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Agar gel pads have been used for electrochemical measurements for some time. For zinc in particular, a standard method for measuring the stability of the corrosion product layer is being established. The main interpretation factor is the corrosion product layer resistance RL, as it is easy to determine and interpret. A high corrosion product layer resistance indicates a high level of protection. However, it is not yet known how low the corrosion product layer resistance is for freshly produced zinc samples. As zinc is highly active, it reacts immediately with the environment to form a corrosion product layer, which affects the corrosion product layer resistance. The addition of zinc acetate to the agar gel pads prevents the formation of a surface layer and destroys existing ones.
This makes it possible to measure an almost corrosion product-free zinc surface. This is important in defining the range of corrosion product layer resistance for a protective surface.
The offshore environment is inherently corrosive. Consequently, pits may nucleate on exposed steel surfaces. Corrosion pits can be a source of crack initiation when the structure is subject to fatigue loading. The criticality of a corrosion pit with respect to the structural integrity depends on its shape and size and can be quantified using a stress concentration factor (𝐾𝑡). In this work, a parametric 3D finite element model is developed to perform stress analysis of a pitted plate subjected to uniaxial tensile stress. The model is used for an extensive parameter study in which 𝐾𝑡 is determined for various pit configurations. It is demonstrated that each one of the geometrical parameters holds a substantial influence on the location of the Most Critical Region (MCR). It is shown that 𝐾𝑡 increases as the pit gets narrower. Pits with an elliptical mouth yield higher 𝐾𝑡 values when the angle between the load direction and the pit mouth major axis increases. Moreover, 𝐾𝑡 increases with the increase in the localized thickness loss which is more pronounced for relatively wider pits. Finally, a regression model is presented for estimating 𝐾𝑡 based on the geometric parameters of a pit.
Une transition mondiale vers des systèmes énergétiques plus durables, abordables et fiables a été initiée par l’accord de Paris et l’Agenda 2030 des Nations unies pour un développement durable. Il s’agit là d’un défi industriel majeur car les systèmes et infrastructures énergétiques résilients au changement climatique exigent de se positionner pour le long terme. Se pencher sur le comportement dans la durée des matériaux structurels - principalement des métaux et des alliages - s’impose alors comme une nécessité. Dans cette optique, « La corrosion : un défi pour une société durable »présente une série de cas montrant l’importance de la tenue à la corrosion et de la protection anticorrosion des métaux et des alliages pour le développement de systèmes durables, économiques et fiables de production d’énergie.
With increasing demand and environmental concerns, researchers are exploring new materials that can perform as well or better than traditional materials while reducing environmental impact. The BAMline, a real-life sample materials research beamline, provides unique insights into materials’ electronic and chemical structure at different time and length scales. The beamline specializes in x-ray absorption spectroscopy, x-ray fluorescence spectroscopy, and tomography experiments. This enables real-time optimization of material properties and performance for various applications, such as energy transfer, energy storage, catalysis, and corrosion resistance. This paper gives an overview of the analytical methods and sample environments of the BAMline, which cover non-destructive testing experiments in materials science, chemistry, biology, medicine, and cultural heritage. We also present our own synthesis methods, processes, and equipment developed specifically for the BAMline, and we give examples of synthesized materials and their potential applications. Finally, this article discusses the future perspectives of the BAMline and its potential for further advances in sustainable materials research.
In this study, we propose the use of nondestructive, depth-resolved, element-specific characterization using grazing exit X-ray absorption near-edge structure spectroscopy (GE-XANES) to investigate the corrosion process in compositionally complex alloys (CCAs). By combining grazing exit X-ray fluorescence spectroscopy (GE-XRF) geometry and a pnCCD detector, we provide a scanning-free, nondestructive, depth-resolved analysis in a sub-micrometer depth range, which is especially relevant for layered materials, such as corroded CCAs. Our setup allows for spatial and energy-resolved measurements and directly extracts the desired fluorescence line, free from scattering events and other overlapping lines. We demonstrate the potential of our approach on a compositionally complex CrCoNi alloy and a layered reference sample with known composition and specific layer thickness. Our findings indicate that this new GE-XANES approach has exciting opportunities for studying surface catalysis and corrosion processes in real-world materials.
Two hybrid alkaline cements (HAC) based on Portland clinker, ground granulated blast furnace slag (GGBFS), fly ash and sodium sulfate, as well as an alkali-activated GGBFS/fly ash blend and a Portland cement paste were exposed to a saturated saline solution for 70 days. The combined chemical attack of chloride, magnesium and sulfate ions and the associated changes of the phase assemblage of the materials were studied by X-ray diffraction, thermal analysis and spatially resolved X-ray fluorescence spectroscopy. The experimental results revealed dissolution of ettringite, C-N-A-S-H and calcite, and the formation of gypsum, Kuzel's salt and Friedel's salt; thermodynamic modeling indicated the formation of M-S-H. The resistance of the HAC against attack by the saline solution increased with Portland clinker fraction. The capacity of portlandite to maintain pH at values above 10 is found to be a major factor controlling the resistance of HAC against corrosion in the saline solution.
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.
The suitability of an Al2O3 coating for corrosion protection on X20Cr13 was evaluated in various artificial geothermal brines, focusing on the influence of different pH (4, 6 and 8) and their chemical compositions on the coating properties. All experiments were performed in the laboratory using autoclaves at 150 ◦C and 1 MPa in deaerated condition for 1 and 7 days. Results showed that the pH of geothermal waters is the most detrimental factor in the transformation of ɣ-Al2O3 and its protective abilities. Delaminations were found in the Coating exposed to geothermal brines with pH 4. FTIR spectra indicated a transformation of ɣ-Al2O3 to boehmite AlOOH after exposure to pH 4 and 6, and bayerite Al(OH)3 was formed after exposure to pH 8. Different Crystal structures of the hydrated Al2O3 also contribute to the stability of the coatings, observed by the SEM- EDX of the surface and cross-section of coatings. This study indicated that ɣ-Al2O3 sol-gel coating presents a promising aspect of corrosion protection in geothermal environment with a neutral pH.
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.
Often 3D‐printing and additive manufacturing are mentioned as the 3rd industrial revolution. In this conjunction this book provides a brief overview on additively manufactured metal pieces.
This book fulfills its intension to serve as an educational guide, providing a holistic picture encompassing science, technology and applications for the real‐life use of Metal Additive Manufacturing.
In 2019 CRC Press published the "Steel‐Reinforced Concrete Structures" as a paperback. This book does not vary in terms of content from the hardback publication of 2008. But it is first reviewed here in corrosion news. The book provides eight of nine chapters in which the author discusses technical aspects of assessment and repair of steel‐reinforced concrete structures.
To sum up, this book is recommended for students and people involved with the assessment and repair of reinforced‐concrete structures, who want to get a quick introduction into the different aspects of the field. Readers also learn much about the economic interactions besides the topic. However, for experienced technicians and corrosion experts, this book may not be exact enough in both the electrochemical description of deterioration processes and the practical aspects of repair and control methods. Despite that, the discussions of the author are scientifically correct.
Literature data on the influence of concrete cracks on corrosion propagation of reinforcing steel are contradictory. This might be due to very different exposure and test conditions but also to a lack of time-resolved data in cyclic wetting–drying exposure. Here, the influence of the environmental conditions on the corrosion rates in cracked concrete is studied experimentally. The results show that the corrosion rate in cracked concrete depends on the duration of wetting and drying phases and the relative humidity (RH) during the drying phase. The lower the ambient RH in the drying phase, the faster the cracks dry, which depresses the corrosion rate in the periods between the wetting events. A model is proposed to estimate corrosion rates in cracked concrete cyclic wetting/drying exposure.
In coal-fired power plants using oxyfuel combustion process with carbon capture and sequestration, instead of air, a mixture of oxygen and recirculated flue gas is injected in the boiler. A series of steels were exposed to CO2-SO2-Ar-H2O gas mixtures at 600 °C for 1000 h to compare their high temperature corrosion behavior. During the corrosion process, carburization, decarburization and recrystallization were observed underneath the oxide scale depending on the gas mixture and alloy composition. The conditions that lead to carburization are not yet completely understood, but decarburization can be simulated using thermodynamic and kinetic models. In this work, the results of these simulations are compared with measured values for one of the alloys that displayed a decarburized region. Since the mobility of carbon in the scale is not known, two strategies were adopted: simulation of alloy-atmosphere contact; and estimation of the carbon flux to produce the observed decarburization. The second approach might give an insight on how permeable to carbon the scale is.
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 .
Roaldite – Fe4N – has been identified in the São Julião de Moreira iron meteorite using electron backscatter diffraction (EBSD) and simultaneously acquired energy-dispersive x-ray spectroscopy (EDS). Mean-periodic-number images derived from raw EBSD patterns confirm this phase by an even higher spatial resolution compared to EDS.
Roaldite appears in the form of systematically and repetitively aligned plates. Despite the locally heavy plastic deformation, it is shown that the origin of the oriented precipitation of roaldite is linked to the orientation of the kamacite matrix. Roaldite can be considered to be precipitated from kamacite using an inverse Kurdjumov-Sachs (K-S) or Nishiyama-Wassermann (N-W) orientation relationship. A more accurate discrimination is impossible due to the accumulated shock deformation, which blurs the local reference orientation of kamacite. The habit plane of roaldite is found to be {112}R, which is most likely parallel to {120}K of kamacite. Some of the roaldite plates contain two orientation variants which repeatedly alternate. Their misorientation angle is about 12°.
Today glass is broadly used in modern architecture. For indoor applications it is possible to produce decorated glass by using enamel colours and glass painting techniques without any problems. However, this is more limited for applications out of doors. Humidity and environmental pollution attack the surface of the coating and can damage it. There are only a few colours on the market which are resistant towards acids and bases until now. Additionally, most of those colours are opaque. To extend the colour palette, chemically resistant low melting coloured glasses are being developed which are transparent and intensively toned even in thin coating thicknesses. To achieve such an ambitious aim, many parameters have to combine and act in a complex manner. New compositions of lead borosilicate, zinc borosilicate and lead-zinc borosilicate glasses were produced and milled as powder. The thermal properties as well as the environmental stability were analysed. The influence of PbO and ZnO on the thermal properties and the environmental stability were investigated. Evaluation of the fusing results shows that the production and mixture of transparent vitreous enamels for the exterior side of glasses is possible. The tests made it clear that the original materials for making the vitreous enamels must be excellently ground and prepared to achieve a satisfactory result. The method to produce durable vitreous enamels for exterior application also seems to allow the production of glass colours.
This work presents machine learning-inspired data fusion approaches to improve the non-destructive testing of reinforced concrete. The principal effects that are used for data fusion are shown theoretically. Their effectiveness is tested in case studies carried out on largescale concrete specimens with built-in chloride-induced rebar corrosion. The dataset consists of half-cell potential mapping, Wenner resistivity, microwave moisture and ground penetrating radar measurements. Data fusion is based on the logistic Regression algorithm.
It learns an optimal linear decision boundary from multivariate labeled training data, to separate intact and defect areas. The training data are generated in an experiment that simulates the entire life cycle of chloride-exposed concrete building parts. The unique possibility to monitor the deterioration, and targeted corrosion initiation, allows data labeling.
The results exhibit an improved sensitivity of the data fusion with logistic regression compared to the best individual method half-cell potential.
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.
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.
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.
The steel–concrete interface (SCI) is known to influence corrosion of steel in concrete. However, due to the numerous factors affecting the SCI—including steel properties, concrete properties, execution, and exposure conditions—it remains unclear which factors have the most dominant impact on the susceptibility of reinforced concrete to corrosion. In this literature review, prepared by members of RILEM technical committee 262-SCI, an attempt is made to elucidate the effect of numerous SCI characteristics on chloride-induced corrosion initiation of steel in concrete. We use a method to quantify and normalize the effect of individual SCI characteristics based on different literature results, which allows comparing them in a comprehensive context. It is found that the different SCI characteristics have received highly unbalanced research attention. Parameters such as w/b ratio and cement type have been studied most extensively. Interestingly, however, literature consistently indicates that those parameters have merely a moderate effect on the corrosion susceptibility of steel in concrete. Considerably more pronounced effects were identified for (1) steel properties, including metallurgy, presence of mill scale or rust layers, and surface roughness, and (2) the moisture state. Unfortunately, however, these aspects have received comparatively little research attention. Due to their apparently strong influence, future corrosion studies as well as developments towards predicting corrosion initiation in concrete would benefit from considering those aspects. Particularly the working mechanisms related to the moisture conditions in microscopic and macroscopic voids at the SCI is complex and presents major opportunities for further research in corrosion of steel in concrete.
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.
Samples of the austenitic stainless steel grade X5CrNi18‐10 (1.4301, AISI 304) were ground industrially with various grinding parameters to study their influence on corrosion resistance. The ability of the mechanically ground surfaces to form a stable passive layer was evaluated by KorroPad test and a modified electrochemical potentiodynamic reactivation test based on a single loop (EPR‐SL). Furthermore, the surfaces were characterized by surface analytical methods. The main influence was determined regarding abrasive belt type. Surfaces mechanically ground with granulate abrasive belts constantly had a lower corrosion resistance than surfaces ground with single‐coated grain. The granulate abrasive belts generated more sensitized surface areas and left formations of welded sample material on the mechanically ground surfaces. A post‐treatment with a nonwoven abrasive proved to be an effective finishing process by which the surface defects and sensitized material got removed and the surfaces regained the expected corrosion resistance.
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.
Electrochemical potential mapping according to guideline B3 of DGZfP (German Society for Nondestructive Testing) is a recognized technique for the localization of corroding reinforcing steels. In reinforced concrete structures the measured potentials are not necessarily directly linked to the corrosion likelihood of the reinforcing steel. The measured values may be significantly affected, different from, e.g., stress measurement, by different influences on the potential formation at the phase boundary metal/concrete itself as well as the acquisition procedure. Due to the complexity of influencing factors there is a risk that the results are misinterpreted. Therefore, in a training concept firstly the theoretical basics of the test method should be imparted. Then, frequently occurring practical situations of various influencing factors will be made accessible to the participants by a model object specially designed for this purpose. The aim is to impart profound knowledge concerning the characteristics of potential mapping for detecting corrosion of reinforcing steel in order to apply this technique in practice as reliable and economical test method.
Hard and wear resistant coatings deposited by PVD techniques have been characterized for decades for their capabilities to protect steel substrates from corrosion. In the present work the effect of Mg incorporated into TiN coatings is described in terms of the corrosion behavior as well as the mechanical and structural properties.
TiN and TiMgN films with Mg contents between 10 and 35 at.% were deposited onto mirror polished 100Cr6 (1.3505) steel samples with 2.5 and 5 μm thickness by using DC magnetron sputtering. The corrosion protection capabilities of the coatings were characterized by neutral salt spray (NSS) test, considering the amounts and sizes of growth defects inherent in each coated sample as determined by a recently developed optical scan method (Large Area High Resolution mapping). The defect data were statistically analyzed for improved interpretation of NSS test results. Chosen growth defects were additionally analyzed by focused ion beam technique. Furthermore the coating composition and morphology, the hardness and the tribological behavior were characterized.
Polished steel samples coated with 2.5 μm TiMgN containing about 35 at.% Mg were in the plane free of corrosion after 24 h in a NSS test. TiMgN with 10 or 20 at.% Mg only provided a slightly improved corrosion protection in relation to pure TiN coatings, which was limited to certain types of growth defects. The highest Mg containing coatings exhibited a decreased hardness down to 1200 or 1800 HV depending on type of deposition (HV 1200: Ti- and Mg-target with rotating substrate holder, 1800: Mg-plugged Ti-target with static substrate holder), but also showed a strongly improved wear resistance against Al2O3 related to pure TiN. By analyzing the NSS test results it was found that the corrosion behavior of the coated samples did not only depend strongly on the Mg content, but also on the sample individual defect concentrations. Therefore this subject is extensively discussed.
The present study shows the potential of high-resolution imaging and nano-Fourier-transform infrared (nano-FTIR) spectroscopy for corrosion science. The protective oxidation layers of different chlorine-gas treated silicon
carbides (SiCs) were characterized with these techniques. A nitrified SiC showed the highest resistant strength against chlorine corrosion at 1000 °C compared to the other SiCs. Nano-FTIR spectroscopy with a lateral resolution below 40 nm detected differences in the crystallinity of the bulk-SiC and in the transitional region to the protective layer. Furthermore, high-resolution imaging provides deep insight in the interfacial layer between bulk-SiC and the protective oxidation layer on sub-micrometer scale.
Nine different stainless steel alloys were exposed for 5 years under marine environment and their corrosion behaviour was compared and assessed. The investigation of four different surface finishes for all alloys tested further enabled to consider industry-specific features of the surface finish for the material comparison. The results of the exposure tests yield conclusions regarding the influence of alloy composition, surface finish and exposure duration under marine environment. The three duplex stainless steels revealed excellent corrosion resistance even in case of crevices during the 5 years of exposure under the given exposure conditions. Also the molybdenum-alloyed ferritic steel 1.4521 showed good corrosion resistance comparable to the classical austenitic materials 1.4301 and 1.4404.
The development of organic coatings for corrosion protection is an elaborate process with a multitude of often interminable investigations and tests of protection properties. Electrochemical methods support the processes of development to a great extent and help to understand mechanisms of action and failure. They are usually carried out on applied coating systems with a completed formulation. An examination possibility is presented in this publication that enables the characterization of waterbased coatings with different formulation variations in the liquid (aqueous) state with the aid of electrochemical noise technique. Thus, selection of binders, pigments, and other additives is supported essentially and made more efficient in a very early Phase of formulation development. The paper shows that a unique insight into the dynamic processes of a metal in contact with an aqueous coating dispersion is possible using the example of the development of zinc-free corrosion-inhibiting pigments for waterbased coatings. In addition, it is presented in which way the results correlate with the performance of applied coatings.
Potential of martensitic stainless steel X5CrNiCuNb 16-4 as pipe steel in corrosive CCS environment
(2017)
Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site (heat, pressure, salinity of the aquifer, CO2-partial pressure). X5CrNiCuNb16-4 has been proven to be sufficient resistant in corrosive environments, but shows rather unusual corrosion behaviour in CCS environment. Therefore differently heat treated coupons of 1.4542 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in an a) water saturated supercritical CO2 and b) CO2-saturated synthetic aquifer environment similar to on-shore CCS-sites in the Northern German Basin. Additionally fatigue tests were performed via push-pull tests with a series of 30 specimens was tested at stress amplitudes between 150 MPa and 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). Best corrosion resistance in the liquid phase is achieved via normalizing prior to exposure and hardening+tempering at 670 °C leads to lowest corrosion rates in the supercritical phase. With no regard to atmosphere discontinuously ellipsoidal surface corrosion regions appear after exposure of 4000 h and more. The endurance limit of X5CrNiCuNb16-4 measured in air is reduced by more than 50% when exposed to CCS environment (maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa) The scatter range TN = 1:34 is disproportionately large contributing to an overall unusual corrosion behaviour.
In coal-fired power plants using oxyfuel combustion process with carbon capture and sequestration, instead of air, a mixture of oxygen and recirculated flue gas is injected in the boiler. A series of steels were exposed to CO2-SO2-Ar-H2O gas mixtures at 600 °C for 1000 h to compare their high temperature corrosion behavior. During the corrosion process, carburization, decarburization and recrystallization were observed underneath the oxide scale depending on the gas mixture and alloy composition. The conditions that lead to carburization are not yet completely understood, but decarburization can be simulated using thermodynamic and kinetic models. In this work, the results of these simulations are compared with measured values for one of the alloys that displayed a decarburized region. Since the mobility of carbon in the scale is not known, two strategies were adopted: simulation of alloy-atmosphere contact; and estimation of the carbon flux to produce the observed decarburization. The second approach might give an insight on how permeable to carbon the scale is.
Similar to the success story of digital photography a major upheaval has been observed in digital industrial radiology. This paper is split into 3 parts:
Part 1: Film Replacement and Backscatter Imaging: Computed radiography with phosphor imaging plates substitutes film applications. Digital Detector Arrays enable an extraordinary increase of contrast sensitivity in comparison to film radiography. The increased sensitivity of digital detectors enables the efficient usage for dimensional measurements and functionality tests substituting manual maintenance. The digital measurement of wall thickness and corrosion status is state of the art in petrochemical industry. Photon counting and energy discriminating detectors are applied up to 300 Kv provide increased thickness dynamic and material discrimination by synchronously acquisition of images of the high and low energy part of the spectrum. X-ray back scatter techniques have been applied in safety and security relevant applications with single sided access of source and detector. First inspections of CFRP in aerospace industry were successfully conducted with newly designed back scatter cameras. Numeric modeling is used to design X-Ray optics and inspection scenarios as well as conducting RT training.
Part 2: Computed tomography (CT)
Part 3: Micro Radiography and Micro CT.
CO2 streams captured from power stations or industrial plants may contain impurities that impact the consecutive steps of the CO2 capture and storage (CCS) chain. As the basis for an optimization of CO2 purity over the whole CCS chain, impacts of different impurities were investigated at key steps including studies on (i) corrosion of metallic materials in CO2 streams and brine, (ii) fluid and interfacial properties as a function of pressure, temperature and CO2 stream composition and their implications for CO2 transport, injection and geological storage, (iii) costs of different pipeline design options, (iv) geochemical alterations at typical reservoir conditions and their implications for geomechanical rock properties. Major findings are synthesized for two exemplary single source-single sink CCS chain scenarios involving CO2 stream compositions typical for pre-combustion capture and oxyfuel combustion. Recommendations for material selection for compression, transport and injection were derived for various CO2 stream compositions. To reliably control corrosion, a limitation of water contents to 50 ppmv is recommended for pipeline transportation of all CO2 streams. At geological storage conditions, the presence of either O2, NOx or SO2 only weakly affected fluid-mineral/rock interactions that still impacted geomechanical rock properties.
Adhesion and corrosive delamination of epoxy films on chemically etched ZnMgAl-alloy coatings
(2016)
The effect of alkaline and acidic pretreatment steps on the surface chemical
composition and adhesion properties of ZnMgAl-alloy coated steel was
investigated by means of spectroscopic methods, scanning Kelvin probe (SKP)
and peel test measurements.The spectroscopic results indicate that the surface
film composition can be adjusted by the wet-chemical treatment. To study the
corresponding surface adhesive properties, the samples were coated with an
epoxy amine adhesive. Peel tests under humid conditions indicated an
increased interaction between the acidic pre-treated surface and the adhesive.
The results of the SKP analysis show that the acidic cleaned substrates have the
highest resistance to delamination, which can be explained by the shift of the
interfacial electrode potential.
Manganese alloyed stainless steels represent a cost-effective alternative to conventional CrNi- stainless steels due to strong fl uctuations of the market prices for nickel seen during the last years. In CrMnNi steels, nickel is partially replaced by lower-cost manganese and small amounts of nitrogen for stabilization of the austenitic phase. This also brings benefi ts regarding the mechanical properties, as it results in an increased material strength. Laser beam welding of such materials was investigated for direct comparison with Standard CrNi steels. Main emphasis was laid on fi nding adequate process parameters to achieve a stable welding process and obtain a good weld quality. Two different laser sources, a 4.4 kW Nd:YAG and a 5 kW CO2 laser, were used to weld 1.5 mm stainless steel sheets in continuous wave mode. A high-Mn austenitic (1.4376) and a lean duplex (1.4162) steel, as well as the standard austenitic (1.4301) and duplex (1.4362) grades were selected as test materials. Both butt and lap joint confi gurations were studied. Experiments were carried out systematically, varying the welding speed, laser power and focal point position in order to determine adequate process windows. The infl uence of the shielding gas type and fl ow rate on the process stability and the weld quality were investigated. The effects of weld edge preparation on the weld appearance and quality levels attained were also examined. The obtained welded joints were subjected to radiographic tests for detection of internal imperfections. Also a metallurgical characterization of the samples regarding the resulting phase composition or balance and hardness depending on the welding process parameters was conducted. Furthermore, tensile and potentiodynamic tests were performed to evaluate the mechanical and corrosion properties, respectively. The results provide an insight into the advantages and limitations of the laser beam welding process for joining high-manganese alloyed stainless steels. Conditions for the production of defect-free and corrosion-resistant welds having good mechanical properties could be determined.
Investigation of chloride-induced pitting corrosion of steel in concrete with innovative methods
(2016)
The combination of electrochemical and 3D computed tomography (CT) investigations offers the possibility of verifying electrochemical measurements non-destructively. Determining the steel surfaces damaged by pitting corrosion allows developing specimens having damage pattern corresponding to practice. Corrosion phenomena like decoupled pitting corrosion cannot be verified by electrochemical measurements only, but with the combination of those two kinds of investigations it is possible. Another advantage is the minimization of the number of samples. The classical experimental procedure requires the destruction of samples after each damage step.This can be avoided by the use of 3D computed tomography. As long as the corrosion phenomena are completely within the examination zone shown by the 3D computed tomography, the electrochemical measurements can be calculated on an area basis to get the specific corrosion rate or polarization resistance.
In order to provide basic information on corrosion resistance to the designers and users of geothermal plants different metallic materials including duplex and austenitic stainless steels as well as a nickel alloy have been evaluated in artificial geothermal fluids simulating the conditions in some locations with geothermal potential in Germany as well as two sites in Indonesia. By electrochemical and long-term exposure tests at 100 °C and 150 °C the suitability of low alloyed steel UNS G41300, stainless steels UNS S31603 UNS S31803, UNS S32760, super austenitic steel UNS N08031 and nickel based alloy UNS N06059 was investigated in these geothermal fluids, using critical potentials and corrosion rates. In high-saline environments the crevice corrosion turned out to be the determining mechanism. The nickel based alloy shows excellent corrosion resistance against pitting corrosion. Excluding its high cost, it is very good to be used in the construction of geothermal facilities having highly saline brines. Stainless and duplex steels exhibit a limited corrosion resistance concerning pitting and crevice corrosion. Therefore they are not suitable for highly saline brines. The super austenite UNS N08031 showed a temperature depending behavior. In non-saline environments the low-alloyed steel UNS G41300 (beside of the higher alloyed materials) could be employed as a constructional material for the geothermal power plant, as long as a sufficient wall thickness of the material is considered.
Electron backscatter diffraction (EBSD) and scanning electron microscopy were combined to study the effect of residual defect density on corrosion initiation in aluminium alloy AA2024-T3. EBSD was used to determine the level of misorientation (MO), from pixel to pixel, within individual grains. The MO can be determined with respect to either the average orientation angle of the grain or with respect to the average orientation angle of the surrounding pixels (in this instance, a matrix of 7×7 surrounding pixels has been applied). Herein, the MO, determined using the surrounding pixels, was used as the means for the assessing the level of defect density within a grain. It was found that there was a noteworthy, but not definitive, correlation of MO with corrosion initiation after 1 min exposure to 0.1 M NaCl solution. Additionally, the S and θ-phase particles were also identified using EBSD, displaying a range of MO and therefore defect density.
Inspection and maintenance of concrete bridges is a major cost factor in transportation infrastructure, and there is significant potential for using information gained during inspection to update predictive models of the performance and reliability of such structures. In this context, this paper presents an approach for assessing and updating the reliability of prestressed concrete bridges subjected to chloride-induced reinforcement corrosion. The system deterioration state is determined based on a Dynamic Bayesian Network (DBN) model that considers the spatial variability of the corrosion process. The overall system reliability is computed by means of a probabilistic structural model coupled with the deterioration model. Inspection data are included in the system reliability calculation through Bayesian updating on the basis of the DBN model. As proof of concept, a software prototype is developed to implement the method presented here. The software prototype is applied to a typical highway bridge and the influence of inspection information on the system deterioration state and the structural reliability is quantified taking into account the spatial correlation of the corrosion process. This work is a step towards developing a software tool that can be used by engineering practitioners to perform reliability assessments of ageing concrete bridges and update their reliability with inspection and monitoring data.
Carbon-based conductive coatings are complex composites, consisting of an organic or inorganic binder and conductive carbon components, for application as anodes in impressed current cathodic protection systems of reinforced concrete structures. The electrochemical properties of three coatings at different humidity and in saturated calcium hydroxide solution were studied by electrochemical methods, such as electrochemical impedance measurement, measuring of open circuit potential over time and galvanostatic polarization. The dissolved organic and inorganic carbons in electrolyte solution were quantified by using a photometric method. The structures of the coatings were investigated before and after the electrochemical tests by microscopy and scanning electron microscope/EDX analysis. The results of the electrochemical impedance measurements show that the tested coatings all have a relatively low resistance, which is between 100 and 200 Ω. The binder and the surface porosity influence the degradation behavior of those coatings. Especially the organic binder reacts with the strong alkaline medium under dissolving of organic carbon.
When storage of spent nuclear fuel or high level waste is carried out in dual purpose casks (DPC), the effects of aging on safety relevant DPC functions and properties have to be managed in a way that a safe transport after the storage period of several decades is capable and can be justified and certified permanently throughout that period. The effects of aging mechanisms (e.g. radiation, different corrosion mechanisms, stress relaxation, creep, structural changes and degradation) on the transport package design safety assessment features have to be evaluated. Consideration of these issues in the DPC transport safety case will be addressed. Special attention is given to all cask components that cannot be directly inspected or changed without opening the cask cavity, like the inner parts of the closure system and the cask internals, like baskets or spent fuel assemblies. The design criteria of that transport safety case have to consider the operational impacts during storage. Aging is not the subject of technical aspects only but also of intellectual aspects, like changing standards, scientific/technical knowledge development and personal as well as institutional alterations. Those aspects are to be considered in the management system of license holders and in appropriate design approval update processes. The paper addresses issues that are subject of an actual International Atomic Energy Agency TECDOC draft 'Preparation of a safety case for a dual purpose cask containing spent nuclear fuel'.
Recent results from a three-year multi-disciplinary project on Ancient Egyptian gold jewellery revealed that items of jewellery from the Middle Kingdom to the New Kingdom were manufactured using a variety of alluvial gold alloys. These alloys cover a wide range of colours and the majority contain Platinum Group Elements inclusions. However, in all the gold foils analysed, these inclusions were found to be absent. In this work a selection of gilded wood and leather items and gold foil fragments, all from the excavations by John Garstang at Abydos (primarily from Middle Kingdom graves), were examined using Scanning Electron Microscopy-Energy Disperse Spectroscopy (SEM-EDS), X-Ray Fluorescence (µXRF), Particle Induced X-Ray Emission (µPIXE) and Double Dispersive X-Ray Fluorescence (D²XRF). The work allowed us to characterise the composition of the base-alloys and also to reveal the presence of Pt at trace levels, confirming the use of alluvial gold deposits. Corrosion products were also investigated in the foils where surface tarnish was visually observed. Results showed that the differences in the colour of corrosion observed for the foils are related not only to the thickness of the corrosion layer but also to a multi-layer structure containing the various corrosion products.
Geothermal sources are found to be the most aggressive natural environments for construction materials in terms of corrosion. This study was focused on investigating the suitability of stainless steel UNS S31603 in volcanic areas of geothermal sites Sibayak and Lahendong (Indonesia). Influence of different factors (temperatures up to 175 °C, chloride content up to 1500 mg/L and pH down to 2) was assessed to determine a 'safe operating window' of a power plant and assure the system integrity. Investigations were performed by means of electrochemical methods and long-term exposure tests.
Microstructure, mechanical properties and corrosion behaviour of WZ21 (%wt.) alloy prepared by a powder metallurgy route from rapidly solidified powders have been studied. Results were compared to those of the same alloy prepared through a conventional route of casting and extrusion. The microstructure of the extruded ingot consisted of α-Mg grains and Mg3Zn3Y2 (W-phase) and LPSO-phase particles located at grain boundaries. Moreover, stacking faults were also observed within α-Mg grains. The alloy processed by the powder metallurgy route exhibited a more homogeneous and finer microstructure, with a grain size of 2 µm. In this case W-phase and Mg24Y5 phase were identified, but not the LPSO-phase. The microstructural refinement induced by the use of rapidly solidified powders strengthened the alloy at room temperature and promoted superplasticity at higher strain rates. Corrosion behaviour in PBS medium evidenced certain physical barrier effect of the almost continuous arrangements of second phases aligned along the extrusion direction in conventionally processed WZ21 alloy, with a stable tendency around 7 mm/year. On the other hand, powder metallurgy processing promoted significant pitting corrosion, inducing accelerated corrosion rate during prolonged immersion times.
The Stolt Rotterdam tanker ship, filled with nitric acid, was unloading at the Krefeld-Uerdingen terminal on the Rhine River in November 2001. Nitric acid ran out of the stainless steel tanks into the ship's hull and damaged the structural steel. The ship then caught fire and sank at the terminal. Large quantities of nitrogen oxides were emitted, which drifted towards a residential area. Additionally, a mixture of acid and water was introduced into the Rhine River. The area became hazardous to people and the natural environment; however, the imminent danger for the residents and the environment was reduced because of the protective measures against pollution and the good teamwork between local authorities, fire brigades and the Bayer AG company. The acid was drained off of the ship using a controlled discharge of the acid into the river. Through the use of this measure, the ship was salvaged, limiting the pollution to the area and removing the health hazards to the people and the environment. After the ship was salvaged, the river police, along with assistance from the BAM Federal Institute for Materials Research and Testing, impounded the ship and selected corroded parts for further examination. Some of these components have been examined in detail by the BAM. These material investigations contributed to the elucidation of the origin of the leak in the floor panel. The cause of damage was deemed to be a result of a construction flaw at the enamelled valve on the load and discharge pipes.
The results from the comparative corrosion testing using the original structural steel and 60% acid revealed that the valves began to leak at least 8 h prior to the incident at the terminal.
The development of anti-corrosive pigments for the most diverse coating Systems is extremely time consuming and expensive, owing to the necessary climatic testing, such as testing under salt spray exposure. To accelerate work on a new zinc-free pigment with improved protection, modern, electrochemical investigation methods have been used successfully and verified using traditional tests.
Development of anti-corrosive pigments for diverse coating systems is both time-consuming and costly, due to the necessary climatic testing, such as testing under salt spray exposure. To accelerate work on a new zinc-free pígment with improved protection, modern, electrochemical investigation methods have been used successfully and verified using traditional tests.
Corrosion resistance of duplex stainless steel (SS) (UNS S32101) and super austenitic SS (UNS NO8031) (Alloy 31) was investigated in crevice conditions in a saline brine. Rubber was used to form a metal/non-metal-crevice confguration. UNS NO8031 did not exhibit any signs of pitting corrosion even by applying potentials much more positive than the corrosion potential.
Sixteen laboratories have performed electrochemical noise (EN) measurements based on two systems. The first uses a series of dummy cells consisting of a 'star' arrangement of resistors in order to validate the EN measurement equipment and determine its baseline noise performance, while the second system, based on a previous round-robin in the literature, examines the corrosion of aluminium in three environments. All participants used the same measurement protocol and the data reporting and analysis were performed with automatic procedures to avoid errors. The measurement instruments used in the various laboratories include commercial general-purpose potentiostats and custom-built EN systems. The measurements on dummy cells have demonstrated that few systems are capable of achieving instrument noise levels comparable to the thermal noise of the resistors, because of its low level. However, it is of greater concern that some of the instruments exhibited significant artefacts in the measured data, mostly because of the absence of anti-aliasing filters in the equipment or because the way it is used. The measurements on the aluminium samples involve a much higher source noise level during pitting corrosion, and most (though not all) instruments were able to make reliable measurements. However, during passivation, the low level of noise could be measured by very few systems. The round-robin testing has clearly shown that improvements are necessary in the choice of EN measurement equipment and settings and in the way to validate EN data measured. The results emphasise the need to validate measurement systems by using dummy cells and the need to check systematically that the noise of the electrochemical cell to be measured is significantly higher than the instrument noise measured with dummy cells of similar impedance.
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 safety assessment of railway axles is based on a two-stage approach: fatigue strength design and regular inspections which, in terms of a general safety philosophy refer to safe-life and damage tolerance concepts. Starting with a recent failure case, a broken axle of a German high speed train, a discussion is presented on issues of both safety levels. These include ideas for finite life design, the treatment of in-service effects on the fatigue strength due to flying ballast damage and corrosion pits, the effect of corrosion on fatigue crack initiation and propagation, potential effects of non-metallic inclusions in steels, the way to detect them by quality control measures and reliability aspects of non-destructive testing with respect to the detection of fatigue cracks. Proposals are made how the safety level could be further improved.
In corrosive environments such as CCS bore holes or geothermal power plants the materials loaded cyclically are also exposed constantly to the highly corrosive hot thermal water. The lifetime reduction of (X46Cr13, AISI 420C) is demonstrated in in-situ-laboratory experiments (T=60 °C, geothermal brine: Stuttgart Aquifer flow rate: 9 Nl/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 is most likely failure cause.
Bei der Qualitätsbewertung von Schneidwaren aus nichtrostenden martensitischen Chrom-Stählen stellt die Überprüfung der Korrosionsbeständigkeit ein wichtiges Kriterium dar. Allgemein üblich sind Wechseltauchversuche mit relativ hohem zeitlichem und auswertungsbedingtem Aufwand, die noch dazu zerstörend sind und teilweise fragwürdige Ergebnisse liefern. In den letzten Jahren wurden neue Ansatze der Prüfung geschaffen, die eine nahezu zerstörungsfreie Kurzzeit-Korrosionsprüfung erlauben. Es wird gezeigt, dass mit dem elektrochemischen Rauschen sehr empfindlich Einflüsse des Härtens und der Oberflächenbehandlung auf die Korrosionsbeständigkeit nachgewiesen werden können, wodurch eine schnelle und objektive Qualitätsbewertung innerhalb des Fertigungsprozesses und der Endkontrolle von Produkten möglich ist. Das für die Prüfmethodik ausgenutzte Phänomen des elektrochemischen Rauschens zielt darauf ab, den Beginn der Korrosion empfindlich und schnell zu detektieren, ohne die Prüfbedingungen maßlos zu verschärfen und Produkte damit zu zerstören. Neben der Funktionalität der Prüfung stehen aber auch die Anwenderfreundlichkeit und somit die Akzeptanz bei den Herstellern im Vordergrund. Aus diesem Grund wurde zusätzlich ein Indikatortest (KorroPad) als praxistaugliche Alternative zum elektrochemischen Rauschen angewendet. Die Ergebnisse zeigen eine gute Übereinstimmung beider Methoden und ermöglichen eine effektive betriebliche Qualitätsüberwachung von Schneidwaren.
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 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.
During the compression of emission gasses into deep geological layers (Carbon Dioxide Capture and Storage, CCS) CO2-corrosion will become a relevant safety issue. The reliability of the steels used at a geological onshore CCS-site in the Northern German Bassin 42CrMo4 (1.7225, AISI 4140) used for casing, and the injection pipe steels X46Cr13 (1.4034, AISI 420 C), X20Cr13 (1.4021, AISI 420 J) as well as X35CrMo17 (1.4122) is demonstrated in laboratory experiments. Samples were kept in a synthetic aquifer environment at T = 60 °C. This corrosive environment is then saturated with technical CO2 at a flow rate of 3 l/h. Microstructures were characterized by X-ray diffraction, light microscopy, scanning electron microscopy, and energy dispersive X-ray analysis, after a series of heat treatments (700 h to 2 years). The non-linear isothermal surface corrosion behaviour of the steels reveals surface corrosion rates around 0.10.8 mm/year, when obtained by mass gain. Severe pit corrosion (pit heights ca. 4.5 mm) are only located on the injection pipe steels. Main phases of the continuous scales are siderite FeCO3 and goethite α-FeOOH. The formation of the non-protective layer is likely to form via a
transient Fe(OH)2-phase.
Basic research on the corrosive effect of flue gases has been performed at the BAM Federal Institute for Materials Research and Testing (Germany). Conditions at both high and low temperatures were simulated in specially designed experiments. Carburization occured in flue gases with high CO2 content and temperatures higher than 500 °C. In SO2 containing flue gases sulphur was detected in the oxide scale. At lower temperatures no corrosion was observed when gases with low humidity were investigated. Humidity higher than 1500 ppm was corrosive and all steels with Cr contents lower than 12% revealed corroded surfaces. At low temperatures below 10 °C a mixture of sulphuric and nitric acid condensed on metal surfaces. Acid condensation caused severe corrosion. Humidity, CO2, O2, and SO2 contents are the important factors determining corrosion. Below 300 °C acid condensation is the primary reason for corrosion. Low humidity and low temperatures are conditions which can be expected in the CO2 separation and treatment process. This work includes major conditions of the flue gas and CO2 stream in CCS plants and CCS technology.
In lightweight car body shell mass production, due to requirements on vehicle weight reduction and carbon dioxide emissions, joining of advanced high strength steels (AHSS) with different joining procedures and especially hybrid bonding techniques is becoming more and more important. One of these hybrid bonding techniques is the combination of resistance spot welding and adhesive bonding called weldbonding. One of the important advantages of weldbonded joints in comparison to resistance spot welded joints are the enhanced mechanical properties. To guarantee sufficiently high quality conditions regarding the strength of the weldbonded joints, the influences of the applied adhesive systems and of different base metal combinations are studied. This is carried out for both non-corrosive and corrosive environments and for the choice of different joining parameters settings. In particular, the mechanical behaviour of the weldbonded joints is investigated under quasi-static, impact and fatigue loads. Furthermore, the energy absorption of the weldbonded joints for both non-corrosive and corrosive environments is studied. It is shown that the weldbonded joints possess higher mechanical strengths in all load cases (quasi-static, impact and fatigue). Corrosive attack affects weldbonded joints, and the quasi-static strength is reduced. Resistance spot welded joints are not affected by the corrosive attack, but even after several weeks of corrosive attack, the quasi-static strength of weldbonded joints remains higher than that of resistance spot welded joints.
Surface treatments usually are used to modify the appearance and properties of stainless steel surfaces. Simultaneously, the corrosion resistance of the stainless steel surface being related intrinsically to the spontaneous formation of a passive layer also will be affected. In this respect, the influence of different surface treatments on the corrosion resistance of Type 304 (UNS S30400) stainless steel to pitting corrosion has been evaluated by means of potentiostatic electrochemical noise measurements and surface characterization. Typical industrial treatments including mechanical grinding, glass blasting, and pickling were taken into account. Additionally, special consideration was put on the effect of aging conditions of the passive layer after surface treatments, in particular on the relative humidity. Benefits and limitations of the different applied surface treatments concerning protectiveness of the stainless steel surface were determined and discussed.
When emission gasses are compressed into deep geological layers (CCS) CO2-corrosion of injection pipe steels is a relevant safety issue. The reliability of the steels used at the geological onshore CCS-site at Ketzin, Germany, is demonstrated in 2 years laboratory experiments under an equivalent corrosive environment at ambient pressure (T=60 °C, aquifer water, CO2-flow rate of 3 l/h). Corrosion kinetics and microstructures were characterized using samples of the heat treated steel 42CrMo4 (casing), and samples of the martensitic stainless steel X46Cr13 (injection).
Single-pass solid-state laser welding of plates in the thickness range of 10 to 20 mm became possible with the invention of the fibre laser. This new technique provides excellent beam quality at powers as high as 20 kW or more, and has proved applicable in several industrial applications. By replacing conventional methods with the fibre laser, it is possible to avoid multiple-pass welding that requires time-consuming bevelling. The high energy density of the fibre laser beam also reduces the heat input and consequently the distortion. However, the rapid solidification and cooling associated with laser welding can cause imbalance of the microstructure of duplex stainless steel weldments, where excessively high ferrite contents may reduce the corrosion resistance and the ductility of the material. The solution is normally to add nickel-based filler wire and to increase the heat input. By using a hybrid welding process where the laser beam and the gas metal arc (GMA) process act in a common process zone, filler metal can be added to the molten pool at higher heat input and at the same time, higher welding speed and deeper penetration can be achieved. In this work, 13.5 mm thick 2205 (EN 1.4462, UNS S31803) was fibre laser-GMA hybrid welded in a single-pass using 14 kW of laser power and ISO 22 9 3 N L as filler wire for the GMA process. The resulting welds were free from defects, with smooth surfaces and full penetration. The investigation examines the weld metal microstructure and the effect on corrosion resistance and mechanical properties. The option to add nickel foil, when hybrid welding, was also investigated, as comparison, and the effect on austenite formation was evaluated.