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Eingeladener Vortrag
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The screening of coatings shows that the modification by adding individual pigment was not sufficient to protect carbon steel even during a short-term exposure, indicated by the discoloration after only seven days of exposure.
Electrochemical tests indicated that the coating cathodically protects carbon steel or slows down the corrosion reaction.
A long-term exposure test confirmed that the PANI/SiO2 modified coating successfully protects the carbon steel in the Sibayak artificial geothermal water at 150 °C for 6 months.
Corrosive geothermal brines are a major challenge to geothermal power-plants. For cost reasons, plant designers favorize low alloyed steels, e.g., carbon steel, which are susceptible to uniform and localized corrosion when exposed to geothermal brines having acidic and saline properties. To solve such problem, coatings or inhibitors would be a protective solution as an alternative to the use of high alloyed materials.
This study investigated a coating system consisting of polyaniline/silicon dioxide basing on locally available resources. Protection against corrosion of carbon steel is shown by long-term exposure and electrochemical tests of coated carbon steels, performed in an artificial acidic and saline geothermal brine, comparable to real conditions at a site in Indonesia.
Therefore, an integrated coating system is presented for corrosion protection, combining the electro-chemical functionality of polyaniline and the physical advantages of silica.
Nachdem im Verbundprojekt COORAL das Hauptaugenmerk auf überkritisches CO2 gelegt wurde, d. h. Transport über kurze Strecken bei erhöhter Temperatur, wurde in CLUSTER ein größeres lokales Transport-Netzwerk betrachtet, bei dem CO2 bei geringeren Temperaturen, also vorwiegend im flüssigen Zustand transportiert wird. Wurden in COORAL die CO2-Ströme von Kohlekraftwerken untersucht, ging es in CLUSTER zusätzlich um die Emissionen von relevanten Industrien, deren CO2-Emissionen nicht ohne Weiteres vermieden werden können.
Aufgrund der Erfahrungen in COORAL konnte eine Auswahl von kommerziellen Werkstoffen getroffen werden, die für einen konkreten Einsatz für CCS zur Verfügung stünden. Die gemischten und fluktuierenden CO2-Zusammensetzungen sind bei geeigneten Begrenzungen der Begleit¬stoffe im CO2 bezüglich Korrosionsvorgänge beherrschbar. Die Machbarkeit eines lokalen CCS-Clusters erscheint daher gegeben, soweit dies die Anlagen für Kompression, Transport und Injektion betrifft.
This book fulfills its intention to provide a comprehensive overview on 3D-printing of metals.
The interested reader can get a lot of information about the topics one should deal with when working with additively manufactured metallic parts. It gives a general roadmap where to start, what to learn and how it fits together.
This book provides a state‐of‐the‐art overview on the processing, characterization, and modelling of metallic and ceramic materials used for energy and environmental applications. 17 scientists show a collection of current knowledge in 8 chapters.
This book fulfills its intention to provide a reference book containing a collection of publications on thin films and coatings made of ceramic and metals used for energy and environmental applications. It covers a broad range of this topic and provides a comprehensive insight. Graduate and undergraduate students of materials science and mechanical engineering can find an overview on this topic to step in this interesting field of engineering.
Aging of passive film formed on UNS N08031 was investigated as a function of passivation time in Green-Death solution at 40°C. The specimen surface was in a stable passive state in the solution.
The passive current density increased with an increase in the passivation potential. Electrochemical Impedance Spectroscopy and Mott–Schottky (M–S) analyses revealed that a more defective n-type
semiconductive passive film formed as the potential increased while the film became stable as the defects in the film decreased at potential lower than 1.0 VSSE. The increase of the applied potential and the polarisation time are likely reasons for the change in passive film stability.
Im ISO/TC 265 werden Normen zur Entwicklung, Konstruktion, Betrieb, Umweltplanung und -Management, Risikomanagement, Quantifizierung, Monitoring und Verifizierung sowie weitere Aktivitäten für die einzelnen Stufen der CCS-Prozesskette erstellt.
Als neuer Aspekt wurde die Zusammensetzung des CO2-Stroms angesprochen. In Form eines "State-of-the-Art-Reports" soll der derzeitige Kenntnisstand zusammengestellt werden. Dieses soll für einen späteren Normenentwurf als Grundlage dienen.
BAM, IKS Dresden und ThyssenKrupp VDM haben ein umfangreiches Versuchsprogramm mit geschweißten Werkstoffprüfblechen durchgeführt, um neue Erkenntnisse über das Korrosionsverhalten der Superaustenite und der Nickelbasislegierung zu gewinnen und um diese Bewertungen im Abschnitt 5 der BAM-Liste zu berücksichtigen. Das Versuchsprogramm umfasste Korrosionsbeständigkeitsbewertungen der drei höherlegierten Werkstoffe in Stoffen aus 12 Gruppen von korrosiven Gefahrgütern, wie z. B. anorganische Halogenide, organische Säurehalogenide, Halogencarbonsäuren, Chlorsilane, Chlorate, Perchlorate, Chlorite, Hypochlorite, Hydrogensulfate und Nitriersäuren.
In der DIN 6601 - Beständigkeit der Werkstoffe von Behältern/Tanks aus Stahl gegenüber Flüssigkeiten (Positiv-Flüssigkeitsliste) ist die Beständigkeit unlegierter Stähle, austenitischer CrNi- und CrNiMo-Stähle gegenüber den reinen Ottokraftstoffen bewertet. Mit der verstärkten Verwendung bioethanol- und biodieselhaltiger Kraftstoffe und Heizöl stellt sich auch die Frage nach der Beständigkeit der handelsüblichen Tank- und Behälterwerkstoffe sowie der Dichtungswerkstoffe unter dem Einfluss dieser Medien.
Comparison of the corrosion resistance to dangerous goods of austenitic CrNiMo and duplex steels
(2014)
The “BAM-List - Requirements for Tanks for the Transport of Dangerous Goods” is the basis in Germany for substance-related prototype approvals for tank Containers in Germany. Compatibility evaluations of selected metallic materials and polymeric materials under the influence of approximately 7200 dangerous goods have been published in the BAM-List since 1989. The austenitic CrNi- and CrNiMo-steels - UNS S30403, UNS S31600, UNSS31603 and UNS S31635 - are the materials mostly used worldwide for transport tanks. The duplex Steel UNS S31803 has been put on the BAMList due to the great interest of tank producers and transport Companies. Using UNS S31803 instead of 316L, the weight of the tanks can be reduced, and the list of transportable goods can be extended. The objective of these investigations was to compare the corrosion resistance of duplex Steel UNS S31803 and austenitic Steel UNS S31603. Therefore, test specimens of both steels were exposed to selected corrosive substances, such as formic acid, acetic acid, phosphoric acid, sulfuric acid, nitrating acid, monochloroacetic acid and trichloroacetone at 55 °C (30 °C, 70 °C). The test results have shown that the duplex Steel UNSS31803 is a good alternative to austenitic CrNiMo-steel UNS S31603 for tanks carrying corrosive dangerous goods.
Biodiesel (FAME) from rapeseed is an environmentally friendly alternative to common fossil fuels. It is also suitable to serve as blending component to fuels like heating oil. If the fuel composition is changed, materials compatibility must be guaranteed. Adding polar biodiesel to nonpolar heating oil, changes the blend’s solvency and might cause swelling, extraction and solvation of polymers.
The objective of this research was to investigate the compatibility of polymeric materials, which are commonly used for components in middle distillate facilities, along with blends of heating oil and 20 % biodiesel (B20). For this propose, ACM, HNBR, FKM, PE, PA 6, POM, PUR and PVC were exposed to heating oil and B20 for 42 and 84 days at 40 °C. In addition, the polymers HNBR, FKM, PA, POM and PVC were also exposed at 70 °C. Furthermore, the resistance of polymers in eight-year aged B10 at 40 °C was evaluated. Ageing of biodiesel increases acidity which might propagate polymer corrosion.
The materials were evaluated as resistant, if the loss in tensile properties (tensile strength and elongation at break) and Shore hardness remained under 15 % compared to the initial unexposed material values. For investigations under compressed conditions, the compression set was determined for specimens of ACM, FKM and HNBR after exposure in heating oil B0 and B20 for 3,7,14, 28, 56 and 90 days at 40 °C according to ISO 815-1.
It was found that the resistance in B20 at 40 °C was given for all tested polymers except PUR. In the 8 years aged B10, PUR and POM were not compatible and ACM just conditionally compatible. At 70 °C, FKM and PVC were resistant in B20, whereas HNBR and PA 6 were not compatible. Swelling occurred for the elastomers ACM, HNBR and PUR.
Biodiesel (FAME) from rapeseed is an environmentally friendly alternative to common fossil fuels. It is also suitable to serve as blending component to fuels like heating oil. If the fuel composition is changed, materials compatibility must be guaranteed. Adding polar biodiesel to nonpolar heating oil, changes the blend’s solvency and might cause swelling, extraction and solvation of polymers. The objective of this research was to investigate the compatibility of polymeric materials, which are commonly used for components in middle distillate facilities, along with blends of heating oil and 20 % biodiesel (B20). For this propose, ACM, HNBR, FKM, PE, PA 6, POM, PUR and PVC were exposed to heating oil and B20 for 42 and 84 days at 40 °C. In addition, the polymers HNBR, FKM, PA, POM and PVC were also exposed at 70 °C. Furthermore, the resistance of polymers in eight-year aged B10 at 40 °C was evaluated. Ageing of biodiesel increases acidity which might propagate polymer corrosion. The materials were evaluated as resistant, if the loss in tensile properties (tensile strength and elongation at break) and Shore hardness remained under 15 % compared to the initial unexposed material values. For investigations under compressed conditions, the compression set was determined for specimens of ACM, FKM and HNBR after exposure in heating oil B0 and B20 for 3,7,14, 28, 56 and 90 days at 40 °C according to ISO 815-1. It was found that the resistance in B20 at 40 °C was given for all tested polymers except PUR. In the 8 years aged B10, PUR and POM were not compatible and ACM just conditionally compatible. At 70 °C, FKM and PVC were resistant in B20, whereas HNBR and PA 6 were not compatible. Swelling occurred for the elastomers ACM, HNBR and PUR.
CO2 quality specifications are not only a matter of CO2 purity (i.e. CO2 content).
The “rest” also matters, in particular contents of reactive impurities affecting material corrosion (and rock alteration).
Also chemical reactions in CO2 stream needs to be considered, in particular when combining CO2 streams of different compositions.
Finally, it can be summarized that the second edition of this popular textbook provides a comprehensive overview on the practical basics and applications of conducting polymers. It fulfills its intension of assisting various researchers from diverse fields to become familiar with fundamentals and applications of conducting polymers.
In this also completely rewritten and reorganized second part of the two‐volume set 45 international experts comprise the current knowledge of conjugated polymers. In addition to part one on properties, processing characterization and morphology, 16 chapters cover perspectives, theory and new materials.
Finally, it can be concluded that this 4th edition of this handbook fulfills, like the first part, its intention, to be the definitive resource on the topic of conducting polymers. This is assured by the updated and added contributions of all authors, which consider the significant developments both in fundamental understanding, progress and applications since publication of the previous edition. So, it can be recommended to everyone, who wants to get a comprehensive overview on conjugated polymers, not just to researchers, advanced students, and industry professionals working in materials science and engineering.
Interfacial properties related to wettability and corrosion in CO2 transport pipelines are experimentally determined by the sessile and the pendant drop methods. The contact angle of a water drop in a compressed CO2 atmosphere is analyzed on an X70 pipeline carbon steel and compared to that on a martensitic steel S41500 to elucidate the effect of corrosion process on active wetting behaviour. The measurements are performed with liquid CO2 at 278 K and pressures ranging from 5 to 20 MPa. The results show that the contact angle (CA) increases with pressure from 132 ° to 143 ° for S41500 and from 117 ° to 137 ° for X70 and decreases with drop age by 20 ° to 24 ° regardless of the pressure and of the fact that corrosion only occurs on X70, which is confirmed by scanning electron microscopy, element mapping and energy dispersive x-ray spectrometry (EDS) analysis. At higher pressure, the contact angles on both materials converge. Further, related properties like density and interfacial tension were determined. CO2 - saturated water has a higher density than pure water: At 5 MPa saturated water reaches a density of 1017 kg⋅m^(-3) and at 20 MPa 1026 kg⋅m^(-3) compared to pure water with a density of 1002 kg⋅m^(-3) and 1009 kg⋅m^(-3), respectively. In this pressure range the IFT drops from 33 mN⋅m^(-1)at 5 MPa to 23 mN⋅m^(-1) at 20 MPa.
This contribution provides current findings regarding materials susceptibility for carbon capture, utilization and storage (CCUS) applications. Basing on results gathered in 2 German long-term projects (COORAL and CLUSTER) suitable materials are introduced as well as dominating impurities of the CO2-stream and corrosion mechanisms. Investigations cover the whole CCUS process chain and provide material recommendations for certain parts.
This contribution provides current findings regarding materials susceptibility for carbon capture, utilization and storage (CCUS) applications. Basing on results gathered in 2 German long-term projects (COORAL and CLUSTER) suitable materials are introduced as well as dominating impurities of the CO2-stream and corrosion mechanisms. Investigations cover the whole CCUS process chain and provide material recommendations for certain parts.
The geological storage of carbon dioxide (Carbon Capture and Storage, CCS) in depleted gas reservoirs or in saline aquifers is a widely discussed issue. Carbon dioxide may induce corrosion on the piping steels during compression, transportation and injection. Therefore,
selection of appropriate piping steels is a key factor in order to increase the safety and reliability of the CCS technology, and to keep the processes cost-effective.
The here described subproject of the COORAL project (German acronym for “C02 purity for capture and storage”) deals with the levels of impurities in the C02 stream that will be acceptable when using specific steels. Material exposure to carbon dioxide (C02) containing
specific amounts of water vapor, oxygen (02) sulfur dioxide (S02), nitrogen dioxide (N02), carbon monoxide (CO) can be a challenge to steels. Within this subproject 13 different Steels are tested for suitability as materials used for compression, transportation and injection Units within the CCS chain.
Within the last years the use of geothermal energy as feasible energy source has risen and is going to replace fossil fuel supply more and more. 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. Since the construction of geothermal power plants shall be economical with maximum life Service, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable Operation ofthose facilities.
The materials selection depends on the location of a power plant respectively on the Chemical composition of the produced aquifer fluid. The duplex Steel is often used as allround solution not only for the construction of geothermal power plants, because of its combination of good mechanical and corrosion properties and its lower costs compared to other highly alloyed materials. But there are limits for the use of the duplex-steel 1.4462 regarding its corrosion behavior, with which this contribution deals.
The limitations of suitability of duplex steel 1.4462 in the geothermal fluids of Molasse Basin and Upper Rhine Graben obtained by means of electrochemical measurements and exposure tests are presented below. While 1.4462 in the artificial Molasse Basin Fluid shows an excellent corrosion resistance against pitting and uniform corrosion it presents low corrosion resistance in the artificial Upper Rhine Graben Fluid due to the difference in salinity. Besides it shows a limited corrosion resistance concerning crevice corrosion.
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.
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.
Corrosion behavior of high-alloyed materials in an artificial geothermal fluid at service conditions
(2010)
C02-corrosion on piping steels might cause problems during injection of flue gases for their storage in deep geological aquifer fluids. Therefore, the selection of appropriate piping steels is a key factor to increase safety and reliability of the Carbon Capture and Storage (CCS) technology, and to keep the process cost-efficient.
Within the project COORAL (German acronym for “C02 purity for capture and storage”) corrosion studies on injection piping steels exposed to C02 and artificial brine with high Chloride concentration have been carried out. Corrosion of the injection pipe in C02-rich aquifer fluid may occur within the aquifer brine or when at injection interruptions the aquifer fluid may flow back into the injection pipe. Because of high salinity of aquifer brine and C02-corrosion an appropriate material ranking of injection piping steels should be made.
Corrosion resistance of steels 1.4034, 1.4021, 1.4542, 1.4162 and 1.4562 was investigated in a corrosive environment using electrochemical and metallographic techniques. Electrochemical experiments in order to investigate the surface corrosion kinetics and polarization measurements in order to investigate localized corrosion phenomena have been carried out. Critical pitting potentials and repassivation potentials were determined by polarization curves of investigated materials and compared with measured corrosion potentials. Measured values were used in order to determine the suitability and performance of tested steels in C02-injection conditions.
The process chain for Carbon Capture and Sequestration (CCS) includes tubing for injection of CO2 into saline aquifers. The compressed CO2 is likely to contain specific impurities; small concentrations of SO2 and NO2 in combination with oxygen and humidity are most harmful. In addition, CO2 saturated brine is supposed to rise in the well when the injection process is interrupted. The material selection has to ensure that neither CO2 nor brine or a combination of both will leak out of the inner tubing. In this comprehensive paper the investigated materials range from low-alloy steels and 13% Cr steels up to high-alloy materials. Electrochemical tests as well as long term exposure tests were performed in CO2, in brine and combination of both; pressure was up to 100 bar, temperature up to 60 °C. Whereas the CO2 stream itself can be handled using low alloy steels, combinations of CO2 and brine require more resistant materials to control the strong tendency to pitting corrosion. The corrosion behavior of heat-treated steels depends on factors such as microstructure and carbon content. For different sections of the injection tube, appropriate materials should be used to guarantee safety and consider cost effectiveness.
The corrosion behaviour of martensitic stainless injection-pipeline steel X46Cr13 exposed to CO2 saturated artificial saline brine with high chloride concentration similar to onshore CCS-site at Ketzin, Germany has been investigated by means of electrochemical technique and microscopic observations at short exposure times (up to 24?h) and by mass loss and metallographic observations at exposure times up to 17520?h. Pitting corrosion kinetics has been characterised and the predictions about the corrosion mechanism are made.
Geothermal energy is an interesting alternative to polluting fossil energy sources. Therefore, in Belgium, two wells have been drilled for a deep geothermal power plant. However, the environment to which the installations are exposed is challenging. The geothermal brine has 165 g/l total dissolved solids (of which 90% are sodium and chlorine) and the production temperature can be up to 130 °C. To assess their suitability to be used in a geothermal power plant, the corrosivity of the artificial brine to three common construction materials was investigated with exposure and electrochemical tests. The metals under consideration are a low-alloyed carbon steel (S235JR), an austenitic stainless steel (UNS S31603) and a duplex stainless steel (UNS S31803). The carbon steel, that was found to corrode uniformly, could be considered as a constructional material if a sufficient wall thickness is chosen. The austenitic stainless steel and the duplex stainless steel demonstrate very low uniform
corrosion rates. They are however susceptible to pitting and crevice corrosion. To guarantee safe operation of the geothermal power plant, the susceptibility of the alloys to stress corrosion cracking should be tested and in situ experiments should be performed.
A global transition towards more sustainable, affordable and reliable energy systems is being stimulated by the Paris Agreement and the United Nation's 2030 Agenda for Sustainable Development. This poses a challenge for the corrosion industry, as building climate‐resilient energy systems and infrastructures brings with it a long‐term direction, so as a result the long‐term behaviour of structural materials (mainly metals and alloys) becomes a major prospect. With this in mind “Corrosion Challenges Towards a Sustainable Society” presents a series of cases showing the importance of corrosion protection of metals and alloys in the development of energy production to further understand the science of corrosion, and bring the need for research and the consequences of corrosion into public and political focus. This includes emphasis on the limitation of greenhouse gas emissions, on the lifetime of infrastructures, implants, cultural heritage artefacts, and a variety of other topics.
Finally it can be summarized that this book fulfills its intention of providing theoretical background and examples for practical applications of coatings used for corrosion protection.
It can be recommended to those being interested in coatings, serving as an overview on aspects which needs to be considered when working with such systems.
Commercially available carbon steels are suitable for compression and pipelines as long as moisture content and impurities are limited. (water 50 to 100 ppmv, SO2 and NO2 ca. 100 ppmv) Corrosion rates increase with increasing water content. (0.2 – 20 mm/a) Condensation of acids and therefore droplet formation is always possible, even at low water contents. A low SO2 content within the CO2-stream might be more important than a low water content. Cr13-steels showed a general susceptibility to shallow pitting and pitting. So, they seem to be not suitable for CCUS applications. Low alloyed steels showed better corrosion behavior (predictable uniform corrosion). For direct contact with saline aquifer fluids only high alloyed steels shall be used.
This study focuses on the corrosion mechanism of carbon steel exposed to an artificial geothermal brine influenced by carbon dioxide (CO2) gas. The tested brine simulates a geothermal source in Sibayak, Indonesia, containing 1500 mg/L of Cl-, 20 mg/L of SO4 2-, and 15 mg/L of HCO3-with pH 4. To reveal the temperature effect on the corrosion behavior of carbon steel, exposure and electrochemical tests were carried out at 70 °C and 150 °C. Surface analysis of corroded specimens showed localized corrosion at both temperatures, despite the formation of corrosion products on the surface. After 7 days at 150 °C, SEM images showed the formation of an adherent, dense, and crystalline FeCO3 layer. Whereas at 70 °C, the corrosion products consisted of chukanovite (Fe2(OH)2CO3) and siderite (FeCO3), which are less dense and less protective than that at 150 °C.
Control experiments under Ar-environment were used to investigate the corrosive effect of CO2. Free corrosion potential (Ecorr) and electrochemical impedance spectroscopy (EIS) confirm that at both temperatures, the corrosive effect of CO2 was more significant compared to that measured in the Ar-containing solution. In terms of temperature effect, carbon steel remained active at 70 °C, while at 150 °C, it became passive due to the FeCO3 formation. These results suggest that carbon steel is more susceptible to corrosion at the near ground surface of a geothermal well, whereas at a deeper well with a higher temperature, there is a possible risk of scaling (FeCO3 layer). A longer exposure test at 150 °C with a stagnant solution for 28 days, however, showed the unstable FeCO3 layer and therefore a deeper localized corrosion compared to that of seven-day exposed specimens.
Condensates from the gas stream in simulated CO2 transport pipelines have been identified during the experiments in the laboratory. Because of their acidic origin the corrosion resistance of pipeline steels used for CCS (carbon capture and storage) technology might be limited. Over the last years it has become clear that the amount of water and acid building constituents in the CO2 stream has to be controlled very well. In this work, condensates formed in experiments using gaseous CO2 containing high amounts of water, NO2 and SO2 were analyzed, replicated, and used for extensive electrochemical experiments. These highly acidic condensates were enriched with CO2 and then applied to characteristic steels planned to use in the CCS transport chain. Even high alloy steels are susceptible to localized corrosion under these conditions. The results implicate that condensation of aggressive acid droplets has to be avoided or the locations where condensation takes place have to be controlled extensively.
The composites combining aluminum and silica nanoparticles with the addition of tetramethylammonium hydroxide (Al-SiO2(T)) and butanol (Al-SiO2(B)) as mixing media have been successfully fabricated. Corrosion behavior of Al-SiO2 composites before and after exposure in 1M NaCl solution was examined using potentiodynamic polarization (Tafel curve analysis). The study was also equipped with scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and X-ray diffraction (XRD) investigations. Before exposure, Al-SiO2(T) exhibited the best corrosion resistance. Performance improvement was indicated by Al-SiO2(B) up to 10 times better than Al-SiO2(T) after exposure. The increased SiO2 content did not significantly enhance the corrosion resistance of the composites. The Al-SiO2 composites with 5% SiO2 content showed very high corrosion resistance (as the optimum composition). Furthermore, pitting corrosion was observed in the Al-SiO2 composites, indicated by the formation of corrosion products at grain boundaries. The product was affected by the presence of SiO2 in the Al matrix and the NaCl environment at 90 °C (approach to synthetic geothermal media: Na+, Cl, H+, OH-). Our study revealed the presence of γ-Al2O3, γ-Al(OH)3, and Al(OH)2Cl as the dominant corrosion products.
Corrosion resistance of high-alloyed and alternative materials in an artificial geothermal water
(2014)
Many technologies have been developed to take advantage of geothermal energy, which became a feasible energy source to replace fossil fuel supply. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal fluids and involved high 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 two high-alloyed metallic materials and α-Al2O3 in an artificial geothermal fluid simulating the conditions in the Northern German Basin, a location with high geothermal potential. The suitability of the super austenitic stainless steel UNS N08031 and the nickel base alloy UNS N06059 in this geothermal fluid obtained by electrochemical measurements and exposure tests is addressed. As an alternative to the suitable but costly UNS N06059 that showed excellent corrosion resistance against pitting corrosion, ceramic made of α-Al2O3 represents an interesting possibility for selected components to be used in the construction of geothermal facilities
Corrosion Resistance of High-alloyed and Alternative Materials in an Artificial Geothermal Water
(2014)
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 waters 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 different steels in flowing low saline, slightly alkaline, artificial geothermal water simulating the conditions in the Molasse-Basin, a location with geothermal potential in Germany.
Test results for steels UNS S31603 and UNS S31803 exposed to this geothermal water obtained by electrochemical measurements and exposure tests are presented. Results obtained in static and flowing water condition show good performance of both alloys with a possible onset of localized corrosion at UNS S31603 in static conditions.
Corrosion Resistance of the Super-Austenitic Stainless Steel UNS S31266 for Geothermal Applications
(2017)
Super-austenitic stainless steels cover grades with high chromium (20 to 27 %), high nickel (18 to 31 %) and high molybdenum (4 to 6 %) contents. Within this family, the 6%Mo high nitrogen grade S31266 was developed to combine the beneficial influence of chromium, tungsten, molybdenum and nitrogen on its mechanical and corrosion properties. Due to 22 % nickel, 24 % chromium and 0.4 % nitrogen additions, this alloy exhibits a very stable microstructure, being less prone to intermetallic phase precipitation than the other highly alloyed super-austenitic stainless steels.
This paper deals with the corrosion resistance of S31266 in artificial geothermal water with moderate salinity and low pH. Long-term static exposures and electrochemical tests were conducted at various temperatures to evaluate the pitting, crevice and stress corrosion cracking resistance of this material.
The results show that S31266 is resistant up to 220 °C. As a consequence, it can be a good candidate material for geothermal applications involving a highly corrosive environment, especially salinity and low pH.
Corrosion Resistance of the Super-Austenitic Stainless Steel UNS S31266 for Geothermal Applications
(2017)
Super-austenitic stainless steels cover grades with high chromium (20 to 27 %), high nickel (18 to 31 %) and high molybdenum (4 to 6 %) contents. Within this family, the 6%Mo high nitrogen grade S31266 was developed to combine the beneficial influence of chromium, tungsten, molybdenum and nitrogen on its mechanical and corrosion properties. Due to 22 % nickel, 24 % chromium and 0.4 % nitrogen additions, this alloy exhibits a very stable microstructure, being less prone to intermetallic phase precipitation than the other highly alloyed super-austenitic stainless steels.
This paper deals with the corrosion resistance of S31266 in artificial geothermal water with moderate salinity and low pH. Long-term static exposures and electrochemical tests were conducted at various temperatures to evaluate the pitting, crevice and stress corrosion cracking resistance of this material.
The results show that S31266 is resistant up to 220 °C. As a consequence, it can be a good candidate material for geothermal applications involving a highly corrosive environment, especially salinity and low pH.
Within the project COORAL (German acronym for ''C02 purity for capture and storage") studies on pipeline steels exposed to circulating supercritical impure C02 have been carried out. For this purpose, a loop consisting of compressors, flow meter and two autoclaves was constructed. In order to simulate the real conditions in pipelines, impurities such as H20, CO, S02, N02 and 02 were added to the C02 stream before compression. Exposure experiments were carried out with Steel specimens placed in the autoclaves. Carbon Steel L360NB, pure iron X20Cr13, X46Cr13, X2CrMnNiN22-5-2 and alloy 31 have been exposed to circulating (flow rate 4 L/min) supercritical impure C02 for one week at 60 °C and 10 MPa Surface analysis and weight loss experiments in order to determine the corrosion products and the corrosion rates showed that the impurities cause corrosion problems. Slight general corrosion by L360NB and soft iron was observed. The initiation of pitting corrosion was observed at the surfaces of the materials X20Cr13, X46Cr13, X2CrMnNiN22-5-2. No visible signs of corrosion have been observed on alloy 31.
For reliability and safety issues of injection wells, corrosion resistance of materials used needs to be determined. Herein, representative low-cost materials, including carbon steel X70/1.8977 and low alloyed steel 1.7225, were embedded in mortar to mimic the realistic casing-mortar interface. Two types of cement were investigated: (1) Dyckerhoff Variodur commercial Portland cement, representing a highly acidic resistant cement and (2) Wollastonite, which can react with CO2 and become stable under a CO2 stream due to the carbonation process. Exposure tests were performed under 10 MPa and at 333 K in artificial aquifer fluid for up to 20 weeks, revealing crevice corrosion and uniform corrosion instead of expected pitting corrosion. To clarify the role of cement, simulated pore water was made by dispersing cement powder in aquifer fluid and used as a solution to expose steels. Surface analysis, accompanied by element mapping on exposed specimens and their crosssections, was carried out to trace the chloride intrusion and corrosion process that followed.
This contribution provides current findings regarding materials susceptibility for CCUS applications. Basing on results gathered in 2 German long-term projects (COORAL and CLUSTER) suitable materials are introduced as well as dominating impurities of the CO2 stream and corrosion mechanisms. Investigations cover the whole CCUS process chain and provide the following recommendations for certain parts. Commercially available carbon steels are suitable for compression and pipelines as long as moisture content and impurities are limited (water 50 to 100 ppmv, SO2 and NO2 ca. 100 ppmv).
Corrosion rates increase with increasing water content (0.2 – 20 mm/a).
Condensation of acids and therefore droplet formation is always possible, even at low water contents.
A low SO2 content within the CO2-stream might be more important than a low water content.
Cr13-steels showed a general susceptibility to shallow pitting and pitting. So, they seem to be not suitable for CCUS applications.
Low alloyed steels showed better corrosion behavior (predictable uniform corrosion).
For direct contact with saline aquifer fluids only high alloyed steels shall be used.
This paper summarizes the investigation of a serious explosion, which shattered the chemical facility of a chlorine/alkaline plant in Northern Germany in 1981. A pressure tank made from HSB 50 S steel and used as storage of liquid residues from a chlorine liquefaction process violently ruptured and the explosion threw parts of the tank approximately 100 m through the air. The local county government ordered an investigation to determine the root cause of this incident.
The main objective of the investigation was to determine whether a nitrogen overpressure or a chemical reaction of residuals inside the so-called 'Taffy' receiver caused the explosion. A fracture mechanics based analyses evaluated the conditions the material was exposed to during the damage. Metallographic and mechanical tests confirmed that the material specifications were within the values specified by the guidelines but corrosion had reduced the wall thickness considerably.
Analytical calculations to determine the minimum required pressure for the rupture and to cause plastic deformation to the tank confirmed that the failure did not occur due to nitrogen overpressure and therefore, a chemical reaction must have occurred. A detailed chemical analysis confirmed that the explosive disintegration of methylnitrate, which is highly sensitive to heat and impact, and its halogenated derivatives likely caused the incident. Due to the design and operational mode of the plant, impurities could accumulate and form explosive compounds in the Taffy receivers without control.
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 in many cases extreme in terms of corrosion due to the chemical composition of hydrothermal fluids and temperatures. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities. During operation of a geothermal research facility in Groß Schönebeck copper and lead effects have been found downhole. Occurring mechanisms and measures to prevent precipitation or scaling needed to be investigated as well as potential influences of such precipitates on corrosion resistance of metallic materials used for equipment.
This contribution deals with the evaluation of the corrosion behavior of carbon steel and corrosion resistant alloys in copper and/or lead containing artificial geothermal water, simulating the conditions in the Northern German Basin.
The behavior of these materials in an artificial geothermal water obtained by electrochemical measurements and exposure tests are presented. While carbon steel exhibits precipitation and deposition, higher alloyed material shows different response to such species and a higher resistance in saline geothermal water.
Basing on these results the suitability of the investigated corrosion resistant alloy is given for use in such conditions, whereas carbon steel creates difficulties due to its susceptibility to Cu- and Pb-precipitation.
In der Bundesrepublik Deutschland ist die „BAM-Liste - Anforderungen an Tanks für die Beförderung gefährlicher Güter” die Grundlage für die stoffbezogenen Baumusterzulassungen für Tankcontainer und ortsbewegliche Tanks zur Beförderung gefährlicher Güter durch die BAM Bundesanstalt für Materialforschung und -prüfung. Beständigkeitsbewertungen sowohl von ausgewählten metallischen Werkstoffgruppen als auch von polymeren Dichtungs- und Beschichtungswerkstoffen unter dem Einfluss von Gefahrgütern und wassergefährdenden Stoffen sind in der BAM-Liste enthalten. Sofern nicht anders angegeben, gelten die Werkstoffbeständigkeitsbewertungen für Betriebstemperaturen bis max. 50 °C und für handelsüblich technisch reine Stoffe. Entsprechend den gültigen Gefahrgutverordnungen für den Transport von Gefahrgütern auf der Straße, derSchiene und zur See wird eine innere Besichtigung der Tanks nach einer vorgegebenen Prüffrist der Tanks gefordert. Für die Dauer der Prüfintervalle ist die Werkstoffbeständigkeit zu gewährleisten. Unter den über 7000 in der BAM-Liste enthaltenen Stoffen ist ein großer Anteil von Gefahrgütern und wassergefährdenden Stoffen mit hohem Transportaufkommen enthalten, die nicht korrosiv auf die meisten metallischen Werkstoffe wirken und somit bestehen keine Unterschiede in der Bewertung der Beständigkeit zwischen den häufig im Tankbau eingesetzten austenitischen CrNi- oder CrNiMo-Stählen 1.4401 (X5CrNiMo17-12-2), 1.4404 (X2CrNiMo17-12-2) und 1.4571 (X6CrNiMoTi17-12-2) und dem Duplexstahl 1.4362 (X2CrNiN23-4, UNS S 32304). Es gibt nur eine sehr geringe Anzahl von Ergebnissen von Korrosionsversuchen mit diesem Werkstoff unter dem Einfluss von korrosiven Gefahrgütern. Zur Gewinnung von Korrosionsdaten wurden in Absprache mit dem Auftraggeber relevante Stoffe aus der BAMListe ausgewählt, in denen die im Transporttankbau gebräuchlichen CrNiMo-Werkstoffe unter Berücksichtigung stoffspezifischer und betrieblicher Auflagen einsetzbar sind. Die Korrosionstests sollen zeigen, inwieweit der betrachtete Duplexstahl in Analogie zu den austenitischen CrNiMo-Stählen bewertet werden kann. Aus den Versuchsergebnissen kann die Schlussfolgerung gezogen werden, dass der untersuchte Duplexstahl in alkalischen Medien eine Alternative zu austenitischen Stählen für den Transport von Gefahrgütern darstellt. Aufgrund des verringerten Legierungsgehaltes, insbesondere an Nickel (3,7 %) und Molybdän (0,15 %), wurde eine geringere Korrosionsbeständigkeit des untersuchten Duplexstahls 1.4362 im Vergleich zu den austenitischen CrNiMo-Stählen, insbesondere in „sauren“ Medien beobachtet. Die Beständigkeitsbewertungen dieses Werkstoffes werden in der 10. Auflage der BAM-Liste veröffentlicht und dem interessierten Anwenderkreis auch in Form von Beständigkeitslisten zur Verfügung gestellt.
“Corrosive to Metals” (H290) describes the general potential danger of a substance to metallic materials. Uniform and localized attack is considered. It has nothing to do with containment material. Corrosion resistance of materials is determined similarly, but with much lower threshold values.
Manual shall provide a simple test to easily determine the aggressivity potential to cause corrosion on metallic materials.
Even a simple test requires experienced personnel. There seems to be a need of awareness and understanding training for both officials and applicants.
Dictionary of Metallurgy and Metal Processing - English-German – German-English (Book review)
(2019)
The first issue of this classic dictionary contains highly specialized terms, not only of the area of metallurgy but also of welding, soldering and corrosion. Special attention was paid by the author to a correct reference of each term according to the field of application.
Finally, this book fulfills the intension of its author, to collect relevant terms with the correct pendant from a huge variety of sources and applications. It provides the user a foundation for correct terminology and communication for international contacts.
This work examined the droplet corrosion of CO2 pipeline steels caused by impurities in CO2 supercritical/dense phase at 278 K, simulating the underground transport condition. The wetting properties of carbon steels (X52 and X70) as well as martensitic steel UNS S41500, and superaustenite UNS N08031 were studied by contact angle measurement, revealing reactive wetting behavior of carbon steels. Exposure tests with CO2 saturated water droplet on steel surface showed that the impurities (220 ppmv SO2 and 6700 ppmv O2) diffused into the droplet and then reacted with metal coupons in supercritical/dense phase condition, forming the corrosion product instantly during pumping process. Due to the active wetting behavior, the carbon steels suffered from heavily attack, while negligible corrosion product was observed in cases of martensitic steel UNS S41500 and superaustenite UNS 08031 coupons. Condensation experiments that were carried out on fresh polished coupons in CO2 with 1200 ppmv H2O showed that the formation and aggregation of droplet is dependent on the presence of impurities. Without SO2 and O2, the same concentration of H2O did not cause observable corrosion process after a week of exposure. With 220 ppmv SO2 and 6700 ppmv O2 even low water concentration (5-30 ppmv) still resulted in heterogeneous nucleation and subsequent growth of droplets, leading to corrosive process on carbon steel surface albeit to a lesser extent.
In this work, the focus was set on the corrosion process of condensate as drops on the surface of carbon steels (X52, X70), martensitic steel UNS S41500, and superaustenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the transportation condition in a buried pipeline). Exposure tests were performed at both normal pressure and high pressure where CO2 is supercritical or in dense phase. The drop, 1 ‑ 10 μL in volume, was prepared by dropping CO2 saturated ultra-pure water onto the surface of steel coupons in a one-liter-autoclave. The CO2 gas stream, simulating the oxyfuel flue gas with varying concentration of impurities (SO2 and O2 ), was then pumped into the autoclave to observe the condensation and corrosion impacts of impurities. Comparable exposure tests were carried out with the same gas mixture and the same volume of water as vapor to observe the drop formation and the corrosion process that follows. The wettability and stability of drops on the surface of steel coupons in CO2 supercritical/dense phase environment was evaluated additionally by contact angle measurement.
The research focus of this study was set on the corrosion process of condensate as droplets on the surface of carbon steels (X52, X70) martensitic steel UNS S41500, and super austenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the offshore transportation condition in a buried pipeline). The possibility of dew/droplet formation on the steel surface and wetting behavior of corresponding materials were evaluated by contact angle measurement in dense CO2 at 278 K. To observe the effect of impurities (SO2 and O2) on droplet corrosion process, exposure tests were carried out in the mixed atmosphere with a drop, 1 ‑ 10 µL in volume, of CO2 saturated ultra-pure water on steel surface. Comparable exposure tests were carried out with the same gas mixture and the same volume of water, as vapor, to observe the droplet formation and the corrosion process that follows. Effects of surface roughness on the droplet formation and its corrosion process were further studied and showed no significant role upon long time exposure. The results from droplet experiments were compared to those from the bulk electrolyte for the further recommendation on the quality control of gas stream along with the use of carbon steels as transport pipelines in CCS - Carbon Capture and Storage system.
In Germany the "BAM-List - Requirements for Tanks for the Transport of Dangerous Goods" is the basis for substance-related prototype approvals for tank Containers undertaken by the BAM - Federal Institute for Materials Research and Testing. Compatibility evaluations of selected metallic materials as well as of polymeric gasket and lining materials under the influence of approximately 7000 dangerous goods have been published in the BAM-List since 1989.
The duplex Steel 1.4362 (2304, UNS S32304) was originally developed as substitute for the austenitic grades 1.4404 (316L, UNS S31603) and 1.4571 (316Ti, UNS S31635). Due to its characteristic profile this Steel was qualified for applications requiring high strength values at concomitant adequate corrosion resistance. Because of its lower content of the alloy elements nickel and molybdenum this duplex Steel is a cost-efficient alternative to the molybdenum containing austenite. Only a limited number of corrosion test results of 1.4362 under the influence of dangerous goods published in the BAM-List were available. Therefore test specimens of this Steel were exposed to selected corrosive substances.
Due to the reduced alloy content a reduced corrosion resistance of the duplex Steel 1.4362 in acidic substances, such as formic acid, acetic acid and sulfuric acid, in comparison to the austenitic CrNiMosteels was observed. Tests in the alkaline medium showed a sufficient resistance.
Early Stage of Corrosion Formation on Pipeline Steel X70 Under Oxyfuel Atmosphere at Low Temperature
(2020)
The early stage of corrosion formation on X70 pipeline steel under oxyfuel atmosphere was investigated by applying a simulated gas mixture (CO2 containing 6700 ppmv O2, 100 ppmv NO2, 70 ppmv SO2 and 50 ppmv H2O) for 15 h at 278 K and ambient pressure. Short-term tests (6 h) revealed that the corrosion starts as local spots related to grinding marks progressing by time and moisture until a closed layer was formed. Acid droplets (pH 1.5), generated in the gas atmosphere, containing a mixture of H2SO4 and HNO3, were identified as corrosion starters. After 15 h of exposure, corrosion products were mainly X-ray amorphous and only partially crystalline. In-situ energy-dispersive X-ray diffraction (EDXRD) results showed that the crystalline fractions consist primarily of water-bearing iron sulfates. Applying Raman spectroscopy, water-bearing iron nitrates were detected as subordinated phases. Supplementary long-term tests exhibited a significant increase in the crystalline fraction and formation of additional water-bearing iron sulfates. All phases of the corrosion layer were intergrown in a nanocrystalline network. In addition, numerous globular structures have been detected above the corrosion layer, which were identified as hydrated iron sulphate and hematite. As a type of corrosion, shallow pit formation was identified, and the corrosion rate was about 0.1 mma−1. In addition to in-situ EDXRD, SEM/EDS, TEM, Raman spectroscopy and interferometry were used to chemically and microstructurally analyze the corrosion products.
Geothermal energy is one of the most promising energy resources to replace fossil fuel. To extract this energy, hot fluids of various salts and gases are pumped up from a geothermal well having a certain depth and location. Geothermal wells in volcanic regions often contain highly corrosive CO2 and H2S gases that can be corrosive to the geothermal power-plants, which are commonly constructed of different steels, such as carbon steel. This research focuses on the corrosion behaviour of carbon steel exposed to an artificial geothermal fluid containing CO2 gas, using an artificial acidic-saline geothermal brine as found in Sibayak, Indonesia. This medium has a pH of 4 and a chloride content of 1,500 mg/L. Exposure tests were conducted for seven days at 70 °C and 150 °C to simulate the operating temperatures for low and medium enthalpy geothermal sources. Surface morphology and cross-section of the specimens from the above experiments were analysed using scanning electron microscope (SEM) and energy dispersive X-ray (EDX). Electrochemical tests via open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS) were performed to understand the corrosion processes of carbon steel in CO2-containing solution both at 70 °C and 150 °C. Localized corrosion was observed to a greater extent at 70 °C due to the less protectiveness of corrosion product layer compared to that at 150 °C, where FeCO3 has a high corrosion resistance. However, a longer exposure test for 28 days revealed the occurrence of localized corrosion with deeper pits compared to the seven-day exposed carbon steel. In addition, corrosion product transformation was observed after 28 days, indicating that more Ca2+ cations incorporate into the FeCO3 structure.
In engineering storage sites for Carbon Sequestration the CO2-induced corrosion of injection pipe steels is a relevant safety issue when emission gasses are compressed in deep geological layers. The reliability of the steels suitable for the geological onshore CCS-site (Carbon Capture and Storage) at Ketzin, Germany, is demonstrated in laboratory experiments in equivalent corrosive environment (T = 60 °C, p = 160 bar, aquifer water, CO2-flow rate of 3 L/h, 7008000 h exposure time). Corrosion kinetics and microstructures were characterized using specimens of the heat treated steel 42CrMo4 (1.7225) used for casing, and specimens of the martensitic stainless injection-pipe steel X46Cr13 (1.4034).
Geothermal brines often contain high amounts of lead and copper ions that can precipitate as native Cu and Pb as consequence of galvanic corrosion when brines react with carbon steel materials. This contribution evaluates which materials could overcome the problem of galvanic corrosion at geothermal environment.
The behavior of these materials in water containing high chloride concentration (> 100 g/L NaCl) as well as various amounts of dissolved bCl2 and/or CuCl2 was characterized by electrochemical and exposure measurements.
Both methods reveal carbon steel suffers corrosion susceptibility, accompanied by Cu◦ and/or Pb◦ precipitation on the surface. Electrochemical measurements on stainless steels result in significant difference in corrosion and repassivation potentials (Ecorr = -189 mV, Erep = 70 mV), indicating a good corrosion resistance.
The electrochemical behavior of UNS(1) N08031 was investigated as a function of electrode potential in Green-Death(2) solution at 40 °C. The UNS N08031 surface is in a stable passive state during cyclic potentiodynamic polarization without an initiation and/or propagation of localized corrosion. In potentiostatic polarization of UNS N08031 for 3600 s, passive current density increases with an increase in the passivation potential from 0.7 to 1.0 VSSE (silver/silver chloride reference electrode in saturated potassium chloride) Electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) analysis showed that a more defective n-type semiconductive passive film forms as the potential increases. X-ray photoelectron spectroscopy (XPS) revealed that passive film consists of mainly chromium and minor iron and nickel oxides. The mechanism of the defective passive film formation is discussed. The increase of the applied potential is considered to be a reason for the change in passive film stability.
The electrochemical behavior of UNS N08031 was investigated as a function of electrode potential in Green-Death solution at 40 °C. The UNS N08031 surface is in a stable passive state during cyclic potentiodynamic polarization without an initiation and/or propagation of localized corrosion. In potentiostatic polarization of UNS N08031 for 3600 s, passive current density increases with an increase in the passivation potential from 0.7 to 1.0 VSSE (silver/silver chloride reference electrode in saturated potassium chloride) Electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) analysis showed that a more defective n-type semiconductive passive film forms as the potential increases. X-ray photoelectron spectroscopy (XPS) revealed that passive film consists of mainly chromium and minor iron and nickel oxides. The mechanism of the defective passive film formation is discussed. The increase of the applied potential is considered to be a reason for the change in passive film stability.
To reveal the corrosion resistance of casing steel/mortar interface in CO2 injection condition, sandwich samples were prepared and exposed up to 20 weeks in aquifer fluid under 10 MPa and 60 °C. Cross section analysis revealed the crevice corrosion as main mechanism instead of pitting corrosion, which would be expected to happen in the extremely high Chloride concentration. Detailed analysis using EDS line scan shown the slow diffusion of Chloride, suggesting why pitting did not happen after 20 weeks. To mimic the passivated steel surface, the steel coupon was passivated in simulated pore solution having pH 13.5 for 42 days. The passivated coupon was further exposed to NGB solution for 28 days. Electrochemical characterization was performed along the exposure processes to reveal the change in impedance, indicating the corrosion resistance of steel casing/mortar interface.
To reveal the corrosion resistance of casing steel/mortar interface in CO2 injection condition, sandwich samples were prepared and exposed up to 20 weeks in aquifer fluid under 10 MPa and 60 °C.
Cross section analysis revealed the crevice corrosion as main mechanism instead of pitting corrosion despite very high concentration of Cl in NGB.
EDS element line scan analysis of the 20-week-exposed metal/mortar coupon showed Chloride distribution, which still not reached the metal/mortar interface, explaining no pitting was observed.
It was confirmed that FeCO3 cannot protect the steel surface in CO2 saturated NGB.
To verify the protective possibility of passivation happened on casing steel/mortar interface, simulated pore solution was synthesized and used to passivate the steel for 42 days. OCP and EIS confirmed the formation of passive layer.
The 42 day passivated layer was broken during the first minute of exposure in CO2 saturated NGB.
However, due to high concentration of Ca2+, a new carbonate CaCO3 dense layer was formed, increased the corrosion resistance of steel surface.
Within the last years the use of feasible alternative energy sources has risen and is going to replace fossil resources more and more. Nevertheless, service conditions in solar facilities are due to the chemical composition of heat transmission media and temperatures, in many cases, extreme in terms of corrosion. Since the construction of power plants shall be economical with maximum life service, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of those facilities.
The materials selection depends on the operation temperature of a power plant on the chemical composition of the transmission fluid used. In high corrosive environments Ni-based alloys are often used as an all-round solution for the construction of corrosion resistant parts, because of their good corrosion properties. However, there might be limits for their use regarding their corrosion behavior, with which this contribution deals.
Experiences from the electrochemical characterization of materials in aqueous solutions are transferred to molten salts, providing a good addition to common exposure tests at temperatures from 450 0C to 600 0C.
By means of electrochemical measurements and exposure tests the suitability of high alloyed materials in molten nitrate salt (60 % NaNO3/40 % KNO3) can be characterized. The method was verified on different Ni-based alloys (UNS N08810, UNS N06600) and Titanium (UNS R50250).
Electrochemical deposition of polyaniline on carbon steel for corrosion study in geothermal solution
(2019)
Polyaniline has been widely developed for many applications, e.g. sensor, supercapacitor components, electrochromic devices, and anticorrosion pigments. Although the addition of polyaniline pigment in organic coatings has been an alternative for corrosion protection in industrial applications, the protection mechanism is still not fully understood. Herein in this study, as a part of the development of polyaniline/silicon dioxide coating for geothermal application, polyaniline has been deposited electrochemically on carbon steel surface in oxalic acid medium and tested in geothermal solution to understand the contribution of polyaniline to the corrosion protection of a polyaniline-based composite in the geothermal system. To observe the surface/interface reaction between the electrolyte and electrode surface during the electrochemical polymerization, electrochemical impedance spectroscopy (EIS) was applied after each cycle. For corrosion study in the geothermal application, an artificial geothermal solution was used with the composition of 1,500 mg/l Cl⁻, 20 mg/l SO₄²⁻, 15 mg/l HCO₃⁻, 200 mg/l Ca²⁺, 250 mg/l K⁺, and 600 mg/l Na⁺, and pH 4 to simulate a geothermal brine found in Sibayak, Indonesia. An electrochemical measurement was performed by monitoring the open circuit potential over seven days, with the interruption by EIS every 22 hours. The experiments were performed at room temperature and 150 °C (1 MPa) in an oxygen-free environment. Impedance spectra showed a reduction of the total impedance value of approximately 10 times for specimens measured at 150 °C compared to the specimens measured at room temperature, suggesting a less stable layer at high temperature.
Electrochemical evaluation of corrosion behavior of metallic materials in geothermal applications
(2008)
Within the project COORAL (German acronym for 'CO2 purity for capture and storage') first studies on piping steels exposed to CO2 and artificial brine with high chloride concentration have been carried out. Corrosion behavior of martensitic Cr13 steel (1.4034) was investigated in a corrosive environment (artificial saline brine, T = 60 °C, CO2-flow rate 3 – 5 L/h, atmospheric pressure, exposure times from 1 h up to 14 days) using electrochemical and metallographic techniques. Different corrosion kinetics were observed as a function of exposure times and chloride concentration in the artificial brine. In CO2-saturated brine pitting corrosion was observed at free corrosion potential, whereas in the brine without addition of NaCl a stable passive layer built up. Predictions about corrosion mechanism are made and verified by means of surface analytical techniques.
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).
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells the corrosion resistance of the materials used needs to be determined.
In this study, representative low cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were embedded in cement to mimic the realistic casing-cement interface. Electrochemical studies were carried out using these metal-cement specimens in comparison with those made of metal only in CO2 saturated synthetic aquifer fluid, at 333 K, to reveal the effect of cement on the steel performance. The results showed the protective effect of cement on the performance of pipeline metals during polarisation process. However, the corrosion current density was high in all cases, with and without cement, indicating that the corrosion resistance of these materials is low. This conclusion was supported by the surface analysis of the polarized specimens, which revealed both homogenous and pitting corrosions.