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The appropriate strength of steels used for saline aquifer carbon capture and storage sites (CCS) is usually achieved by applying heat treatments. Thus, heat treatment influences the corrosion resistance for injection pipe steels with 13% chromium and different carbon content: 1.4034/X46Cr13 and 1.4021/X20Cr13 in CO2 saturated saline aquifer water at 60 °C, 1 and 100 bar. X46Cr13 shows better corrosion resistance with respect to corrosion rate, number of pits and maximum intrusion depth. Low corrosion rates are obtained for steels with martensitic microstructures exposed to supercritical CO2 at 100 bar, whereas normalized steels show better corrosion resistance at ambient pressure.
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).
In the field of water pipelines, geothermal energy production as well as carbon capture and storage technology (CCS) materials have to provide a high resistance to corrosion and mechanical stress. The combination of cyclic load and corrosive aqueous environment leads to corrosion fatigue of pipes and components (e.g. pumps) and thus inevitably to the reduction of the lifetime of these components. To estimate the reliability of components from adjusted in-situ-laboratory experiments a corrosion chamber was designed and tested with CO2 saturated corrosive aqueous media flowing at a steady rate. Unique feature of this special chamber is its installation directly onto the sample and thus providing flexible usability in almost every testing machine. This allows simultaneous mechanical loading of the sample, operation at temperatures up to 100 °C and exposure to fluid flow of corrosive liquids and gases. The lifetime reduction of AISI 420C (X46Cr13, 1.4034) is demonstrated at T=60 °C, geothermal brine: Stuttgart Aquifer flow rate: 9 l/h, CO2. S-N plots, micrographic-, phase-, fractographic- and surface analysis were applied to obtain sustainable information on the corrosion fatigue behavior. Maximum number of cycles (here 12.5 x 106 cycles to failure) is reached at σa =173 MPa. No typical fatigue strength exists and passive corrosion fatigue may be identified as failure cause.
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.
During carbon dioxide storage technology (carbon capture and storage, CCS) components are exposed to a corrosive environment and mechanical stress, which results in corrosion fatigue and inevitably followed by the a lifetime reduction of these components. In order to gain knowledge upon the corrosion fatigue strength of materials, Samples of high alloyed stainless injection-pipe steels AISI 420 X46Cr13, and X5CrNiCuNb16-4 AISI 630 were tested in a at T=60 °C and ambient pressure in a CO2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Therefore a corrosion chamber applied to a resonant testing machine allowing for “in situ” test conditions was designed and successfully tested. In-situ tension compression experiments were established using a resonant testing machine at a frequency as low as 30 – 40 Hz. In addition technical CO2 was introduced into the closed system at a rate close to 9 L/h to keep stable environmental conditions. Simultaneously electrochemical testing was performed to get information on failure causes and the mechanism of failure during the injection of CO2 into deep geological layers. S-N plots, micrographic analysis, and surface analysis of the fracture surface were applied to obtain sustainable information on the corrosion fatigue behavior of injection pipe steels. Samples used have a surface roughness of Rz = 4, to simulate technically machined surfaces. X46Cr13 reached the maximum number of cycles (12.5 x 106) at a stress amplitude of 173 MPa. X5CrNiCuNb16-4 reached the maximum number of cycles (10 x 106) at a stress amplitude at 150 MPa. The scatter range of X5CrNiCuNb16-4 is very high (1:34); by comparison the scatter range of X46Cr13 is only 1:3.5.
Samples of differently heat treated high alloyed stainless injection-pipe steels AISI 420 X46Cr13, AISI 420J X20Cr13 as well as X5CrNiCuNb16-4 AISI 630 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2- saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Corrosion rates and scale growth are lowest after long term exposure for steels hardened and tempered at 600 to 670 °C and pits - indicating local corrosion- decrease in diameter but increase in number as a function of carbon content of the steel. Martensitic microstructure is preferred with respect to this particular CCS-site.
In geothermal power plants materials e.g. pumps are exposed to extremely corrosive thermal water. This results in corrosion fatigue and so inevitably the reduction of the lifetime of these components. Also in the field of the carbon dioxide storage technology (carbon capture and storage CCS) components are exposed to a corrosive environment and mechanical stress. In order to gain knowledge upon the corrosion fatigue strength of materials a corrosion chamber for "in situ" conditions was designed and successfully applied.Two different steels X46Cr13 and X5CrNiCuNb16-4 have been tested and their corrosion fatigue behavior was compared. To simulate the frequency of operating pumps (30 – 40 Hz) a resonant testing machine was used. In addition technical CO2 was introduced into the closed system at a rate close to 9 L/h to keep stable environmental conditions. The samples have a surface roughness of Rz = 4 to simulate technical machined surfaces. The calculated tensile strength of X46Cr13 with soft annealed microstructure (coagulated cementite in ferrite-perlite matrix) is about 680 MPa and the yield strength is about 345 MPa. The tensile strength of X5CrNiCuNb16-4 is about 1078 MPa and the yield strength about 928 MPa. Testing parameters are: corrosion media: saline aquifer water (Stuttgart Aquifer) temperature of the brine at 60 °C and load ratio of R=-1. For X46Cr13 a stress amplitude between 160 MPa to 270 MPa and for X5CrNiCuNb16-4 a stress amplitude between 150 to 500 was chosen. Cycles until crack initiation differ strongly and were found to start at 5 x 104 up to 12.5 x 106 cycles.X46Cr13 has reached a maximum number of cycles (12.5 x 106) at a stress amplitude of 173 MPa. X5CrNiCuNb16-4 has reached the maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa. The range of scatter for X5CrNiCuNb16-4 is very high (1:34) in comparison the range of scatter for X46Cr13 (1:3.5).
Design of a high pressure system for in-situ tests on the corrosion fatigue of metallic materials
(2014)
In geothermal power plants pumps are exposed to corrosive and oscillating loads. This leads to corrosion fatigue and reduces the lifetime of certain components. Usually underwater power pumps are placed inside the borehole. In this case an installation depth of 600 to 800 meters below ground level is typical. In these depths an additional load due to high pressure and high temperature is introduced which is based on geothermal brine. Therefore the material which is used for the pump is steel.For fatigue testing at loads existing in deep geological layers an appropriate system for fatigue tests under in-situ conditions was set up. The requirements of the design are: temperature of the corrosion medium of 200 °C pressure of 200 bars and the complete immersion of the specimen in flowing corrosion medium containing mixtures of corrosive gasses during the entire test period.The test system has three main components the corrosion chamber the heating module and the reservoir. It is important that the corrosion chamber is only fixed onto the specimen which allows for highest flexibility of the test system operational in many different test machines. The heating module heats the corrosion medium up to 200 °C. The reservoir make sure that the volume of the corrosion medium satisfies requirements of the DIN 50905 Part 1 is conformed providing minimum required corrosive medium of 10 ml/cm² in relation to the sample surface.This innovative fatigue test system aims at performing in- situ fatigue corrosion tests simultaneously at high pressure and high temperature in liquid and gaseous corrosive environment. Results from the tests will allow determining the fatigue life of several materials influenced by pressure and temperature under corrosive conditions.
With CO2 being one reason for climate change carbon capture and storage (CCS) is discussed to mitigate climate change. When emission gases are compressed into deep geological layers CO2-corrosion can easily cause failure of injection pipes. Different steels 42CrMo4, X46Cr13 and X20Cr13 were tested as well as X35CrMo17 and X5CrNiCuNb16-4 in a laboratory Environment similar to the conditions of the CCS engineering site at the Northern German Bassin. Samples were exposed to synthetic aquifer water saturated with technical CO2 at a flow rate of 3 NL/h.
Corrosion rates obtained via mass loss vary in a wide range (0,005 to 2.5 mm/year). The precipitations within the corrosion scale revealed a complicated multiphase layer containing siderite FeCO3, goethite α-FeOOH, lepidocrocite γ-FeOOH, mackinawite FeS and akaganeite Fe8O8(OH)8Cl1,34 and spinelphases of various compositions.
Die Lebensdauer von Bauteilen welche gleichzeitig mechanisch und korrosiv belastet werden kann mit vorhandenen Literaturwerkstoffdaten nicht ausreichend bestimmt werden. So kommt es entweder im Betrieb frühzeitigen versagen, oder einer Überdimensionierung bei der Konstruktion. Um Werkstoffe unter Bedingen der SchwingungsrisskorroSIOn zu prüfen und somit belastbare Materialkennwerte zu bekommen, ist es notwendig diese unter Realbedingungen in hierfür geeigneten Prüfanlagen zu testen.
Corrosion fatigue (CF) of duplex stainless steel (DSS) X2CrNiMoN22-5-3 was investigated in in-situ geothermal conditions of the Northern German Basin (NGB). The influence of the load type on CF behavior of the alloy was examined by applying push/pull and rotating bending cyclic load to failure. The hour-glass shaped specimens with both polished and precisely turned surface finish were tested in corrosion chambers allowing for the permanent circulation of Northern German Basin electrolyte heated to 369 K. Additionally, the influence of a protective cathodic potential on the CF life expectancy was investigated by employing a potentiostat. The rotating bending cyclic load led to a higher CF life expectancy, which decreased with increasing duration of the experiment due to a higher deterioration rate of the material. The application of a cathodic potential caused a significant increase of the CF lifespan from 4.7 x 105 (open-circuit potential (OCP)) to 107 cycles (preset threshold cycle number) for the potential range from USHE = – 450 to – 900 mV. Microstructural analysis of the CF damage revealed horizontal grain attack within corrosion pit cavities, multiple fatigue cracks and preferable deterioration of the austenitic phase.
High-temperature-high pressure stress-strain testing of materials in CO2-containing saline solutions
(2015)
In-situ stress-strain testing under corrosive environment, such as corrosive gasses (e.g. CO2) and highly saline water, is a challenge in testing corrosion fatigue of materials, e.g. for geothermal application or CCS (carbon capture and storage). The first corrosion chamber system was designed for performance at ambient pressure up to 100 °C. The second allows for corrosion fatigue testing at high pressure up to 200 bar and 400 °C. The highly flexible corrosion chambers allow for fast changing and easy alignment of test samples, visual monitoring, CAD-camera monitoring electrochemical measurements, O2-partial pressure or gas partial pressure measurement. Novelty is the fixing of the corrosion chamber directly onto the specimen, that guarantees best fitting and enables the test system to be modified easily suiting a variety of fatigue test machines. All parts of the test system are conforming to the technical rules.
To resist the corrosive geothermal environment during carbon capture and storage CCS -such as: heat, pressure, salinity of the aquifer, CO2-partial pressure, properties of pipe steels-require certain specification. For evaluation samples of differently heat treated high alloyed stainless injection-pipe steels AISI 420 X46Cr13, AISI 420J X20Cr13 as well as X5CrNiCuNb16–4 AISI 630 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h up to 8000 h in a CO2-saturated synthetic aquifer environment similar to a possible geological situation in the northern German Basin. Corrosion rates and scale growth are lowest after long term exposure for steels hardened and tempered at 600 °C to 670 °C and pits -indicating local corrosion- decrease in diameter but increase in number as a function of carbon content of the steel. Martensitic microstructure is preferred with respect to these particular conditions.
The nucleophilic thiol–ene (thia-Michael) reaction between molecular rods bearing terminal thiols and bis-maleimides was investigated. The molecular rods have oligospiroketal (OSK) and oligospirothioketal (OSTK) backbones. Contrary to the expectations, cyclic oligomers were always obtained instead of linear rigid-rod polymers. Replacing the OS(T)K rods with a flexible chain yielded polymeric products, suggesting that the OS(T)K structure is responsible for the formation of cyclic products. The reason for the preferred formation of cyclic products is due to the presence of folded conformations, which have already been described for articulated rods.
To mitigate carbon dioxide emissions CO2 is compressed and sequestrated into deep geological layers (Carbon Capture and Storage CCS). The corrosion of injection pipe steels is induced when the metal is in contact with CO2 and at the same time the geological saline formation water. Stainless steels X35CrMo17 and X5CrNiCuNb16-4 with approximately 17% Cr show potential as injection pipes to engineer the Northern German Basin geological onshore CCS-site. Static laboratory experiments (T = 60 ◦C, p = 100 bar, 700–8000 h exposure time, aquifer water, CO2-flow rate of 9 L/h) were conducted to evaluate corrosion kinetics. The anomalous surface corrosion phenomena were found to be independent of heat treatment prior to exposure. The corrosion process is described as a function of the atmosphere and diffusion process of ionic species to explain the precipitation mechanism and better estimate the reliability of these particular steels in a downhole CCS environment.
During capture and storage technology (CCS) as well as in geothermal energy production Steels need to withstand the corrosive environment such as: heat, pressure, salinity of the aquifer and CO2-partial pressure. 1.4542 shows unusual corrosion phenomena, but is still sufficiently resistant in corrosive environments. To better understand its behaviour differently heat treated coupons of 1.4542 and for comparison X20Cr13 and X46Cr13 were kept in the artificial brine of the Northern German Basin at T=60 °C. Ambient pressure as well as p=100 bar for 700 h - 8000 h in water saturated supercritical CO2 and CO2-saturated synthetic aquifer Environment was applied. Fatigue tests were performed via push-pull tests with a series of 30 specimens from 150 MPa to 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). FeCO3 and FeOOH are corrosion products also after dynamic corrosion tests. Martensitic microstructure offers good corrosion resistance in geothermal environment. The S-N-curve showing no typical fatigue strength and very steep slopes of possible fatigue strength for finite life. Possible influencing artefacts, such as Al-inclusions could not be correlated to early rupture despite specimens containing inclusions at the fracture surface and cross section reached lower number of cycles. Applied potential proofed to enhance fatigue life tremendously.
Corrosion fatigue specimen with different surfaces (technical surfaces after machining and polished surfaces) of high alloyed martensitic stainless steel X46Cr13 (1.4043) and duplex stai nless steel X2CrNiMoN22 3 2 (1.4462) were compared at load amplitudes from 175 MPa to 325 MPa in the geothermal brine of the N orthern German Basin at 98 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO 3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness . At high stress amplitudes above 275 MPa technical surfaces (P50% at σa 300 MPa=5 × 10 5 ) resulted in more cycles to failure than polished (P50% at σa 300 MPa=1.5 × 10 5 ). The greater slope coefficient for technical surfaces k = 19.006 compared to polished surfaces k =8.78 demonstrate s earlier failure at given stress amplitude σa .
In CCS environment (carbon capture and storage) pipes are loaded statically and/or cyclically and at the same time exposed constantly to the highly corrosive hot thermal water. Experimental procedures such as ambient pressure immersions tests, in-situ corrosion fatigue experiments using a flexibly designed corrosion chamber at ambient pressure and a specially designed corrosion chamber at high pressure. Experimental set-ups for push/pull and rotation bending load are introduced. The corrosion behavior and lifetime reduction of high alloyed steels (X46Cr13, 1.4043), (X5CrNiCuNb16-4, 1.4542) and (X2CrNiMoN22-5-3, 1.4462) is demonstrated (T=60 °C, geothermal brine: Stuttgart Aquifer flow rate: 9 l/h, CO2 ).