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Sensors for the detection of general corrosion are well established. However, the detection of early phases of localized corrosion still remains a challenging task since the initiation steps can proceed without showing significant contribution to the electrochemical signal of a macroscopic surface. Along with electrochemical noise based methods, utilization of multielectrode arrays can be used to address this problem.
The aim of this study is to develop and test multielectrode arrays for early detection of corrosion processes. By means of a multielectrode analyser the current flow, potential and impedance spectra on each single electrode can be measured as a function of time. Thus, maps of the probe can be generated with real time information for instance showing individual electrodes persistent anodic or cathodic signals. This approach has been utilized in combination with scanning electrochemical techniques such as scanning electrochemical microscope or scanning vibrating electrode to select active electrodes for detailed investigation.
As the sensitivity is strongly dependent on the wire diameter and array configuration, a systematical investigation has been performed to optimize the preparation procedures and probe geometry. Stainless steel X5CrNi18-10 (1.4301) wires of different diameters have been embedded in a carrier material made of epoxy resin providing electrical insulation. The multielectrode probes consisting of at least 3 x 3 and a maximum of 10 x 10 single electrodes have been tested in corrosive media, with different chloride concentrations, as well as in the presence of metal reducing bacteria to assess their applicability in the detection of the onset of corrosion. This contribution will summarize our optimization study and the evaluation of the sensor performance.
Multielectrodes are arrays of single electrodes arranged in a particular geometry. In our work, all the single electrodes are identical stainless steel X5CrNi18-10 (1.4301) wire electrodes. Using a multielectrode analyser all single electrodes are connected via zero resistance ammeters, simulating a galvanically coupled single electrode surface. The advantage of the multielectrode analyser (MMA) is that the currents flowing between single electrodes can be measured. Thus, real-time maps can be generated indicating where anodic and cathodic areas lie on the surface of the multielectrode and how they behave.
The combination of the multielectrode analyser with the scanning electrochemical microscopy (SECM) enables the identification of corrosion sites and the detailed electrochemical analysis.
High resolution analysis of corrosion processes on stainless steels is a challenging task. The application of local electrochemical techniques such as scanning electrochemical microscopy (SECM) has opened new possibilities for the detection of corrosion products and activity on metallic surfaces. However, due to its stochastic nature, the analysis of pitting corrosion requires being at the right place at the right time. Scanning over large areas at a high resolution not only leads to long scan durations but also leaves many short-lived processes undetected. In this paper we present the combined automated operation of SECM and wire multi-electrodes connected to a multi-electrode analyzer (MMA). The inter-electrode currents between 25 wire electrodes connected via zero resistance ammeters (ZRA) are measured by the MMA at open circuit potential (OCP) and the electrodes reporting anodic currents are detected automatically to be analyzed by means of SECM. The results demonstrate the successful application of this methodology for the detection of unstable and stable pitting processes on 304 stainless steel in a corrosive aqueous environment.
The corrosion behavior of carbon Steel and different high-alloyed metals including duplex and austenitic stainless steels as well as a nickel alloy have been evaluated in artificial geothermal fluids simulating the conditions in some locations with geothermal potential in Germany, as well as two sites in Indonesia.
The suitability of low alloyed Steel UNS G41300, stainless steels UNS S31603 UNS S31803, UNS S32760 and super austenitic Steel UNSN08031 in these geothermal waters, investigated by electrochemical measurements and exposure tests, is limited. The nickel based alloy UNS N06059 shows excellent corrosion resistance against pitting corrosion. Excluding its high cost, it is a very good alternative to be used in the construction of geothermal facilities having highly sahne brines. Stainless and duplex steels exhibit a limited corrosion resistance concerning pitting and crevice corrosion.
Besides the higher alloyed materials, also the low-alloyed Steel UNS G41300 could be employed as a constructional material for the geothermal power plant in non-saline environments with moderate pH, as long as the wall thickness of the material vs. corrosion rate is taken into account.
In the last years, geothermal power has become a reliable and significant energy source. Because service conditions in geothermal facilities from deeply located aquifers are usually critical in terms of corrosion, materials selection is a very important issue. Preliminary evaluation of the material's suitability represents therefore a valuable strategy to ensure a secure and reliable operation of the facilities. In geothermal applications, the use of high-alloyed materials such as superaustenitic stainless steels, duplex stainless steels, and nickel-based alloys has been considered as a good alternative because of their remarkable corrosion resistance and appropriate mechanical properties. Nevertheless, the corrosion behavior of those metallic materials in geothermal fluids at service conditions has not been determined in many cases. In this work, laboratory tests including electrochemical investigations and exposure tests at 100 degrees C and 150 degrees C (1,500 kPa) showed the limits of suitability concerning localized corrosion of three different, corrosion-resistant alloys in the highly saline fluid of the North German Basin.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal fluids and temperatures, in many cases, extreme in terms of corrosion. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities.
The corrosion behavior of different high-alloyed metals including duplex and austenitic stainless steels as well as a nickel alloy have been evaluated in artificial geothermal fluids simulating the conditions in some locations with geothermal potential in Germany as well as two sites in Indonesia.
The suitability of carbon steel 25CrMo4, stainless steels X2CrNiMo17-12-2, X2CrNiMo-22-5, X2CrNiMoCuWN25-7-4 and super austenitic steel X1CrNiMoCu32-28-7 in these geothermal fluids obtained by electrochemical measurements and exposure tests is limited. The nickel alloy NiCr23Mo16Al shows an excellent corrosion resistance against pitting corrosion. Excluding its high cost, it is a very good alternative to be used in the construction of geothermal facilities having highly saline brines. Stainless and duplex steels exhibit a limited corrosion resistance concerning pitting and crevice corrosion.
Beside of the higher alloyed materials, also the low-alloyed steel 25CrMo4 could be employed as a constructional material for the geothermal power plant in stagnant highly acidic non saline environments, as long as the wall thickness of the material vs. corrosion rate is taken into account.
The generation of active disinfectants by electrochemical processes gains market share due to the lack of need for transportation and storage of dangerous goods as well as the ease of operation. Usually the process involves the use of specific electrodes for electrolysis of water to produce active chlorine species, sometimes supported by addition of chlorides to the process water. The resulting ECA (ElectroChemically Activated) solutions can cause corrosion due to the content of free active chlorine (FAC) or due to the chloride content of the process solution. These fluids are widely used because they show a good chemical and microbiological stability, are well suited for the standard cleaning procedures and allow reducing germ concentrations to meet hygienic standards. The influence of the respective agents to alloy 1.4301 is investigated by storage experiments and by electrochemical investigations. The results show, that the influence of chlorides is higher for short-term experiments. ECA-Fluids with low chloride concentrations are preferable. The goal of the investigations is to creat evaluation guidelines for the application parameters to provide a sufficient cleansing effect without causing corrosion of the surfaces.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal fluids and temperatures, in many cases, extreme in terms of corrosion. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities.
This contribution deals with the evaluation of the corrosion behavior of duplex steel S31803 (318LN, X2CrNiMoN22-5-3, 1.4462) conducted by electrochemical measurements and exposure tests in artificial geothermal waters simulating the conditions in different locations with geothermal potential in Germany.
The duplex steel S31803 shows limited suitability for applications in artificial geothermal waters due to its susceptibility to pitting and crevice corrosion.
For low saline geothermal waters it can be considered suitable at moderate temperatures. Slight crevice corrosion susceptibility needs to be considered.
Results are being incorporated into a materials catalogue for geothermal applications which shall provide basic information for designers and users of geothermal facilities.