5 Werkstofftechnik
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Organisationseinheit der BAM
- 5 Werkstofftechnik (39)
- 5.1 Mikrostruktur Design und Degradation (39)
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Eingeladener Vortrag
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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.
Thin Sol-Gel Alumina Coating as Protection of a 9% Cr Steel Against Flue Gas Corrosion at 650 °C
(2018)
Samples of sol-gel alumina coated and uncoated P92 steel were exposed to flue gas at 650 °C for 300 h. As result of this treatment a 50 µm thick bi-layered oxide scale had formed on the surface of the uncoated sample. Below the scale a 40 µm thick inner oxidation zone was detected. In contrast, the porous, micron thick alumina coating enabled the formation of a chromium oxide scale with a thickness of some nanometers at the interface between steel substrate and coating. In this case high temperature corrosion of the steel was prevented so far.
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 .
Coupons of X5CrNiCuNb16-4 that may be used as injection pipe with 16% Chromium and 0.05% Carbon (1.4542, AISI 630) were exposed for 3000 h to CO2-saturated saline aquifer water similar to the conditions in the Northern German Basin at ambient pressure and 60 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness. Corrosion rates for polished and technical surfaces were below 0.005 mm/year compared to corrosion rates of 0.035 mm/year after shot peening.
The Ni-Cr-Mo-W alloy is characterized by the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. To protect the surface of the substrate 13CrMo4-5 steel against aggressive environments the Inconel 686 as clad layer was used. The corrosion process was performed in oxidizing mixture of gases like O2, COx, SOx. The second part of corrosion Experiment concerned the corrosion test of the coating in reducing atmosphere of the specified gases with ashes, which contained e.g. Na, Cl, Ca, Si, C, Fe, Al.
This work presents the microstructure and chemical composition of oxide scales created on Ni – base coating after corrosion experiments in aggressive gases and ashes. The Inconel 686 coating applied on the low carbon steel 13CrMo4-5 was performed by a CO2 laser cladding process. The experiments were carried out in oxidizing gas atmospheres containing O2, COx, SOx. The second Variation of corrosion experiments were performed in a reducing atmosphere with ashes containing elements such as: Na, Cl, Ca, Si, C, Fe, Al etc. After 240 h and 1.000 h corrosion experiments the oxide scales on the substrate and overlay were created in both cases.
The sulfur compounds were found on the top of the coating surface (EPMA) and also higher contents of silica compounds were revealed on specimens covered by ashes during the experiments. The microstructure and chemical composition of the clad and scales were investigated by means of a light microscope and an electron microscope (SEM)equipped with an EDS detector.
Comprehensive insights into the early stages of corrosion mechanisms provide fundamental knowledge to further understand and model long time material behaviour. The present work studies the early stages of combined oxidation and sulphidation of ferritic model alloys for time scales up to 250 h at 650 °C to observe the influence of chromium during the corrosion under SO2. Model alloys were used to focus on the reaction of the intended elements: Fe, Cr, S, and O. Pure iron simultaneously forms magnetite and iron sulphide in an early stage of corrosion, covered by a pure oxide layer after 100 h. Iron with 13 wt% Cr shows hematite and mixed Fe-Cr-oxides first, before sulphides nucleate in the inner corrosion zone. With increasing ageing time a magnetite layer is observed below the hematite layer. Quantitative phase fractions of all corrosion products observed were determined from cross section images. Characterization of the Fe13Cr corrosion scale by FIB revealed a highly porous structure in the inner corrosion zone where Cr-rich (Fe, Cr)-sulphides are present, and caused the scale to spall easily.
Insights into early damage mechanisms during high-temperature gas corrosion provide important aspects for the prediction of the long-term stability of hightemperature materials exposed to a hot and corrosive environment. The current work presents a real time study concerning the combined oxidation and sulfidation of ferritic model alloys in a hot SO2 containing atmosphere using energy dispersive X-ray diffraction. The applied high temperature reactor allows the transmittance of high energetic X-rays in order to collect X-ray diffraction pattern of the sample surface in situ during the reaction with the reactive environment. The results revealed that the first phases crystallizing on iron with 2 wt% chromium and with 9 wt% chromium are oxides. The aging experiments at T = 650° C with 0.5% SO2 and 99.5% Ar were followed in situ and caused an external mixed oxide-sulfide layer on top of iron with 2 wt% chromium. On the higher alloyed material the external scale consists of iron oxides and the inner scale of mixed (Fe,Cr)-oxides and chromium-sulfides. The oxide content continuously increases parallel to an increase of the sulfide amount. Thus, the initially formed (Fe,Cr)-oxides do not have a protective character and support the transport of sulfur through the growing oxide scale.
To increase efficiency, modern steam plants are pushing their operational regime from super-critical (600 °C/300 bar) to ultra-super-critical (740/760 °C/350 bar) stretching existing turbine materials to their limits. The focus is on new generation functional materials and technologies which complement the inherent properties of existing materials.
Current work proposes a novel High Power Impulse Magnetron Sputtering (HIPIMS) Deposition technology, for the first time, for deposition of a ceramic based CrN/NbN coating with a nanoscale multilayer structure (bi-layer thickness Δ = 1.9 nm) with superior adhesion (LC2 = 80 N) to protect low Chromium P92 steel widely used in steam power plants. Thermodynamic calculations predict the equilibrium phases and aggressive gaseous compounds generated by the interaction of steam with the coating. CrN/NbN coated P92 steel samples oxidised at 600 °C in a high pressure (50 bar) 100% steam atmosphere for up to 1000 h reveal the coating's superior oxidation resistance and protective mechanisms, especially against the detrimental effect of Hydrogen. High temperature (650 °C) Tensile Strength, Low Cycle Fatigue and Creep tests confirm that, unlike other state-of-the-art PVD technologies, HIPIMS is not detrimental to the mechanical properties of the substrate material. Water droplet erosion tests confirm no measurable weight loss after 2.4 X 10⁶ impacts.
The work presents the microstructure, chemical composition and mechanical properties of Inconel 686 coatings after high - temperature corrosion in environment of aggressive gases and ashes. To produce the Ni - based coatings the QS Nd:YAG laser cladding process was carried out. As the substrate used 13CrMo4-5 boilers plate steel. Ni - base alloys characterize the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. Formed clad were characterized by high quality of metallurgical bonding with the substrate material and sufficiently low amount of the iron close to the clad layer surface. After corrosion experiment the oxide scale on the substrate and clad created. The scale on 13CrMo4-5 steel had 70 μm thickness while the scale of the clad had less than 10 μm. The microstructure, chemical composition of the obtained clad and scales were investigated by scanning electron microscope (SEM) and electron probe microanalyzer (EPMA) equipped with the EDS detectors.
The Ni-Cr-Mo-W alloy is characterized by the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. To protect the surface of the substrate 13CrMo4-5 steel against aggressive environments the Inconel 686 as clad layer was used. The corrosion process was performed in oxidizing mixture of gases like O2, COx, SOx. The second part of corrosion Experiment concerned the corrosion test of the coating in reducing atmosphere of the specified gases with ashes, which contained e.g. Na, Cl, Ca, Si, C, Fe, Al.
T92 steel was oxidized at 650 °C for 1000 h in dry and wet oxyfuel gases. The microstructure of inner oxide layer was investigated using scanning transmission electron microscopy and energy dispersive spectroscopy on thin lamellas of oxide cross-sections. The oxides were composed of fine equiaxed grains and separated into Fe-rich and Cr-rich regions. Fe-rich regions were wustite and iron sulphide while Cr-rich regions consisted of Fe-Cr spinel with different stoichiometries. Precipitates of (W,Mo)-rich oxides were formed within the oxide scale and beneath the oxide/alloy interface. Often iron sulphide and (W,Mo)-rich oxide were surrounded by Cr-rich spinel.
Molten salt containing systems gain in importance for sustainable energy use and production. For research and development, interactions of molten salts with potential container materials are of major interest. This article introduces preparation procedures to display an intact metal and salt microstructure and their interface using light optical microscopy and scanning electron microscopy. The exemplary material combination is the ternary salt mixture NaCl-KCl-MgCl2 and the low alloyed steel 1.4901 (T92) with a maximum service temperature of 550 °C. These are potential elements/materials for use in latent heat thermal energy storages.
Carbon Capture and Storage (CCS) is well acknowledged to mitigate climate change. Therefore, pipe Steels suitable for CCS technology require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe Steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 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. Main corrosion products analysed on pits are FeCO3 and FeOOH. The carbon content does not show significant influence on the pitting behaviour. Generally, higher chromium Content results in better corrosion resistance. Although X35CrMo17-1 and X5CrNiCuNb16-4 show low surface corrosion rates, their resistance against local corrosion in CCS environment is not significantly better compared to the much less costly Steels X20Cr13 and X46Cr13.
Specific amounts of oxidizing and reductive impurities as well as some moisture were added to dense phase CO2 to replicate CO2 streams from sources in a CCS pipeline network. Due to the moisture content being only 50 ppmV no visible acid condensation took place. To simulate stress conditions at the inside pipeline surface due to fluid pressure (10 MPa) specimens were preloaded using a load frame. Experiments conducted at 278 K and at 313 K revealed the highest corrosion rate at lower temperature. Corrosive effect of impurities was strongest applying mixed atmosphere, containing oxidizing and reductive components, closely followed by CO2 streams with pure oxidizing character. By far, the lowest corrosion rate (10x lower) resulted from reductive atmosphere. In general, at constant temperature and pressure the CO2 stream composition strongly influences the morphology, thickness and composition of the corrosion products. Applying oxidizing or mixed impurities, iron hydroxides or oxides (e.g. goethite, hematite) occur as dominating corrosion products, capable to incorporate different amounts of sulfur. In contrast, using reductive atmosphere very thin corrosion layers with low crystallinity were developed, and phase identification by XRD was unfeasible. SEM/EDX analysis revealed the formation of Fe-O compounds, most likely attributed to the oxygen partial pressure in the system induced by CO2 (≥0.985 volume fraction) and volatile H2O. In addition to the surface covering corrosion layer, secondary phases had grown locally distributed on top of the layer. These compounds are characteristic for the applied atmosphere and vary in number, shape and chemical composition.
Coupons of X5CrNiCuNb16-4 with different surface roughness that may be utilized as injection pipe with 16% Chromium and 0.05% Carbon (1.4542, AISI 630) were exposed for 3000 h to CO2-saturated saline aquifer water simulating the conditions in the Northern German Basin at ambient pressure and 60 °C. Additionally, corrosion fatigue experiments (ambient pressure, technically clean CO2, saline aquifer water of Stuttgart Aquifer) were performed using specimen of X46Cr13 (1.4043, AISI 420C) with regard to the influence of the roughness of technical surfaces on the number of cycles to failure at different stress amplitudes. Specimen of Duplex stainless steel X2CrNiMoN22-3-2 (1.4462) for corrosion fatigue experiments were provided with technical surfaces after machining as well as polished surfaces. Results were obtained at load amplitudes ranging from 175 MPa to 325 MPa in the geothermal brine of the Northern German Basin at 98 °C. The main precipitation phases on the surface as well as within pits reveal carbonates or hydroxides such as siderite (FeCO3) and ferrous hydroxide goethite (FeOOH) independent of the original surface roughness. Corrosion rates for polished and technical surfaces were below 0.005 mm/year compared to corrosion rates of 0.035 mm/year after shot peening. Specimen with technical surfaces tested at high stress amplitudes (>275 MPa) lasted longer (cycles to failure: P50% at Sa 300 MPa=5x105) than specimen with polished surfaces (cycles to failure: P50% at Sa 300 MPa=1.5x105). This behavior is emphasized by the slope coefficient (technical surfaces k = 19.006, polished surfaces k=8.78) meaning earlier failure for polished at high stress amplitude Sa. Although rather low scatter ranges (technical surface: TN=1:1.35, polished surface: TN=1.1.95) indicate no change in failure mechanism it may be assumed that at low stress pitting is the initiating crack growth process whereas at high stress amplitudes the formation of micro cracks is reason for crack propagation and failure.
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 ).
The 13CrMo4-5 ferritic steel is commonly used in power plants, due to its favorable mechanical properties. According to EN 10028-2, this steel can be used at temperatures up to 570°C because of its creep behavior. The inefficient corrosion resistance limits the application of this steel to lower temperatures depending on the gas temperature and slag formation. Therefore, the application of a highly resistant Ni-based coating is proposed to extend the corrosion resistance of elements made of ferritic steel. The corrosion test was performed in an environment containing a mixture of gases, like O2, COx, and SOx, and deposited ashes with elements, e.g., Na, Cl, Ca, Si, C, Fe, and Al. The exposure time was, respectively, 240 h, 1000 h and 4500 h at a temperature of 600°C. The oxide scale formed on the 13CrMo4-5 steel was significantly thicker than on the IN686 coating. The microstructure and chemical and phase compositions of the oxide scale were investigated using light optical microscopy together with scanning and transmission electron microscopy techniques. Energy dispersive x-ray analyses were performed when appropriate.
The steam side oxidation of ferritic–martensitic VM12-SHC steel was investigated under thermo-cyclic conditions in water steam at 620/320 °C and 30 bar with a focus on assessing the influence of pre-oxidation time, specimen geometry and surface finish. The specimens were pre-oxidized under isothermal conditions in water steam at 620 °C and 30 bar for 500 h or 1500 h. After pre-oxidation treatment, all specimens were subjected up to 258 thermal cycles. Three different geometries—rectangular coupons, U-shaped ring segments and ring samples—were investigated to evaluate the influence of open/closed shape, and flat/curved surface on corrosion rate. At the same time, two types of surface finish were considered: “as received” and “ground.” The formation of a protective scale by pre-oxidation was investigated. EBSD and ESMA analyses revealed that the Cr-content of the alloy appeared to be insufficient for obtaining a protective oxide scale under studied conditions, at the same time the anayses confirmed that initial oxidation depends on presence of minor alloying elements as Si and Mn, strong oxide formers which can alter the kinetics and morphology of the corrosion reaction. Moreover, rectangular coupons with small wall thickness and flat surface exhibited the highest corrosion rate, while “ground” curved samples showed only local oxidation. This indicates that for same pre-oxidation time, oxidation kinetics is controlled by curvature.
Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 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. Main corrosion products are FeCO3 and FeOOH. Corrosion rates obtained at 100 bar are generally much lower than those measured at ambient pressure. Highest surface corrosion rates are 0.8 mm/year for 42CrMo4 and lowest 0.01 mm/year for X5CrNiCuNb16-4 in the vapour phase at ambient pressure. At 100 bar the highest corrosion rates are 0.01 mm/year for 42CrMo4, X20Cr13 (liquid phase), X46Cr13 and less than 0.01 mm/year for X35CrMo4 and X5CrNiCuNb16-4 after 8000 h of exposure with no regard to atmosphere. Martensitic microstructure offers good corrosion resistance.