Apgress

in Organic Coatings, 23 (1993) 186-200

185

The use of electrochemical impedance measurements to assess the performance of organic coating systr IS on naval steel
E. Cavalcanti and 0. Ferraz I~~titutoNQcaonal de Tecndogh, m) Jan&-u (Brazil) A.R. Di Sarli* Av. Vaezuela 82, Cenho-CEP 20081RG de

(Received January 26, 1993; in revised form February 12, 1993; accepted March 1, 1993)

Abstract
Ei~~o~~c~ impedance and corrosion potential measurements were carried out on naval steel coated with various organic paints systems whilst immersed in 3% NaCl solution. These techniques have been used to determine the mechanisms involved in the corrosion process as well as to sssess the protective power of paint systems commonly used in marine environments. The paint systems studied consisted of a zinc-rich ethyl silicate primer (ZRP) with a chlorinated rubber or epoxy poiy(amide) topcoat, in different thicknesses. Prior to immersion the painted specimens were subjected to thickness and adhesion measurements. After immersion, impedance measurements were carried out periodically as well as the standard tests according to ASTM D-610/68 and AS!lM D714/67. The latter were undertaken iu order to assess the degree of rusting and bhsterhtg of the painted steel surfaces, respectively, in an attempt to correlate the visual observations with the electrochemical data. Complex plane plots of the resistive and reactive components of impedance, obtained over the frequency range from 65 KHz to 1 mHx were analyxed in accordance with resistive-capacitive equivalent eIectricaJ circuit models assumed to describe the painted metallsohttion interfaces. The experimental results suggest that both the type and the thickness of the topcoat paints could be of paramount importance in controlling the rate of action of the zinc-rich primer and hence allowing an extension of its useful life. At the same time, the cathodic protection incresses the tendency of cathodic reactions occurring at the costed steel interface and consequently increases the likelihood of delamination and biistering of the coating near a defect.

K&g wmfs:

Zinc-rich primer; Electrochemical impedance; Corrosion potential

Introduction The ability of a coating to protect a given metal against corrosion generally depends on: (a) the quality of the yoating; (b) the characteristics of the metal; and (c) the properties of the metal/coating interface. No coating
*CIC Researcher.

0300-9440193/$24.00

Q 1993 - Elsevier Sequoia. Ah rights reserved

186

is totally impermeable and therefore ions, oxygen and water will diffuse towards the metal surface at a rate and to an extent determined by the coating and the environment. For iron-type metallic substrates exposed to industrial or saline atmospheres, zinc metal is one of the materials most used in corrosion protection coatings [l, 21. Two methods which can effectively prevent, or at least retard the corrosion of a steel substrate are the use of electrodeposited coatings of zinc alloyed with such elements as nickel or cobalt [ 3, 41, and the application of paints containing a high percentage of zinc particles dispersed in organic or inorganic binders. In the zinc-based paints a high pigmentation level is required for electrical contact between adjacent zinc particles and between these particles and the steel substrate. Consequently, when the electrolyte solution reaches the steel/ coating interface the dissolution reaction of the active fraction of the zinc provides cathodic protection to the steel over a period of time. Initially, the coating porosity is high and the aforementioned processes are rapid [5-9 ]. Accordingly, the substrate remains cathodically protected even where discontinuities in the coating are present, causing the partial exposure of bare steel. The accumulation of zinc corrosion products, which have poor electrical conductivity, promotes the loss of electrical contact and diminishes the active surface area of the zinc pigment, consequently the galvanic action becomes less effective. As the exposure time increases, the deposition of corrosion inhibiting zinc compounds at the base of the pores in the coating, followed by the sealing of the porous structure by the zinc corrosion products, must undoubtedly contribute to assuring long-term protection [7, lo]. ZRP can be used as a single coat shop primer for temporary protection or as a primer in a multilayer coating system for long-term protection. The protective mechanism of single coat zinc-rich primers has been previously studied for zinc-rich epoxy poly(amide) and zinc-rich ethyl silicate paints [ll]. The objective of the present paper is to study the protective capacity of coatings using a zinc-rich ethyl silicate paint as primer and al~inium pigmented chlorinated rubber or epoxy poly(amide) as topcoat paint, combined in different thicknesses on steel. Time-dependent changes in impedance and in open circuit potential measurements were determined at various exposure times on samples immersed in 3% NaCl solution. The standardized test procedures ASTM D-6 1O/68 and ASTM D-71 4/87 were also performed in order to assess visually both the rusting and the degree of blistering suffered by the coated steel surfaces. Experimental SAE 1020 steel plates (20 X 8 X 0.2 cm) were used as metallic substrate. The surface was sandblasted to Swedish Standard SIS 05 59 00/67 Sa 24-3.

187

A roughness profile of 24 f 4 pm was obtained. The specimens were degreased with toluene and coated with the primer and topcoats whose compositions and thicknesses are shown in Table 1 and Table 2, respectively. A Bird applicator was used to spread the organic coatings; the desired f&n thicknesses were achieved by successive applications, with drying periods of 7 days between each coat. In order to avoid contamination with atmospheric dust, the test plates were kept in desiccators at room temperature (20f 2 C). Dry film thickness was measured with an electromagnetic gauge, using a bare sanded plate and standards of known thickness as reference. On each plate two cylimlrical tubes of transparent acrylic were fixed by using an epoxy adhesive in order to get good adhesion to the coated substrate. The geometrical area of each cell exposed for impedance measurements was
TABLE 1 Composition of paints (g/100 g) Component Ethyl silicate Zinc Total solids Zn content (%) in the dry paint film Epoxy poly(amide) AhmIinium Chlorinated rubber AhmIinium Primer 31.6 68.5 81.7 83.8 60 40 60 40 Top paint

TABLE 2 Coating thickness @I-I) Sample Thickness Zinc ethyl silicate 1A 2A 3A 4A 5A 6A 7A 1B 2B 3B 4B 5B 6B 7B 50 70 80 90 90 70 13 80 60 40 45 200 200 200 Al epoxy poly(amide) Al chlorinated rubber

10 20 40 70 90 80 25 35 45 50 100

188

Fig. 1. Photographic image of sample A surface after 56 days immersion.

17 cm2. within each cell the coating was scribed to the substrate in the form of a cross (see Pig. 1). A large cylinder of graphite axially placed, was used as the counterelectrode and a saturated calomel electrode (SCE) as reference. The electrolyte was 3% NaCl solution, pH 8.2. All impedance spectra in the frequency range 10m3G< 6.5 X lo4 Hz were performed in the potentiostatic mode at the corrosion potential (I&,), as a function of the exposure time in the electrolyte solution, using a 1255 Solartron Frequency Analyzer and a 1186 Solartron Electrochemical Interface. Data processing was carried out with an Olivetti PC and a set of programs developed by Boukamp [ 12 1. After immersion, the coatings were assessed weekly using the ASTM Standards D-61 O/68 and D-714/87 in order to evaluate the degree of rusting and blistering, respectively, of the painted steel surfaces in an attempt to correlate visual observations with electrochemical data.
Results and discussion

Before exposure, the zinc-rich ethyl silicate paint was examined using scanning electron microscopy (SEM) and it was found to comprise of spherical particles with distributed radius values in the 0.5-5 pm range. One hour after immersion, the corrosion potential (&,J for all the steel/ coating/396 NaCl solution systems was about - 1.04/- 0.90 V/WE, confkming that there was electrical contact between the steel substrate and zinc particles

TABLE 3

Corrosion

potentials

(-E,,,,)/SCE

(V)

Immersion time 5A 6A 7A 1B 3B 5B 6B 2B 4B 7B

Sample 1A

2A

3A

4A

(days) 1.011 0.999 0.966 0.940 0.985 0.996 0.965 0.966 0.953 0.954 0.945 0.897 0.812 0.761 0.809 0.788 0.734 0.663 0.988 0.970 0.965 0.903 0.964 0.949 0.945 0.927 0.917 1.025 1.016 0.993 0.951 0.943 0.973 0.956 0.957 0.959 1.010 0.997 1.006 0.990 0.995 1.004 1.008 1.005 1.002 0.996 0.952 0.944 0.907 0.894 0.900 0.887 0.871 0.852 1.010 1.007 0.914 0.805 0.767 0.783 0.770 0.759 0.763 1.021 1.040 1.028 0.992 0.993 0.984 0.986 0.983 0.988 1.035 1.044 1.038 0.996 0.934 0.836 0.982 0.892 0.823 1.038 1.032 1.006 0.936 0.903 0.900 0.890 0.929 0.913

0 7 14 21 28 35 42 49 66

1.008 0.991 0.998 0.944 0.945 0.947 0.944 0.739 0.666

0.998 0.968 0.982 0.974 0.991 0.900 1.000 1.000 1.005

1.010 1.001 0.963 0.964 0.980 0.941 0.990 0.968 0.989

1.001 0.987 0.958 0.952 0.977 0.984 0.986 0.983 1.000

190

in the primer, see Table 3. These E,, values remain practically unchanged with immersion time for sample type A (except sample 1A with primer alone and 7A with the thinnest coat of primer) while for sample type B (except sample 1B and 5B with primer alone) the corrosion potentials move gradualIy in, a positive direction, approaching a value between those corresponding to E corr zinc and steel when exposed to environments with similar aggresfor siveness. In spite of this, the E,,, values reached by the samples 3B( - 0.825 V/SCE), 4B( -0.763 V/SCE) and 6B( -0.823 V/SCE) indicate that the Zn particles in the primer were still in contact with the steel substrate and the electrolyte after more than 1200 hours immersion, and hence still cathodically protecting. However, the E,,, of samples 1A and 7A fluctuated randomly around - 0.60 f0.06 V/SCE after 50 days exposure, suggesting that there was no significant residualzinc galvanic action, probably due to the partial stabilization of the vol~ous white corrosion products on the pigment surface, and that the systemshave not yet reached a steady state. Under these circumstances attack of the substrate (reddish rust) was seen as spots locahzed at the cross scribes, (Pig. 1). Prom these corrosion potential results, it may be inferred that: (a) thicker ZRP primers provide longer galvanic protection and (b) for thin ZRP such protection is better when thicker coats of topcoat paints are applied; this is more clearly shown by the chlorinated rubber topcoat than by the epoxy poly(amide) and this unequal behaviour is attributed to the different oxygen permeability, and consequently the different polarization of the cathodic reaction, shown by the two formulations [ 131. The impedance spectra contain valuable nonagon on the characteristic coating parameters as well as on the charge transfer kinetics of corrosion processes going on extensively within pores and cracks in the coatings. In the systems steel/ZRP/aqueoussolution, the latter processes were found to be mainly associated with the pigment dissolution reaction as can clearly be seen by the dependence of the corrosion potential on the immersion time [III. In order to improve the barrier properties of these porous ZRP coatings, one or more coats of a topcoat paint are applied over the primer, creating a second barrier between the steel and the environment which can limit the access of corrosive species to the primer and substrate. Such an increase in the isolating properties of the coating system can extend the useful life of coated metals exposed to aggressive media. Typical impedance spectra obtained at increasing immersion times for the systems naval steel/zinc-rich ethyl silicate primer/pigmented epoxy or chlorinated rubber top paint/396 NaCl solution, are shown in Pigs. 2-4. Owing to the dynamic character of rust formation, the impedance spectra of coated naval steel/3% NaCl solution systems change throughout the ~me~ion time. A fairly good description of the experimental impedance diagmms can be obtained in terms of a transfer function analysis using non-. linear fit routines as developed by Boukamp [ 12J.

20 Z.rea1. [ohm]

:lO3) +

60

Fig. 2. Complex plane plot (experimental and simulation) for sample 2B after one hour immersion in 3% NaCl solution.

0.5

1.5

Z-real.

roz

(x10-31

-_,

2.0

Fig. 3. Complex plane plot (experimental and simulation)for sample 4B after the 14thimmersion day in 3% NaCl solution.

Rm
200 Z.reel. 400 [ohm] ---, 600

Rt
600

Fig. 4. Complex plane plot (experimental and simulation) for sample 2B after the 42nd immersion day in 3% NaCl solution.

Because of the complex nature of the processes taking place at a coated steel interface it is necessary to derive models that account for the impedance measured at such interfaces. Three types of equivalent circuit models have been used to explain the impedance data. In principle, a general circuit model would consist of the electrolyte resistance, R,, the coating capacitance, C1, the ionic resistance, R,, resulting from the fact that penetration of electrolyte into the coating produces ionically conducting paths, and a general impedance element, Z,, characterizing processes related to reactions at the metal/coating interface (Fig. 5). The contribution of Z,, (representing a combination of passive electrical elements in the equivalent circuit), to the total impedance depends on both the system and the exposure time considered. In some instances, for example after one hours immersion, (see Fig. 2), the main feature of the Nyquist diagram involves at high frequencies a resistive-capacitive (RC) semicircle which contains information on the coating properties (R,, C, values), followed by a straight line in the low frequencies part with a slope of approximately - l/2. The slight distortion in the resistive-capacitive contribution indicates a deviation from ideal RC behaviour in terms of a distribution of relaxation time constants, due to tangential penetration of the electrolyte at the metal/coating interface, surface

193

Rm Fig.

Zx

5. Generalized equivalent circuit.

inhomogeneities, roughness effects and/or diffusion processes in the pores, which must be considered in a dispersion formula for the corresponding transfer function [ 14, 151. Some, or all, of these mechanisms are plausible in the coating systems treated in this paper; it is therefore difficult to provide an accurate physical description of the processes involved. A first interpretation of the complex plane plot obtained at high frequencies establishes that it may be described by a transfer function corresponding to an equivalent circuit built up from a series combination of R, with a parallel R,-CPE element, where the constant phase element (CPE) is dellned as: CPE = C1= [ C@O)~] -I; in tam, this circuit would be connected with a general Warburg type element 2, (where Z,= [K&O)] which is obtained at low frequencies and is related to the relaxation of a mass transport process linked with the oxygen reduction reaction [ 111.In using the overall equivalent circuit, an optimum fit of the experimental results is obtained as shown in Pig. 2. After a certain exposure time has elapsed, for instance 14 days (Pig. 3), some impedance spectra show a second time constant which is associated with the corrosion process at the metal/coating interface. Its impedance, Z,, is represented by a charge transfer resistance, R,, (related as l/R, with the corrosion rate), in series with a general Warburg type element 2, and both in parallel with a constant phase element CPE = C, assumedto be representative of the double layer capacitance. So the high frequency time constant would be the result of the coating capacitance (C,) and ionic resistance (R3 interaction while the low frequency relaxation time would be given by the charge transfer resistance (R+,) and the double layer capacitance (C,). The equivalent circuit that models this impedance data is shown together with the fitted results in Pig. 3. It must also be recognized that for thick coatings, immediately after immersion in an aqueous electrolyte, or after a longer period of exposure such as 42 days, when the coating defects are tightly sealed by the corrosion products, an impedance spectrum similar to that shown in Pig. 4 can be obtained. In the current study, the experimental data are better fitted by using an equivalent circuit in which the coating and faradaic impedances are connected as a series combination. However, if their time constants have

194

a ratio G 50 they overlap and little or no information can be deduced. In order to select the most appropriate model of equivalent circuit, the value of the standard deviation obtained from the fitting process has been used as the final criterion. These results are summarized in Table 4 and Figs. 6-13. Adhesion tests performed according to ASTM StandardD-4545/81showed a poor adhesion (5-8 Kg cm-) between the primer and the steel substrate due to the high pigment content in the ZRP. However, the visual assessment of corrosion and blistering within the same cells used for impedance measurements showed very good anticorrosive properties since corrosion rating (ASTM Standard D-610/68) did not drop below a value of 8 (0.1% coverage by steel corrosion products) after 56 days of immersion (see Table 4). It must be observed that where there was steel corrosion, as in samples 7A and lB, the small amount of rust was localized only at the cross scribe. Reproducible information derived from impedance data obtained from the two cells on each coated steel panel, suggests that almost independently of the coating thickness used in both the A and B type systems, the value of generalized ionic resistance R,,,,which describes paths of lower resistance short circuiting the polymeric lllm, can fluctuate by about 4-5 orders of magnitude during the test, (Pigs. 6 and 7). This dynamic behaviour is attributed to the fact that as the zinc particles dissolve, their voluminous corrosion products seal the initial intrinsicand extrinsic coating discontinuitiesenhancing its barrier properties [ 161,as is shown by the increase of R, values. However, the constant exposure to aqueous electrolyte gives rise to the appearance of other localized weak points in the coating matrix which causes that R,, and consequently the barrier properties, to decrease again. This effect of the corrosion products, added to the plasticizing action of water penetrating through the paint matrix towards the metallic substrate, explains the large fluctuations (five or more orders of magnitude) exhibited by the coating capacitance (C,) during the immersion time, (Pigs. 8 and 9). & and C, are dependent on both the type and the thickness of the coatings used. Initially, the Rt values for samples of type A are markedly influenced by the top paint thickness, (Pig. 10). It must be assumed that in the early stages the organic topcoat paint has a high resistance and therefore the electric pathways near the cross scribe are very short; the zinc at the cross scribe dissolves as Zn2+ and the oxygen reduction reaction takes place on the steel under the paint, forming hydroxyl ions. However, once the electrolyte permeates the coating, its resistance gradually decreases, and hence so too do the & values. This corresponds to an increasing Zn reactivity caused by a gain in electrical conductivity between the zinc particles themselves and between them and the substrate. As the conducting pathways formed through the film increase, alkaline solution accumulates under the coating and the Zn dissolves in it [ 17-211. Two consequences arise from these last processes: (a) as a result of alkali attack, a slow but continuous loss of adhesion occurs at the steel/coating interface, starting from the scribe, and is followed by blistering due to water accumulating osmotically, (see Table

TABLE 4 and D-714/87 as a function of time

Results of tests performed according

to ASTM standards D-610/68

Sample 21 49 b a 10 10 10 10 10 10 9 10 10 10 10 9 10 10 9 b a 10 10 b 56 a 10 10 10 10 10 10 10 10 10 9 10 10 medium n. 4 10 medium n. 4 10 medium n. 4 10 10 10 10 10 10 10 10 10 10 10 10 10 10 few n. 6 10 10 10 10 10 10 b a b a b a 28 35 42

Time (days)

7.

14

1A

10

10

10

10

10

10

2A

10

10

10

10

10

10

3A medium n. 8 medium n. 8 medium n. 6 medium n. 6 medium n. 6 medium n. 6 medium n. 6 medium n. 4

10

10

10

10

10

4A

10

10

10

10

10

few n. 8 few n. 8

few n. 8 medium n. 6 medium n. 4

5A

10

10

10

10

10

few n. 8

medium dense n. 6 medium n. 6 medium n. 6 medium dense n. 4 medium

6A

10

10

10 few n. 2 medium n. 2 medium n. 6 10 10 10 10 10 10 10 10 10 10 10 10 10 medium n. 6 10 9 10 10 10 ;oe 10 10 few n. 6 few n. 6 10 few n. 2 medium n. 2 few n. 2 medium n. 2

10

10

10

7A

10

10

10

few n. 8 10 10 10 10 10 10 10 few n. 8 10 10

10

few n. 6

medium n. 2 medium n. 6

medium dense n. 4 medium n. 2 medium n. 2 9 10 10 10 10 10 10

n. 4 medium n. 2 medium dense n. 2 8 10 9 10 10 10 10

1B

10

10

10

10

10

few n. 8

2B

10

10

10

10

10

3B

10

10

10

10

10

few n. 8 few few n. 8 few n. 6 10 few n.8 medium n. 6 few n. 8 10

4B

10

10

10

10

10

;08

medium dense n. 6 medium n. 8 medium n. 6 medium

5B

10

10

10

10

10

10

medium dense n. 6 medium n. 8 medium n. 6 medium n. 6 10

6B

10

10

10

10

10

10

7B

10

10

10

10

10

10

few n. 6 few n. 6

few n. 4 few n. 6

medium dense n. 6 medium n. 8 medium n. 6 medium n. 6 medium n. 8 few n. 4 few n. 4

medium dense n. 4 medium n. 6 medium n. 6 medium n. 4 medium n. 6 few n. 4 few n.2 i

a- Standard ASTM D-610/68.

b-Standard

ASTM D-714/87.

196

102
0 Immersion Fig. 6. Dependence of R, R, time /days

14

20

42

56

Immersion

time / doys

on exposure time for samples type on exposure time for samples type
I ,

A. B.
1

Fig. 7. Dependence of

YE 10-2 IY : y us4 5 f= 10 -6

yE 10-2

lo-*;

14

28

42

56

10-10;

14

2%

Immersion

time /days

Immersion

42 56 time/days

Fig. 8. Dependence of C1 on exposure time for samples type Fig. 9. Dependence of C1 on exposure time for samples type

A. B.

4); (b) as the blistering increases, new areas of zinc are exposed to the electrolyte increasing the conductivity (lower & values). In addition, the accumulation of corrosion products forms a barrier layer which is responsible for transitorily slower corrosion rates (higher & values). All samples of type B (with or without topcoat paint) show similar values of R, one hour after immersion (Fig. 11); later,during the ilrst 10 days immersion, the sample-response depends on the top paint thickness.Whereas, in samples 1B and 5B (primer alone), the pigment reactivity increases, in other words, & decreases when 3245 pm of chlorinated rubber paint is added as topcoat, the increasing R, values suggest that the pigment reactivity is reduced, probably due to the better barrier effect afforded by the overall

1021
0

14

28 42 56 Immersion time / days

lo314 0

62 56 Immersion time /days

Fig. 10. Dependence of & on exposure time for samples type A. Fig. 11. Dependence of I& on exposure time for samples type B.

coating. At intermediate times, the electrochemical response for samples of both type B and type A was similar and it is therefore believed that both systems behave in the same way. At the end of the test, the Rt values for samples without chlorinated rubber topcoat or with only thin topcoats (poor barrier effect) were similar (except for sample 6B) and sulllcient to ensure continued protection of the steel substrate. It has been shown elsewhere [ 111 that the thinner the zinc-rich ethyl silicate anticorrosive primer is, the faster the electrochemically active surface area decreases with increasing exposure time. Such a decrease is related to the loss in electrical contact between the zinc particles, owing to accumulation of corrosion products as confirmed by SEM. By comparing the & values published in ref. 11 with the ones obtained in the present work, it can be seen that the useful life of a ZBP may be extended by using either a thicker anticorrosive primer or a topcoat paint whose optimum thickness and formulation will depend on the aggressiveness of the environment. The double layer capacitance (Ca) for samples of both type A and type B exhibit the same fluctuating characteristics as the other parameters (Pigs. 12 and 13). Its instability may therefore also be attributed to the continuous changes occurring at the coating/substrate interface and the discontinuous gaIvanic action at the surface of the zinc particles. Parameters derived from electrochemical impedance spectroscopy (EIS) data correlate well with the corrosion potential values over the period of the test. It must however be recognized that the equivalent circuit parameters were derived with reference to the geometric area of the samples which at any one time may differ from the effective electrochemically active area because of flhn porosity. Work is now in progress to clarify this situation.

10-J-----J 0
14 28

42

56

Immersion time / days

Immersion ilme / days

Fig. 12. Dependence of C, on exposure time for samples type A. Fig. 13. Dependence of C, on exposure time for samples type B.

Conclusions

Results of the electrochemical measurementsused to assessthe protective performance of a paint system comprising a zinc-rich ethyl silicate primer with a pigmented chlorinated rubber or epoxy poly(amide) topcoat, in a 3% NaCl solution, correlate well with one another and with standardized visual observations. For example, when E,,, for samples 1A and 7A approaches the typical value for bare steel in such a solution, reddish corrosion products can be observed at localized zones at the damage site (cross scribe) on the coating. In all the samples voluminous white corrosion products were found on the coating surfaces. Throughout the immersion time the impedance data can be interpreted in terms of transfer function models describing equivalent circuits for the coated steel and involving the contribution of one or two parallel R-CPE elements for the coating electrical properties (highest frequencies), the faradaic processes (intermediate frequencies) and a Warburg type behaviour at the lowest frequencies. The relative influence of diffusion processes occurring through the overall paint film depends on the exposure time of the system in the aggressive medium. Electrochemical impedance spectroscopy provides a predictive tool capable of detecting and evaluating the deterioration of the coating with time. However, it should be recognized that the value of such evaluations is specific to the coated metal/aqueoussolution considered. The present study of changes occurring with time in the system steel substrateBRP/topcoatpaint immersed in NaCl electrolyte, takes into consideration coating defects, penetration of electrolyte through the coating, loss of adhesion, blistering and the corrosion of pigment and substrate. EIS data can be used to evaluate the degradation of such systems.

199

Results suggest that the optimum selection of the type and thickness of the painting scheme (primer alone or with a topcoat paint) could be of paramount importance for controlling the rate of action of anticorrosive zincrich paints and hence extending their useful life and consequently reducing maintenance costs. In order to improve knowledge about this subject, further work is in progress to introduce models based on transmission line equivalent circuits for other types of painting schemes. The blistering of coated steel is attributed to the penetration of water through the coating by osmotic pressure, whose magnitude increases with the concentration of the salt solution beneath the coating. Cathodic protection of coated steel enhances the cathodic reactions occurring at the steel interface and, consequently, delamination and blistering of the coating near a defect is a likely mode of failure.

Acknowledgements

The authorswould like to thankthe Comisi6nde Investigaciones Cientfflcas de la Provincia de Buenos Aires (CIC), the Consejo National de Investigaciones Cientfflcas y T&micas (CONICET) of Argentina, the Instituto National de Tecnologfa @NT) and the Conselho National de Pesquisas (CNPq) of Brazil for their financial support of this research work.

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16 C.G. Munger, in J.D. Keaue (ed.), Good Puiding Pmctke, Steel Structaw Painting ~a~~ Vof. 1, 125 SSPC, Fittsburglt,1982. I? Y. Miyoshi, M. Kitayama, K. Nishimura and S. Naito, SAE Tech. Papa, 850&?7, 1985. 18 H. Leidheiser, Jr., Corro&oq 39 (1983) 189. 19 W. Funke, in H. Leidheiser, Jr. (ed.), CorrosGn Control bp t3rgunic Coat~~s, NACE, 1981, 97. 20 JJ. Ritter and J. Kruger, in H. Leidheiser, Jr. (ed.), Corrosiota Cm&-o1 bg Orgmic Coatings, NACE, 1981, 28. 21 R.T. Ruggeri and T.R. Beck, Cm 39 (1983) 452.