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- C. Pitting corrosion (5) (entfernen)
Corrosion of metallic engineering materials accounts for problems during geothermal operation in the Upper Rhine Graben (URG). Herein, we study the electrochemical behaviour of various metal alloys in an 80 °C simulated geothermal environment by using potentiodynamic polarisation and open-circuit potential measurements. Two different natural geothermal waters from URG geothermal sites were used for the experiments. The measurements reveal spontaneous passivation to be a key process for all alloys. This ennoblement protects more noble alloys from significant corrosion (e.g. titanium gr. 2, alloy 625) and brings less noble alloys to failure, mostly due to pitting corrosion (e.g. 316L).
CO2-induced corrosion of casing and tubing steels is a relevant safety issue for compressing emission gasses into deep geological layers (CCS, Carbon Capture and Storage). The influence of CO2 and pressure of the surrounding media on steels is demonstrated in laboratory experiments providing a corrosive environment similar to a geological onshore CCS-site in the Northern German Basin (T = 60 °C, p = 1 - 100 bar, Stuttgart Aquifer, CO2-flow rate of 3 l/h, 7008000 h exposure time). Corrosion kinetics and microstructures were characterized using specimens of heat treated 42CrMo4 (1.7225, casing) and soft annealed X46Cr13 (1.4034, tubing).
The lifetime reduction of cyclically loaded AISI 420C (X46Cr13, 1.4034) constantly exposed to highly corrosive CO2-saturated hot thermal water is demonstrated in in situ-laboratory experiments (60 °C, brine: Stuttgart Aquifer, flowing CO2: 30 L/h). SN plots, micrographic-, phase-, fractographic- and surface analysis were applied to obtain sustainable information on the corrosion and corrosion fatigue behavior. Maximum number of cycles (here 12.5 × 106 cycles to failure) is reached at σa = 173 MPa. Hydroxide and siderite layers were found on pits and crack surfaces. No typical fatigue limit exists and pit corrosion prior to crack initiation may be identified as failure cause.
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.
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.