Assessment of protective properties of organic coatings by thermal cycling L.

Fedrizzia,
a ,

, A. Bergoa, F. Deflorianb, L. Valentinellia

Department of ICMMPM, University of Rome La Sapienza, Via Eudossiana 18, 00184 Rome, Italy b Department of Material Engineering, University of Trento, Via Mesiano 77, 38100 Trento, Italy Available online 2 September 2003.

Abstract
Researchers efforts are focused on understanding how coatings can be tested in order to determine their real capabilities and selected for different purposes. Outdoor exposures are certainly reliable and offer a good representation of the actual service life. However, such tests cannot be considered quick. On the other hand, a quick test, even if reliable, very often disagrees with the actual degradation mechanisms occurring under natural conditions. In fact, in order to determine an acceleration of the natural weathering, it is necessary to increase the effect of natural parameters affecting the protection properties of a coating . The usual modern way to operate is to take advantage of ageing tests where temperature plays a big role in the ageing of the material, permitting to gather faster information for coating corrosion resistance evaluation. Following the recent new experience realised by the Bierwagen group, we carried out different thermal cycling tests consisting in daily series of electrochemical measurements on coated samples, carried out using electrochemical impedance spectroscopy (EIS). The cumulative effects of such a thermal cycling on the film, based on a large variety of theoretical explanations, should permit the ranking of a variety of materials, by constituents, characteristics and application purposes, in a short time while remaining objective and reliable. The used ageing procedure and data evaluation allowed to quickly and precisely obtain information concerning both barrier properties and adhesion properties of the studied materials. Keywords: Electrochemical impedance; Thermal cycling ; Weathering test; Organic coating ; Adhesion

Article Outline
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1. Introduction 2. Experimental 3. Results and discussion

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3.1. Microstructural characterisation 3.2. Characterisation of resistance to thermal ageing 4. Conclusions Acknowledgements References

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1. Introduction
Quick and reliable tests to evaluate protection properties of organic coatings is the continuous demand of coating designers and industrial manufacturers. For this purpose, a large variety of outdoor and laboratory equipment and procedures have been proposed and used for decades. Outdoor exposures are certainly reliable and offer a good representation of the actual service life. Data collected in this way provide a base for the selection of current coatings for specific applications and they also provide an insight into how new coatings could be formulated. However, such tests cannot be considered quick. On the other hand, a quick test, even if reliable, very often disagrees with the actual degradation mechanisms occurring under natural conditions. In fact, in order to determine an acceleration of the natural weathering, it is necessary to increase the effect of natural parameters affecting the protection properties of a coating . Aggressiveness of the environment is then enhanced (increase in salt amounts, use of specific chemical agents, changes in pH), temperature is increased and exposure to solar degradation is changed by using UV radiation-producing apparatus. Different tests and techniques have been studied and performed in recent years to cut down the time demand and to improve the capabilities to match the characteristics of natural weathering. To this aim, the most common method (salt-spray testing following the ISO 7253 standard) was implemented by modifying chemical composition of the solution, or by introducing several degradation steps in one cycle. As an example, the Prohesion test (ASTM G85) was supplemented by Skerry and Simpson [1] with an alternate cycle of UV and continuous condensation. Chong et al. [2] created a variation of the ASTM D 5894 cycle and added low temperature stress to it. The Norsok M 501 test is a standardised Norwegian weathering test designed for testing materials intended to work at very hard environmental conditions. In this cyclic test, the described coated panel undergoes sessions of UV exposure with humidity, salt fog and a conditioning period at room temperature as the dry part of the cycle. Nevertheless, these tests usually need several thousand hours to be completed and damage evaluation seems to be always rather subjective, determined by the ability of the operator. Bierwagen et al. recently described [3] and [4] electrochemical studies of organic coats performed at room temperature exposure to give reproducible information on film performances, and an experimental set up in which the temperature of the sample is varied cyclically above and below the glass transition temperature to establish a synergic degradation effect into the material. This is due to electrolyte

transport through the film and its eventual accumulation, loss of adhesion, chemical and physical ageing as a consequence of thermal fatigue effects, dielectric characteristic variations due to a more open polymer structure. The cumulative effects of such a thermal cycling in the coat, controlled by means of changes in electrochemical parameters, should permit the ranking of a variety of materials, by constituents, characteristics and application purposes, in just a week, while remaining objective and reliable. Following this, we carried out several different thermal cycling tests, which consisted of a daily series of electrochemical measurements on a metallic coated sample, performed by means of electrochemical impedance spectroscopy (EIS) at different temperatures. Aim of the work was to establish if a proper interpretation of impedance measurements performed on coated coil samples submitted to thermal cycles allowed to evaluate and distinguish barrier and adhesion properties of the analysed systems.

2. Experimental
Three different kinds of coil coating products were studied: two polyester systems composed by a primer and a topcoat applied on a steel substrate (Spol) and on a galvanised steel (Zpol), and one PVDF system composed of a primer and topcoat applied on galvanised steel (Zpvdf). All these materials were produced following an industrial painting cycle and their main characteristics are shown in Table 1. The samples for testing were obtained by cutting out plane panel rectangles and glass cylinders were glued to the surface and filled with a solution of Na2SO4 0.3 wt.% before impedance measurements. Testing area was of about 20 cm2. Table 1. Main characteristics of the samples Samples Zpol Substrate Pretreatment Primer Topcoat Thickness (mm) NiCo salts Polyester Polyester 27 2

Zpvdf NiCo salts PVDF PVDF 25 2 40

Spol Iron phosphates Polyester Polyester 27 2 36

Galvanised steel Galvanised steel Steel

Glass transition temperature (C) 38

Sample ageing was always performed under wet conditions (electrolyte remained always in contact with the organic coating ) and using different kinds of thermal treatments, both cyclic or continuous, at different temperatures. Every cycle consisted of the repetition of daily exposure sequences according to the scheme shown in Table 2. Table 2. Cycle Single sequence ATL Heating from room temperature to 95 C, 4 h of permanence at 95 C, slow cooling till room temperature (about 150 min in oven), the rest of the time up to 24 h at room temperature

ATV As the previous sequence but with a faster cooling till room temperature (about 50 min in freezer) BTL Heating from room temperature to 45 C, 6 h of permanence at 45 C, slow cooling till room temperature (about 90 min in oven), the rest of the time up to 24 h at room temperature The thermal treatments performed via exposure at constant temperature are described by the symbols CE25, CE45 and CE95, corresponding to a continuous permanence at 25, 45 and 95 C, respectively. These ageing procedures were followed by a very slow cooling to room temperature, in order to perform impedance measurements. It should be noted that every experimental point obtained under these experimental conditions (exposure to a constant temperature) was obtained by using a different sample, in order to avoid introducing thermal cycling effects. Impedance measurements were carried out by using an Autolab PG STAT 30 in the frequency range 105 to 102 Hz. A silversilver chloride electrode was used as reference electrode and a platinum wire as counter electrode. All measurements were performed in a Faraday cage in order to minimise external interferences with the measuring system. The obtained impedance spectra were fitted using ZView software, through an appropriate equivalent electrical circuit. The glass transition temperature of the polymers was measured using differential scanning calorimetry (DSC). For this purpose the samples were submitted to linear heating from 30 to 150 C, at a heating rate of 3 C/min. For each sample two temperature scans were made: the first one provided information on the Tg of the coatings , the second one showed the post reticulation phenomena of the polymer. The measures were performed by a Mettler DSC 30 cell with a Mettler TC 10A interface. FTIR measurements were performed in reflectance using a Bio-Rad FTS 165 spectrophotometer.

3. Results and discussion

3.1. Microstructural characterisation Materials studied in the present work are industrial products obtained by a coil coating process. Manufacturer information suggests that the organic coating thickness is very similar for the three different samples. Thickness data, obtained by using a magnetic device, are shown in Table 1. Apart from possible systematic experimental errors due to the different metal substrates composition, the organic coating thickness for the whole set of samples is in the range of 2527 m, typical values for coil coating products. The thickness of the hot dip zinc layer of the galvanised substrates was measured to be in the range of 810 m. Before paint application the metal substrates were pretreated using traditional products for industrial processes. In particular, to prepare the steel substrate a phosphatisation bath was used obtaining a thin amorphous iron phosphate layer. Although observation of surface morphology, using a scanning electron microscope (SEM), does not allow to

identify a conversion layer microstructure, a small peak related to phosphorus can be detected by energy dispersive X-ray spectroscopy (EDXS). Galvanised steel substrates were prepared for organic coating application by immersion in an environmentally friendly conversion bath containing nickel and cobalt salts. Moreover, a passivation-like treatment in a bath containing zirconium salts was performed. In this case also the morphology of the conversion layer was not observed by SEM; moreover, no signal of the elements composing the pretreatment bath was detected on the substrate surface after treatment. We can suppose that the conversion layer is really very thin and that more sensitive surface analysis techniques must be used to analyse such a layer. Fig. 1a and b shows FTIR spectra of the studied organic coatings . FTIR spectrum of the polyester coating applied onto the not galvanised steel substrate (Fig. 1a) shows the characteristic absorption peaks of a polyester resin. In particular, stretching of CH2 and CH3 groups is visible just below 3000 cm1 wave number and stretching vibration of C O bonds clearly appears at 16501750 cm1. The absorption band visible in the range of 12001300 cm1 seems to be related to bending vibrational mode of CH bonds in the aromatic ring. The analysis carried out on the polyester coating applied to the steel substrate gives a very similar FTIR spectrum.

Full-size image (26K) Fig. 1. (a) FTIR spectrum of the sample Spol; (b) FTIR spectrum of the sample Zpvdf. EDXS microanalysis performed on these polyester coatings shows the presence of the same elements such as Si, Al and Ti together with the chemical elements of the organic component-like carbon and oxygen. These chemical signals reveal the presence of the same pigments or additives in the coatings , in the form of metal oxides. Thus the two polyester coatings applied onto galvanised and non-galvanised substrates can be considered equal from a chemical point of view as far as both the binder and the inorganic pigments are concerned. In Fig. 1b the FTIR spectrum of the PVDF coating is shown. In this case too, the characteristic peaks of CH2 and CH3 groups are present at about 3000 cm1 and in particular a characteristic large absorption band at about 1200 cm1 is observed corresponding to stretching of the CF bond. Moreover, at about 850 cm1 CH deformation out of plane or bending of possible aromatic components is present. In this case, EDXS analysis shows the presence of many signals: F, O and C relevant to the binder and Ti, Si, Al together with Cr, Co and Ni present as pigments and additives.

The glass transition temperatures (Tg) of the applied polymers were measured using DSC analysis; relative data are shown in Table 1. All these values are small, as expected by analysing this type of organic coating that must be quite plastic and flexible in order to sustain bending and deep drawing as is customary when producing artefacts from a coil. The PVDF coating presents the highest glass transition temperature, in the range of 40 C, and Tg values of both polyester samples are very similar (in the range of 3638 C). All values can be considered higher than usual ambient temperatures in a temperate climate; however, it is also possible to suppose that all coatings can undergo working temperatures higher than their glass transition temperatures during an actual service life under outdoor exposure. Microstructural characterisation revealed that the materials under study match the standard characteristics of coil coating products and in particular that:
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1. coating thickness is quite similar;

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2. polyester coatings have similar microstructure and curing degree (as revealed by DSC measurements) and a similar chemistry of both binder and pigments;
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3. PVDF has a slightly higher Tg than polyester coatings . 3.2. Characterisation of resistance to thermal ageing As described in the experimental section, coated samples were submitted to thermal cycling under wet conditions or exposed to a constant temperature, and impedance data were collected in order to evaluate coating degradation after each cycle, when the whole measuring system (metal substrate, organic coating and electrolyte) had reached the room temperature (25 C). In this way, impedance data are not affected by a measuring temperature (which is always the same) but by the thermal life of the specimens. As an example, some typical impedance spectra, in the Bode phase and modulus representations, are shown in Fig. 2a and b. For the sake of comparison, data of the polyester coating applied on a steel substrate (Fig. 2a) and on the galvanised steel (Fig. 2b) are discussed. The organic coatings applied on both metal substrates show an almost pure capacitive behaviour before being submitted to thermal cycles, while the impedance values of both coatings , at the lowest frequencies, are in the range of 109 , suggesting the presence of a similar degree of defects in the coatings before testing.

Full-size image (14K) Fig. 2. (a) Bode plots (modulus and phase) of the Spol sample after 0, 1 and 3 ATL cycles; (b) Bode plots (modulus and phase) of the Zpol sample after 0, 1 and 3 ATL cycles. When submitted to thermal cycles (up to 95 C with a slow cooling rateATL) coating degradation occurs. Already after the first thermal cycle, the impedance modulus at the lowest frequencies decreases (by about two orders of magnitude for the galvanised sample) and the presence of a resistive component in the electrochemical system clearly appears. Cycle by cycle, organic coating degradation is enhanced by a further decrease of the impedance modulus and by the appearance at the lowest frequencies of a second time constant which takes into account Faradic reactions occurring at the metal surface. As previously discussed, samples are coated with very similar products of polyester type (see the microstructural characterisation), and a superficial observation of the impedance diagrams shows their corrosion behaviour to be almost similar. However, in order to better evaluate corrosion protection properties , impedance data have been analysed in depth by using suitable fitting software. The fitting procedure was carried out using the equivalent electrical circuit of Fig. 3 that is the most commonly used model to represent painted metal substrates [5] and [6]. Notoriously, Qc represents the non-ideal coating capacitance, Rp represents the ionic resistance of the coating through its intact or damaged structure, Qdl is the non-ideal capacitance describing the double layer and Rct is the charge transfer resistance at the metal interface. All capacitances introduced in this model are mathematically described by constant phase elements (CPE) [7] and [8].

Full-size image (2K) Fig. 3. Equivalent electrical circuit used to analyse impedance data. The shape of the impedance spectrum, obtained under our experimental conditions, changes depending on the coating chemistry and on the coating degradation induced by ageing. In order to avoid introducing systematic errors in the elaboration of the different experimental data, the frequency range for fitting was maintained constant and an equivalent circuit with two time constants was always used even when the second time constant was not clearly visible in the impedance spectrum. In fact, data elaborated

from the fitting procedure not only depend on the choice of the most suitable equivalent circuit but on the selected frequency range too. Such a procedure allowed to obtain good and reliable data as far as the first time constant was concerned, but data related to the second time constant sometimes showed rather large fitting errors. Thus, in order to discuss coating degradation, it was decided to only consider the trend of the electrical parameters related to the organic coating and in particular only Qc will be here discussed. In fact, it is well known that Qc[9] well describes the barrier properties of an organic coating (resistance to water uptake) and some works suggest also a possible correlation between this parameter and adhesion properties of the organic coating or Faradic reaction at the metal/polymer interface [10] and [11]. In Fig. 4ac, the coating capacitance trend in time for coated samples exposed to the testing electrolyte at three different constant temperatures is shown. All impedance measurements were carried out after reaching room temperature using very low cooling rates and each point in the graph was obtained using one different individual sample in order to avoid introducing thermal cycles in this test.

Full-size image (10K) Fig. 4. (a) Coating capacitance Qc versus time of sample Spol after exposure to different constant testing temperatures; (b) Qc versus time of sample Zpvdf after exposure to different constant testing temperatures; (c) Qc versus time of sample Zpol after exposure to different constant testing temperatures. The three materials tested show similar trends and in particular:
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• Qc increases with time whatever the testing temperature;

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• Qc increases with the testing temperature. The behaviour indicated in the first point is usual for organic coating and is due to water uptake which occurs with different kinetics at the different temperatures. The second effect observed is also expected because the structural changes of the polymer with a temperature increase (higher intermolecular voids and higher polymer chains mobility) allow higher water permeation. However, capacitance increase is in general very small, between 25 and 45 C (Zpol has higher values at 25 C, probably within the errors limits), although all the tested coatings have a glass transition temperature

lower than 45 C, as shown in Table 1. In fact, impedance measurements were carried out always at room temperature, by which it is possible to suppose that a large part of water, absorbed in the polymer structure during exposure at 45 C, is desorbed due to polymer shrinkage during the very slow cooling phase. Such an absorptiondesorption mechanism was already observed by other researchers [12] and [13] and suggested as being due to an irreversible behaviour of polymer coatings when submitted to thermal cycles, that can produce cumulative structural damage. Fig. 5 shows the coating capacitance changes when coated galvanised steel samples are submitted to continuous exposure to 45 C or to cyclic thermal testing up to 45 C using a low cooling rate and following the procedure described as BTL in Table 2. The time of exposure to 45 C is reported in the graphs abscissa. The last point obtained after 84 h corresponds, for the cycled samples, to 14 complete cycles of 24 h. In fact, this thermal cycle includes only 6 h at 45 C before cooling.

Full-size image (5K) Fig. 5. Coating capacitance Qc versus time for Zpol and Zpvdf samples during continuous exposure at 45 C (CE) or after thermal cycling following the BTL cycle (maximum temperature 45 C). The effect of sample cycling is different for the two considered samples. The PVDF sample seems to be almost unaffected by temperature variations and small differences with respect to a continuous exposure at 45 C only appear after 84 h. On the contrary, the polyester sample shows to be highly affected by thermal cycling and the coating capacitance continuously increases. At the end of the test (after 84 h of exposure to 45 C), the coating capacitance of the sample continuously exposed is of about 8109 F, whereas after the same time the cycled sample shows a capacitance of about 1.2108 F. This result demonstrates that water uptake and consequently coating degradation not only depends on the service temperature but on the whole thermal life of a specimen. Something similar to thermal fatigue is produced by cycling , which can favour coating degradation depending on the chemical structure of the polymer and on the types of polymer interfaces involved in the degradation phenomena. Returning to Fig. 4, it is possible to note that by increasing the testing temperature up to 95 C, capacitance increase is much more evident. The PVDF coating s capacitance grows from about 4109 to about 9109 F, whereas the polyester coating shows a capacitance increase from about 5109 to about 1.1108 F when applied to a steel substrate and to about 2.4108 F when applied to a galvanised steel substrate. All tested samples also are strongly affected by exposure to a temperature much higher than Tg and the high water amount absorbed during this period cannot be completely removed during the very low cooling to room temperature. A large amount of water remains entrapped in the coating structure as already observed in other studies [12]

and [13]. However, a very particular observation in our study is the quite different coating degradation observed in the two polyester coatings , which are really quite similar to each other but applied onto different metal substrates. The behaviour of these samples was then studied at high temperature (95 C), but by performing two different thermal cycles, the first one using a low cooling rate and the second one using a high cooling rate. Both daily thermal cycles were characterised by the same exposure time to the high temperature (4 h). In this way, it was possible to highlight the extent to which a thermal cycle can affect coating degradation and in particular whether the cooling rate can also affect coating degradation. Fig. 6 shows the coating capacitance trend of the two polyester coatings when exposed for the same time at 95 C continuously or following the two different thermal cycles. The two investigated materials show quite different behaviours, and degradation of the polyester system applied onto galvanised steel is always stronger than that observed when steel is used as substrate. In particular, polyester coating on steel seems to be slightly affected by thermal cycling even when cooling rate is high. The capacitance values after a 20 h exposure to 95 C (5 cycles) never exceed 1.3108 F. On the contrary, the behaviour of the polyester coating applied on the galvanised steel seems to be highly affected both by thermal cycling and by the rate of cooling. The different behaviour from simple exposure to a constant temperature appears clearly after the second cycle for both cooling rate conditions (low or high) and becomes more and more evident after the subsequent cycles.

Full-size image (5K) Fig. 6. Coating capacitance Qc versus time for Zpol and Spol samples during continuous exposure at 95 C (CE) or after thermal cycling following the ATL or ATV cycles (maximum temperature 95 C). It is possible therefore to state that for this kind of system, thermal cycling has a negative effect on resistance to water permeation into the coating and that this effect is enhanced by a rapid temperature variation. The clearly irreversible behaviour can be correlated with the chemical and physical ageing determined in organic coatings during a test which allows electrolyte accumulation in the polymer voids, or at the polymer/pigment interfaces. However, as the polymer composition and structure of the two polyester systems considered in this work are very similar, in order to explain the different behaviour shown by the two materials when exposed to high temperature under wet conditions, we must suppose that observed degradation is not only due to water uptake in the polymer structure but also to water accumulation at the coating /substrate interface.

In fact, when the large amount of water absorbed during exposure to high temperature is only partially expelled by polymer shrinkage during the cooling period, internal stresses can be produced which can affect coating adhesion to the metal substrate. In this case, if coating bonding is poor, delamination of the coating can occur producing blisters and coating detachments. From our test, it clearly appears that adhesion of the polyester system is higher on the steel substrate than on the galvanised one. Such a conclusion is confirmed by coating observation after the thermal cycling test (5 cycles). The micrographs of the coatings applied on galvanised steel and on steel are shown in Fig. 7a and b, respectively. On the galvanised steel many very large blisters can be easily observed, whereas very few and small blisters can be observed on the steel substrate. Moreover, in this last case several small rust spots can be seen in the centre of the blisters.

Full-size image (108K) Fig. 7. (a) Blister morphology in sample Zpol; (b) blister morphology in sample Spol. Hence a rapid coating degradation seems to be related to the presence of a galvanised substrate. However, such a statement is not a general rule, as highlighted in our study. In fact the PVDF coating applied on a galvanised substrate shows good behaviour as far as thermal ageing is concerned. In Fig. 8, the capacitance trend of this sample is compared to that of a polyester coating applied onto a steel substrate when exposed to two different thermal cycles (up to 45 C or up to 95 C with a low cooling rate). Thermal ageing at the lowest temperature determines the increase of the capacitance of the two samples, after the first cycle, in the range of 5109 F. The behaviour of the two coatings appears to be very similar during the whole test. As expected, by increasing the cycle maximum temperature (up to 95 C), resistance to water absorption is worsened, as shown by the increase of the coating capacitance of both samples. Moreover, the behaviour of the two specimens differs more and more as the number of cycles increases. The PVDF coating reaches a capacitance value of about 8.5109 F after 5 cycles, whereas the capacitance of the polyester coating , after the same period arrives at about 1.2108 F.

Full-size image (5K) Fig. 8.

Coating capacitance Qc versus time for Zpvdf and Spol samples after thermal cycling following the ATL (maximum temperature 95 C) or BTL (maximum temperature 45 C) cycles. As discussed above, we can suppose that the observed coating capacitance increase is related to water absorption involving water accumulation both in the polymer structure and in correspondence of all the possible interfaces such as polymer/pigments, but mainly coating /substrate. To produce water accumulation at the metal substrate, coating adhesion forces have to be smaller with respect to the stresses induced by water ingress during the thermal cycle. In order to explain the behaviour observed in Fig. 8, we could suppose that adhesion of the PVDF system on the galvanised substrate is comparable to that of the polyester coating on the steel substrate. Moreover, it is also possible that barrier properties of the PVDF topcoat at the high testing temperature are better that those of the polyester one. Finally, it is interesting to note that almost all the capacitance trends obtained in this study show the highest capacitance increase after the first ageing period, as usually observed when water diffusion is analysed during continuous exposure to a constant temperature (almost Fickian-like behaviour). In our study such a behaviour is frequently shown after thermal cycles too. It seems that as from the first cycle, weak points at the substrate/ coating interface are affected by delamination due to water chemical action and to the internal stresses which are produced. Metal/ coating interface areas with good adhesion frequently are no longer affected by delamination during the subsequent cycles.

4. Conclusions
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• Electrochemical impedance showed to be a sensible and reliable tool in evaluating coating degradation consequent to thermal ageing (cyclic or at constant temperature) and in monitoring the variations of the metal/ coating system. However, a simple qualitative evaluation of impedance spectra evolution can be misleading and a proper fitting procedure and selection of meaningful electrical parameters is important.
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• The thermal cycles have proved to be useful in accelerating degradation of the polymeric coatings and high temperature tests are necessary when coating systems can work over their glass transition temperature. Thermal cycling can produce greater damage in a polymer coating system than exposure to a constant temperature, particularly when the coating to substrate adhesion is a critical factor.
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• Coating degradation depends on water permeation which is

favoured by exposure to wet environments at high temperature. Water uptake causes damage to the molecular structure of the coating and favours its loss of adhesion from the substrate.
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• By using thermal ageing, it was possible to clearly rank the different behaviours of the analysed systems. In particular, the better behaviour of the PVDF system with respect to the polyester one was highlighted; moreover, it was shown that the protection properties of the polyester system strictly depend on the kind of metal substrate.
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• The ageing procedure and data evaluation method used allowed to quickly and precisely obtain information concerning both barrier properties and adhesion properties of the studied materials.

Acknowledgements
Authors are grateful to La Magona dItalia in particular to Dr. Giancarlo Donati who provided coil coated samples, to Luca Benedetti who performed FTIR measurements and to Prof. PierLuigi Bonora who encouraged this study.

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