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The copper alloyed stainless steel 1.4542 (X5CrNiCuNb16-4) is used in different areas due to its good mechanical properties and corrosion resistance. Strength and corrosion resistance can be adjusted by the heat treatment, which is of importance for the application of this alloy. The mechanical properties (strength and hardness) are attributed to the dispersive precipitation of the copper rich ε–Phase. The additional precipitation of chromium carbides can reduce the corrosion resistance. Different ageing states were produced to investigate the precipitation behaviour with various methods. Furthermore, the influence of cold-rolling on the precipitation behaviour was studied in comparison to a solution annealed state without deformation. The microstructure was studied by SEM and the variations of hardness and magnetic proportion were characterised. The electrochemical potentiodynamic reactivation
(EPR) was used to determine the corrosion resistance and detect chromium depletion in all heattreated states. The results show that a work hardening accelerates the precipitation rate, while ageing at 600 °C reduces the corrosion resistance due to chromium depletion.
Cellulose ethers, like methyl cellulose (MC) or hydroxypropyl cellulose (HPC), are widely used in conservation. They also occur as additives and rheology modifiers in various products like dispersions or gels. Do such products release harmful volatile organic compounds (VOC) during their accelerated aging? A mass testing series utilizing the Oddy test of 60 commercial cellulose ethers ranks the products in safe for permanent use (P, no corrosion), only for temporary use (T, slight corrosion), and unsuitable at all (F, heavy corrosion). Results show that 55% of the products passed the test whereas 33% are for temporary use as slight corrosion occurred on at least one metal coupon and only 11% failed the Oddy test. Raman measurements of the corrosion products identified oxides like massicot, litharge, cuprite, and tenorite among carbonates (hydrocerussite, plumbonacrite), and acetates like basic lead acetate, lead acetate trihydrate as well as lead formate as main phases. For example, commercial, industrial Klucel® G (HPC) scored a T rating through slight corrosion on the lead coupon. Basic lead acetate among other phases indicates the presence of acetic acid. Additional measurements of the sample with thermal desorption GC–MS utilizing the BEMMA scheme confirm the high acetic acid outgassing and reveal the presence of a small amount of formaldehyde.
Static immersion tests of potential injection pipe steels 42CrMo4, X20Cr13, X46Cr13, X35CrMo4, and X5CrNiCuNb16-4 at T = 60 °C and ambient pressure, as well as p = 100 bar were performed for 700–8000 h in a CO₂-saturated synthetic aquifer environment similar to CCS sites in the Northern German Basin (NGB). Corrosion rates at 100 bar are generally lower than at ambient pressure. The main corrosion products are FeCO₃ and FeOOH with surface and local corrosion phenomena directly related to the alloy composition and microstructure. The appropriate heat treatment enhances corrosion resistance. The lifetime reduction of X46Cr13, X5CrNiCuNb16-4, and duplex stainless steel X2CrNiMoN22-5-3 in a CCS environment is demonstrated in the in situ corrosion fatigue CF experiments (axial push-pull and rotation bending load, 60 °C, brine: Stuttgart Aquifer and NGB, flowing CO₂: 30 L/h, +/- applied potential). Insulating the test setup is necessary to gain reliable data. S-N plots, micrographic-, phase-, fractographic-, and surface analysis prove that the life expectancy of X2CrNiMoN22-5-3 in the axial cyclic load to failure is clearly related to the surface finish, applied stress amplitude, and stress mode. The horizontal grain attack within corrosion pit cavities, multiple fatigue cracks, and preferable deterioration of austenitic phase mainly cause fatigue failure. The CF life range increases significantly when a protective potential is applied.
Static immersion tests of potential injection pipe steels 42CrMo4, X20Cr13, X46Cr13, X35CrMo4, and X5CrNiCuNb16-4 at T = 60°C and ambient pressure, as well as p = 100 bar were performed for 700–8000 h in a CO2-saturated synthetic aquifer environment similar to CCS sites in the Northern German Basin (NGB). Corrosion rates at 100 bar are generally lower than at ambient pressure. The main corrosion products are FeCO3 and FeOOH with surface and local corrosion phenomena directly related to the alloy composition and microstructure. The appropriate heat treatment enhances corrosion resistance. The lifetime reduction of X46Cr13, X5CrNiCuNb16-4, and duplex stainless steel X2CrNiMoN22-5-3 in a CCS environment is demonstrated in the in situ corrosion fatigue CF experiments (axial push-pull and rotation bending load, 60°C , brine: Stuttgart Aquifer and NGB, flowing CO2: 30 L/h, +/- applied potential). Insulating the test setup is necessary to gain reliable data. S-N plots, micrographic-, phase-, fractographic-, and surface analysis prove that the life expectancy of X2CrNiMoN22-5-3 in the axial cyclic load to failure is clearly related to the surface finish, applied stress amplitude, and stress mode. The horizontal grain attack within corrosion pit cavities, multiple fatigue cracks, and preferable deterioration of austenitic phase mainly cause fatigue failure. The CF life range increases significantly when a protective potential is applied.
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.
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.
Corrosion monitoring of reinforced concrete structures:The DGZfP specification B12 Collaboration
(2023)
Corrosion monitoring of reinforced or prestressed concrete structures has becomeincreasingly important in recent years. Areas of application include componentsthat are no longer accessible after completion or where potential fieldmeasurements cannot be carried out due to existing coatings. Corrosion monitoringcan also be used to monitor the progress of corrosion in corroding systems, e.g. toprove the success of repair measures according to repair principle 8 in accordancewith EN 1504‐9 or repair method 8.3 in accordance with the DIBt repair guideline.It also could be used to prove the functionality of cathodic corrosion protectionsystems in accordance with ISO 12696. Despite the increasing importance ofcorrosion monitoring, no guidelines orrecommendations existed until 2018. Thisgap was closed by the English version of specification B12,“Corrosion Monitoringof Reinforced and Prestressed Concrete Structures,”of the German Society for Non‐Destructive Testing, which was published in 2021. This article introducesspecification B12 by explaining the basicmeasurement principles and illustratingthe potential of corrosion monitoring in new and existing buildings.
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.
Hard coated steel components are used in a wide application range, mostly for protective, wear resistant and decorative purposes. Despite of these coatings being regarded as relatively dense, there is always a high risk of localized corrosion when a coated low alloyed steel component encounters a surrounding high humidity atmosphere or even an aqueous medium. An approach to enhance the corrosion properties is the addition of magnesium to physical vapor deposited hard coatings, like TiN. It has been found that there is a remarkable increase in corrosion resistance in dependence of magnesium content of the TiMgN coating and its surface properties. In this work the authors will explain the underlying corrosion protection mechanisms by means of electrochemical and analytical studies. The positive impact of magnesium in the coating relates on its preferred dissolution vs. steel. This causes the potential to shift to more negative direction with respect to the steel substrate and additionally leads to a temporarily passivation of the steel due to alkalization of the surrounding electrolyte by formation of magnesium hydroxide.
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.
Melanised cell walls and extracellular polymeric matrices protect rock-inhabiting microcolonial fungi from hostile environmental conditions. How extracellular polymeric substances (EPS) perform this protective role was investigated by following development of the model microcolonial black fungus Knufia petricola A95 grown as a sub-aerial biofilm. Extracellular substances were extracted with NaOH/formaldehyde and the structures of two excreted polymers studied by methylation as well as NMR analyses. The main polysaccharide (~ 80%) was pullulan, also known as α-1,4-; α-1,6-glucan, with different degrees of polymerisation. Αlpha-(1,4)-linked-Glcp and α-(1,6)-linked-Glcp were present in the molar ratios of 2:1. A branched galactofuromannan with an α-(1,2)-linked Manp main chain and a β-(1,6)-linked Galf side chain formed a minor fraction (~ 20%). To further understand the roles of EPS in the weathering of minerals and rocks, viscosity along with corrosive properties were studied using atomic force microscopy (AFM). The kinetic viscosity of extracellular K. petricola A95 polysaccharides (≈ 0.97 × 10-6 m2 s-1) ranged from the equivalent of 2% (w/v) to 5% glycerine, and could thus profoundly affect diffusion-dominated processes. The corrosive nature of rock-inhabiting fungal EPS was also demonstrated by its effects on the aluminium coating of the AFM cantilever and the silicon layer below.
This paper considers an indirect measurement approach to reconstruct a defect in a two-dimensional waveguide model for a non-destructive ultrasonic inspection via derivative-based optimization. The propagation of the mechanical waves is simulated by the scaled boundary finite element method that builds on a semi-analytical approach. The simulated data are then fitted to given data associated with the reflected waves from a defect which is to be reconstructed. For this purpose, we apply an iteratively regularized Gauss-Newton method in combination with algorithmic differentiation to provide the required derivative information accurately and efficiently. We present numerical results for three kinds of defects, namely, a crack, delamination, and corrosion. The objective function and the properties of the reconstruction method are investigated. The examples show that the parameterization of the defect can be reconstructed efficiently as well as robustly in the presence of noise.
Civilization and modern societies would not be possible without manmade materials. Considering their production volumes, their supporting role in nearly all industrial processes, and the impact of their sourcing and production on the environment, metals and alloys are and will be of prominent importance for the clean energy transition. The focus of materials discovery must move to more specialized, application-tailored green alloys that outperform the legacy materials not only in performance but also in sustainability and resource efficiency. This white paper summarizes a joint Canadian-German initiative aimed at developing a materials acceleration platform (MAP) focusing on the discovery of new alloy families that will address this challenge. We call our initiative the “Build to Last Materials Acceleration Platform” (B2L-MAP) and present in this perspective our concept of a three-tiered self-driving laboratory that is composed of a simulation-aided pre-selection module (B2L-select), an artificial intelligence (AI)-driven experimental lead generator (B2L-explore), and an upscaling module for durability assessment (B2L-assess). The resulting tool will be used to identify and subsequently demonstrate novel corrosion-resistant alloys at scale for three key applications of critical importance to an offshore, wind-driven hydrogen plant (reusable electrical contacts, offshore infrastructure, and oxygen evolution reaction catalysts).
Although zinc and zinc coatings have been widely used for corrosion protection for decades new zinc coatings are constantly being developed. Characterizing the corrosion protectiveness of these new coatings, however, should not be underestimated. While exposure tests are time intensive, cyclic tests can only be used for a very limited field of application. Thus, electrochemical measurements provide both an efficient and an effective alternative. Conventional aqueous bulk electrolytes influence the surface layers of a tested zinc coating and are therefore not reliable. Gel electrolytes, however, have evolved over the last few years, are minimally invasive and provide reliable results.
This work describes experiments with gel electrolytes made of agar. Unlike previous work, it proposes a composition of gel electrolyte for minimally invasive description of the protective power of naturally formed oxide layers on zinc and zinc coatings. Therefore, as a first part, the gel electrolyte made of agar is verified as a method for zinc and zinc-coated samples. Afterwards, this paper introduces the corrosion product layer resistance RL as a promising parameter to evaluate the protective power of zinc coatings. Results are verified with EIS and FTIR measurements. An example on a representative zinc coating demonstrates the practical application.
Early material damage in equimolar CrMnFeCoNi in mixed oxidizing/sulfiding hot gas atmosphere
(2022)
The challenges to use more varied fuels at medium and high temperatures above 500 °C need to be addressed by tuning the materials toward a better resistance against increased corrosion. As a first step the corrosion processes need to be better understood, especially in the case of the unavoidable and highly corrosive sulfur-based gases. Herein, oxidation/sulfidation of an equimolar CrMnFeCoNi high-entropy alloy is studied at an early stage after hot gas exposure at 600 °C for 6 h in 0.5% SO2 and 99.5% Ar. The oxidation process is studied by means of X-ray diffraction, scanning and transmission electron microscopy, and supported by thermodynamic calculations. It is found that the sulfur does not enter the bulk material but interacts mainly with the fast-diffusing manganese at grain boundary triple junctions at the alloy surface. Submicrometer scaled Cr–S–O-rich phases close to the grain boundaries complete the sulfur-based phase formation. The grains are covered in different Fe-, Mn-, and Cr-based spinels and other oxides.
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.
The corrosion behavior of galvanized steels and zinc components under atmospheric exposure depends mostly on the corrosion product‐based cover layer formation under the prevailing conditions. The use of agar‐based gel electrolytes makes it possible to use electrochemical methods to obtain a characteristic value from these cover layers that describe their current and future protective capacity. It is shown here that different states of galvanized steel can be distinguished very well under laboratory conditions and that this method is also suitable for use under practical conditions. Based on the characteristic values and assuming future time of wetness, it is very easy to draw up a forecast for the future corrosion rate, which provides plausible values.
Novel agar-based test electrolytes are used to perform electrochemical corrosion investigations on ZnFe and ZnNi binary as well as ZnFeMo ternary zinc coatings. The objectives of the electrochemical investigations include the characterization of the corrosion behavior, the description of the protective effect of the coatings as well as the investigation of the layer formation and degradation under artificial aging. ZnFe and ZnFeMo coatings are applied with varying iron content as well as an additional passivation layer, respectively, to study the effect on corrosion resistance. The results show that the protective effect of the coatings is not negatively influenced by different iron contents or the addition of molybdenum. Additional passivation of the ZnFe-containing coatings by means of a passivating agent leads to a significant improvement in the protective effect. Artificial aging leads to slight degradation of the additional passivation layer whereas coatings without post-treatment enhance their protective effect by the formation of corrosion product layers.
An important aspect with regard to the service life of zinc based galvanic anodes and the durability of the corrosion protection of steel in concrete is the “galvanic chloride extraction”. Chloride ions move in the electric field generated by the current, flowing between the galvanic anode and the cathodic steel. Migration leads to an accumulation of anions, e.g. chloride ions, at the anode and depletion of chlorides near the steel rebar surface. The ion migration was studied on steel reinforced concrete specimens admixed with 3 wt.% chloride/wt. cement and galvanically protected by a surface applied embedded zinc anode (EZA). The zinc anode was embedded and glued to the concrete surface by a geo-polymer based chloride free binder. The EZA was operated over a period of 1 year and the ion distribution between anode (EZA) and cathode (steel reinforcement) was studied by laser induced breakdown spectroscopy (LIBS) after 5 months, 7 months and 12 months. The results show that chloride ions efficiently migrate in the direction of the zinc-anode and accumulate there. Chloride distribution in the EZA correlates with the distribution of zinc ions generated by the anodic dissolution of the zinc anode in the binder matrix. The microstructure of the binder matrix and its interface to the zinc-anode are studied by REM/EDX – preliminary results will be reported.
High-entropy alloys (HEAs) are characterized by a solid solution of minimum five and medium-entropy alloys (MEAs) of minimum three principal alloying elements in equiatomic proportions. They show exceptional application properties, such as high-strength and ductility or corrosion resistance. Future HEA/MEA-components could be exposed to hydrogen containing environments like vessels for cryogenic or high-pressure storage where the hydrogen absorption and diffusion in these materials is of interest. In our study, we investigated the HEA Co20Cr20Fe20Mn20Ni20 and the MEA Co33.3Cr33.3Ni33.3. For hydrogen ingress, cathodic charging was applied and diffusion kinetic was measured by high-resolution thermal desorption spectros-copy using different heating rates up to 0.250 K/s. Peak deconvolution resulted in high-temperature desorption peaks and hydrogen trapping above 280 °C. A total hydrogen concentration > 40 ppm was identified for the MEA and > 100 ppm for HEA. This indicates two important effects: (1) delayed hydrogen diffusion and (2) considerable amount of trapped hydrogen that must be anticipated for hydrogen assisted cracking phenomenon. Local electrochemical Volta potential maps had been measured for the hydrogen free condition by means of high-resolution Scanning Kelvin Probe Force Microscopy (SKPFM).