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After 24 h of free corrosion, the impedance was lowest in the sample without pigment, which reveals the higher activity of this system, and another time constant appeared at the high frequencies. Fitting of the spectra was made using the equiv-alent circuit in Fig. 8, where the high frequency impedance (1 k¦¸ cm2) is due to the electrolytic solution at the scribe.RHF and QHF describe the high frequency process, and Rct and Qdl correspond to the charge transfer resistance and the double layer capacitance, respectively. Finally, a component describing the mass transfer impedance was considered in some cases in order to account for a small tail appearing below 0.1 Hz. The high frequency process had a resistance of 5¨C10 k¦¸ cm2, as shown in Fig. 9, whereas the Y0 for this process has a value of roughly 10−8 to 10−5 Fcm−2. This capacitance is too high for a polymer film, which generally has values in the range of 10−10to 10−8Fcm−2.Further, in the presence of chromate Y0 decreases with time, a behaviour that is the opposite to the known evolution of coating capacitance values (which tend to increase due to water uptake). This high frequency time constant can how-ever be explained by the formation of the passivating film, of either chromium hydroxide or zinc phosphate. The formation of this film starts in the first minutes of exposure, possibly with the precipitation of a monolayer, and grows afterwards, during the first 24¨C48 h. The low frequency process gives Rct = 20¨C80 k¦¸ cm2 and is maximum for the chromate. The double layer CPE grows with time, revealing the growth of the active area underneath the coating, i.e., delamination. The ratio of Y0 with and without pigment is roughly 0.1, mean-ing that the loss of adhesion was weaker in samples with pigment. The delamination rate, estimated from the CPE, was minimum in the epoxychromate coating, followed by the epoxyphosphate and finally by the clear coat. This was the same rate that was determined by visual inspection of the samples at the end of the test. The SVET was also used to study the ionic current distribution above the scribed samples, for the three coatings in 0.1 M NaCl. The evolution of the current maps and the current density values have not show any significant differ-ences among the specimens with the various coatings. As an example, Fig. 10 shows SVET measurements of the scribed HDG sample, coated with the clear epoxy paint. In the first 2¨C3 days of immersion there was a clear separation between the cathode and the anode along the scribe ( Fig. 10 a) and there were no signs of delamination in the micro-video im-age. For longer exposure times, however, the anodic activity along the scribe increased and the signs of cathodic activity disappeared from the map, as delamination progressed away from the scribe ( Fig. 10 b) |
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perry20008
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RXMCDM: ²»ÏëÓ¦Öú¾ÍËãÁË£¡ 2014-05-12 09:16:51
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After 24 h of free corrosion, the impedance was lowest in the sample without pigment, which reveals the higher activity of this system, and another time constant appeared at the high frequencies. Fitting of the spectra was made using the equiv-alent circuit in Fig. 8, where the high frequency impedance (1 k¦¸ cm2) is due to the electrolytic solution at the scribe.RHF and QHF describe the high frequency process, and Rct and Qdl correspond to the charge transfer resistance and the double layer capacitance, respectively. Finally, a component describing the mass transfer impedance was considered in some cases in order to account for a small tail appearing below 0.1 Hz. The high frequency process had a resistance of 5¨C10 k¦¸ cm2, as shown in Fig. 9, whereas the Y0 for this process has a value of roughly 10−8 to 10−5 Fcm−2. This capacitance is too high for a polymer film, which generally has values in the range of 10−10to 10−8Fcm−2.Further, in the presence of chromate Y0 decreases with time, a behaviour that is the opposite to the known evolution of coating capacitance values (which tend to increase due to water uptake). This high frequency time constant can how-ever be explained by the formation of the passivating film, of either chromium hydroxide or zinc phosphate. The formation of this film starts in the first minutes of exposure, possibly with the precipitation of a monolayer, and grows afterwards, during the first 24¨C48 h. The low frequency process gives Rct = 20¨C80 k¦¸ cm2 and is maximum for the chromate. The double layer CPE grows with time, revealing the growth of the active area underneath the coating, i.e., delamination. The ratio of Y0 with and without pigment is roughly 0.1, mean-ing that the loss of adhesion was weaker in samples with pigment. The delamination rate, estimated from the CPE, was minimum in the epoxychromate coating, followed by the epoxyphosphate and finally by the clear coat. This was the same rate that was determined by visual inspection of the samples at the end of the test. The SVET was also used to study the ionic current distribution above the scribed samples, for the three coatings in 0.1 M NaCl. The evolution of the current maps and the current density values have not show any significant differ-ences among the specimens with the various coatings. As an example, Fig. 10 shows SVET measurements of the scribed HDG sample, coated with the clear epoxy paint. In the first 2¨C3 days of immersion there was a clear separation between the cathode and the anode along the scribe ( Fig. 10 a) and there were no signs of delamination in the micro-video im-age. For longer exposure times, however, the anodic activity along the scribe increased and the signs of cathodic activity disappeared from the map, as delamination progressed away from the scribe ( Fig. 10 b) |
2Â¥2014-05-11 21:49:59
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3Â¥2014-05-12 08:25:44
jiangguofeng
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