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J. Chil. Chem. Soc. v.50 n.2 Concepcin jun.

doi: 10.4067/S0717-97072005000200010
J. Chil. Chem. Soc., 50, N 2 (2005), pgs.: 489-494


D. Ramrez1, R. Vera1, H. Gmez 1, C. Coajahua


Instituto de Qumica, Facultad de Ciencias Bsicas y Matemticas, Pontificia Universidad Catlica de Valparaso, Avda. Brasil 2950, Valparaso. 2 Direccin de Ingeniera y Sistemas Navales, Armada de Chile, Prat 773, Valparaso.

Abstract Electrochemical Impedance Spectroscopy (EIS), open circuit potential (o.c.p.) measurements and saline fog chamber experiments were employed to study the protective action of four epoxy coatings on navy steel immersed in artificial seawater. From EIS data such as pore resistance, coating capacitance, and the use of the proper electric equivalent circuits it was possible to obtain information regarding the corrosion behavior under each coating. Results have been interpreted under the assumption that it is possible to predict the lifetime of conventional paintings as compared with chemically modified coatings. After 40 days of immersion, variable results between electrochemical experiments and saline fog chamber experiments were obtained. Keywords: epoxy coatings, protection, electrochemical impedance, corrosion.

Epoxy based paints are within the best organic coatings employed as insulating from a marine medium to protect navy steels against corrosion [1]. When a metal surface is covered with a polymeric film and then immersed in an electrolytic solution, an interaction is produced between the film and the solution. Water charged with electrolyte is transported through the coating by two simultaneous mechanisms: convection through the pores and coating imperfections (fast step) and by diffusion through the polymeric matrix (low step) [2]. In continuous and defect-free films, only the transport of ionic species through the polymer is favored [3]. The epoxy coatings are usually formed by an epoxy resin and a hardener that are mixed

before the application. Polyamines, such as di-ethylentriamine and hydroxidiethylentriamina are frequently used as hardeners. They are relatively small, low molecular weight compounds as compared with epoxy resins. Thus, the crossing over produced by the reaction of both components generates a three dimensional network that, after solvent evaporation, settles down on the substrate forming a very smooth surface. On the other hand, some of the unreacted amine can migrate out of the polymeric matrix forming a discontinuous white powder [11]. This two characteristics to decrease the adherence of a new paint layer (over-coating) to very long time between application of one coat and other. Decreasing the quantity of powder in the time is difficult to get in epoxy coatings, but can achieve decreasing the smoothing grade through formulation of coating. EIS has been successfully used to evaluate the protecting character of different metal coatings in electrolytic solutions [4-8]. The analysis of the information obtained from this method can be achieved over a wide frequency interval employing Nyquist and Bode diagrams with the aim of determining the individual components of an equivalent electric circuit model representing the covered-metal/solution interface [9]. The transfer functions based on the reaction mechanism taking place at the interface consider the contribution of the anodic as well as the cathodic processes [10]. In general, physical as well as chemical properties such as film adherence, presence of defects, barrier properties, inhibition, etc., affect the electrochemical response measured by EIS, with further effect on the equivalent electric circuit model needed to simulate the experimental results [6]. On the other hand, o.c.p. measurements are a simple additional tool that provide complementary information to EIS results regarding the corrosion undergone by steel substrate after several days of immersion in aggressive solutions . Following the preceding considerations, the current work aimed to evaluate the protecting properties against artificial sea water of four epoxy coatings based on an analysis of o.c.p. values and EIS spectra. Results were compared with the visual observation of samples from the same coatings that had been exposed to a saline fog chamber during forty days. In some cases it was possible to correlate both series of experiments; in others, however, a more complex behavior made difficult to extract reliable conclusions.

Triplicate carbon steel (A36) samples were washed with pressurized sand (Sa 2 grade), the grease removed with CCl4, and lastly recovered with the different epoxy coatings through Airless pulverization. The dry thickness was 40 mm determined with a Elcometer 345-F apparatus following ASTM 1186 standard. Table 1 summarizes the main characteristics of each coating.

Table 1. Main components and maximum re-painting times (25 C) for each coating.

A group of samples was dried at room temperature during 20 days and then set-up for electrochemical measurements. The electrochemical cell for o.c.p. and impedance measurements was disposed as shown in Fig. 1. The artificial seawater was prepared according to ASTM D 1141-90 standard. The geometric exposed area corresponding to the working electrode was 2.5 cm2. A platinum wire mesh was used as counter electrode and SCE as reference electrode. The cell was connected to IM6e Bass-Zanher potentiostat driven by a PC (A Bas-Zanher potenciostat model IM6e connected to PC-IBM, was employed to carry out the electrochemical measurement). Impedance spectra were recorded within the 100kHz-10mHz frequency interval using a 5 mV peak to peak signal amplitude. A group of samples was exposed to a saline fog chamber following the ASTM B-117 standard. Every specimen remained in the chamber for 40 days.

Fig. 1. Electrochemical cell employed for study of epoxy coatings through EIS and o.c.p.


Open circuit potential measurements Fig. 2 presents the o.c.p. variation over time for the four coatings considered in present study. The evolution of the curves is clearly related to differences in the surface characteristics among coatings, the most important being the porous morphology. As

comparison, the figure also includes naked carbon steel, which undergoes an active dissolution process starting at ca. -550 mV vs. SCE. The worst behavior is observed for the IG0366 coating that presents an initial o.c.p. of 535 mV, very close to the value presented by the naked steel, meaning that the solution easily penetrates through the defects caused by the coating porosity and not by diffusion through the polymeric matrix. After the sixth-day, the same sample shows a net tendency to shift its o.c.p. towards more negative values. These indicate a fast damage produced by an accelerated corrosion process due to the loss of adherence of the coating to the substrate. The presence of corrosion products visible to the naked eye confirms this assumption. Besides, the poor isolating character of the film facilitates the corrosive action of chloride ions, finally leading to the lowest o.c.p. value of the series (close to -670 mV) after 40 days.

Fig. 2. Evolution of the open circuit potential for the navy steal coated with four different epoxy coatings immersed in artificial seawater. The IS0300 coating shows first a decrease and then an increase in o.c.p., evolution that is probably due to an initial mechanism of barrier layer protecting effect [2]. However, after the tenth day, its tendency is to evolve towards negative values. Again, this means that chloride ions from the electrolyte penetrate through the coating pores causing a continuous decrease in o.c.p., that after 40 days reaches a value close to -600 mV. On the other hand, in spite of an initial unstable behavior before the fifth day, the o.c.p of the M0HS coating evolves towards a value comprised between -82 and -122 mV, which is the highest of all the samples assayed. This behavior is probably related to the formation of a passive film due to the presence of oxygen containing water at the metal/coating interface, contributing in this way to establish a cathodic area at the surface. Finally, after 15 days M0646 coating, presents an intermediate protection action, reaching a o.c.p of -230 mV that remains almost constant from the 29th day onwards. EIS results To avoid significant changes in the possible equilibriums established at the metal/solution interface, the EIS spectra were recorded at potentials close to the corrosion potential of the samples and they were simulated using the equivalent electric circuit shown in Fig. 3

[12]. In this circuit, Zm represents the general complex impedance of the processes that take place at low frequency, values which are usually submitted to different interpretations [6]. In Fig. 3a, each element represents a component of the electrochemical system considered: Rs corresponds to the solution resistance that due to the high ionic strength of the artificial seawater solution presents an almost constant value. This element is in series with a time constant RC corresponding to the protecting metal barrier, Cc representing the coating capacitance and Rp the resistance of the pores to the electrolyte permeability. As with the other capacitances, Cc was best simulated using a Constant Phase Element (CPE) obtained from EIS data [14].

Fig. 3. Electric equivalent circuit utilized in the simulation of the EIS spectra. Zm containing: two time constant: Rp Cc y Rct Cdl (a) and three time constant: Rp Cc , Rct Cdl y Rdiff Cdiff.(b). EIS spectra were sensitive to the protecting characteristics of the coatings, mainly regarding the pores capacity to either facilitate or lower the rate of water absorption. Accordingly, for a proper simulation of the experimental data, it was necessary to adapt the general equivalent electric circuit model to a particular situation. For instance, figure 4a shows that after 10 days of immersion the Nyquist diagram for the IG0366 coating (the one apparently with an important amount of defects) shows three hemi-circles, two of them overlapped in the 100000-72.79 Hz frequency interval. This response evidences the presence of three different time constants, behavior that approaches better to the components of Zm in the electric circuit b of figure 3. In fact, Bonora et al. proposed this model for interpreting their data in a previous study [6]. However, considering the first time constant as representative of the protective barrier layer, the origin of the other two is not easy to interpret. Nevertheless, taking into account that this coating presented visible corrosion products together with a loss of adherence after few days of immersion, the second hidden hemi-circle could be related to the charge transfer resistance (Rct) and the double layer capacitance (Cdl) associated to the electrochemical processes taking place at the metal/solution interface (see Fig. 5). Is important to consider the fact that there are two time constant associated to the apparition of two overlapped hemi-circles in the Nyquist diagram of the metal-coating -

electrolyte [5]. The third hemi-circle could probably be associated to the diffusion of corrosion products, represented by a time constant RC (Rdiff and Cdiff)[6]. The 10-days Nyquist diagrams for the rest of the coatings are not well defined, so it is very difficult to define a characteristic frequency interval for each sample (figure 4b). Rather, they behave as a capacitive system that does not close a circle in the real impedance axis. In spite of this behavior, the simulation was made employing the equivalent electric circuit of Fig. 3, without including the Zm term. Following the same kind of considerations used to explain the behavior of the IG0366 coating, its differences with EIS spectra for M0HS, M0646, and IS0300 can be explained by assuming that they probably present less amount of defects (less porosity) slowing thus the arriving of the electrolyte at the substrate surface. In other words, retarding the formation of the metal/solution interface needed for initiating the corrosion process. Thus, developing charge transfer time constant in this interval is very difficult to attain. Besides, except for the case of the IS0300 coating whose spectra was possible to simulate in the whole frequency interval during the 40 days, the capacitive response of the others samples precludes a clear definition of the impedance spectra at lower frequency values.

Fig. 4. Nyquist diagrams for the 4 coatings after 10 days of immersion in artificial seawater: a) full scale ; b) expanded scale for better visualization of hemicircles of IG0366 coating.

The remarkable decrease of the IS0300 coating protecting properties is not in complete agreement with o.c.p. results, however there were no corrosion products visible to the naked eye as was the case for IG0366. This means that an important anodic area has been formed at the metal/solution interface, but the corrosion products are held under the coating film.

Fig. 5. Overlaping of hemi-circles in Nyquist diagram for IG0366 to inmersed 10 days artificial seawater. It is important to point out that the literature reports Nyquist diagrams presenting only one hemi-circle whose diameter corresponds to the addition of the ionic resistance of the coating and the charge transfer resistance [7]. In these circumstances it was not possible to get a direct information of the latter parameter. As is seen in Fig. 6, after 40 days the impedance spectra of M0HS and M0646 coatings hold their protecting properties, whereas IS0300 and IG0366 spectra reveal that the corrosion of the underlying metal is still occurring. The simulation of the IG0366 spectra fits well with the model with three time constants of figure 3a, in turn; IS0300 fits better with that of 3b.

Fig. 6. Nyquist diagrams for the 4 coatings after 40 of immersion in artificial seawater. a) full scale ; b) expanded scale for better visualization of hemi-circles of IS0300 and IG0366 coatings.

From the simulation of EIS spectra it was possible to obtain useful information to characterize the coating behaviors. In general, following the water absorption process as a time function, capacitance and resistance values must increase and decrease respectively. According to the equivalent circuits used, equation (1) shows the relationship between the impedance module and the time constants of the coating film:

where Rp y C have the meaning previously described, w is the frequency and j = (-1)1/2. As is shown in equation (2) the coating capacitance, Cc, is inversely related to the coating thickness d:

In this equation e is the coating dielectric constant (usually 3.8 for epoxy), the vacuum permittivity and A the surface area exposed to the electrolytic solution. Further, according to equation (3) the value of pore resistance is proportional to d,

0 is

where k is the solution conductivity (-1cm-1), N the number of coating pores and Ap the mean pore area. Thus, the impedance increases when d increases [13]. Fig. 7 shows the evolution of Rp with exposure time. At the beginning as well as at the end of the measurements, the M0HS and M0646 coatings present the higher Rp values (4,567,000 and the 3,264,000 cm2, respectively), correlating very well with the tendency of o.c.p. results for these samples. IG0366 presents a progressive deterioration, with an almost constant 68,430 cm2 value. After 20 days of immersion, IS0300 undergoes resistance decay, attaining a value very close from that found for IG0366

(68,102 at


Fig. 7. Evolution of Rp of the 4 coatings immersed in artificial seawater. Fig. 8. shows that except for IG0366, Cc presents slight variations with immersion time. Furthermore, although the coating capacitance does not need to be inversely proportional to Rp, actually an inverse correlation was found for this coating.

Fig. 8. Evolution of Cc for the 4 coatings immersed in artificial seawater. Saline fog chamber results The visual observation of the four samples showed that ISO300 was the coating with the best aspect, whereas the worst was M0646. It presented blisters and a high content of oxide as main failures. IG0366 and M0HS coatings presented a very similar intermediate aspect. These results are partially consistent with the electrochemical evaluation of the coating behavior demonstrating the limitation of this kind of assays to ascertain the

events occurring under the protecting film.

Information obtained from the EIS spectra, such as pore resistance, coating capacitance, and the proper equivalent electric circuit, proved to be useful to explain the corrosion process of the steel under each coating. Coatings properties such as adherence to substrate and the amount of defects requires leads to adapt the proposed models to each particular situation in order to the impedance spectra. From the analysis of results, IG0366 coating presented the worst protecting effect of the steel, but this could not be satisfactorily confirmed by the visual observation of the samples in the saline fog chamber. M0HS and M0646 coatings, those with the longer re-painting time, presented comparatively better protecting properties. Furthermore, M0HS coating showed better performance in the saline fog chamber. Finally, the IS0300 coating presented deficient protecting character over a long term period. How the samples were exposed to the aggressive medium seem to be important for the changes undergone by the coating. This is probably the reason why the electrochemical techniques employed to evaluate their protecting properties correlate well between them but not with the visual observation of the samples exposed to the saline fog chamber. This is an issue that deserves further attention to examine the correlation between these approaches.

This work has been performed with the suppport of Direccin de Investigacin, PUCV (research Project No 125.753 ) and Direccin de Ingeniera y Sistemas Navales, Armada de Chile.

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