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Eingeladener Vortrag
- nein (8)
En los últimos anos el registro y análisis del ruido electroquímico ha posibilitado importantes avances en la investigación de fenómenos de corrosión localizada tales como el picado y la corrosión en rendijas. Así mismo, esta técnica a abierto enormes posibilidades para el monitoreo in situ de tales procesos corrosivos en la industria. Sin ninguna duda, la posibilidad de registrar en tiempo real y con extrema sensibilidad los procesos de nucleación de la corrosión localizada, hace de la técnica de ruido electroquímico una invaluable herramienta para alcanzar una mejor comprensión de su origen y propagación. A continuación se discutirán las fuentes de ruido electroquímico relacionadas con la corrosión localizada así como los avances alcanzados para una confiable adquisición y análisis de la información electroquímica suministrada por las senales de ruido electroquímico y se ilustrarán con ejemplos prácticos las ventajas de la técnica de ruido electroquímico para la evaluación de la corrosión localizada.
Electrochemical noise (EN) enables corrosion research and monitoring in real time and with high sensitivity. In the case of submicroscopic nucleation events of pitting corrosion it has been observed that the cathodic process plays a decisive role in the mechanism as well as in the origin of EN signals, which depend not only on the metallic dissolution reaction but also on the electron-consuming process. EN signals arising from the nucleation process of localized corrosion on stainless steels can only be recorded due to the inhibition effect on the cathodic process achieved by the spontaneous formation of the passive layer. In consequence, passive layer stability becomes a significant factor in influencing EN signals. The way in which the passive layer stability affects the acquisition and analysis of EN signals arising from pitting corrosion on stainless steels is discussed in detail.
Unwanted corrosive phenomena on stainless steel surfaces like rouging had been observed for years occurring at certain service conditions. Rouging consists in the formation of a colored surface film containing mainly iron on metallic surfaces in contact with high-purity waters. In spite of numerous hypotheses and experimental examinations a clear explanation about the origin of rouging on stainless steels is currently still lacking. Because rouging occurs even at well passivated stainless steel surfaces the origin of this corrosive phenomenon should be related to the weakness of the stability of the passive film. In the present paper electrochemical noise measurements regarding the stability of the passive layer of alloy 904L (1.4539, X1NiCrMoCu25-20-5) in high-purity water at 70 °C depending on the cathodic process are presented. In addition, the importance of the cathodic reaction on the passivation and stability of the passive layer is discussed.
Oxygen reduction occurring at the passive layer is probably the most important cathodic reaction involved in corrosion processes on stainless steel. Furthermore, the influence of the surface state on the oxygen reduction reaction is a key point for the understanding of the mechanism of localized corrosion on stainless steel. In this study, electrochemical noise measurements under cathodic polarization were carried out to obtain new information about this influence. It has been confirmed that the surface state of stainless steel plays a very important role in the kinetic of this cathodic reaction. Oxygen reduction kinetics was significantly reduced on passivated surfaces and improved on pre-reduced and ground surfaces. In addition, electrochemical current noise measurements allowed to differentiate between the electrochemical activity produced by the oxygen reduction reaction and that due to the reduction of the passive layer, in direct dependence on the characteristics of the different surface states investigated.
The use of electrochemical noise (EN) measurements for the investigation and monitoring of corrosion has allowed many interesting advances in the corrosion science in recent years. A special advantage of EN measurements includes the possibility to detect and study the early stages of localized corrosion. Nevertheless, the understanding of the electrochemical information included in the EN signal is actually very limited. The role of the cathodic process on the EN signals remains uncertain and has not been sufficiently investigated to date. Thus, an accurate understanding of the influence of the cathodic process on the EN signal is still lacking. On the basis of different kinetics of the oxygen reduction it was established that the anodic amplitude of transients arising from pitting corrosion on stainless steel can be decreased by the corresponding electron consumption of the cathodic process. Therefore, the stronger the electron consumption, the weaker the anodic amplitude of the EN signal becomes. EN signals arising from pitting corrosion on stainless steel can be measured because the cathodic process is inhibited by the passive layer. This was confirmed by means of EN measurements under cathodic polarisation. Since the cathodic process plays a decisive role on the form of transients arising from pitting corrosion, its influence must be considered in the evaluation and interpretation of the EN signals.
Electrochemical noise measurements on anodically polarised type 304 stainless steel surfaces in contact with buffer solutions of neutral pH were performed to study the effect of chloride ions in the nucleation of pitting corrosion. Passive layer stability and susceptibility to pitting corrosion after pickling and passivation at different environmental conditions were also investigated by means of electrochemical current noise measurements under cathodic and anodic polarisation. According to the obtained experimental results pits nucleate independently on the presence of chloride ions. It has been also shown that protectiveness of stainless steel surfaces after pickling strongly depends on the relative humidity of the environment in which the surface is subsequently passivated.
Recent progress in the qualification of materials used in geothermal energy conversion systems
(2010)
Recent progress in the qualification of mateirals used in geothermal energy conversion systems
(2010)