 2-MB. The measurement of the 2-MB-filled sample showed some interesting results compared to the hollow nanospheres. This fact indicates the presence of mesopores in the sample. 2005). due to evaporation of the inhibitor under the preparation conditions (high vacuum. 5 TGA and DTA curves of cerium titanium oxide hollow nanospheres Fig.H method at desorption isotherm and the mean pore radius found to be 1.9° (204) represent to tetragonal anatase. showed a decrease in the pore volume from 0. The observation of steps at the adsorption isotherm clearly denotes the presence of different size of pores in the sample. respectively. According to the JCPDS Library.546 J Nanopart Res (2011) 13:541–554 Fig.

a second weight loss between 330 and 850 °C due to the oxidative degradation of the inhibitor that are enclosed into the nanocontainers. The third experiment was done using different amounts of loaded nanocontainers in the solution (e.g.36% w/w for the Ce–Ti nanocontainers loaded with 2-MB. 2-MB 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. 0.J Nanopart Res (2011) 13:541–554 Fig.37% w/w. This can be observed by EIS. G2 is taken at 900 °C. The weight losses observed by the TGA measurements were used to determine the amount of inhibitors loaded into the nanocontainers. The burn off 2-MB between 330 and 850 °C corresponds to inhibitor that is inside the shell of the nanocontainers. This result indicates that 8-HQ is encapsulated into nanocontainers. We estimate rm about 25. We take the weight of the sample at 170 °C (G1) and at 850 °C (G2). In the case of Ce–Ti nanocontainers loaded with 2-MB. 10 and 12 for 8-HQ and 2-MB.G2) and last we divide DG by G1 to obtain the ratio mass loss. and correspond to the 123 . 7 BJH pore distribution of cerium titanium oxide hollow nanospheres 547 Fig. One can perceive an influence of the concentration on the corrosion protection attributed to the release of the inhibitors from the nanocontainers. This retardation (roughly 200 °C higher than pure inhibitor) is attributed to the protection provided by the shell of nanocontainers.1% w/v in a salt solution) in order to clarify the extend of corrosion protection attributed to the inhibitors (Figs. rm = DG*100/G1 due to 8-HQ. and 0. they should provide corrosion protection of the AA2024-T3 panels.1% w/v) shown in Figs. it is observed that pure 8-HQ is burned off at higher temperatures in the samples of cerium titanium nanocontainers loaded with this inhibitor. the weight loss corresponds to mass encapsulated in the nanocontainer. The best results against corrosion were obtained for 0. 13) in order to observe the effect of protection due to the inhibitor release from the nanocontainers. rm is about 4.g. The second experiment was carried out using filled nanocontainers with inhibitors (8-HQ Fig. Above this temperature.01. 0. 13). 11.1% w/v. we consider the sample of nanocontainers loaded with 8-HQ. we take G1 at 330 °C because the 2-MB burns off at this temperature. If the inhibitors are released from the nanocontainers. respectively. The same analysis can be made for the nanocontainers loaded with 2-MB. The release of the inhibitors was studied via EIS. Comparing the TGA diagrams. 11. 2-MB 0. The first experiment was accomplished using pure inhibitors in the solution (e. First.05. In the case of Ce–Ti nanocontainers loaded with 8-HQ. we then subtract G2 from G1 (DG = G1 .

2 mM. b pure inhibitor 8-HQ. 0.1% w/v of nanocontainers loaded with 8-HQ and without nanocontainers Fig. 9 TGA curves of: pure 8-HQ. the concentration of 2-MB in 0. 13). therefore. The impedance at low frequencies corresponds to the polarization resistance of the AA2024-T3 electrode and.548 Fig.05.05 M NaCl with 0. 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. and cerium titanium oxide nanocontainers loaded with 8-HQ and 2-MB J Nanopart Res (2011) 13:541–554 Fig. 11. It can be clearly seen that both chemical compounds worked as 123 . 11 Bode diagrams of AA2024 after 72 h of immersion in 0. pure 2-MB. In the low frequency region. 12. According to TGA measurements. 0.1 mM and the concentration of 8-HQ is 17.1% w/v nanocontainers is 86. and c bare AA2024 protection provided by the same concentration of pure inhibitor (0. 2007).1% w/v of nanocontainers loaded with 8-HQ.01. 10.1% w/v of 8-HQ and 2-MB). 10 Bode diagrams of AA2024 after 72 h of immersion in 0.05 M NaCl with a 0. can be used to estimate the corrosion protection (Lamaka et al.

01. a wide time constant is observed consisted of the two phases that are mentioned above.1% w/v of nanocontainers loaded with 2-MB and without nanocontainers where Z is the impedance. The capacitance of the inhibitor is calculated by the following equation: Cinh ¼ Qinh ðxmax Þðninh À1Þ ð2Þ Fig. Figure 14 shows the equivalent circuit used to fit the experimental data.1% w/v of nanocontainers loaded with 2-MB. 0. Rsol is the resistance of the solution.J Nanopart Res (2011) 13:541–554 549 Instead of capacitances. xmax is the frequency at which the imaginary impedance reaches a maximum for the respective time constant. 16.05 and 0. 12 Bode diagrams of AA2024 after 72 h of immersion in 0. Cinh and ninh are the parameters of the CPE describing the capacitance of the inhibitor layer. The low frequency time constant is related to a diffusion limitation of the corrosion process (Lamaka et al. Tables 3 and 4 summarize the parameters obtained after fitting.1% w/v nanocontainers.01 Hz for the solution with nanocontainers. Rinh is resistance of the inhibitor layer and Rpol is the polarization resistance. and c bare AA2024 corrosion inhibitors comparing to the solution without loaded nanocontainers. and 17 present the evolution of the capacitance of the inhibitor layer as a function of the time for different nanocontainer concentrations. x is the frequency and n B 1 a power coefficient calculated as ratio of phase angle at maximum of corresponding time constant to -90°. 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). Figures 15. The impedance of the CPE depends on frequency according to the following equation 1 ¼ QðjxÞn Z ð1Þ Fig. 2005b). Two time constants revealed at 5 and 0.05 M NaCl with 0. One 123 . The impedance of the CPE depends on frequency according to the following equation (Kartsonakis et al.05 M NaCl with a 0. 0. In the case of 2-MB. 13 Bode diagrams of AA2024 after 72 h of immersion in 0. the time constant attributed to the presence of the adsorbed layer is better observed at 72 h in NaCl with 0. 2007. The higher frequency time constant can be assigned to the capacitance of the double layer on the surface of the alloy. b pure inhibitor 2-MB. 2007). Rox is the resistance of the native oxide layer. Q a parameter equals to (1/ |Z|) at x = 1 rad s-1. Cdl and ndl are the parameters of CPE which characterize the capacitance of the double layer capacitance (Lamaka et al. Cox and nox are the parameters of constant phase element (CPE) describing the capacitance of the oxide layer. 2007). Constant Phase Elements (CPE) were used in all fittings procedures because the phase angle of the capacitor is different from -90°. Zheludkevich et al. In the case of 8-HQ.05.

1% w/v Ce–Ti 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. 16.05 M NaCl solution. 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. A prolonged decrease of the capacitance is observed for the solution with 0. This result demonstrates that the inhibitors are not trapped permanently in the nanocontainers.84E-5 0. As it was mentioned.760 6.541 5.322 much higher values than 8-HQ loaded nanocontainers (Figs.780 7. The values of Rox at 0.310 1. 14 Equivalent circuit used for fitting 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 0.820 4.05% 132 1.01E-4 0.1% 131. though. One can perceive a fully corroded sample with many pits. the addition of the nanocontainers has decreased the number of the pits on the surface of AA2024-T3.8 305.550 J Nanopart Res (2011) 13:541–554 Fig.67E-4 0. This observation is a strong support of the assumption of the release of the inhibitors from the nanocontainers.53E-4 0. 2-MB loaded nanocontainers exhibit Table 3 Calculated values for EIS data obtained at different immersion times for NaCl solution with 0.015 0.414 0.204 123 .75E-4 554. these shifts are also of an order of magnitude with much higher absolute values.23E-5 8. the parameters of capacitance and resistance of 8-HQ do not change significantly as the time goes by compared to 2-MB.612 3. 15.61E-5 5. This may be attributed to the fast formation of a stable layer of the inhibitor on the aluminum surface. In the case of 2-MB loaded nanocontainers.790 3.49E-5 1.8 1.01% w/w.05 M NaCl solution with nanocontainers (Lamaka et al.810 3.05% 145. 0. Both inhibitors form a dense layer on the surface of the aluminum alloy 2024-T3.45E-5 351 1.16 9.64E-5 1796 8.4 552.866 0.1% w/v Ce–Ti 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 0.720 2.25E-5 0.01% w/w. On the other hand.7 5.01.307 8. Low values of Rox are obtained for concentration 0.84E-5 0.01. 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. One can highlight at this position. 16. This result is in agreement with the respective EIS measurements. that the curves of the theta versus frequency match for the inhibitor solution and loaded nanocontainer solution.106 1. Rox.4 69.01% 124 3.01% 141.05 and 0. It is observed that each inhibitor affects the time evolution and the extend of the capacitance in a different fashion.6 5. Figures 15. 17). Figure 18 demonstrates the degradation of the bare sample exposed in the corrosive environment without the presence of nanocontainers. 0.677 7. and 17 present the direct effect of the concentration of the 8-HQ-loaded nanocontainers to the resistance of the aluminum oxide layer. the action of the nanocontainers is based on the formation of chelate complexes on the aluminum surface that are difficult to be dissolved.1% w/w concentration of nanocontainers which can be attributed to the increase of thickness of the inhibitor layer.05 and 0.1% 130 1.1% w/w are one order of magnitude higher than for concentration of 0.747 0. Furthermore. 2007).

16 Evolution of resistance of aluminum oxide layer after exposure for 72 h in 0. 17 Evolution of capacitance and resistance of inhibitor film after exposure for 72 h in 0.05 M NaCl solution containing Ce–Ti nanocontainers loaded with: 2-MB.05 M NaCl solution containing Ce–Ti nanocontainers loaded with 8-HQ 123 . 8-HQ Fig.05 M NaCl solution containing Ce–Ti nanocontainers loaded with 2-MB Fig. 15 Evolution of capacitance and resistance of inhibitor film after exposure for 72 h in 0.J Nanopart Res (2011) 13:541–554 551 Fig.

20. Fig. or Cu2? that are formed through the initial stages of corrosion. 19. b magnification 50. 21 and Fig. 2008). the formation of the inhibitor layer can be observed using SEM as shown in Fig. The totally corroded AA2024-T3 is presented in Fig.552 J Nanopart Res (2011) 13:541–554 Fig. 18 Visual photograph of AA2024-T3 sample after exposure for 72 h in 0. 22. 20 SEM images of AA2024-T3 panel after exposure for 72 h in 0. b 0.05%. 19 Visual photographs of AA2024-T3 panel after exposure for 72 h in 0. Mg2?. 2007. 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.000 and c EDX analysis 123 . e 0.000.05 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?.01%. c 0. 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.1% w/v of nanocontainers loaded with 8-HQ and d 0.01%.1% w/v of nanocontainers loaded with 2-MB Fig. On the other hand.05 M NaCl solution without nanocontainers a magnification 1. f 0.05%. Yasakau et al.05 M NaCl with a 0.

Zhang L.36% w/w of 2-MB. Biomacromolecules 7:1766–1772 Hu Y. Polymer 46: 12703–12710 Jablonski AE. Thermal treatments with TGA and DTA proved that hollow nanospheres are produced due to burn off of polystyrene cores. Thermal treatments with TGA and DTA proved that nanocontainers were loaded with 4. Jiang X (2006) Synthesis and magnetic properties of biocompatible hybrid hollow spheres.05 M NaCl solution with nanocontainers loaded with 2-MB a magnification 1. Their size was characterized by SEM measurements and was 170 ± 10 nm.000. b magnification 50. References Ding Y. 21 SEM images of AA2024-T3 panel after exposure for 72 h in 0. The synthesized nanocontainers have different size of pores. through the release of the inhibitor from the nanocontainers. Yang C (2005) Synthesis and stimuli-responsive properties of chitosan/ poly(acrylic acid) hollow nanospheres. respectively. Furthermore. Hu Y.05 M NaCl solution with nanocontainers loaded with 8-HQ a magnification 1.J Nanopart Res (2011) 13:541–554 Fig.37% w/w of 8-HQ and 25.000. Chen Q. Lang AJ. The abbreviation ‘‘MUST’’ stands for ‘‘Multi-Level Protection of Materials for Vehicles by ‘‘SMART’’ Nanocontainers’’ (EC Grant Agreement Number NMP3-LA-2008-214261). b magnification 50. XRD analysis showed that the nanospheres consist of anatase and cerianite crystalline phases. 22 SEM images of AA2024-T3 panel after exposure for 72 h in 0. shows that as the concentration of loaded nanocontainers is increased. Moreover. Acknowledgments This project was supported by FP7 Collaborative Project ‘‘MUST’’. Vyazovkin S (2008) Isoconversional kinetics of degradation of polyvinylpyrrolidone used as a 123 . These nanocontainers can be used in a vast field of implementations such as additives in corrosion protective coatings. these nanocontainers were loaded with the corrosion inhibitors 8-HQ and 2-MB. the introduction of nanocontainers loaded with inhibitor to a corrosive environment to which an AA2024-T3 is exposed. Chen Y. Chen Y.000 and c EDX analysis Conclusion Cerium titanium hollow nanocontainers were synthesized. a more effective protective layer is formed on the surface of the metal alloy.000 and c EDX analysis 553 Fig. Jiang X. Zhang L.

Prog Org Coat 63:352–361 Zheludkevich ML. Karavai OV. Ma X (2006) Preparation of oxide hollow spheres by colloidal carbon spheres. Poznyak SK. Coluccia S. Ferreira MGS (2005b) Nanosractured so–gel coatings with cerium nitrate as pre-treatments for AA2024T3 corrosion protection performance. Prog Org Coat 62: 226–235 Raps D. Yasakau KA. characterization and antibacterial action of hollow titania spheres. Kordas G (2008) Synthesis and characterization of new SiO2–CaO hollow nanospheres by sol–gel method: bioactivity of the new system. Zheludkevich ML. Corros Sci 51:1012–1021 Sanyal B (1981) Organic compounds as corrosion inhibitors in different environments–a review. Yasakau KA. Bakshi AK. Chem Mater 19:402–411 Zheludkevich ML. Ferreira MGS (2005c) Triazole and thiazole derivatives as corrosion inhibitors for AA2024 aluminium alloy. Kartsonakis IA. Sood KN (2007) Effect of precursor sol’s aging on properties of nanostructured thin films with coexistent CeO2 and CeTi2O6 phases. Srivastava AK. Montemor MF. Anpo M (2005) Investigations of the structure of H2O clusters adsorbed on TiO2 surfaces by near-infrared absorption spectroscopy. Cao J. Donley MS (2004) Hybrid organo-ceramic corrosion protection coatings with encapsulated organic corrosion inhibitors. Raps D. Corros Sci 47:3368–3383 ¨ Zheludkevich ML. Electrochem Commun 9: 2622–2628 Zheng M. Serra R. Ferreira MGS (2008) Preparation and corrosion protective properties of nanostructures titania-containing hybrid sol–gel coatings on AA2024. J Am Ceram Soc 91:372–378 Kartsonakis IA. J Phys Chem B 109:7387–7391 Verma A. J Phys Chem C 112:958–964 Takeuchi M. J Non Cryst Solids 354:755–760 Poznyak SK. Mater Lett 60:2991–2993 123 . Wehr J. Ferreira MGS (2007a) Anticorrosion coatings with selfhealing effect based on nanocontainers impregnated with corrosion inhibitor. Zheludkevich ML. Liu J. Electrochim Acta 51:208–217 Zheludkevich ML. Samanta SB. Ferreira MGS (2007) High effective organic corrosion inhibitors for 2024 aluminium alloy. Ferreira MGS (2007c) On the application of electrochemical impedance spectroscopy to study the self-healing properties of protective coatings. Karavai OV. Gammel F. Zheludkevich ML. Salvador IM. Danilidis I. Zheludkevich ML. Omata T. characterization. Yasakau KA. Liatsi P. Daniilidis I. and antibacterial action of hollow ceria nanospheres with/without a conductive polymer coating. Agnihotry SA (2004) Optimization of CeO2–TiO2 composition for fast switching kinetics and improved Li ion storage capacity. Kordas G (2007) Synthesis. Shchukin DG. Bastos AC. Zheludkevich ML. Solid State Ionics 171:81–90 Verma A. Chang X. Chem Mater 19:402–411 ¨ Zheludkevich ML. Mohwald H (2008) Active anticorrosion J Nanopart Res (2011) 13:541–554 coatings with halloysite nanocontainers. Hack T. Yasakau KA. Ferreira MGS (2005a) Oxide nanoparticle reservoirs for storage and prolonged release of corrosion inhibitors. Yasakau KA. Yasakau KA. Baun WL (1964) Infrared absorption study of metal oxides in the low frequency region (700–240 cm-1). J Alloy Compd 376:262–267 Pappas GS. Shchukin DG. Ferreira M. Electrochim Acta 52:7231–7247 Mc Devitt NT. Voevodin NN. Mohwald H. Thermochim Acta 78–80 Kartsonakis IA. Solid State Ionics 178:1288–1296 Yasakau KA. Nuyken O (2009) Electrochemical study of inhibitor-containing organic–inorganic hybrid coatings. CeTiO4 and CeTi2O6 and their composite powders with SrtiO3. Liatsi P. Prog Org Coat 9:165 Shchukin DG. Danilidis I. Yasakau KA. Kordas G (2009) Synthesis and characterization of cerium molybdate nanocontainers and their inhibitor complexes.554 matrix for ammonium nitrate stabilization. Marta G. Thin Solid Films 447:549–557 Lamaka SV. ¨ Ferreira MGS. Montemor MF. Liatsi P. Serra R. Yoshimura M (2004) Photocatalytic behavior of cerium titanates. Ferreira MGS. Spectrochim Acta 20:799–808 Otsuka-Yao-Matsuo S. J Am Ceram Soc 93:65–73 Kartsonakis IA. Balbyshev VN. Ferreira MGS (2008) Influence of inhibitor addition an the corrosion protection performance of sol–gel coatings on AA2024. Electrochem Commun 7:836–840 Zheludkevich ML. Lamaka SV. Yasakau KA. Mohwald H. Bastos AC.GS (2007b) Anticorrosion coatings with selfhealing effect based nanocontainers impregnated with corrosion inhibitor. Montemor MF. Sol Energy Mater Sol C 36:397–408 Khramov AN. J Phys Chem Solids 69:214–221 Keomany D (1995) Electrochemical insertion in sol–gel made CeO2–TiO2 from lithium conducting polymer electrolyte: relation with the material structure. Kordas G (2008) Synthesis. Wang J. Bouzarelou D.

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